Patent Grant
6887657
The present invention relates to a silver halide color photographic photosensitive material and an image-forming method.
Particularly, the present invention relates to a silver halide color photographic photosensitive material that is excellent in color reproduction, image-stability, and processing properties.
Further, the present invention relates to a silver halide color photographic photosensitive material and an image-forming method that are excellent in rapid processing suitability, color-forming properties, color reproduction, whiteness, and image fastness after processing. Further, the present invention relates to a silver halide color photographic photosensitive material and an image-forming method that are excellent in processing stability when processed with a running solution.
A photosensitive material generally has silver halide emulsion layers light-sensitive to three primary colors of blue, green, and red, and it forms a dye image according to so-called subtractive color photography, in which a dye image is formed by color-forming three kinds color-forming materials (couplers) in these silver halide emulsion layers in relation of complementary colors to the color to which each of the above layers is intrinsically sensitive. The dye image that is obtained by photographic processing of this photosensitive material is generally formed from any of azomethine dyes or indoaniline dyes formed by a reaction between an oxidation product of an aromatic primary amine color-developing agent and a coupler. The thus-obtained color photographic image is not fully stable against light and wet heat, such that the color (dye) image exposed to light, or stored under high-temperature and high-humidity conditions for a long period of time, fades or discolors, which results in deterioration of image quality.
Fading or discoloring of the image is almost a fatal disadvantage for a recording material. As methods to eliminate such disadvantages, various techniques are proposed, such as development of couplers that enable providing a dye excellent in fastness, use of anti-fading agents, and use of ultraviolet-absorbing agents to inhibit an image from deterioration owing to ultraviolet radiation. Among these techniques, the effect of inhibiting an image from deterioration that is obtained by using anti-fading agents is remarkable. For example, it is known to use anti-fading agents, such as hydroquinones, hindered phenols, catechols, gallic acid esters, aminophenols, hindered amines, chromanols, indanes, ethers or esters that are formed by silylation, acylation, or alkylation of a phenolic hydroxyl group of each of these compounds, and metal complexes.
Even though these compounds are recognized as effective agents to inhibit a dye image from fading and discoloring, they are inadequate to respond to customer demand for high image quality. Further, these compounds fail to exhibit synthetically excellent effects that are useful for color photography, because they sometimes cause a hue change, or generate fog, or cause dispersion failure, or produce fine crystals after emulsion coating. Further, to obtain high image quality, sometimes a large amount, or multiple kinds, of compounds are used. Consequently, sometimes it takes a long time to perform processing, which results in difficulty obtaining a sufficient developed dye density. Also from the viewpoint in the aforementioned aspects, development of improved inhibitors has been desired. On the other hand, recently it has been known to use acrylate compounds and compounds derived from them as inhibitors of dye deterioration, as described, for example, in JP-A-8-44020 (“JP-A” means unexamined published Japanese patent application), JP-A-11-258748, and JP-A-11-327101. However, these compounds are unsatisfactory, since they are insufficient in preventing image deterioration, or they adversely affect photographic properties. Further, even though the compounds described in JP-A-6-59390 are effective for resistance against yellowing at the time of processing, they are insufficient to prevent image deterioration.
In silver halide photographic photosensitive materials (hereinafter also referred to simply as “photosensitive materials”) for subtractive color photography, a color image is formed by dyes of three primary colors of yellow, magenta, and cyan. In a color photographic material, (in particular a color print material for direct appreciation, which is used in the color photography that uses a current p-phenylenediamine-series color-developing agent, use is made of an acylacetanilide-series compound as a yellow dye-forming coupler (hereinafter “a dye-forming coupler” is also referred to simply as “a coupler”). However, the hue of yellow dyes obtained from these dye-forming couplers is reddish, due to an inferior sharpness of a peak of the absorption curve at the longer wavelength side (that is, on the absorption curve, the peak in interest has subsidiary absorption at its foot portion at the longer wavelength side), and it is difficult to obtain a yellow hue with high purity. Further, the above-mentioned dyes are sometimes easily decomposed under conditions of high temperature and high humidity, or of irradiation of light, and thus they have insufficient image storability after development processing. Further, because the molecular extinction coefficient of the dye is low, large quantities of the coupler and silver halide are needed to obtain a desired color density, which results in an increase in the film thickness of the photosensitive material. Such increased film thickness sometimes reduces sharpness of the dye image, and also becomes a serious hindrance to the rapid processing that has been strongly utilized in recent years. In this situation, improvement of these performances has been desired.
In order to solve these problems, improvement of acyl groups and anilido groups were proposed on the couplers. Recently, as improved couplers of the conventional acylacetanilide-series couplers, there were proposed, for example, 1-alkylcyclopropanecarbonyl acetanilide-series compounds, cyclomalondiamide-type couplers, pyrrole-2- or 3-yl- or indole-2- or 3-yl-carbonylacetanilide-series couplers. The dyes formed from these couplers were improved in terms of both hue and molecular extinction coefficient of dyes formed, compared with the conventional ones. However, these improved couplers are not satisfactory in image storability still. Further, owing to their complicated chemical structure, the synthesis route became longer, and consequently cost of the couplers became higher, causing a practical problem.
On the other hand, in recent years, acetic acid ester-series and acetanilide-series couplers, to which 1,2,4-benzothiadiazine-1,1-dioxide is bonded, are proposed, for example, in U.S. Pat. No. 3,841,880, JP-A-52-82423, and JP-A-2-28645. These couplers, however, are low in color-forming property, and they are inferior in sharpness of a peak of the adsorption curve owing to the subsidiary absorption at the foot portion on the longer wavelength side. Further, acetic ester-series and acetanilide-series couplers, to which 1,2,4-benzothiadiazine-1,1-dioxide is bonded, as described in European Patent Publication No. 1246006, are remarkably improved in these points, and thereby these couplers give dyes having high color-forming property and provide excellent absorption characteristics. Nonetheless, dyes obtained from these couplers are insufficient in fastness to light at low-density areas, under conditions of storage at high temperature. Therefore, there is a need to improve light fastness at a low-density area, particularly when a picture is exposed to light under high-temperature storage conditions (for example, the situation seen regarding displays in a commercial photo studio). Because a low density of yellow is employed for image reproduction of a human face, light fastness in such a density region is important. The bisphenol-series image-stabilizing agents described in EP-A-1246006 and the like still do not perform adequately under such severe storage conditions. On the contrary, reduction in color density and deterioration of processing stability with a running solution are seen with addition of the bisphenol compound. Therefore, further improvement has been desired.
The present invention resides in a silver halide color photographic photosensitive material, which comprises, in at least one layer on a support, at least one compound which has a microhardness value of 200 or less when forming a polymerized film and contains at least three alkenylcarbonyl groups in the molecule.
Further, the present invention resides in a silver halide color photographic photosensitive material, which comprises, in at least one layer on a support, at least one compound represented by formula (A):
wherein, in formula (A), R1, R2 and R3 each independently represent a hydrogen atom, an aliphatic group, or an aryl group; R4 represents a hydrogen atom or a substituent; X1 represents a divalent organic group; n represents 0 or 1; a represents an integer of 1 to 6; b represents an integer of 0 to 5; a+b is 6; when a is 2 or more, a plurality of —(X1)n—COC(R1)═C(R2)R3 may be the same or different; and when b is 2 or more, R4's may be the same or different.
Further, the present invention resides in a silver halide color photographic photosensitive material, which comprises, in at least one layer on a support, at least one compound represented by the above-described formula (A) and having a microhardness value of 200 or less when forming a polymerized film.
Further, the present invention resides in a silver halide color photographic photosensitive material, which comprises, on a support, at least one yellow color-forming photosensitive silver halide emulsion layer, at least one magenta color-forming photosensitive silver halide emulsion layer, and at least one cyan color-forming photosensitive silver halide emulsion layer,
wherein, in formula (I), Q represents a group of non-metal atoms that forms a 5- to 7-membered ring in combination with the —N═C—N(R1)—; R1 represents a substituent; R2 represents a substituent; m represents an integer of 0 or more and 5 or less; when m is 2 or more, R2s may be the same or different, or R2s may bond together to form a ring; and X represents a hydrogen atom, or a group capable of being split-off upon a coupling reaction with an oxidized product of a developing agent;
Further, the present invention resides in a method of forming an image, which comprises the step of subjecting any one of the above-described silver halide color photographic photosensitive materials to exposure to light and development processing under specific conditions.
Other and further features and advantages of the invention will appear more fully from the following description.
According to the present invention, there are provided the following means:
wherein, in formula (A), R1, R2 and R3 each independently represent a hydrogen atom, an aliphatic group, or an aryl group; R4 represents a hydrogen atom or a substituent; X1 represents a divalent organic group; n represents 0 or 1; a represents an integer of 1 to 6; b represents an integer of 0 to 5; a+b is 6; when a is 2 or more, a plurality of —(X1)n—COC(R1)═C(R2)R3 may be the same or different; and when b is 2 or more, R4's may be the same or different.
wherein at least one yellow dye-forming coupler represented by formula (I) and the compound which has a microhardness value of 200 or less when forming a polymerized film and contains at least three alkenylcarbonyl groups in the molecule are contained in the same layer:
wherein, in formula (I), Q represents a group of non-metal atoms that forms a 5- to 7-membered ring in combination with the —N═C—N(R1)—; R1 represents a substituent; R2 represents a substituent; m represents an integer of 0 or more and 5 or less; when m is 2 or more, R2s may be the same or different, or R2s may bond together to form a ring; and X represents a hydrogen atom, or a group capable of being split-off upon a coupling reaction with an oxidized product of a developing agent.
wherein at least one yellow dye-forming coupler represented by the above-described formula (I) and the compound represented by formula (A) are contained in the same layer.
wherein at least one yellow dye-forming coupler represented by the above-described formula (I), and the compound represented by formula (A) and having a microhardness value of 200 or less when forming a polymerized film are contained in the same layer.
wherein, in formula (Ph), Rb1 represents an aliphatic group, an aryl group, a carbamoyl group, an acylamino group, a carbonyl group, or a sulfonyl group; and Rb2, Rb3, Rb4 and Rb5 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an aliphatic group, an aryl group, a heterocyclic group, an alkyloxy group, an aryloxy group, a heterocyclic oxy group, an oxycarbonyl group, an acyl group, an acyloxy group, an oxycarbonyloxy group, a carbamoyl group, an acylamino group, a sulfonyl group, a sulfinyl group, a sulfamoyl group, an alkylthio group, or an arylthio group.
wherein the compound represented by formula (Ph) is a compound represented by any one of formulae (Ph-1), (Ph-2) and (Ph-3):
wherein, in formulae (Ph-1), (Ph-2) and (Ph-3), Rb6 represents an aliphatic group, an aryl group, an amino group, or an acyl group; Rb1 has the same meaning as defined in formula (Ph); Rb7, Rb8, Rb9, Rb11, Rb12, Rb13, Rb14, Rb15, Rb16, Rb19, and Rb20 each independetly have the same meanings as Rb2, Rb3, Rb4, and Rb5 in formula (Ph); Rb10 represents a hydrogen atom, an aliphatic group, an acyl group, an oxycarbonyl group, a silyl group, or a phosphoryl group; Xb represents an alkylene group, a phenylene group, —O—, or —S—; and Rb17 and Rb18 each independently represent an aliphatic group or an aryl group.
wherein, in formulae (E-1), (E-2) and (E-3), R41 represents an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an aliphatic sulfonyl group, an arylsulfonyl group, a phosphoryl group, or —Si(R47)(R48)(R49), in which R47, R48 and R49 each independently represent an aliphatic group, an aryl group, an aliphatic oxy group, or an aryloxy group; R42, R43, R45 and R46 each independently represent a hydrogen atom or a substituent; and Ra1, Ra2, Ra3 and Ra4 each independently represent a hydrogen atom or an aliphatic group.
wherein, in formula (TS-I), R51 represents a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an aliphatic sulfonyl group, an aryl sulfonyl group, a phosphoryl group, or —Si(R58)(R59)(R60), in which R58, R59 and R60 each independently represent an aliphatic group, an aryl group, an aliphatic oxy group or an aryloxy group; X51 represents —O— or —N(R57)—, in which R57 has the same meaning as R51; X55 represents —N═ or —C(R52)═; X56 represents —N═ or —C(R54)═; X57 represents —N═ or —C(R56)═; R52, R53, R54, R55 and R56 each independently represent a hydrogen atom or a substituent; each combination of R51 and R52, R57 and R56, and R51 and R57 may bond together to form a 5- to 7-membered ring; each combination of R52 and R53, and R53 and R54 may bond together to form a 5- to 7-membered ring, a spiro ring, or a bicyclo ring; each of R51, R52, R53, R54, R55, R56 and R57 cannot simultaneously represent a hydrogen atom; the total of carbon atoms of the compound represented by formula (TS-I) is 10 or more; and the compound represented by formula (TS-I) is neither identical to the compound represented by formula (Ph) nor the compound represented by any one of formulae (E-1), (E-2) and (E-3);
wherein, in formula (TS-II), R61, R62, R63 and R64 each independently represent a hydrogen atom or an aliphatic group; each combination of R61 and R62, and R63 and R64 may bond together to form a 5- to 7-membered ring; X61 represents a hydrogen atom, an aliphatic group, an aliphatic oxy group, an aliphatic oxycarbonyl group, an aryl oxycarbonyl group, an acyl group, an acyloxy group, an aliphatic oxycarbonyloxy group, an aryl oxycarbonyloxy group, an aliphatic sulfonyl group, an aryl sulfonyl group, an aliphatic sulfinyl group, an aryl sulfinyl group, a sulfamoyl group, a carbamoyl group, a hydroxy group, or an oxy radical group; X62 represents a group of non-metal atoms necessary to form a 5- to 7-membered ring together with the —C(—R61)(—R62)—N(—X61)—C(—R63)(—R64)—; and the total of carbon atoms of the compound represented by formula (TS-II) is 8 or more;
wherein, in formula (TS-III), R65 and R66 each independently represent a hydrogen atom, an aliphatic group, an aryl group, an acyl group, an aliphatic oxycarbonyl group, an aryl oxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, or an aryl sulfonyl group; R67 represents a hydrogen atom, an aliphatic group, an aliphatic oxy group, an aryloxy group, an aliphatic thio group, an arylthio group, an acyloxy group, an aliphatic oxycarbonyloxy group, an aryl oxycarbonyloxy group, a substituted amino group, a heterocyclic group, or a hydroxyl group; each combination of R65 and R66, R66 and R67, and R65 and R67 may bond together to form a 5- to 7-membered ring except 2,2,6,6-tetraalkylpiperidine skeleton; each of R65 and R66 cannot simultaneously represent a hydrogen atom; and the total of carbon atoms of R65 and R66 is 7 or more;
wherein, in formula (TS-IV), R71 represents a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, Li, Na, or K; R72 represents an aliphatic group, an aryl group, or a heterocyclic group; R71 and R72 may bond together to form a 5- to 7-membered ring; q represents 0, 1 or 2; and the total of carbon atoms of R71 and R72 is 10 or more;
wherein, in formula (TS-V), R81, R82 and R83 each independently represent an aliphatic group, an aryl group, an aliphatic oxy group, an aryloxy group, an aliphatic amino group, or an aryl amino group; t represents 0 or 1; each combination of R81 and R82, and R81 and R83 may bond together to form a 5- to 8-membered ring; and the total of carbon atoms of R81, R82 and R83 is 10 or more;
wherein, in formula (TS-VI), R85, R86, R87 and R88 each independently represent a hydrogen atom, or a substituent except a carbonyl group, and any two of R85, R86, R87 and R88 may bond together to form a 5- to 7-membered ring except an aromatic ring only consisting of carbon atoms as a skeleton atom; the total of carbon atoms of the compound represented by formula (TS-VI) is 10 or more; and each of R85, R86, R87 and R88 cannot simultaneously represent a hydrogen atom; and
wherein, in formula (TS-VII), R91 represents a hydrophobic group having total carbon atoms of 10 or more; and Y91 represents a monovalent organic group containing an alcoholic hydroxyl group.
wherein, in formula (II), R1 represents a substituent; R2 represents a substituent; m represents an integer of 0 to 5; when m is 2 or more, R2s may be the same or different, or R2s may bond each other to form a ring; R3 represents a substituent; na represents an integer of 0 to 4; when na is 2 or more, R3s may be the same or different, or R3s may bond each other to form a ring; and X represents a hydrogen atom, or a group capable of being split-off upon a coupling reaction with an oxidized product of a developing agent.
wherein, in the dye-forming coupler represented by formula (II), R1 is a substituted or unsubstituted alkyl group.
wherein the dye-forming coupler represented by formula (II) is a dye-forming coupler represented by formula (III):
wherein, in formula (III), R1, R2 and R3 each independently represent a substituent; ma represents an integer of 0 to 4; when ma is 2 or more, R2s may be the same or different, or R2s may bond each other to form a ring; na represents an integer of 0 to 4; when na is 2 or more, R3s may be the same or different, or R3s may bond each other to form a ring; R4 represents an alkylthio group; and X represents a hydrogen atom, or a group capable of being split-off upon a coupling reaction with an oxidized product of a developing agent.
wherein, in the dye-forming coupler represented by formula (III), R1 is an alkoxypropyl group.
wherein, in the dye-forming coupler represented by formula (III), at least one R2 is a t-butyl group located in the para-position to the —S—R4 group.
wherein, in the dye-forming coupler represented by formula (III), X is a 5,5-dimethyloxazolidine-2,4-dione-3-yl group.
wherein a total amount of coated silver in entire photographic constitutional layers is 0.45 g/m2 or less.
(Hereinafter, a first embodiment of the present invention means to include the silver halide color photographic photosensitive materials described in the items (1) to (17) above, and the image-forming methods described in the items (18) to (19) above.)
wherein at least one yellow dye-forming coupler represented by the above-described formula (I), and at least one compound represented by formula (B) and having a molecular weight of 200 or more are contained in the same layer:
wherein, in formula (B), R11, R12 and R13 each independently represent a hydrogen atom, an aliphatic group or an aryl group; Rb represents a n1-valent aliphatic, aryl or heterocyclic group; X2 represents a divalent organic group; n1 represents an integer of 1 or more; n2 represents an integer of 0 or more; when n2 is 2 or more, X2's may be the same or different.
wherein the yellow dye-forming coupler represented by formula (I) is a yellow dye-forming coupler represented by formula (YC-I):
wherein, in formula (YC-I), Qa represents a group of non-metal atoms necessary to form a 5- to 7-membered ring in combination with the —N═C—N((CH2)3O—R21)—; R21 represents an alkyl group having carbon atoms of 4 or more and 8 or less; R22 represents a substituent; R24 represents a primary alkyl group; mb represents an integer of 0 or more and 4 or less; when mb is 2 or more, R22s may be the same or different, or R22s may bond together to form a ring; and Xa represents a hydrogen atom, or a group capable of being split-off upon a coupling reaction with an oxidized product of a developing agent.
wherein, in formula (B), n1 is 1.
wherein, in formula (B), n1 is 2.
wherein, in formula (B), n1 is 3; and Rb is a heterocyclic group.
wherein, in formula (B), n1 is 3; and X2 is represented by formula (C):
*—RcO— Formula (C)
The sign * indicates
wherein, in formula (C), Rc represents an alkylene group; and when n2 is 2 or more, —RcO—'s may be the same or different.
wherein, in formula (B), n1 is 4.
wherein, in formula (B), R11, R12 and R13 each are a hydrogen atom.
wherein the compound represented by formula (Ph) is a compound represented by any one of the above-described formulae (Ph-1), (Ph-2) and (Ph-3).
wherein a total amount of coated silver in entire photographic constitutional layers is 0.45 g/m2 or less.
(Hereinafter, a second embodiment of the present invention means to include the silver halide color photographic photosensitive materials described in the items (20) to (32) above, and the image-forming methods described in the items (33) to (35) above.)
Herein, the present invention means to include both of the above first and second embodiments, unless otherwise specified.
The present invention is explained below in detail.
The term “aliphatic (group)” used in the present specification means such moieties or groups, in which the aliphatic moiety may be a saturated or unsaturated, and straight chain, branched chain, or cyclic, and the aliphatic moiety embraces, for example, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, and a cycloalkynyl group; and these can be unsubstituted or substituted. Further, the term “aryl (group)” used herein means a substituted or unsubstituted, monocyclic or condensed ring. The term “heterocyclic (group)” used herein means such moieties or groups, in which the heterocycle contains at least one hetero atom (such as nitrogen, sulfur and oxygen atoms) in the ring skeleton, and the heterocycle embraces a substituted or unsubstituted, saturated or unsaturated, and monocyclic or condensed ring.
The term “substituent” used in the present specification means any groups or atoms that are able to substitute for other groups or atoms; and embraces, for example, an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aryloxy group, a heterocyclic oxy group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, an arylsulfonyl group, a heterocyclic sulfonyl group, an aliphatic sulfonyloxy group, an arylsulfonyloxy group, a heterocyclic sulfonyloxy group, a sulfamoyl group, an aliphatic sulfonamido group, an aryl sulfonamido group, a heterocyclic sulfonamido group, an amino group, an aliphatic amino group, an arylamino group, a heterocyclic amino group, an aliphatic oxycarbonylamino group, an aryloxycarbonylamino group, a heterocyclic oxycarbonylamino group, an aliphatic sulfinyl group, an aryl sulfinyl group, an aliphatic thio group, an arylthio group, a hydroxy group, a cyano group, a sulfo group, a carboxyl group, an aliphatic oxyamino group, an aryloxyamino group, a carbamoylamino group, a sulfamoylamino group, a halogen atom, a sulfamoylcarbamoyl group, a carbamoylsulfamoyl group, a dialiphatic oxyphosphinyl group, and a diaryloxyphosphinyl group.
Hereinafter, the compound for use in the present invention is explained below.
The alkenylcarbonyl-series compound for use in the first embodiment of the present invention is explained below.
The alkenylcarbonyl-series compound for use in the first embodiment of the present invention is a compound having a microhardness value of 200 or less when forming a polymerized film and containing at least three alkenylcarbonyl groups in the molecule; or an alkenylcarbonyl-series compound represented by formula (A).
The alkenylcarbonyl-series compound used in the first embodiment of the present invention is preferably an alkenylcarbonyl-series compound represented by formula (A); more preferablly an alkenylcarbonyl-series compound having a microhardness value of 200 or less at the time of forming a polymerized film and represented by formula (A).
The microhardness value is preferably in the range of from 20 to 200, more preferably in the range of from 50 to 200.
The compound containing at least three alkenylcarbonyl groups in the molecule for use in the first embodiment of the present invention is explained below.
There is no particular restriction in the chemical structure of the compound containing at least three alkenylcarbonyl groups in the molecule, as long as the compound has at least three alkenylcarbonyl groups. However, it is necesarry that the microhardness value of the compound be 200 or less. The number of alkenylcarbonyl groups is preferably in the range of from 3 to 12, more preferably in the range of from 3 to 6. Plural (at least three) alkenylcarbonyl groups may be the same or different from each other. The basic skeleton of the alkenylcarbonyl group is preferably —CO—C(R1)═C(R2)R3, in which R1, R2, and R3 each independently represent a hydrogen atom, an aliphatic group, or an aryl group.
The “microhardness value when forming a polymerized film” as used in the present invention is defined as the value of universal hardness (HU value) according to an ultramicro-Vickers hardness test of the film obtained by a film production of polymerizing a monomer. Specifically, the microhardness value can be measured by the following method.
First, a coating solution of a monomer having the composition described below is prepared, and then it is coated on a 188-μm-thick PET support, so that a polymer film becomes 40 μm in thickness after polymerization.
A mixture of the above-mentioned composition is stirred at room temperature for 3 hours, to make a coating solution.
Then, after drying at 120° C. for 2 minutes, the coating film is subjected to photoirradiation using a metal halide lamp, with a illumination intensity of 750 mJ/cm2, to thereby polymerize the alkenylcarbonyl-series compound.
Last, the aforementioned sample is subjected to thermal treatment at 120° C. for 5 minutes, to complete a polymer film on the support.
The thus-completed sample is adhered to a glass dry plate, and the sample on the plate is subjected to ultramicro-Vickers testing using a universal hardness tester (trade name: Fisher Scope Model H100V, manufactured by F. Fisher Co., Ltd.) under the measuring conditions described below, to measure the microhardness value.
(Measuring Conditions)
Shape of indenting tool: Square pyramid of 136° in terms of a point angle between the opposite faces
Indenting load: 100 mN
Indentation depth: 4 μm
Specific examples of the compound having a microhardness value of 200 or less and containing at least three alkenylcarbonyl groups in the molecule are shown below. However, the present invention is not limited to these compounds.
KAYARAD DPCA 20 [trade name, manufactured by Nippon Kayaku Co., Ltd.]
KAYARAD DPCA 30 [trade name, manufactured by Nippon Kayaku Co., Ltd.]
KAYARAD DPCA 60 [trade name, manufactured by Nippon Kayaku Co., Ltd.]
Next, the compound represented by formula (A) for use in the first embodiment of the present invention is explained in detail below.
In the formula (A), R1, R2 and R3 each independently represent a hydrogen atom, an aliphatic group (preferably a substituted or unsubstituted aliphatic group having 1 to 24 carbon atoms, more preferably an alkyl group; e.g., methyl, ethyl, isopropyl, dodecyl, hexadecyl, methoxyethyl), or an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, e.g., phenyl, 4-methylphenyl); R4 represents a hydrogen atom, or a substituent (any substitutive groups, for example, an aliphatic group, an acyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, an arylsulfonyl group, a heterocyclic sulfonyl group, a sulfamoyl group); and X1 represents a divalent organic group. The term “divalent organic group” means an organic group having two bonding hands of a single bond (at two sites); for example, organic groups having two bonding hands (i.e. divalent groups) that are formed by further release of an arbitrary hydrogen atom from a group (i.e. monovalent substituent), as exemplified in the foregoing explanation of the substituent for use in the present invention. Examples of the divalent organic group include groups described later, and other divalent groups, such as —O—, —S—, —SO—, —SO2—, and —NRx— (Rx represents a hydrogen atom, an aliphatic group, or a heterocyclic group).
n represents 0 (zero) or 1. a represents an integer of 1 to 6, and b represents an integer of 0 to 5, providing that a plus b is 6. When a is 2 or more, plural —(X1)n—COC(R1)═C(R2)R3 may be the same or different. When b is 2 or more, plural R4's may be the same or different. However, it is necessary that —(X1)n—COC(R1)═C(R2)R3 or R4 bonds to the “—” portion at the end of each O atom from 6 groups of CH2O— in the basic structure shown by [ ] in formula (A).
In the present invention, R1, R2 and R3 are each preferably a hydrogen atom, a methyl group, or an ethyl group; most preferably a hydrogen atom. In the present invention, R4 is preferably an aliphatic group, an acyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, or a carbamoyl group; more preferably an acyl group. In the present invention, X1 is preferably a divalent group described below, more preferably any one of ((1)) to ((10)) and ((14)) to ((17)) described below, and most preferably any one of ((1)) to ((4)) and ((6)) to ((8)) described below.
the sign * indicates a bonding site
In the present invention, it is preferable that R1 is a hydrogen atom or a methyl group, R2 and R3 are each a hydrogen atom, and R4 is an acryloyl group; and more preferably that R1, R2 and R3 are each a hydrogen atom, and R4 is an acryloyl group.
Further, it is more preferable that n is 1, X1 is any one of ((1)) to ((4)), ((6)) or ((7)) described above, and R1, R2 and R3 are each a hydrogen atom. Furthermore preferably, a is 2 or more.
Preferable specific examples of the compound represented by formula (A) defined in the present invention are shown below. However, the present invention is not limited to these compounds.
The compound represented by formula (A) defined in the present invention may be used singly or in combination of two or more of the compounds. Many of these compounds are commercially available. For example, KAYARAD D-310 (trade name) manufactured by Nippon Kayaku Co., Ltd., which is a commercially availble product, contains the above-exemplified compound (A-2) as a main component. Likewise, the readily available products under the trade names of KAYARAD DPCA 60, KAYARAD DPCA 30, and KAYARAD DPCA 20 are commercially available from the same company and contain the above-exemplified compounds (A-8), (A-11) and (A-12), respectively as a main component. Besides, these compounds can be synthesized according to the method of reacting dipentaerythritol (if necessary, it may have been previously subjected to esterification, amidation (amide modification), or alkylation, or alternatively to reaction with lactone) with a derivative of acrylic acid or the like.
The alkenylcarbonyl-series compound for use in the first embodiment of the present invention and a dye-forming coupler may be added to separate layers, or the same layer. However, it is preferable that the alkenylcarbonyl-series compound and the dye-forming coupler be incorporate in the same layer. As the dye-forming coupler used in the first embodiment of the present invention, a dye-forming coupler described below (preferably, a yellow dye-forming coupler) is preferred. An addition amount of the alkenylcarbonyl-series compound, particularly the compound represented by formula (A), for use in the present invention is preferably in the range of 10 to 400% by mass, more preferably in the range of 20 to 300% by mass, and most preferably in the range of 20 to 200% by mass, to the dye-forming coupler.
The compound represented by formula (A) defined in the present invention may be used in combination with various kinds of dye-forming couplers, thereby exhibiting advantageous effects of the present invention. As a result, an image high in fastness can be obtained, so that disadvantages in conventional techniques can be improved.
Next, the compound represented by formula (B) for use in the second embodiment of the present invention is explained in detail below.
In formula (B), R11, R12 and R13 each independently represent a hydrogen atom, an aliphatic group (preferably a substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, e.g., methyl, ethyl, isopropyl, dodecyl, hexadecyl, methoxyethyl) or an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, e.g., phenyl, 4-methylphenyl). Rb represents an n1-valent aliphatic group (preferably an n1-valent substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, e.g., methyl, ethyl, isopropyl, dodecyl, hexadecyl, methoxyethyl, methylene, methylidene, 1,2,3-propanetri-yl), an aryl group (preferably an n1-valent substituted or unsubstituted aryl group having 6 to 30 carbon atoms, e.g., phenyl, 4-methylphenyl, phenylene), or a heterocyclic group (preferably a substituted or unsubstituted heterocyclic group containing at least one nitrogen, oxygen or sulfur atom, and having 2 to 30 carbon atoms; e.g., those formed of a hetero ring such as pyridine, triazine, morpholine, and thiophene). X2 represents a divalent organic group (the detail thereof is described above). When n2 is 2 or more, plural X2's may be the same or different from each other.
Herein, the compound represented by formula (B) has a molecular weight of 200 or more.
In the present invention, R11, R12 and R13 are each preferably a hydrogen atom, or an aliphatic group; more preferably a hydrogen atom, or an alkyl group; and most preferably a hydrogen atom. In the present invention, Rb is preferably an n1-valent aliphatic group or heterocyclic group, more preferably an n1-valent alkyl group. In the present invention, n1 is preferably an integer of 1 to 6, more preferably an integer of 2 to 4. X2 is preferably a divalent group described below; more preferably any one of ((1)) to ((10)), ((14)) to ((17)), ((20)), and ((23)); and most preferably any one of ((1)) to ((4)), ((6)) to ((8)), ((20)), and ((23)). The molecular weight of the compound represented by formula (B) is 200 or more (preferably from 200 to 3,000). In the present invention, the molecular weight is more preferably 350 or more; further preferably from 350 to 2,000; and furthermore preferably from 350 to 1,000.
The sign * indicates a bonding site with Rb.
In the present invention, it is preferable that n1 is 1, 2 or 3. When n1 is 3, Rb is preferably a heterocyclic group.
Further, X2 is preferably a group represented by formula (C) described below, particularly preferably when n1 is 3.
*—RcO— Formula (C)
The sign * indicates
In formula (C), Rc represents an alkylene group [preferably a substituted or unsubstituted alkylene group having 1 to 24 (preferably 1 to 12, more preferably 1 to 6) carbon atoms, e.g., methylene, ethylene, propylene, 2-methyl-1,3-propylene, 1,6-hexylene]. When n2 is 2 or more, plural —RcO—'s may be the same or different from each other.
In the present invention, it is preferable that R11 is a hydrogen atom or a methyl group; R12 and R13 are each a hydrogen atom; n1 is 2, 3 or 4; n2 is 1 or 2; X2 is any one of ((1)) to ((4)), ((6)) to ((8)), ((20)), and ((23)); and Rb is an n1-valent alkyl group. It is more preferable that R11, R12 and R13 are each a hydrogen atom; n1 is 3 or 4; X2 is any one of ((1)) to ((4)), ((6)) to ((8)), ((20)), and ((23)); and Rb is an n1-valent alkyl group.
Preferable specific examples of the compound represented by formula (B) defined in the present invention are shown below. However, the present invention is not limited to these compounds.
The compound represented by formula (B) defined in the present invention may be used singly or in combination of two or more of the compounds. Many of these compounds are commercially avaliable. For example, the product that is commercially available under the trade name of NK Ester AMP-60G from Shin-Nakamura Chemical Co., Ltd. contains the aforementioned exemplified compound (B-1). Likewise, the product that is commercially available under the trade name of KAYARAD HDDA from Nippon Kayaku Co., Ltd. contains the aforementioned exemplified compound (B-24), and the product that is commercially available under the trade name of ARONIX M315 from Toagosei Co., Ltd. contains the aforementioned exemplified compound (B-38), each of these products are readily available. Besides, these compounds can be synthesized according to the method of reacting a starting substance, for example, pentaerythritol (if necessary, it may have been previously subjected to esterification, amidation (amide modification), or alkylation, or alternatively to reaction with lactone), with a derivative of acrylic acid or the like. Other compounds can be also easily synthesized by an ordinary reaction such as esterification and amidation.
The compound represented by formula (B) defined in the present invention and a dye-forming coupler may be contained in separate layers, or the same layer. However, in order to exhibit advantageous effects of the present invention, it is preferable that the compound represented by formula (B) and a dye-forming coupler be incorporated in the same layer. The dye-forming coupler that can be used is preferably a dye-forming coupler described below. An addition amount of the compound represented by formula (B) is preferably in the range of 10 to 400% by mass, more preferably in the range of 20 to 300% by mass, and most preferably in the range of 20 to 200% by mass, to the dye-forming coupler.
Next, the dye-forming coupler represented by formula (I) that can be used in the present invention is explained in detail.
In formula, R1 represents a substituent except for a hydrogen atom. As examples of the substituent, there are illustrated a halogen atom, an alkyl group in which a cycloalkyl group and a bicycloalkyl group are embraced; an alkenyl group in which a cycloalkenyl group and a bicycloalkenyl group are embraced; an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group, an aryloxy group, a silyloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an amino group in which an alkylamino group and an anilino group are embraced; an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkyl- or aryl-sulfonylamino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, a sulfo group, an alkyl- or aryl-sulfinyl group, an alkyl- or aryl-sulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an aryl- or heterocyclic-azo group, an imido group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group.
These substituents may be further substituted with another substituent. Examples of this another substituent are the same as described as the examples of the above-mentioned substituent.
R1 is preferably a substituted or unsubstituted alkyl group. The total of carbon atoms of R1 is preferably in the range of from 1 to 60, more preferably in the range of from 2 to 50, furthermore preferably in the range of from 4 to 40, and most preferably in the range of from 7 to 30. When R1 is a substituted alkyl group, can be mentioned as the substituent are atoms and groups set forth as examples of the substituent of the above-mentioned R1.
R1 is preferably an unsubstituted alkyl group having the total of carbon atoms of at least 11, or a substituted alkyl group substituted with an alkoxy group or an aryloxy group in the 2-, 3-, or 4-position, and having the total of carbon atoms of at least 4 including the number of carbon atoms of substituents; more preferably an unsubstituted alkyl group having the total of carbon atoms of at least 16, or a substituted alkyl group substituted with an alkoxy group or an aryloxy group in the 3-position, and having the total of carbon atoms of at least 6 including the number of carbon atoms of substituents; furthermore preferably a C16H33 group, a C18H37 group, a 3-lauryloxypropyl group, a 3-hexyloxy propyl group, a 3-butoxypropyl group, or a 3-(2,4-di-t-amylphenoxy)propyl group; and most preferably a 3-butoxypropyl group.
In formula (I), Q represents a group of non-metal atoms that forms a 5- to 7-membered ring in combination with the —N═C—N(R1)—. Preferably, the 5- to 7-membered ring thus formed is a substituted or unsubstituted, and monocyclic or condensed heterocycle. More preferably, the ring-forming atoms are selected from carbon, nitrogen and sulfur atoms. Still more preferably, Q represents a group represented by —C(—R11)═C(—R12)—SO2— or —C(—R11)═C(—R12)—CO— (in the present invention, these expressions of the foregoing groups do not limit the bonding orientation of the group in formula (I), to the ones shown by these expressions). Among these, Q is preferably —C(R11)═C(—R12)—SO2—. R11 and R12 are groups that bond each other to form a 5- to 7-membered ring together with the —C═C— moiety, or R11 and R12 each independently represent a hydrogen atom or a substituent. The 5- to 7-membered ring thus formed may be saturated or unsaturated, and the ring may be an alicyclic, aromatic or heterocyclic ring. Examples of the ring include benzene, furan, thiophene, cyclopentane, and cyclohexane rings. Further, when R11 and R12 represent a substituent, or when the ring has a substituent, examples of these substituents are those enumerated as the substituent of the above-described R1 (hereinafter also referred to as the substituent of R1).
These substituents and the rings formed through bonding of plural substituents may be further substituted with another substituent. Examples of this another substituent are the same as described as the examples of the above-mentioned substituent of R1.
In formula (I), R2 represents a substituent except for a hydrogen atom. Examples of the substituent are the atoms and groups set forth as the substituent of R1. R2 is preferably a halogen atom (for example, fluorine, chlorine, bromine), an alkyl group (for example, methyl, isopropyl, t-butyl), an aryl group (for example, phenyl, naphthyl), an alkoxy group (for example, methoxy, isopropyloxy), an aryloxy group (for example, phenoxy), an acyloxy group (for example, acetyloxy), an amino group (for example, dimethylamino, morpholino), an acylamino group (for example, acetamido), a sulfonamido group (for example, methane sulfonamido, benzene sulfonamido), an alkoxycarbonyl group (for example, methoxycarbonyl), an aryloxycarbonyl group (for example, phenoxycarbonyl), a carbamoyl group (for example, N-methylcarbamoyl, N,N-diethylcarbamoyl), a sulfamoyl group (for example, N-methylsulfamoyl, N,N-diethylsulfamoyl), an alkylsulfonyl group (for example, methane sulfonyl), an arylsulfonyl group (for example, benzene sulfonyl), an alkylthio group (for example, methylthio, octylthio, dodecylthio), an arylthio group (for example, phenylthio, naphthylthio, 2-methoxyphenylthio), a cyano group, a carboxyl group, and a sulfo group. Further, it is preferred that at least one R2 is located at an ortho-site to the —CONH— group. R2 located in an ortho-position to the —CONH— group is preferably a halogen atom, an alkoxy group, an aryloxy group, an alkyl group, an alkylthio group or an arylthio group; more preferably an alkylthio group or an arylthio group; and further preferably an alkylthio group (preferably a primary alkylthio group or a tertiary alkylthio group, more preferably a primary alkylthio group, furthermore preferably a primary alkylthio group that is branched at the β-position, and most preferably a 2-ethylhexylthio group). Furthermore, it is preferred that one R2 is also located in the para-position to another R2 located in an ortho-position to the above-described —CONH— group. In this case, R2 located in the para-position is preferably an alkyl group, more preferably a teritiary alkyl group, and furthermore preferably a t-butyl group. It is most preferred that R2 located in the 2-position to the —CONH— group is a 2-ethylhexylthio group, and another R2 located in the 5-position to the —CONH— group is a t-butyl group.
The total of carbon atoms of R2 is preferably in the range of from 0 to 60, more preferably in the range of from 0 to 50, and furthermore preferably in the range of from 0 to 40.
In formula (I), m represents an integer of 0 or more and 5 or less. When m is 2 or more, R2s may be the same or different, and the R2s may bond together to form a ring. m is preferably in the range of 1 to 3, more preferably in the range of 1 to 2, and most preferably 2.
In formula (I), X represents a hydrogen atom, or a group capable of being split-off upon a coupling reaction with an oxidized product of a developing agent. In the present invention, X is preferably a group capable of being split-off upon a coupling reaction with an oxidized product of a developing agent.
Examples of the group capable of being split-off upon a coupling reaction with an oxidized product of a developing agent include a group that splits off with a nitrogen, oxygen or sulfur atom (a splitting-off atom); or a halogen atom (e.g., chlorine, bromine).
Examples of the group that splits off with a nitrogen atom include a heterocyclic group (preferably a 5- to 7-membered substituted or unsubstituted saturated or unsaturated aromatic (herein the term “aromatic” is used to embrace a substance that has (4n+2) cyclic conjugated electrons) or non-aromatic, monocyclic or condensed heterocyclic group; more preferably a 5- or 6-membered heterocyclic group, in which the ring-forming atoms are selected from carbon, oxygen, nitrogen and sulfur atoms and in addition at least one of hetero atoms selected from nitrogen, oxygen and sulfur atoms is incorporated; specific examples of the heterocyclic group include succinimido, maleinimido, phthalimido, diglycolimido, pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, indole, benzopyrazole, benzimidazole, benzotriazole, imidazolidine-2,4-dione, oxazolidine-2,4-dione, thiazolidine-2-one, benzimidazoline-2-one, benzoxazoline-2-one, benzothiazoline-2-one, 2-pyrroline-5-one, 2-imidazoline-5-one, indoline-2,3-dione, 2,6-dioxypurine, parabanic acid, 1,2,4-triazolidine-3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone, 6-pyridazone, 2-pyrazone, 2-amino-1,3,4-thiazolidine-4-one), a carbonamido group (e.g., acetamido, trifluoroacetamido), a sulfonamido group (e.g., methanesulfonamido, benzenesulfonamido), an arylazo group (e.g., phenylazo, naphthylazo), and a carbamoylamino group (e.g., N-methyl carbamoylamino).
Preferred of the group that splits off with a nitrogen atom are heterocyclic groups; more preferably aromatic heterocyclic groups having 1, 2, 3 or 4 ring-forming nitrogen atoms, or heterocyclic groups represented by the following formula (L):
wherein, in formula (L), L represents a moiety that forms a 5- to 6-membered nitrogen-containing heterocycle with the —NC(═O)—.
Examples of the moiety are enumerated in the explanation of the above-mentioned heterocyclic group, and such moieties as enumerated above are more preferred. Particularly preferably, L is a moiety that forms a 5-membered nitrogen-containing heterocyclic ring.
Preferred of the group that splits off with a nitrogen atom are imidazolidine-2,4-dione, oxazolidine-2,4-dione, imidazole and pyrazole, each of which may have a substituent; and most preferred is 5,5-dimethyloxazolidine-2,4-dione-3-yl.
Examples of the group that splits off with an oxygen atom include an aryloxy group (e.g., phenoxy, 1-naphthoxy), a heterocyclic oxy group (e.g., pyridyloxy, pyrazolyloxy), an acyloxy group (e.g., acetoxy, benzoyloxy), an alkoxy group (e.g., methoxy, dodecyloxy), a carbamoyloxy group (e.g., N,N-diethylcarbamoyloxy, morpholinocarbamoyloxy), an aryloxycarbonyloxy group (e.g., phenoxycarbonyloxy), an alkoxycarbonyloxy group (e.g., methoxycarbonyloxy, ethoxycarbonyloxy), an alkylsulfonyloxy group (e.g., methanesulfonyloxy), and an aryl sulfonyloxy group (e.g., benzenesulfonyloxy, toluenesulfonyloxy).
Preferred of the group that splits off with an oxygen atom are an aryloxy group, an acyloxy group and a heterocyclic oxy group.
Examples of the group that splits off with a sulfur atom include an arylthio group (e.g., phenylthio, naphthylthio), a heterocyclic thio group (e.g., tetrazolylthio, 1,3,4-thiadiazolylthio, 1,3,4-oxazolylthio, benzimidazolyl thio), an alkylthio group (e.g., methylthio, octylthio, hexadecylthio), an alkylsulfinyl group (e.g., methane sulfinyl), an arylsulfinyl group (e.g., benzenesulfinyl), an arylsulfonyl group (e.g., benzenesulfonyl), and an alkylsulfonyl group (e.g., methansulfonyl).
Preferred of the group that splits off with a sulfur atom are an arylthio group and a heterocyclic thio group. A heterocyclic thio group is more preferred.
X may be substituted with a substituent. Examples of the substituent substituting on X include those exemplified as the substituent of the above-mentioned R1.
X is preferably a group that splits off with a nitrogen atom, a group that splits off with an oxygen atom, or a group that splits off with a sulfur atom. More preferably X is a group that splits off with a nitrogen atom, and further preferably X is one of the above-mentioned preferable examples of the group that splits off with a nitrogen atom, and they are preferable in the described order. Particularly preferably, X is a 5,5-dimethyloxazolidine-2,4-dione-3-yl group.
X may be a photographically useful group. Examples of the photographically useful group include a group to give any of a development inhibitor, a desilvering accelerator, a redox compound, a dye, a coupler, or a precursor of these compounds.
In order to render the coupler immobile in the photosensitive material, at least one of Q, R1, X, R2 and R4 described below has preferably 7 to 50 carbon atoms, more preferably 8 to 40 carbon atoms in total respectively, including carbon atoms of substituent(s) thereon.
In the present invention, it is preferable that the compound represented by formula (I) is a compound represented by formula (II).
In formula (II), R1, R2, m, and X each have the same meanings as described in formula (I). Preferable ranges thereof are also the same.
In formula (II), R3 represents a substituent. Examples of the substituent include those groups and atoms exemplified as the substituent of the above-mentioned R1. Preferably R3 is a halogen atom (i.e., fluorine, chlorine, bromine), an alkyl group (e.g., methyl, isopropyl), an aryl group (e.g., phenyl, naphthyl), an alkoxy group (e.g., methoxy, isopropyloxy), an aryloxy group (e.g., phenoxy), an acyloxy group (e.g., acetyloxy), an amino group (e.g., dimethylamino, morpholino), an acylamino group (e.g., acetamido), a sulfonamido group (e.g., methanesulfonamido, benzenesulfonamido), an alkoxycarbonyl group (e.g., methoxycarbonyl), an aryloxycarbonyl group (e.g., phenoxycarbonyl), a carbamoyl group (e.g., N-methylcarbamoyl, N,N-diethylcarbamoyl), a sulfamoyl group (e.g., N-methylsulfamoyl, N,N-diethylsulfamoyl), an alkylsulfonyl group (e.g., methane sulfonyl), an arylsulfonyl group (e.g., benzene sulfonyl), a cyano group, a carboxyl group, or a sulfo group.
na represents an integer of 0 to 4. When na is 2 or more, R3s may be the same or different, and the R3s may bond each other to form a ring.
Among the dye-forming coupler represented by formula (II), a dye-forming coupler represented by formula (III) is further prefereble.
In formula (III), R1, R2, R3, na, and X each have the same meanings as those described in formula (II). Preferable ranges thereof are also the same.
In formula (III), R4 represents an alkyl group. ma represents an integer of from 0 to 4. When ma is 2 or more, R2s may be the same or different, and the R2s may bond to each other to form a ring. ma is preferably 0, 1, or 2, more preferably 0 or 1, and most preferably 1.
The alkyl group of R4 may have a substituent. As the substituent, atoms and groups set forth as a substituent of the above-mentioned R1 can be mentioned. The substituent is preferably an alkyl group or an aryl group; more preferably an alkyl group. The alkyl group of R4 is preferably a primary alkyl group or a tertiary alkyl group; more preferably a primary alkyl group; furthermore preferably a primary alkyl group that is branched at the β-position; and most preferably a 2-ethylhexyl group.
The total of carbon atoms of R4 including its substituent is preferably in the range of from 1 to 30; more preferably in the range of from 3 to 30; furthermore preferably in the range of from 3 to 20; and most preferably in the range of from 4 to 12.
Further, in the present invention, particularly in the second embodiment of the present invention, a yellow dye-forming coupler represented by formula (YC-I) is also preferably used.
In formula (YC-I), R21 represents a substituted or unsubstituted alkyl group having 4 to 8 carbon atoms. As the substituent that R21 may have, those atoms and groups set forth as the substituent of the above-mentioned R1 in formula (I), can be mentioned. R21 is preferfably an unsubstituted alkyl group having 4 to 6 carbon atoms; and further preferably a n-butyl group.
In formula (YC-I), Qa represents a group of non-metal atoms that forms a 5- to 7-membered ring in combination with the —N═C—N((CH2)3O—R21)—. (Qa has substantially the same meaning as Q in formula (I), though literal expression of Qa is different from that of Q in formula (I).) Preferred examples of Qa include rings and groups exemplified as Q in formula (I).
In formula (YC-I), R22 has the same meaning as R2 described in formula (I). Preferable range thereof is also the same.
In formula (YC-I), R22 is more preferably a t-alkyl group, furthermore preferably a t-butyl group, and most preferably a t-butyl group in the para-position to the —S—R24.
In formula (YC-I), mb represents an integer of from 0 to 4. When mb is 2 or more, R22s may be the same or different from each other, and the R22s may bond to each other to form a ring. In the present invention, mb is preferably 0 or 1.
In formula (YC-I), R24 represents a primary alkyl group that may have a substituent. Examples of the substituent are the atoms and groups set forth above as the substituent of R21. A preferable carbon number of R24 including its substituent is in the range of from 3 to 30, more preferably in the range of from 3 to 20, and furthermore preferably in the range of from 6 to 12. As the substituent, preferred are an alkyl group and an aryl group, more preferably an alkyl group. R24 is most preferably a 2-ethylhexyl group.
Herein, the term “primary alkyl group” in this specification is used to mean that, taking, in the carbon skeleton of the alkyl group, the carbon atom bonding to S in formula (I) or (YC-I) as a central carbon, the central carbon has at least two hydrogen atoms.
In formula (YC-I), Xa has the same meaning as described in formula (I). Preferable range thereof is also the same.
In order to render the coupler immobile in the photosensitive material, at least one of Qa, R21, Xa and R22 has preferably 8 to 60 carbon atoms; more preferably 8 to 50 carbon atoms in total respectively, including carbon atoms of substituent(s) that they may have.
It is preferable, in the present invention, that the compound represented by formula (YC-I) is a compound represented by formula (YC-II). Here, the compound represented by formula (YC-II) is also referred to as a yellow dye-forming coupler. The compound represented by formula (YC-II) is explained in detail below.
In formula (YC-II), R21, R22, R24, mb, and Xa have the same meanings as described in formula (YC-I). Preferable ranges thereof are also the same.
In formula (YC-II), R23 and nb have the same meanings as R3 and na described in formula (II), respectively. Preferable ranges thereof are also the same.
Preferable specific examples of the coupler represented by any of formula (I), (II), (III), (YC-I) and (YC-II) that can be preferably used in the present invention are shown below. However, the present invention is not limited to these compounds. Herein, the present invention also embraces tautomers, in which the hydrogen atom at the coupling site (the hydrogen atom on the carbon atom to which X is substituting) is transferred on the nitrogen atom in the C═N portion bonding to the coupling site.
In the following explanation, when the exemplified compounds shown above are referred to, they are expressed as “coupler (x)”, with using the number x labeled to each of the exemplified compounds in the parenthesis.
Specific synthetic examples of the dye-forming coupler represented by the foregoing formula (I), (II), (III), (YC-I) or (YC-II) are described below.
Coupler (3) was synthesized according to the following synthesis route:
To a solution containing 438 g of 3-(2,4-di-t-amylphenoxy)propylamine, 210 ml of triethylamine and 1 liter of acetonitrile, under ice-cooling, 333 g of orthonitrobenzene sulfonyl chloride was added gradually with stirring. The temperature of the reaction system was elevated up to room temperature, and then, agitation was further continued for 1 hour. To the reaction mixture, ethyl acetate and water were added for separation. The organic layer was washed with dilute hydrochloric acid and saturated brine, and then dried with anhydrous magnesium sulfate. Thereafter, the solvent was distilled off under a reduced pressure. Crystallization from a mixed solvent of ethyl acetate and hexane gave 588 g of compound (A-1).
To a mixture of 540 ml of isopropanol and 90 ml of water, 84.0 g of a reduced iron and 8.4 g of ammonium chloride were dispersed and heated under reflux for 1 hour. To this dispersion, 119 g of compound (A-1) was gradually added, while stirring. Further, the reaction mixture was heated under reflux for 2 hours, and then suction-filtered through celite. To the filtrate, ethyl acetate and water were added for separation. The separated organic solvent layer was washed with saturated brine and dried with anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, to obtain 111 g of compound (A-2) as an oily product.
A solution of 111 g of compound (A-2), 68.4 g of a hydrochloride of imino ether (A-0) and 150 ml of ethyl alcohol was stirred for 1 hour while heating under reflux. Further, 4.9 g of a hydrochloride of imino ether was added and stirred with heating under reflux for 30 minutes. After cooling, the reaction mixture was suction-filtered. To the filtrate, 100 ml of p-xylene was added and heated under reflux for 4 hours, while eliminating ethanol by distillation. The reaction solution was purified by silica gel column chromatography using a mixed solvent of ethyl acetate and hexane as an eluent. Crystallization from methanol gave 93.1 g of compound (A-3).
A solution of 40.7 g of compound (A-3), 18.5 g of 2-methoxyaniline and 10 ml of p-xylene was stirred while heating under reflux for 6 hours. To the reaction mixture, ethyl acetate and water were added for separation. The organic solvent layer was washed with dilute hydrochloric acid and saturated brine, and then dried with anhydrous magnesium sulfate. Thereafter, the solvent was distilled off under a reduced pressure. The residue was purified by silica gel column chromatography using a mixed solvent of ethyl acetate and hexane as an eluent, to obtain 37.7 g of compound (A-4) as an oily product.
To a solution containing 24.8 g of compound (A-4) and 400 ml of methylene chloride, under ice-cooling, 35 ml of a methylene chloride solution containing 2.1 ml of bromine was added dropwise. After stirring for 30 minutes while cooling on ice, methylene chloride and water were added for separation. The separated organic solvent layer was washed with saturated brine and dried with anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, to obtain a crude product of compound (A-5).
To a solution of 15.5 g of 5,5-dimethyloxazolidine-2,4-dione and 16.8 ml of triethylamine dissolved in 200 ml of N,N-dimethylacetamide, a solution of the whole quantity of the previously synthesized crude product of compound (A-5) dissolved in 40 ml of acetonitrile was added dropwise, over 10 minutes, at room temperature. After the temperature of the reaction system was elevated up to 40° C., and then, agitation was continued for 30 minutes. To the reaction solution, ethyl acetate and water were added to conduct separation. The separated organic layer was washed with a 0.1 normal aqueous solution of potassium hydroxide, dilute hydrochloric acid and saturated brine, and then dried with anhydrous magnesium sulfate. The solvent was eliminated by vacuum distillation. The residue was purified by silica gel column chromatography using a mixed solvent of acetone and hexane as an eluent. Crystallization from a mixed solvent of ethyl acetate and hexane gave 23.4 g of coupler (3).
Coupler (6) was synthesized according to the following synthesis rout.
To a solution containing 181.2 g of 3-butoxypropylamine, 198.2 ml of triethylamine and 840 ml of toluene, 300.0 g of orthonitrobenzene sulfonyl chloride was added gradually with stirring while ice-cooling. After the temperature of the reaction system was elevated up to 40° C., agitation was further continued for 1 hour. To the reaction solution, 50 ml of hydrochloric acid and 750 ml of water were added for separation. The separated organic layer was washed with 750 ml of an aqueous solution of sodium bicarbonate, to obtain a reaction solution of compound (B-1).
To a mixture of 8.5 g of 10% Pd/C and 50 ml of water, the previously prepared reaction solution of compound (B-1) and 100 ml of toluene were added, and then 165 g of 80% hydrazine hydrate and 50 ml of water were added dropwise over 1 hour at 40° C. Thereafter, the reaction solution was further stirred for 1 hour at 45° C., and then filtered through celite. The reaction mixture was washed with 350 ml of toluene, 500 ml of isopropanol and 1.5 liter of water. After separation, the organic layer was washed twice with 500 ml of water, to obtain a reaction solution of compound (B-2). Thereafter, 800 ml of the solvent was eliminated by vacuum concentration. To the resulting residue, 400 ml of toluene, 305.7 g of ethyl 3,3-diethoxyacrylate and 2.6 g of p-toluene sulfonic acid monohydrate were added, and stirred at 85° C. for 30 minutes. Further, 13.8 g of 90% sodium ethoxide was added, and then the mixture was stirred with heating at 120° C. for 4 hours. After cooling, 25 ml of hydrochloric acid and 500 ml of water were added for separation. Further, 50 g of p-toluene sulfonic acid monohydrate and 500 ml of water were added for washing. Thereafter, the solvent was eliminated by concentration under reduced pressure. To the resulting residue, 600 ml of methanol and 30 ml of water were added for crystallization. Further, 100 ml of methanol and 110 ml of water were added dropwise, and the mixture was cooled to 0° C. The resulting precipitate was suction-filtered, and then washed with a mixed solvent of methanol/water, to obtain 440.1 g of Compound (B-3).
To a mixture of 343 g of 2-ethylhexanethiol, 800 ml of N,N-dimethyl acetamide and 364 g of potassium carbonate, 470 g of 4-t-butyl-2-nitrochlorobenzene was added under a nitrogen atmosphere, and stirred with heating, at 90° C., for 2 hours. Thereafter, the reaction mixture was poured into 1000 ml of ice water, and then extracted with 1000 ml of ethyl acetate. The separated organic solvent layer was washed twice with saturated brine, and dried with anhydrous magnesium sulfate. After separating magnesium sulfate by filtration, the solvent was distilled off under a reduced pressure, to obtain 806 g of compound (B-4) as an oily product.
To a mixture of 2200 ml of isopropanol and 370 ml of water, 740 g of a reduced iron and 74.0 g of ammonium chloride were dispersed, and stirred with heating under reflux, for 1 hour. To this dispersion, 806 g of compound (B-4) was gradually added. Further, the reaction mixture was stirred with heating under reflux for 2 hours, and then suction-filtered through celite. To the filtrate, ethyl acetate and water were added for separation. The separated organic solvent layer was washed with saturated brine, and dried with anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, to obtain 671 g of compound (B-5) as an oily product.
A mixture of 110 g of compound (B-3) and 84.5 g of compound (B-5) was stirred with heating, at the temperature of 145 to 150° C. for 6 hours, under a reduced pressure, to obtain a crude product of compound (B-6). To the reaction crude product, 750 ml of toluene was added, and then 41.2 g of 1,3-dibromo-5,5-dimethylhydantoin was added, with stirring, over 15 minutes, while ice-cooling. After stirring at room temperature for 1 hour, water was added for separation. The separated organic layer was washed with water, to obtain a reaction solution of compound (B-7).
To a mixture of 39.0 g of 5,5-dimethyloxazolidine-2,4-dione, 41.8 g of potassium carbonate and 150 ml of N,N-dimethylacetamide, the whole quantity of the previously synthesized reaction solution of compound (B-7) was added dropwise, over 30 minutes, at room temperature with stirring. Thereafter, the temperature of the reaction system was elevated up to 50° C., and agitation was continued for 2 hours. After separation, the separated organic layer was washed with a 0.1 normal aqueous solution of potassium hydroxide; dilute hydrochloric acid, and water. The solvent was eliminated by vacuum distillation. Crystallization from a methanol solvent gave 171.6 g of coupler (6).
Other dye-forming couplers can be also synthesized according to the above-mentioned method, or according to the method described in U.S. Pat. No. 5,455,149.
In the silver halide photographic photosensitive material of the present invention, the amount to be added of the coupler represented by formula (I), (II), (III), (YC-I) or (YC-II) in the photosensitive material is preferably in the range of from 0.01 g to 1.0 g, more preferably in the range of from 0.1 g to 2 g, per m2 of the photosensitive material. The amount of the coupler to be added in a photosensitive emulsion layer is preferably in the range of from 1×10−3 mol to 1 mol, and more preferably in the range of from 2×10−3 mol to 3×10−1 mol, per mol of silver halide in the same photosensitive emulsion layer.
Next, the compound represented by formula (Ph) that is preferably used in combination with the alkenylcarbonyl-sereis compound for use in the present invention, is explained in detail below.
In formula (Ph), Rb1 represents an aliphatic group, an aryl group, a carbamoyl group, an acylamino group (this group is also referred to as an amino group), a carbonyl group (this group is also referred to as an acyl group), or a sulfonyl group. Rb2, Rb3, Rb4 and Rb5 each represent a hydrogen atom, a halogen atom, a hydroxyl group, an aliphatic group, an aryl group, a heterocyclic group, an alkyloxy group, an aryloxy group, a heterocyclic oxy group, an oxycarbonyl group, an acyl group, an acyloxy group, an oxycarbonyloxy group, a carbamoyl group, an acylamino group, a sulfonyl group, a sulfinyl group, a sulfamoyl group, an alkylthio group, or an arylthio group.
The compound represented by formula (Ph) is explained in more detail below.
Rb1 represents an aliphatic group, an aryl group, a carbamoyl group, an acylamino group, a carbonyl group, or a sulfonyl group. Further, each of these groups may be further substituted with other substituent(s). Examples of the aliphatic group include a methyl group, an ethyl group, an i-propyl group, a t-butyl group, a t-octyl group, and a cyclohexyl group. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the carbamoyl group include a N,N-diethylcarbamoyl group, a N,N-dibutylcarbamoyl group, a hexylcarbamoyl group, and a N,N-diphenylcarbamoyl group. Examples of the acylamino group include a butylamido group, a hexylamido group, an octylamido group, and a benzamido group. Examples of the carbonyl group include a hexyloxycarbonyl group, an octyloxycarbonyl group, and a dodecyloxycarbonyl group. Examples of the sulfonyl group include a butylsulfonyl group, an octylsulfonyl group, and a dodecylsulfonyl group.
Rb2, Rb3, Rb4 and Rb5 each independently represent a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, iodine), a hydroxyl group, an alkyl group (for example, methyl, ethyl, butyl, allyl), an aryl group (for example, phenyl, naphthyl), a heterocyclic group (for example, piperidyl, pyrrolyl, indolyl), an aliphatic oxy group (for example, methoxy, octyloxy, cyclohexyloxy), an aryloxy group (for example, phenoxy, naphthoxy), a heterocyclic oxy group (for example, piperidyloxy, pyrrolyloxy, indolyloxy), an oxycarbonyl group (for example, methoxycarbonyl, hexadecyloxycarbonyl, phenoxycarbonyl, p-chlorophenoxycarbonyl), an acyl group (for example, acetyl, pivaloyl, methacryloyl), an acyloxy group (for example, acetoxy, benzoyloxy), an oxycarbonyloxy group (for example, methoxycarbonyloxy, octyloxycarbonyloxy, phenoxycarbonyloxy), a carbamoyl group (for example, N,N-dimethylcarbamoyl, N,N-diethylcarbamoyl, diphenylcarbamoyl, hexylcarbamoyl), an acylamino group (for example, heptylamido, undecylamido, pentadecylamido, 1-hexylnonylamido), a sulfonyl group (including an aliphatic sulfonyl group and an arylsulfonyl group, for example, methane sulfonyl, butane sulfonyl, octane sulfonyl, benzene sulfonyl, p-toluene sulfonyl), a sulfinyl group (for example, methane sulfinyl, octane sulfinyl, benzene sulfinyl, p-toluene sulfinyl), a sulfamoyl group (for example, dimethylsulfamoyl), an alkylthio group (for example, methylthio, octylthio, dodecylthio), or an arylthio group (for example, phenylthio). Further, Rb1 to Rb5 each may be a linking group that links at least two phenol skeletons (mother nuclei).
As Rb1, an alkyl group, a carbonyl group and an acylamino group are preferable. An alkyl group is more preferable of all. A methyl group is particularly preferred. As Rb2, an amido group, an aliphatic oxy group and an alkylene-linking group are preferable. In the case of the alkylene-linking group, it is preferred that two phenol skeletons are linked via the linking group.
Preferable structures of the compounds represented by formula (Ph) are shown below.
The compounds represented by formula (Ph-1) are explained in detail below.
Rb6 represents an aliphatic group, an aryl group, an amino group, or an acyl group. Rb1 has the same meaning as defined in formula (Ph) and the same preferable range as described above with respective to the Rb1. Rb7, Rb8 and Rb9 each independently have the same meanings as Rb2 to Rb5 defined in formula (Ph) and the same preferable ranges as described above with respective to the Rb2 to Rb5. Rb6 is preferably an aliphatic group, more preferably an unsubstituted aliphatic group, and especially preferably a branched aliphatic group. The total of carbon atoms in Rb6 is preferably in the range of from 8 to 25, especially preferably in the range of from 12 to 20. Rb1 is preferably an aliphatic group, an aryl group, a carbamoyl group, or an oxycarbonyl group, more preferably an aliphatic group, and especially preferably a methyl group. Rb7, Rb8 and Rb9 each are preferably a hydrogen atom or an aliphatic group, especially preferably a hydrogen atom.
The compounds represented by formula (Ph-2) are explained in detail below.
Rb1 has the same meaning as defined in formula (Ph) and the same preferable range as described above with respective to the Rb1 in formula (Ph). Rb10 represents a hydrogen atom, an aliphatic group (for example, butyl, benzyl), an acyl group (for example, acryloyl, 1-methylacryloyl, 2-methylacryloyl), an oxycarbonyl group (for example, methoxycarbonyl, butoxycarbonyl, phenoxycarbonyl), a silyl group, or a phosphoryl group. Xb represents an alkylene group (for example, methylene, ethylene, propylene, isopropylmethylene, pentylmethylene), a phenylene group (for example, phenylene), —O—, or —S—. Rb11 to Rb16 each independently have the same meaning as Rb2 to Rb5 defined in formula (Ph) and the same preferable ranges as described above with respective to each of them.
From the viewpoint of improvement in fastness to light, Rb10 is preferably a hydrogen atom, an acyl group or an alkyl group, more preferably a hydrogen atom or an acyl group. It is especially preferred from the viewpoint of improvement in fastness to light that Rb10 is a hydrogen atom. However, if Rb10 is a hydrogen atom, the compound represented by formula (Ph-2) itself reacts with an oxidation product of a paraphenylene diamine to develop a cyan color, thereby causing a color mixing, which is not preferable. Therefore, from this aspect, it is not most preferred that Rb10 is a hydrogen atom. Xb is preferably an alkylene-linking group, more preferably —CHRb21 (Rb21 represents a hydrogen atom, an aliphatic group, or an aryl group). Rb21 is especially preferably an aliphatic group. Rb11 and Rb14 each are preferably an aliphatic group, more preferably an aliphatic group having 6 or less carbon atoms, and especially preferably a methyl group.
Rb1 is preferably an aliphatic group, an aryl group, a carbamoyl group, or an oxycarbonyl group, more preferably an aliphatic group, and especially preferably a methyl group. Rb12, Rb13, Rb15 and Rb16 each are preferably a hydrogen atom or an aliphatic group, and especially preferably a hydrogen atom.
The compounds represented by formula (Ph-3) are explained in detail below.
Rb17 and Rb18 each independently represent an aliphatic group, or an aryl group. Rb1 has the same meaning as defined in formula (Ph) and the same preferable range as described above with respective to the Rb1. Rb19 and Rb20 each have the same meanings as Rb2 to Rb5 defined in formula (Ph) and the same preferable ranges as described above with respective to each of them.
Rb17 and Rb18 each are preferably an aliphatic group. Rb19 and Rb20 each are preferably a hydrogen atom or an aliphatic group, and especially preferably a hydrogen atom. Rb1 is preferably a carbamoyl group, an oxycarbonyl group or an aliphatic group, especially preferably a carbamoyl group or an oxycarbonyl group.
Preferable specific examples of the compounds represented by formula (Ph) that can be used in the present invention are shown below, but the present invention is not limited to these compounds.
The compound represented by formula (Ph) for use in the present invention may be used solely or in combination with two or more kinds of these compounds. It is preferred that at least one compound represented by formula (Ph) for use in the present invention is added to the layer incorporating therein the dye-forming coupler represented by formula (I) for use in the present invention.
The compound represented by formula (Ph) for use in the present invention, if used in combination with the alkenylcarbonyl-sereis compound described above, enables to inhibit discoloration, thereby to improve image fastness after processing. The addition amount of the compound represented by formula (Ph) for use in the present invention is preferably in the range of from 10 mole % to 200 mole %, more preferably in the range of from 20 mole % to 150 mole %, especially preferably in the range of from 40 mole % to 120 mole %, to the dye-forming coupler, respectively.
Next, a concrete synthesis example of the compounds represented by formula (Ph) is shown below.
To 28.7 g (0.233 mole) of 2-amino-p-cresol and 38.6 g (0.460 mole) of sodium bicarbonate, 126 ml of acetonitrile was added and 63.2 g (0.23 mole) of isopalmitinic acid chloride was added dropwise over 30 minutes with heating and stirring. After additional heating and stirring for 1 hour, 100 ml of methanol was added thereto. The resulting insoluble residue was separated by filter and washed with 100 ml of methanol. To the thus-obtained solution, 50 ml of water was added dropwise over 25 minutes with stirring at room temperature for crystallization. Further stirring was continued for 2 hours with water-cooling. The precipitated crystals were separated by filter and washed with 250 ml of methanol/water=5/1, and further washed with 250 ml of water. The thus-obtained crystals were dried at 45° C. for 1 day by means of a blast drier. 80.5 g of white crystals were obtained. Yield: 96.8%, Melting point: 82 to 84° C.
Other compounds can also be synthesized in the similar manner as in the method set forth above.
The compounds represented by any one of formulae (E-1) to (E-3) that can be preferably used in the photosensitive material of the present invention are explained in detail below.
In formulae (E-1), (E-2), and (E-3), R41 represents an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an aliphatic sulfonyl group, an arylsulfonyl group, a phosphoryl group, or —Si(R47)(R48)(R49) in which R47, R48 and R49 each independently represent an aliphatic group, an aryl group, an aliphatic oxy group, or an aryloxy group. R42, R43, R45 and R46 each independently represent a hydrogen atom, or a substituent. Ra1, Ra2, Ra3, and Ra4 each independently represent a hydrogen atom, or an aliphatic group (for example, methyl, ethyl).
With respect to the compounds represented by any one of formulae (E-1) to (E-3), the groups preferable in the present invention, are explained below.
In formulae (E-1) to (E-3), it is preferred that R41 represents an aliphatic group, an acyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, or a phosphoryl group, and R42, R43, R45 and R46 each independently represent a hydrogen atom, an aliphatic group, an aliphatic oxy group, or an acylamino group. It is more preferred that R41 represents an aliphatic group, and R42, R43, R45 and R46 each independently represent a hydrogen atom, or an aliphatic group.
Preferable specific examples of the compounds represented by any one of formulae (E-1) to (E-3) for use in the present invention are shown below, but the present invention is not limited to these compounds.
The compound represented by any one of formulae (E-1) to (E-3) for use in the present invention may be used solely or in combination with two or more kinds of these compounds. Further, the layer to which the compound represented by any one of formulae (E-1) to (E-3) for use in the present invention is added may be different from, or identical to a layer incorporating therein the dye-forming coupler represented by formula (I). It is preferred that the compound represented by any one of formulae (E-1) to (E-3) and the dye-forming coupler represented by formula (I) are added to the identical layer. Further, it is preferred that the compound represented by any one of formulae (E-1) to (E-3) is used in combination with the compound represented by formula (Ph).
The compound represented by any one of formulae (E-1) to (E-3) that can be preferably used in the present invention, if used in combination with the alkenylcarbonyl-sereis compound described above and the compound represented by formula (Ph) (preferably, these all compounds are added to the identical layer), enables to further improve image fastness after processing. The addition amount of the compound represented by any one of formulae (E-1) to (E-3) that can be preferably used in the present invention, is preferably in the range of from 10 mole % to 100 mole %, more preferably in the range of from 20 mole % to 80 mole %, especially preferably in the range of from 30 mole % to 60 mole %, to the dye-forming coupler, respectively.
Next, a compound represented by any one of formulae (TS-I) to (TS-VII), a metal complex, a ultraviolet absorbing agent, and a water-insoluble homopolymer or copolymer, each of which can be preferably used in the present invention in combination with the above-described alkenylcarbonyl-sereis compound and the compound represented by formula (Ph), or in combination with the compound represented by any one of formulae (E-1) to (E-3) as well as the above-described alkenylcarbonyl-sereis compound and the compound represented by formula (Ph), are explained in detail below.
First, the compounds represented by any one of formulae (TS-I) to (TS-VII) are explained in detail below.
The compound represented by formula (TS-I) is described in more detail.
In formula (TS-I), R51 represents a hydrogen atom, an aliphatic group (e.g., methyl, i-propyl, s-butyl, dodecyl, methoxyethyl, allyl, benzyl), an aryl group (e.g., phenyl, p-methoxyphenyl), a heterocyclic group (e.g., 2-tetrahydrofuryl, pyranyl), an acyl group (e.g., acetyl, pivaroyl, benzoyl, acryloyl), an aliphatic oxycarbonyl group (e.g., methoxycarbonyl, hexadecyloxycarbonyl), an aryloxycarbonyl group (e.g., phenoxycarbonyl, p-methoxy phenoxycarbonyl), an aliphatic sulfonyl group (e.g., methane sulfonyl, butane sulfonyl), an aryl sulfonyl group (e.g., benzene sulfonyl, p-toluene sulfonyl), a phosphoryl group (e.g., diethyl phosphoryl, diphenyl phosphoryl, diphenoxy phosphoryl), or —Si(R58)(R59)(R60). R58, R59, and R60, which may be the same or different from each other, each independently represent an aliphatic group (e.g., methyl, ethyl, t-butyl, benzyl, allyl), an aryl group (e.g., phenyl), an aliphatic oxy group (e.g., methoxy, butoxy), or an aryloxy group (e.g., phenoxy).
X51 represents —O— or —N(R57)—, in which R57 has the same meaning as R51. X55 represents —N═ or —C(R52)═, X56 represents —N═ or —C(R54)═, X57 represents —N═ or —C(R56)═. R52, R53, R54, R55, and R56 each independently represent a hydrogen atom, or a substituent. As the preferable substituent exemplified are an aliphatic group (e.g., methyl, t-butyl, t-hexyl, benzyl), an aryl group (e.g., phenyl), an aliphatic oxycarbonyl group (e.g., methoxycarbonyl, dodecyloxycarbonyl), an aryloxycarbonyl group (e.g., phenoxycarbonyl), an aliphatic sulfonyl group (e.g., methane sulfonyl, butane sulfonyl), an aryl sulfonyl group (e.g., benzene sulfonyl, p-hydroxybenzene sulfonyl), or —X51—R51.
However, all of R51 to R57 cannot simultaneously represent hydrogen atoms, respectively, and the total number of carbon atoms in each of these groups is generally 10 or more (preferably 10 to 50), and more preferably 16 or more (preferably 16 to 40). Further, the compound represented by formula (TS-I) is neither identical to the compound represented by formula (Ph) nor the compound represented by any one of formulae (E-1) to (E-3). In other words, both the compound represented by formula (Ph) and the compound represented by any one of formulae (E-1) to (E-3) are excluded from the compound represented by formula (TS-I).
The compound represented by formula (TS-I) for use in the present invention includes those compounds represented by any of, for example, formula (I) of JP-B-63-50691 (“JP-B” means examined Japanese patent publication), formula (IIIa), (IIIb), or (IIIc) of JP-B-2-37575, formula of JP-B-2-50457, formula of JP-B-5-67220, formula (IX) of JP-B-5-70809, formula of JP-B-6-19534, formula (I) of JP-A-62-227889, formula (I) or (II) of JP-A-62-244046, formula (I) or (II) of JP-A-2-66541, formula (II) or (III) of JP-A-2-139544, formula (I) of JP-A-2-194062, formula (B), (C), or (D) of JP-A-2-212836, formula (III) of JP-A-3-200758, formula (II) or (III) of JP-A-3-48845, formula (B), (C), or (D) of JP-A-3-266836, formula (I) of JP-A-3-969440, formula (I) of JP-A-4-330440, formula (I) of JP-A-5-297541, formula of JP-A-6-130602, formula (1), (2), or (3) of International Patent Application Publication WO 91/11749, formula (I) of German Patent Publication DE4,008,785A1, formula (II) of U.S. Pat. No. 4,931,382, formula (a) of European Patent No. 203,746B1, formula (I) of European Patent No. 264,730B1, and formula (III) of JP-A-62-89962. These compounds can be synthesized according to the methods described in these publications, or general methods described in Shin Jikken Kagaku Koza, Vol. 14 (Maruzen Co., Ltd.) (1977, 1978).
In the present invention, the compound represented by formula (TS-I) is preferably any of those compounds represented by any one of formulae (TS-ID), (TS-IE), (TS-IF), (TS-IG), and (TS-IH) shown below.
In formulae (TS-ID) to (TS-IH), R51, R52, R53, R54, R55, R56, R57, and X51 have the same meanings as those defined in formula (TS-I). X52 and X53 each independently represent a divalent linking group. Examples of the divalent linking group include an alkylene group, an oxy group, and a sulfonyl group. In the formulae, the same symbols in the same molecule may be the same or different in meanings.
The compound represented by any one of formulae (TS-ID) to (TS-IG) is neither identical to the compound represented by formula (Ph) nor the compound represented by any one of formulae (E-1) to (E-3).
As to the compounds represented by any one of formulae (TS-ID) to (TS-IH), the groups thereon preferable in the present invention are described below.
In formula (TS-ID), preferable is the case where R51 is a hydrogen atom, an aliphatic group, an acyl group, an aliphatic oxycarbonyl group, an aryl oxycarbonyl group, or a phosphoryl group, and R52, R53, R55, and R56 each independently are a hydrogen atom, an aliphatic group, an aliphatic oxy group, or an acyl amino group. More preferable is the case where R51 is an aliphatic group, and R52, R53, R55, and R56 each independently are a hydrogen atom, or an aliphatic group. In formulae (TS-IE), (TS-IF), and (TS-IG), preferable is the case where R51 is a hydrogen atom, an aliphatic group, an acyl group, an aliphatic oxycarbonyl group, an aryl oxycarbonyl group, or a phosphoryl group, and R52, R53, R55, and R56 each independently are a hydrogen atom, an aliphatic group, an aliphatic oxy group, or an acyl amino group, and R54 is an aliphatic group, a carbamoyl group, or an acyl amino group, and X52 and X53 each independently are an alkylene group or an oxy group. More preferable is the case where R51 is a hydrogen atom, an aliphatic group, an acyl group, or a phosphoryl group, and R52, R53, R55, and R56 each independently are a hydrogen atom, an aliphatic group, an aliphatic oxy group, or an acylamino group, and R54 is an aliphatic group, or a carbamoyl group, and X52 and X53 each are —CHR158— (R158 is an alkyl group). In formula (TS-IH), preferable is the case where R51 is an aliphatic group, an aryl group, or a heterocyclic group, and R53 and R55 each independently are an aliphatic oxy group, an aryloxy group, or a heterocyclic oxy group. More preferable is the case where R51 is an aryl group, or a heterocyclic group, and R53 and R55 each independently are an aryloxy group, or a heterocyclic oxy group.
In the present invention, the compounds represented by formula (TS-I) are preferably the compounds represented by formula (TS-IE) or (TS-IG).
The compound represented by formula (TS-II) is described in detail below.
In formula (TS-II), R61, R62, R63, and R64 each independently are a hydrogen atom, or an aliphatic group (preferably an alkyl group, e.g., methyl, ethyl), X61 represents a hydrogen atom, an aliphatic group (e.g., methyl, ethyl, allyl), an aliphatic oxy group (e.g., methoxy, octyloxy, cyclohexyloxy), an aliphatic oxycarbonyl group (e.g., methoxycarbonyl, hexadecyl oxycarbonyl), an aryloxycarbonyl group (e.g., phenoxycarbonyl, p-chlorophenoxycarbonyl), an acyl group (e.g., acetyl, pivaloyl, methacryloyl), an acyloxy group (e.g., acetoxy, benzoyloxy), an aliphatic oxycarbonyloxy group (e.g., methoxycarbonyloxy, octyloxycarbonyloxy), an aryloxycarbonyloxy group (e.g., phenoxycarbonyloxy), an aliphatic sulfonyl group (e.g., methane sulfonyl, butane sulfonyl), an aryl sulfonyl group (e.g., benzene sulfonyl, p-toluene sulfonyl), an aliphatic sulfinyl group (e.g., methane sulfinyl, octane sulfinyl), an arylsulfinyl group (e.g., benzene sulfinyl, p-toluene sulfinyl), a sulfamoyl group (e.g., dimethylsulfamoyl), a carbamoyl group (e.g., dimethylcarbamoyl, diethylcarbamoyl), a hydroxyl group, or an oxy radical group. X62 represents a group of non-metal atoms necessary to form a 5- to 7-membered ring (e.g., piperidine ring, piperazine ring). The total number of carbon atoms of the compound represented by formula (TS-II) is 8 or more (preferably 8 to 60).
The compound represented by formula (TS-II) for use in the present invention include those compounds represented by, for example, formula (I) of JP-B-2-32298, formula (I) of JP-B-3-39296, formula of JP-B-3-40373, formula (I) of JP-A-2-49762, formula (II) of JP-A-2-208653, formula (III) of JP-A-2-217845, formula (B) of U.S. Pat. No. 4,906,555, formula of European Patent Publication EP309,400A2, formula of European Patent Publication EP309,401A1, and formula of European Patent Publication EP309,402A1. These compounds can be synthesized according to the methods described in these publications or general methods described in Shin Jikken Kagaku Koza, Vol. 14 (Maruzen Co., Ltd.) (1977, 1978).
As to the compound represented by formula (TS-II), the groups thereon preferable in the present invention are described below. In the present invention, R61, R62, R63 and R64 each are preferably an aliphatic group, and more preferably a methyl group. In the present invention, X61 is preferably a hydrogen atom, an aliphatic group, an aliphatic oxy group, an acyl group, an acyloxy group, or an oxyradical group; more preferably a hydrogen atom, an aliphatic group, an aliphatic oxy group, an acyl group, or an oxyradical group; and most preferably an aliphatic group, or an aliphatic oxy group. In the present invention, X62 forms preferably a 6-membered ring, more preferably a piperidine ring. In the present invention, the compound represented by formula (TS-II) is preferably in an embodiment where R61, R62, R63, and R64 each are a methyl group, X61 is a hydrogen atom, an aliphatic group, an aliphatic oxy group, an acyl group, or an oxy radical group, and X62 forms a 6-membered ring; and more preferably in an embodiment where R61, R62, R63, and R64 each are a methyl group, X61 is an aliphatic group, or an aliphatic oxy group, and X62 forms a piperidine ring.
The compound represented by formula (TS-III) is described in more detail below.
In formula (TS-III), R65 and R66 each independently represent a hydrogen atom, an aliphatic group (e.g., methyl, ethyl, t-butyl, octyl, methoxyethyl), an aryl group (e.g., phenyl, 4-methoxyphenyl), an acyl group (e.g., acetyl, pivaloyl, methacryloyl), an aliphatic oxycarbonyl group (e.g., methoxycarbonyl, hexadecyl oxycarbonyl), an aryloxycarbonyl group (e.g., phenoxycarbonyl), a carbamoyl group (e.g., dimethylcarbamoyl, phenylcarbamoyl), an aliphatic sulfonyl group (e.g., methane sulfonyl, butane sulfonyl), or an aryl sulfonyl group (e.g., benzene sulfonyl). R67 represents a hydrogen atom, an aliphatic group (e.g., methyl, ethyl, t-butyl, octyl, methoxyethyl), an aliphatic oxy group (e.g., methoxy, octyloxy), an aryloxy group (e.g., phenoxy, p-methoxyphenoxy), an aliphatic thio group (e.g., methylthio, octylthio), an arylthio group (e.g., phenylthio, p-methoxyphenylthio), an acyloxy group (e.g., acetoxy, pivaloyloxy), an aliphatic oxycarbonyloxy group (e.g., methoxycarbonyloxy, octyloxycarbonyloxy), an aryloxycarbonyloxy group (e.g., phenoxycarbonyloxy), a substituted amino group (the substituent may be any one that is able to substitute for the hydrogen atom(s) on the amino group, e.g., amino groups substituted with a substituent such as an aliphatic group, an aryl group, an acyl group, an aliphatic sulfonyl group or an arylsulfonyl group), a heterocyclic group (e.g., a piperidine ring, a thiomorpholine ring), or a hydroxyl group. If possible, each combination of R65 and R66, R66 and R67, and R65 and R67 combine together to form a 5- to 7-membered ring (e.g. a morpholine ring and a pyrazolidine ring), but they never form a 2,2,6,6-tetraalkylpiperidine ring. In addition, both R65 and R66 are not hydrogen atoms at the same time. Further, the total number of carbon atoms of the compound represented by formula (TS-III) is generally 7 or more (preferably 7 to 50).
The compound represented by formula (TS-III) for use in the present invention include compounds represented by, for example, formula (I) of JP-B-6-97332, formula (I) of JP-B-6-97334, formula (I) of JP-A-2-148037, formula (I) of JP-A-2-150841, formula (I) of JP-A-2-181145, formula (I) of JP-A-3-266836, formula (IV) of JP-A-4-350854, and formula (I) of JP-A-5-61166. These compounds can be synthesized according to the methods described in these publications or general methods described in Shin Jikken Kagaku Koza, Vol. 14 (Maruzen Co., Ltd.) (1977, 1978).
In the present invention, the compounds represented by formula (TS-III) are preferably the compounds represented by any one of formulae (TS-IIIA), (TS-IIIB), (TS-IIIC), and (TS-IIID) shown below.
In formulae (TS-IIIA) to (TS-IIID), R65 and R66 each have the same meanings as those defined in formula (TS-III). Rc1, Rc2, Rc3, and Rc5 each independently have the same meaning as R65. Rc4 represents a hydrogen atom, an aliphatic group (e.g., octyl, dodecyl, 3-phenoxypropyl), or an aryl group (e.g., phenyl, 4-dodecyloxyphenyl). X63 represents a group of non-metal atoms necessary to form, together with the —N—N—, a 5- to 7-membered ring, such as a pyrazolidine ring and a pyrazoline ring.
As to the compounds represented by any one of formulae (TS-IIIA) to (TS-IIID), the groups thereon preferable in the present invention are described below. In formula (TS-IIIA), preferable is the case where R65 and Rc1 each independently represent a hydrogen atom, an aliphatic group, or an aryl group, and R66 and Rc2 each independently represent an aliphatic group, an aryl group, or an acyl group; and more preferable is the case where R65 and Rc1 each independently represent an aliphatic group, and R66 and Rc2 each independently represent an aliphatic group, an aryl group, or an acyl group. In formula (TS-IIIB), preferable is the case where R65 represents a hydrogen atom, an aliphatic group, an aryl group, an acyl group, or an aliphatic oxycarbonyl group, Rc3 represents an aliphatic group, an aryl group, or an acyl group, and X63 represents a group of non-metal atoms necessary to form a 5-membered ring; and more preferable is the case where R65 represents a hydrogen atom, or an aliphatic group, and Rc3 represents an aliphatic group, or an aryl group, and X63 represents a group of non-metal atoms that forms a pyrazolidine ring. In formula (TS-IIIC), preferable is the case where R65 and R66 each independently represent a hydrogen atom, an aliphatic group, an aryl group, an acyl group, an aliphatic oxycarbonyl group, or an aryl oxycarbonyl group, and Rc3 represents a hydrogen atom, an aliphatic group, or an acyl group; and more preferable is the case where R65 and R66 each independently represent an aliphatic group, an acyl group, or an aliphatic oxycarbonyl group, and Rc3 represents a hydrogen atom, an aliphatic group, or an acyl group. In formula (TS-IIID), preferable is the case where R65 represents a hydrogen atom, an aliphatic group, an aryl group, an acyl group, or a carbamoyl group, Rc5 represents an aliphatic group, or an aryl group, and Rc4 represents an aliphatic group, or an aryl group; and more preferable is the case where R65 represents an aliphatic group, an aryl group, an acyl group, or a carbamoyl group, Rc5 represents an aliphatic group, or an aryl group, and Rc4 represents an aliphatic group, or an aryl group.
In the present invention, the compounds represented by formula (TS-III) are more preferably those compounds represented by any one of formulae (TS-IIIB), (TS-IIIC), and (TS-IIID), and most preferably those compounds represented by formula (TS-IIIB), or (TS-IIIC).
The compound represented by formula (TS-IV) is described in more detail below.
In formula (TS-IV), R71, and R72 each independently represent an aliphatic group (e.g., methyl, methoxycarbonylethyl, dodecyloxycarbonylethyl, benzyl), an aryl group (e.g., phenyl, 4-octyloxyphenyl, 2-butoxy-5-(t)octylphenyl), or a heterocyclic group (e.g., 2-pyridyl, 2-pyrimidyl). Further, R71 represents a hydrogen atom, Li, Na, or K. R71 and R72 may combine together to form a 5- to 7-membered ring, such as a tetrahydrothiophene ring and a thiomorpholine ring. q represents 0, 1, or 2. In the above, the total number of carbon atoms of R71 and R72 is 10 or more, preferably 10 to 60.
The compound represented by formula (TS-IV) for use in the present invention include compounds represented by, for example, formula (I) of JP-B-2-44052, formula (T) of JP-A-3-48242, formula (A) of JP-A-3-266836, formula (I), (II) or (III) of JP-A-5-323545, formula (I) of JP-A-6-148837, formula (I) of U.S. Pat. No. 4,933,271, and formula (I) of U.S. Pat. No. 4,770,987. These compounds can be synthesized according to the methods described in these publications or general methods described in Shin Jikken Kagaku Koza, Vol. 14 (Maruzen Co., Ltd.) (1977, 1978).
In the present invention, in formula (TS-IV), q is preferably 0 or 2. When q is 0, it is preferable that R71 and R72 each independently represent an aliphatic group, or an aryl group, or that R71 and R72 combine together to form a 6-membered ring. When q is 2, it is preferable that R71 represents a hydrogen atom, Na, K, an aliphatic group, or an aryl group, and R72 represents an aliphatic group, or an aryl group; it is more preferable that R71 represents a hydrogen atom, Na, or K, and R72 represents an aryl group.
The compound represented by formula (TS-V) is described in more detail below.
In formula (TS-V), R81, R82, and R83 each independently represent an aliphatic group (e.g., methyl, ethyl, t-octyl, allyl), an aryl group (e.g., phenyl, 4-t-butylphenyl, 4-vinylphenyl), an aliphatic oxy group (e.g., methoxy, t-octyloxy), an aryloxy group (e.g., phenoxy, 2,4-di-t-butylphenoxy), an aliphatic amino group (e.g., butyl amino, dibutyl amino), or an arylamino group (e.g., anilino, 4-methoxyanilino, N-methylanilino), and t represents 0 or 1. Each combination of R81 and R82, and R81 and R83 may combine together to form a 5- to 8-membered ring. The number of total carbon atoms of R81, R82, and R83 is 10 or more (preferably 10 to 50).
The compound represented by formula (TS-V) for use in the present invention include compounds represented by, for example, formula (I) of JP-A-3-25437, formula (I) of JP-A-3-142444, formula of U.S. Pat. No. 4,749,645, and formula of U.S. Pat. No. 4,980,275. These compounds can be synthesized according to the methods described in these publications or general methods described in Shin Jikken Kagaku Koza, Vol. 14 (Maruzen Co., Ltd.) (1977, 1978).
In formula (TS-V), in the present invention, preferable is the case where t is 1, and R81, R82 and R83 each independently represent an aliphatic group, an aryl group, an aliphatic oxy group, an aryloxy, or an arylamino group (more preferably at least one of R81, R82, and R83 is an aliphatic group, an aryl group, an aliphatic oxy group, or an aryloxy group). Also preferable is the case where R81 and R82 combine together to form an 8-membered ring. More preferable is the case where t is 1, and R81, R82, and R83 each independently represent an aryl group, an aliphatic oxy group, or an aryloxy group (more preferably at least one of R81, R82, and R83 is an aryl group, or an aryloxy group).
The compound represented by formula (TS-VI) is described in more detail below.
In formula (TS-VI), R85, R86, R87, and R88 each independently represent a hydrogen atom or a substituent (prefearbly a substituent except a carbonyl group, e.g., an aliphatic group, an aryl group, a phosphoryl group, an acylamino group, or a carbamoyl group). However, all of R85, R86, R87, and R88 cannot simultaneously represent hydrogen atoms, respectively. Any two of R85, R86, R87, and R88 may combine together to form a 5- to 7-membered ring (e.g., a cyclohexene ring, a cyclohexane ring), however the ring is not an aromatic ring consisting only of carbon atoms. The total number of carbon atoms of the compound represented by formula (TS-VI) is 10 or more (preferably 10 to 50). Further, the compound represented by formula (TS-VI) is not identical to the above-described alkenylcarbonyl-sereis compound.
The compound represented by formula (TS-VI) for use in the present invention include compounds represented by, for example, formula (I) of U.S. Pat. No. 4,713,317, formula (I) of JP-A-8-44017, formula (I) of JP-A-8-44018, formula (I) of JP-A-8-44019, formula (I) or (II) of JP-A-8-44020, formula (I) of JP-A-8-44021 and formula (I) or (II) of JP-A-8-44022. These compounds can be synthesized according to the methods described in these publications or general methods described in Shin Jikken Kagaku Koza, Vol. 14 (Maruzen Co., Ltd.) (1977, 1978).
In the present invention, the compounds represented by formula (TS-VI) are preferably the compounds represented by formula (TS-VIB) or (TS-VIC).
In formulae (TS-VIB) and (TS-VIC), R85 has the same meaning as defined in formula (TS-VI). Rd2 and Rd3 each independently represent an alkenyl group (e.g., vinyl, allyl, oleyl). Rd4 represents a hydrogen atom, an aliphatic group (e.g., methyl, allyl, vinyl, octyl), or an aryl group (e.g., phenyl, naphthyl, 4-vinylphenyl). u and v each independently represent 1, 2 or 3.
As to the compounds represented by formulae (TS-VIB) or (TS-VIC), the groups thereon preferable in the present invention are described below. In formula (TS-VIB), preferable is the case where R85 is an aliphatic group or an aryl group, Rd2 is an alkenyl group, and u is 1, 2 or 3; and more preferable is the case where R85 is an aliphatic group or an aryl group, Rd2 is an alkenyl group, and u is 2 or 3. In formula (TS-VIC), preferable is the case where R85 is an aliphatic group or an aryl group, Rd3 is an alkenyl group, Rd4 is a hydrogen atom, or an aliphatic group, and v is 1, 2 or 3; and more preferable is the case where R85 is an aliphatic group or an aryl group, Rd3 is an alkenyl group, Rd4 is a hydrogen atom, or an alkenyl group, and v is 2 or 3.
In the present invention, the compounds represented by formula (TS-VI) are preferably the compounds represented by formula (TS-VIB).
The compounds represented by formula (TS-VII) are explained below.
R91 represents an aliphatic or aromatic hydrophobic group having the total number of carbon atoms of 10 or more (preferably from 10 to 50, more preferably from 10 to 32). Examples of preferable aliphatic hydrophobic groups include an alkyl group having 1 to 32 carbon atoms, an alkenyl group having 2 to 32 carbon atoms, an alkynyl group having 2 to 32 carbon atoms, a cycloalkyl group having 3 to 32 carbon atoms and a cycloalkenyl group having 3 to 32 carbon atoms. The above alkyl group, alkenyl group and alkynyl group each may be straight-chain or branched.
Further, each of these aliphatic hydrophobic groups may have a substituent(s).
Examples of aromatic hydrophobic groups include an aryl group (for example, phenyl) and an aromatic heterocyclic group (for example, pyridyl, furyl). Further, each of these aromatic groups may have a substituent(s).
R91 is preferably an alkyl group or an aryl group.
As the substituent with which the aliphatic or aromatic group represented by R91 may be substituted, there is no particular limitation, but as a preferable substituent, for example, there are illustrated an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an acylamino group and an amino group. An aliphatic group is more preferred.
Y91 represents a monovalent organic group containing an alcoholic hydroxyl group. Y91 is preferably a monovalent organic group represented by formula [AL] set forth below.
Y92—(L92)m92— Formula [AL]
In the formula, Y92 represents a group from a compound in which a hydrogen atom is removed from at least one of hydroxyl groups in a polyhydric alcohol. L92 represents a divalent linking group. m92 is 0 or 1.
The polyhydric alcohol from which a hydrogen atom is removed to form a group represented by Y92, is preferably glycerol, polyglycerol, pentaerythritol, trimethylolpropane, neopentylglycol, sorbitan, sorbide, sorbitol, sugars, and the like. The divalent linking group represented by L92 is preferably —C(═O)— or —SO2—.
Preferable compounds in another embodiment of the compounds represented by formula (TS-VII) are compounds in which R91 represents an aliphatic group having carbon atoms of 12 or more (preferably alkyl or alkenyl groups having 12 to 32 carbon atoms) and Y91 represents an OH group.
The metal complex for use in the present invention is explained below.
The metal complex for use in the present invention, is preferably those having Cu, Co, Ni, Pd, or Pt as a central metal, and more preferably those having Ni as a central metal. It is preferable that they are low in solubility to water. Specifically, the solubility at room temperature is preferably 50% or less, more preferably 25% or less, and furthermore preferably 10% or less. The category of a preferable compound can also be defined in terms of total number of carbon atoms of the whole compound. Specifically, the compound has carbon atoms preferably in the range of 15 to 65, more preferably in the range of 20 to 60, furthermore preferably in the range of 25 to 55, and most preferably in the range of 30 to 50, in total.
The metal complex for use in the present invention may have any kind of ligand. Dithiolate-series metal complexes and salicylaldoxime-series metal complexes are preferable, and salicylaldoxime-series metal complexes are more preferable.
As the metal complex for use in the present invention, there are many known metal complexes, including dithiolate-series nickel complexes and salicylaldoxime-series nickel complexes, which are effective. Preferable examples include compounds represented, for example, by, formula (I) of JP-B-61-13736, formula (I) of JP-B-61-13737, formula (I) of JP-B-61-13738, formula (I) of JP-B-61-13739, formula (I) of JP-B-61-13740, formula (I) of JP-B-61-13742, formula (I) of JP-B-61-13743, formula (I) of JP-B-61-13744, formula of JP-B-5-69212, formula (I) or (II) of JP-B-5-88809, formula of JP-A-63-199248, formula (I) or (II) of JP-A-64-75568, formula (I) or (II) of JP-A-3-182749, formula (II), (III), (IV) or (V) of U.S. Pat. No. 4,590,153, or formula (II), (III), or (IV) of U.S. Pat. No. 4,912,027.
As the metal complex that can be used in the present invention, the compound represented by formula (TS-VIIIA) is preferable.
In formula (TS-VIIIA), R101, R102, R103, and R104 each independently represent a hydrogen atom or a substituent (e.g., an aliphatic group, an aliphatic oxy group, an aliphatic sulfonyl group, an aryl sulfonyl group, an acyl amino group). R105 represents a hydrogen atom, an aliphatic group (e.g., methyl, ethyl, vinyl, undecyl), or an aryl group (e.g., phenyl, naphthyl). R106 represents a hydrogen atom, an aliphatic group (e.g., methyl, ethyl), an aryl group (e.g., phenyl, 4-methylphenyl), or a hydroxyl group. M represents Cu, Co, Ni, Pd, or Pt. Two R106s may combine together to form a 5- to 7-membered ring. R101 and R102, R102 and R103, R103 and R104, and R104 and R105, each two of which are adjacent to each other, may combine together to form a 5- to 6-membered ring.
In formula (TS-VIIIA), it is preferable in the present invention that R101, R102, R103, and R104 each independently represent a hydrogen atom, an aliphatic group, or an aliphatic oxy group, R105 is a hydrogen atom, R106 is a hydrogen atom, an aliphatic group, or a hydroxyl group, and M is Ni; and it is more preferable that R101, R102, R103, and R104 each independently represent a hydrogen atom, or an aliphatic oxy group, R105 is a hydrogen atom, R106 is a hydroxyl group, and M is Ni.
An ultraviolet absorbing agent for use in the present invention is explained below.
The ultraviolet absorbing agent for use in the present invention is not particularly limited, so long as the compound has the maximum absorption wavelength (λmax) at 400 nm or less. The compounds represented by any of formulae (UA), (UB), (UC), (UD) and (UE) are preferred.
In the formula (UA), R21 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. R22 and R23, which may be the same or different each other, each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.
Preferably, R21 represents a hydrogen atom, a halogen atom (for example, Cl, Br), an alkyl group having 1 to 5 carbon atoms (for example, methyl, ethyl, butyl), or an alkoxy group having 1 to 4 carbon atoms (for example, methoxy, butoxy). R22 and R23, which may be the same or different from each other, each represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, sec-butyl, tert-butyl, tert-octyl, dodecyl, carboxyethyl, n-octyloxycarbonylethyl), or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms (for example, phenyl, p-chlorophenyl, p-methoxyphenyl).
In the formula (UB), R24, R25 and R26, which may be the same or different from each other, each independently represent a hydrogen atom, an alkoxy group having 1 to 12 carbon atoms (for example, methoxy, ethoxy, dodecyloxy), or a hydroxyl group.
In the formula (UC), R27 represent a hydroxyl group, an alkoxy group, or an alkyl group. R28 and R29 each independently represent a hydrogen atom, a hydroxyl group, an alkoxy group, or an alkyl group. R28 and R27, or R29 and R27 may adjoin each other to form a 5- or 6-membered ring. Xa and Ya, which may be the same or different from each other, each represent CN, —COR38, —COOR38, —SO2R38, —CON(R38)(R39), or —COOH. R38 and R39 each independently represent an alkyl group or an aryl group. R39 may be a hydrogen atom.
Preferably, R27 represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms (for example, methoxy, ethoxy, n-butoxy), or an alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, t-butyl, isopropyl). R28 and R29 each represent a hydrogen atom, a hydroxyl group, an alkoxy group or an alkyl group, in which the alkoxy group and the alkyl group each have the same meanings as in R27. R28 and R27, or R29 and R27 may adjoin each other to form a 5- or 6-membered ring (for example, methylenedioxy ring). Xa and Ya, which may be the same or different from each other, each represent —CN, —COR38, —COOR38, —SO2R38, —CON(R38)(R39), or —COOH. R38 and R39 each represent a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms (for example, methyl, ethyl, methoxyethyl, n-hexyl, phenoxyethyl) or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms (for example, phenyl, p-chlorophenyl, p-methylphenyl, p-tert-butylphenyl). R39 may be a hydrogen atom.
In the formula (UD), R30 and R31 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group. R30 and R31 may be the same or different from each other, but they cannot be a hydrogen atom at the same time. Further, a 5- or 6-membered ring may be formed by R30 and R31 together with the N. Xa and Ya have the same meanings as defined in formula (UC).
Preferably, R30 and R31 each represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms (for example, methyl, ethyl, t-butyl, n-dodecyl, methoxyethyl, ethoxyethyl), an alkenyl group having 3 to 6 carbon atoms, or an aryl group (for example, phenyl, tolyl, p-chlorophenyl, p-methoxyphenyl). R30 and R31 may be the same or different from each other, but they can not be a hydrogen atom at the same time. Further, a 5- or 6-membered ring, e.g. a piperidine ring or a morpholine ring, may be formed by R30 and R31 together with the N. Xa and Ya have the same meanings as mentioned in formula (UC).
In the formula (UE), R32, R33 and R34 each independently represent a substituted or unsubstituted alkyl group, aryl group, alkoxyl group, aryloxy group, or heterocyclic group, in which at least one of the above R32, R33 and R34 is represented by formula (UF) set forth below.
In the formula (UF), R35 and R36 each independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group, alkoxyl group or aryloxy group.
Examples of specific compounds of the compound represented by any one of formulae (TS-I) to (TS-VII), the metal complex, and the ultraviolet absorbing agent are set forth below, but the present invention is not limited to these compounds.
Next, water-insoluble and organic solvent-soluble homopolymers or copolymers that can be used in the present invention are explained in detail below.
In the present invention, the term “water-insoluble” is used to mean that solubility to water is 0.1% or less. As the water-insoluble and organic solvent-soluble homopolymer or copolymer (hereinafter referred to as a polymer or copolymer for use in the present invention), various kinds of polymers and copolymers can be used. For example, those set forth below can be preferably used.
(1) Vinyl-Series Polymers and Copolymers
Monomers that form the vinyl-series polymers and copolymers that can be used in the present invention are more specifically set forth below.
There are illustrated, for example:
Acrylic acid esters: for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxylpropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-iso-propoxyethyl acrylate, 2-butoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, 2-(2-butoxyethoxy)ethyl acrylate, ω-methoxypolyethyleneglycol acrylate (addition number of moles: n=9), 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate;
Methacrylic acid esters: for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2-(3-phenylpropyloxy)ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethyleneglycol monomethacrylate, dipropyleneglycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2-(2-methoxyethoxy)ethyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, 2-(2-butoxyethoxy)ethyl methacrylate, ω-methoxypolyethyleneglycol methacrylate (addition number of moles: n=6);
Vinyl esters: for example, vinyl acetate, vinyl propionate, vinyl butylate, vinyl isobutylate, vinyl caproate, vinyl chloroacetate, vinyl methoxyacetate, vinyl phenylacetate, vinyl benzoate, vinyl salicylate;
Acrylamides: for example, acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, N-(2-acetoacetoxyethyl)acrylamide, diacetonacrylamide;
Methacrylamides: for example, methacrylamide, methylmethacrylamide, ethylmethacrylamide, propylmethacrylamide, butylmethacrylamide, tert-butylmethacrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide, dimethylaminoethylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, β-cyanoethylmethacrylamide, N-(2-acetoacetoxyethyl)methacrylamide;
Olefins: for example, dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene;
Styrenes: for example, styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, vinylbenzoate methyl ester;
Crotonic acid esters: for example, butyl crotonate, hexyl crotonate;
Itaconic acid diesters: for example, dimethyl itaconate, diethyl itaconate, dibutyl itaconate;
Maleic acid diesters: for example, diethyl maleate, dimethyl maleate, dibutyl maleate; and
Fumaric acid diesters: for example, diethyl fumarate, dimethyl fumarate, dibutyl fumarate.
Examples of other monomers are set forth below.
There are illustrated, for example:
Allyl compounds: for example, allyl acetate, allyl caproate, allyl laurate, allyl benzoate;
Vinyl ethers: for example, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether;
Vinyl ketones: for example, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone;
Vinyl heterocyclic compounds: for example, vinyl pyridine, N-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, N-vinylpyrrolidone;
Glycidyl esters: for example, glycidyl acrylate, glycidyl methacrylate; and
Unsaturated nitrites: for example, acrylonitrile, methacrylonitrile.
The polymer that can be preferably used in the present invention may be a homopolymer of any of the above-mentioned monomers, or it may be a copolymer of at least two kinds of the monomers, if necessary. Further, the polymer for use in the present invention may contain a monomer component having an acid group in such a proportion that the acid group does not render the polymer water-soluble. The proportion of the monomer component having an acid group is preferably 20% or less. It is preferred that the polymer for use in the present invention contains none of the monomer component having an acid group. However, the present invention is not limited to the above so long as the monomer is a compound represented by formula (A) or (B) for use in the present invention. Examples of the monomer having an acid group include acrylic acid; methacrylic acid; itaconic acid; maleic acid; monoalkyl itaconate (for example, monomethyl itaconate), monoalkyl maleate (for example, monomethyl maleate), citraconic acid; styrene sulfonic acid; vinylbenzylsulfonic acid; vinylbenzene sulfonic acid; acryloyloxyalkyl sulfonic acid (for example, acryloyloxymethyl sulfonic acid); methacryloyloxyalkyl sulfonic acid (for example, methacryloyloxymethyl sulfonic acid, methacryloyloxyethyl sulfonic acid, methacryloyloxypropyl sulfonic acid); acrylamidoalkyl sulfonic acid (for example, 2-acrylamido-2-methylethane sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 2-acrylamido-2-methylbutane sulfonic acid); methacrylamidoalkyl sulfonic acid (for example, 2-methacrylamido-2-methylethane sulfonic acid, 2-methacrylamido-2-methylpropane sulfonic acid, 2-methacrylamido-2-methylbutane sulfonic acid); acryloyloxyalkylphosphate (for example, acryloyloxyethylphosphate, 3-acryloyloxypropyl-2-phosphate); and methacryloyloxyalkylphosphate (for example, methacryloyloxyethylphosphate, 3-methacryloyloxypropyl-2-phosphate).
These monomers having an acid group may be an alkali metal salt (for example, Na, K salts), or an ammonium salt.
As the monomer that forms the polymer for use in the present invention, acrylate-series, methacrylate-series, acrylamido-series and methacrylamido-series monomers are preferred.
The polymers formed from the above-mentioned monomers can be obtained according to the processes such as solution polymerization, bulk polymerization, suspension polymerization, and latex polymerization. As the initiator that can be used for these polymerizations, use can be made of a water-soluble polymerization initiator and a lipophilic polymerization initiator.
As the water-soluble polymerization initiator, for example, use can be made of persulfate salts, such as potassium persulfate, ammonium persulfate, and sodium persulfate; water-soluble azo compounds, such as sodium 4,4′-azobis-4-cyanovalerate and 2,2′-azobis(2-amidinopropane)hydrochloride; and hydrogen peroxide.
As the lipophilic polymerization initiator, for example, mention can be made of lipophilic azo compounds, such as azobisisobutyronitrile, 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1′-azobis(cyclohexanone-1-carbonitrile), 2,2′-azobisisobutyric acid dimethyl ester, and 2,2′-azobisisobutyric acid diethyl ester; benzoyl peroxide, lauryl peroxide, diisopropylperoxy dicarbonate, and di-tert-butyl peroxide.
(2) Polyester Resins Obtained by Condensation of Polyhydric Alcohols and Polybasic Acids
As the polyhydric alcohol, glycols having the structure set forth below or polyalkyleneglycols are useful.
HO—Ra—OH
In the formula, Ra represents a hydrocarbon (especially an aliphatic hydrocarbon) having 2 to about 12 carbon atoms.
As the polybasic acid, acids having the structure set forth below are useful.
HOOC—Rb—COOH (Rb represents a single bond or a hydrocarbon having 1 to 12 carbon atoms.)
As specific examples of the polyhydric alcohol, there are illustrated ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, trimethylolpropane, 1,4-butanediol, isobutylenediol, 1,5-pentanediol, neopentylglycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, glycerol, diglycerol, triglycerol, 1-methyl glycerol, erythritol, mannitol, and sorbitol.
As specific examples of the polybasic acid, there are illustrated oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, cork acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, metaconic acid, isopimelic acid, cyclopentadiene-anhydrous maleic acid adducts, and rosin-anhydrous maleic acid adducts.
(3) Polyesters Obtained by a Ring-Opening Polymerization Process
These polyesters can be obtained from β-propiolactone, ε-caprolactone, dimethylpropiolactone or the like.
(4) Others
There are illustrated polycarbonate resins obtained by polycondensation of a glycol or divalent phenol and a carbonate or phosgene; polyurethane resins obtained by polyaddition of polyhydric alcohols and polyisocyanates; and polyamide resins obtained from polyamines and polybasic acids.
The number-average molecular weight of the polymer for use in the present invention is not particularly limited, but it is preferably 200,000 or less, and more preferably in the range of from 800 to 100,000.
Specific examples of the polymer for use in the present invention are shown below, but the present invention is not limited to these compounds. (The composition of a copolymer is indicated by a mass ratio.)
The polymer of still another preferable mode that can be preferably used in the present invention, is a polymer substantially insoluble in water, which comprises as a constituent element thereof a monomer unit having at least one kind of aromatic group, and which has a number average molecular weight of less than 2,000. The number average molecular weight is preferably 200 or more but less than 2,000, and more preferably 200 or more but 1,000 or less. The polymer that can be used in the present invention may be a so-called homopolymer composed of one kind of monomer unit, or a copolymer composed of two kinds or more of monomer units. In the case of a copolymer, it preferably comprises the monomer unit having the aromatic group, according to the present invention in a proportion of 20% or more of the mass composition of the copolymer. The polymer structure is not particularly limited in so far as the above-mentioned condition is fulfilled. Examples of the polymer having the preferred polymer structure include a polymer whose constituent element is styrene, α-methylstyrene, β-methylstyrene, or a monomer having a substituent on the benzene ring of such a monomer; a polymer whose constituent element is an aromatic acrylamide, an aromatic methacrylamide, an aromatic acrylic ester, or an aromatic methacrylic ester. Examples of the aromatic group include a phenyl group, a naphthyl group, a benzyl group, a biphenyl group, and the like. These aromatic groups may have a substituent(s) such as an alkyl group, a halogen atom, and the like. In the case of a copolymer, comonomers listed, for example, in JP-A-63-264748 can be used preferably. From the viewpoints of availability of raw materials and aging characteristics of an emulsion, a polymer derived from styrene, α-methylstyrene or β-methylstyrene is preferable.
In the present invention, among the compound represented by any one of formulae (TS-I) to (TS-VII), the metal complex, the ultraviolet absorbing agent, and the water-insoluble homopolymer or copolymer, it is preferred to use at least one selected from the compound represented by any of formulae (TS-I), (TS-II), (TS-VI), (TS-V), (TS-VI), or (TS-VII), the ultraviolet absorbing agent, and the water-insoluble homopolymer or copolymer; and more preferred to use at least one selected from the compound represented by formula (TS-I), (TS-II), (TS-V), (TS-VI) or (TS-VII), the ultraviolet absorbing agent, and the water-insoluble homopolymer or copolymer.
The compound represented by any one of formulae (TS-I) to (TS-VII), the metal complex, the ultraviolet absorbing agent, or the water-insoluble homopolymer or copolymer, each of which can be used in the present invention, each may be used singly or in combination with two or more kinds thereof. These additives may be added to the same layer as the layer containing the dye-forming coupler represented by formula (I), or to a separate layer from the layer containing the dye-forming coupler, with the former being preferred.
An addition amount of the compound represented by any one of formulae (TS-I) to (TS-VII), the metal complex, the ultraviolet absorbing agent, or the water-insoluble homopolymer or copolymer is preferably in the range of from 1 to 400 mass %, more preferably in the range of from 10 to 300 mass %, and most preferably in the range of from 15 to 200 mass %, to the dye-forming coupler represented by formula (I).
The above-described alkenylcarbonyl-series compound for use in the present invention, may be used in combination with other compounds than those described above. Examples of the compound that may be used in combination with the above alkenylcarbonyl-series compound, include boron compounds represented by formula (I) described in JP-A-4-174430, epoxy compounds represented by formula (II) described in U.S. Pat. No. 5,183,731 or formula (S1) described in JP-A-8-53431, disulfide-series compounds represented by formula described in European Patent Publication EP271,322 B1 or formula (I), (II), (III) or (IV) described in JP-A-4-19736, reactive compounds represented by formula (I), (II), (III) or (IV) described in U.S. Pat. No. 5,242,785, cyclic phosphorous compounds represented by formula (1) described in JP-A-8-283279, alcoholic compounds represented by formula (SO) described in JP-A-7-84350, formula (G) described in JP-A-9-114061, formula (II) described in JP-A-9-146242, formula (A) described in JP-A-9-329876, or formula (VII) described in JP-A-62-175748. If the above-mentioned publications include exemplified compounds that are embraced in any of formulae (TS-I) to (TS-VII) that can be used in the present invention, these compounds are also included in the exemplified compounds that can be used in the present invention.
The dye-forming coupler represented by formula (I), the above-described alkenylcarbonyl-sereis compound, the compound represented by formula (Ph), the compound represented by any one of formulae (E-1) to (E-3), the compound represented by any one of formulae (TS-I) to (TS-VII), the metal complex, the ultraviolet absorbing agent, the water-insoluble homopolymer or copolymer, and the like additives for use in the present invention, may be introduced into the photosensitive material, according to any of dispersion methods. It is preferable to use a water-in-oil dispersion method in which such a compound or additive is dissolved in a high-boiling organic solvent (optionally in combination with a low-boiling organic solvent), and the solution is emulsified and dispersed in an aqueous gelatin solution, and then it is added to a silver halide emulsion. Further, it is preferable to use the metal complex for use in the present invention with dispersing it with a high-boiling organic solvent.
Examples of the high-boiling organic solvent that can be used in a water-in-oil dispersion method are described, for example, in U.S. Pat. No. 2,322,027. Further, specific examples of a latex dispersion method as one of polymer dispersion methods are described, for example, in U.S. Pat. No. 4,199,363, West German Patent (OLS) No. 2,541,274, JP-B-53-41091, European Patent Publication EP0,727,703 A1, and EP0,727,704 A1. Further, a dispersion method using a polymer that is soluble in an organic solvent is described in PCT International Publication WO88/723.
Examples of the high-boiling organic solvent that can be used in a water-in-oil dispersion method include phthalic acid esters (e.g., dibutyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate), esters of phosphoric acid or phosphonic acid (e.g., triphenyl phosphate, tricresyl phosphate, tri-2-ethylhexyl phosphate), fatty acid esters (e.g., di-2-ethylhexyl succinate, tributyl citrate), benzoic esters (e.g., 2-ethylhexyl benzoate, dodecyl benzoate), amides (e.g., N,N-diethyldodecane amide, N,N-dimethylolein amide), alcohols or phenols (e.g., iso-stearyl alcohol, 2,4-di-tert-amyl phenol), anilines (e.g., N,N-dibutyl-2-butoxy-5-tert-octylaniline), chlorinated paraffins, hydrocarbons (e.g., dodecyl benzene, diisopropyl naphthalene), and carboxylic acids (e.g., 2-(2,4-di-tert-amyl phenoxy)butyric acid). Further, the high-boiling point organic solvent may be used in combination with an auxiliary solvent, which is an organic solvent having a boiling point of 30° C. or more and 160° C. or less, such as ethyl acetate, butyl acetate, methyl ethyl ketone, cyclohexanone, methylcellosolve acetate, and dimethylformamide. The high-boiling organic solvent is preferably used in an amount of 0 to 10 times (more preferably 0 to 4 times) that of a dye-forming coupler, in terms of mass ratio.
In order to emulsify and disperse the dye-forming coupler for use in the present invention and the compound for use in the present invention in a hydrophilic protective colloid to make lipophilic fine particles, dispersion is carried out using a dispersant such as a surface active agent, by means of a stirrer including a stirrer (agitator), a homogenizer, a colloid mill, a flow-jet mixer (mill), a ultrasonic wave apparatus, and the like.
All or a part of the auxiliary solvent may be removed from an emulsified dispersion by means of a vacuum distillation, a noodle washing, an ultrafiltration, or the like, as occasion demands, for the purpose of improving aging characteristics during storage in the state of the emulsified dispersion, or inhibiting fluctuation in photographic properties or improving aging characteristic of the final coating composition in which the emulsified dispersion is mixed with a silver halide emulsion.
The average particle size of the oleophilic fine particle dispersion thus obtained is preferably in the range of 0.04 to 0.50 μm, more preferably in the range of 0.05 to 0.30 μm, and most preferably in the range of 0.08 to 0.20 μm. The average particle size can be determined with a measuring device such as Coulter submicron particle analyzer model N4 (trade name, manufactured by Coulter Electronics Co., Ltd.).
The silver halide color photographic photosensitive material of the present invention, which may be referred to simply as “the photosensitive material” hereinafter, is explained in detail below.
The silver halide color photographic photosensitive material of the present invention is preferably a silver halide color photographic photosensitive material which has, on a support, at least one silver halide emulsion layer containing a yellow dye-forming coupler, at least one silver halide emulsion layer containing a magenta dye-forming coupler, and at least one silver halide emulsion layer containing a cyan dye-forming coupler.
In the present invention, the above-said silver halide emulsion layer containing a yellow dye-forming coupler functions as a yellow color-forming layer, the above-said silver halide emulsion layer containing a magenta dye-forming coupler functions as a magenta color-forming layer, and the above-said silver halide emulsion layer containing a cyan dye-forming coupler functions as a cyan color-forming layer. The silver halide emulsions contained in the yellow color-forming layer, the magenta color-forming layer, and the cyan color-forming layer may preferably have photosensitivities to mutually different wavelength regions (such as light in a blue region, light in a green region, and light in a red region).
The photosensitive material of the present invention may, if necessary, have a hydrophilic colloid layer, an antihalation layer, an intermediate layer, and a colored layer as described below, in addition to the above-said yellow color-forming layer, magenta color-forming layer, and cyan color-forming layer.
The silver halide photographic photosensitive material of the present invention can be used for various materials, such as color negative films, color positive films, color reversal films, color reversal papers, color papers, motion-picture color negatives, motion-picture color positives, display photosensitive materials, and color proof (especially, digital color proof) photosensitive materials.
The present invention is preferably applied to a photosensitive material that is used for direct view or appliciation, such as a color photographic printing paper (color paper), a display photosensitive material, a color proof, a color reversal film (color reversal), a color reversal paper, and a motion picture color positive. Of these photosensitive materials, a color paper and a color reversal film are preferred.
In the case where the present invention is applied to a color paper, for example, the photosensitive materials described in JP-A-11-7109 are preferred. Particularly the description of the paragraph Nos. 0071 to 0087 in the JP-A-11-7109 is herein incorporated by reference.
In the case where the present invention is applied to a color negative film, the description of the paragraph Nos. 0115 to 0217 in JP-A-11-305396 is preferably applied, and the description is herein incorporated by reference.
In the case where the present invention is applied to a color reversal film, the photosensitive materials described in JP-A-2001-142181 are preferred. Specifically, the description of the paragraph Nos. 0164 to 0188 in the JP-A-2001-142181 and the description of the paragraph Nos. 0018 to 0021 in JP-A-11-84601 are preferably applied, and these descriptions are herein incorporated by reference.
The preferred silver halide photosensitive materials according to the present invention are explained in detail below.
Silver halide grains in the silver halide emulsion which can be used in the present invention, are preferably cubic or tetradecahedral crystal grains substantially having {100} planes (these grains may be rounded at the apexes thereof and further may have planes of higher order), or octahedral crystal grains. Alternatively, a silver halide emulsion in which the proportion of tabular grains having an aspect ratio of 2 or more and composed of {100} or {111} planes accounts for 50% or more in terms of the total projected area, can also be preferably used. The term “aspect ratio” refers to the value obtained by dividing the diameter of the circle having an area equivalent to the projected area of an individual grain by the thickness of the grain. In the present invention, cubic grains, or tabular grains having {100} planes as major faces, or tabular grains having {111} planes as major faces are preferably used.
As a silver halide emulsion which can be used in the present invention, for example, silver chloride, silver bromide, silver iodobromide, or silver chloro(iodo)bromide emulsions may be used. It is preferable for enhancement of processing speed to use a silver chloride, silver chlorobromide, silver chloroiodide, or silver chlorobromoiodide emulsion having a silver chloride content of 90 mol % or greater, more preferably the silver chloride, silver chlorobromide, silver chloroiodide, or silver chlorobromoiodide emulsion having a silver chloride content of 98 mol % or greater. Preferred of these silver halide emulsions are those having in the shell parts of silver halide grains a silver iodochloride phase of 0.01 to 0.50 mol %, more preferably 0.05 to 0.40 mol %, per mol of the total silver, in view of high sensitivity and excellent high illumination intensity exposure suitability. Further, especially preferred of these silver halide emulsions are those containing silver halide grains having on the surface thereof a silver bromide localized phase of 0.2 to 5 mol %, more preferably 0.5 to 3 mol %, per mol of the total silver, since both high sensitivity and stabilization of photographic properties are attained.
The silver halide emulsion for use in the present invention preferably contains silver iodide. In order to introduce iodide ions, an iodide salt solution may be added alone, or it may be added in combination with both a silver salt solution and a high chloride salt solution. In the latter case, the iodide salt solution and the high chloride salt solution may be added separately or as a mixture solution of these salts of iodide and high chloride. The iodide salt is generally added in the form of a soluble salt, such as alkali or alkali earth iodide salt. Alternatively, the iodide salt may be introduced by cleaving the iodide ions from an organic molecule, as described in U.S. Pat. No. 5,389,508. As another source of the iodide ion, fine silver iodide grains may be used.
The addition of an iodide salt solution may be concentrated at one time of grain formation process or may be performed over a certain period of time. For obtaining an emulsion with high sensitivity and low fog, the position of the introduction of an iodide ion to a high silver chloride emulsion is restricted. The deeper in the emulsion grain the iodide ion is introduced, the smaller is the increment of sensitivity. Accordingly, the addition of an iodide salt solution is preferably started at 50% or outer side of the volume of a grain, more preferably 70% or outer side, and most preferably 80% or outer side. Moreover, the addition of an iodide salt solution is preferably finished at 98% or inner side of the volume of a grain, most preferably 96% or inner side. When the addition of an iodide salt solution is finished at a little inner side of the grain surface, thereby an emulsion having higher sensitivity and lower fog can be obtained.
The distribution of an iodide ion concentration in the depth direction of a grain can be measured according to an etching/TOF-SIMS (Time of Flight-Secondary Ion Mass Spectrometry) method by means of, for example, a TRIFT II Model TOF-SIMS apparatus (trade name, manufactured by Phi Evans Co.). A TOF-SIMS method is specifically described in Nippon Hyomen Kagakukai edited, Hyomen Bunseki Gijutsu Sensho Niji Ion Shitsuryo Bunsekiho (Surface Analysis Technique Selection-Secondary Ion Mass Spectrometry), Maruzen Co., Ltd. (1999). When an emulsion grain is analyzed by the etching/TOF-SIMS method, it can be analyzed that iodide ions ooze toward the surface of the grain, even though the addition of an iodide salt solution is finished at an inner side of the grain. When the silver halide emulsion for use in the present invention contains silver iodide, it is preferred that the emulsion has the maximum concentration of iodide ions at the surface of the grain, and the iodide ion concentration decreases inwardly in the grain, in analysis by the etching/TOF-SIMS method.
The silver halide emulsion grains to be used in the photosensitive material of the present invention preferably have a silver bromide localized phase.
When the silver halide emulsion for use in the present invention contains a silver bromide localized phase, the silver bromide localized phase is preferably formed by epitaxial growth of the localized phase having a silver bromide content of at least 10 mol % or more on the grain surface. In addition, the emulsion grains preferably have the outermost shell portion having a silver bromide content of 1 mol % or more in the vicinity of the surface of the grains.
The silver bromide content of the silver bromide localized phase is preferably in the range of 1 to 80 mol %, and most preferably in the range of 5 to 70 mol %. The silver bromide localized phase is preferably composed of silver having population of 0.1 to 30 mol %, more preferably 0.3 to 20 mol %, to the molar amount of entire silver which constitutes silver halide grains for use in the present invention. The silver bromide localized phase is preferably contained (doped) with complex ions of a metal of the Group VIII, such as iridium ions. The amount of these compounds to be contained can be varied in a wide range depending on the purposes, and it is preferably in the range of 1×10−9 to 1×10−2 mol per mol of silver halide.
In the present invention, ions of a metal ion, for example, a transition metal, are preferably added in the course of grain formation and/or growth of the silver halide grains, to include the metal ions in the inside and/or on the surface of the silver halide grains. The metal ions to be used are preferably ions of a transition metal. Preferable examples of the transition metal are iron, ruthenium, iridium, osmium, lead, cadmium or zinc. Further, 6-coordinated octahedral complex salts of these metal ions which have ligands are more preferably used. The ligand to be used may be an inorganic compound. When employing an inorganic compound as a ligand, cyanide ion, halide ion, thiocyanato, hydroxide ion, peroxide ion, azide ion, nitrite ion, water, ammonia, nitrosyl ion, or thionitrosyl ion is preferably used. Such a ligand is preferably coordinated to any metal ion selected from the above-mentioned iron, ruthenium, iridium, osmium, lead, cadmium and zinc. Two or more kinds of these ligands are also preferably used in one complex molecule.
Among them, the silver halide emulsion for use in the present invention particularly preferably contains an iridium ion having at least one organic ligand for the purpose of improving high-intensity reciprocity law failure.
It is common in the case of other transition metal, when an organic compound is used as a ligand, preferable examples of the organic compound include chain compounds having a main chain of 5 or less carbon atoms and/or heterocyclic compounds of 5- or 6-membered ring. More preferable examples of the organic compound are those having at least a nitrogen, phosphorus, oxygen, or sulfur atom in a molecule as an atom which is capable of coordinating to a metal. Most preferred organic compounds are furan, thiophene, oxazole, isooxazole, thiazole, isothiazole, imidazole, pyrazole, triazole, furazane, pyran, pyridine, pyridazine, pyrimidine and pyrazine. Further, organic compounds which have a substituent introduced into a basic skeleton of the above-mentioned compounds are also preferred.
Among these compounds, 5-methylthiazole among thiazole ligands is particularly preferably used as the ligand preferable for the iridium ion.
Preferable combinations of a metal ion and a ligand are those of iron and/or ruthenium ion and cyanide ion. Preferred of these compounds are those in which the number of cyanide ions accounts for the majority of the coordination sites (number) intrinsic to the iron or ruthenium that is the central metal. The remaining coordination sites are preferably occupied by thiocyan, ammonia, water, nitrosyl ion, dimethylsulfoxide, pyridine, pyrazine, or 4,4′-bipyridine. Most preferably each of 6 coordination sites of the central metal is occupied by a cyanide ion, to form a hexacyano iron complex or a hexacyano ruthenium complex. These metal complexes having cyanide ion ligands are preferably added, during grain formation, in an amount of 1×10−8 mol to 1×10−2 mol, most preferably 1×10−6 mol to 5×10−4 mol, per mol of silver.
In case of the iridium complex, preferable ligands are fluoride, chloride, bromide and iodide ions, not only the organic ligands. Among these ligands, chloride and bromide ions are more preferably used. Specifically, preferable examples of the iridium complex include the following compounds, in addition to those that have the above organic ligands: [IrCl6]3−, [IrCl6]2−, [IrCl5(H2O)]2−, [IrCl5(H2O)]−, [IrCl4(H2O)2]−, [IrCl4(H2O)2]0, [IrCl3(H2O)3]0, [IrCl3(H2O)3]+, [IrBr6]3−, [IrBr6]2−, [IrBr5(H2O)]2−, [IrBr5(H2O)]−, [IrBr4(H2O)2]−, [IrBr4(H2O)2]0, [IrBr3(H2O)3]0, and [IrBr3(H2O)3]+.
These iridium complexes are preferably added during grain formation in an amount of 1×10−10 mol to 1×10−3 mol, most preferably 1×10−8 mol to 1×10−5 mol, per mol of silver. In case of the ruthenium complex and the osmium complex, nitrosyl ion, thionitrosyl ion, or water molecule, and chloride ion are preferably used as ligands. More preferably these ligands form a pentachloronitrosyl complex, a pentachlorothionitrosyl complex, or a pentachloroaquo complex. The formation of a hexachloro complex is also preferred. These complexes are preferably added during grain formation in an amount of 1×10−10 mol to 1×10−6 mol, more preferably 1×10−9 mol to 1×10−6 mol, per mol of silver.
In the present invention, the above-mentioned complexes are preferably added directly to the reaction solution at the time of silver halide grain formation, or indirectly to the grain-forming reaction solution via addition to an aqueous halide solution for forming silver halide grains or other solutions, so that they are incorporated to the inside of the silver halide grains. Further, these methods may be combined, to incorporate the complex into the inside of the silver halide grains.
In case where these complexes are incorporated to the inside of the silver halide grains, they are preferably uniformly distributed in the inside of the grains. On the other hand, as disclosed in JP-A-4-208936, JP-A-2-125245 and JP-A-3-188437, they are also preferably distributed only in the grain surface layer. Alternatively they are also preferably distributed only in the inside of the grain while the grain surface is covered with a layer free from the complex. Further, as disclosed in U.S. Pat. Nos. 5,252,451 and 5,256,530, it is also preferred that the silver halide grains are subjected to physical ripening in the presence of fine grains having complexes incorporated therein to modify the grain surface phase. Further, these methods may be used in combination. Two or more kinds of complexes may be incorporated in the inside of an individual silver halide grain. The halogen composition at the position (portion) where the complexes are incorporated, is not particularly limited, but they are preferably incorporated in any of a silver chloride layer (phase), a silver chlorobromide layer (phase), a silver bromide layer (phase), a silver iodochloride layer (phase) and a silver iodobromide layer (phase).
The silver halide grains contained in the silver halide emulsion for use in the present invention have an average grain size (the grain size herein means the diameter of the circle equivalent to the projected area of the grain, and the number average is taken as the average grain size) of preferably from 0.01 μm to 2 μm.
With respect to the distribution of sizes of these grains, so called monodisperse emulsion having a variation coefficient (the value obtained by dividing the standard deviation of the grain size distribution by the average grain size) of 20% or less, more preferably 15% or less, and further preferably 10% or less, is preferred. For obtaining a wide latitude, it is also preferred to blend the above-described monodisperse emulsions in the same layer or to form a multilayer structure using the monodisperse emulsions.
Various compounds or precursors thereof can be included in the silver halide emulsion for use in the present invention to prevent fogging from occurring or to stabilize photographic performance, during manufacture, storage or photographic processing of the photosensitive material. Specific examples of compounds useful for the above purposes are disclosed in JP-A-62-215272, pages 39 to 72, and they can be preferably used. In addition, 5-arylamino-1,2,3,4-thiatriazole compounds (the aryl residual group has at least one electron-attractive group) disclosed in European Patent No. 0447647 can also be preferably used.
In the present invention, a total amount of coated silver of the entire photographic constitutional layers is preferably 0.5 g/m2 or less (preferably in the range of 0.2 g/m2 to 0.5 g/m2), more preferably 0.45 g/m2 or less (preferably in the range of 0.2 g/m2 to 0.45 g/m2), and most preferably 0.4 g/m2 or less (preferably in the range of 0.2 g/m2 to 0.4 g/m2).
Further, in the present invention, in view of effects on restrain of a photosensitive material from fogging, it is preferable that a compound having a recurring unit represented by formula (X) shown below is incorporated in the photosensitive material.
In formula (X), R7 represents —OR, —SR or —N—R(—R′). R and R′ each independently represent a hydrogen atom, an alkyl group that may be substituted (preferably an alkyl group having 1 to 12 carbon atoms, more preferably an unsubstituted alkyl group, a hydroxyalkyl group, a sulfoalkyl group or a salt thereof, a carboxyalkyl group or a salt thereof), an aryl group that may be substituted (preferably an aryl group having 6 to 12 carbon atoms, more preferably an unsubstituted aryl group, or an aryl group substituted with a substituent selected from a sulfo group or a salt thereof, a carboxyl group or a salt thereof, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom), an aralkyl group that may be substituted, a cycloalkyl group that may be substituted, or a heterocyclic group that may be substituted. In addition, R and R′ may bond to each other, to form a saturated carbon ring, or a hetero ring composed of an (—O—)-containing alkylene group.
R8 and R9 each independently represent a hydrogen atom, or an alkyl group that may be substituted (preferably an alkyl group having 1 to 4 carbon atoms, more preferably an unsubstituted alkyl group, or an alkyl group substituted with a substituent, such as a hydroxyl group, a sulfo group or a salt thereof, a carboxyl group or a salt thereof).
Y1 and Y2 each independently represent a polymethylene group that may be substituted (preferably a polymethine group having 2 to 12 carbon atoms, more preferably an unsubstituted polymethine group, a polymethylene group substituted with an alkyl group having 1 to 4 carbon atoms), an arylene group that may be substituted (preferably an arylene group having 6 to 12 carbon atoms, more preferably an unsubstituted arylene group, or an arylene group substituted with a substituent selected from a sulfo group or a salt thereof, a carboxyl group or a salt thereof, an alkyl group having 1 to 4 carbon atoms, or a halogen atom), or a cycloalkylene group that may be substituted (preferably a cycloalkylene group having 3 to 12 carbon atoms). Z represents —O—, —SO2—, or —CH2—. p represents 0 or 1.
Each of the aforementioned groups in formula (X) is not necessary to be identical in each recurring unit, and further there is no particular restriction in regularity of sequence with respect to the recurring units. It is also preferable to use a compound containing by turns two kinds of diamine components, as described as specific examples of formula (I) in JP-B-4-32375.
The compound having a recurring unit represented by the aforementioned formula (X) is a compound containing a 1,3,5-triazine ring. The number of said recurring unit is preferably 2 or more. Both ends of the recurring units may bond to each other to form a ring. The compound having a recurring unit represented by formula (X) is explained from the aspect of a preparation method (synthesis method) of the compound.
A preparation method of the above compound is outlined below. The compound having a recurring unit represented by formula (X) can be obtained by a polymerization reaction between a 1,3,5-triazine compound represented by formula (XA) described below and a diamino compound represented by formula (XB) described below, or alternatively by a polymerization condensation reaction between a bis(halogeno-1,3,5-triazine) compound represented by formula (XC) described below and a diamino compound represented by formula (XB) described above.
In formula (XA), X21 represents a halogen atom (e.g., chlorine, bromine). R7 has the same meaning as that described in the aforementioned formula (X), with a preferable range being identical thereto.
H(R8—)N—(Y1-Z)p—Y2—N(—R9)H Formula (XB)
In formula (XB), R8, R9, Y1, Y2, Z and p each have the same meanings as in the aforementioned formula (X), with preferable ranges being identical thereto.
In formula (XC), X21 has the same meaning as that described in the aforementioned formula (XA); and R7, R8, R9, Y1, Y2, Z and p each have the same meanings as those in the aforementioned formula (X), with preferable ranges being identical thereto.
Halogeno-1,3,5-triazine compounds represented by the aforementioned formula (XA) or (XC) can be prepared according to, for example, the method of using cyanuric chloride as a starting material, as described in Journal of the American Chemical Society, Vol. 73, pp. 2981 to 2992 (1951).
The compounds having a recurring unit represented by formula (X) are explained in more detail below.
Examples of R7 in the aforementioned formula (X), and in formula (XA) or (XC) that represents a starting material, include the following groups.
Examples of the group —N(R8)—(Y1—)p—Y2—N(R9)— in the aforementioned formula (X) that represents the compound that is preferably used in the present invention, and in the aforementioned formulae (XB) and (XC) that each represent a starting material or a reagent for a polycondensation reaction, include the following groups.
Specifically describing a method of preparing the compound containing a recurring unit represented by the aforementioned formula (X) in the molecule, there are two general methods of the following (a) and (b):
The compounds containing a recurring unit represented by the aforementioned formula (X) may be those prepared by any of general methods of the aforementioned (a) and (b), or those obtained by other methods.
Specific examples of the compound containing a recurring unit represented by the aforementioned formula (X) are shown below. The number of the recurring unit is preferably 2 or more, more preferably in the range of from 2 to 20.
In the case where the compound containing a recurring unit represented by the aforementioned formula (X) is a chain polymer, said polymer has two end groups of X11 and X12. It is assumed that X11 is usually a halogen atom that is represented by X21 in the aforementioned formula (XA), or a hydroxyl group, and that X12 is a hydrogen atom or a group represented by said formula (XA) except for one X21 being omitted (another X21 is a halogen atom or a hydroxyl group like the above X11). The compound containing a recurring unit represented by the aforementioned formula (X) may have a certain distribution as to the number of recurring units containing a 1,3,5-triazine ring, or may contain impurities having a substituent bonded at an unintended site introduced during synthesis process (for example, those in which the aforementioned end group X11 is the same group as R7).
A photosensitive material can contain the compound having a recurring (repeating) unit represented by the formula (X), by the addition and mixing of the compound at any time point in the process of preparing the photosensitive material (for example, at the step of preparing a silver halide emulsion, or at the step of preparing a coating solution of the photosensitive material). In addition, any of a non-photosensitive layer and a photosensitive silver halide emulsion layer can contain the compound having a recurring unit represented by formula (X). Preferably, the said compound is contained in a photosensitive silver halide emulsion layer. In one preferable mode, the said compound is contained in a blue-light-sensitive silver halide emulsion layer. Further, the said compound may also be contained in two or more light-sensitive silver halide emulsion layers. The content of the said compound in the photosensitive material varies depending on its purposes, but generally it is preferably 0.001 mg to 100 mg, more preferably 0.01 mg to 20 mg, still more preferably 0.05 mg to 10 mg, per m2 of the light-sensitive material. Further, when containing the said compound in a silver halide emulsion layer, the amount to be added of the compound having a repeating unit represented by formula (X) is preferably 1 mg to 10 g, more preferably 5 mg to 5 g, and further preferably 10 mg to 2 g, per mol of the silver halide in the said layer.
Further, in order to enhance storability (storage stability) of the silver halide emulsion for use in the present invention, it is also preferred in the present invention to use hydroxamic acid derivatives described in JP-A-11-109576; cyclic ketones having a double bond adjacent to a carbonyl group, both ends of the double bond being substituted with an amino group or a hydroxyl group, as described in JP-A-11-327094 (particularly compounds represented by formula (S1); the description at paragraph Nos. 0036 to 0071 of JP-A-11-327094 is incorporated herein by reference); sulfo-substituted catecols and hydroquinones described in JP-A-11-143011 (for example, 4,5-dihydroxy-1,3-benzenedisulfonic acid, 2,5-dihydroxy-1,4-benzenedisulfonic acid, 3,4-dihydroxybenzenesulfonic acid, 2,3-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzenesulfonic acid, 3,4,5-trihydroxybenzenesulfonic acid, and salts of these acids); water-soluble reducing agents represented by formula (I), (II), or (III) of JP-A-11-102045.
Spectral sensitization can be carried out for the purpose of imparting spectral sensitivity in a desired light wavelength region to the photosensitive emulsion in each layer of the photosensitive material of the present invention.
Examples of spectral sensitizing dyes, which can be used in the photosensitive material of the present invention, for spectral sensitization of blue, green and red light regions include, for example, those disclosed by F. M. Harmer, in Heterocyclic Compounds—Cyanine Dyes and Related Compounds, John Wiley & Sons, New York, London (1964). Specific examples of compounds and spectral sensitization processes that can be preferably used in the present invention include those described in JP-A-62-215272, from page 22, right upper column to page 38. In addition, the spectral sensitizing dyes described in JP-A-3-123340 are very preferred as red-sensitive spectral sensitizing dyes for silver halide emulsion grains having a high silver chloride content, from the viewpoint of stability, adsorption strength, the temperature dependency of exposure, and the like.
The amount of these spectral sensitizing dyes to be added can be varied in a wide range depending on the occasion, and it is preferably in the range of 0.5×10−6 mole to 1.0×10−2 mole, more preferably in the range of 1.0×10−6 mole to 5.0×10−3 mole, per mole of silver halide.
The silver halide emulsions for use in the present invention are generally chemically sensitized. Chemical sensitization can be performed by utilizing a sulfur sensitization, represented by the addition of an unstable sulfur compound, noble metal sensitization represented by gold sensitization, and reduction sensitization, each singly or in combination thereof. Compounds that are preferably used for chemical sensitization include those described in JP-A-62-215272, from page 18, right lower column to page 22, right upper column. Of these, gold-sensitized silver halide emulsion are particularly preferred, since a change in photographic properties which occurs when scanning exposure with laser beams or the like is conducted, can be further reduced by gold sensitization.
In order to conduct gold sensitization to the silver halide emulsion to be used in the present invention, various inorganic gold compounds, gold (I) complexes having an inorganic ligand, and gold (I) compounds having an organic ligand may be used. Inorganic gold compounds, such as chloroauric acid or salts thereof; and gold (I) complexes having an inorganic ligand, such as dithiocyanato gold compounds (e.g., potassium dithiocyanatoaurate (I)), and dithiosulfato gold compounds (e.g., trisodium dithiosulfatoaurate (I)), are preferably used.
As the gold (I) compounds having an organic ligand, the bis gold (I) mesoionic heterocycles described in JP-A-4-267249, for example, gold (I) tetrafluoroborate bis(1,4,5-trimethyl-1,2,4-triazolium-3-thiolate), the organic mercapto gold (I) complexes described in JP-A-11-218870, for example, potassium bis(1-[3-(2-sulfonatobenzamido)phenyl]-5-mercaptotetrazole potassium salt) aurate (I) pentahydrate, and the gold (I) compound with a nitrogen compound anion coordinated therewith described in JP-A-4-268550, for example, gold (I) bis (1-methylhydantoinate) sodium salt tetrahydrate may be used. Also, the gold (I) thiolate compound described in U.S. Pat. No. 3,503,749, the gold compounds described in JP-A-8-69074, JP-A-8-69075 and JP-A-9-269554, and the compounds described in U.S. Pat. Nos. 5,620,841, 5,912,112, 5,620,841, 5,939,245, and 5,912,111 may be used.
The amount of these compounds to be added can be varied in a wide range depending on the occasion, and it is generally in the range of 5×10−7 mole to 5×10−3 mole, preferably in the range of 5×10−6 mole to 5×10−4 mole, per mole of silver halide.
The silver halide emulsion for use in the present invention is preferably subjected to gold sensitization using a colloidal gold sulfide. A method of producing the colloidal gold sulfide is described in, for example, Research Disclosure, No. 37154, Solid State Ionics, Vol. 79, pp. 60 to 66 (1995), and Compt. Rend. Hebt. Seances Acad. Sci. Sect. B, Vol. 263, p. 1328 (1966). Colloidal gold sulfide having various grain sizes are applicable, and even those having a grain diameter of 50 nm or less are also usable. The amount of these compounds to be added can be varied in a wide range depending on the occasion, and it is generally in the range of 5×10−7 mol to 5×10−3 mol, preferably in the range of 5×10−6 mol to 5×10−4 mol, in terms of gold atom, per mol of silver halide.
In the present invention, gold sensitization may be used in combination with other sensitizing methods, for example, sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, or noble metal sensitization using a noble metal compound other than gold compounds.
The photosensitive material of the present invention preferably contains, in their hydrophilic colloid layers, dyes (particularly oxonole dyes and cyanine dyes) that can be discolored by processing, as described in European Patent No. 0337490 A2, pages 27 to 76, in order to prevent irradiation or halation or to enhance, for example, safelight safety (immunity). Further, dyes described in European Patent No. 0819977 are also preferably used in the present invention. Among these water-soluble dyes, some deteriorate color differentiation (separation) or safelight safety when used in an increased amount. Preferable examples of the dye which can be used and which does not deteriorate color separation include water-soluble dyes described in JP-A-5-127324, JP-A-5-127325 and JP-A-5-216185.
In the present invention, it is possible to use a colored layer which can be discolored during processing, in place of the water-soluble dye, or in combination with the water-soluble dye. The colored layer that can be discolored with a processing, to be used, may contact with a photosensitive emulsion layer directly, or indirectly through an interlayer containing an agent for preventing color-mixing during processing, such as gelatin and hydroquinone. The colored layer is preferably provided as a lower layer (closer to a support) with respect to the emulsion layer which develops the same primary color as the color of the colored layer. It is possible to provide colored layers independently, each corresponding to respective primary colors. Alternatively, only one layer selected from them may be provided. In addition, it is possible to provide a colored layer subjected to coloring so as to match a plurality of primary-color regions. About the optical reflection density of the colored layer, it is preferred that, at the wavelength which provides the highest optical density in a range of wavelengths used for exposure (a visible light region from 400 nm to 700 nm for an ordinary printer exposure, and the wavelength of the light generated from the light source in the case of scanning exposure), the optical density is within the range of 0.2 to 3.0, more preferably 0.5 to 2.5, and particularly preferably 0.8 to 2.0.
The colored layer described above may be formed by a known method. For example, there are a method in which a dye in a state of a dispersion of solid fine-particles is incorporated in a hydrophilic colloid layer, as described in JP-A-2-282244, from page 3, upper right column to page 8, and JP-A-3-7931, from page 3, upper right column to page 11, left under column; a method in which an anionic dye is mordanted in a cationic polymer, a method in which a dye is adsorbed onto fine grains of silver halide or the like and fixed in the layer, and a method in which a colloidal silver is used as described in JP-A-1-239544. As to a method of dispersing fine-powder of a dye in solid state, for example, JP-A-2-308244, pages 4 to 13 describes a method in which fine particles of dye which is at least substantially water-insoluble at the pH of 6 or less, but at least substantially water-soluble at the pH of 8 or more, are incorporated. The method of mordanting anionic dyes in a cationic polymer is described, for example, in JP-A-2-84637, pages 18 to 26. U.S. Pat. Nos. 2,688,601 and 3,459,563 disclose a method of preparing a colloidal silver for use as a light absorber. Among these methods, preferred are the methods of incorporating fine particles of dye and of using a colloidal silver.
When the present invention is applied to a color paper, the color photographic printing paper preferably has at least one yellow color-forming silver halide emulsion layer, at least one magenta color-forming silver halide emulsion layer, and at least one cyan color-forming silver halide emulsion layer, on a support. Generally, these silver halide emulsion layers are in the order, from the support, of the yellow color-forming silver halide emulsion layer, the magenta color-forming silver halide emulsion layer, and the cyan color-forming silver halide emulsion layer.
However, another layer arrangement which is different from the above, may be adopted.
In the photosensitive material of the present invention, a yellow coupler-containing silver halide emulsion layer may be provided at any position on a support. In the case where silver halide tabular grains are contained in the yellow coupler-containing layer, it is preferable that the yellow coupler-containing layer is positioned more apart from the support than at least one of a magenta coupler-containing silver halide emulsion layer and a cyan coupler-containing silver halide emulsion layer. Further, it is preferable that the yellow coupler-containing silver halide emulsion layer is positioned most apart from the support of other silver halide emulsion layers, from the viewpoint of color-development acceleration, desilvering acceleration, and reduction in a residual color due to a sensitizing dye. Further, it is preferable that the cyan coupler-containing silver halide emulsion layer is provided in the middle of other silver halide emulsion layers, from the viewpoint of reduction in blix fading. On the other hand, it is preferable that the cyan coupler-containing silver halide emulsion layer is the lowest layer, from the viewpoint of reduction in light fading. Further, each of a yellow-color-forming layer, a magenta-color-forming layer and a cyan-color-forming layer may be composed of two or three layers. It is also preferable that a color-forming layer is formed by providing a silver halide emulsion-free layer containing a coupler in adjacent to a silver halide emulsion layer, as described in, for example, JP-A-4-75055, JP-A-9-114035, JP-A-10-246940, and U.S. Pat. No. 5,576,159.
For example, as a photographic support (base), a transmissive type support or a reflective type support may be used. As the transmissive type support, it is preferred to use transparent supports, such as a cellulose nitrate film, and a transparent film of polyethyleneterephthalate, a cellulose triacetate film, or a polyester of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG), or a polyester of NDCA, terephthalic acid and EG, provided thereon with an information-recording layer such as a magnetic layer. In the present invention, a reflective support (reflective-type support) is preferable. As the reflective type support, it is especially preferable to use a reflective support having a substrate laminated thereon with a plurality of polyethylene layers or polyester layers (water-proof resin layers or laminate layers), at least one of which contains a white pigment such as titanium oxide.
In the present invention, as the above-described reflective support and silver halide emulsion, as well as the different kinds of metal ions to be doped in the silver halide grains, the storage stabilizers or antifogging agents of the silver halide emulsion, the methods of chemical sensitization (sensitizers), the methods of spectral sensitization (spectral sensitizers), the cyan, magenta, and yellow couplers and the emulsifying and dispersing methods thereof, the dye image stability-improving agents (stain inhibitors and discoloration inhibitors), the dyes (colored layers), the kinds of gelatin, the layer structure of the photosensitive material, and the film pH of the photosensitive material, those described in the patent publications as shown in the following table are particularly preferably used in the present invention.
As cyan, magenta and yellow couplers which can be additionally used in the present invention, in addition to the above mentioned ones, those disclosed in JP-A-62-215272, page 91, right upper column, line 4 to page 121, left upper column, line 6, JP-A-2-33144, page 3, right upper column, line 14 to page 18, left upper column, bottom line, and page 30, right upper column, line 6 to page 35, right under column, line 11, European Patent No. 0355,660 (A2), page 4, lines 15 to 27, page 5, line 30 to page 28, bottom line, page 45, lines 29 to 31, page 47, line 23 to page 63, line 50, are also advantageously used.
Further, it is preferred in the present invention to add compounds represented by formula (II) or (III) in WO 98/33760 and compounds represented by formula (D) described in JP-A-10-221825.
As the cyan dye-forming coupler (hereinafter also referred to as “cyan coupler”) which can be used in the present invention, pyrrolotriazole-series couplers are preferably used, and more specifically, couplers represented by any of formulae (I) and (II) in JP-A-5-313324 and couplers represented by formula (I) in JP-A-6-347960 are preferred. Exemplified couplers described in these publications are particularly preferred. Further, phenol-series or naphthol-series cyan couplers are also preferred. For example, cyan couplers represented by formula (ADF) described in JP-A-10-333297 are preferred. As preferable cyan couplers other than the foregoing cyan couplers, there are pyrroloazole-type cyan couplers described in European Patent Nos. 0 488 248 and 0 491 197 (A1), 2,5-diacylamino phenol couplers described in U.S. Pat. No. 5,888,716, pyrazoloazole-type cyan couplers having an electron-withdrawing group or a group bonding via hydrogen bond at the 6-position, as described in U.S. Pat. Nos. 4,873,183 and 4,916,051, and particularly pyrazoloazole-type cyan couplers having a carbamoyl group at the 6-position, as described in JP-A-8-171185, JP-A-8-311360 and JP-A-8-339060.
In addition, the cyan dye-forming coupler for use in the present invention can also be a diphenylimidazole-series cyan coupler described in JP-A-2-33144; as well as a 3-hydroxypyridine-series cyan coupler (particularly a 2-equivalent coupler formed by allowing a 4-equivalent coupler of a coupler (42), to have a chlorine splitting-off group, and couplers (6) and (9), enumerated as specific examples are particularly preferable) described in EP 0333185 A2; a cyclic active methylene-series cyan coupler (particularly couplers 3, 8, and 34 enumerated as specific examples are particularly preferable) described in JP-A-64-32260; a pyrrolopyrozole-type cyan coupler described in European Patent No. 0456226 A1; and a pyrroloimidazole-type cyan coupler described in European Patent No. 0484909.
Among these cyan couplers, pyrroloazole-series cyan couplers represented by formula (I) described in JP-A-11-282138 are particularly preferred. The descriptions of the paragraph Nos. 0012 to 0059 including exemplified cyan couplers (1) to (47) of the above JP-A-11-282138 can be entirely applied to the present invention, and therefore they are preferably incorporated herein by reference.
As the magenta dye-forming coupler (which may be referred to simply as a “magenta coupler” hereinafter) that can be used in the present invention, use can be made of any of 5-pyrazolone-series magenta couplers and pyrazoloazole-series magenta couplers such as those described in the above-mentioned patent publications in the above table. Among these, preferred are pyrazolotriazole couplers in which a secondary or tertiary alkyl group is directly bonded to the 2-, 3- or 6-position of the pyrazolotriazole ring, such as those described in JP-A-61-65245; pyrazoloazole couplers having a sulfonamido group in its molecule, such as those described in JP-A-61-65246; pyrazoloazole couplers having an alkoxyphenylsulfonamido ballasting group, such as those described in JP-A-61-147254; and pyrazoloazole couplers having an alkoxy or aryloxy group at the 6-position, such as those described in European Patent Nos. 0226849 A2 and 0294785 A, in view of the hue and stability of image to be formed therefrom and color-forming property of the couplers. Particularly as the magenta coupler, the pyrazoloazole couplers represented by formula (M-I) described in JP-A-8-122984 are preferred. The description of paragraph Nos. 0009 to 0026 of the above JP-A-8-122984 is applied to the present invention and herein incorporated by reference. In addition, the pyrazoloazole couplers having a steric hindrance group at both of the 3- and the 6-positions, as described in European Patent (EP) Nos.854,384 and 884,640 are also preferably used.
The yellow dye-forming coupler (herein also referred to simply as “yellow coupler”) that can be used in the present invention, is not limited in particular, and, for example, those described in the above table can be used as the yellow dye-forming coupler. It is preferable, in the present invention, that the yellow dye-forming coupler represented by formula (I) is used singly or in combination with other yellow dye-forming coupler(s). As the above other yellow dye-forming coupler to be used in combination, use can be preferably made of acylacetamide-type yellow couplers in which the acyl group has a 3-membered to 5-membered cyclic structure, as described in European Patent No. 0 447 969 A1; malondianilide-type yellow couplers having a cyclic structure, as described in European Patent No. 0482552 A1; pyrrole-2 or 3-yl- or indole-2 or 3-yl-carbonylacetoanilide-series couplers, as described in European Patent Nos. 953 870 A1, 953 871 A1, 953 872 A1, 953 873 A1, 953 874 A1 and 953 875 A1; acylacetamide-type yellow couplers having a dioxane structure, as described in U.S. Pat. No. 5,118,599; and acetamide-type yellow couplers that is substituted with a heterocycle at the α-position thereof, as described in U.S. Pat. No. 5,455,149 and Europan Patent No. 1 246 006, in addition to the compounds described in the above-mentioned table. Above all, acylacetamide-type yellow couplers in which the acyl group is a 1-alkylcyclopropane-1-carbonyl group, malondianilide-type yellow couplers in which one of the anilido groups constitutes an indoline ring, and acetamide-type yellow couplers that is substituted with a heterocycle at the α-position thereof, are especially preferably used. These couplers may be used singly or in combination.
It is preferred that couplers for use in the present invention, are pregnated into a loadable latex polymer (as described, for example, in U.S. Pat. No. 4,203,716) in the presence (or absence) of the high-boiling-point organic solvent described in the foregoing table, or they are dissolved in the presence (or absence) of the foregoing high-boiling-point organic solvent with a polymer insoluble in water but soluble in an organic solvent, and then emulsified and dispersed into an aqueous hydrophilic colloid solution. Examples of the water-insoluble but organic solvent-soluble polymer which can be preferably used, include the homo-polymers and co-polymers as disclosed in U.S. Pat. No.4,857,449, from column 7 to column 15 and WO 88/00723, from page 12 to page 30. The use of methacrylate-series or acrylamide-series polymers, especially acrylamide-series polymers are more preferable in view of color-image stabilization and the like.
In the present invention, known color mixing-inhibitors may be used. Among these compounds, those described in the following patent publications are preferred.
For example, high molecular weight redox compounds described in JP-A-5-333501; phenidone- or hydrazine-series compounds as described in, for example, WO 98/33760 and U.S. Pat. No. 4,923,787; and white couplers as described in, for example, JP-A-5-249637, JP-A-10-282615 and German Patent Publication No. 19629142 A1, may be used. Particularly, in order to accelerate developing speed by increasing the pH of a developing solution, redox compounds described in, for example, German Patent No. 19,618,786 A1, European Patent Nos. 0,839,623 A1 and 0,842,975 A1, German Patent No. 19,806,846 A1 and French Patent No. 2,760,460 A1, are also preferably used.
In the present invention, as an ultraviolet absorber, it is preferred to use compounds having a high molar extinction coefficient and a triazine skeleton. For example, those described in the following patent publications can be used. These compounds are preferably added to the photosensitive layer or/and the light-nonsensitive layer. For example, use can be made of those described, in JP-A-46-3335, JP-A-55-152776, JP-A-5-197074, JP-A-5-232630, JP-A-5-307232, JP-A-6-211813, JP-A-8-53427, JP-A-8-234364, JP-A-8-239368, JP-A-9-31067, JP-A-10-115898, JP-A-10-147577, JP-A-10-182621, German Patent No. 19,739,797A, European Patent No. 0,711,804 A and JP-T-8-501291 (“JP-T” means searched and published International patent application), and the like.
As the binder or protective colloid, which can be used in the photosensitive material according to the present invention, gelatin is used advantageously, but another hydrophilic colloid can be used singly or in combination with gelatin. It is preferable for the gelatin that the content of heavy metals, such as Fe, Cu, Zn and Mn, included as impurities, be reduced to 5 ppm or below, more preferably 3 ppm or below. Further, the amount of calcium contained in the photosensitive material is preferably 20 mg/m2 or less, more preferably 10 mg/m2 or less, and most preferably 5 mg/m2 or less.
In the present invention, it is preferred to add an antibacterial (fungi-preventing) agent and antimold agent, as described in JP-A-63-271247, in order to destroy various kinds of molds and bacteria which propagate in a hydrophilic colloid layer and deteriorate the image. Further, the pH of the coated film of the photosensitive material is preferably in the range of 4.0 to 7.0, more preferably in the range of 4.0 to 6.5.
In the present invention, a surface-active agent may be added to the photosensitive material, in view of improvement in coating-stability, prevention of static electricity from being occurred, and adjustment of the charge amount. As the surface-active agent, there are anionic, cationic, betaine and nonionic surfactants. Examples thereof include those described in JP-A-5-333492. As the surface-active agent for use in the present invention, a fluorine-containing surface-active agent is also preferred. The fluorine-containing surface-active agent may be used singly or in combination with known another surface-active agent. The fluorine-containing surfactant is preferably used in combination with known another surface-active agent. The amount of the surface-active agent to be added to the photosensitive material is not particularly limited, but generally in the range of 1×10−5 to 1 g/m2, preferably in the range of 1×10−4 to 1×10−1 g/m2, and more preferably in the range of 1×10−3 to 1×10−2 g/m2.
The photosensitive material of the present invention can form an image, by an exposure step in which the photosensitive material is irradiated with light according to image information, and a development step in which the photosensitive material irradiated with light is processed to develop an image.
The photosensitive material of the present invention can preferably be used, in a scanning exposure system using a cathode ray tube (CRT), in addition to the printing system using a usual negative printer. The cathode ray tube exposure apparatus is simpler and more compact, and therefore less expensive than an apparatus using a laser. Further, optical axis and color (hue) can easily be adjusted. In a cathode ray tube which is used for image-wise exposure, various light-emitting materials which emit a light in the spectral region, are used as occasion demands. For example, any one of red-light-emitting materials, green-light-emitting materials, blue-light-emitting materials, or a mixture of two or more of these light-emitting materials may be used. The spectral regions are not limited to the above red, green and blue, and fluorophoroes which can emit a light in a region of yellow, orange, purple or infrared can be used. Particularly, a cathode ray tube which emits a white light by means of a mixture of these light-emitting materials, is often used.
In the case where the photosensitive material has a plurality of photosensitive layers each having different spectral sensitivity distribution from each other and also the cathode ray tube has a fluorescent substance which emits light in a plurality of spectral regions, exposure to a plurality of colors may be carried out at the same time. Namely, a plurality of color image signals may be input into a cathode ray tube, to allow light to be emitted from the surface of the tube. Alternatively, a method in which an image signal of each of colors is successively input and light of each of colors is emitted in order, and then exposure is carried out through a film capable of cutting a color other than the emitted color, i.e., a surface successive exposure, may be used. Generally, among these methods, the surface successive exposure is preferred from the viewpoint of high quality enhancement, because a cathode ray tube having a high resolving power can be used.
The photosensitive material of the present invention can preferably be used in the digital scanning exposure system using monochromatic high density light, such as a gas laser, a light-emitting diode, a semiconductor laser, a second harmonic generation light source (SHG) comprising a combination of nonlinear optical crystal with a semiconductor laser or a solid state laser using a semiconductor laser as an excitation light source. It is preferred to use a semiconductor laser, or a second harmonic generation light source (SHG) comprising a combination of nonlinear optical crystal with a solid state laser or a semiconductor laser, to make a system more compact and inexpensive. In particular, to design a compact and inexpensive apparatus having a longer duration of life and high stability, use of a semiconductor laser is preferable; and it is preferred that at least one of exposure light sources would be a semiconductor laser.
When such a scanning exposure light source is used, the maximum spectral sensitivity wavelength of the photosensitive material of the present invention can be arbitrarily set up according to the wavelength of a scanning exposure light source to be used. Since oscillation wavelength of a laser can be made half, using a SHG light source (a second harmonic generation light source) obtainable by a combination of a nonlinear optical crystal with a semiconductor laser or a solid state laser using a semiconductor as an excitation light source, blue light and green light can be obtained. Accordingly, it is possible to have the spectral sensitivity maximum of a photosensitive material in normal three wavelength regions of blue, green and red. The exposure time in such a scanning exposure is defined as the time necessary to expose the size of the picture element (pixel) with the density of the picture element being 400 dpi, and preferred exposure time is 1×10−4 sec or less and more preferably 1×10−6 sec or less. Particularly preferably, the exposure is carried out by scanning exposure, wherein the exposure time is 1×10−8 to 1×10−4 sec per picture element and adjacent rasters are overlapped (the overlap between rasters is preferably in the range of from ⅛ to ⅞, more preferably in the range of from ⅕ to ⅘), because improvement is made with respect to the reciprocity law failure. Preferable scanning exposure systems that can be applied to the present invention are described in detail in the aforementioned table.
The silver halide color photographic photosensitive material of the present invention can be preferably used in combination with the exposure and development systems described, for example, in the following known literatures. Example of the development system include the automatic print and development system described in JP-A-10-333253, the photosensitive material conveying apparatus described in JP-A-2000-10206, a recording system including the image reading apparatus, as described in JP-A-11-215312, an exposure systems with the color image recording method, as described in JP-A-11-88619 and JP-A-10-202950, a digital photo print system including the remote diagnosis method, as described in JP-A-10-210206, and a photo print system including the image recording apparatus, as described in JP-A-2000-310822.
The preferred scanning exposure methods which can be applied to the present invention are described in detail in the publications in the above table 1.
It is preferred to use a band stop filter, as described in U.S. Pat. No.4,880,726, when the photographic material of the present invention is subjected to exposure with a printer. Color mixing of light can be excluded and color reproducibility is remarkably improved by the above means.
In the present invention, a yellow microdot pattern may be previously formed by pre-exposure before giving an image information, to thereby perform a copy restraint, as described in European Patent Nos. 0789270 A1 and 0789480 A1.
The photosensitive material of the present invention is particularly suitable for a silver halide color photographic light-sensitive material having a silver halide emulsion layer containing a dye-forming coupler that forms a dye upon a coupling reaction with an oxidation product of an aromatic primary amine color developing agent.
Further, in order to process the photosensitive material of the present invention, processing materials and processing methods described in JP-A-2-207250, page 26, right lower column, line 1, to page 34, right upper column, line 9, and in JP-A-4-97355, page 5, left upper column, line 17, to page 18, right lower column, line 20, can be preferably applied, and these are herein preferably incorporated by reference. Further, as the preservative that can be used for this developing solution, compounds described in the patent publications listed in the above Table are preferably used.
The present invention is also preferably applied to a photosensitive material having rapid processing suitability. In the case of conducting rapid processing, the color-developing time is preferably 60 sec or less, more preferably from 50 sec to 6 sec, further preferably from 30 sec to 6 sec, and most preferably from 20 sec to 10 sec. Likewise, the blix time is preferably 60 sec or less, more preferably from 50 sec to 6 sec, further preferably from 30 sec to 6 sec, and most preferably from 20 sec to 10 sec. Further, the washing or stabilizing time is preferably 150 sec or less, and more preferably from 130 sec to 6 sec.
Herein, the term “color-developing time” as used herein means a period of time required from the beginning of dipping a photosensitive material into a color-developing solution until the photosensitive material is dipped into a blix solution in the subsequent processing step. In the case where a processing is carried out using, for example, an autoprocessor, the color-developing time is the sum total of a time in which a photosensitive material has been dipped in a color-developing solution (so-called “time in the solution”) and a time in which the photosensitive material has left the solution and been conveyed in air toward a bleach-fixing bath in the step subsequent to color development (so-called “time in the air”). Likewise, the term “blix time” as used herein means a period of time required from the beginning of dipping the photosensitive material into a blix solution until the photosensitive material is dipped into a washing bath or a stabilizing bath in the subsequent processing step. Further, the term “washing or stabilizing time” as used herein means a period of time required from the beginning of dipping the photosensitive material into a washing solution or a stabilizing solution until the end of the dipping toward a drying step (so-called “time in the solution”).
Examples of a development method applicable to the photosensitive material of the present invention after exposure, include a conventional wet system, such as a development method using a developing solution containing an alkali agent and a developing agent, and a development method wherein a developing agent is incorporated in the photosensitive material and an activator solution, e.g., a developing agent-free alkaline solution is employed for the development, as well as a heat development system using no processing solution. In particular, the activator method is preferred to the other methods, because the processing solutions contain no developing agent, thereby it enables easy management and handling of the processing solutions and reduction in waste disposal load to make for environmental preservation.
The preferable developing agents or their precursors incorporated in the photosensitive materials in the case of adopting the activator method include the hydrazine-type compounds described in, for example, JP-A-8-234388, JP-A-9-152686, JP-A-9-152693, JP-A-9-211814 and JP-A-9-160193.
Further, the processing method in which the photographic material reduced in the amount of silver to be applied undergoes the image amplification processing using hydrogen peroxide (intensification processing), can be employed preferably. In particular, it is preferable to apply this processing method to the activator method. Specifically, the image-forming methods utilizing an activator solution containing hydrogen peroxide, as disclosed in JP-A-8-297354 and JP-A-9-152695 can be preferably used. Although the processing with an activator solution is generally followed by a desilvering step in the activator method, the desilvering step can be omitted in the case of applying the image amplification processing method to photographic materials having a reduced silver amount. In such a case, washing or stabilization processing can follow the processing with an activator solution to result in simplification of the processing process. On the other hand, when the system of reading the image information from photographic materials by means of a scanner or the like is employed, the processing form requiring no desilvering step can be applied, even if the photographic materials are those having a high silver amount, such as photographic materials for shooting.
As the processing materials and processing methods of the activator solution, desilvering solution (bleach/fixing solution), washing solution and stabilizing solution, which can be used in the present invention, known ones can be used. Preferably, those described in Research Disclosure, Item 36544, pp. 536-541 (September 1994), and JP-A-8-234388 can be used in the present invention.
According to the present invention, it is possible to provide a photosensitive material, in which a color image is not discolored for a long time, and that has high storability. Further, according to the present invention, it is possible to provide a photosensitive material, in which a photographic additive that exhibits a sufficient effect to prevent a dye image from fading or discoloring is contained, and by which material a sufficient dye density is obtained even in a short development processing time.
According to the present invention, it is possible to provide a silver halide color photographic photosensitive material and an image-forming method that are excellent in rapid processing suitability. Further, it is possible to provide a silver halide color photographic photosensitive material that is excellent in color-forming property, color reproduction, whiteness, and image fastness after processing. Furthermore, it is possible to provide an image-forming method that is excellent in processing stability when processed with a running solution.
The present invention will be described in more detail based on the following examples, but the present invention is not limited thereto.
(Preparation of Blue-sensitive Layer Emulsion B-H)
To deionized and distilled water containing a deionized gelatin, silver nitrate and sodium chloride were added and mixed, with stirring, according to a double jet method, to prepare high silver chloride cubic grains. During a process of the preparation, potassium bromide was added at the step of from 60% to 95% addition of the entire silver nitrate amount, so that the potassium bromide amount became 1.5 mol % per mol of the finished silver halide. At the step of from 70% to 90% addition of the entire silver nitrate amount, K4[Fe(CN)6], K4[IrCl6] and K2[RhBr5(H2O)] were added. Further, K2[IrCl5(H2O)] and K[IrCl4(H2O)2] were added at the step of from 75% to 98% addition of the entire silver nitrate amount. Furthermore, a potassium iodide solution was added and mixed with vigorous stirring at the step of completion of 90% addition of the entire silver nitrate amount, so that the iodine amount became 0.27 mol % per mol of the finished silver halide. The obtained emulsion grains were monodisperse cubic silver iodobromochloride grains having a side length of 0.54 μm and a variation coefficient of 8.5%. After being subjected to a flocculation desalting treatment, the following were added to the resulting emulsion: gelatin, compounds (Ab-1), (Ab-2) and (Ab-3), and calcium nitrate, to carry out re-dispersion.
The thus re-dispersed emulsion was dissolved at 40° C., and sensitizing dye S-1, sensitizing dye S-2 and sensitizing dye S-3 were added thereto, for optimal spectral sensitization. Then, the resulting emulsion was ripened by adding sodium benzene thiosulfonate, triethylthiourea as a sulfur sensitizer, and Compound-4 as a gold sensitizer, for optimal chemical sensitization. Further, 1-(5-methylureidophenyl)-5-mercaptotetrazole; Compound-5; a mixture whose major components were a compound having two recurring units represented by Compound-6 (in which n was 2), a compound having three recurring units represented by Compound-7, in which both ends of this compound each were a hydroxyl group; a compound having three recurring units represented by Compound-6; Compound-8; and potassium bromide were added, to complete chemical sensitization. The thus-obtained emulsion was referred to as Emulsion B-H.
(Preparation of Blue-sensitive Layer Emulsion B-L)
Emulsion grains were prepared in the same manner as in the preparation of emulsion B-H, except that the temperature and the addition rate at the step of mixing silver nitrate and sodium chloride by simultaneous addition were changed, and that the amounts of respective metal complexes that were to be added in the course of the addition of silver nitrate and sodium chloride were changed. The thus-obtained emulsion grains were monodisperse cubic silver iodobromochloride grains having a side length of 0.34 μm and a variation coefficient of 9.5%. After re-dispersion of this emulsion, Emulsion B-L was prepared in the same manner as emulsion B-H, except that the amounts of various compounds to be added in the preparation of Emulsion B-H were changed.
(Preparation of Green-sensitive Layer Emulsion M-H)
Emulsion grains were prepared in the same manner as in the preparation of the above-described Blue-sensitive emulsion. The thus-obtained emulsion grains were monodisperse cubic silver iodobromochloride grains having a side length of 0.48 μm and a variation coefficient of 8.0%. The emulsion was subjected to a flocculation desalting process, followed by re-dispersion.
The emulsion was dissolved at 40° C., and sodium benzene thiosulfate, p-glutaramidophenyldisulfide, sodium thiosulfate pentahydrate as a sulfur sensitizer, and (bis(1,4,5-trimethyl-1,2,4-triazolium-3-thiorato)aurate (I).tetrafluoroborate) as a gold sensitizer were added, and the emulsion was ripened for optimal chemical sensitization. Thereafter, 1-(3-acetoamidophenyl)-5-mercaptotetrazole, 1-(5-methylureidophenyl)-5-mercaptotetrazole, Compound-5, Compound-8, and potassium bromide were added. Further, in a midway of the emulsion preparation step, Dye-1, Dye-2, Dye-3, and Dye-4 were added as sensitizing dyes, to conduct spectral sensitization. The thus-obtained emulsion was referred to as Emulsion M-H.
(Preparation of Green-sensitive Layer Emulsion M-L)
Emulsion grains were prepared in the same manner as in the preparation of emulsion M-H, except that the temperature and the addition rate at the step of mixing silver nitrate and sodium chloride by simultaneous addition were changed, and that the amounts of respective metal complexes that were to be added in the course of the addition of silver nitrate and sodium chloride were changed. The thus-obtained emulsion grains were monodisperse cubic silver iodobromochloride grains having a side length of 0.25 μm and a variation coefficient of 9.8%. After re-dispersion of this emulsion, Emulsion M-L was prepared in the same manner as emulsion M-H, except that the amount of various compounds to be added in the preparation of Emulsion M-H were changed.
(Preparation of Red-sensitive Layer Emulsion C-H)
To deionized and distilled water containing a deionized gelatin, silver nitrate and sodium chloride were added and mixed, with stirring, according to a double jet method, to prepare high silver chloride cubic grains. During a process of the preparation, potassium bromide was added at the step of from 65% to 90% addition of the entire silver nitrate amount, so that the potassium bromide amount became 2.5 mol % per mol of the finished silver halide. At the step of from 60% to 85% addition of the entire silver nitrate amount, K4[Ru(CN)6], K2[Ir(5-methylthiazole)Cl5], Cs2[RuCl5(NO)], and Cs2[OsCl5(NO)] were added. Further, K2[IrCl5(H2O)] was added at the step of from 75% to 98% addition of the entire silver nitrate amount. Furthermore, a potassium iodide aqueous solution was added and mixed with vigorous stirring at the step of completion of 88% addition of the entire silver nitrate amount, so that the iodine amount became 0.15 mol % per mol of the finished silver halide. The obtained emulsion grains were monodisperse cubic silver iodobromochloride grains having a side length of 0.39 μm and a variation coefficient of 10%. The resulting emulsion was subjected to a flocculation desalting treatment and re-dispersing treatment in the same manner as described in the above.
The emulsion was dissolved at 40° C., and Sensitizing dye Dye-5, Compound-9, triethylthiourea as a sulfur sensitizer, and Compound-4 as a gold sensitizer were added, and the emulsion was ripened for optimal chemical sensitization. Thereafter, 1-(3-acetoamidophenyl)-5-mercaptotetrazole, 1-(5-methylureidophenyl)-5-mercaptotetrazole, Compound-5, Compound-8, and potassium bromide were added. The thus-obtained emulsion was referred to as Emulsion C-H.
(Preparation of Red-sensitive Layer Emulsion C-L)
Emulsion grains were prepared in the same manner as in the preparation of emulsion C-H, except that the temperature and the addition rate at the step of mixing silver nitrate and sodium chloride by simultaneous addition were changed, and that the amounts of respective metal complexes that were to be added in the course of the addition of silver nitrate and sodium chloride were changed. The thus-obtained emulsion grains were monodisperse cubic silver iodobromochloride grains having a side length of 0.29 μm and a variation coefficient of 9.9%. After this emulsion was subjected to a flocculation desalting treatment and re-dispersion, Emulsion C-L was prepared in the same manner as emulsion C-H, except that the amounts of various compounds to be added in the preparation of Emulsion C-H were changed.
(Preparation of a Coating Solution for the First Layer)
Into 17 g of a solvent (Solv-4), 17 g of a solvent (Solv-9), and 60 ml of ethyl acetate were dissolved 34.0 g of a yellow coupler (Examplified Compound (6)). This solution was emulsified and dispersed in 270 g of a 20 mass % aqueous gelatin solution containing 4 g of sodium dodecylbenzenesulfonate with a high-speed stirring emulsifier (dissolver). Water was added thereto, to prepare 900 g of Emulsified Dispersion A.
Separately, the above-described Emulsified Dispersion A and the above-described Emulsions B-H and B-L were mixed and dissolved, to prepare a coating solution for the first layer having the composition shown below. The coating amount of the emulsion is in terms of silver.
The coating solutions for the second to seventh layers were prepared in the similar manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt (H-1), (H-2), and (H-3) were used. Further, (Ab-1), (Ab-2), and (Ab-3) were added to each layer, so that their total amounts would be 15.0 mg/m2, 60.0 mg/m2, and 5.0 mg/m2, respectively.
Further, 1-(3-methylureidophenyl)-5-mercaptotetrazole was added to the second layer, the fourth layer, and the sixth layer, in amounts of 0.2 mg/m2, 0.2 mg/m2, and 0.6 mg/m2, respectively.
Further, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer, in amounts of 1×10−4 mol and 2×10−4 mol, respectively, per mol of the silver halide.
Further, to the red-sensitive emulsion layer, was added a copolymer latex of methacrylic acid and butyl acrylate (1:1 in mass ratio; average molecular weight, 200,000 to 400,000) in an amount of 0.05 g/m2.
Further, disodium catecol-3,5-disulfonate was added to the second layer, the fourth layer and the sixth layer, so that respective amounts would be 6 mg/m2, 6 mg/m2 and 18 mg/m2.
Further, to each layer, sodium polystyrene sulfonate was optionally added to adjust viscosity of the coating solutions.
Further, in order to prevent irradiation, the following dyes (coating amounts are shown in parentheses) were added.
(Layer Constitution)
The composition of each layer is shown below. The numbers show coating amounts (g/m2). With respect to silver halide emulsions, the coating amount is in terms of silver.
Support
Polyethylene resin-laminated paper
[The polyethylene resin on the first layer side contained a white pigment (TiO2, content of 16 mass %; ZnO, content of 4 mass %), a fluorescent whitening agent (4,4′-bis(5-methylbenzoxazolyl)stilbene, content of 0.03 mass %) and a bluish dye (ultramarine, content of 0.33 mass %). The amount of the polyethylene resin was 29.2 g/m2]
Samples 1102 to 1110 were prepared in the same manner as in the thus-prepared Sample 1101, except that the composition of the first layer was changed as shown below.
Samples 1102 to 1110 were prepared in the same manner as Sample 1101, except for further adding the compound, as shown in Table 2, to the first layer. The alkenylcarbonyl-series compound was added to the first layer in an amount of 0.15 g/m2. When adding these compounds, each sample was prepared in such a reduced amount of solvent that oil-soluble contents in the first layer would be a prescribed amount.
Processing Process
Each of the above photosensitive materials was processed into a form of a roll with a width of 127 mm, and the resultant samples were exposed with a standard photographic image, by using Digital Mini Lab FRONTIER 330 (trade name, manufactured by Fuji Photo Film Co., Ltd.). Thereafter, a continuous processing (running test) was performed until the volume of the color-developer replenisher used in the following processing step became twice the volume of the color-developer tank. The following processing and test were conducted, using this running processing solution.
The composition of each processing solution was as follows.
After being coated, the photosensitive material Samples 1101 to 1110 were kept for 10 days under conditions of 25° C. and 55% relative humidity, followed by the evaluation set forth below.
(Evaluation: Fastness to Light)
Each sample was subjected to color-development processing in the above-described processing process.
As light sources, a semiconductor laser was used to obtain a light source at 688 nm (R light), a semiconductor laser was combined with SHG to obtain a light source at 532 nm (G light), and a light source at 473 nm (B light). The quantity of light of R light was modulated with using an outer modulator, and scanning exposure was performed to a sample moving in a direction orthogonal to the scanning direction, by reflecting these lights on a rotating polygon. The scanning exposure was performed at the density of 400 dpi, and the average exposure time per 1 pixel was 8×10−8 sec. The temperature of the semiconductor lasers was kept constant, with using a Peltier element, to prevent the quantity of light from being changed by temperature.
Using the samples processed by the above-described processing process, densitometry was conducted before and after exposure to a Xenon lamp of 100,000 lux for 14 days. The surface temperature of the photosensitive materials was adjusted to become 50° C. A relative residual rate (%) after storage was calculated for a yellow color-developing area of an initial density of 0.3.
The results are shown in Table 2.
As is apparent from the results in Table 2, the Samples 1102 to 1110 according to the present invention containing the alkenylcarbonyl-series compound defined in the present invention were remarkably improved in light fastness, compared to Sample 1101 containing no alkenylcarbonyl-series compound. In particular, among the Samples according to the present invention, the samples containing the compound of microhardness value of 200 or less when forming a polimerized film, such as DPCA 20, DPCA 30, DPCA 60, were particularly remarkably improved.
Any of the compounds used in Samples 1102 to 1110 in Example 1-1 was added to the third layer of Sample 1101, in an equivalent coating amount of the compound per m2, to prepare corresponding samples, respectively. When adding these compounds, each sample was prepared in such a reduced amount of solvent that oil-soluble contents in the third layer would be a prescribed amount.
After the thus-prepared samples were exposed to light and processed in the same manner as in Example 1-1, light fastness of these samples was evaluated in the same manner as in Example 1-1. In this case, a relative residual rate for a magenta dye-developing area was calculated.
The samples containing the compound defined in the present invention in the third layer (magenta color-forming layer) were also improved in light fastness, as well as the samples in Example 1-1.
Any of the compounds used in Samples 1102 to 1110 in Example 1-1 was added to the fifth layer of Sample 1101, in an equivalent coating amount of the compound per m2, to prepare corresponding samples, respectively. When adding these compounds, each sample was prepared in such a reduced amount of solvent that oil-soluble contents in the fifth layer would be a prescribed amount.
After the thus-prepared samples were exposed to light and processed in the same manner as in Example 1-1, light fastness of these samples was evaluated in the same manner as in Example 1-1. In this case, a relative residual rate for a cyan dye-developing area was calculated.
The samples containing the compound defined in the present invention in the fifth layer (cyan color-forming layer) were also improved in light fastnesss, as well as the samples in Example 1-1.
(Preparation of Sample 2001)
Sample 2001 was prepared in the same manner as in the above-mentioned preparation of Sample 1101 in Example 1-1, except that the compositions of the first and third layers were changed as shown below, and further that a mixture comprising the compound having 3 to 8 recurring units represented by Compound X-1 (X11 is a hydroxyl group, and X12 is a 4-hydroxy-6-(2-hydroxyethyl)amino-1,3,5-triazine-2-yl group) and the compound having 2 and 3 recurring units represented by Compound X-2 was added to the first layer, in an amount of 150 mg per mol of the silver halide in the first layer.
Sample 2101 was prepared in the same manner as in the above-mentioned preparation of Sample 2001, except that the composition of the first layer was changed as shown below.
Samples 2102 to 2121 were prepared in the same manner as Sample 2101, except for further adding the compound(s), as shown in Table 3, to the first layer. The alkenylcarbonyl-series compound was added to the first layer in an amount of 0.15 g/m2. The addition amount of the compound represented by formula (Ph) was set to be 70 mol % based on the dye-forming coupler. When adding these compounds, each sample was prepared in such a reduced amount of solvent that oil-soluble contents in the first layer would be a prescribed amount.
The aforementioned photosensitive materials were processed into a roll with a width of 127 mm, and then a standard photographic image was exposed on the photosensitive materials by means of Digital Mini-Lab FRONTIER 330 (trade name, manufactured by Fuji Photo Film Co., Ltd.). Thereafter, using the exposed photosensitive materials, a continuous processing (running test) was conducted until the replenisher volume of the color developer used in the processing process set forth below became twice the volume of the color developer tank. Two kinds of processing in which both the composition of processing solutions and the process time were different from each other were carried out, to evaluate photosensitive materials.
Processing Process A
The processing using the following running processing solution was named Processing A.
The composition of each processing solution was as follows.
Processing Process B
The above photosensitive material samples were processed into a form of a roll with a width of 127 mm, and the photosensitive material was exposed with a standard photographic image, by using Digital Mini Lab FRONTIER 330 (trade name) manufactured by Fuji Photo Film Co., Ltd. Thereafter, a continuous processing (running test) was performed until the volume of the color-developer replenisher used in the following processing step became twice the volume of the color-developer tank. The processing using this running processing solution was named processing B.
The composition of each processing solution was as follows.
After being coated, the photosensitive material Samples 2101 to 2121 were kept for 10 days under conditions of 25° C. and 55% relative humidity, followed by the evaluation set forth below.
(Evaluation 1: Fastness to Light)
Each sample was subjected to exposure necessary to give a gray in the above-described processing process B, followed by color-development processing in the above-described processing processes A and B.
As light sources, a semiconductor laser was used to obtain a light source at 688 nm (R light), a semiconductor laser was combined with SHG to obtain a light source at 532 nm (G light), and a light source at 473 nm (B light). The quantity of light of R light was modulated with using an outer modulator, and scanning exposure was performed to a sample moving in a direction orthogonal to the scanning direction, by reflecting these lights on a rotating polygon. The scanning exposure was performed at the density of 400 dpi and the average exposure time per 1 pixel was 8×10−8 sec. The temperature of the semiconductor lasers was kept constant, with using a Peltier element, to prevent the quantity of light from being changed by temperature.
Each sample was subjected to light exposure, so that an overlap between each rasters became ⅓.
The value of ΔDmax(=DA−DB) of each sample was calculated. In this connection, “DA” means a density at a maximum color density portion for yellow when the light-sensitive material was processed by the processing process A, while “DB” means a density at a maximum color density portion for yellow when the light-sensitive material was processed by the processing process B.
The value of ΔDmax of each sample is shown in Table 3.
Using the samples processed by the above-described processing processes A and B, densitometry was conducted before and after exposure to a Xenon lamp of 100,000 lux for 14 days. The surface temperature of the photosensitive materials was adjusted to become 50° C. A relative residual rate (%) after storage was calculated for a yellow color-forming area of an initial density of 0.3.
The results obtained by evaluating the samples processed according to the processing process B are shown in Table 3. Further, the samples processed according to the processing process A showed essentially the same results as the samples processed according to the processing process B.
It can be seen, from the results in Table 3, that the Samples to which the alkenylcarbonyl-series compound was added exhibited effects of remarkably improving light fastness, compared to the Sample containing no alkenylcarbonyl-series compound. It can be seen, from a comparison, for example, between Samples 2103 to 2104 and 2105 to 2107, and Samples 2108 to 2109 and 2110 to 2111, that the Samples containing, among various compounds, the compound represented formula (A) and having a microhardness value of 200 or less when forming a polimerized film, such as DPCA 20, DPCA 30, or DPCA 60, exhibited effects of particularly remarkable improvement in light fastness. It can be also seen, from a comparison, for example, between Samples 2105 to 2111 and Samples 2112 to 2121, that light fastness is furthermore remarkably improved by further addition of the compound represented by formula (Ph).
Samples 2201 to 2221 were prepared in the same manner as Samples 2112 to 2118 prepared in Example 2-1, except for further adding the compounds to the first layer, as shown in Table 4. The amount of the additional compounds was to achieve 20 mol % of the coupler, respectively. In this addition of the additional compounds, each sample was prepared in such a reduced amount of solvent that oil-soluble contents in the first layer would be a prescribed amount.
Similarly to Example 2-1, each sample was subjected to exposure to light and a development process, and light fastness was evaluated in the same manner as in Example 2-1. The results obtained are shown in Table 4.
The results in Table 4 clearly show that supplementary addition of the compound represented by any one of formulae (E-1) to (E-3) further improved image fastness.
Samples 2301 to 2314 were prepared in the same manner as sample 2204 in Example 2-2, except that the respective compound, set forth in Table 5, was additionally incorporated in the first layer. The amount of the additional compound was to be 20 mol % to the coupler, respectively. In this addition of the additional compounds, each sample was prepared in such a reduced amount of solvent that oil-soluble contents in the first layer would be a prescribed amount. The compound represented by P-2 was added in the proportion of 0.05 g in the above composition of the first layer (blue-sensitive emulsion layer) of Sample 2101.
Similarly to Example 2-1, each sample was subjected to exposure to light, and a development processing, and fastness to light was evaluated in the same manner as in Example 2-1. The results are summarized in Table 5.
The results shown in Table 5 clearly show that supplementary addition of one or more of: the metal complex, the ultraviolet absorbing agent, the water-insoluble homopolymer or copolymer, and the compound, represented by any one of formulae (TS-I) to (TS-VII), further improved image fastness.
Samples 2401 to 2406 were prepared in the same manner as Sample 2314 in Example 2-3, except that the kind of the coupler in the first layer was changed, as shown in Table 6. Photographic properties of the samples were evaluated in the same manner as in Example 2-1, except for changing the processing process B in Evaluation 1 to the processing process A. The results obtained by evaluation of light fastness are shown in Table 6.
It can be seen that the samples using couplers, in which the structure of the coupler had an alkylthio group or an arylthio group at the ortho-position to the —CONH— group, were excellent in fastness to light. Among them, the samples using couplers, in which the structure of the coupler had an alkylthio group at the ortho-position to the —CONH— group, were more excellent in fastness to light. Moreover, the sample using the coupler, in which the structure of the coupler also had a t-butyl group at the para-position to the alkylthio group, was even more excellent in fastness to light.
Samples were prepared in the same manner as samples 2101 to 2121 in Example 2-1, Samples 2201 to 2221 in Example 2-2, Samples 2301 to 2314 in Example 2-3, and Samples 2401 to 2406 in Example 2-4, except that the support to be coated was replaced with a PET reflection support of 175 μm thickness, in which PET was kneaded with barium sulfate. An evaluation according to Example 2-1 was carried out, and essentially the same results as Examples 2-1 to 2-4 were obtained.
Samples 2101 to 2121 in Example 2-1, Samples 2201 to 2221 in Example 2-2, Samples 2301 to 2314 in Example 2-3, and Samples 2401 to 2406 in Example 2-4 were scan-exposed by means of each exposure apparatus set forth below. An evaluation according to Example 2-1 was conducted. The thus-obtained results demonstrate that each sample according to the present invention exhibited the effects of the invention of excellent fastness to light and processing stability, regardless of the kind of exposure apparatus used.
Exposure Apparatus
Digital Mini-Lab FRONTIER 330 (trade name, manufactured by Fuji Photo Film Co., Ltd.)
Lambda 130 (trade name, manufactured by Durst Co.)
LIGHTJET 5000 (trade name, manufactured by Gretag Co.)
Samples were prepared in the same manner as the samples in Examples 2-1, 2-2 and 2-3, except for changing the composition as set forth below.
Each of these samples was processed according to processing process B in Example 2-1, except that, in this processing process, each of the processing steps was prolonged by 2.7 times. The same evaluation as in Example 2-1 was conducted. The thus-obtained results demonstrate that use of the yellow coupler and the additive(s) for use in the present invention, in combination, gave photosensitive materials excellent in image fastness.
(Preparation of Sample 3001)
Sample 3001 was prepared in the same manner as in the above-mentioned preparation of Sample 2001 in Example 2-1, except that the composition of the first layer was changed as shown below.
Sample 3101 was prepared in the same manner as in the above-mentioned preparation of Sample 3001, except that the composition of the first layer was changed as shown below.
Samples 3102 to 3129 were prepared in the same manner as Sample 3101, except for adding the compound shown in Table 7 to the first layer. The amount of the alkenylcarbonyl-series compound to be added was set so as to become 0.15 g/m2, to the composition of the first layer of the aforementioned Sample 3101. The addition amount of the compound represented by formula (Ph) was set so as to become 70 mol % to the dye-forming coupler. When adding these compounds, each sample was prepared in such a reduced amount of solvent that oil-soluble contents in the first layer would be a prescribed amount.
After being coated, the photosensitive material Samples 3101 to 3129 were kept for 10 days under conditions of 25° C. and 55% relative humidity, followed by the evaluation set forth below.
Each sample was subjected to exposure necessary to give a gray in the above-described processing process B, followed by color-development processing in the above-described processing processes A and B.
As light sources, a semiconductor laser was used to obtain a light source at 688 nm (R light), a semiconductor laser was combined with SHG to obtain a light source at 532 nm (G light), and a light source at 473 nm (B light). The quantity of light of R light was modulated with using an outer modulator, and scanning exposure was performed to a sample moving in a direction orthogonal to the scanning direction, by reflecting these lights on a rotating polygon. The scanning exposure was performed at the density of 400 dpi and the average exposure time per 1 pixel was 8×10−8 sec. The temperature of the semiconductor lasers was kept constant, with using a Peltier element, to prevent the quantity of light from being changed by temperature.
(Evaluation 3-1: Rapid-processing Property)
The value of ΔDmax(=DA−DB) of each sample was calculated in the same manner as in Example 2-1.
The value of ΔDmax of each sample is shown in Table 7.
(Evaluation 3-2: Fastness to Light)
Using the samples processed by the above-described processing processes A and B, densitometry was conducted before and after exposure to a Xenon lamp of 100,000 lux for 14 days. The surface temperature of the photosensitive materials was adjusted to become 50° C. A relative residual rate (%) after storage was calculated for a yellow color-developing area of an initial density of 0.3.
The results obtained by evaluating the samples processed according to processing process B are shown in Table 7. Further, the samples processed according to processing process A showed essentially the same results as the samples processed according to processing process B.
(Evaluation 3-3: Raw Stock Storability)
After non-exposed photosensitive materials were stored (being kept) for 3 days under conditions of temperature of 40° C. and humidity of 80%(RH), the resultant samples were exposed to light using the above-mentioned method, followed by color-development processing in the above-described processing process B. Yellow densities in the unexposed area were measured before and after 3-day storage. The evaluation values were obtained in terms of the density after 3-day storage minus the density before 3-day storage (which indicate increase in yellow density after thermo-raw stock storability test). The results are shown in Table 7.
It can be seen, from comparing, for example, Samples 3103 to 3114 with Sample 3101, that addition of the alkenylcarbonyl-series compound defined in the present invention, to the samples, enabled remarkable improvement in light fastness, compared with the samples for comparison free of the compound. Further, it can be seen from comparing, for example, Samples 3107 to 3114 and 3119 to 3126 with Samples 3103 to 3106 and 3115 to 3118, that the compound defined in the above-described items (23) to (26) in which n1 was an integer of 2 to 4 in formula (B), among the compounds for use in the present invention, exhibited a particularly excellent light fastness.
Furthermore, it can be seen from comparing, for example, Samples 3103 to 3114 with Samples 3115 to 3118, that addition of the compound represented by formula (Ph), to the samples, enabled further remarkable improvement in fastness.
It can be seen from comparing, for example, Samples 3103 to 3114 with Sample 3101, that addition of the alkenylcarbonyl-series compound defined in the present invention, to the samples, enabled to prevent increase in yellow density after raw stock reservation from occurring, compared with samples for comparison free of the compounds.
Samples 3201 to 3227 were prepared in the same manner as Samples 3116, 3117, 3119, 3121, 3122, 3123, 3124, 3125 and 3126 in Example 3-1, except that the respective compound represented by any one of formulae (E-1) to (E-3), as shown in Table 8, was additionally incorporated in the first layer. The compound represented by any one of formulae (E-1) to (E-3) was added in an amount to be 20 mol % based on the coupler. When adding these compounds, each sample was prepared using such a reduced amount of solvent that oil-soluble contents in the first layer became a fixed quantity.
Similarly to Example 3-1, each sample was subjected to exposure to light, and development processing, and fastness to light was evaluated in the same manner as in Example 3-1.
The results in Table 8 clearly show that supplementary addition of the compound represented by any one of formulae (E-1) to (E-3) further improved image fastness. It is also seen that addition of any of these compounds did not cause increase in yellow density after raw stock storage.
Samples 3301 to 3328 were prepared in the same manner as Samples 3213 and 3216 in Example 3-2, except that the respective other inhibitor, as shown in Table 9, was additionally incorporated in the first layer. The amount of the other inhibitors except for Compound represented by P-2 was added so as to become 20 mol % based on the coupler. In this occasion, each sample was prepared using such a reduced amount of solvent that oil-soluble contents in the first layer became a fixed quantity. The Compound represented by P-2 was added in the proportion of 0.05 g in the above composition of the first layer (blue-sensitive emulsion layer) of sample 3101.
Similarly to Example 3-1, each sample was subjected to exposure to light, and development processing, and fastness to light was evaluated in the same manner as in Example 3-1.
The results in Table 9 clearly show that supplementary addition of one or more of: the metal complex, the ultraviolet absorbing agent, the water-insoluble homopolymer or copolymer, and the compound, represented by any one of formulae (TS-I) to (TS-VII), further improved image fastness. It is also seen that addition of any of these compounds or additives did not cause increase in yellow density after stock storage.
Samples 3401 to 3403 were prepared in the same manner as Sample 3314 prepared in Example 3-3, except that the kind of the coupler in the first layer was changed, as shown in Table 10. Photographic properties of the samples were evaluated in the same manner as in Example 3-1, except for changing the processing process B in Evaluation 3-2 to the processing process A. The results obtained by evaluation of light fastness are shown in Table 10.
It can be seen from the results shown in Table 10 that the yellow dye-forming couplers defined in the present invention, as well as the yellow dye-forming coupler (102), exhibited excellent effects. It is also seen that addition of any of these couplers did not cause increase in yellow density after stock storage.
Samples were prepared in the same manner as Samples 3101 to 3129 in Example 3-1, Samples 3201 to 3227 in Example 3-2, Samples 3301 to 3328 in Example 3-3, and Samples 3401 to 3403 in Example 3-4, except that the support was replaced with a PET reflection support of 175 μm thickness, in which PET was kneaded with barium sulfate. An evaluation according to Example 3-1 was carried out, and essentially the same results were obtained.
Samples 3101 to 3129 in Example 3-1, Samples 3201 to 3227 in Example 3-2, Samples 3301 to 3328 in Example 3-3, and Samples 3401 to 3403 in Example 3-4 were scan-exposed by means of each exposure apparatus set forth below. An evaluation according to Example 3-1 was conducted. The thus-obtained results demonstrate that each sample according to the present invention exhibited the effects of the invention of excellent fastness to light and processing stability, regardless of the kind of exposure apparatus used.
Exposure Apparatus
Digital Mini-Lab FRONTIER 330 (trade name, manufactured by Fuji Photo Film Co., Ltd.)
Lambda 130 (trade name, manufactured by Durst Co.)
LIGHTJET 5000 (trade name, manufactured by Gretag Co.)
Samples were prepared in the same manner as the samples in Examples 3-1, 3-2 and 3-3, except for changing the composition as set forth below.
Each of these samples was processed according to processing process B in Examples 3-1, 3-2 and 3-3, except that, in this processing process, each of the processing steps was prolonged by 2.7 times. The same evaluation as in Example 3-1 was conducted. The thus-obtained results demonstrate that use of the yellow coupler and the additive(s) defined in the present invention, in combination, gave photosensitive materials excellent in image fastness.
Having described our invention as related to the present embodiments, it is our intention that the invention not be limited by any of the details of the description, unless otherwise specified, but rather be construed broadly within its spirit and scope as set out in the accompanying claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2003-133163 | May 2003 | JP | national |
| 2003-133509 | May 2003 | JP | national |
| 2003-133667 | May 2003 | JP | national |
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| 3841880 | Kertel | Oct 1974 | A |
| 6068969 | Mikoshiba et al. | May 2000 | A |
| 20030073047 | Takeuchi et al. | Apr 2003 | A1 |
| Number | Date | Country |
|---|---|---|
| 6-59390 | Mar 1994 | JP |
| 8-44020 | Feb 1996 | JP |
| Number | Date | Country | |
|---|---|---|---|
| 20040234908 A1 | Nov 2004 | US |
