Patent Grant
7105288
The present invention relates to a silver salt photothermographic dry imaging material and in particular, to a silver salt photothermographic material exhibiting a high image density and a low fog density, minimized lowering of density with aging after being subjected to thermal processing, and an improved density uniformity when processed in a thermal processor.
In the field of medical diagnosis and graphic arts, there have been concerns in processing of photographic film with respect to effluent produced from wet-processing of image forming materials, and recently, reduction of the processing effluent is strongly demanded in terms of environmental protection and space saving. Silver salt photothermographic dry imaging materials forming images only by application of heat have been put into practical use and spread rapidly in the foregoing fields.
Silver salt photothermographic dry imaging materials (hereinafter, also denoted as thermally developable photothermographic materials or simply as photothermographic materials) have been proposed so far, as described in U.S. Pat. Nos. 3,152,904 and 3,487,075; D. Morgan, Dry Silver Photographic Material; and D. H. Klosterboer, “Thermally Processed Silver Systems” in IMAGING PROCESSES and MATERIALS, Neblette's Eighth Edition, edited by J. M. Sturge, V. Walworth, and A. Shepp (1969) page 279.
Photothermographic materials are processed using a thermally processing apparatus, usually called a thermal processor, which uniformly heats photothermographic material to form images. Such thermal processors are readily available in the market along with the recent spread thereof.
Recently, more downsizing of laser imagers and more rapid access thereof are further desired. There have been proposed various processing techniques, including a method of rotating a heated drum while bringing a photothermographic material into contact with the drum surface, a method of transporting a photothermographic material while pressing the photothermographic material onto the surface of a pre-heater and compressing it with a roller and a method of inserting a photothermographic material between plural roller pairs to transport it while allowing the rollers to rotate to perform thermal development. However, either one of the foregoing methods is easily influenced by fluctuation in temperature of the thermal developing section, producing problems such as unevenness in development and transportation troubles.
Performing thermal development at high temperatures of 100° C. or more results in highly heated photothermographic material immediately after completion of thermal processing, so that it is important to cool it down at a high speed to achieve rapid access. To overcome such problems, JP-A (hereinafter, the term, JP-A refers to a Japanese Patent Application publication) 3-208048 disclosed a method for cooling. However, such a method resulted in problems such as marked unevenness in density or transportation troubles, markedly vitiating commercial values. It was further proved that aging change of density increased due to differences in cooling process after processing.
Accordingly, it is an object of the present invention to provide a silver salt photothermographic imaging material exhibiting high image density, reduced fog density, minimized aging density change before or after being subjected to thermal processing, and achieving improved tracking characteristics without causing unevenness of density when processed in a thermal processor.
Further, it is an object of the invention to provide a silver salt photothermographic imaging material exhibiting superior silver image stability and high image quality, even when subjected to rapid processing.
The present invention has come into being as a result of systematic study by the inventors of this application, thereby achieving a silver salt photothermographic material, which is rapid-processable and exhibits improved raw stock stability and silver image stability, and superior image quality. Thus, the foregoing objects of the invention can be accomplished by the following constitution:
wherein X1 and X2 are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a heterocyclic group, a group which is attached to an aryl or heterocyclic group or COOM, in which M is a hydrogen atom or a cation, provided that at least one of X1 and X2 is COOM; R1, R2 and R3 are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a heterocyclic group or a group which is attached to an aryl or heterocyclic group, provided that adjacent groups of the foregoing substituents on the benzene ring may combine with each other to form a ring;
wherein Z is —S— or —C(R33)(R33′)—, in which R33 and R33′ are each a hydrogen atom or a substituent; R31, R32, R31′ and R32′ are each a substituent; X31 and X31′ are each a hydrogen atom or a substituent;
wherein X5, X6, X7 and X8 are each a halogen atom; B1 and B2 are each a hydrogen atom, halogen atom or a substituent; p is 1, 2 or 3; J is an alkylene group, cycloalkylene group, alkenylene group or alkynylene group or a trivalent or tetravalent group derived from the foregoing groups; G1 and G2 are each a linkage group, provided that when both G1 and G2 are —SO2—, p is 2 or 3.
In the formula (A-1), X1 and X2, each represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a heterocyclic group, a group boded to an aryl or heterocyclic group (i.e., a univalent group which is comprised of a divalent linkage group and an aryl or heterocyclic group bonded to the linkage group), or a carboxyl group represented by COOM, in which M is a hydrogen atom or a cation, provided that at least one of X1 and X2 is COOM. The cation is one compensating for a charge of COO−. Alternatively, the carboxyl group may be represented by COO[1/k·M′], in which M′ is a k-valent cation. Examples of the cation include a hydrogen ion (or oroton), metal ions and unsubstituted or substituted ammonium ion. R1, R2 and R3 which may be the same or different, each represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, cycloalkenyl group, an aryl group, a heterocyclic group or a group linked to an aryl or heterocyclic group (i.e., a group which is comprised of a divalent linkage group and an aryl or heterocyclic group bonded to the linkage group). Further, of the foregoing X1, X2, R1, R2 and R3, adjacent groups may combine with each other to form a ring. At least one of R1, R2 and R3 is preferably a group linked to an aryl or heterocyclic group.
Examples of a halogen atom include a fluorine atom, chlorine atom, bromine atom and iodine atom. The alkyl group, which may be straight-chained or branched is one having 1 to 30 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl and dodecyl. Examples of a cycloalkyl include cyclopentyl and cyclohexyl. The alkenyl group, which may be a straight-chained or branched is one having 2 to 30 carbon atoms, such as propenyl, butenyl and nonenyl. Examples of an aryl group include phenyl and naphthyl, which may be substituted; and examples of a substituent include a halogen atom, alkyl group, sulfonyl group, amido group and carboxyl group. Examples of a heterocyclic group include tetrahydropyranyl, pyridyl, furyl, thienyl, imidazolyl, thiazolyl, thiadiazolyl, oxadiazolyl. The heterocyclic group may be substituted and the substituent thereof is preferably one containing an electro-withdrawing group.
The compound of the formula (A-1) is contained preferalby at 0.001 to 1 mol, and more preferably 0.001 to 0.25 mol per mo of silver.
Specific example of the compound represented by the formula (A-1) are below.
Next, bisphenol compounds represented by the foregoing formula (A-2) will be described. In the formula (A-2), Z represents —S— or —C(R33)(R33′)-, in which R33 and R33′ each represents a hydrogen atom or a substituent. Examples of the substituent represented by R33 and R33′ include an alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl), cycloalkyl group (e.g., cyclopropyl, cyclohexyl, 1-methyl-cyclohexyl), alkenyl group (e.g., vinyl, propenyl, butenyl, pentenyl, isohexenyl, butenylidene, isopentylidene), cycloalkenyl group (e.g., e.g., cyclohexenyl), alkynyl group (e.g., ethynyl, propynylidene), aryl group (e.g., phenyl, naphthyl), heterocyclic group (e.g., furyl, thienyl, pyridyl, tetrahydrofuranyl), halogen atom, hydroxyl, alkoxy group, aryloxy group, acyloxy group, sulfonyloxy group, nitro, amino group, acylamino group, sulfonylamino group, sulfonyl group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfamoyl group, cyano and sulfo. Of these, R33 and R33′ are each preferably a hydrogen atom, an alkyl group or a cycloalkyl group.
R31, R32, R31′ and R32′ each represents a substituent. Substituents represented by R31, R32, R31′ and R32′ are the same as those described above for R33 and R33′. R31, R32, R31′ and R32′ are each preferably an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group or heterocyclic group, and more preferably an alkyl group or cycloalkyl group. The alkyl or cycloalkyl group may be substituted and substituents thereof are the same as described in R33 and R33′. R31, R32, R31′ and R32′ are still more preferably t-butyl, t-amyl, t-octyl or 1-methylcyclohexyl.
X31 and X311 each represents a hydrogen atom or a substituent. The substituent is the same as described in R33 and R33′.
Specific examples of the bisphenol compound represented by formula (A-2) are shown below but by no means limited to these.
The compounds represented by the formula (A-1) or (A-2) are dispersed in water or dissolved in an organic solvent, and incorporated into a coating solution for the light-sensitive layer or a layer adjacent to the light-sensitive layer. The organic solvent can optionally be selected from alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone and aromatic solvents such as toluene and xylene.
The compound represented by the formula (A-2) is used preferably in an amount of 1×10−2 to 10 mol, and more preferably 1×10−2 to 1.5 mol per mol of silver. The molar ratio of the compound represented by formula (A-1) to the compound represented by formula (A-2) is preferably 0.001 to 1.0, and more preferably 0.005 to 0.5.
Next, the compound represented by the foregoing formula (B) will be described. In the formula (B), the halogen atom represented by X5, X6, X7 and X8 is a fluorine, chlorine, bromine or iodine atom, preferably a chlorine, bromine or iodine atom, more preferably a chlorine or bromine atom, and still more preferably a bromine atom.
Substituents represented by B1 and B2 include, for example, an alkyl group, aryl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, amino group, acyl group, acyloxy group, acylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, sulfonyl group, alkylsulfonyl group, sulfinyl group, cyano group and heterocyclic group. Linkage groups represented by G1 and G2 include, for example, —SO2—, —CO—, —NHCO—, —OOC—, —N(R8)SO2—, in which R8 is substituent group, and a linkage group linking through an alkyl group with a group selected from —S—, —NH—, —CO—, and —O—. Examples of the substituent group represented by R8 include an alkyl group, aryl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, amino group, acyl group, acyloxy group, acylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, sulfonyl group, alkylsulfonyl group, sulfinyl group, cyano group and heterocyclic group. G1 and G2 may be the same or different, provided that when both of G1 and G2 are —SO2—, p is 2 or 3.
J is an alkylene group, cycloalkylene group, alkenylene group or alkynylene group (when p is 1), or a tri-valent or tetra-valent group derived from each of the foregoing alkylene group, cycloalkylene group, alkenylene group or alkynylene group (when p is 2 or 3); preferably an alkylene group having 2 to 20 carbon atoms, cycloalkylene group, or a tri-valent or tetra-valent group derived from each of the foregoing alkylene and cycloalkylene groups; and more preferably an alkylene group having 2 to 10 carbon atoms, cycloalkylene group, or a tri-valent or tetra-valent group derived from each of the foregoing alkylene and cycloalkylene groups. These groups described above may be substituted. Examples of substituents include a halogen atom (e.g., fluorine, chlorine, bromine), cycloalkyl group (e.g., cyclohexyl, cycloheptyl), cycloalkenyl group (e.g., 1-cyclalkenyl, 2-cycloalkenyl), alkoxy group (e.g., methoxy, ethoxy, propoxy), alkylcarbonyloxy group (e.g., acetyloxy), alkylthio group (e.g., methylthio, trifluoromethylthio), carboxyl group, alkylcarbonylamino group (e.g., acetylamino), ureido group (e.g., methylaminocarbonylamino), alkylsulfonyl group (e.g., methanesulfonyl, trifluoromethanesulfonyl), carbamoyl group (e.g., carbamoyl, N,N-dimethylcarbamoyl, N-morpholinocarbonyl), sulfamoyl group (e.g., sulfamoyl, N,N-dimethylsulfamoyl, morpholinosulfamoyl), trifluoromethyl, hydroxy, nitro, cyano, alkylsulfonamido group (e.g., methanesulfonamido, butanesulfoneamido), alkylamino group (e.g., N,N-dimethylamino, N,N-diethylamino), sulfo group, phosphono group, sulfite group, sulfino group, alkylsulfonylaminocarbonyl group (e.g., methanesulfonylaminocarbonyl, ethanesulfonylaminocarbonyl), alkylcarbonylaminosulfonyl group (e.g., acetoamidosulfonyl, methoxyacetoamidosulfonyl), alkynylaminocarbonyl group (e.g., acetoamidocarbonyl, methoxyacetoamidocarbonyl), and alkylsulfinylaminocarbonyl group (e.g., methanesulfinylaminocarbonyl, ethane sulfinylaminocarbonyl). In the case of being substituted by plural substituents, the plural substituents may be the same or different. In the foregoing substituent groups, however, substituents containing an aryl group or a heterocyclic group are excluded.
The polyhalogeno-compound represented by the foregoing formula (B) may be incorporated into the light-sensitive layer or light-sensitive layer, and preferably the light-sensitive layer or a layer adjacent to the light-sensitive layer. The polyhalogeno-compound is incorporated in an amount of 1×10−4 to 1.0 mol, and preferably 1×10−3 to 0.3 mol per mol of silver halide. The molar ratio of compound of formula (B) to compound of formula (A) is preferably 0.001 to 1.0, and more preferably 0.005 to 0.5.
Specific examples of the polyhalogeno-compound represented by the formula (B) are shown below.
In this invention, the use of a compound containing a vinylsulfone group is preferred. The compound containing a vinylsulfone group (hereinafter, also denoted as vinylsulfone group-containing compound) is preferably represented by the following formula (A-5):
(R1R2C═CR3—SO2)n-L formula (A-5)
wherein R1, R2 and R3 each represents a hydrogen atom, an alkyl group or an aryl group, provided that two adjacent groups of these groups (R1, R2 and R3) may combine with each other to form a ring; n is 1, 2, 3 or 4; and L represents a n-valent group (i.e., mono- to tetra-valent). Such n-valent groups include those which are derived from an alkane or alkene having not more than 20 carbon atoms, or an aromatic hydrocarbon (including alkyl-substituted aromatic hydrocarbons). The foregoing aromatic hydrocarbon may be substituted (substituents, e.g., halogen such as Br, Cl, hydroxy, amino, alkyl, alkoxy).
Specific examples of the foregoing compound containing a vinylsulfone group are shown below but are not limited to these.
CH2═CHSO2CH2CH2OCH2CH2SO2CH═CH2 VS-2
CH2═CHSO2CH2CH2SO2CH═CH2 VS-3
CH2═CHSO2CH2OCH2SO2CH═CH2 VS-4
The compound containing a vinylsulfone group is described in literature, U.S. Pat. Nos. 2,994,611, 3,061,436, 3,132,945, 3,490,911, 3,527,807, 3,593,644, 3,642,486, 3,642,908, 3,839,042, 3,841,872, 3,957,882, 4,088,495, 4,108,848, 4,137,082, 4,142,897; Belgian patent No. 819,015 and U.S. Pat. No. 4,173,481. The compound containing a vinylsulfone group is usually incorporated in an amount of 0.001 mol or more, preferably 0.01 to 5 mol. and more preferably 0.02 to 0.6 mol per mol of silver.
In this invention, the light-sensitive layer or a layer adjacent to the light-sensitive layer preferably contains a compound represented by the following formula (A-3):
Z-SO2—SM formula (A-3)
wherein Z is an aliphatic hydrocarbon group, aryl group or a heterocyclic group; M is a cation.
In the formula (A-3), aliphatic hydrocarbon groups designated by “Z” include a straight-chain, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 1 to 8 carbon atoms, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-octyl, iso-amyl, tert-amyl, hexyl, dodecyl, octadecyl, and cyclohexyl), alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and still more preferably 2 to 8 carbon atoms, such as vinyl, allyl, 2-butenyl, and 3-pentenyl), alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and still more preferably 2 to 8 carbon atoms, such as propargyl, and petynyl) Of these, an alkyl group is preferred and a branched alkyl group is more preferred. The aliphatic hydrocarbon group may be substituted. Examples of a substituent include an aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms, such as phenyl, p-methylphenyl and naphthyl), amino group (preferably having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, and still more preferably 0 to 6 carbon atoms, such as amino. methylamino, dimethylamino, diethylamino and dibenzylamino), alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 1 to 8 carbon atoms, such as methoxy, ethoxy and butoxy), aryloxy group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, and still more preferably 6 to 12 carbon atoms, such as penyloxy and naphthyloxy), acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and still more preferably 1 to 12 carbon atoms, such as acetyl, benzoyl, formyl, pivaloyl), alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and still more preferably 2 to 12 carbon atoms, such as methoxycarbonyl and ethoxycarbonyl), aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, and still more preferably 7 to 10 carbon atoms, such as phenoxycarbonyl), aryloxy group (preferably having 1 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and still more preferably 2 to 10 carbon atoms, such as acetoxy and benzoyloxy), acylamino group (preferably having 1 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and still more preferably 2 to 10 carbon atoms, such as acetylamino, valerinoamino and benzoylamino), alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and still more preferably 2 to 12 carbon atoms, such as methoxycarbonylamino), aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, and still more preferably 7 to 12 carbon atoms, such as phenyoxycarbonylamino), sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and still more preferably 1 to 12 carbon atoms, such as methanesulfonylamino, and benzenesulfonylamino), sulfamoyl group (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, and still more preferably 0 to 12 carbon atoms, such as sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, and phenylsulfamoyl), carbamoyl group (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, and still more preferably 0 to 12 carbon atoms, such as carbamoyl, dimethylcarbamoyl, and phenylcarbamoyl), ureido group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and still more preferably 1 to 12 carbon atoms, such as ureido, methylureido and phenylureido), alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and still more preferably 1 to 12 carbon atoms, such as methylthio and ethylthio), arylthio group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, and still more preferably 6 to 12 carbon atoms, such as phenylthio), sulfonyl (preferably having 1 to 16 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 12 carbon atoms, such as messy and tosyl), sulfinyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and still more preferably 1 to 12 carbon atoms, such as methanesulfinyl and benzenesulfonyl), phosphoric acid amide group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and still more preferably 1 to 12 carbon atoms, such as diethylphosphoric acid amide, and phenylphosphoric acid amide), hydroxyl, mercapto group, halogen atom (such as fluorine atom, chlorine atom, bromine atom and iodine atom), cyano, sulfo, carboxy, nitro, hydroxam group, sulfino group, hydrazine group, sulfonylthio, thiosulfonyl, heterocyclic group (such as imidazolyl, pyridyl, furyl, piperidyl, orphoryl, and morpholine), and disulfide group. Of these groups, a group capable of forming a salt may form a salt. The substituents described above may further be substituted. In cases where substituted by plural substituents, the substituents may be the same or different.
The aryl group, designated Z is preferably a monocyclic or condensed aryl group having 6 to 30 carbon atoms (more preferably 6 to 20 carbon atoms), and examples thereof include phenyl and naphthyl, and phenyl is preferred. The aryl group, designated Z may be substituted. Examples of substituents include the substituents described for the foregoing aliphatic hydrocarbon group and an alkyl group (having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms, e.g., methyl, ethyl, iso-propyl, n-butyl, tert-butyl, n-octyl, tert-amyl, cyclohexyl), alkenyl group (having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms, e.g., vinyl, allyl, 2-butenyl, 3-pentenyl), and alkynyl group (having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms, e.g., propargyl, 3-pentynyl).
The heterocyclic group, designated Z is a saturated or unsaturated, N-, O- or S-containing, 3- to 10-membered ring, which may be a monocycle or form a condensed ring with other rings. Specific examples of the heterocyclic group include thienyl, furyl, pyranyl, 2H-pyrrolyl, pyrrolyl, imidazolyl, pyrazolyl, isothiazolyl, isooxazolyl, thiazolyl, oxazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1,3,4-oxadiazoyl, 1,3,4-thiadiazolyl, pyridyl, pirazinyl, pyrimidinyl, pyridazinyl, indolinidyl, isoindolidinyl, 3H-indolyl, indolyl, 1H-indazolyl, purinyl, 4H-quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthylidinyl, quinoxalinyl, quinazolinyl, cinnolinyl, puteridinyl, carbazolyl, carbonylyl, phenthrolinyl, phenazinyl, phenarusadinyl, phenothiazinyl, brazanyl, phenoxazinyl, isochromanyl, chromanyl, pyrrolidinyl, pyrrolyl, imidazolidinyl, imidazoliyl, pyrazinyl, pyrazolinyl, piperidyl, piperazinyl, indolinyl, isoindolinyl, quinuclidinyl, morpholinyl, tetrazolyl, benzimidazolyl, benzoxazolyl, benzthiazolyl, benztriazolyl, triazinyl, uracil, and triazopyrimidinyl. Of these, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1,3,4-oxadiazoyl, 1,3,4-thiadiazolyl, pyridyl, pirazinyl, pyrimidinyl, pyridazinyl, indolyl, 1H-indazolyl, purinyl, 4H-quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthylidinyl, quinoxalinyl, quinazolinyl, cinnolinyl, puteridinyl, tetrazolyl, benzimidazolyl, benzoxazolyl, benzthiazolyl, benztriazolyl, triazinyl, uracil, and triazopyrimidinyl are preferred. Further, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1,3,4-oxadiazoyl, 1,3,4-thiadiazolyl, pyridyl, pirazinyl, pyrimidinyl, pyridazinyl, indolyl, 1H-indazolyl, purinyl, quinolyl, phthalazinyl, naphthylidinyl, quinoxalinyl, quinazolinyl, cinnolinyl, puteridinyl, tetrazolyl, benzimidazolyl, benzoxazolyl, benzthiazolyl, benztriazolyl, triazinyl, and triazopyrimidinyl are more preferred.
Z is preferably a chained alkyl group and aryl group (e.g., phenyl) are preferred. M is a cation, such as hydrogen, ion, alkali metal (e.g., Na, K) ion and substituted or unsubstituted ammonium ion.
Specific examples of the compound represented by the formula (A-3) are shown below, but are by no means limited to these.
CH3SO2SNa (Z-1)
C2H5SO2SNa (Z-2)
HOOC—CH2CH2SO2SK (Z-3)
(n)C4H9SO2SNa (Z-4)
NC—CH2CH2CH2SO2SNa (Z-5)
(n)C8H17SO2SNa (Z-6)
(n)C12H25SO2SNa (Z-7)
ClCH2(CH2)4SO2SK (Z-8)
(n)C18H37SO2SNa (Z-9)
(n)C4H9SO2SK (Z-10)
(n)C8H17SO2SK (Z-11)
(n)C8H17SO2S−.(n)(C4H9)4N+ (Z-15)
H2N—CH2CH2SO2SH (Z-17)
CH3O—CH2CH2SO2SNa (Z-18)
Of the compounds of the formula (A-3), there may be used commercially available ones or they may be synthesized in accordance with the methods known in the art, for example, by the reaction of sulfonyl halide with an alkali sulfide or reaction of a sulfonic acid salt with sulfur.
The compound of formula (A-3) is used through solution in organic solvents such as alcohols (e.g., methanol, ethanol, propanol, fluorinated alcohol), ketones (e.g., acetone, methyl ethyl ketone), dimethylformamide, dimethylsulfoxide, and methyl cellosolve. According to the emulsion dispersing method known in the art, the compound is dissolved using oil such as dibutyl phthalate, tricresyl phthalate, glyceryl triacetate or diethyl phthalate or an auxiliary solvent such as ethyl acetate or cyclohexane, followed by being mechanically dispersed. According to the method known as solid particle dispersion, the compound may be used in the form of solid particles dispersed in water, using a ball mill, colloid mill, sand grinder mill, Manton-Gaulin homogenizer, microfluidizer or ultrasonic homogenizer.
The compound of formula (A-3) may be incorporated into any layer provided on the light-sensitive layer side of the support, and preferably into the light-sensitive layer containing a silver halide emulsion or a layer adjacent to the light-sensitive layer. The compound of formula (A-3) is incorporated preferably in an amount of 0.2 to 200 mmol, more preferably 0.3 to 100 mmol, and still more preferably 0.5 to 30 mmol per mol of silver. The compounds may be used alone or in combination.
Light-sensitive silver halide grains used in this invention are those which are capable of absorbing light as an inherent property of silver halide crystal or capable of absorbing visible or infrared light by artificial physico-chemical methods, and which are treated or prepared so as to cause a physico-chemical change in the interior and/or on the surface of the silver halide crystal upon absorbing light within the region of ultraviolet to infrared.
The silver halide grains used in the invention can be prepared according to the methods described in P. Glafkides, Chimie Physique Photographique (published by Paul Montel Corp., 19679; G. F. Duffin, Photographic Emulsion Chemistry (published by Focal Press, 1966); V. L. Zelikman et al., Making and Coating of Photographic Emulsion (published by Focal Press, 1964). Any one of acidic precipitation, neutral precipitation and ammoniacal precipitation is applicable and the reaction mode of aqueous soluble silver salt and halide salt includes single jet addition, double jet addition and a combination thereof. Specifically, preparation of silver halide grains with controlling the grain formation condition, so-called controlled double-jet precipitation is preferred. The halide composition of silver halide is not specifically limited and may be any one of silver chloride, silver chlorobromide, silver iodochlorobromide, silver bromide, silver iodobromide and silver iodide.
The grain forming process is usually classified into two stages of formation of silver halide seed crystal grains (nucleation) and grain growth. These stages may continuously be conducted, or the nucleation (seed grain formation) and grain growth may be separately performed. The controlled double-jet precipitation, in which grain formation is undergone with controlling grain forming conditions such as pAg and pH, is preferred to control the grain form or grain size. In cases when nucleation and grain growth are separately conducted, for example, a soluble silver salt and a soluble halide salt are homogeneously and promptly mixed in an aqueous gelatin solution to form nucleus grains (seed grains), thereafter, grain growth is performed by supplying soluble silver and halide salts, while being controlled at a pAg and pH to prepare silver halide grains. After completing the grain formation, the resulting silver halide grain emulsion is subjected to desalting to remove soluble salts by commonly known washing methods such as a noodle washing method, a flocculation method, a ultrafiltration method, or electrodialysis to obtain desired emulsion grains.
In order to minimize cloudiness after image formation and to obtain excellent image quality, the less the average grain size, the more preferred, and the average grain size is preferably not more than 0.2 μm, more preferably between 0.01 and 0.17 μm, and still more preferably between 0.02 and 0.14 μm. The average grain size as described herein is defined as an average edge length of silver halide grains, in cases where they are so-called regular crystals in the form of cube or octahedron. Furthermore, in cases where grains are tabular grains, the grain size refers to the diameter of a circle having the same area as the projected area of the major faces. Furthermore, silver halide grains are preferably monodisperse grains. The monodisperse grains as described herein refer to grains having a coefficient of variation of grain size obtained by the formula described below of not more than 30%; more preferably not more than 20%, still more preferably not more than 3%, and most preferably not more than 15%:
Coefficient of variation of grain size=standard deviation of grain diameter/average grain diameter×100(%)
The grain form can be of almost any one, including cubic, octahedral or tetradecahedral grains, tabular grains, spherical grains, bar-like grains, and potato-shaped grains. Of these, cubic grains, octahedral grains, tetradecahedral grains and tabular grains are specifically preferred.
The aspect ratio of tabular grains is preferably 1.5 to 100, and more preferably 2 to 50. These grains are described in U.S. Pat. Nos. 5,264,337, 5,314,798 and 5,320,958 and desired tabular grains can be readily obtained. Silver halide grains having rounded corners are also preferably employed.
Crystal habit of the outer surface of the silver halide grains is not specifically limited, but in cases when using a spectral sensitizing dye exhibiting crystal habit (face) selectivity in the adsorption reaction of the sensitizing dye onto the silver halide grain surface, it is preferred to use silver halide grains having a relatively high proportion of the crystal habit meeting the selectivity. In cases when using a sensitizing dye selectively adsorbing onto the crystal face of a Miller index of [100], for example, a high ratio accounted for by a Miller index [100] face is preferred. This ratio is preferably at least 50%; is more preferably at least 70%, and is most preferably at least 80%. The ratio accounted for by the Miller index [100] face can be obtained based on T. Tani, J. Imaging Sci., 29, 165 (1985) in which adsorption dependency of a [111] face or a [100] face is utilized.
It is preferred to use low molecular gelatin having an average molecular weight of not more than 50,000 in the preparation of silver halide grains used in the invention, specifically, in the stage of nucleation. Thus, the low molecular gelatin has an average molecular eight of not more than 50,000, preferably 2,000 to 40,000, and more preferably 5,000 to 25,000. The average molecular weight can be determined by means of gel permeation chromatography. The low molecular weight gelatin can be obtained by subjecting an aqueous gelatin conventionally used and having an average molecular weight of ca. 100,000 to enzymatic hydrolysis, acid or alkali hydrolysis, thermal degradation at atmospheric pressure or under high pressure, or ultrasonic degradation.
The concentration of dispersion medium used in the nucleation stage is preferably not more than 5% by weight, and more preferably 0.05 to 3.0% by weight.
In the preparation of silver halide grains, it is preferred to use a compound represent by the following formula, specifically in the nucleation stage:
YO(CH2CH2O)m(C(CH3)CH2O)p(CH2CH2O)nY
where Y is a hydrogen atom, —SO3M or —CO—B—COOM, in which M is a hydrogen atom, alkali metal atom, ammonium group or ammonium group substituted by an alkyl group having carbon atoms of not more than 5, and B is a chained or cyclic group forming an organic dibasic acid; m and n each are 0 to 50; and p is 1 to 100. Polyethylene oxide compounds represented by foregoing formula have been employed as a defoaming agent to inhibit marked foaming occurred when stirring or moving emulsion raw materials, specifically in the stage of preparing an aqueous gelatin solution, adding a water-soluble silver and halide salts to the aqueous gelatin solution or coating an emulsion on a support during the process of preparing silver halide photographic light sensitive materials. A technique of using these compounds as a defoaming agent is described in JP-A No. 44-9497. The polyethylene oxide compound represented by the foregoing formula also functions as a defoaming agent during nucleation. The compound represented by the foregoing formula is used preferably in an amount of not more than 1%, and more preferably 0.01 to 0.1% by weight, based on silver.
The compound is to be present at the stage of nucleation, and may be added to a dispersing medium prior to or during nucleation. Alternatively, the compound may be added to an aqueous silver salt solution or halide solution used for nucleation. It is preferred to add it to a halide solution or both silver salt and halide solutions in an amount of 0.01 to 2.0% by weight. It is also preferred to make the compound represented by formula [5] present over a period of at least 50% (more preferably, at least 70%) of the nucleation stage.
The temperature during the stage of nucleation is preferably 5 to 60° C., and more preferably 15 to 50° C. Even when nucleation is conducted at a constant temperature, in a temperature-increasing pattern (e.g., in such a manner that nucleation starts at 25° C. and the temperature is gradually increased to reach 40° C. at the time of completion of nucleation) or its reverse pattern, it is preferred to control the temperature within the range described above.
Silver salt and halide salt solutions used for nucleation are preferably in a concentration of not more than 3.5 mol/l, and more preferably 0.01 to 2.5 mol/l. The flow rate of aqueous silver salt solution is preferably 1.5×10−3 to 3.0×10−1 mol/min per liter of the solution, and more preferably 3.0×10−3 to 8.0×10−2 mol/min. per liter of the solution. The pH during nucleation is within a range of 1.7 to 10, and since the pH at the alkaline side broadens the grain size distribution, the pH is preferably 2 to 6. The pBr during nucleation is 0.05 to 3.0, preferably 1.0 to 2.5, and more preferably 1.5 to 2.0.
Silver halide may be incorporated into an image forming layer by any means, in which silver halide is arranged so as to be as close to reducible silver source (aliphatic carboxylic acid silver salt) as possible. It is general that silver halide, which has been prepared in advance, added to a solution used for preparing an organic silver salt. In this case, preparation of silver halide and that of an organic silver salt are separately performed, making it easier to control the preparation thereof. Alternatively, as described in British Patent 1,447,454, silver halide and an organic silver salt can be simultaneously formed by allowing a halide component to be present together with an organic silver salt-forming component and by introducing silver ions thereto. Silver halide can also be prepared by reacting a halogen containing compound with an organic silver salt through conversion of the organic silver salt. Thus, a silver halide-forming component is allowed to act onto a pre-formed organic silver salt solution or dispersion or a sheet material containing an organic silver salt to convert a part of the organic silver salt to photosensitive silver halide.
The silver halide-forming components include inorganic halide compounds, onium halides, halogenated hydrocarbons, N-halogeno compounds and other halogen containing compounds. These compounds are detailed in U.S. Pat. Nos. 4,009,039, 3,457,075 and 4,003,749, British Patent 1,498,956 and JP-A 53-27027 and 53-25420. Exemplary examples thereof include inorganic halide compound such as a metal halide and ammonium halide; onium halides, such as trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, and trimethylbenzylammonium bromide; halogenated hydrocarbons, such as iodoform, bromoform, carbon tetrachloride and 2-brom-2-methylpropane; N-halogenated compounds, such as N-bromosucciimde, N-bromophthalimide, and N-bromoacetoamide; and other halogen containing compounds, such as triphenylmethyl chloride, triphenylmethyl bromide, 2-bromoacetic acid, 2-bromoethanol and dichlorobenzophenone. As described above, silver halide can be formed by converting a part or all of an organic silver salt to silver halide through reaction of the organic silver salt and a halide ion. The silver halide separately prepared may be used in combination with silver halide prepared by conversion of at least apart of an organic silver salt. The silver halide which is separately prepared or prepared through conversion of an organic silver salt is used preferably in an amount of 0.001 to 0.7 mol and more preferably 0.03 to 0.5 mol per mol of organic silver salt.
Silver halide used in the invention preferably occludes ions of metals belonging to Groups 6 to 11 of the Periodic Table. Preferred as the metals are W; Fe, Co, Ni, Cu, Ru, Rh, Pd, Re, Os, Ir, Pt and Au. These metals may be introduced into silver halide in the form of a complex. In the present invention, regarding the transition metal complexes, six-coordinate complexes represented by the general formula described below are preferred:
(ML6)m Formula:
wherein M represents a transition metal selected from elements in Groups 6 to 11 of the Periodic Table; L represents a coordinating ligand; and m represents 0, 1-, 2-, 3- or 4-. Exemplary examples of the ligand represented by L include halides (fluoride, chloride, bromide, and iodide), cyanide, cyanato, thiocyanato, selenocyanato, tellurocyanato, azido and aqvo, nitrosyl, thionitrosyl, etc., of which aqvo, nitrosyl and thionitrosyl are preferred. When the aquo ligand is present, one or two ligands are preferably coordinated. L may be the same or different.
Compounds, which provide these metal ions or complex ions, are preferably incorporated into silver halide grains through addition during the silver halide grain formation. These may be added during any preparation stage of the silver halide grains, that is, before or after nuclei formation, growth, physical ripening, and chemical ripening. However, these are preferably added at the stage of nuclei formation, growth, and physical ripening; furthermore, are preferably added at the stage of nuclei formation and growth; and are most preferably added at the stage of nuclei formation. These compounds may be added several times by dividing the added amount. Uniform content in the interior of a silver halide grain can be carried out. As disclosed in JP-A Nos. 63-29603, 2-306236, 3-167545, 4-76534, 6-110146, 5-273683, the metal can be non-uniformly occluded in the interior of the grain.
These metal compounds can be dissolved in water or a suitable organic solvent (e.g., alcohols, ethers, glycols, ketones, esters, amides, etc.) and then added. Furthermore, there are methods in which, for example, an aqueous metal compound powder solution or an aqueous solution in which a metal compound is dissolved along with NaCl and KCl is added to a water-soluble silver salt solution during grain formation or to a water-soluble halide solution; when a silver salt solution and a halide solution are simultaneously added, a metal compound is added as a third solution to form silver halide grains, while simultaneously mixing three solutions; during grain formation, an aqueous solution comprising the necessary amount of a metal compound is placed in a reaction vessel; or during silver halide preparation, dissolution is carried out by the addition of other silver halide grains previously doped with metal ions or complex ions. Specifically, the preferred method is one in which an aqueous metal compound powder solution or an aqueous solution in which a metal compound is dissolved along with NaCl and KCl is added to a water-soluble halide solution. When the addition is carried out onto grain surfaces, an aqueous solution comprising the necessary amount of a metal compound can be placed in a reaction vessel immediately after grain formation, or during physical ripening or at the completion thereof or during chemical ripening.
Silver halide grain emulsions used in the invention may be desalted after the grain formation, using the methods known in the art, such as the noodle washing method and flocculation process.
Organic silver salts used in the invention are reducible silver source, and silver salts of organic acids are preferred and silver salts of long chain fatty acid (preferably having 10 to 30 carbon atom and more preferably 15 to 25 carbon atoms) are more preferred.
The organic silver salts used in the invention are a reducible silver source, which is relatively stable to light and capable of releasing silver ions upon heating at a temperature of 80 to 250° C., in the presence of an exposed photocatalyst (such as a latent image of photosensitive silver halide) and a reducing agent. Examples of organic silver salts include silver salts of long fatty acids, silver salts of compounds containing a mercapto group or thione group organic or inorganic complexes, ligand of which have a total stability constant to a silver ion of 4.0 to 10.0, as described in Research Disclosure (hereinafter, also designated simply as RD) 17029 and 29963.
Of organic silver salts are preferred silver salts of long fatty acids having 10 to 30 carbon atoms (preferably 12 to 25 carbon atoms). Examples of long fatty acids include cerotic acid (having 25 carbons), behenic acid (having 22 carbons), arachidic acid (having 20 carbons) stearic acid (having 18 carbons), palmitic acid (having 16 carbons), myristic acid (having 14 carbons) and lauric acid (having 12 carbons). Fatty acids having 12 to 25 carbon atoms are more preferred. Behenic acid, arachidic acid, stearic acid and palmitic acid are specifically preferred. Examples of organic silver salts other than silver salts of fatty acids include carboxyalkylthiourea salts (e.g., 1-(3-carboxypropyl)thiourea, 1-(3-caroxypropyl)-3,3-dimethylthiourea, etc.); silver complexes of polymer reaction products of aldehyde with hydroxy-substituted aromatic carboxylic acid (e.g., aldehydes such as formaldehyde, acetaldehyde, butylaldehyde), hydroxy-substituted acids (e.g., salicylic acid, benzoic acid, 3,5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid, silver salts or complexes of thiones (e.g., 3-(2-carboxyethyl)-4-hydroxymethyl-4-(thiazoline-2-thione and 3-carboxymethyl-4-thiazoline-2-thione), complexes of silver with nitrogen acid selected from imidazole, pyrazole, urazole, 1,2,4-thiazole, and 1H-tetrazole, 3-amino-5-benzylthio-1,2,4-triazole and benztriazole or salts thereof; silver salts of saccharin, 5-chlorosalicylaldoxime, etc.; and silver salts of mercaptides.
Of the foregoing organic silver salts, long fatty acid silver salts are specifically preferred in terms of easy release of silver ions on thermal development and user-friendliness. Specifically, silver behenate is most easily usable. The ratio of silver behenate to total organic silver salt is preferably 70% to 99% by weight, and more preferably 78% to 99% by weight. Organic acid(s) used in organic silver salts may be comprised of long fatty acid(s) alone or in combination with other organic acids such as a nitrogen containing heterocyclic compound or thio-compound described above, in a ratio of not more than 5% by weight, preferably not more than 1% by weight, and more preferably not more than 0.1% by weight.
Organic silver salts can be obtained by mixing an aqueous-soluble silver compound with a compound capable of forming a complex. Normal precipitation, reverse precipitation, double jet precipitation and controlled double jet precipitation, as described in JP-A 9-127643 are preferably employed. For example, to an organic acid can be added an alkali metal hydroxide (e.g., sodium hydroxide, potassium hydroxide, etc.) to form an alkali metal salt soap of the organic acid (e.g., sodium behenate, sodium arachidate, etc.), thereafter, the soap and silver nitrate are mixed by the controlled double jet method to form organic silver salt crystals. In this case, silver halide grains may be concurrently present.
Organic silver salt grains preferably have a mean thickness of 0.005 to 0.05 μm (more preferably 0.005 to 0.03 μm) and a mean diameter of 0.05 to 0.5 μm. The grain diameter was determined in the following manner. An organic silver salt dispersion was diluted, dispersed on the grid provided with a carbon support membrane, and then photographed at a direct magnification of 5,000 times using a transmission type electron microscope (TEM, 2000 FX type, available from Nihon Denshi Co., Ltd.). The thus obtained negative electron micrographic images were read as a digital image by a scanner to determine the diameter (circular equivalent diameter) using appropriate software. At least 300 grains were so measured to determine an average diameter.
The grain thickness is determined using a transmission type electron microscope in the following manner. First, a light sensitive layer, coated onto a support, is pasted onto a suitable holder employing an adhesive and is cut perpendicular to the support surface employing a diamond knife to prepare an ultra-thin slice, at a thickness of 0.1 to 0.2 μm. The thus prepared ultra-thin slice is supported on a copper mesh, and is placed onto a carbon membrane, which has been made to be hydrophilic by means of a glow discharge. Then, while cooling the resulting slice to not more than −130° C., the image in a bright visual field is observed at a magnification of 5,000 to 40,000 employing a transmission electron microscope (hereinafter referred to as TEM), and then images are quickly recorded employing an image plate, a CCD camera, etc. In such a case, it is recommended to suitably select a portion of said slice, which has neither been torn nor distorted in the visual field for observation. The carbon membrane, which is supported by an organic film such as an extremely thin collodion, Formvar, etc., is preferably employed, and a film composed of only carbon, which is obtained by forming the film on a rock salt substrate and then dissolving away the substrate or by removing the foregoing organic film, employing an organic solvent or ion etching, is more preferably employed. The acceleration voltage of said TEM is preferably 80 to 400 kV, and is most preferably 80 to 200 kV.
Details of other means such as electron microscopic technology and sample preparation techniques can be referred to in “Igaku•Seibutsugaku Denshikenbikyo Kansatsuho (Medical and Biological Electron Microscopy”, edited by Nippon Denshikenbikyo Gakkai, Kanto-Shibu, (Maruzen), and “Denshikenbikyo Seibutsu Shiryo Sakuseiho (Preparation Method of Biological Samples for Electron Microscopy)”, edited by Nippon Denshikenbikyo Gakkai, Kanto-Shibu, (Maruzen).
The TEM image, recorded in an appropriate medium, is decomposed to at least 1024×1024 pixels or preferably at least 2048×2048 pixels, and is then subjected to image processing employing a computer. In order to carry out image processing, an analogue image recorded on a film strip is converted into a digital image employing a scanner etc., and the resulting image is preferably subjected to shading correction, contrast-edge enhancement, etc., based on specific requirements. Thereafter, a histogram is prepared and the portions corresponding to organic silver are extracted employing binary processing. At least 300 grains of the organic silver salt were manually measured with respect to the thus extracted thickness employing appropriate software.
The method for preparing organic silver salt grains having a mean thickness of 0.005 to 0.05 μm and a mean diameter of 0.05 to 0.5 μm is not specifically limited. The optimization of various conditions such as maintaining the mixing state during the formation of an organic acid alkali metal salt soap and/or the mixing state during the addition of silver nitrate to said soap. The shape of organic silver salt grains is not specifically limited, including various forms such as tabular, bar-like, needle and spherical forms. Tabular grains, each of which has a relatively large surface area so that supplying silver ions is promoted during thermal development, are preferred.
In this invention, mechanical pulverization of organic silver salt grains formed is not so preferable, specifically in the method of forming silver halide grains during the formation of organic silver salt grains. However, in cases when dispersing dried cakes containing organic silver salt grains and silver halide grains, there may be employed a suitable dispersing machine. An intensive mixer, such as a high pressure homogenizer is also usable, if used for a short period. During said preliminary dispersion, ordinary stirrers such as an anchor type, a propeller type, etc., a high speed rotation centrifugal radial type stirrer (Dissolver), as a high speed shearing stirrer (homo-mixer) may be employed. Furthermore, employed as the media homogenizer may be rolling mills such as a ball mill, a satellite ball mill, a vibrating ball mill, medium agitation mills such as a bead mill, atriter, and others such as a basket mill. Employed as high pressure homogenizer may be various types such as a type in which collision occurs against a wall or a plug, a type in which liquid is divided into a plurality of portions and said portions are subjected to collision with each other, a type in which liquid is forced to pass through a narrow orifice, etc. Examples of ceramics employed as the ceramic beads include Al2O3, BaTiO3, SrTiO3, MgO, ZrO, BeO, Cr2O3, SiO3, SiO2-Al2O3, Cr2O3—MgO, MgO—CaO, MoO—C, MgO—Al2O3 (spinel), SiC, TiO2, K2O, Na2O, BaO, PbO, B2O3, BeAl2O4, Y3Al5O12, ZrO2—Y2O3 (cubic zirconia), 3BeO—Al2O3—6SiO2 (artificial emerald), C (artificial diamond), SiO2—nH2O, silicone nitride, yttrium-stabilized-zirconia, zirconia-reinforced-alumina. Yttrium-stabilized-zirconia and zirconia-reinforced-alumina are preferably employed in view that little impurity is generated by friction among the beads or the classifier during classifying them. The ceramics containing zirconia are called zirconia as an abbreviation.
In devices employed for dispersing the tabular organic silver salt grains employed in the present invention, preferably employed as the members which are in contact with the organic silver salt grains are ceramics such as zirconia, alumina, silicone nitride, boron nitride, or diamond. Of these, zirconia is the one most preferably employed. While carrying out of the above-mentioned dispersion, the binder is preferably added so as to achieve a concentration of 0.1 to 10 wt % with reference to the weight of the organic silver salt, and the temperature is preferably maintained at no less than 45° C. from the preliminary dispersion to the main dispersion process. An example of the preferable operation conditions of a homogenizer, when employing high-pressure homogenizer as the dispersing machine, is twice or more operations at 300 to 1,000 kgf/cm2. In the case when a media-dispersing machine is employed, a circumferential speed of 6 to 13 m/sec. is preferable.
In the preparation process of organic silver salt grains, it is preferred to prepare aliphatic carboxylic acid silver salt grains concurrently in the presence of a compound capable of functioning as a crystal growth retarding agent or dispersing agent for aliphatic carboxylic acid silver salt grains. The compound capable of functioning as a crystal growth retarding agent or dispersing agent for aliphatic carboxylic acid silver salt grains refers to one which has a function or effect of forming grains with reduced size and enhanced uniformity thereof when prepared in the presence of the compound, as compared to the absence thereof. Specific examples of such compounds include monohydric alcohols having 10 or less carbon atoms (preferably secondary and tertiary alcohols), glycols such as ethylene glycol and propylene glycol, poly-ethers such as polyethylene glycol, and glycerin. Such compounds are added in an amount of 10 to 200% by weight, based on aliphatic carboxylic acid silver salt.
Branched aliphatic carboxylic acids including isomers thereof are also preferable, such as iso-heptanoic acid, iso-decanoic acid, iso-tridecanoic acid, iso-myristic acid, iso-palmitic acid, iso-stearic acid, iso-arachidic acid, iso-behenic acid and iso-hexanoic acid. In this case, a preferable branched chain is an alkyl or alkenyl group having 4 or less carbon atoms. Further, unsaturated aliphatic carboxylic acids are cited, such as palmothreic acid, oleic acid, linolic acid, linoleic acid, moroctic acid, eicosenic acid, arachidonic acid, eicopentaenic acid, erucic acid, docosapentaenic acid, and selacholeic acid. These compounds are added in an amount of 0.5 to 10 mol %, based on aliphatic carboxylic acid silver salt.
Preferred compounds include glycosides such as gluciside, galactoside and fructoside; trehalose type disaccharides such as trahalose and sucrose; polysaccharides such as glycogen, dextrin, dextran and alginic acid cellosolves such as methyl cellosolve and ethyl cellosolve; wate-soluble organic solvents such as sorbitan, sorbitol, ethyl acetate, methyl acetate, and dimethyl formamide; water-soluble polymers such as polyvinyl alcohol, polyacrylic acid, acrylic acid copolymer, maleic acid copolymer, carboxymethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose, polyvinyl pyrrolidone and gelatin. These compounds are added preferably in an amount of 0.1 to 20% by weight.
Alcohols having 10 or less carbon atoms are preferred, and the use of secondary or tertiary alcohols enhances solubility of sodium salt of an aliphatic carboxylic acid, resulting in reduced viscosity and enhancing stirring efficiency, leading to formation of monodisperse fine grains. Branched aliphatic carboxylic acids and unsaturated carboxylic acids exhibit higher steric hindrance than straight chain aliphatic carboxylic acids, resulting in fine crystals due to increased disorder in crystal lattice.
With regard to the difference in constitution between a conventional silver salt photographic material and a photothermographic imaging material, the photothermographic imaging material contains relatively large amounts of light sensitive silver halide, a carboxylic acid silver salt and a reducing agent which often cause fogging and silver printing-out (print out silver). In the photothermographic imaging material, therefore, an enhanced technique for antifogging and image-lasting is needed to maintain storage stability not only before development but also after development. In addition to commonly known aromatic heterocyclic compounds to restrain growth of fog specks and development thereof, there were used mercury compounds having a function of allowing the fog specks to oxidatively die away. However, such a mercury compound causes problems with respect to working safety and environment protection.
Next, antifoggants and image stabilizers used in the photothermographic imaging material relating to the invention will be described.
In photothermographic materials relating to this invention are employed reducing agents containing a proton, such as bisphenols and sulfonamidophenols. Accordingly, a compound generating a labile species which is capable of abstracting a proton to deactivate the reducing agent is preferred. More preferred is a compound as a non-colored photo-oxidizing substance, which is capable of generating a free radical as a labile species on exposure. Any compound having such a function is applicable. However, a halogen radical, which easily forms silver halide is not preferred. An organic free radical composed of plural atoms is preferred. Any compound having such a function and exhibiting no adverse effect on the photothermographic material is usable irrespective of its structure.
Of such free radical generation compounds, a compound containing an aromatic, and carbocyclic or heterocyclic group is preferred, which provides stability to the generated free radical so as to be in contact with the reducing agent for a period sufficient to react with the reducing agent to deactivate it. Representative examples of such compounds include biimidazolyl compounds and iodonium compounds.
Of such imidazolyl compounds, a compound represented by the following formula (1) is preferred:
wherein R1, R2 and R3, which may be the same or different, are each a hydrogen atom, an alkyl group, an alkenyl group, an alkoxyl group, an aryl group, hydroxy, a halogen atom, an aryloxyl, an alkylthio group, an arylthio group, an acyl group a sulfonyl group, an acylamino group, sulfonylamino group, an acyloxy group, carboxy, cyano, a sulfo group, or an amino group. Of these groups are preferred an aryl group, an alkenyl group and cyano group.
The biimidazolyl c0mpounds can be synthesized in accordance with the methods described in U.S. Pat. No. 3,734,733 and British Patent 1,271,177. Preferred Examples thereof are shown below.
Similarly preferred compounds include an iodonium compound represented by the following formula (2):
wherein Q1 is a group of atoms necessary to complete a 5-, 6-, or 7-membered ring, and the atoms being selected from a carbon atom, nitrogen atom, oxygen atom and sulfur atom; and R1, R12 and R13, which may be the same or different, are each a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, hydroxy, a halogen atom, an aryloxy, an alkylthio group, an arylthio group, an acyl group a sulfonyl group, an acylamino group, sulfonylamino group, an acyloxy group, carboxy, cyano, a sulfo group, or an amino group. Of these groups are preferred an aryl group, an alkenyl group and cyano group. Of these groups are preferred an aryl group, an alkenyl group and cyano group, provided that R11, R12 and R13 may be bonded with each other to form a ring; R14 is a carboxylate group or O−; m is 0 or 1, provided that when R13 is a sulfo group or a carboxy group, m is 0 and R14 is O−; X− is an anionic counter ion, including CH3CO2—, CH3SO3— and PF6−. Of these is specifically preferred a compound represented by the following formula (3):
wherein R1, R12, R13, R14, X− and m are each the same as defined in the foregoing formula (2); Y is a carbon (i.e., —CH═) to form a benzene ring or a nitrogen (i.e., —N═) to form a pyridine ring.
The iodonium compounds described above can be synthesized in accordance with the methods described in Org. Syn., 1961 and Fieser, “Advanced Organic Chemistry” (Reinhold, N.Y., 1961). Substituents and specific examples thereof are detailed in, for example, JP-A No. 2000-321711.
The compound releasing a labile species other than a halogen atom, such as represented by formula (1) or (2) is incorporated preferably in an amount of 10−3 to 10−1 mol/m2, and more preferably 5×10−3 to 5×10−2 mol/m2. The compound may be incorporated into any component layer of the photothermographic material relating to the invention and is preferably incorporated in the vicinity of a reducing agent.
As a compound capable of deactivating a reducing agent to inhibit reduction of an organic silver salt to silver by the reducing agent are preferred compounds releasing a labile species other than a halogen atom. However, these compounds may be used in combination with a compound capable of releasing a halogen atom as a labile species.
Examples of the compound releasing an active halogen atom include a compound represented by the following formula (4):
wherein Q2 is an aryl group or a heterocyclic group; X1, X2 and X3 are each a hydrogen atom, a halogen atom, a haloalkyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group, an aryl group or a heterocyclic group, provided that at least of them a halogen atom; Y is —C(═O)—, —SO— or —SO2—. The aryl group represented by Q2 may be a monocyclic group or condensed ring group and is preferably a monocyclic or di-cyclic aryl group having 6 to 30 carbon atoms (e.g., phenyl, naphthyl), more preferably a phenyl or naphthyl group, and still more preferably a phenyl group. The heterocyclic group represented by Q2 is a 3- to 10-membered, saturated or unsaturated heterocyclic group containing at least one of N, O and S, which may be a monocyclic or condensed with another ring to a condensed ring. Substituents are detailed in JP-A No. 2001-263350, paragraph [0100] through [0103].
The amount of this compound to be incorporated is preferably within the range in which an increase of printed-out silver caused by formation of silver halide becomes substantially no problem, more preferably not more than 150% by weight and still more preferably not more than 100% by weight, based on the compound releasing no active halogen atom.
Further, in addition to the foregoing compounds, compounds commonly known as an antifoggant may be incorporated in the photothermographic imaging material used in the invention. In such a case, the compounds may be those which form a labile species similarly to the foregoing compounds or those which are different in antifogging mechanism. Examples thereof include compounds described in U.S. Pat. Nos. 3,589,903, 4,546,075 and 4,452,885; JP-A No. 59-57234; U.S. Pat. Nos. 3,874,946 and 4,756,999; and JP-A Nos. 9-288328 and 9-90550. Further, other antifoggants include, for example, compounds described in U.S. Pat. No. 5,028,523 and European patent Nos. 600,587, 605,981 and 631,176.
Reducing agents for silver ions (also referred to as reducing agent) are used in this invention, including polyphenol compounds described in U.S. Pat. Nos. 3,589,903, 4,021,249, British Patent No. 1,486,148, JP-A Nos. 51-51933, 50-36110, 50-116023, 52-84727 and JP-B No. 51-35727 (hereinafter, the term, JP-B refers to Japanese Patent Publication); bisnaphthols such as 2,2′-dihydroxy-1,1′-binaphthyl described in U.S. Pat. No. 3,672,904; and sulfonamidophenols or sulfoneamidonaphthols such as 4-benzenesulfoneamidophenol, 2-benzeneamidophenol, 2,6-dichloro4-benzenesulfoneamidophenol and 4-benzenesulfoneamidonaphthol, described in U.S. Pat. No. 3,801,321.
Further, a reducing agent represented by the following formula (A-4) is preferably used in this invention:
wherein R11 and R12 are each a hydrogen atom, a 3- to 10-membered non-aromatic ring group or 5- or 6-membered aromatic ring group, provided that R11 and R12 are not hydrogen atoms at the same time; R13 and R14 are each a hydrogen atom, an alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group or heterocyclic group; Q is a substituent capable of being substituted on a benzene ring; n is an integer of 0, 1 or 2, provided that when n is 2, two Qs may be the same or different.
Of the 3- to 10-membered non-aromatic ring groups represented by R11 and R12, 3-membered non-aromatic ring groups include, for example, cyclopropyl, aziridyl and oxiranyl; 4-membered ring groups include cyclobutyl, cyclobutenyl, oxetanyl and azetiddinyl; 5-membered ring groups include cyclopentyl, cyclopentenyl, cyclopentadienyl, tetrahydrofuranyl, pyrrolidinyl and tetrahydrothienyl; 6-membered ring groups include cyclohexyl, cyclohexenyl, cyclohexadienyl, tetrahydropiranyl, piperidinyl, dioxanyl, tetrahydrothiopyranyl, norcaranyl, norpiranyl and norbonyl; 7-membered ring groups include cycloheptyl, cycloheptenyl and cycloheptadienyl; 8-membered ring groups include cyclooctanyl, cyclooctenyl, cyclootadienyl and cyclooctatrienyl; 9-membered ring groups include cyclononanyl, cyclononenyl, cyclononadienyl and cyclononatrienyl; 10-membered ring groups include cyclodecanyl, cyclodecenyl, cyclodecadienyl andcyclodecatrienyl. Of the foregoing 3- to 10-membered ring groups, 3- to 6-membered ring groups are preferred, 5- and 6-membered ring groups are more preferred, and a 6-membered ring group is still more preferred. Further, hydrocarbon rings containing no heteroatom are specifically preferred. These rings may form a spiro-bonding through a spiro atom or may be condensed with other rings including an aromatic ring.
The foregoing ring groups may be substituted. Examples of substituent groups include a halogen atom (e.g., fluorine, chlorine, bromine), cycloalkyl group (e.g., cyclohexyl, cycloheptyl), cycloalkenyl group (e.g., 1-cyclalkenyl, 2-cycloalkenyl), alkoxy group (e.g., methoxy, ethoxy, propoxy), alkylcarbonyloxy group (e.g., acetyloxy), alkylthio group (e.g., methylthio, trifluoromethylthio), carboxyl group, alkylcarbonylamino group (e.g., acetylamino), ureido group (e.g., methylaminocarbonylamino), alkylsulfonyl group (e.g., methanesulfonyl, trifluoromethanesulfonyl), carbamoyl group (e.g., carbamoyl, N,N-dimethylcarbamoyl, N-morpholinocarbonyl), sulfamoyl group (e.g., sulfamoyl, N,N-dimethylsulfamoyl, morpholinosulfamoyl), trifluoromethyl, hydroxy, nitro, cyano, alkylsulfonamido group (e.g., methanesulfonamido, butanesulfoneamido), alkylamino group (e.g., N,N-dimethylamino, N,N-diethylamino), sulfo group, phosphono group, sulfite group, sulfino group, alkylsulfonylaminocarbonyl group (e.g., methanesulfonylaminocarbonyl, ethanesulfonylaminocarbonyl), alkylcarbonylaminosulfonyl group (e.g., acetoamidosulfonyl, methoxyacetoamidosulfonyl), alkynylaminocarbonyl group (e.g., acetoamidocarbonyl, methoxyacetoamidocarbonyl), and alkylsulfinylaminocarbonyl group (e.g., methanesulfinylaminocarbonyl, ethane sulfinylaminocarbonyl). In the case of being substituted by plural substituents, the plural substituents may be the same or different. Of the foregoing substituent groups, an alkyl group is specifically preferred.
The 5- or 6-membered aromatic ring group designated by R11 and R12 may be a monocyclic group or a condensed ring group, and is preferably a monocyclic or bicyclic aromatic carbon ring (e.g., benzene ring, naphthalene ring), and more preferably a benzene ring. An aromatic heterocycle is preferably a 5- or 6-membered aromatic heterocycle, and more preferably a 5-membered aromatic heterocycle, which may be condensed with other rings. Examples of preferred heterocycles include imidazole, pyrazolo, thiophene, furan, pyrrole, pyridine, pyrimidine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazolone, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, benzthiazole, indolenine and tetrazaindene; and imidazole, pyrazole, thiophene, furan, pyrrole, triazole, thiadiazole, tetrazole, thiazole, benzimidazole, and benzthiazole are more preferred. The foregoing rings may be condensed with other rings, on which any substituent may be substituted. Examples of such substituents are the same as described in the foregoing 3- to 10-membered non-aromatic ring groups.
Most preferred combination of R11 and R12 is R11 of a 5-membered aromatic heterocyclic group and R12 of a hydrogen atom.
R13 and R14 are each a hydrogen atom, an alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group or heterocyclic group. The alkyl group is preferably one having 1 to 10 carbon atoms. Examples thereof include methyl, ethyl, propyl, iso-propyl, butyl, t-butyl, pentyl, iso-pentyl, 2-ethyl-hexyl, octyl, decyl, cyclohexyl, cyclopropyl, 1-methylcyclohexyl, ethenyl-2-propenyl, 3-butenyl, 1-methyl-3-propenyl, 3-pentenyl, 1-methyl-3-butenyl, 1-cycloalkenyl group, 2-cycloalkenyl group, ethynyl and 1-propynyl. R13 is preferably methyl, ethyl, iso-propyl, t-butyl, cyclohexyl, and 1-methylcyclohexyl, more preferably methyl, t-butyl, and 1-methylcyclohexyl, and still more preferably t-butyl and 1-methylcyclohexyl. R14 is preferably methyl, ethyl, iso-propyl, t-butyl, cyclohexyl, 1-methylcyclohexyl, and 2-hydroxyethyl, and more preferably methyl and 2-hydroxyethyl. Examples of an aryl group represented by R13 and R14 include phenyl, naphthyl and anthranyl group. Examples of a heterocyclic group represented by R13 and R14 include aromatic heterocyclic groups such as a pyridine group, quinoline group, isoquinoline group, imidazole group, pyrazole group, triazole group, oxazole group, thiazole group, oxadiazole group, thiadiazole group, and tetrazole group, and non-aromatic heterocyclic groups such as piperidino, morpholino group, tetrahydrofuryl, tetrahydrothienyl, and tetrahydropyranyl. These groups may be substituted, and substituent are the same as described above. The most preferable combination of R13 of a tertiary alkyl group (e.g., t-butyl, 1-methylcyclohexyl) and R14 of a primary alkyl group (e.g., methyl, 2-hydroxyethyl) is most preferred.
Q is a group capable of being substituted on a benzene ring. Specific example thereof include an alkyl group having 1 to 25 carbon atoms (e.g., methyl, ethyl, propyl, iso-propyl, t-butyl, pentyl), halogenated alkyl group (e.g., trifluoromethyl, perfluorooctyl), cycloalkyl group (e.g., cyclohexyl, cyclopentyl), alkynyl group (e.g., propargyl), glycidyl group, acrylate group, methacrylate group, aryl group (e.g., phenyl), heterocyclic group (pyridyl, thiazolyl, pyrimidyl, pyridadinyl, selenazolyl, sulfolanyl, piperidinyl, pyrazolinyl, pyrazolyl, tetrazolyl), halogen atom (e.g., chlorine, bromine, iodine, fluorine), alkoxy group (e.g., methoxy, ethoxy, propyloxy, pentyloxy, cyclopentyloxy, hexyloxy, cyclohexyloxy), aryloxy group (e.g., phenoxy), alkoxycarbonyl group (e.g., methyloxycarbonyl, ethyloxycarbonyl, butyloxycarbonyl), aryloxycarbonyl group (e.g., phenyloxycarbonyl), sulfoneamido group (e.g., methanesulfoneamido, ethanesulfoneamido, butanesulfoneamido, hexanesulfoneamido, cycohexanesulfoneamido, benzenesulfoneamido), sulfamoyl group (e.g., aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, butylaminosulfonyl, hexylaminosulfonylcyclohexylaminosulfonyl, phenylaminosulfonyl, 2-pyridylaminosulfonyl), urethane group (e.g., methylureido, ethylureido, pentylureido, cylohexylureido, phenylureido, 2-pyridylureido), acyl group (e.g., acetyl, propionyl, butanoyl, hexanoyl, cyclohexanoyl, benzoyl, pyridinoyl), carbamoyl group (e.g., aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, propylaminocarbonyl, pentylaminocarbonyl, cyclohexylaminocarbonyl, phenylamiocarbonyl, 2-pyridylaminocarbonyl), amido group (e.g., acetoamide, propioneamido, butaneamido, hexaneamido, benzamido), sulfonyl group (e.g., methylsulfinyl, ethylsulfinyl, butylsulfonyl, cyclohexylsulfonly, phenylsulfinyl, 2-pyridylsulfonyl), amino group (e.g., amino, ethylamino, dimetylamino, butylamino, cyclopentylamino, anilino, 2-pyridylamino), cyano, nitro, sulfo, carboxyl, hydroxy, and oxamoyl. These groups may further be substituted by the foregoing group. In the formula (A-4), n is 0, 1 or 2, and preferably 0. Plural Qs may be the same or different.
Specific example of the compound represented by formula (A-4) are shown below.
The amount of a reducing agent for silver ions to be used in photothermographic materials relating to this invention, depending on the kind of organic silver salts, reducing agent, or other additives is usually 0.05 to 10 mol, and preferably 0.1 to 3 mol per mol of organic silver salt. wo or more reducing agents may be used in combination, in an amount within the foregoing range. Addition of the reducing agent to a light sensitive emulsion comprising a light sensitive silver halide, organic silver salt grains and a solvent immediately before coating the emulsion is often preferred, thereby minimizing variation in photographic performance during standing.
Silver halide grains used in the invention can be subjected to chemical sensitization. In accordance with methods described in Japanese Patent Application Nos. 2000-57004 and 2000-61942, for example, a chemical sensitization center (chemical sensitization speck) can be formed using compounds capable of releasing chalcogen such as sulfur or noble metal compounds capable of releasing a noble metal ion such as a gold ion. In the invention, it is preferred to conduct chemical sensitization with an organic sensitizer containing a chalcogen atom, as described below. Such a chalcogen atom-containing organic sensitizer is preferably a compound containing a group capable of being adsorbed onto silver halide and a labile chalcogen atom site. These organic sensitizers include, for example, those having various structures, as described in JP-A Nos. 60-150046, 4-109240 and 11-218874. Specifically preferred of these is at least a compound having a structure in which a chalcogen atom is attacked to a carbon or phosphorus atom through a double bond. The amount of a chalcogen compound added as an organic sensitizer is variable, depending on the chalcogen compound to be used, silver halide grains and a reaction environment when subjected to chemical sensitization and is preferably 10−8 to 10−2 mol, and more preferably 10−7 to 10−3 mol per mol of silver halide. In the invention, the chemical sensitization environment is not specifically limited but it is preferred to conduct chemical sensitization in the presence of a compound capable of eliminating a silver chalcogenide or silver specks formed on the silver halide grain or reducing the size thereof, or specifically in the presence of an oxidizing agent capable of oxidizing the silver specks, using a chalcogen atom-containing organic sensitizer. To conduct chemical sensitization under preferred conditions, the pAg is preferably 6 to 11, and more preferably 7 to 10, the pH is preferably 4 to 10 and more preferably 5 to 8, and the temperature is preferably not more than 30° C.
In photothermographic imaging materials used in the invention, it is preferred to use a light sensitive emulsion, in which light sensitive silver halide has been subjected to chemical sensitization using a chalcogen atom-containing organic sensitizer at a temperature of 30° C. or higher, concurrently in the presence of an oxidizing agent capable of oxidizing silver specks formed on the silver halide grains, then, mixed with an organic silver salt, dehydrated and dried.
Chemical sensitization using the foregoing organic sensitizer is also preferably conducted in the presence of a spectral sensitizing dye or a heteroatom-containing compound capable of being adsorbed onto silver halide grains. Thus, chemical sensitization in the present of such a silver halide-adsorptive compound results in prevention of dispersion of chemical sensitization center specks, thereby achieving enhanced sensitivity and minimized fogging. Although there will be described spectral sensitizing dyes used in the invention, preferred examples of the silver halide-adsorptive, heteroatom-containing compound include nitrogen containing heterocyclic compounds described in JP-A No. 3-24537. In the heteroatom-containing compound, examples of the heterocyclic ring include a pyrazolo ring, pyrimidine ring, 1,2,4-triazole ring, 1,2,3-triazole ring, 1,3,4-thiazole ring, 1,2,3-thiadiazole ring, 1,2,4-thiadiazole ring, 1,2,5-thiadiazole ring, 1,2,3,4-tetrazole ring, pyridazine ring, 1,2,3-triazine ring, and a condensed ring of two or three of these rings, such as triazolotriazole ring, diazaindene ring, triazaindene ring and pentazaindene ring. Condensed heterocyclic ring comprised of a monocycic hetero-ring and an aromatic ring include, for example, a phthalazine ring, benzimidazole ring indazole ring, and benzthiazole ring. Of these, an azaindene ring is preferred and hydroxy-substituted azaindene compounds, such as hydroxytriazaindene, tetrahydroxyazaindene and hydroxypentazaundene compound are more preferred. The heterocyclic ring may be substituted by substituent groups other than hydroxy group. Examples of the substituent group include an alkyl group, substituted alkyl group, alkylthio group, amino group, hydroxyamino group, alkylamino group, dialkylamino group, arylamino group, carboxy group, alkoxycarbonyl group, halogen atom and cyano group. The amount of the heterocyclic ring containing compound to be added, which is broadly variable with the size or composition of silver halide grains, is within the range of 10−6 to 1 mol, and preferably 10−4 to 10−1 mol per mol silver halide.
As described earlier, silver halide grains can be subjected to noble metal sensitization using compounds capable of releasing noble metal ions such as a gold ion. Examples of usable gold sensitizers include chloroaurates and organic gold compounds. In addition to the foregoing sensitization, reduction sensitization can also be employed and exemplary compounds for reduction sensitization include ascorbic acid, thiourea dioxide, stannous chloride, hydrazine derivatives, borane compounds, silane compounds and polyamine compounds. Reduction sensitization can also conducted by ripening the emulsion while maintaining the pH at not less than 7 or the pAg at not more than 8.3. Silver halide to be subjected to chemical sensitization may be one which has been prepared in the presence of an organic silver salt, one which has been formed under the condition in the absence of the organic silver salt, or a mixture thereof.
Light sensitive silver halide grains used in the invention are preferably subjected to spectral sensitization by allowing a spectral sensitizing dye to adsorb to the grains. Examples of the spectral sensitizing dye include cyanine, merocyanine, complex cyanine, complex merocyanine, holo-polar cyanine, styryl, hemicyanine, oxonol and hemioxonol dyes, as described in JP-A Nos. 63-159841, 60-140335, 63-231437, 63-259651, 63-304242, 63-15245; U.S. Pat. Nos. 4,639,414, 4,740,455, 4,741,966, 4,751,175 and 4,835,096. Usable sensitizing dyes are also described in Research Disclosure (hereinafter, also denoted as RD) 17643, page 23, sect. IV-A (December, 1978), and ibid 18431, page 437, sect. X (August, 1978). It is preferred to use sensitizing dyes exhibiting spectral sensitivity suitable for spectral characteristics of light sources of various laser imagers or scanners. Examples thereof include compounds described in JP-A Nos. 9-34078, 9-54409 and 9-80679.
Useful cyanine dyes include, for example, cyanine dyes containing a basic nucleus, such as thiazoline, oxazoline, pyrroline, pyridine, oxazole, thiazole, selenazole and imidazole nuclei. Useful merocyanine dyes preferably contain, in addition to the foregoing nucleus, an acidic nucleus such as thiohydatoin, rhodanine, oxazolidine-dione, thiazoline-dione, barbituric acid, thiazolinone, malononitrile and pyrazolone nuclei. In the invention, there are also preferably used sensitizing dyes having spectral sensitivity within the infrared region. Examples of the preferred infrared sensitizing dye include those described in U.S. Pat. Nos. 4,536,478, 4,515,888 and 4,959,294.
The infrared sensitizing dye relating to the invention is preferably a long chain polymethine dye, in which a sulfinyl group is substituted on the benzene ring of the benzothiazole ring.
The infrared sensitizing dyes and spectral sensitizing dyes described above can be readily synthesized according to the methods described in F. M. Hammer, The Chemistry of Heterocyclic Compounds vol. 18, “The cyanine Dyes and Related Compounds” (A. Weissberger ed. Interscience Corp., New York, 1964).
The infrared sensitizing dyes can be added at any time after preparation of silver halide. For example, the dye can be added to a light sensitive emulsion containing silver halide grains/organic silver salt grains in the form of by dissolution in a solvent or in the form of a fine particle dispersion, so-called solid particle dispersion. Similarly to the heteroatom containing compound having adsorptivity to silver halide, after adding the dye prior to chemical sensitization and allowing it to be adsorbed onto silver halide grains, chemical sensitization is conducted, thereby preventing dispersion of chemical sensitization center specks and achieving enhanced sensitivity and minimized fogging.
These sensitizing dyes may be used alone or in combination thereof. The combined use of sensitizing dyes is often employed for the purpose of supersensitization. A super-sensitizing compound, such as a dye which does not exhibit spectral sensitization or substance which does not substantially absorb visible light may be incorporated, in combination with a sensitizing dye, into the emulsion containing silver halide grains and organic silver salt grains used in photothermographic imaging materials of the invention.
Useful sensitizing dyes, dye combinations exhibiting super-sensitization and materials exhibiting supersensitization are described in RD17643 (published in December, 1978), IV-J at page 23, JP-B 9-25500 and 43-4933 (herein, the term, JP-B means published Japanese Patent) and JP-A 59-19032, 59-192242 and 5-341432. In the invention, an aromatic heterocyclic mercapto compound represented by the following formula (6) is preferred as a supersensitizer:
Ar—SM formula (6)
wherein M is a hydrogen atom or an alkali metal atom; Ar is an aromatic ring or condensed aromatic ring containing a nitrogen atom, oxygen atom, sulfur atom, selenium atom or tellurium atom. Such aromatic heterocyclic rings are preferably benzimidazole, naphthoimidazole, benzthiazole, naphthothiazole, benzoxazole, naphthooxazole, benzoselenazole, benzotellurazole, imidazole, oxazole, pyrazole, triazole, triazines, pyrimidine, pyridazine, pyrazine, pyridine, purine, and quinoline. Other aromatic heterocyclic rings may also be included.
A disulfide compound which is capable of forming a mercapto compound when incorporated into a dispersion of an organic silver salt and/or a silver halide grain emulsion is also included in the invention. In particular, a preferred example thereof is a disulfide compound represented by the following formula:
Ar—S—S—Ar Formula [7]
wherein Ar is the same as defined in the mercapto compound represented by the formula described earlier.
The aromatic heterocyclic rings described above may be substituted with a halogen atom (e.g., Cl, Br, I), a hydroxy group, an amino group, a carboxy group, an alkyl group (having one or more carbon atoms, and preferably 1 to 4 carbon atoms) or an alkoxy group (having one or more carbon atoms, and preferably 1 to 4 carbon atoms).
In addition to the foregoing supersensitizers, a compound described in U.S. Pat. No. 6,457,710, represented by the following formula (5) and a macrocyclic compound can also employed as a supersensitizer in the invention:
wherein H31Ar represents an aromatic hydrocarbon group or aromatic heterocyclic group; T31 represents a bivalent aliphatic hydrocarbon linkage group, or a bond; J31 represents a linkage group containing at least one of an oxygen atom, sulfur atom and nitrogen atom, or a bond; Ra, Rb, Rc and Rd each represent a hydrogen atom, an acyl group, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group, provided that Ra and Rb, Rc and Rd, Ra and Rc, or Rb and Rd combine with each other to form a nitrogen containing heterocyclic ring; M31 represents an ion necessary to compensate for intramolecular charge; k31 is the number of ions necessary to compensate for intramolecular charge.
Details of substituents in the formula (5) and specific examples of the compound are described in U.S. Pat. No. 6,457,710. The supersensitizer is incorporated into a light-sensitive layer containing organic silver salt and silver halide grains, preferably in an amount of 0.001 to 1.0 mol, and more preferably 0.01 to 0.5 mol per mol of silver.
The silver-saving agent used in the invention refers to a compound capable of reducing the silver amount necessary to obtain a prescribed silver density. The action mechanism for the reducing function has been variously supposed and compounds having a function of enhancing covering power of developed silver are preferred. Herein the covering power of developed silver refers to an optical density per unit amount of silver. Examples of the preferred silver-saving agent include hydrazine derivative compounds represented by the following formula (H), vinyl compounds represented by formula (G) and quaternary onium compounds represented by formula (P):
In formula (H), A0 is an aliphatic group, aromatic group, heterocyclic group, each of which may be substituted, or -G0-D0 group; B0 is a blocking group; A1 and A2 are both hydrogen atoms, or one of them is a hydrogen atom and the other is an acyl group, a sulfonyl group or an oxalyl group, in which G0 is a —CO—, —COCO—, —CS—, —C(═NG1D1)—, —SO—, —SO2— or —P(O)(G1D1)— group, in which G1 is a bond, or a —O—, —S— or —N(D1)— group, in which D1 is a hydrogen atom, or an aliphatic group, aromatic group or heterocyclic group, provided that when a plural number of D1 are present, they may be the same with or different from each other and D0 is a hydrogen atom, an aliphatic group, aromatic group, heterocyclic group, amino group, alkoxy group, aryloxy group, alkylthio group or arylthio group. D0 is preferably a hydrogen atom, an alkyl group, an alkoxy group or an amino group.
In formula (H), an aliphatic group represented by A0 of formula (H) is preferably one having 1 to 30 carbon atoms, more preferably a straight-chained, branched or cyclic alkyl group having 1 to 20 carbon atoms. Examples thereof are methyl, ethyl, t-butyl, octyl, cyclohexyl and benzyl, each of which may be substituted by a substituent (such as an aryl, alkoxy, aryloxy, alkylthio, arylthio, sulfo-oxy, sulfonamido, sulfamoyl, acylamino or ureido group). An aromatic group represented by A0 of formula (H) is preferably a monocyclic or condensed-polycyclic aryl group such as a benzene ring or naphthalene ring. A heterocyclic group represented by A0 is preferably a monocyclic or condensed-polycyclic one containing at least one hetero-atom selected from nitrogen, sulfur and oxygen such as a pyrrolidine-ring, imidazole-ring, tetrahydrofuran-ring, morpholine-ring, pyridine-ring, pyrimidine-ring, quinoline-ring, thiazole-ring, benzthiazole-ring, thiophene-ring or furan-ring. The aromatic group, heterocyclic group or -G0-D0 group represented by A0 each may be substituted. Specifically preferred A0 is an aryl group or -G0-D0 group.
A0 contains preferably a non-diffusible group or a group for promoting adsorption to silver halide. As the non-diffusible group is preferable a ballast group used in immobile photographic additives such as a coupler. The ballast group includes an alkyl group, alkenyl group, alkynyl group, alkoxy group, phenyl group, phenoxy group and alkylphenoxy group, each of which has 8 or more carbon atoms and is photographically inert. The group for promoting adsorption to silver halide includes a thioureido group, thiourethane, mercapto group, thioether group, thione group, heterocyclic group, thioamido group, mercapto-heterocyclic group or a adsorption group as described in JP A 64-90439.
In Formula (H), B0 is a blocking group, and preferably -G0-D0. These substituents are detailed in Japanese Patent Application No. 2001-26335.
The compounds represented by the foregoing formula (H) can be readily synthesized according to method known in the art, for example, U.S. Pat. Nos. 5,464,738 and 5,496,695.
Furthermore, preferred hydrazine derivatives include compounds H-1 through H-29 described in U.S. Pat. No. 5,545,505, col. 11 to col. 20; and compounds 1 to 12 described in U.S. Pat. No. 5,464,738, col. 9 to col. 11. These hydrazine derivatives can be synthesized in accordance with commonly known methods.
In formula (G), X and R may be either cis-form or trans-form. The structure of its exemplary compounds is also similarly included.
In formula (G), X is an electron-with drawing group; W is a hydrogen atom, an alkyl group, alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a halogen atom, an acyl group, a thioacyl group, an oxalyl group, an oxyoxalyl group, a thiooxalyl group, an oxamoyl group, an oxycarbonyl group, a thiocarbonyl group, a carbamoyl group, a thiocarbmoyl group, a sulfonyl group, a sulfinyl group, an oxysulfinyl group, a thiosulfinyl group, a sulfamoyl group, an oxysulfinyl group, a thiosulfinyl group, a sulfinamoyl group, a phosphoryl group, nitro group, an imino group, a N-carbonylimino group, a N-sulfonylimino group, a dicyanoethylene group, an ammonium group, a sulfonium group, a phosphonium group, pyrylium group, or an inmonium group.
R40 is a halogen atom, hydroxy, an alkoxy group, an aryloxy group, a heterocyclic-oxy group, an alkenyloxy group, an acyloxy group, an alkoxycarbonyloxy group, an aminocarbonyloxy group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic-thio group, an alkenylthio group, an acylthio group, an alkoxycarbonylthio group, an aminocarbonylthio group, an organic or inorganic salt of hydroxy or mercapto group (e.g., sodium salt, potassium salt, silver salt, etc.), an amino group, a cyclic amino group (e.g., pyrrolidine), an acylamino group, an oxycarbonylamino group, a heterocyclic group (5- or 6-membered nitrogen containing heterocyclic group such as benztriazolyl, imidazolyl, triazolyl, or tetrazolyl), a ureido group, or a sulfonamido group. X and W, or X and R may combine together with each other to form a ring. Examples of the ring formed by X and W include pyrazolone, pyrazolidinone, cyclopentadione, β-ketolactone, and β-ketolactam.
In formula (G), the electron-withdrawing group represented by X refers to a substituent group exhibiting a negative Hammett's substituent constant σp. Details of these substituents are described in Japanese Patent Application No. 2001-263350.
In formula (P), Q3 is a nitrogen atom or a phosphorus atom; R41, R42, R43 and R44 each are a hydrogen atom or a substituent, provided that R41, R42, R43 and R44 combine together with each other to form a ring; and X− is an anion. Substituents represented by R41 through R44 and the ring formed by linking of R41 through R44 are detailed in Japanese Patent Application No. 2001-263350.
The quaternary onium salt compounds described above can be readily synthesized according to the methods commonly known in the art. For example, the tetrazolium compounds described above may be referred to Chemical Review 55, page 335–483.
Binders suitable for photothermographic materials are transparent or translucent and generally colorless, including natural polymers, synthetic polymers or copolymers and film forming mediums. Exemplary examples thereof include gelatin, gum Arabic, polyvinyl alcohol, hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, polyvinyl pyrrolidine, casein, starch, polyacrylic acid, poly(methyl methacrylate), poly(methylmethacrylic acid), polyvinyl chloride, polymethacrylic acid, copoly(styrene-anhydrous maleic acid), copoly(styrene-acrylonitrile), copoly(styrene-butadiene9, polyvinyl acetals (e.g., polyvinyl formal, polyvinyl butyral), polyesters, polyurethanes, phenoxy resin, polyvinylidene chloride, polyepoxides, polycarbonates, polyvinyl acetate, cellulose esters, and polyamides, these of which may be hydrophilic or hydrophobic.
Of these, polyvinyl acetals are preferred as a binder used for the light sensitive layer, and polyvinyl acetal is specifically preferred binder. Further, for a light insensitive layer such as an over-coating layer or a sublayer, specifically, a protective layer or a back coating layer are preferred cellulose esters exhibiting a relatively high softening temperature, such as triacetyl cellulose and cellulose acetate-butyrate. The foregoing binders may optionally be used in combination.
The binder is used in an amount within the range effective to function as a binder. The effective range can be readily determined by one skilled in the art. As a measure to hold an organic silver salt in the light sensitive layer, the ratio by weight of a binder to an organic silver salt is preferably 15:1 to 1:2, and more preferably 8:1 to 1:1. Thus, the amount of a binder in the light sensitive elayer is preferably 1.0 to 10 g/m2. The amount of less than 1.0 g/m2 results in an increase in unexposed areas, leading to levels unacceptable in practical use.
In one preferred embodiment of the invention, the photothermographic material which has been thermally developed at a temperature of 100 to 200° C., exhibits a thermal transition point of not less than 46 to 200° C. The thermal transition point is a value represented in Vicat softening point or a value represented in the ring and ball method, indicating an endothermic peak obtained when measuring the light-sensitive layer separated from the thermally developed photographic material, using a differential scanning calorimeter (or DSC, for example, EXSTAR 6000, available from SEIKO DENSHI KOGYO Co., Ltd.; DSC 220C, SEIKO DENSHI KOGYO Co., Ltd; and DSC-7, available from Perkin Elmer Co.). In general, polymeric compounds have a glass transition point (Tg). It was found by the inventors of the present invention that a large endothermic peak emerged at a temperature lower than the Tg value of binder resin used in the light-sensitive layer. As a result of further study of this thermal transition point temperature, it was newly found that setting the thermal transition point to a temperature of not less than 46° C. and not more than 200° C. prevented softening of the coating layer, thereby preventing abrasion marks.
The glass transition point (Tg) can be determined in accordance with the method described in “Polymer Handbook” at page III-139 to III-179 (1966, published by Wirey and Sons).
In cases where the binder is a copolymer resin, Tg is defined by the following equation:
Tg(copolymer)=v1Tg1+v2Tg2+ . . . +vnTgn
where v1, v2, . . . vn each represent a weight fraction of respective monomers of the copolymer; Tg1, Tg2, . . . Tgn each represent a glass transition point, Tg (° C.) of a homopolymer obtained by each of monomers constituting the copolymer. The precision of the Tg calculated by the foregoing equation is within ±5° C.
There can be employed commonly known polymeric compounds as a binder. The glass transition point is preferably 70 to 105° C.; the number average molecular weight is preferably 1,000 to 1,000,000, and more preferably 10,000 to 500,000; and the degree of polymerization is preferably 50 to 1000. Examples thereof include compounds of a polymer or copolymer containing ethylenically unsaturated monomers as a constituting unit, such as vinyl chloride, vinyl acetate, vinyl alcohol, maleic acid, acrylic acid, acrylic acid ester, vinylidene chloride, acrylonitrile, methacrylic acid, methacrylic acid ester, styrene, butadiene, ethylene, vinyl butyral, vinyl acetal and vinyl ether; polyurethane resin, and various kinds of rubber resin. In addition thereto, phenol resin, epoxy resin, polyurethane thermally hardening type resin, urea resin, melamine resin, alkyd resin, formaldehyde resin, silicone resin, epoxy-polyamide resin, and polyester resin are also usable. These resins are detailed in “Plastic Handbook” published by Asakura-shoten. The foregoing polymeric compounds are not specifically limited and there is usable any one having a glass transition point (Tg) of 70 to 105° C., including homopolymers and copolymers.
Examples of polymer containing an ethylenically unsaturated monomer as a constituting unit and its copolymer include acrylic acid alkyl esters, acrylic acid aryl esters, methacrylic acid alkyl esters, methacrylic acid aryl esters, cyanoacrylic acid alkyl esters, and cyanoacrylic acid aryl esters, in which the alkyl or aryl group may be substituted. Examples of substituent groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, amyl, hexyl, cyclohexyl, benzyl, chlorobenzyl, octyl, stearyl, sulfopropyl, N-ethyl-phenylethyl, 2-(3-phenylpropyloxy)ethyl, dimethylaminophenoxyethyl, furfuryl, tetrahydrofurfuryl, phenyl, cresyl, naphthyl, 2-hydroxyethyl, 4-hydroxybutyl, triethylene glycol, dipropylene glycol, 2-methoxyethyl, 3-methoxybutyl, 2-aetoxyethyl, 2-acetoxyacetoxyethyl, 2-ethoxyethyl, 2-iso-propoxy, 2-butoxyethyl, 2-(2-methoxy)ethyl, 2-(2-ethoxyethoxy)ethyl, 2-(2-butoxyethoxy)ethyl, 2-diphenylphosphorylethyl, ω-methoxyethylene glycol (addition mole number n=6)allyl, and a dimethylaminoethyl chloride salt. In addition, the following monomers are also usable, including vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxyacetate, vinyl phenylacetate, vinyl benzoate, and vinyl salicylate; N-substituted acrylamides, N-substituted methacrylamides, acrylamides and methacrylamides, in which N-substituting groups include, for example, methyl, ethyl, propyl, butyl, tert-butyl, cyclohexyl, benzyl, hydroxymethyl, methoxyethyl, dimethylaminoethyl, phenyl, dimethyl, diethyl, β-cyanoethyl, N-(2-acetoacetoxyethyl) and diacetone; olefins such as dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloprene, butadiene, and 2,3-dimethylbutadiene; styrenes such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, tert-butylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, and methyl vinylbenzoate; vinyl ethers such as methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, and dimethylaminoethyl vinyl ether; N-substituted maleimides, in which N-substituting groups include, for example, methyl, ethyl, propyl, butyl, tert-butyl, cyclohexyl, benzyl, n-dodecyl, phenyl, 2-methylphenyl, 2,6-diethylphenyl and 2-chlorophenyl; and others such as butyl crotonate, hexyl crotonate, dimethylitaconate, dibutyl itaconate, diethyl maleate, dimetyl maleate, dibutyl maleate, diethyl fumarate, dimethyl fumarate, dibutyl fumarate, methyl vinyl ketone, phenyl vinyl ketone, methoxy ethyl ketone, glycidyl acrylate, glycidyl methacrylate, N-vinyl oxazolidone, N-vinyl pyrrolidone, acrylonitrile, methacrylonitrile, methylene malonitrile, and vinylidene chloride.
Of these polymer compounds are preferred methacrylic acid alkyl esters, methacrylic acid aryl esters and styrenes. Specifically, polymer compounds containing an acetal group are preferred, which are superior in miscibility with organic acids produced, preventing softening of the layer.
The polymer compound containing an acetal group is preferably represented by the following formula (V):
wherein R51 is an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted aryl group, and a substituted aryl group; R52 is an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted aryl group, a substituted aryl group, —COR53 or —COR53, in which R53 is the same as defined in R51. The foregoing substituents are detailed in Japanese Patent Application No. 2001-263350.
Polyurethane resins having commonly known structures are usable in the invention, such as polyester-polyurethane, polyether-polyurethane, polyether-polyester-polyurethanepolycarbonate-polyurethane, polyester-polycarbonate-polyurethane, and polycaprolactone-polyurethane. In the foregoing polyurethanes, at least one polar group selected from —COOM, —SO3M, —OSO3M, —P═O(OM)2, —O—P═(OM)2 (in which M is a hydrogen atom or an alkali metal salt), —NR54, —N+R54 (in which R54 is a hydrocarbon group), epoxy group, —SH, and —CN is preferably introduced in copolymerization or addition reaction. Such a polar group is preferably contained in an amount of 10−8 to 10−1 mol/g, and more preferably 10−6 to 10−2 mol/g. In addition to the polar group, it is preferred to contain at least one OH group on the end of a polyurethane molecule, i.e., at least two Oh groups in total. The OH group is capable of reacting with a polyisocyanate as a hardening agent to form a three-dimensional network structure so that the more is contained in the molecule, the more preferred. Specifically, the OH group on the molecular end, which exhibits relatively high reactivity is preferred. Polyurethane having at least three OH groups (and preferably at least four OH groups) on the molecular end is preferred. Specifically, polyurethane exhibiting a glass transition point of 70 to 105° C., a rupture elongation of 100 to 2000% and a rupture stress of 0.5 to 100 N/mm2 is preferred.
Polymer compounds represented by the foregoing formula (V) can be synthesized in accordance with commonly known methods, as described, for example, in “Vinyl Acetate Resin” edited by Ichiro Sakurada (KOBUNSHIKAGAKU KANKOKAI, 1962).
Other polymer compounds, as shown in Table 1 were synthesized in a similar manner. These polymer compounds may be used singly or in a blended form of at least two thereof. The layer containing light-sensitive silver salt (preferably, light-sensitive layer) preferably contains the foregoing polymer compounds as a main binder. The main binder refers to the state in which at least 50% by weight of the total binder of the light-sensitive silver salt-containing layer is accounted for by the foregoing polymer. Accordingly, other polymer(s) may be blended within the range of less than 50% by weight of the total binder. Such polymer(s) are not specifically limited so long as a solvent capable of dissolving the foregoing polymer is used. Examples of such polymer(s) include polyvinyl acetate, polyacryl resin and polyurethane resin.
The composition of the foregoing polymers and a comparative polymer are shown below, in which Tg was determined using a differential scanning calorimeter (DSC, produced by SEIKO DENSHI KOGYO Co., Ltd.). Comp.P-9 is polyvinyl butyral, B-79 (available from SORCIA Co.).
Although it is commonly known that the use of a cross-linking agent in such a binder as described above improves layer adhesion and lessens unevenness in development.
Crosslinking agents usable in the invention include various commonly known crosslinking agents used for photographic materials, such as aldehyde type, epoxy type, vinylsulfon type, sulfonester type, acryloyl type, carbodiimide type crosslinking agents, as described in JP-A 50-96216. In this invention, at least one of crosslinking agents is preferably carbodiimide type crosslinking agent.
The carbodiimide type crosslinking agent refers to a compound containing at least two carbodiimido groups or it's adduct. Specific examples thereof include aliphatic dicarbodiimides, alicyclic dicarbodiimides, bebzene dicarboimides, naphthalene dicarbodiimides, biphenyl dicarbodiimides, diphenylmethane dicarbodiimides, triphenymethane dicarbodiimides, tricarbodiimides, tetracarbodiimides, and the foregoing carbodiimide adducts and adducts of the foregoing carbodiimides with dihydric or trihydric alcohols. Such carbodiimides can be synthesized by reacting corresponding isocyanates with a primary amine in the presence of phosphorus catalyst, such as phosphorane compounds.
A polyfunctional carbodiimide compound is a compound containing at least two carbidiimido groups or at least two carbodithioimido groups within the molecule, and preferably polyfunctional aromatic carbidiimide compound containing carbodiimide groups and aromatic group.
The preferred polyfuctional carbodiimide compounds used in this invention are those represented by the following formula (CI):
R1-J1-N═C═N-J2-(L)n-(J3-N═C═N-J4-R2)v formula (CI)
In the formula (CI), R1 and R2 each represent an alkyl group (e.g., methyl, ethyl, propyl, butyl, pentyl), aryl group (e.g., benzene, naphthalene, toluene or xylene moiety) or heterocyclic group (furan, thiophene, dioxane, pyridine, piperazine or morpholine moiety) or a group formed by the foregoing groups through a linking group. J1 and J4 represent a linkage group or a bond. The linkage group comprises an oxygen atom, nitrogen atom, sulfur atom or phosphorus atom, which may further contain a carbon atom and specific examples thereof include O, S, NH, CO, COO, SO, SO2, NHCO, NHCONH, PO and PS. J2 and J3 each represent an alkylene group (e.g., methylene, ethylene, trimethylene, tetramethylene, hexamethylene) or arylene group (e.g., phenylene, tolylene, naphthalene).
L represents a (v+1)-valent group derived from an alkyl group (e.g., methyl, ethyl, propyl, butyl, pentyl), alkenyl group (ethenyl, propenyl, butadiene, pentadiene), aryl group (e.g., benzene, naphthalene, toluene or xylene) or heterocyclic group (furan, thiophene, dioxane, pyridine, piperazine or morpholine). The foregoing groups may be boded through a linking group. The linking group comprises an oxygen atom, nitrogen atom, sulfur atom or phosphorus atom, which may further containa carbon atom and specific examples thereof include O, S, NH, CO, COO, SO, SO2, NHCO, NHCONH, PO and PS. Further, v represents an integer of 1 or more. preferably an integer of 1 to 6, and more preferably 1, 2 or 3.
Specific examples of cross-linking agents represented by formula (CI) are shown below.
The foregoing carbodiimide cross-linking agents may be incorporated into any portion of the photothermographic material relating to this invention. For example, it may be incorporated into a support (specifically, in the case of paper support, it may be incorporated into a size composition thereof), or at least one layer on the light-sensitive layer side of the support, such as a light-sensitive layer, surface protective layer, interlayer, antihalation layer or sublayer.
The crosslinking agent can be incorporated in an amount of 0.001 to 2 mol, preferably 0.005 to 1 mol per mol of silver. At least two crosslinking agents may be used in combination, within the range od amounts described above.
Silane compounds usable as a crosslinking agent include, for example, a compound represented by the following formula (1) or (2), as described in U.S. Pat. No. 6,461,805:
formula (1)
(R1O)m—Si—[(L1)xR2]n
wherein R1, R2, R3, R4, R5, R6, R7 and R8 represent each an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; L1, L2, L3 and L4 represent each a bivalent linkage group; m and n are each an integer of 1 to 3, provided that m+n is 4; p1 and p2 are each an integer of 1 to 3 and q1 and q2 are each 0, 1 or 2, provided that p1+q1 and p2+q2 are each 3; r1 and t are each 0 or an integer of 1 to 1000; and x is 0 or 1.
The epoxy compound usable as a crosslinking agent in the invention may be any one containing at least one epoxy group and is not limited with respect to the number of the epoxy group, molecular weight and other parameters. The epoxy group is preferably contained in the form of a glycidyl group through an ether bond or an imino bond in the molecule. The epoxy compound may be any one of a monomer, oligomer and polymer, in which the number of the epoxy group in the molecule is preferably 1 to 10 and more preferably 2 to 4. In cases where the epoxy compound is a polymer, it may be either one of a homopolymer and a copolymer. The number-averaged molecular weight (Mn) thereof is preferably 2,000 to 20,000. The epoxy compound used in the invention is preferably a compound represented by the following formula (9):
wherein an alkylene group represented by R in formula (9) may be substituted by a substituent selected from a halogen atom, a hydroxyalkyl group and an amino group; R in formula (9) preferably contains an amide linkage, ether linkage or thioether linkage; a bivalent linkage group represented by X is preferably —SO2—, —SO2NH—, —S—, —O— or —NR′—, in which R′ is a univalent linkage group and preferably an electron-withdrawing group.
The acid anhydride used in the invention is preferably a compound containing at least an acid anhydride group represented as below:
—CO—O—CO—
The acid anhydride usable in the invention may be any compound containing one or more acid anhydride group, the number of the acid anhydride group, molecular weight or other parameters are not specifically limited, and a compound represented by the following formula [B] is preferred:
wherein Z is an atomic group necessary to form a monocyclic or polycyclic ring, which may be substituted. Examples of substituent include an alkyl group (e.g., methyl, ethyl, hexyl), an alkoxyl group (e.g., methoxy, ethoxy, octyloxy), an aryl group (e.g., phenyl, naphthyl, tolyl), hydroxy group, an aryloxy group (e.g., phenoxy), an alkylthio group (e.g., methylthio, butylthio), an arylthio group (e.g., phenylthio), an acyl group (e.g., acetyl, propionyl, butylyl), a sulfonyl group (e.g., methylsulfonyl, phenylsulfonyl), an acylamino group, a sulfonylamino group, an acyloxy group (e.g., acetoxy, benzoxy), carboxy group, cyano group, sulfo group and an amino group. It is preferred not to contain a halogen atom as a substituent.
Photothermographic imaging materials of the invention, which form photographic images on thermal development, comprises a reducible silver source (such as aliphatic carboxylic acid silver salts), light sensitive silver halide grains, a reducing agent, and optionally a color toning agent for adjusting silver image color tone, which are contained in the form of a dispersion in a binder matrix. Exemplary preferred toning agents are described in RD17029, U.S. Pat. Nos. 4,123,282, 3,994,732, 3,846,136 and, 4,021,249. Specifically preferred toning agents include phthalazinone, a combination of phthalazine, and phthalic acids or phthalic acid anhydrides.
With regard to image tone of the outputted image used for medical diagnosis, it has been supposed that more exact diagnostic observation results can be easily achieved with cold image tone. The cold image tone refers to pure black tone or bluish black tone and the warm image tone refers to a brownish black image exhibiting a warm tone.
The expression regarding to the tone, i.e., “colder tone” or “warmer tone can be determined based on a hue angle, hab at a density of 1.0, as defined in JIS Z 8729. The hue angle, hab can be represented as hab=tan−1(b*/a*) obtained from a XYZ color system, or tristimulus values X, Y and Z or X10, Y10 and Z10 defined in JIS Z 8701, using color coordinates a* and b* in L*a*b* color system defined in JIS Z 8729.
With regard to the term “colder tone” and “warmer tone”, it was proved that when in CIE 1976, (L*u*v*) color space or (L*a*b*) color space, various densities were plotted in terms of abscissa u* and ordinate v*, or abscissa a* and ordinate b* to prepare a linear regression line (y=ax+b), adjusting the slope (a) of the linear regression line to the range of 0.5 to 1.5 (preferably 0.75 to 1.25), the intercept (b) to the range of −3 to 3 (preferably −1 to 1), and the multiple decision (R2) to the range of 0.8000 to 1.0000 (preferably 0.9000 to 1.0000) resulted in superior recognizing ability in a low density region to an intermediate density region of the diagnostic photograph, specifically in mediastinum portions of the lung, as compared to the use of conventional wet-type silver salt photographic materials, thereby leading to enhanced recognizing ability in the low density region of diagnostic photography, specifically in the mediastinum portion of the lung.
In the present invention, a matting agent is preferably incorporated into the surface layer of the photothermographic imaging material (on the light sensitive layer side or even in cases where a light insensitive layer is provided on the opposite side of the support to the light sensitive layer). In order to minimize the image abrasion after thermal development, the matting agent is provided on the surface of a photosensitive material and the matting agent is preferably incorporated in an amount of 1 to 30% by weight of the binder.
Materials of the matting agent employed in the invention may be either organic substances or inorganic substances. Examples of the inorganic substances include silica described in Swiss Patent No. 330,158, etc.; glass powder described in French Patent No. 1,296,995, etc.; and carbonates of alkali earth metals or cadmium, zinc, etc. described in U.K. Patent No. 1.173,181, etc. Examples of the organic substances include starch described in U.S. Pat. No. 2,322,037, etc.; starch derivatives described in Belgian Patent No. 625,451, U.K. Patent No. 981,198, etc.; polyvinyl alcohols described in Japanese Patent Publication No. 44-3643, etc.; polystyrenes or polymethacrylates described in Swiss Patent No. 330,158, etc.; polyacrylonitriles described in U.S. Pat. No. 3,079,257, etc.; and polycarbonates described in U.S. Pat. No. 3,022,169.
The matting agent used in the invention preferably has an average particle diameter of 0.5 to 10 μm, and more preferably of 1.0 to 8.0 μm. Furthermore, the variation coefficient of the size distribution is preferably not more than 50%, is more preferably not more than 40%, and is still more preferably not more than 30%. The variation coefficient of the grain size distribution as described herein is a value represented by the following formula:
(standard deviation of particle size/average particle size)×100.
Addition methods of the matting agent include those in which a matting agent is previously dispersed into a coating composition and is then coated, and prior to the completion of drying, a matting agent is sprayed. When plural matting agents are added, both methods may be employed in combination.
Suitable supports used in the photothermographic imaging materials of the invention include various polymeric materials, glass, wool cloth, cotton cloth, paper, and metals (such as aluminum). Flexible sheets or roll-convertible one are preferred. Examples of preferred support used in the invention include plastic resin films such as cellulose acetate film, polyester film, polyethylene terephthalate film, polyethylene naphthalate film, polyamide film, polyimide film, cellulose triacetate film and polycarbonate film, and biaxially stretched polyethylene terephthalate (PET) film is specifically preferred. The support thickness is 50 to 300 μm, and preferably 70 to 180 μm.
To improve electrification properties of photothermographic imaging materials, metal oxides and/or conductive compounds such as conductive polymers may be incorporated into the constituent layer. These compounds may be incorporated into any layer and preferably into a sublayer, a backing layer, interlayer between the light sensitive layer and the sublayer. Conductive compounds described in U.S. Pat. No. 5,244,773, col. 14–20.
The photothermographic material of the invention comprises at least one light-sensitive layer on the support, and further thereon, preferably having a light-insensitive layer. For example, a protective layer is provided on the light-sensitive layer. On the opposite side of the support to the light-sensitive layer, a back coating layer is preferably provided to protect the light-sensitive layer or prevent adhesion. Binders used in the protective layer or back coating layer are preferably selected from polymers which have a glass transition point higher than that of the thermally developable layer and are hard to cause abrasion or deformation, such as cellulose acetate and cellulose acetate-butylate. To adjust contrast, two or more light-sensitive layers may be provided on one side of the support, or one or more layers may be provided on both sides of the support.
It is preferred to form a filter layer on the same side as or on the opposite side to the light sensitive layer or to allow a dye or pigment to be contained in the light sensitive layer to control the amount of wavelength distribution of light transmitted through the light sensitive layer of photothermographic imaging materials relating to the invention. Commonly known compounds having absorptions in various wavelength regions can used as a dye, in response to spectral sensitivity of the photothermographic material. In cases where the photothermographic imaging material relating to the invention are applied as a image recording material using infrared light is preferred the use of squarilium dye containing a thiopyrylium nucleus (also called as thiopyrylium squarilium dye), squarilium dye containing a pyrylium nucleus (also called as pyrylium squarilium dye), thiopyrylium chroconium dye similar to squarilium dye or pyrylium chroconium. The compound containing a squarilium nucleus is a compound having a 1-cyclobutene-2-hydroxy-4one in the molecular structure and the compound containing chroconium nucleus is a compound having a 1-cyclopentene-2-hydroxy, 4,5-dione in the molecular structure, in which the hydroxy group may be dissociated. Hereinafter, these dyes are collectively called a squarilium dye.
Compounds described in JP-A 8-201959 are also preferably usable as a dye.
Materials used in respective constituent layers are dissolved or dispersed in solvents to prepare coating solutions, which were coated on the support and further subjected to a heating treatment to form a photothermographic material. A coating solution for the light-sensitive layer preferably contains at least 30%, and more preferably at least 50% by weight of water. The amount of solvents are not specifically limited, but the less solvent is more preferred in terms of environment protection and it is preferred that all of solvents used are water. In one preferred embodiment of the invention, plural coating solutions are simultaneously coated to form multi-layers and then subjected to a heating treatment. Thus, coating solutions for respective constituent layers (for example, light-sensitive layer, protective layer) and coating and drying are not repeated for respective layers but plural layers are simultaneously coated and dried to form respective constituent layers. The upper layer is provided before the remaining amount of total solvents in the lower layer reaches 70% or less.
Methods for simultaneously coating plural constituent layers are not specifically limited and commonly known methods, such as a bar coating method, curtain coating method, air-knife method, hopper coating method and extrusion coating method are applicable. Of these, extrusion coating, that is, pre-measuring type coating is preferred. The extrusion coating is suitable for accurate coating or organic solvent coating since no evaporation occur on the slide surface, as in a slide coating system. This coating method is applicable not only to the light-sensitive layer side but also to the case when simultaneously coating a backing layer with the sublayer.
The coating amount of silver is optimally selected in accordance with objectives of photothermographic materials and preferably 0.5 to 1.1.5 g/m2, more preferably 0.6 to 1.4 g/m2, and still more preferably 1.0 to 1.3 g/m2. Of the coating amount of silver described above, the amount of silver relying on silver halide accounts for preferably 2 to 18%, and more preferably 3 to 15%, based on total silver amount. The coating density of silver halide grains of at least 0.01 μm or (circular equivalent diameter) is preferably 1×1014 to 1×1018 grains/m2, and more preferably 1×1015 to 1×1017 grains/m2. The coating density of aliphatic carboxylic acid silver salt of at least 0.01 μm (circular equivalent diameter) is preferably 10−16 to 10−14 g, and more preferably 10−17 to 10−15 g per silver halide grain. Coating under the condition falling the ranges described above leads to preferable results in term of the maximum silver image density per a given coating amount of silver (that is, silver covering power) and silver image tone.
The developing conditions for photographic materials are variable, depending on the instruments or apparatuses used, or the applied means and typically accompany heating the imagewise exposed photothermographic imaging material at an optimal high temperature. Latent images formed upon exposure are developed by heating the photothermographic material at an intermediate high temperature (ca. 80 to 200° C., and preferably 100 to 200° C.) over a period of ample time (generally, ca. 1 sec. to ca. 2 min.). Sufficiently high image densities cannot be obtained at a temperature lower than 80° C. and at a temperature higher than 200° C., the binder melts and is transferred onto the rollers, adversely affecting not only images but also transportability or the thermal processor. An oxidation reduction reaction between an organic silver salt (functioning as an oxidant) and a reducing agent is caused upon heating to form silver images. The reaction process proceeds without supplying any processing solution such as water from the exterior.
Heating instruments, apparatuses and means include typical heating means such as a hot plate, hot iron, hot roller or a heat generator employing carbon or white titanium. In the case of a photothermographic imaging material provided with a protective layer, it is preferred to thermally process while bringing the protective layer side into contact with a heating means, in terms of homogeneous-heating, heat efficiency and working property. It is also preferred to conduct thermal processing while transporting, while bringing the protective layer side into contact with a heated roller.
Exposure of photothermographic imaging materials desirably uses a light source suitable to the spectral sensitivity of the photothermographic materials. An infrared-sensitive photothermographic material, for example, is applicable to any light source in the infrared light region but the use of an infrared semiconductor laser (780 nm, 820 nm) is preferred in terms of being relatively high power and transparent to the photothermographic material.
In the invention, exposure is preferably conducted by laser scanning exposure and various methods are applicable to its exposure. One of the preferred embodiments is the use of a laser scanning exposure apparatus, in which scanning laser light is not exposed at an angle substantially vertical to the exposed surface of the photothermographic material. The expression “laser light is not exposed at an angle substantially vertical to the exposed surface” means that laser light is exposed preferably at an angle of 55 to 88°, more preferably 60 to 86°, still more preferably 65 to 84°, and optimally 70 to 82°. When the photothermographic material is scanned with laser light, the beam spot diameter on the surface of the photosensitive material is preferably not more than 200 μm, and more preferably not more than 100 μm. Thus, the smaller spot diameter preferably reduces the angle displaced from verticality of the laser incident angle. The lower limit of the beam spot diameter is 10 μm. The thus configured laser scanning exposure can reduce deterioration in image quality due to reflected light, such as occurrence of interference fringe-like unevenness.
In the second preferred embodiment of the invention, exposure applicable in the invention is conducted preferably using a laser scanning exposure apparatus producing longitudinally multiple scanning laser light, whereby deterioration in image quality such as occurrence of interference fringe-like unevenness is reduced, as compared to scanning laser light with longitudinally single mode. Longitudinal multiplication can be achieved by a technique of employing backing light with composing waves or a technique of high frequency overlapping. The expression “longitudinally multiple” means that the exposure wavelength is not a single wavelength. The exposure wavelength distribution is usually not less than 5 nm and not more than 10 nm. The upper limit of the exposure wavelength distribution is not specifically limited but is usually about 60 nm.
In the first, second and third preferred embodiments of the image recording method of the invention, lasers for scanning exposure used in the invention include, for example, solid-state lasers such as ruby laser, YAG laser, and glass laser; gas lasers such as He—Ne laser, Ar laser, Kr ion laser, CO2 laser, Co laser, He—Cd laser, N2 laser and eximer laser; semiconductor lasers such as InGa laser, AlGaAs laser, GaAsP laser, InGaAs laser, InAsP laser, CdSnP2 laser, and GSb laser; chemical lasers; and dye lasers. Of these, semiconductor lasers of wavelengths of 600 to 1200 nm are preferred in terms of maintenance and the size of the light source. When exposed onto the photothermographic imaging material in the laser imager or laser image-setter, the beam spot diameter on the exposed surface is 5 to 75 μm as a minor axis diameter and 5 to 100 μm as a major axis diameter. The laser scanning speed is set optimally for each photothermographic material, according to its sensitivity at the laser oscillation wavelength and the laser power.
A thermal processing apparatus usable in this invention comprises a a film supplying section, a laser image recording section, a thermal developing section for uniformly and stably heating the overall of photothermographic material and a transport section from the film supplying section, via laser recording, to discharging the photothermographic material image-forming through thermal development to the outside of the apparatus.
Thermal processing apparatus (100) comprises a supplying section (110) for supplying photothermographic material (also denoted simply as film) sheet by sheet, an exposure section (120) to expose the supplied film (F), a developing section (130) to develop the exposed film (F), a cooling section (150) to stop development and an accumulating section (160), the numeral 151 designates a cooling roller pair and the numeral 152 designates a cooling fan. The apparatus further comprises plural roller pairs, such as a supply roller pair (140) to supply the film (F) supplied from the supplying section (110), a supply roller pair (144) to supply the film to the developing section, and transporting roller pairs (141, 142, 143) to smoothly transport the film (F) between the respective sections. The thermal developing section comprises a heating drum (1) as a developing means, onto the circumference of which plural opposed rollers (2) capable of heating are tightly in contact and a peeling nail (6) to peel off the developed film (F) and supply it to the cooling section.
The transporting speed of the photothermographic material is preferably 20 to 200 mm/sec. The cooling speed in the cooling section is preferably 3 to 20° C.
The present invention will be further described based on examples but embodiments of the invention are by no means limited to these examples.
Preparation of Photographic Support
On one side of blue-tinted 175 μm thick polyethylene terephthalate film (PET) exhibiting a density of 0.170 which was previously subjected to a corona discharge treatment at 0.5 kV·A·min/m2, sublayer (a) was coated using the following sublayer coating solution A so as to have a dry layer thickness of 0.2 μm. After the other side of the film was also subjected to a corona discharge treatment at 0.5 kV·A·min/m2, sublayer (b) was coated thereon using sublayer coating solution B described below so as to have dry layer thickness of 0.1 μm. Thereafter, a heating treatment was conducted at 130° C. for 15 min in a heating treatment type oven having a film transport apparatus provided with plural rolls.
Sublayer Coating Solution A
Copolymer latex solution (30% solids) of 270 g, comprised of n-butyl acrylate/t-butyl acrylate/styrene/2-hydroxyethyl acrylate (30/20/25/25%) was mixed with 0.6 g of compound (UL-1) and 0.5 g of methyl cellulose. Further thereto a dispersion in which 1.3 g of silica particles (SILOID, available from FUJI SYLYSIA Co.) was previously dispersed in 100 g of water by a ultrasonic dispersing machine, Ultrasonic Generator (available from ALEX Corp.) at a frequency of 25 kHz and 600 W for 30 min., was added and finally water was added to make 100 ml to form sub-coating solution A.
Synthesis of Colloidal Tin Oxide Dispersion
Stannic chloride hydrate of 65 g was dissolved in 2000 ml of water/ethanol solution. The prepared solution was boiled to obtain co-precipitates. The purified precipitate was taken out by decantation and washed a few times with distilled water. To the water used for washing, aqueous silver nitrate was added to confirm the presence of chloride ions. After confirming no chloride ion, distilled water was further added to the washed precipitate to make the total amount of 2000 ml. After adding 40 ml of 30% ammonia water was added and heated, heating was further continued and concentrated to 470 ml to obtain colloidal tin oxide dispersion.
Sub-Coating Solution B
The foregoing colloidal tin oxide dispersion of 37.5 g was mixed with 3.7 g of copolymer latex solution (30% solids) comprised of n-butyl acrylate/t-butyl acrylate/styrene/2-hydroxyethyl acrylate (20/30/25/25%), 14.8 g of copolymer latex solution (30% solids) comprised of n-butyl acrylate/styrene/glycidyl methacrylate (40/20/40%), and 0.1 g of surfactant UL-1 (as a coating aid) and water was further added to make 1000 ml to obtain sub-coating solution B.
Back Layer-Side Coating
To 830 g of methyl ethyl ketone (also denoted as MEK), 4.2 g of polyester resin (Vitel PE2200B, available from Bostic Corp.) and 84.2 g of cellulose acetate-butyrate (CAB381-20, available from Eastman Chemical Co.) were added and dissolved. To the resulting solution were added 0.30 g of infrared dye 1, 4.5 g of fluorinated surfactant (1) and 1.5 g of fluorinated surfactant (FTOP EF-105, available from Jemco Co.) were added, and 43.2 g of methanol was further added with sufficiently stirring until being dissolved. To the resulting solution was added 75 g of silica particles (SYLYSIA, available from FUJI SYLYSIA Co.) to prepare a coating solution for the back-layer side.
Fluorinated surfactant-1: CgF17O(CH2CH2O)22C9F17
The thus prepared back layer coating solution was coated on the sublayer (b) side of the support so as to form a dry thickness of 3.5 μm, using an extrusion coater and dried at a dry bulb temperature of 100° C. and a dew temperature of 10° C. for 5 min.
Compound (A): HO(CH2CH2O)n—(CH(CH3)CH2O)17—CH2CH2O)mH (m+n=5 to 7)
Using a stirring mixer described in JP-B Nos. 58-58288 and 58-58289, ¼ of solution B1, the total amount of solution C1 were added to solution A1 by the double jet addition for 4 min 45 sec. to form nucleus grain, while maintaining a temperature of 45° C. and a pAg of 8.09. After 1 min., the total amount of solution F1 was added thereto, while the pAg was adjusted using solution E1. After 6 min, ¾ of solution B1 and the total amount of solution D1 were further added by the double jet addition for 14 min 15 sec., while mainlining a temperature of 45° C. and a pAg of 8.09. After stirring for 5 min., the reaction mixture was lowered to 40° C. and solution G1 was added thereto to coagulate the resulting silver halide emulsion. Remaining 2000 ml of precipitates, the supernatant was removed and after adding 10 lit. water with stirring, the silver halide emulsion was again coagulated. Remaining 1500 ml of precipitates, the supernatant was removed and after adding 10 lit. water with stirring, the silver halide emulsion was again coagulated. Remaining 1500 ml of precipitates, the supernatant was removed and solution H1 was added. The temperature was raised to 60° C. and stirring continued for 120 min. Finally, the pH was adjusted to 5.8 and water was added there to so that the weight per mol of silver was 1161 g, and light-sensitive silver halide emulsion A was thus obtained. It was proved that the resulting emulsion was comprised of monodisperse silver iodobromide cubic grains having an average grain size of 0.040 μm, a coefficient of variation of grain size of 12% and a [100] face ratio of 92%.
Next, to the foregoing emulsion, 240 ml of sulfur sensitizer S-5 (0.5% methanol solution), gold sensitizer Au-5 was further added in an amount of 1/20 molar equivalent to the sulfur sensitizer and chemical sensitization was carried out at 55° C. for 120 min. The light-sensitive silver halide emulsion A was thus obtained.
The silver behenate content was determined according to the following procedure. About 10 mg of organic silver salts was accurately weighed and put into a 200 ml eggplant-shape flask. Methanol of 15 ml and 3 ml of 4 mol/l hydrochloric acid were further added thereto and stirred for 1 min. using an ultrasonic homogenizer. Adding a boiling stone of Teflon, reflux was conducted over period of 60 min. After cooling, 5 ml of methanol was added from top to wash out adherend onto the reflux condenser (twice). The thus obtained reaction solution was extracted twice with ethyl acetate solution (comprising 100 ml ethyl acetate and 70 ml water). Vacuum drying was carried out for 30 min. To 10 ml messflask, 1 ml of benzanthrone solution (internal standard). Sample was dissolved in toluene, put into a mess flask and made up with toluene. The sample was measured by gas chromatography (GC), in which contents (mol %) of the respective organic acids were determined from their peak areas and the weight percentage thereof was further calculated to determine the composition of organic acids.
Subsequently, organic acids that were free from formation of silver salts were quantitatively determined. Thus, about 20 mg of an organic silver salt sample was accurately weighed and dispersed in 10 ml methanol using an ultrasonic homogenizer for 1 min. The dispersion was filtered and the filtrate was dried to obtain free organic acids. Similarly to the above-described determination of total organic acids, composition of free organic acids and the ratio of free organic acids to total organic acids were determined. The difference of the total organic acids minus free acids was to be the content of silver salts.
Preparation of Powdery Organic Silver Salt A
Organic silver salt particles were prepared using commercially available unpurified behenic acid. Such behenic acid was analyzed according to the manner described above. It was proved that the content of behenic acid was 80% by weight and the remainder was arachidic acid and stearic acid. Accordingly, 130.8 g of behenic acid, arachidic acid of 67.7 g, stearic acid of 43.6 g and palmitic acid of 2.3 g were dissolved in 4720 ml of water at 90° C. Then, 540.2 ml of aqueous 1.4 mol/l NaOH was added, and after further adding 6.9 ml of concentrated nitric acid, the mixture was cooled to 55° C. to obtain a fatty acid sodium salt solution. To the thus obtained fatty acid sodium salt solution, 45.3 g of the light-sensitive silver halide emulsion A obtained above and 450 ml of water were added and stirred for 5 min., while being maintained at 55° C. Subsequently, 702.6 ml of 1 mol/l aqueous silver nitrate solution was added in 2 min. and stirring continued further for 10 min. to obtain dispersion A of particulate organic silver salt containing silver halide grains. The dispersion A was transferred to a washing vessel and after adding deionized water thereto, the dispersion was allowed to stand and dispersion A of organic silver salt containing silver halide grains was separated by the floatation process and lower water-soluble salts were removed.
Thereafter, washing with deionized water and filtration were repeated until the filtrate reached a conductivity of 2 μS/cm. Using a flush jet dryer (produced by Seishin Kigyo Co., Ltd.), the thus obtained cake-like organic silver salt was dried under an atmosphere of nitrogen gas according to the operation condition of a hot air temperature at the inlet of the dryer until reached a moisture content of 0.1%. The moisture content was measured by an infrared ray aquameter. Analysis of behenic acid contained in the organic silver salt particles A revealed 54% by weight of behenic acid. Further, as a result of analysis of the mixture of organic acids, it was proved that the heavy metal content was 5 ppm and the iodine value was 1.5.
Preparation of Dispersion A
In 1457 g MEK was dissolved 14.57 g of polymer P-9 and further thereto, 500 g of the foregoing powdery organic silver salt A was gradually added to obtain preliminarily dispersed mixture, dispersion A, while stirring by a dissolver type homogenizer (DISPERMAT Type CA-40M, available from VMA-GETZMANN).
Preparation of Light-Sensitive Emulsion A
Thereafter, using a pump, the foregoing dispersion A was transferred to a media type dispersion machine (DISPERMAT Type SL-C12 EX, available from VMA-GETZMANN), which was packed 1 mm Zirconia beads (TORAY-SELAM, available from Toray Co. Ltd.) by 80%, and dispersed at a circumferential speed of 8 m/s and for 1.5 min. of a retention time with a mill to obtain light-sensitive emulsion A.
Preparation of Stabilizer Solution
In 4.97 g methanol were dissolved 1.0 g of Stabilizer-1 and 0.31 g of potassium acetate to obtain stabilizer solution.
Preparation of Infrared Sensitizing Dye Solution A
In 31.3 ml MEK were dissolved 19.2 mg of infrared sensitizing dye-1, 1.488 g of 2-chlorobenzoic acid, 2.779 g of Stabilizer-2 and 365 mg of 5-methyl-2-mercaptobenzimidazole in a dark room to obtain an infrared sensitizing dye solution A.
Preparation of Additive Solution (a)
In 110 g MEK were dissolved 27.98 g of developer 1,1-bis(2-hydroxy-3,5-dimethylphenyl)-3,5,5-trimethylhexane, 1.54 g of 4-methylphthalic acid and 0.48 g of the infrared dye-1 to obtain additive solution (a).
Preparation of Additive Solution (b)
Antifoggants-2, of 3.56 g were dissolved in 40.9 g MEK to obtain additive solution (b).
Preparation of Light-Sensitive Layer Coating Solution A
Under inert gas atmosphere (97% nitrogen), 50 g of the light-sensitive emulsion A and 15.11 g of MEK were maintained at 21° C. with stirring, and 390 μm of antifoggant-1 (10% methanol solution) was added and stirred for 1 hr. Further thereto, 494 μl of calcium bromide (10% methanol solution) was added and after stirring for 20 min. Subsequently, 1.32 g of infrared sensitizing dye solution A was added and stirred for 1 hr. Then, the mixture was cooled to 13° C. and stirred for 30 min. Further thereto, 13.31 g of polymer P-9, as binder resin was added and stirred for 30 min, while maintaining the temperature at 13° C., and 1.084 g of tetrachlorophthalic acid (9.4% MEK solution) and stirred for 15 min. Then, 12.43 g of additive solution (a), 1.6 ml of 10% MEK solution of Desmodur N3300 (aliphatic isocyanate, product by Movey Co., 10% MEK solution)) and 4.27 g of additive solution (b) were successively added with stirring to obtain coating solution A of the light-sensitive layer.
Preparation of Matting Agent Dispersion
To 42.5 g of MEK, 7.5 g of cellulose acetate-butyrate (CAB171-15, available from Eastman Chemical Co.) was added with stirring. Further thereto, 5 g of Silica particles (SYLOID 320, available from FUJI SYLYSIA Co.) was added and stirred a for 30 min. to obtain a matting agent dispersion.
Preparation of Surface Protective Layer Coating Solution
To 865 g of MEK, 96 g of cellulose acetate-butyrate (CAB171-15, available from Eastman Chemical Co.), 4.5 g of polymethyl methacrylate (Paraloid A-21, available from Rohm & Haas Corp.), 1.0 g of benzotriazole and 1.0 g of a fluorinated surfactant (EFTOP EF-105, available from JEMCO Co.) were added. Subsequently, 30 g of the foregoing matting agent dispersion was added thereto to prepare a surface protective layer coating solution.
Image Forming Layer-Side Coating
The light-sensitive layer coating solution A and the surface protective layer coating solution were simultaneously coated on the support using an extrusion coater. Coating was conducted so as to form a light-sensitive layer having a silver coverage of 1.7 g/m2 and a 2.5 μm thick surface protective layer. Drying was carried out for 10 min with hot air of a dry bulb temperature of 75° C. and a dew point of 10° C. Sample No. 101 was thus obtained.
Samples No. 102 through 120 were each prepared similarly to Sample No. 101, provided that compounds represented by formulas (A-1) and (A-2) were incorporated into the additive solution (a) added to the light-sensitive layer coating solution, in amounts of 100 mg/m2 and 30 mg/m2, respectively; polymer (P-9) was replaced by an equal amount of a polymer shown in Table 1; a vinylsulfone-containing compound of formula (A-5) and a compound of formula (A-3) were incorporated into the light-sensitive layer coating solution in an amounts of 25 mg/m2, as shown in Table 1.
Exposure and Processing
Samples each were subjected to laser scanning exposure from the emulsion side using an exposure apparatus having a light source of 800 nm to 820 nm semiconductor laser of longitudinal multi-mode, which was made by means of high frequency overlapping. In this case, exposure was conducted at an angle of 75°, between the exposed surface and exposing laser light and as a result, images with superior sharpness were unexpectedly obtained, as compared to exposure at an angle of 90°. Subsequently, using an automatic processor provided with a heated drum and a cooling zone, exposed samples were subjected to thermal development with varying a developing temperature and a transporting speed (linear speed) shown in Table 2, while bringing the protective layer surface of the photothermographic material into contact with the drum surface. Thermal development was conducted in an atmosphere at 23° C. and 50% RH. Obtained images were evaluated based on densitometry. Thus, samples were evaluated with respect to sensitivity, minimum density (designated Dmin or Fog) and maximum density (Dmax). Sensitivity was represented by a relative value of the reciprocal of exposure giving a density of 1.0 above the density of an unexposed area (minimum density), based on the sensitivity of sample No. 101 being 100.
Thermal Transition Point
The thermal transition point temperature was determined in accordance with the following procedure. Light-sensitive layer coating solutions for the respective samples were each coated on a Teflon (R) plate using a wire-bar and dried under the same condition as in the respective samples. The thus coated samples were exposed under conditions giving the maximum density and were then thermally developed. Thereafter, the constitution layer coated onto the Teflon (R) plate was peeled off from the plate. The thus peeled layer of about 10 mg was charged into an aluminum pan and the thermal transition point was determined using a differential scanning calorimeter (EXSTAR 6000, available from SEIKO DENSHIKOGYO Co., Ltd.), in accordance with JIS K7121. In the measurement, the temperature was raised at a rate of 10° C./min within the range of from 0 to 200° C. and then, the temperature was lowered to 0° C. at a cooling rate of 20° C/min. This procedure was repeated twice to determine the thermal transition point.
Evaluation of Image Lasting Quality
Thermally processed samples were measure with respect to image lasting quality, based on variation in minimum density and maximum density to evaluate image lasting quality, in accordance with the following procedure.
(1) Variation in Minimum Density
Samples which were thermally processed similarly to the foregoing sensitometry were continuously exposed to light in an atmosphere at 45° C. and 55% RH for 3 days, in which commercially available white fluorescent lamp was arranged so as to exhibit an illumination intensity of 500 lux on the surface of each sample. Thereafter, exposed and unexposed samples were measured for the minimum density, and variation in fog density was determined in accordance with the following equation 1:
Variation in minimum density=(D2−D1)/D1×100(%).
wherein D1 represents the minimum density of a sample unexposed to fluorescent lamp light and D2 represents the minimum density of a sample exposed to fluorescent lamp light. A value closer to 100 indicates a superior result.
(2) Variation in Maximum Density
Thermally developed samples were prepared similarly to the determination of variation in fog density. After being allowed to stand under the environment of 25° C. or 45° C. for 3 days, maximum densities after being allowed to stand were measured and variation in image density was determined as a measure of image lasting quality, in accordance with the following equation:
Variation in maximum density=(maximum density of sample aged at 45° C.)/(maximum density of sample aged at 25° C.)×100(%)
Evaluation of Image Tone
To evaluate silver image tone, imaging areas of the respective processed samples were each measured using CM-3600d (produced by MINOLTA Co., LTD.) to determine u* and v* or a* and b* on the chromaticity diagram. Measurement was conducted in the transmission measurement mode using a F7 light source at a visual field angle of 10°. On the coordinate comprising u*- or a*-abscissa and v*- or b*-ordinate, measured values of u* and v* or a* and b* were plotted to determine a linear regression line, from which a multiple decision (or denoted as R2), intersection (denoted as “a”) and slope (denoted as “b”) were determined.
Uniformity of Density
Photothermographic material samples were exposed so as to give a density of 1.5 and processed with varying developing temperature and developing rat using a processor, as shown in
A: no uneven density was observed;
B: weak uneven density was slightly observed;
C: weak uneven density was observed;
D: marked uneven density was slightly observed;
C: marked uneven density was observed.
Results are shown in Table 2.
As can be seen from Table 2, it was proved that photothermographic material samples according to this invention exhibited enhanced sensitivity, minimized fogging and superior image lasting quality. It was further proved that the inventive samples provided minimized unevenness in density and blue-black tone images suitable for diagnostic imaging.
Similarly to Example 1, photothermographic material samples were prepared as follows.
Preparation of Powdery Organic Silver Salt B
Similarly to the powdery silver halide-containing organic silver salt A in Example 1, powdery organic silver salt B was prepared, provided that 150.0 g of behenic acid, 20.0 g of arachidic acid and 17.3 g of stearic acid were mixed and dissolved in at 90° C. The content of silver behenate contained in the organic silver salt B, which was determined in accordance with the method described in Example 1, was 60% by weight.
Preparation of Powdery Organic Silver Salt C
Powdery organic silver salt C was prepared similarly to the powdery silver halide-containing organic silver salt A in Example 1, provided that, using commercially available high content behenic acid, 217.0 g of behenic acid, 20.0 g of arachidic acid and 17.3 g of stearic acid were mixed and dissolved in at 90° C. The content of silver behenate contained in the organic silver salt C, which was determined in accordance with the method described in Example 1, was 85% by weight. The heavy metal content and the iodine value were 3.55 ppm and 0.8, respectively.
Preparation of Powdery Organic Silver Salt D
Powdery organic silver salt D was prepared similarly to the powdery silver halide-containing organic silver salt A in Example 1, provided that, unpurified behenic acid was purified through recrystallization (in which 92% by weight of behenic acid was contained together with 8% by weight of arachidic acid, 217.0 g of behenic acid, 20.0 g of arachidic acid and 17.3 g of stearic acid were mixed and dissolved in at 90° C. The content of silver behenate contained in the organic silver salt D, which was determined in accordance with the method described in Example 1, was 85% by weight. The heavy metal content and the iodine value were 2 ppm and 0.5, respectively.
Preparation of Powdery Organic Silver Salt E
Powdery organic silver salt E was prepared similarly to the powdery silver halide-containing organic silver salt A in Example 1, provided that, unpurified behenic acid was purified three times through recrystallization to 98% by weight of behenic acid was used and dissolved in at 90° C. The content of silver behenate contained in the organic silver salt D, which was determined in accordance with the method described in Example 1, was 98% by weight. The heavy metal content and the iodine value were proved to be 2 ppm and 0.3, respectively.
Dispersions B through E were prepared similarly to the foregoing dispersion A, except that the powdery organic silver salt was replaced by the foregoing powdery organic silver salt B through E.
Light-sensitive emulsion B through E were prepared similarly to the light-sensitive emulsion A used in Example 1, except that the dispersion A was replaced by the foregoing dispersion B through E.
Using the foregoing light-sensitive emulsion B, light-sensitive layer coating solution B was prepared similarly to the light-sensitive layer coating solution A of Example 1.
Using the foregoing light-sensitive layer coating solution B and the surface protective layer coating solution used in Example 1, photothermographic material sample No. 201 was prepared similarly to sample 101 of Example 1. Further, Samples No. 202 through 214 were prepared similarly to the foregoing sample No. 201, provided that the light-sensitive emulsion and compounds relating to this invention contained in the light-sensitive layer coating solution were varied as shown in Table 3. In any of the samples, polymer P-1 was used as binder resin of the light-sensitive layer coating solution and the thermal transition point was adjusted to ca. 55° C.
The thus prepared samples were exposed, processed and evaluated similarly to Example 1. Results thereof are shown Table 3.
As can be seen from Table 3, it was proved that photothermographic material samples according to this invention exhibited enhanced sensitivity, minimized fogging and superior image lasting quality and little unevenness in density, as compared to comparative samples.
Photothermographic material samples No. 301 through 320 were prepared similarly to samples No. 101 through 120 of Example 1 using the light-sensitive layer coating solution A and surface protective layer coating solution used in Example 1, except that the developer, 1,1-bis(2-hydroxy-3,5-dimethylphenyl)-3,5,5-trimethylhexane was replaced by a developer as shown in Table 4. In any of the samples, polymer P-1 was used as binder resin of the light-sensitive layer coating solution and the thermal transition point was adjusted to ca. 55° C. Development was carried out at a temperature of 125° C. and a transporting speed of 20 mm/sec. Results are shown in Table 4.
Photothermographic material sample No. 401 was prepared similarly to sample No. 101 in Example 1, provided that in the additive solution (a) added to the light-sensitive layer coating solution, developer (or reducing agent) 1,1-bis(2-hydroxy-3,5-dimethylphenyl)-3,5,5-trimethylhexane was replaced by the following compound (A-3), and exemplified compound (3-1) and polyhalogeno-compound (B′), as described below were further incorporated thereto.
Photothermographic material samples No. 402 through 416 were prepared similarly to sample No. 401, provided that the compound (3-1) and compound (B′) were replaced, as shown in Table 5.
The thus prepared samples No. 401 through 416 were exposed, processed and evaluated similarly to Example 1, provided that thermal processing was conducted at 110° C. for 15 sec. The samples were further evaluated with respect to raw stock stability (or pre-exposure storage stability) according to the following procedure. Thus, unexposed samples were allowed to stand for 10 days under two different conditions, A and B, as described below. The thus aged samples were exposed and thermally developed to determine sensitivity in the same manner as in the foregoing sensitometry. Variation in sensitivity between conditions A and B was determined as a measure of pre-exposure storage stability, in accordance with the following equation:
Condition A: 25° C., 55% RH
Condition B: 40° C., 80% RH
Variation in sensitivity=(sensitivity at condition B)/(sensitivity at condition A)×100(%)
Results are shown in Table 5.
As can be seen from table 5, it was proved that photothermographic material samples according to this invention exhibited enhanced sensitivity, minimized fogging, improved storage stabily and superior image lasting quality, as compared to the comparative sample.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2002-241870 | Aug 2002 | JP | national |
| 2002-256480 | Sep 2002 | JP | national |
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| 1096310 | May 2001 | EP |
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| Number | Date | Country | |
|---|---|---|---|
| 20040043341 A1 | Mar 2004 | US |
