Silver halide color photographic material containing acylacetamide yellow dye-forming coupler

FIELD OF THE INVENTION
The present invention relates to novel acylacetamide-type yellow dye-forming couplers and silver halide color photographic materials containing the same.
BACKGROUND OF THE INVENTION
In a silver halide color photographic material, a color image is formed when the material is exposed to light and then is subjected to color development so that an oxidized aromatic primary amine color developer and a dye-forming coupler (hereinafter-referred to as coupler) may interact.
Generally, in such a process, the color reproduction method employed is a subtractive color process wherein to reproduce blue, green and red, a yellow color image, a magenta color image, and a cyan color image respectively complementary thereto are formed. To form a yellow color image, generally acylacetamide couplers and malondianilide couplers are used as a yellow dye-forming coupler (hereinafter referred to as yellow coupler); to form a magenta color image, generally, for example, 5-pyrazolone couplers and pyrazolotriazole couplers are used as a magenta coupler; and to form a cyan color image, generally phenol couplers and naphtol couplers are used as a cyan coupler.
Yellow dyes, magenta dyes, and cyan dyes obtained from these couplers are generally formed in silver halide emulsion layers or layers adjacent thereto having color sensitivities to radiations respectively complementary to the radiations that are absorbed by them.
As yellow couplers, particularly for forming images, acylacetamide couplers, represented by benzoylacetanilide couplers and pivaloylacetanilide couplers, are generally used. Since the former are generally high in coupling activity with the oxidized products of aromatic primary amine developers at the time of development and the yellow dyes formed are high in the molar extinction coefficient, they are used mainly in photographing color photographic materials that require a high sensitivity, particularly color negative films. On the other hand, the latter are excellent in the spectral absorption characteristics and fastness of the yellow dye and are mainly used in color papers and color reversal films.
However, although benzoylacetanilide-type couplers are high in coupling reactivity with the oxidized products of aromatic primary amine developers at the time of color development and they are great in the molar extinction coefficient of the yellow azomethine dye formed, they have a defect that they are poor in spectral absorption characteristics for the yellow image. Likewise, while pivaloylacetanilide-type couplers are excellent in the spectral absorption characteristics for the yellow image formed, they have defects in that their coupling reactivity with the oxidized products of aromatic primary amine developers at the time of color development is low and the molar extinction coefficient of the yellow azomethine dyes formed is small.
A high coupling reactivity of a coupler and a high molar extinction coefficient of a dye formed therewith make possible a high sensitivity, a high gamma value and a high color density, and bring about what is called a high color-forming property. Additionally, excellent spectral absorption characteristics in a yellow color image implies absorption characteristics such that, for example, the sharpness of the spectral absorption-curve on the long wavelength side is good and undesirable absorption in the green region is minimal.
Therefore, it is desired to develop yellow couplers having the advantages of both benzoylacetanilide-type and pivaloylacetanilide-type couplers, i.e., a high color-forming property (high coupling reactivity of the coupler and the high molar absorption coefficient of the dye) and spectral absorption characteristics which are excellent in the color image.
As acyl groups of acylacetamide-type couplers, for example, a pivaloyl group, a 7,7-dimethylnorbornane-1-carbonyl group, and a 1-methylcyclohexane-1-carbonyl group are disclosed in U.S. Pat. No. Re. 27,848 and, for example, a cyclopropane-1-carbonyl group and a cyclohexane-1-carbonyl group are disclosed in JP-A ("JP-A" means unexamined published Japanese patent application) No. 26133/1972. However, these couplers are poor in some points; for example, their coupling reactivity is poor, the molar extinction coefficient of the dyes is small, or the spectral absorption characteristics of the color images is poor.
A higher sensitivity, higher image quality, and higher toughness have been earnestly desired in recently developed photographic materials. Therefore, the development of couplers excellent in color-forming property and spectral absorption characteristics of the color image has been strongly pursued. However, prior yellow couplers including those disclosed in the above two patents, have had difficulty in satisfying all these requirements.
SUMMARY OF THE INVENTION
Therefore, the first object of the present invention is to provide a yellow coupler excellent in color-forming property and a silver halide color photographic material containing the same.
The second object of the present invention is to provide a yellow coupler excellent in the spectral absorption characteristics for the yellow color image produced by color development and a silver halide color photographic material containing the same.

Other and further objects, features, and advantages of the invention will appear more evident from the following description taken in connection with the accompanying drawing.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a diagram of the absorption spectra of dyes, wherein the absorbence is plotted along the ordinate and the absorption wave length (nm) is plotted along the abscissa.
FIG. 2 is a diagram of the absorption spectra of other dyes, wherein the absorbence is plotted in the same manner as in FIG. 1.

DETAILED DESCRIPTION OF THE INVENTION
The above objects are attained by providing the following yellow coupler (1) and silver halide color photographic material (2):
(1) An acylacetamide-type yellow dye-forming coupler wherein the acyl group is represented by the following formula (I): ##STR2##
wherein R.sub.1 represents a monovalent group, Q represents a group of non-metallic atoms required to form together with the C a 3- to 5-membered cyclic hydrocarbon group or a 3- to 5-membered heterocyclic group having in the group at least one hereto atom selected from a group consisting of N, O, S, and P, provided that R.sub.1 is not a hydrogen atom and does not bond to Q to form a ring.
(2) A silver halide color photographic material having on a base at least one silver halide emulsion layer containing yellow dye-forming couplers, wherein at least one of said yellow dye-forming couplers is a yellow dye-forming coupler described in item (1).
The acylacetamide-type yellow couplers of the present invention will now be described in more detail.
The acylacetamide-type yellow couplers of the present invention are preferably represented by the following formula (II): ##STR3##
In formula (II), R.sub.1 and Q are the same as R.sub.1 and Q in formula (I), respectively, X represents a hydrogen atom or a group capable of being released upon a coupling reaction thereof with the oxidized product of an aromatic primary amine developing agent (hereinafter referred to as coupling split-off group), and R' and R" each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, wherein R' and R" may be combined together to form a ring with N.
Further, the acylacetamide-type yellow couplers of the present invention are preferably represented by the following formula (Y): ##STR4##
In formula (Y), R.sub.1 represents a monovalent substituent other than hydrogen; Q represents a group of non-metallic atoms required to form together with the C, a substituted or unsubstituted 3- to 5-membered cyclic hydrocarbon group or a substituted or unsubstituted 3- to 5-membered heterocyclic group having in the group at least one hetero atom selected from a group consisting of N, O, S, and P; R.sub.2 represents a hydrogen atom, a halogen atom (e.g., F, Cl, Br, and I, which is applied hereinafter to the description of formula (Y)), an alkoxy group, an aryloxy group, an alkyl group, or an amino group; R.sub.3 represents a group capable of substitution onto a benzene ring; X has the same meaning as in formula (II); l is an integer of 0 to 4, and when l is 2 or more, the R.sub.3 groups may be the same or different.
When any of the substituents in formula (Y) is an alkyl group or contains an alkyl group, unless otherwise specified the alkyl group is a straight-chain or branched chain or cyclic alkyl group that may be substituted and may contain an unsaturated bond such as methyl, isopropyl, t-butyl, cyclopentyl, t-pentyl, cyclohexyl, 2-ethylhexyl, 1,1,3,3-tetramethylbutyl, dodecyl, hexadecyl, allyl, 3-cyclohexenyl, oleyl, benzyl, trifluoromethyl, hydroxymethylmethoxyethyl, ethoxycarbonylmethyl, and phenoxyethyl. Moreover, unless otherwise specified the alkyl group contains 1 to 30 carbon atoms (exclusive of any substituents).
When any of the substituent in formula (Y) is an aryl group or contains an aryl group, unless otherwise specified the aryl group is a monocyclic or condensed ring aryl group containing 3 to 8 ring members selected from the group consisting of carbon, oxygen, nitrogen and sulfur. The aryl groups may be further substituted and include aryl groups such as phenyl, 1-naphthyl, p-tolyl, o-tolyl, p-chlorophenyl, 4-methoxyphenyl, 8-quinolyl, 4-hexadecyloxyphenyl, pentafluorophenyl, p-hydroxyphenyl, p-cyanophenyl, 3-pentadecylphenyr, 2,4-di-t-pentylphenyl, p-methanesulfonamidophenyl, and 3,4-dichlorophenyl.
When the substituent in formula (Y) is a heterocyclic group or contains a heterocyclic ring, unless otherwise specified the heterocyclic ring group is a 3- to 8-membered monocyclic or condensed ring heterocyclic group that contains at least one hetero atom selected from the group consisting of O, N, S, P, Se, and Te, and contains from 2 to 36 carbon atoms and may be substituted such as 2-furyl, 2-pyridyl, 4-pyridyl, 1-pyrazolyl, 1-imidazolyl, 1-benzotriazolyl, 2-benzotriazolyl, succinimido, phthalimido, and 1-benzyl- 2,4-imidazolidinedione-3-yl.
Substituents preferably used in formula (Y) will now be described below.
R.sub.1 in formula (Y) preferably represents a halogen atom, a cyano group, a monovalent aliphatic-type group that may be substituted and has a total number of carbon atoms (hereinafter, abbreviated as C-number) of 1 to 30 such as an alkyl group and an alkoxy group, or a monovalent aryl-type group that may be substituted and has a total C-number of 6 to 30 such as an aryl group and an aryloxy group, and examples of substituents therefor are a halogen atom, an alkyl group (straight, branched or cyclic), an alkoxy group, a nitro group, an amino group, a carbonamido group, a sulfonamido group, and an acyl group.
Preferably Q in formula (Y) represents a group of non-metallic atoms which forms together with the C (carbon atom), a substituted or unsubstituted 3 to 5-membered hydrocarbon ring having a total C-number of a substituted or unsubstituted, 3- to 5-heterocyclic ring moiety having in the ring at least one hetero atom selected from the group consisting of N, O, S, and P, and preferably containing from 1 to 3 hetero atom ring members. The ring formed by Q together with the C may have an unsaturated bond in the ring. As examples of the ring formed by Q together with the C are a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclopropene ring, a cyclobutene ring, a cyclopentene ring, an oxetane ring, an oxolane ring, a 1,3-dioxolane ring, a thiethane ring, a thiolane ring, and a pyrrolidine ring. Examples of substituent for the rings include a halogen atom, a hydroxyl group, an alkyl group, an aryl group, an acyl group, an alkoxy group, an aryloxy group, a cyano group, an alkoxycarbonyl group, an alkylthio group, and an arylthio group.
R.sub.2 in formula (Y) preferably represents a halogen atom, an alkoxy group that may be substituted and has a total C-number of 1 to 30, an aryloxy group that may be substituted and has a total-C-number of 6 to 30, an alkyl group that may be substituted and has a total C-number of 1 to 30, or an amino group that may be substituted and has a total C-number of 0 to 30 and the substituent is, for example, a halogen atom, an alkyl group, an alkoxy group, or an aryloxy group.
Preferably, R.sub.3 in formula (Y) is a halogen atom, an alkyl group (as defined above), an aryl group (as defined above), an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, a arylsulfonyl group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an alkoxysulfonyl group, a nitro group, a heterocyclic group (as defined above), a cyano group, an acyl group, an acyloxy group, an alkylsulfonyloxy group, and an arylsulfonyloxy group, and examples of the coupling split-off group are a heterocyclic group (as defined above) bonded to the coupling active site through the nitrogen atom, an aryloxy group, an arylthio group, an acyloxy group, an alkylsulfonyloxy group, an arylsulfonyloxy group, a heterocyclic oxy group (wherein heterocyclic is as defined above), and a halogen atom.
R.sub.3 in formula (Y) preferably represents a halogen atom, an alkyl group that may be substituted and has a total C-number of 1 to 30, more preferably 1 to 18, an aryl group that may be substituted and has a total C-number of 6 to 30, more preferably 6 to 24, an alkoxy group that may be substituted and has a total C-number of 1 to 30, more preferably 1 to 18, an aryloxy group that may be substituted and has a total C-number 6 to 30, more preferably 6 to 24, an alkoxycarbonyl group that may be substituted and has a total C-number of 2 to 30, more preferably 2 to 19, an aryloxycarbonyl group that may be substituted and has a total C-number of 7 to 30, more preferably 7 to 24, a carbonamido group that may be substituted and has a total C-number of 1 to 30, more preferably 1 to 20, a sulfonamido group that may be substituted and has a total C-number of 1 to 30, more preferably 1 to 24, a carbamoyl group that may be substituted and has a total C-number of 1 to 30, more preferably 1 to 20, a sulfamoyl group that may be substituted and has a total C-number of 0 to 30, more preferably 1 to 24, an alkylsulfonyl group that may be substituted and has a total C-number of 1 to 30, more preferably 1 to 20, an arylsulfonyl group that may be substituted and has a total C-number of 6 to 30, more preferably 6 to 24, a ureido group that may be substituted and has a total C-number of 1 to 30, more preferably 1 to 20, a sulfamoylamino group that may be substituted and has a total C-number of 0 to 30, preferably 0 to 20, an alkoxycarbonylamino group that may be substituted and has a total C-number of 2 to 30, preferably 2 to 20, a heterocyclic group (as defined above) that may be substituted and has a total C-number of 1 to 30, preferably 1 to 20, an acyl group that may be substituted and has a total C-number of 1 to 30, preferably 1 to 20, an alkylsulfonyloxy group that may be substituted and has a total C-number of 1 to 30, preferably 1 to 20, or an arylsulfonyloxy group that may be substituted and has a total C-number of 6 to 30, preferably 6 to 24; and examples of the substituents for these R.sub.3 moieties include a halogen atom, an alkyl group, an aryl group, a heterocyclic group (as defined above), an alkoxy group, an aryloxy group, a heterocyclic oxy group (wherein heterocyclic is as defined above), an alkylthio group, an arylthio group, a heterocyclic thio group (wherein heterocyclic is as defined above), an alkylsulfonyl group, an arylsulfonyl group, an acyl group, a carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonylamino group, a sulfamoylamino group, a ureido group, a cyano group, a nitro group, an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyloxy group, and an arylsulfonyloxy group.
In formula (Y), preferably l is an integer of 1 or 2 and the position of the substitution of R.sub.3 is preferably the meta-position or ortho-position relative to ##STR5##
In formula (Y), preferably X represents a heterocyclic group (as defined above) bonded to the coupling active site through a nitrogen atom or an aryloxy group.
When X represents a heterocyclic group, X is most preferably a heterocyclic group (as defined above) comprising a 5- to 7-membered monocyclic group or condensed ring group that may be substituted. Exemplary of such groups are succinimido, maleinimido, phthalimido, diglycolimido, pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, indazole, benzimidazole, benztriazole, imidazolidin-2,4-dione, oxazolidin-2,4-dione, thiazolidin-2,4-dione, imidazolidin-2-one, oxazolidin-2-one, thiazolidin-2-one, benzimidazolin-2-one, benzoxazolidin-2-one, benzothiazolin-2-one, 2-pyrrolin-5-one, 2-imidazolin-5-one, indolin-2,3-dione, 2,6-dioxypurine, parabanic acid, 1,2,4-triazolidin-3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone, 6-pyridazone-2-pyrazone, 2-amino-1,3,4-thiazolidine, 2-imino-1,3,4-thiazolidin-4-one and the like, any of which heterocyclic ring groups may be substituted. Examples of the substituent of these heterocyclic rings include a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a sulfo group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an acyloxy group, an amino group, a carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, a ureido group, an alkoxycarbonylamino group, and a sulfamoylamino group. When X represents an aryloxy group, preferably X represents an aryloxy group having a total C-number of 6 to 30 which may be substituted by a substituent selected from the group consisting of the substituents mentioned above for the heterocyclic ring represented by X. Most preferably, the substituent of the aryloxy group is a halogen atom, a cyano group, a nitro group, a carboxyl group, a trifluoromethyl group, an alkoxycarbonyl group, a carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a cyano group.
Particularly preferably substituents used in formula (Y) will now be described.
Particularly preferably R.sub.1 is a halogen atom or an alkyl group (as defined above) and most preferably a methyl group.
Particularly preferably Q represents a group of non-metallic atoms required to form together with the C a 3- to 5-membered hydrocarbon ring, for example, ##STR6## R represents a halogen atom, a hydrogen atom, or an alkyl group (as defined above). The groups R may be the same or different. Most preferably Q forms together with the C a 3-membered ring, that is, represented by ##STR7## wherein R is as defined above.
Particularly preferably R.sub.2 represents a chlorine atom, a fluorine atom, a substituted or unsubstituted alkyl group having a C-number of 1 to 6 (e.g., halogen substituted C.sub.1-6 alkyl, methyl, trifluoromethyl, ethyl, isopropyl, and t-butyl) exclusive of its substituents, an alkoxy group having a C-number of 1 to 8 (e.g., methoxy, ethoxy, methoxyethoxy, and butoxy), or an aryloxy group having C-number of 6 to 24 (e.g., phenoxy, p-tolyloxy, and p-methoxyphenoxy); with a chlorine atom, a methoxy group, or a trifluoromethyl group most preferred.
Particularly preferably R.sub.3 represents a halogen atom, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonamido group, a sulfonamido group, a carbamoyl group, or a sulfamoyl group, with an alkoxy group, an alkoxycarbonyl group, a carbonamido group, or a sulfonamido group most preferred.
Particularly preferably X is a group represented by the following formula (Y-1) or (Y-2): Formula (Y-1) ##STR8##
In formula (Y-1), Z represents ##STR9##
wherein R.sub.4, R.sub.5, R.sub.8 and R.sub.9, are the same or different, each represent a hydrogen atom, an alkyl group (as defined above), an aryl group (as defined above), an alkoxy group having C-number of 1 to 24, an aryloxy group having C-number of 6 to 24, an alkylthio group having C-number of 1 to 24, an arylthio group having C-number of 6 to 24, an alkylsulfonyl group having C-number of 1 to 24, an arylsulfonyl group having C-number of 6 t 24, or an amino group, any of which may be substituted (except hydrogen); R.sub.6 and R.sub.7 each represent a hydrogen atom, an alkyl group (as defined above), an aryl group (as defined above), an alkylsulfonyl group having C-number of 1 to 24, an arylsulfonyl group having C-number of 6 to 24, or an alkoxycarbonyl group having C-number of 1 to 24, any of which may be substituted (except hydrogen); R.sub.10 and R.sub.11 each represent a hydrogen atom, an alkyl group (as defined above), or an aryl group (as defined above), R.sub.10 and R.sub.11 may bond together to form a benzene ring, and R.sub.4 and R.sub.5, R.sub.5 and R.sub.6, R.sub.6 and R.sub.7, or R.sub.4 and R.sub.8 may bond together to form a 3 to 8 membered heterocyclic or hydrocarbon ring (e.g., cyclobutane, cyclohexane, cycloheptane, cyclohexene, pyrrolidine, and piperidine), any of which groups may be substituted (except hydrogen).
Among the heterocyclic groups represented by formula (Y-1), particularly preferable ones are heterocyclic groups wherein Z represent ##STR10## and R.sub.4, R.sub.5, R.sub.6 and R.sub.7, same or different are as defined above.
The total number of carbon atoms of the heterocyclic group represented by formula (Y-1) is 2 to 30, preferably 4 to 20, and more preferably 5 to 16. ##STR11##
In formula (Y-2), at least one of R.sub.12 and R.sub.13 represents a group selected from a halogen atom, a cyano group, a nitro group, a trifluoromethyl, a carboxyl group, or one of the following groups, any of which may be substituted (except hydrogen), an alkoxycarbonyl group having C-number of 2 to 24, a carbonamido group having C-number of 1 to 24, a sulfonamido group having C-number of 1 to 24, a carbamoyl group having C-number of 1 to 24, a sulfamoyl group having C-number of 0 to 24, an alkylsulfonyl group having C-number of 1 to 24, an arylsulfonyl group having C-number of 6 to 24, and an acyl group having C-number of 1 to 24 and the other is a hydrogen atom, an alkyl group (as defined above), or an alkoxy group having C-number of 1 to 24; R.sub.14 has the same meaning as that of R.sub.12 or R.sub.13 ; and m is an integer of 0 to 2. The total number of carbon atoms of the aryloxy group represented by formula (Y-2) is 6 to 30, preferably 6 to 24, and more preferably 6 to 15.
The coupler represented by formula (Y) may form a dimer or higher polymer formed by joining at the substituent R.sub.1, X or through a bivalent or ##STR12## higher polyvalent group. In such cases, the carbon numbers thereof may fall outside the specified range defined for each substituent.
(1) Samples of the ##STR13## group formed by R.sub.1 and Q with C are shown below. ##STR14##
(2) Examples of R.sub.2 ##STR15##
(3) Examples of R.sub.3 ##STR16##
(4) Examples of X ##STR17##
Exemplified yellow couplers represented by (Y) are shown below. ##STR18##
The present yellow couplers represented by formula (Y) can be synthesized through the following synthesis routes: ##STR19##
Compound a can be synthesized by any process described, for example, in J. Chem. Soc. (C), 1968, 2548; J. Am. Chem. Soc., 1934, 56, 2710; Synthesis, 1971, 258; J. Org. Chem., 1978, 43, 1729, and CA, 1960, 66, 18533y.
The synthesis of Compound b is carried out by a reaction using thionyl chloride, oxalyl chloride, etc., optionally in a solvent such as methylene chloride, chloroform, carbon tetrachloride, dichloroethane, toluene, N,N-dimethylformamide, and N,N-dimethylacetamide, generally at a reaction temperature of about -20.degree. to 150.degree. C., and preferably at about -10.degree. to 80.degree. C.
Compound c is synthesized by making ethyl acetoacetate into an anion using magnesium methoxide or the like and adding b thereto. The-reaction is carried out optionally using a solvent such as tetrahydrofuran and ethyl ether, and the reaction temperature is generally about -20.degree. to 60.degree. C., preferably about -10.degree. to 30.degree. C. Compound d is synthesized by carrying out a reaction using Compound c and, as a base, an aqueous solution of ammonia, NaHCO.sub.3, or NaOH, optionally in a solvent such as methanol, ethanol, and acetonitrile. The reaction temperature is generally about -20.degree. to 50.degree., preferably about -10.degree. to 30.degree. C.
Compound e is synthesized by reacting compound d and compound g together without using a solvent. The reaction temperature is generally about 100.degree. to 150.degree. C., preferably about 100.degree. to 120.degree. C. When X is not H, after chlorination or bromination, the coupling split-off group X is introduced to synthesize compound f. Compound e is made into a chlorine-substituted product using, for example, a sulfuryl chloride or N-chlorosuccinimide in a solvent such as dichloroethane, carbon tetrachloride, chloroform, methylene chloride, and tetrahydrofuran, or it is made into a bromine-substituted product using, for example, bromine or N-bromosuccinimide in a solvent as above. In this case the reaction temperature is about -20.degree. to 70.degree. C., preferably about -10.degree. to 50.degree. C. Then, when the chlorine-substituted product or bromine-substituted product and the proton adduct H-X of the coupling split-off group are reacted in a solvent, such as methylene chloride, chloroform, tetrahydrofuran, acetone, acetonitrile, dioxane, N-methylpyrrolidone, N,N'-dimethylimidazolidin-2-one, N,N-dimethylformamide, and N,N-dimethylacetamide, at a reaction temperature of about -20.degree. to 150.degree. C., preferably about -10.degree. to 100.degree. C., Coupler f of the present invention can be obtained. At that time a base may be used, such as triethylamine, N-ethylmorpholine, tetramethylguanidine, potassium carbonate, sodium hydroxide, and sodium bicarbonate.
Synthesis Examples of couplers of the present invention are given below.
SYNTHESIS EXAMPLE 1
Synthesis of Exemplified Compound Y-30
38.1 g of oxalyl chloride was added dropwise to a mixture of 25 g of 1-methylcyclopropanecarboxylic acid, which was synthesized in accordance with the process described by Gotkis, D, et al., J. Am. Chem. Soc., 1934, 56, 2710, 100 ml of methylene chloride, and 1 ml of N,N-dimethylformamide over 30 min at room temperature. After the completion of the addition, the reaction was continued for 2 hours at room temperature, and then the methylene chloride and the excess oxalyl chloride were removed under reduced pressure created by an aspirator, to produce an oil of 1-methylcyclopropanecarbonyl chloride.
100 ml of methanol was added dropwise to a mixture of 6 g of magnesium and 2 ml of carbon tetrachloride at room temperature over 30 min, and after the mixture was heated for 2 hours under reflux, 32.6 g of ethyl 3-oxobutanate was added dropwise thereto over 30 min under heating and reflux. After completion of the addition the heating was continued for 2 hours under reflux and then the methanol was distilled off completely under reduced pressure created by an aspirator. 100 ml of tetrahydrofuran was added to the reaction product, to disperse the reaction product, and the previously obtained 1-methylcyclopropanecarbonyl chloride as added dropwise to the dispersion at room temperature. After reacting for 30 min, the reaction liquid was extracted with 300 ml of ethyl acetate and dilute sulfuric acid, the organic layer was washed with water and then dried over anhydrous sodium sulfate, and the solvent was distilled off, to obtain 55.3 g of an oil of ethyl 2-(1-methylcyclopropanecarbonyl)-3-oxobutanate.
A solution of 55 g of ethyl 2-(1-methylcyclopropanecarbonyl)-3-oxobutanate in 160 ml of ethanol was stirred at room temperature and 60 ml of a 30% aqueous ammonia solution was added dropwise to the solution over 10 min. Thereafter the stirring was continued for 1 hour, then extraction with 300 ml of ethyl acetate and dilute hydrochloric acid was carried out, the organic layer was neutralized, washed with water, and dried over anhydrous sodium sulfate, and the solvent was distilled off, to obtain 43 g of an oil of ethyl (1-methylcyclopropanecarbonyl)acetate.
34 g of ethyl (1-methylcyclopropanecarbonyl)acetate and 44.5 g of N-(3-amino-4-chlorophenyl)-2-(2,4-di-t-pentylphenoxy)butaneamide were heated under reflux and reduced pressure created by an aspirator, with the internal temperature being 100.degree. to 120.degree. C. After the reaction was continued for 4 hours, the reaction liquid was refined by column chromatography using a mixed solvent of n-hexane and ethyl acetate, to produce 49 g of a viscous oil of the Exemplified Compound Y-30. The structure of the compound was identified by mass spectrometry, NMR spectrometry, and elemental analysis.
SYNTHESIS EXAMPLE 2
Synthesis of Exemplified Compound Y-1
22.8 g of the Exemplified Compound Y-30 was dissolved in 300 ml of methylene chloride and was added dropwise to 5.4 g of sulfuryl chloride over 10 min with ice cooling. After the reaction had continued for 30 min, the reaction liquid was washed well with water, dried over anhydrous sodium sulfate, and then condensed, to obtain the chloride of the Exemplified Compound Y-30. The thus synthesized chloride of the Exemplified Compound Y-30 was dissolved in 50 ml of N,N-dimethylformaldehyde and was added dropwise to a solution of 50 ml of N,N-dimethylformaldehyde, 11.2 ml of triethylamine, and 18.7 g of 1-benzyl-5-ethoxyhydantoin over 30 min at room temperature.
Thereafter the reaction was allowed to continue for 4 hours at 40.degree. C., and then the reaction liquid was extracted with 300 ml of ethyl acetate, thereafter washed with water and then washed with a 2% aqueous triethylamine solution. This was followed by neutralization with dilute hydrochloric acid. After the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and the resulting oil was crystallized from a mixed solvent of n-hexane and ethyl acetate. The deposited crystals were filtered, then washed with a mixed solvent of n-hexane and ethyl acetate, and dried, to obtain 22.8 g of crystals of the Exemplified Compound Y-1.
The structure of the compound was identified by mass spectrometry, NMR spectrometry, and elemental analysis. The melting point was 132.degree. to 133.degree. C.
The spectral absorption spectra and the molecular extinction coefficients of Dye A, obtained from the present Exemplified Compound Y-31, and Dye B, obtained from a pivaloylacetanilide-type coupler in ethyl acetate, were compared. Dye A showed excellent spectral absorption spectrum characteristics (better than Dye B), and it showed a molecular extinction coefficient which was about 30% higher than that of Dye B (FIG. 1).
______________________________________Dye A ##STR20##Dye B ##STR21## max (nm) mol.sup.-1 (cm-1)______________________________________Dye A 428.8 19900Dye B 433.1 15400______________________________________ Note: max : Wavelength of maximum absorption : Molecular extinction coefficient
SYNTHESIS EXAMPLE 3
Synthesis of Exemplified Compound Y-43
N-[2-Chloro-5-(2-(2,4-di-t-pentylphenoxy)butaneamido)phenyl]-2-(1-methylcyclopentanecarbonyl) acetamide was prepared in the same manner as in Synthesis Example 1, except that, as a raw material, 32 g of 1-methylcyclopentane-carbonic acid that had been synthesized by the method described in Organic Synthesis, Vol. 46, 72 using cyclohexyl alcohol as a starting material was used instead of 1-methylcyclopropanecarbonic acid in Synthesis Example 1 to obtain 50 g of an amorphous product. Then, 23.9 g of his N-[2-chloro-5-(2-(2,4-di-t-pentylphenoxy)butaneamido)phenyl]-2-(methylcyclopentane-carbonyl)acetanide was subjected to the same reaction treatment as in Synthesis Example 2 in which 30 g of exemplified compound 30 was used as a raw material, to obtain an oily product. The thus-obtained oily product was purified by a column chromatography using a mixture solvent of n-hexane and ethyl acetate to obtain 26.5 g of exemplified compound Y-43 in tacky oil. The structure of the compound was identified by mass spectrometry, NNR spectrometry, and elemental analysis.
The method of the present-invention can be adopted to any type of processing process. For example, they can be adopted to the processing of a color paper, a color reverse paper, a color positive film, a color negative film, a color reverse film, or a color direct positive photographic material.
The silver halide emulsion of the color photographic material to be used in the present invention may be any type of halogen composition, including silver bromide, silver iodobromide, silver bromochloroiodide, silver chlorobromide or silver chloride.
Although the halogen compositions of the emulsion may be the same or different from grain to grain, if emulsions whose grains have the same halogen composition are used, it is easy to make the properties of the grains homogeneous. With respect to the halogen composition distribution in a silver halide emulsion grain there can be suitably selected and used for example, a grain having a so-called uniform-type structure, wherein the composition is uniform throughout the silver halide grain, a grain having a so-called layered-type structure, wherein the halogen composition of the core of the silver halide grain is different from that of the shell (which may comprise a single layer or layers) surrounding the core, or a grain having a structure with nonlayered parts different in halogen composition in the grain or on the surface of the grain (if the nonlayered parts are present on the surface of the grain, the structure has parts different in halogen composition joined onto the edges, the corners, or the planes of the grain). To secure high sensitivity, it is more advantageous to use one of the latter two types of grains, rather than using grains having a uniform-type structure. The use of the latter types of grains is also preferable in view of their pressure resistance. If the silver halide grains have the above-mentioned structure, the boundary section between parts different in halogen composition may be a clear boundary, or an unclear boundary, due to the formation of mixed crystals caused by differences in composition, or they may have positively varied continuous structures.
The composition of silver halide may be changed according to the purpose to which the photographic material is to be adopted. For example, a silver halide emulsion comprising mainly silver chlorobromide may be used for a print material, such as a color paper, while an emulsion comprising mainly silver iodobromide being used for a photographic material, such as a color negative film.
Further in a photographic material suitable for the rapid processing of an emulsion having a high silver chloride content, a so-called high-silver-chloride emulsion, may be used preferably. The content of silver chloride in the high-silver-chloride emulsion is preferably 90 mol % or over, more preferably 95 mol % or over.
In these high-silver-chloride emulsions, the structure is preferably such that the silver bromide localized phase in the layered form or nonlayered form is present in the silver halide grain and/or on the surface of the silver halide grain as mentioned above. The silver bromide content of the composition of the above-mentioned localized phase is preferably at least 10 mol %, and more preferably over 20 mol %. The localized phase may be present in the grain, or on the edges, or corners of the grain surfaces, or on the planes of the grains, and a preferable example is a localized phase epitaxially grown on each corner of the grain.
The average grain size of the silver halide grains (expressed in terms of the grain diameter for spherical or semi-spherical grains, the edge length for cubic grains, and the spherical diameter for tabular grains, which can be determined as the average of the projected area diameter) is preferably smaller than 2 .mu.m and larger than 0.1 .mu.m, most preferably smaller than 1.5 .mu.m and larger than 0.15 .mu.m. The distribution of grain size may be either narrow or wide, but it is preferable in the present invention to use the so-called monodisperse emulsion of silver halide having a value (deviation coefficient) obtained by dividing the standard deviation calculated from the size distribution curve by the average grain size of 20% or less, most preferably 15% or less. In order to realize the gradation desired for the photographic material, two or more monodisperse silver halide emulsions (preferably all emulsions having the above-mentioned deviation coefficient) different in grain size may be mixed in a single layer or coated as different layers that have substantially the same color sensitivity. Further, two or more polydisperse silver halide emulsions or a combination of monodisperse and polydisperse emulsions can be used.
Silver halide grains for use in the present invention may have a regular crystal structure, such as cubic, hexahedral, rhombic dodecahedral, tetradecahedral, or a mixture thereof, or an irregular crystal structure, such as spherical or thereof composite crystal structure. Further tabular grains can be employed.
The silver halide photographic emulsions that can be used in this invention may be prepared suitably by known means, for example, by the methods described in I. Emulsion Preparation and Types, in Research Disclosure (RD), No. 17643 (December 1978), pp. 22-23, and in ibid, No. 18716 (November 1979), p. 648; the methods described in P. Glafkides, Chemie et Phisique Photographique, Paul Montel (1967), in G. F. Duffin, Photographic Emulsion Chemistry, Focal Press (1966), and in V. L. Zelikman et al., Making and Coating of Photographic Emulsion, Focal Press (1964).
A monodisperse emulsion, such as described in U.S. Pat. Nos. 3,574,628 and 3,655,394, and in British Patent No. 1.413,748, is also preferable.
Tabular grains having an aspect ratio of 5 or greater can be used in the emulsion of this invention. Tabular grains can be easily prepared by the methods described in, for example, Gutoof, Photographic Science and Engineering, Vo. 14, pp. 248-257 (1970), U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048, and 4,439,520, and British Patent No. 2,112,157.
The crystal structure of the emulsion grains may be uniform, the outer halogen composition of the crystal structure may be different from the inner halogen composition, or the crystal structure may be layered. Silver halides whose compositions are different may be joined by the epitaxial joint, or a silver halide may be joined, for example, to a compound other than silver halides, such as silver rhodanide, lead oxide, etc.
Further, the silver halide may be a mixture of grains having various crystal shapes.
The silver halide emulsion may generally be physically ripened, chemically ripened, and spectrally sensitized. Additives that will be used in these steps are described in Research Disclosure no. 1763 and ibid. No. 18716, and involved sections are listed in the Table shown below.
Known photographic additives that can be used in this invention are also described in the above-mentioned two Research Disclosures, and the involved sections are listed in the same Table below.
______________________________________Additive RD 17643 RD 18716______________________________________1 Chemical sensitizer p. 23 p. 648 (right column) Sensitivity- -- p. 648 (right column) enhancing agents3 Spectral sensitizers pp. 23-24 pp. 648- (right column and Superstabilizers 649 (right column)4 Brightening agents p. 245 Antifogging agents pp. 24-25 p. 649 (right column) and Stabilizers6 Light absorbers, pp. 25-26 pp. 649- (right column) Filter dyes, and 650 (left column) UV Absorbers7 Stain-preventing p. 25 p. 650 (left to right agents (right column) column)8 Image dye p. 25 -- stabilizers9 Hardeners p. 26 p. 651 (left column)10 Binders p. 26 p. 651 (left column)11 Plasticizers and p. 27 p. 650 (right column) Lubricants12 Coating aids and pp. 26-27 p. 650 (right column) Surface-active agents13 Antistatic agents p. 27 p. 650 (right column)______________________________________
Further, in order to prevent the lowering of photographic performances due to formaldehyde gas, a compound described in, for example, U.S. Pat. Nos. 4,411,987 and 4,435,503 that is able to react with formaldehyde to immobilize it can be added to the photographic material.
Various color couplers can be used in this invention, and typical examples are described in the patents in the above-mentioned Research Disclosure No. 17643, VII-C to G.
As yellow couplers for combined use with the couplers of the present invention, those described, for example, in U.S. Pat. Nos. 3,933,501, 4,022,620, 4,326,024, 4,401,752, and 4,428,961. JP-B (JP-B" means examined Japanese patent publication) No. 10739/1983, British Patent Nos. 1,425,020 and 1,476,760, U.S. Pat. Nos. 3,973,968, 4,314,023, and 4,511,649, and European Patent No. 249,473A are preferable.
As magenta couplers, the 5-pyrazolone type and pyrazoloazole type are preferable, those described in U.S. Pat. Nos. 4,310,619 and 4,315,897, European Patent No. 73,636, U.S. Pat. Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A No. 33552/1985, Research Disclosure No. 24230 (June 1984), JP-A Nos. 43659/1985, 72238/1986, 35730/1985, 118034/1980, and 185951/1985, U.S. Pat. Nos. 4,500,630, 4,540,654, and 4,556,630, and International Patent Publication No. WO 88/04795 are particularly preferable.
The cyan couplers include phenol-type couplers and naphthol-type couplers, and those described in U.S. Pat. Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011, and 4,327,173, West German Patent Application (OLS) No. 3,329,729, European Patent Nos. 121,365A and 249,453A, U.S. Pat. Nos. 3,446,622, 4,333,999, 4,775,616, 4,451,559, 4,427,767, 4,690,889, 4,254,212, and 4,296,199, and JP-A No. 42658/1986 are more preferable.
As a colored coupler to rectify the unnecessary absorption of color-forming dyes, those couplers described in paragraph VII-G of Research Disclosure No. 17643, U.S. Pat. No. 4,163,670, JP-B No. 39413/1982, U.S. Pat. Nos. 4,004,929, and 4,138,258, and British Patent No. 1,146,368 are preferable. Further, it is preferable to use couplers to rectify the unnecessary absorption of color-forming dyes by a fluorescent dye released upon the coupling as described in U.S. Pat. No. 4,774,181 and by couplers having a dye precursor, as a group capable of being released, that can react with the developing agent to form a dye as described in U.S. Pat. No. 4,777,120.
As a coupler which forms a dye having moderate diffusibility, those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570, and West German Patent Application (OLS) No. 3,234,533 are preferable.
Typical examples of a polymerized dye-forming coupler are described in U.S. Pat. Nos. 3,451,820, 4,080,211, 4,367,282, 4,409,320, and 4,576,910, and British Patent No. 2,102,173.
A coupler that releases a photographically useful residue accompanied with the coupling reaction can be used favorably in this invention. As a DIR coupler that releases a development retarder, those described in patents cited in paragraph VII-F of the above-mentioned Research Disclosure No. 17643, JP-A Nos. 151944/1982, 154234/1982, 184248/1985, 37346/1988, and 37350/1988, and U.S. Pat. Nos. 4,286,962 and 4,782,012 are preferable.
As a coupler which releases, imagewisely, a nucleating agent or a development accelerator upon developing, those described in British Patent Nos. 2,097,140 and 2,131,188, and JP-A Nos. 157638/1984 and 170840/1984 are preferable.
Other couplers that can be incorporated in the photographic material of this invention include competitive couplers described in U.S. Pat. No. 4,130,427, multi-equivalent couplers described in U.S. Pat. Nos. 4,283,472, 4,338,393, and 4,310,618, couplers which release a DIR redox compound, couplers which release a DIR coupler, and redox compounds which release a DIR coupler or a DIR redox as described in JP-A Nos. 185950/1985 and 24252/1987, couplers which release a dye to regain a color after releasing as described in European Patent Nos. 173,302A and 313,308A, couplers which release a bleaching-accelerator as described in RD. Nos. 11449 and 24241, and JP-A No. 201247/1986, couplers which release a ligand as described in U.S. Pat. No. 4,553,477, couplers which release a leuco dye as described in JP-A No. 75747/1988, and couplers which release a fluorescent dye as described in U.S. Pat. No. 4,774,181.
The coupler to be used in this invention can be incorporated to photographic materials by various known dispersing processes.
Examples of a high-boiling organic solvent for use in an oil-in-water dispersing process are described, for example, in U.S. Pat. No. 2,332,027.
The steps and effects of the latex dispersion method and examples of latex are described, for example, in U.S. Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230, and a dispersion method using a polymer soluble in organic solvent is described in PCT International Publication No. WO 88/00723.
Specific examples of high-boiling organic solvent that are used in the above-mentioned oil-in water dispersing process include alkylester phthalate (e.g., dibutyl phthalate and dioctyl phthalate), phosphate ester (e.g., diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, and dioctylbutyl phosphate), citrate ester (e.g., tributylacetyl citrate), benzoate ester (e.g., 2-ethylhexyl benzoate and 2-ethylhexyl-2, 4-dichloro benzoate), alkylamide (e.g., diethyllaurylamide), ester of aliphatic acid (e.g., dibutoxyethyl succinate, di-2-ethyl-hexyl succinate, 2-hexyldecyl tetradecanate, tributyl citrate, and diethyl azelate), chlorinated paraffin (paraffin having a chlorine content of 10 to 80%), and esters of trimethinate (e.g., tributyl trimethinate), or organic solvents having a boiling point of about 30.degree. to 150.degree. C., for example, lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methylisobutyl ketone, .beta.-ethoxyethyl acetate and methyl cellosolve acetate may be used in combination.
The yellow coupler of the present invention may be used, generally, in the range of 1.times.10.sup.-3 mol to 1 mol, preferably 1.times.10.sup.-2 mol to 8.times.10.sup.-1 mol, per mol of silver halide in the layer to be used. Further the coupler of the present invention may be used in combination with other yellow coupler.
Although the layer to which the yellow coupler of the present invention is added may be any silver halide layer or non-photosensitive layer, preferably it is used in a blue-sensitive silver halide emulsion layer or a layer adjacent to the blue-sensitive layer. When it is used in a blue-sensitive silver halide emulsion layer, preferably the amount of silver is 0.1 to 10 g/m.sup.2. Further, when the yellow coupler of the present invention is used in a non-photosensitive layer, preferably it is used in an amount of 0.1 to 2 mmol/m.sup.2.
The amount of color coupler to be used is, as a standard, in a range of 0.001 to 2 mol per mol of silver halide, preferably 0.01 to 1.5 mol for yellow coupler, 0.003 to 1.0 mol for magenta coupler, and 0.002 to 1.0 mol for cyan coupler, per mol of silver halide.
In the color photographic materials of this invention, it is preferable to add various preservatives or mildew proofing agent, such as 1,2-benzisothiazoline-3-one, n-butyl-p-hydroxy benzoate, phenol, 4-chloro-3, 5-dimethyl phenol, 2-phenoxyethanol, and 2-(4-thiazolyl)-benzimidazole, as described in JP-A Nos. 257747/1988, 272248/1987, and 80941/1989.
A photographic material of this invention is prepared by coating a flexible base, such as a plastic film (e.g., cellulose nitrate, cellulose acetate, and polyethylene telephthalate), a paper (of the type usually used), or a rigid base, such as glass plate. Details relating to the bases and coating methods are described in Research Disclosure, Vol. 176, Item 17643, paragraph XV (p.27) and paragraph XVIII (p. 28)(December 1978).
A photographic material that is prepared by using this invention may contain, as color antifoggant, for example, a hydroquinone derivative, or an ascorbic acid derivative.
In a photographic material of the present invention, various anti-fading agents (discoloration preventing agents) can be used. That is, as organic anti-fading additives for cyan, magenta and/or yellow images, there can typically be used hydroquinones, 6-hydroxychromans, 6-hydroxycoumarans, spirochromans, hindered phenols including p-alkoxyphenols and bisphenols, gallic acid derivatives, methylenedioxy-benzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of these compounds. Metal complexes such as (bissalicyl-aldoximate) nickel complex and (bis-N,N-dialkyldithiocarbamato) nickel complex can also be used.
Specific examples of the organic anti-fading agents are described in the following patent specifications:
Hydroquinones are described, for example, in U.S. Pat. Nos. 2,360,290, 2,418,613, 2,70,453, 2,701,197, 2,728,659, 2,732,300, 2,735,765, 3,982,944, and 4,430,425, British Patent No. 1,363,921, and U.S. Pat. Nos. 2,710,801 and 2,816,028, 6-hydroxychromans; 5-hydroxycoumarans and spirochromans are described, for example, in U.S. Pat. Nos. 3,432,300, 3,573,050, 3,574,627, 3,698,909, and 3,764,337, and JP-A No. 152225/1977; spiroindanes are described in U.S. Pat. No. 4,360,589; p-alkoxyphenols are described, for example, in U.S. Pat. No. 2,735,765, British Patent No. 2,066,975, JP-A No. 10539/1984, and JP-B No. 19765/1982; hindered phenols are described, for example, in U.S. Pat. No. 4,228,235, and JP-B No. 6623/1977; gallic acid derivatives, methylenedioxybenzenes, and aminophenols are described, for example, in U.S. Pat. Nos. 3,457,079 and 4,332,886, and JP-B No. 21144/1981 respectively; hindered amines are described, for example, in U.S. Pat. Nos. 3,336,135, and 4,286,593, British Patent Nos. 1,326,889, 1,354,313, and 1,410,846, JP-B No. 1420/1976, and JP-A Nos. 114036/1983, 53846/1984, and 78344/1984; and metal complexes are described, for example, in U.S. Pat. Nos. 4,050,938 and 4,241,155 and British Patent No. 2,027,731(A). To attain the present purposes, these compounds can be added to the photosensitive layers by coemulsifying them with the corresponding couplers, with the amount of each compound being generally 5 to 100 wt. % for the particular coupler. To prevent the cyan dye image from being deteriorated by heat, and in particular light, it is more effective to introduce an ultraviolet absorber into the cyan coupler-forming layer and the opposite layers adjacent to the cyan color-forming layers.
As the ultraviolet absorber, aryl-substituted benzotriazole compounds (e.g., those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (e.g., those described in U.S. Pat. Nos. 3,314,794 and 3,352,681), benzophenone compounds (e.g., those described in JP-A No. 2784/1971), cinnamic acid ester compounds (e.g., those described in U.S. Pat. Nos. 3,705,805 and 3,707,395), butadiene compounds (e.g., those described in U.S. Pat. No. 4,045,229), or benzoxazole compounds (e.g., those described in U.S. Pat. No. 3,700,455) can be used. Ultraviolet-absorptive couplers (e.g., .alpha.-naphthol type cyan dye forming couplers) and ultraviolet-absorptive polymers can, for example, be used also. These ultraviolet-absorbers may be mordanted in the special layer.
Of these, benzotriazole compounds substituted by an aryl group as described above are preferable.
As a binder or a protective colloid that can be used in the emulsion layers of the photographic material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or in combination with gelatin.
In the present invention, gelatin may be lime-treated gelatin or acid-processed gelatin. Details of the manufacture of gelatin is described by Arther Veis in The Macromolecular Chemistry of Gelatin (published by Academic Press, 1964).
The color-developing solution to be used in the developing process of the photographic material of the present invention is preferably an aqueous alkaline solution whose major component is an aromatic primary amine-type color developing agent. As the color developing agent, aminophenol-type compounds are useful, and p-phenylenediamine-type compounds are preferably used, typical examples thereof being 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-.beta.-hydroxylaniline, 3-methyl-4-amino-N-ethyl-N-.beta.-methanesulfonamidoethylaniline, and 3-methyl-4-amino-N-ethyl-N-.beta.-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. These compounds may be used in combination according to the desired purpose.
Generally the color-developing solution contains pH buffers such as carbonates, borates, or phosphates of alkali metals; antifoggants or development retarders, such as mercapto compounds, benzothiazoles, benzimidazoles, iodides or bromides; and if required, preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, and triethylenediamine (1,4-diazabicyclo[2,2,21]octane); organic solvents such as ethylene glycol and diethylene glycol; development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines; dye-forming couplers; competing couplers; fogging agents such as sodium boron hydride; auxiliary developing agents such as 1-phenyl-3-pyrazolidone; thickening agents; and chelate agents, such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids such as, for example ethylenediaminetetraacetic acid, nitrilotriacetic acid, ethylenetriaminetetraacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethylimidinoacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, and ethylenediamine-di-(o-hydroxyphenylacetic acid), and their salts.
For reversal processing, a color development is generally carried out after a black-and-white development. For the black-and-white developing solution, known black-and-white-developing agents such as dihydroxybenzenes (e.g., hydroquinone), 3-pyrazolidones (e.g., 1-phenyl-3-pyrazolidone), and aminophenols (e.g., N-methyl-p-aminophenol) may be used alone or in combination with others.
Generally the color-developing solution has a pH of 9 to 12. Although the replenishing amount of the developing solution varies depending on the color photographic material to be processed, generally the replenishing amount is 3 l or below per m.sup.2 of the photographic material, and the replenishing amount can be lowered to 500 ml or below if the bromide ion concentration of the replenishing-solution is lowered. If it is required to lower the replenishing amount, it preferable that the area of the processing tank in contact with air is minimized to prevent the solution from evaporating or being oxidized by air. The replenishing amount can also be lowered by suppressing the accumulation of bromide ions in the developing solution.
The photographic emulsion layers are generally subjected to a bleaching process after color development.
The bleaching process can be carried out together with a fixing process (bleach-fixing process), or it can be carried out separately form a fixing process. Further, to quicken the process, bleach-fixing may be carried out after the bleaching process. In accordance with the purpose, the process may be carried out using a bleach-fixing bath having two successive tanks, or a fixing process may be carried out before the bleach-fixing process, or a bleaching process may be carried Out after the bleach-fixing process. As the bleaching agent, use can be made of, for example, compounds of polyvalent metals, such as iron (III), cobalt (III), chromium (VI), and copper (II), peracids, quinones, and nitro compounds. As typical bleaching agents, use can be made of ferricyanides; dichromates; organic complex salts of iron (II) or cobalt (III), such as complex salts of aminopolycarboxylic acids, for example ethylenediaminetetraacetic acid, diethylenetriaminetetraacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol ether diamine tetraacetic acid, citric acid, tartaric acid, and malic acid; persulfates; bromates; permanganates; and nitrobenzenes. Of these, aminopolycarboxylic acid iron (III) complex salts, including ethylenediaminetetraacetic acid iron (III) complex salts, including ethylenediaminetetraacetic acid iron (III) complex salts, and persulfates are preferable in view of rapid processing and the prevention of environmental pollution. Further, aminopolycarboxylic acid iron (III) complex salts are particularly Useful in a bleaching solution as well as a bleach-fix solution. The pH of the bleaching solution or the bleach-fix solution using these aminopolycarboxylic acid iron (III) complex salts is generally 5.5 to 8, but if it is required to quicken the process, the process can be effected at a lower pH.
In the bleaching solution, the bleach-fix solution, and the baths preceding them a bleach-accelerating solution may be used if necessary. Examples of useful bleach-accelerating agents are compounds having a mercapto group or a disulfide linkage, described in U.S. Pat. No. 3,893,858, West German Patent No. 1,290,812, JP-A No. 95630/1978, and Research Disclosure No. 17129 (June 1978); thiazolidine derivatives, described in JP-A No. 140129/1975; thiourea derivatives, described in U.S. Pat. No. 3,706,561; iodide salts, described in JP-A No. 16235/1988; polyoxyethylene compounds, described in West German Patent No. 2,748,430; polyamine compounds, described in JP-B No. 8836/1960; and iodide ions. Of these, compounds having a mercapto group or a disulfide group are preferable in view of higher acceleration effect, and in particular, compounds described in U.S. Pat. No. 3,893,858, West German Patent No. 1,290,812, and JP-A No. 95630/1978 are preferable. Compounds described in U.S. Pat. No. 4,552,834 are preferable. These bleach-accelerating agents may be added into the photographic material. When the color photographic materials for photographing are to be bleach-fixed, these bleach-accelerating agents are particularly effective.
As fixing agent can be mentioned thiosulfates, thiocyanates, thioether-type compounds, thioureas, and large amounts of iodide salts, though the use of thiosulfates is common, and particularly ammonium thiosulfate can be used most widely. It is preferable to use, as a preservative for the bleach fix solution, sulfites, bisulfites, and carbonyl bisulfite adducts.
It is common for the silver halide color photographic material of the present invention to undergo, after a desilvering process such as fixing or bleach-fix, a washing step and/or a stabilizing step. The amount of washing water may be set within a wide range depending on the characteristics (e.g., due to the materials used, such as couplers), the application of the photographic material, the washing temperature, the number of washing tanks (the number of steps), the type of replenishing system, including, for example, the counter-current system and the direct flow system, and other various conditions. Of these, the relationship between the number of water-washing tanks and the amount of washing water in the multi-stage counter-current system can be found according to the method described in Journal of the Society of Motion Picture and Television Engineers, Vol. 64, pages 248 to 253 (May 1955).
According to the multi-stage-counter-current system described in the literature mentioned above, although the amount of washing water can be considerably reduced, bacteria propagate with an increase of retention time of the washing water in the tanks, leading to a problem with the resulting suspend matter adhering to the photographic material. In processing the present color photographic material, as a measure to solve this problem, the method of reducing calcium and magnesium described in JP-A No. 288838/1987 can be used quite effectively. Also chlorine-type bactericides such as sodium chlorinated isocyanurate, cyabendazoles, isothiazolone compounds described in JP-A No. 8542/1982, benzotriazoles, and other bactericides described by Hiroshi Horiguchi in Bokin Bobaizai no Kagaku (1986) published by Sankyo-Shuppan, Biseibutsu no Mekkin, Sakkin, Bobaigijutsu (1982), edited by Eiseigijutsu-kai, published by Kogyogijutsu-kai, and in Bokin Bobaizai Jiten (1986), edited by Nihon Bokin Bobai-Gakkai, can be used.
The pH of the washing water used in processing the present photographic material is 4 to 9, preferably 5 to 8. The washing water temperature and the washing time to be set may very depending, for example, on the characteristics and the application of the photographic material, and they are generally selected in the range of 15.degree. to 45.degree. C. for 20 sec. to 10 min., and preferably in the range of 25.degree. to 40.degree. C. for 30 sec. to 5 min. Further, the photographic material of the present invention Can be processed directly with a stabilizing solution instead of the above washing. In such a stabilizing process, any of known processes, for example, a multi-step counter-current stabilizing process or its low-replenishing-amount process, described in JP-A Nos. 8543/1982, 14834/1983, and 220345/1985, and an ion-exchanging process can be used.
In some cases, the above washing process is further followed by a stabilizing process, and as an example thereof can be mentioned a stabilizing bath that is used as a final bath for color photographic materials for photography, which contains formalin and a surface-active agent. In this stabilizing bath, each kind of the chelating agents and bactericides may be added.
Any over-flowed solution resulting from a replenishing of washing solution and/or stabilizing solution may be reused in other steps, such as a desilvering step.
The silver halide color photographic material of the present invention may contain therein a color-developing agent for the purpose of simplifying and quickening the process. If they contain such a color-developing agent, it is preferable to use a precursor for the color-developing agent. For example, indoaniline-type compounds described in U.S. Pat. No. 3,342,597, Schiff base-type compounds described in U.S. Pat. No. 3,342,599 and Research Disclosure Nos. 14850 and 15159, aldol compounds described in research Disclosure No. 13924, metal salt complexes described in U.S. Pat. No. 3,719,492, and urethane-type compounds described in JP-A No. 135628/1978 can be used.
For the purpose of accelerating the color development, the present silver halide color photographic material may contain, if necessary, various 1-phenyl-3-pyrazolidones. Typical compounds are described in JP-A No. 64339/1981, 144547/1982, and 115438/1983.
The various processing solutions used for the present invention are used at 10.degree. to 50.degree. C. Although generally a temperature of 33.degree. to 38.degree. C. is standard, a higher temperature can be used to accelerate the process to reduce the processing time, or a lower temperature can be used to improve the image quality or the stability of the processing solutions. Also, to save the silver of the photographic material, a process using hydrogen peroxide intensification or cobalt intensification described in West German Patent No. 2,226,770 and U.S. Pat. No. 3,674,499 may be carried out.
As a preservative for the processing solution, sulfites, hydroxylamine can be used. Further, an organic preservative can be substituted for these preservatives.
Herein the term "organic preservative" refers to organic compounds that generally, when added to the processing solution for the color photographic material, reduce the speed of deterioration of the aromatic primary amine color-developing agent. That is, organic preservatives include organic compounds having a function to prevent the color-developing agent from being oxidized, for example, with air, and in particular, hydroxylamine derivatives (excluding hydroxylamine, hereinafter the same being applied), hydroxamic acids, hydrazines, hydrazides, phenols, .alpha.-hydroxyketones, .alpha.-aminoketones, saccharides, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxyradicals, alcohols, oximes, diamide compounds, and condensed cyclic amines are effective organic preservatives. These are disclosed, for example, JP-B No. 30496/1973, in JP-A Nos. 143020/1977, 4235/1988, 30845/1988, 21647/1988, 44655/1988, 53551/1988, 43140/1988, 56654/1988, 58346/1988, 43138/1988, 146041/1988, 44657/1988, and 44656/1988, U.S. Pat. Nos. 3,615,503 and 2,494,903, JP-A Nos. 97953/1989, 186939/1989, 186940/1989, 187557/1989, 306244/1990.
As the other preservative, various metals described, for example, in JP-A Nos. 44148/1982 and 53749/1982, salicylic acids described, for example, in JP-A No. 180588/1984, amines described, for example, in JP-A Nos. 239447/1988, 128340/1988, 186939/1989, 187557/1989, alkanolamines described, for example, in JP-A No. 3532/1979, polyethyleneimines described, for example, in JP-A No. 94349/1981, aromatic polyhydroxyl compounds described, for example, in U.S. Pat. No. 3,746,544 may be included, if needed, It is particularly preferable the addition of alkanolamines such as triethanolamine, dialkylhydroxylamines such as N,N-diethylhydroxylamine and N,N-di(sulfoethyl)hydroxylamine, hydrazine derivatives such as N,N-bis(carboxymethyl)hydrazine, or aromatic polyhydroxyl compounds.
The use of alkanolamines in combination with the dialkylhydroixylamine and/or hydrazine derivatives is preferable in view of stability improvement of the color developer resulting its stability improvement during the continuous processing.
Next, the present invention will be described in more detail in accordance with examples, but the invention is not limited to these Examples.
EXAMPLE 1
8.25 g of YC-1, a coupler for comparison, was weighed, 3.3 g of trioctyl phosphate, as a high-boiling organic solvent, was added thereto, and 25 ml of ethyl acetate was added to dissolve them. The solution was added to 280 g of a 10% aqueous gelatin solution, and 1.0 g of sodium dodecylbenzenesulfonate was added to emulsify and disperse it. 136 g of silver chlorobromide emulsion (65.4 g of silver per kg of emulsion;.silver bromide: 70 mol %) was added to this emulsified dispersion, and then 230 g of a 10% aqueous gelatin solution and 320 ml of water were added. Finally, 0.8 g of 1-oxy-3,5-dichloro-s-triazine acid sodium salt, as a hardener, was added thereto, and it was applied to a primed triacetylcellulose film base so that the coating amount of silver would be 865 mg/m.sup.2 thereby preparing Sample 101. In this case, as a protective layer, a gelatin layer in an amount of 1.55 g/m.sup.2 was applied on top of the applied layer.
YC-2 to YC-6, couplers for comparison, and couplers of the present invention were applied in the same way as above so that the coated amount of the couplers might be equimolar, thereby preparing Samples 102 to 114.
To assess the thus prepared Samples, the Samples were given gradation exposure for sensitometry using a sensitometer (FWH model, manufactured by Fuji Photo Film Ltd., Co.; the color temperature of the light source: 3200.degree. K.). Exposure was effected such that the exposure time was 0.1 sec and the exposure amount was 250 CMS.
The thus exposed Samples were processed by using the below-mentioned processing steps, the processing solutions having the below-mentioned processing solution compositions, using an automatic processor.
______________________________________Processing step Temperature Time______________________________________Color-developing 37.degree. C. 3 min. 30 sec.Bleach-fixing 33.degree. C. 1 min. 30 sec.Water-washing 24 to 34.degree. C. 3 min.Drying 70 to 80.degree. C. 1 min.______________________________________
The compositions of each processing solutions were as follows:
______________________________________Color developerWater 800 mlDiethylenetriaminepentaacetic acid 1.0 gNitrilotriacetic acid 2.0 gBenzyl alcohol 15 mlDiethylene glycol 10 mlSodium sulfite 2.0 gPotassium bromide 1.0 gPotassium carbonate 30 gN-ethyl-N-(.beta.-methanesulfonamidoethyl)-3- 4.5 gmethyl-4-aminoaniline sulfateHydroxylamine sulfate 3.0 gFluorescent brightening agent (WHITEX-4, 1.0 gmade by Sumitomo Chemical Ind.)Water to make 1000 mlpH 10.25Bleach-fixing solutionWater 400 mlAmmonium thiosulfate (70%) 150 mlSodium sulfite 18 gIron (III) ammonium ethylenediamine-tetraacetate dihydrate 55 gDisodium ethylenediaminetetraacetate 5 gWater to make 1000 mlpH 6.70______________________________________
From the curve of the sensitometry in the blue region of each of the obtained samples, the maximum color Dmax and the gradient .gamma. of the tangent line at the concentration of 1/2 of the Dmax were read.
The results are summarized in Table 1.
The structures of couplers for comparison in Examples 1 to 9 are shown below. ##STR22##
TABLE 1______________________________________Sample Coupler Dmax .gamma. Remarks______________________________________101 YC-1 1.58 1.04 Comparative Example102 YC-2 1.63 1.41 Comparative Example103 YC-3 1.60 1.21 Comparative Example104 YC-4 1.43 0.92 Comparative Example105 YC-5 0.85 0.29 Comparative Example106 YC-6 0.67 0.18 Comparative Example107 Y-1 2.04 2.01 This Invention108 Y-9 2.10 2.10 This Invention109 Y-47 2.08 2.14 This Invention110 Y-8 2.06 1.97 This Invention111 Y-42 1.93 1.88 This Invention112 Y-43 1.84 1.82 This Invention113 Y-44 1.97 1.97 This Invention114 Y-45 1.88 1.93 This Invention______________________________________
As is apparent from the results of Table 1, the Dmax of the couplers of the present invention is remarkably great in comparison with that of the comparative examples. Likewise, the .gamma. value of the couplers of the present invention is high, showing that they are highly active couplers.
In particular, it can be said that couplers Y-1, Y-9, Y-47, and Y-8, which have the most preferable coupler structures of the present invention, are couplers which provided excellent performance.
Using some of the above samples that had been color-formed to the maximum density, the transmission absorption spectrum of the films was measured. The results are shown in Table 2.
TABLE 2______________________________________ .lambda.maxSample Coupler (nm) .DELTA..lambda..sub.0.5 .DELTA..lambda..sub.0.1 Remarks______________________________________101 YC-1 444 40.3 74.3 Comparative Example102 YC-2 444 39.3 72.5 Comparative Example103 YC-3 445 40.9 75.1 Comparative Example104 YC-4 446 42.1 76.3 Comparative Example107 Y-1 440 37.7 73.2 This invention (Compared with YC-1)108 Y-9 440 36.7 71.0 This Invention (Compared with YC-2)109 Y-47 441 37.7 73.6 This Invention______________________________________
In Table 2, .lambda. max shows the wavelength that gives the maximum absorbance. .DELTA..lambda..sub.0.5 and .DELTA..lambda..sub.0.1 are respectively differences between the wavelength on the longer wavelength side where the densities of 1/2 and 1/10 of the maximum density are given and the wavelength giving the maximum density. The smaller these values are, the sharper the absorption on the longer wavelength side is, showing it is a preferable absorption wave form in view of the color reproduction.
The couplers of the present invention show absorption peaks on the shorter wavelength side in comparison with the corresponding comparative couplers (only the acyl part is replaced). The .DELTA..lambda..sub.0.5 and .DELTA..lambda..sub.0.1 show smaller values in comparison with those of the corresponding comparative couplers. It can be said that these characteristics are preferable characteristics in view of the color reproduction, in that undesired absorption of the magenta to the yellow part is reduced.
From the above, it can be said that the couplers of the present invention are epoch-making couplers high in activity, great in absorbance, and excellent in hue.
EXAMPLE 2
A multilayer photographic material was prepared by multi-coatings composed of the following layer compositions on both-sides of a polyethylene laminated paper base. Coating solutions were prepared as follows:
Preparation of the First Layer Coating Solution
To a mixture of 12.1 g of yellow coupler (YC-1), 4.4 g of image-dye stabilizer (Cpd-1) and 0.7 g of image-dye stabilizer (Cpd-7), 27.2 ml of ethyl acetate and 4.8 g of solvent (Solv-3) were added and dissolved. The resulting solution was dispersed and emulsified in 185 ml of 10% aqueous gelatin solution containing 8 ml of sodium doecylbenzenesulfonate. Separately another emulsion was prepared by adding two kinds of blue-sensitive sensitizing dyes, shown below, to a blend of silver chlorobromide emulsions (cubic grains, 3:7 (silver mol ratio) blend of grains having 0.85 .mu.m and 0.70 .mu.m of average grain size, and a 0.08 and a 0.10 deviation coefficient of grain size distribution, respectively, each in which 0.2 mol % of silver bromide was located at the surface of grains) in such amounts that each dye corresponded to 2.0.times.10.sup.-4 mol to the large size emulsion and 2.5.times.10.sup.-4 mol to the small size emulsion, per mol of silver, and then the emulsion was sulfur-sensitized. The thus-prepared emulsion and the above-obtained emulsified dispersion were mixed together dissolved to give the composition shown below, thereby preparing the first-layer coating solution.
Coating solutions for the second to seventh layers were also prepared in the same manner as the first-layer coating solution. As a gelatin hardener for the respective layers, 1-hydroxy -3, 5-dichloro-s-triazine sodium salt was used.
As spectral-sensitizing dyes for the respective layers, the following compounds were used:
Blue-Sensitive Emulsion Layer: ##STR23## (each 2.0.times.10.sup.-4 mol to the large size emulsion and 2.5.times.10.sup.-4 mol to the small size emulsion, per mol of silver halide)
Green-Sensitive Emulsion Layer: ##STR24## (4.0.times.10.sup.-4 mol to the large size emulsion and 5.6.times.10.sup.-4 mol to the small size emulsion, per mol of silver halide)
and ##STR25## (7.0.times.10.sup.-5 mol to the large size emulsion and 1.0.times.10.sup.-5 mol to the small size emulsion, per mol of silver halide)
Red-Sensitive Emulsion Layer: ##STR26## (0.9.times.10.sup.-4 mol to the large size emulsion and 1.1.times.10.sup.-4 mol to the small size emulsion, per mol of silver halide)
To the red-sensitive emulsion layer, the following compound was added in an amount of 2.6.times.10.sup.-3 mol per mol of silver halide: ##STR27##
Further, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and red-sensitive emulsion layer in amounts of 8.5.times.10.sup.-5 mol, 7.7.times.10.sup.-4 mol, and 2.5.times.10.sup.-4 mol, per mol of silver halide, respectively.
The dyes shown below were added to the emulsion layers for prevention of irradiation: ##STR28## (Composition of Layers)
The composition of each layer is shown below. The figures represent coating amount (g/m.sup.2). The coating amount of each silver halide emulsion is given in terms of silver.
Supporting Base
Paper laminated on both sides with polyethylene (a white pigment, TiO.sub.2, and a bluish dye, ultramarine, were included in the first layer side of the polyethylene-laminated film.)
__________________________________________________________________________First Layer (Blue-sensitive layer)The above-described silver chlorobromide emulsion 0.30Gelatin 1.86Yellow coupler (YC-1) 0.52Image-dye stabilizer (Cpd-1) 0.19Solvent (Solv-3) 0.35Image-dye stabilizer (Cpd-7) 0.06Second layer (Color-mix preventing layer)Gelatin 0.99Color-mix inhibitor (Cpd-5) 0.08Solvent (Solv-1) 0.16Solvent (Solv-4) 0.08Third layer (Green-sensitive emulsion layer):Silver chlorobromide emulsions (cubic grains, 1:3 (Ag mol ratio) blend ofgrains having 0.120.55 .mu.m and 0.39 .mu.m of average grain size, and a 0.10 and a 0.08deviation coefficientof grain size distribution, respectively, each in which 0.8 mol % of AgBrwas locatedat the surface of grains)Gelatin 1.24Magenta coupler (ExM) 0.20Image-dye stabilizer (Cpd-2) 0.03Image-dye stabilizer (Cpd-3) 0.15Image-dye stabilizer (Cpd-4) 0.02Image-dye stabilizer (Cpd-9) 0.02Solvent (Solv-2) 0.40Fourth layer (Ultraviolet ray absorbing layer):Gelatin 1.58Ultraviolet absorber (UV-I) 0.47Color-mix inhibitor (Cpd-5) 0.05Solvent (Solv-5) 0.24Fifth layer (Red-sensitive emulsion layer):Silver chlorobromide emulsions (cubic grains, 1:4 (Ag mol ratio) blend ofgrains 0.23having 0.58 .mu.m and 0.45 .mu.m of average grain size, and a 0.09 and a0.11 deviationcoefficient of grain size distribution, respectively, each in which 0.6mol % of AgBrwas located at the surface of grains)Gelatin 1.34Cyan coupler (ExC) 0.32Image-dye stabilizer (Cpd-6) 0.17Image-dye stabilizer (Cpd-7) 0.40Image-dye stabilizer (Cpd-8) 0.04Solvent (Solv-6) 0.15Sixth layer (Ultraviolet ray absorbing layer):Gelatin 0.53Ultraviolet absorber (UV-1) 0.16Color-mix inhibitor (Cpd-5) 0.02Solvent (Solv-5) 0.08Seventh layer (Protective layer):Gelatin 1.33Acryl-modified copolymer of polyvinyl alcohol (modification degree : 0.17Liquid paraffin 0.03__________________________________________________________________________Compounds used are as follows:(ExY) Yellow coupler ##STR29##(ExM) Magenta couplerMixture (1:1 in molar ratio) of ##STR30##and ##STR31##(ExC) Cyan couplerMixture (2:4:4 in weight ratio) of R = C.sub.2 H.sub.5 and C.sub.4H.sub.9 of ##STR32##and ##STR33##(Cpd-1) Image-dye stabilizer ##STR34##(Cpd-2) Image-dye stabilizer ##STR35##(Cpd-3) Image-dye stabilizer ##STR36##(Cpd-4) Image-dye stabilizer ##STR37##(Cpd-5) Color-mix inhibiter ##STR38##(Cpd-6) Image-dye stabilizerMixture (2:4:4 in weight ratio) of ##STR39##and ##STR40##(Cpd-7) Image-dye stabilizer ##STR41##Average molecular weight: 60,000(Cpd-8) Image-dye stabilizer ##STR42##(Cpd-9) Image-dye stabilizer ##STR43##(UV-1) Ultraviolet ray absorberMixture (4:2:4 in weight ratio) of ##STR44## ##STR45##and ##STR46##(Solv-1) Solvent ##STR47##(Solv-2) SolventMixture (2:1 in volume ratio) of ##STR48##and ##STR49##(Solv-3) SolventOP( OC.sub.9 H.sub.19 (iso)).sub.3(Solv-4) Solvent ##STR50##(Solv-5) Solvent ##STR51##(Solv-6) Solvent ##STR52## The thus-obtained sample was designated as Sample 1. Samples 202 to12 were prepared in the same manner as Sample 1, except that yellowcoupler was changed to comparative couplers YC-2 to YC-4 and couplers of
The processing method of these samples will be described below.
Each of samples was subjected to a gradation exposure through three color separated filters for sensitometry using a sensitometer (FWH model made by Fuji Photo Film Co., Ltd., the color temperature of light source was 3200 K.). At that time, the exposure was conducted in such a manner that the exposure was 250 CMS with the exposure time being 0.1 sec.
After exposure to light, each sample was subjected to a continuous processing (running test) of the processing process shown below using a paper-processer, until a volume of color-developer twice that of a tank had been replenished.
______________________________________Processing Tempera- Time Replenisher TankProcess ture (.degree.C.) (sec.) (ml)* Volume (l)______________________________________Color developing 35 45 161 17Bleach-fixing 30-35 45 215 17Rinsing (1) 30-35 20 -- 10Rinsing (2) 30-35 20 -- 10Rinsing (3) 30-35 20 -- 10Drying 70-80 60______________________________________ Note: *Replenishing amount per m.sup.2 of photographic material. (Rinsing processes were carried out in 3tanks countercurrent flow system from tank of rinsing (3) toward tank of rinsing (1).)
The compositions of each processing solution were as follows:
______________________________________ Tank Reple- Solution nisher______________________________________Color developerWater 800 ml 800 mlEthylenediamine-N,N,N,N-tetra- 1.5 g 2.0 gmethylenephosphonic acidTriethanolamine 8.0 g 12.0 gSodium chloride 1.4 g --Potassium carbonate 25 g 25 gN-ethyl-N-(.beta.-methanesulfonamido- 5.0 g 7.0 gethyl)-3-methyl-4-aminoanilinesulfonateN,N-Bis(carboxymethyl)hydrazine 5.5 g 7.0 gFluorescent brightening agent 1.0 g 3.5 g(WHITEX-4, made by SumitomoChemical Ind. Co.)Water to make 1000 ml 1000 mlpH (25.degree. C.) 10.05 10.45Bleach-fixing solution(Both tank solution and replenisher)Water 400 mlAmmonium thiosulfate (70%) 100 mlSodium sulfite 17 gIron (III) ammonium ethylenediamine- 55 gtetraacetate dehydrateDisodium ethylenediaminetetraacetate 5 gAmmonium bromide 40 gWater to make 1000 mlpH (25.degree. C. 6.0______________________________________
Rinsing Solution
(Both Tank Solution and Replenisher)
Ion-exchanged water (Calsium and magnesium each are contained in an amount of 3 ppm or below)
The evaluation was carried out at the maximum color density Dmax. The drop of the Dmax at the time when sodium sulfite, as a competing compound was added to the color developer in an amount of 0.5 g per litter was designated as .DELTA. Dmax. The results are shown in Table 3.
TABLE 3______________________________________Sample Coupler Dmax .DELTA. Dmax Remarks______________________________________201 YC-1 1.88 -0.36 Comparative Example202 YC-2 1.94 -0.23 Comparative Example203 YC-3 1.91 -0.30 Comparative Example204 YC-4 1.72 -0.48 Comparative Example205 Y-1 2.20 -0.12 This Invention206 Y-9 2.28 -0.09 This Invention207 Y-47 2.25 -0.10 This Invention208 Y-8 2.24 -0.10 This Invention209 Y-42 2.13 -0.12 This Invention210 Y-43 2.09 -0.14 This Invention211 Y-44 2.10 -0.14 This Invention212 Y-45 2.07 -0.16 This Invention______________________________________
As is apparent from Table 3, it can be said that the couplers of the present invention are high in Dmax and color-forming properties in comparison with the comparative examples. When a competing compound is added, the drop of the density for the coupler of this invention is small, so that it can be said that the couplers of the present invention are highly active couplers. It can be said that such couplers are excellent couplers that can provide stable finish against the fluctuation of the composition of a processing solution.
In particular, Y-1, Y-9, Y-47, and Y-8, which fall in the range of the most preferable couplers of the present invention show a particularly excellent performance.
EXAMPLE 3
15.0 g of YC-1, a coupler for comparison, was weighed, 5.0 g of tricresyl phosphate as a high-boiling organic solvent was added thereto, and 15 ml of ethyl acetate was added to dissolve them. The solution was added to 200 g of a 10 wt. % of aqueous gelatin solution containing 1.5 g of sodium dodecylbenzenesulfonate to emulsify and disperse it.
All amount of thus-prepared emulsified emulsion was added to 310 g of silver iodobromide emulsion (emulsion containing 70.0 g/kg of silver and 10 mol % of silver iodide), and it was applied to a prime-coated triacetate cellulose film base so that the coating amount of silver would be 1.61 g/m.sup.2. On this coating layer, a gelatin layer as a protective layer was provided so that the dried thickness of the layer would be 1.0 .mu.m, thereby preparing sample 301. As a gelatin hardener 1,2-bis(vinylsulfonylacetoamido)ethane was used.
The thus-prepared samples were processed, after an exposure to light, according to the process shown below.
______________________________________Processing processProcess Time Temperature______________________________________Color developing 3 min. 15 sec. 38.degree. C.Bleaching 1 min. 38.degree. C.Bleach-fixing 3 min. 15 sec. 38.degree. C.Water-washing (1) 40 sec. 35.degree. C.Water-washing (2) 1 min. 35.degree. C.Stabilizing 40 sec. 38.degree. C.Drying 1 min. 15 sec. 55.degree. C.______________________________________
The composition of each processing solution was as follows:
______________________________________ (g)______________________________________Color developerDiethylenetriaminepentaacetic acid 1.01-hydroxyethylidene-1,1-diphosphonic acid 3.0Sodium sulfite 4.0Potassium carbonate 30.0Potassium bromide 1.4Potassium iodide 1.5 mgHydroxylamine sulfate 2.44-(N-Ethyl-N-.beta.-hydroxyethylamino)-2- 4.5methyl-4-aminoaniline sulfateWater to make 1.0 lpH 10.05Bleaching solutionIron (III) ammonium ethylenediamine- 120.0tetraacetate dihydrateDisodium ethylenediaminetetraacetate 10.0Ammonium bromide 100.0Ammonium nitrate 10.0Bleaching accelerator 0.005 mol ##STR53##Aqueous ammonia (27%) 15.0 mlWater to make 1.0 lpH 6.3Bleach-fixing solutionIron (III) ammonium ethylenediamine- 50.0tetraacatate dihydrateDisodium ethylenediaminetetraacetate 5.0Sodium sulfite 12.0Ammonium thiosulfate (70%) 240.0 mlAqueous ammonia (27%) 6.0 mlWater to make 1.0 lpH 7.2______________________________________
Washing Solution
Tap water was treated by passage through a hybrid-type column filled with an H-type strong acidic cation-exchange resin (Amberlite IR-120B, tradename, made by Rohm & Haas) and an OH-type strong alkaline anion-exchange resin (Amberlite IR-400, tradename, made by the same as the above) so that each concentration of calcium and magnesium ions would be 3 mg/l or below, followed by addition of 20 mg/l of sodium dichloroisocyanurate and 0.15 g/l of sodium sulfate. The pH of this solution is in a range of 6.5 to 7.5.
______________________________________Stabilizing solution (g)______________________________________Formalin (37%) 2.0 mlPolyoxyethylene-p-monononylphenylether 0.3(average polimerization degree: 10)Disodium ethylenediaminetetraacetate 0.05Water to make 1.0 lpH 5.0-8.0______________________________________
Samples 302 to 309 were prepared by the same method of coating as the above, except that the coupler was changed to the other comparative couplers and couplers of the present invention, respectively, so as to be an equimolar coating amount.
Results are shown in Table 4.
TABLE 4______________________________________Sample Coupler Dmax Remarks______________________________________301 YC-7 2.83 Comparative Example302 YC-9 2.45 Comparative Example303 YC-2 2.39 Comparative Example304 YC-3 2.04 Comparative Example305 Y-9 3.12 This Invention306 Y-12 3.07 This Invention307 Y-47 3.09 This Invention308 Y-44 3.01 This Invention309 Y-45 2.96 This Invention______________________________________
As is apparent from the results in Table 4, in comparison with the couplers YC-9, YC-2, and YC-3 of the pivaloyl type, the couplers of the present invention give remarkably high color densities. Further, it can be understood that the couplers of the present invention are excellent couplers that give color densities higher than that of coupler YC-7 of the benzoyl type that was conventionally considered high in color density.
EXAMPLE 4
Multilayer color photographic material sample was prepared by multi-coating each layer having a composition as shown below on a prime-coated triacetate cellulose film base.
(Composition of Photosensitive Layer)
The figure corresponding to each component is indicated in the coating in an amount of g/m.sup.2, but the coating amount of silver halide emulsion is indicated in terms of silver. As respects the sensitizing dyes, the coating amount is indicated in mol per mol of silver halide in the same layer.
(Sample 401)
______________________________________First layer (Halation preventing layer)Black colloidal silver silver silver 0.18Gelatin 1.40Second layer (Intermediate layer)2,5-Di-t-pentadecylhydroquinin 0.81EX-1 0.07EX-3 0.02EX-12 0.002U-1 0.06U-2 0.08U-3 0.10HBS-1 0.10HBS-2 0.02Gelatin 1.04Third layer (First red-sensitive emulsion layer)Emulsion A silver 0.25Emulsion B silver 0.25Sensitizing dye I 6.9 .times. 10.sup.-5Sensitizing dye II 1.8 .times. 10.sup.-5Sensitizing dye III 3.1 .times. 10.sup.-4EX-2 0.035EX-10 0.020U-1 0.070U-2 0.050U-3 0.070HBS-1 0.060Gelatin 0.87Fourth layer (Second red-sensitive emulsion layer)Emulsion G silver 1.0Sensitizing dye I 5.1 .times. 10.sup.-5Sensitizing dye II 1.4 .times. 10.sup.-5Sensitizing dye III 2.3 .times. 10.sup.-4EX-2 0.400EX-3 0.020EX-4 0.030EX-10 0.015U-1 0.070U-2 0.050U-3 0.070Gelatin 1.30Fifth layer (Third red-sensitive emulsion layer)Emulsion D silver 1.60Sensitizing dye I 5.4 .times. 10.sup.-5Sensitizing dye II 1.4 .times. 10.sup.-5Sensitizing dye III 2.4 .times. 10.sup.-4EX-3 0.010EX-4 0.080EX-2 0.097HBS-1 0.22HBS-2 0.10Gelatin 1.63Sixth layer (Intermediate layer)EX-5 0.040HBS-1 0.020Gelatin 0.80Seventh layer (First green-sensitive emulsion layer)Emulsion A silver 0.15Emulsion B silver 0.15Sensitizing dye V 3.0 .times. 10.sup.-5Sensitizing dye VI 1.0 .times. 10.sup.-4Sensitizing dye VII 3.8 .times. 10.sup.-4EX-6 0.260EX-1 0.021EX-7 0.030EX-8 0.025HBS-1 0.100HBS-3 0.010Gelatin 0.63Eighth layer (Second green-sensitive emulsion layer)Emulsion C silver 0.45Sensitizing dye V 2.1 .times. 10.sup.-5Sensitizing dye VI 7.0 .times. 10.sup.-5Sensitizing dye VII 2.6 .times. 10.sup.-4EX-6 0.094Ex-8 0.018Ex-7 0.026HBS-1 0.160HBS-3 0.008Gelatin 0.50Ninth layer (Third green-sensitive emulsion layer)Emulsion E silver 1.2Sensitizing dye V 3.5 .times. 10.sup.-5Sensitizing dye VI 8.0 .times. 10.sup.-5Sensitizing dye VII 3.0 .times. 10.sup.-4EX-13 0.015Ex-11 0.100Ex-1 0.025HBS-1 0.25HBS-2 0.10Gelatin 1.54Tenth layer (Yellow filter layer)Yellow colloidal silver silver 0.05EX-5 0.08HBS-1 0.03Gelatin 0.95Eleventh layer (First blue-sensitive layer)Emulsion A silver 0.08Emulsion B silver 0.07Emulsion F silver 0.07Sensitizing dye VIII 3.5 .times. 10.sup.-4EX-9 0.721EX-8 0.042HBS-1 0.28Gelatin 1.10Twelfth layer (Second blue-sensitive emulsion layer)Emulsion G silver 0.45Sensitizing dye VIII 2.1 .times. 10.sup.-4EX-9 0.154Ex-10 0.007HBS-1 0.05Gelatin 0.78Thirteenth layer (Third blue-sensitiveemulsion layer)Emulsion H silver 0.77Sensitizing dye VIII 2.2 .times. 10.sup.-4EX-9 0.20HBS-1 0.07Gelatin 0.69Fourteenth layer (First protective layer)Emulsion I silver 0.20U-4 0.11U-5 0.17HBS-1 0.05Gelatin 1.00Fifteenth layer (Second protective layer)Poly(methyl methacrylate) particle 0.54(diameter: about 1.5 .mu.m)S-1 0.20Gelatin 1.20______________________________________
In each layer gelatin hardener H-1 and surface-active agent were added in addition to the above components.
__________________________________________________________________________Average Grain Size Ratio AgI Average Deviation of Content Diameter Coefficient Diameter/ Ratio of Silver AmountEmulsion (%) (.mu.) (%) Thickness (AgI content %)__________________________________________________________________________A 4.0 0.45 27 1 Core/Shell = 1/3 (13/1) Double Structure GrainsB 8.9 0.70 14 1 Core/Shell = 3/7 (25/2) Double Structure GrainsC 10 0.75 30 2 Core/Shell = 1/2 (24/3) Double Structure GrainsD 16 1.05 35 2 Core/Shell = 1/2 (40/0) Double Structure GrainsE 10 1.05 35 3 Core/Shell = 1/2 (24/3) Double Structure GrainsF 4.0 0.25 28 1 Core/Shell = 1/3 (13/1) Double Structure GrainsG 14.0 0.75 25 2 Core/Shell = 1/2 (40/0) Double Structure GrainsH 14.5 1.30 25 3 Core/Shell = 37/63 (34/3) Double Structure GrainsI 1 0.07 15 1 Uniform Grains__________________________________________________________________________EX-1 ##STR54##EX-2 ##STR55##EX-3 ##STR56##EX-4 ##STR57##EX-5 ##STR58##EX-6 ##STR59##EX-7 ##STR60##EX-8 ##STR61##EX-9 ##STR62##EX-10 ##STR63##EX-11 ##STR64##EX-12 ##STR65##EX-13 ##STR66##U-1 ##STR67##U-2 ##STR68##U-3 ##STR69##Sensitizing Dye I ##STR70##Sensitizing Dye II ##STR71##Sensitizing Dye III ##STR72##U-4 ##STR73##x:y = 70:30 (wt %)UV-5 ##STR74##HBS-1Tricrezyl PhosphateHBS-2Di-n-Butyl PhthalateHBS-3 ##STR75##Sensitizing Dye V ##STR76##Sensitizing Dye VI ##STR77##Sensitizing Dye VII ##STR78##Sensitizing Dye VIII ##STR79##S-1 ##STR80##H-1 ##STR81## Samples 402 to 404 were prepared in the same manner as sample401, except that the yellow coupler Ex-9 (YC-7) in the emulsion layers ofthe first blue-sensitive layer, the second blue-sensitive layer, and thethird blue-sensitive layer was changed to the coupler of the present
Further, Samples 405 to 407 were prepared in the same manner as Samples 402 to 404, respectively, except that the respective coating amount of silver halide emulsion in the first, the second, and the third blue-sensitive emulsion layer, each composition being not changed, was changed as shown in Table 5 in such a manner as to obtain the nearly similar gradation in each layer.
These samples were subjected to an exposure of white light through an wedge and then subjected to the same processing process as described in Example 3.
Yellow color densities of thus processed samples were measured and the results are shown in Table 5.
TABLE 5______________________________________Sample CoatingNo. Coupler Amount .DELTA.Fog*.sup.1 D.sub.B *.sup.2 Remarks______________________________________401 YC-7 100% .+-.0 1.80 Comparative Example402 Y-9 100% .+-.0 1.95 This Invention403 Y-54 100% +0.01 2.03 This Invention404 Y-76 100% +0.02 2.08 This Invention405 Y-9 93% .+-.0 1.80 This Invention406 Y-54 88% .+-.0 1.79 This Invention407 Y-76 86% +0.01 1.80 This Invention______________________________________ Note: *.sup.1 Fogging density as compared with that of Sample 401 as standard *.sup.2 Yellow color density on the basis of the density fogging part which exposed to light so as to give a yellow color density of 1.80 compared with that of fogging part of Sample 401
As is apparent from results in Table 5, it can be understood that the coupler of the present invention gives high color density at the same coating amount and the coating amount of the present coupler which is required to obtain the similar density as Sample 401 can be small compared with the comparative coupler YC-7, as shown by Samples 405 to 407. This can not only bring an economical benefit but also make possible to thin the emulsion layer resulting that unpreferable light absorption in casein layer is reduced and the sharpness of image is improved.
A pattern for MTF measurement was printed on Samples 401 and 405 to 407 and MTF value at space frequency of 25 cycle/mm after development processing was measured using a red light. The results are shown in Table 6.
TABLE 6______________________________________Sample Coating MTF Value ofNo. Coupler Amount red light Remarks______________________________________401 Yc-7 100% 0.42 Comparative Example405 Y-9 93% 0.44 This Invention406 Y-54 88% 0.45 This Invention407 Y-76 86% 0.46 This Invention______________________________________
As is apparent from the results in Table 6, it can be noticed that the coupler of the present invention gives higher MTF value than that of comparative coupler to improve sharpness.
Thus it is possible to say that the coupler of the present invention is an excellent coupler that can give higher color density to improve the sharpness of photographic material.
EXAMPLE 5
Preparation of Sample 501
Multilayer color photographic material sample 501 was prepared by multi-coating each layer having a composition as shown below on a prime-coated triacetate cellulose film base having a thickness of 127 .mu.m. The figures provided indicate the coating amounts in g/m.sup.2. The effects of added compounds are not restricted to the shown usage.
______________________________________First layer (Halation preventing layer)Black colloidal silver silver 0.25 gGelatin 1.9 gUV-absorbent U-1 0.04 gUV-absorbent U-2 0.1 gUV-absorbent U-3 0.1 gUV-absorbent U-4 0.1 gUV-absorbent U-6 0.1 gHigh-boiling organic solvent Oil-1 0.1 gSecond layer (Intermediate layer)Gelatin 0.40 gDye D-4 0.4 mgThird layer (Intermediate layer)Fine particle silver iodobromide emulsionfogged the surface and the inner(average particle size: 0.06 .mu.m, deviationcoefficient: 18%, AgI content: 1 mol %)0.05 g silver 0.05 gGelatin 0.4 gFourth layer (Low sensitivity red-sensitive emulsionlayer)Emulsion A silver 0.2 gEmulsion B silver 0.3 gGelatin 0.8 gCoupler C-1 0.15 gCoupler C-2 0.05 gCoupler C-9 0.05 gCompound Cpd-D 10 mgHigh-boiling organic solvent Oil-2 0.1 gFifth layer (Medium sensitivity red-sensitive emulsionlayerEmulsion B silver 0.2 gEmulsion C silver 0.3 gGelatin 0.8 gCoupler C-1 0.2 gCoupler C-2 0.05 gCoupler C-3 0.2 gHigh-boiling organic solvent Oil-2 0.1 gSixth layer (High sensitivity red-sensitive emulsionlayerEmulsion D silver 0.4 gGelatin 1.1 gCoupler C-1 0.7 gCoupler C-2 0.3 gAdditive P-1 0.1 gSeventh layer (Intermediate layer)Gelatin 0.6 gAdditive M-1 0.3 gColor-mix inhibiting agent Cpd-K 2.6 mgUV-absorber U-1 0.1 gUV-absorber U-6 0.1 gDye D-1 0.02 gEighth layer (Intermediate layer)Silver iodobromide emulsion fogged the surface 0.02 gand the inner (average particle size:0.06 .mu.m, deviation coefficient: 16%,AgI content: 0.3 mol %) silverGelatin 1.0 gAdditive P-1 0.2 gColor-mix inhibiting agent Cpd-J 0.1 gColor-mix inhibiting agent Cpd-A 0.1 gNinth layer (Low sensitivity green-sensitive emulsionlayer)Emulsion E silver 0.3 gEmulsion F silver 0.1 gEmulsion G silver 0.1 gGelatin 0.5 gCoupler C-7 0.35 gCompound Cpd-B 0.03 gCompound Cpd-E 0.02 gCompound Cpd-F 0.02 gCompound Cpd-G 0.02 gCompound Cpd-H 0.02 gCompound Cpd-D 10 mgHigh-boiling organic solvent Oil-1 0.1 gHigh-boiling organic solvent Oil-2 0.1 gTenth layer (Medium sensitivity green-sensitive emulsionlayer)Emulsion G silver 0.3 gEmulsion H silver 0.1 gGelatin 0.6 gCoupler C-7 0.3 gCompound Cpd-B 0.03 gCompound Cpd-E 0.02 gCompound Cpd-F 0.02 gCompound Cpd-G 0.05 gCompound Cpd-H 0.05 gHigh-boiling orgaic solvent Oil-2 0.01 gEleventh layer (High sensitivity green-sensitiveemulsion layerEmulsion I silver 0.5 gGelatin 1.0 gCoupler C-4 0.4 gCompound Cpd-B 0.08 gCompound Cpd-E 0.02 gCompound Cpd-F 0.02 gCompound Cpd-G 0.02 gCompound Cpd-H 0.02 gHigh-boiling organic solvent Oil-1 0.02 gHigh-boiling organic solvent Oil-2 0.02 gTwelfth layer (Intermediate layer)Gelatin 0.6 gDye D-2 0.05 gDye D-1 0.1 gDye D-3 0.07 gThirteenth layer (Yellow filter layer)Yellow coloidal silver silver 0.1 gGelatin 1.1 gColor-mix inhibiting agent Cpd-A 0.01 gHigh-boiling organic solvent Oil-1 0.01 gFourteenth layer (Intermediate layer)Gelatin 0.6 gFifteenth layer (Low sensitivity blue-sensitive emulsionlayerEmulsion J silver 0.4 gEmulsion K silver 0.1 gEmulsion L silver 0.1 gGelatin 0.8 gCoupler C-5 0.4 gSixteenth layer (Medium sensitivity blue-sensitiveemulsion layer)Emulsion L silver 0.1 gEmulsion M silver 0.4 gGelatin 0.9 gCoupler C-5 0.20 gCoupler C-6 0.25 gSeventeenth layer (High sensitivity blue-sensitiveemulsion layer)Emulsion N silver 0.4 gGelatin 1.2 gCoupler C-6 0.7 gEighteenth layer (First protective layer)Gelatin 0.7 gUV-absorbent U-1 0.04 gUV-absorbent U-2 0.01 gUV-absorbent U-3 0.04 gUV-absorbent U-4 0.03 gUV-absorbent U-5 0.04 gUV-absorbent U-6 0.05 gHigh-boiling organic solvent Oil-1 0.02 gFormalin scavengerCpd-C 0.2 gCpd-1 0.4 gDye D-3 0.05 gNinteenth layer (Second protective layer)Colloidal silver silver 0.1 mgFine particle silver iodobromide emulsion 0.1 g(average particle diameter: 0.06 .mu.m,AgI content: 1 mol %) silverGelatin 0.4 gTwentieth layer (Third protective layer)Gelatin 0.4 gPolymethylmethacrylate 0.1 g(average grain diameter: 1.5 .mu.m)Copolymer of methylmethacrylate and 0.1 gacrylic acid (4:6) (averagegrain diameter: 1.5 .mu.m)Silicone oil 0.03 gSurface-active agent W-1 3.0 mgSurface-active agent W-2 0.03 g______________________________________
Additives F-1 to F-8 were added to all emulsion layers in addition to the above composition. Further, gelatin hardener H-1 and surface-active agents for emulsifying W-3 and W-4 were added to each layer in addition to the above composition.
Further, phenol, 1,2-benzisothiazoline-3-one, 2-phenoxyethanol, and fenetyl alcohol were added as antiseptics and antimildews.
Silver iodobromide emulsions used for Sample 501 were as follows:
__________________________________________________________________________ Average grain- Deviation AgIEmulsion Feature of grain diameter (.mu.m) coefficient (%) content (%)__________________________________________________________________________A Monodisperse tetradecahedral grain 0.25 16 3.7B Monodisperse cubic internal latent image-type grain 0.30 10 3.3C Monodisperse tetradecahedral grain 0.30 18 5.0D Polydisperse twin crystal grain 0.60 25 2.0E Monodisperse cubic grain 0.17 17 4.0F Monodisperse cubic grain 0.20 16 4.0G Monodisperse cubic internal latent image-type grain 0.25 11 3.5H Monodisperse cubic internal latent image-type grain 0.30 9 3.5I Polydisperse tabular grain, average aspect ratio: 3.8 0.80 28 1.5F Monodisperse tetradecahedral grain 0.30 18 4.0K Monodisperse tetradecahedral grain 0.37 17 4.0L Monodisperse cubic internal latent image-type grain 0.46 14 3.5M Monodisperse cubic grain 0.55 13 4.0N Polydisperse tabular grain, average aspect ratio: 4.5 1.00 33 1.3__________________________________________________________________________Spectral-sensitizing of Emulsions A to N Spectral- Amount of Added Time when spectral- sensitizing g per 1 mol of sensitizingEmulsion dye added Silver Halide dye added__________________________________________________________________________A S-1 0.025 Immediately after chemical sensitization S-2 0.25 Immediately after chemical sensitizationB S-1 0.01 Immediately after grain formation ended S-2 0.25 Immediately after grain formation endedC S-1 0.02 Immediately after chemical sensitization S-2 0.25 Immediately after chemical sensitizationD S-1 0.01 Immediately after chemical sensitization S-2 0.10 Immediately after chemical sensitization S-7 0.01 Immediately after chemical sensitizationE S-3 0.5 Immediately after chemical sensitization S-4 0.1 Immediately after chemical sensitizationF S-3 0.3 Immediately after chemical sensitization S-4 0.1 Immediately after chemical sensitizationG S-3 0.25 Immediately after grain formation ended S-4 0.08 Immediately after grain formation endedH S-3 0.2 During grain formation S-4 0.06 During grain formationI S-3 0.3 Immediately before chemical sensitization S-4 0.07 Immediately before chemical sensitization S-8 0.1 Immediately before chemical sensitizationJ S-5 0.2 During grain formation S-6 0.05 During grain formationK S-5 0.2 During grain formation S-6 0.05 During grain formationL S-5 0.22 Immediately after grain formation ended S-6 0.06 Immediately after grain formation endedM S-5 0.15 Immediately after chemical sensitization S-6 0.04 Immediately after chemical sensitizationN S-5 0.22 Immediately after grain formation ended S-6 0.06 Immediately after grain formation__________________________________________________________________________ endedC-1 ##STR82##C-2 ##STR83##C-3 ##STR84##C-4 ##STR85##Figures represent Wt. %Average Molecular Weight:ca, 25,000C-5 ##STR86##C-6 ##STR87##C-7 ##STR88##C-8 ##STR89##C-9 ##STR90##Oil-1 Dibutyl phthalateOil-2 Tricrezyl phosphateOil-3 ##STR91##Cpd-A ##STR92##Cpd-B ##STR93##Cpd-C ##STR94##Cpd-D ##STR95##Cpd-E ##STR96##Cpd-F ##STR97##Cpd-G ##STR98##Cpd-H ##STR99##Cpd-I ##STR100##Cpd-J ##STR101##Cpd-K ##STR102##U-1 ##STR103##U-2 ##STR104##U-3 ##STR105##U-4 ##STR106##U-5 ##STR107##U-6 ##STR108##S-1 ##STR109##S-2 ##STR110##S-3 ##STR111##S-4 ##STR112##S-5 ##STR113##S-6 ##STR114##S-7 ##STR115##S-8 ##STR116##D-1 ##STR117##D-2 ##STR118##D-3 ##STR119##D-4 ##STR120##H-1 ##STR121##W-1 ##STR122##W-2 ##STR123##W-3 ##STR124##W-4 ##STR125##P-1 ##STR126##M-1 ##STR127##F-1 ##STR128##F-2 ##STR129##F-3 ##STR130##F-4 ##STR131##F-5 ##STR132##F-6 ##STR133##F-7 ##STR134##F-8 ##STR135## Other samples were prepared in the same manner as the above,except that yellow couplers in the blue-sensitive emulsion layers oflow-sensitivity, medium-sensitivity, and high-sensitivity were changed toother comparative couplers and couplers of the present invention such
Thus-prepared samples were subjected to a gradation exposure to light and then to the processing shown below.
______________________________________Processing processProcess Time (min.) Temperature (.degree.C.)______________________________________First developing 6 38Water washing 2 38Reversal developing 2 38Color developing 6 38Compensating 2 38Bleaching 6 38Fixing 4 38Water washing 4 38Stabilizing 1 Ordinary temp.Drying______________________________________
The composition of each processing solution is as follows:
______________________________________First developing solutionWater 700 mlPentasodium nitrilo-N,N,N-trimethylene- 2 gphophonateSodium sulfite 20 gHydroquinonemonosulfonate 30 gSodium carbonate monohydrate 30 g1-Phenyl-4-methyl-4-hydroxymethyl- 2 g3-pyrazolidonePotassium bromide 2.5 gPotassium thiocyanate 1.2 gPotassium iodide (0.1% solution) 2 mlWater to make 1,000 mlReversal developing solutionWater 700 mlPentasodium nitrilo-N,N,N-trimethylene- 2 gphophonateStannous chloride dihydrate 1 gP-Aminophenol 0.1 gSodium hydroxide 8 gGlacial acetic acid 15 mlWater to make 1,000 mlColor developing solutionWater 700 mlPentasodium nitrilo-N,N,N-trimethylene- 3 gphophonateSodium sulfite 7 gSodium tertiary phosphate . 12H.sub.2 O 36 gPotassium bromide 1 gPotassium iodide (0.1% solution) 90 mlSodium hydroxide 3 gCitrazinic acid 1.5 gN-Ethyl-N-(.beta.-methanesulfonamidoethyl)- 11 g3-methyl-4-aminoaniline sulfate3,6-dithiaoctane-1,8-diol 1 gWater to make 1,000 mlCompensating solutionWater 700 mlSodium sulfite 12 gSodium ethylenediaminetetraacetatedihydrate 8 gThioglycerin 0.4 mlGlacial acetic acid 3 mlWater to make 1,000 mlBleaching SolutionWater 800 mlSodium ethylenediaminetetraacetate 2 gdihydrateFe(III) ammonium ethylenediamine- 120 gtetraacetate dihydratePotassium bromide 100 gWater to make 1,000 mlFixing solutionWater 800 mlSodium thiosulfate 80.0 gSodium sulfite 5.0 gSodium bisulfite 5.0 gWater to make 1,000 mlStabilizing solutionWater 800 mlFormalin 5.0 mlFuji Driwell (surface-active agent, 5.0 mlprepared by Fuji Photo Film Co., Ltd.)Water to make 1,000 ml______________________________________
Results are shown in Table 5.
TABLE 5______________________________________Sample Coupler Dmax Remarks______________________________________501 YC-2 2.78 Comparative Example502 YC-8 2.92 Comparative Example503 YC-2, YC-8 2.88 Comparative Example504 Y-9 3.15 This Invention505 Y-8 3.32 This Invention506 Y-6 3.40 This Invention507 Y-46 3.18 This Invention______________________________________
As is apparent from the results in Table 5, it can be understood that couplers of the present invention are excellent couplers giving high color density compared with comparative couplers.
EXAMPLE 6
A color photographic material was prepared by multi-coatings composed of the first to the twelfth layer as shown below on a both-sides polyethylene-laminated paper base. As a white pigment titanium white and as a bluish dye ultramarine blue were included in the first layer side polyethylene film laminated.
Composition of Photosensitive Layers
In the following compositions, each ingredient is indicated in g/m.sup.2 of a coating amount, but the coating amount of the silver halide is indicated in terms of silver.
______________________________________First layer (Gelatin layer)Gelatin 1.30Second layer (Antihalation layer)Black colloidal silver 0.10Gelatin 0.70Third layer (Low-sensitivity red-sensitive emulsion layer)Silver chloroiodobromide emulsion EM1 (AgCl: 0.061 mol %, AgI: 4 mol %; average grain size:0.3 .mu.m, distribution of grain size: 10%;cubic grains, core-shell type with core ofiodide) spectral-sensitized by red-sensitizing dyes (ExS-1, -2 and-3)Silver iodobromide emulsion EM2 (AgI: 5 mol %; 0.10average grain size: 0.45 .mu.m, distributionof grain size: 20%; tabular grains (aspectratio: 5)) spectral-sensitized by red-sensitizing dyes (ExS-1, -2, and-3)Gelatin 1.00Cyan coupler (ExC-1) 0.14Cyan coupler (ExC-2) 0.07Discoloration inhibitor (Cpd-2, -3, -4, 0.12and -9 each in equal amount)Dispersive medium for coupler (Cpd-5) 0.03Solvent for coupler (Solv-1, -2, and -3) 0.06Fourth layer (High-sensitivity red-sensitive emulsionlayer)Silver iodobromide emulsion EM3 (AgI: 6 mol %; 0.15average grain size: 0.75 .mu.m, distributionof grain size: 25%; tabular grains (aspectratio: 8, core: iodide)) spectral-sensitizedby red-sensitizing dyes (ExS-1, -2, and-3)Gelatin 1.00Cyan coupler (ExC-1) 0.20Cyan coupler (ExC-2) 0.10Discoloration inhibitor (Cpd-2, -3, -4, 0.15and -9 each in equal amount)Dispersive medium for coupler (Cpd-5) 0.03Solvent for coupler (Solv-1, -2, and -3) 0.10Fifth layer (Intermediate layer)Magenta colloidal silver 0.02Gelatin 1.00Color-mix inhibitor (Cpd-6 and -7) 0.08Solvent for color-mix inhibitor (Solv-4 0.16and -5)Polymer latex (Cpd-8) 0.10Sixth layer (Low-sensitivity green-sensitive emulsionlayer)Silver chloroiodobromide emulsion EM4 (AgCl: 0.041 mol %, AgI: 2.5 mol %; average grain size:0.28 .mu.m, distribution of grain size: 12%;cubic grains, core-shell type with core ofiodide) spectral-sensitized by green-sensitizing dye (ExS-3)Silver iodobromide emulsion EM5 (AgI: 2.8 0.06mol %; average grain size: 0.45 .mu.m,distribution of grain size: 12%; tabulargrains (aspect atio: 5)) spectral-sensitizedby green-sensitizing dyes (ExS-3)Gelatin 0.80Magenta coupler (ExM-1) 0.10Discoloration inhibitor (Cpd-9) 0.10Stain inhibitor (Cpd-10) 0.01Stain inhibitor (Cpd-11) 0.001Stain inhibitor (Cpd-12) 0.01Dispersive medium for coupler (Cpd-5) 0.05Solvent for coupler (Solv-4 and -6) 0.15Seventh layer (High sensitivity green-sensitive emulsionlayer)Silver iodobromide emulsion EM6 (AgI: 3.5 mol %; 0.10average grain size: 0.9 .mu.m, distributionof grain size: 23%; tabular grains (aspectratio: 9, uniform iodide-type)) spectral-sensitized by green-sensitive dye (ExS-3)Gelatin 0.80Magenta coupler (ExM-1) 0.10Discoloration inhibitor (Cpd-9) 0.10Stain inhibitor (Cpd-10) 0.01Stain inhibitor (Cpd-11) 0.001Stain inhibitor (Cpd-12) 0.01Dispersive medium for coupler (Cpd-5) 0.05Solvent for coupler (Solv-4 and -6) 0.15Eighth layer (Yellow filter layer)Yellow colloidal silver 0.20Gelatin 1.00Color-mix inhibitor (Cpd-7) 0.06Solvent for color-mix inhibitor 0.15(Solv-4 and -5)Polymer latex (Cpd-8) 0.10Ninth layer (Low-sensitivity blue-sensitive emulsionlayer)Silver chloroiodobromide emulsion EM7 (AgCl: 0.072 mol %, AgI: 2.5 mol %; average grain size:0.35 .mu.m, distribution of grain size: 8%;cubic grains, core-shell type with core ofiodide) spectral-sensitized by green-sensitizing dye (ExS-5 and -6)Silver iodobromide emulsion EM5 (AgI: 2.5 0.10mol %; average grain size: 0.45 .mu.m,distribution of grain size: 16%; tabulargrains (aspect ratio: 6)) spectral-sensitizedby green-sensitizing dyes (ExS-5 and -6)Gelatin 0.50Yellow coupler (ExY-1) 0.20Stain inhibitor (Cpd-11) 0.001Discoloration inhibitor (Cpd-6) 0.10Dispersive medium for coupler (Cpd-5) 0.05Solvent for coupler (Solv-2) 0.05Tenth layer (High-sensitivity blue-sensitive emulsionlayer)Silver iodobromide emulsion EM9 (AgI: 2.5 mol %; 0.25average grain size: 1.2 .mu.m, distributionof grain size: 21%; tabular grains (aspectratio: 14)) spectral- sensitized by green-sensitive dyes (ExS-5 and -6)Gelatin 1.00Yellow coupler (ExY-1) 0.40Stain inhibitor (Cpd-11) 0.002Discoloration inhibitor (Cpd-6) 0.10Dispersive medium for coupler (Cpd-5) 0.15Solvent for coupler (Solv-2) 0.10Eleventh layer (UV-absorbing layer)Gelatin 1.50UV absorbent (Cpd-1, -3, and -13) 1.00Color-mix inhibitor (Cpd-6 and -14) 0.06Dispersive medium (Cpd-5) 0.05Solvent for UV-absorbent (Solv-1 and -2) 0.15Irradiation preventing dye (Cpd-15 and -16) 0.02Irradiation preventing dye (Cpd-17 and -18) 0.02Twelfth layer (Protective layer)Fine grain size silver chlorobromide emulsion 0.07(silver chloride 97 mol %, average grainsize : 0.2 .mu.m) 0.07Modified polyvinyl alcohol 0.02Gelatin 1.50Gelatin hardener (H-1) 0.17______________________________________
Further, Alkanol XC (trade name, made by Dupont) and sodium alkylbenzenesulfonate were used as auxiliary agents for the emulsification and dispersion, and succinate ester and Magefac F-120 (trade name, made by Dai Nippon Ink & Chemicals Inc.) were added as coating aids to each layer. In the layers containing silver halide emulsion or colloidal silver, compounds (Cpd-19, -20, and -21) were used as stabilizers. Compounds used in the Example are shown below. ##STR136## Solv-1 Di(2-ethylhexyl) phthalate Solv-2 Trinonyl phosphate
Solv-3 Di(3-methylhexyl) phthalate
Solv-4 Tricrezyl phosphate
Solv-5 Dibutyl phthalate
Solv-6 Trioctyl phosphate
H-1 1,2-bis(vinylsulphonylacetoamido)
(Emulsion A)
Preparation of a Monodisperse Emulsion with (100) Crystal Habit
An aqueous silver nitrate solution and an aqueous solution containing KBr and KI were added by the double-jet method to an aqueous gelatin solution kept at 70.degree. C., with the pBr being kept at 4.5, to prepare a monodisperse emulsion (the length of the edge: 0.68 .mu.m) having (100) crystal habit. This core emulsion was divided into three, and shells were formed under different conditions shown below, so that the final grain size was 0.7 .mu.m and the content of AgI was 3 mol %.
Sodium thiosulfate and potassium chloroaurate were added to the cores to carry out chemical sensitization. Thereafter, the shells were deposited under the same conditions as those for the formation of the cores.
Couplers for comparison and couplers of the present invention were prepared by replacing Yellow Coupler ExY-1 in the low-sensitive blue-sensitive layer and high-sensitive blue-sensitive layer so that it would be equimolar.
These samples were subjected to the processing according to the process shown below and to evaluation.
______________________________________Processing process______________________________________First developing (Black 38.degree. C. 75 secand white developing)Water washing 38.degree. C. 90 secReversal exposure over 100 Lux over 60 secColor developing 38.degree. C. 135 secWater washing 38.degree. C. 45 secBleach-fixing 38.degree. C. 120 secWater washing 38.degree. C. 135 secDrying______________________________________Composition of processing solution______________________________________First developing solutionPentasodium nitrilo-N,N,N-trimethylene- 0.6 gphosphonatePentasodium diethylenetriaminepentaacetate 4.0 gPotassium sulfite 30.0 gPotassium thiocyanate 1.2 gPotassium carbonate 35.0 gPotassium hydroquinonmonosulfonate 25.0 gDiethylene glycol 15.0 ml1-Phenyl-4-hydroxy-methyl-4-methyl- 2.0 g3-pyrazolidonPotassium bromide 0.5 gPotassium iodide 5.0 mgWater to make 1 l (pH 9.70)Color developerBenzyl alcohol 15.0 mlDiethylene glycol 12.0 ml3,6-Dithia-1,8-octanediol 0.2 gPentasodium nitrylo-N,N,N-trimethylene 0.5 gphosphonatePentasodium diethylenetriaminepentaacetate 2.0 gSodium sulfite 2.0 gPotassium carbonate 25.0 gHydroxylamine sulfonate 3.0 gN-Ethyl-N-(.beta.-methanesulfonamidoethyl)- 5.0 g3-methyl-4-aminoaniline sulfonatePotassium bromide 0.5 gPotassium iodide 1.0 mgWater to make 1 l (pH 10.40)Bleach-fixing solution2-Mercapto-1,3,4-triazole 1.0 gDisodium ethylenediaminetetraacetate 5.0 gdihydrateIron(III) ammonium ethylenediamine- 80.0 gtetraacetate monohydrateSodium sulfite 15.0 gAmmonium thiosulfate (700 g/l solution) 150.0 mlGlacial acetic acid 5.0 mlWater to make 1 l (pH 6.50)______________________________________
Water Washing Solution
Tap water was treated by passage through a hybrid-type column filled with an H-type strong acidic cation-exchange resin (Dialon SK-1B, tradename, made by Mitsubishi Chemical Industries, Ltd.) and an OH-type strong alkaline anion-exchange resin (Dinion SA-10A, tradename, made by the same as the above) to obtain water having a quality as shown below. To the thus-treated water, 20 mg/l of sodium dichloroisocyanurate was added as a bactericide.
In this case, the same results as in Example 1 were obtained.
EXAMPLE 7
A photographic material was prepared by multi-coatings composed of the following for the first to fourteenth layers on one side, and for the fifteenth and sixteenth layers on the back side of a double-sided polyethylene-laminated paper base (of thickness 100 .mu.m). Titanium dioxide, as a white pigment, and a small amount of ultramarine blue, as a bluish dye, were included in the polyethylene film of the first-layer side (the chromaticies of the base surface in L*, a*, and b* were 88.0, -0.20, and -0.75, respectively).
Composition of Photosensitive Layers
In the following compositions each ingredient is indicated in g/m.sup.2 of coating amount, but the coating amount of silver halide is indicated in terms of silver. Emulsions for each layer were prepared in accordance with the preparation procedure of EM1, providing that the emulsion of the 14th layer used a Lipman emulsion that was not chemically surface-ripened.
______________________________________First layer (Antihalation layer)Black colloidal silver 0.10Gelatin 0.70Second layer (Intermediate layer)Gelatin 0.70Third layer (Low sensitivity red-sensitive emulsionlayer)Silver bromide emulsion spectral-sensitized by 0.04red-sensitizing dyes (ExS-1, -2, and -3)(average grain size: 0.25 .mu.m, grain sizedistribution (deviation coefficient):8%, octahedral)Silver chlorobromide emulsion spectral- 0.08sensitized by red-sensitizing dyes(ExS-1, -2, and -3) (silver chloride5 mol %, average grain size: 0.40 .mu.m,grain size distribution: 10%,octahedral)Gelatin 1.00Cyan coupler (a blend of ExC-1, -2, and -3 0.30in a ratio of 1:1:0.2)Discoloration inhibitor (a blend of Cpd-1, 0.182, -3, and -4, each in equal amount)Stain inhibitor (Cpd-5) 0.003Coupler dispersion medium (Cpd-6) 0.03Coupler solvent (a blend of Solv-1, -2, 0.12and -3, each in equal amount)Fourth layer (High sensitivity red-sensitive emulsionlayer)Silver bromide emulsion spectral-sensitized by 0.14red-sensitizing dyes (ExS-1, -2, and -3)(average grain size: 0.60 .mu.m, grain sizedistribution: 15%, octahedral)Gelatin 1.00Cyan coupler (a blend of ExC-1, -2, and -3 0.30in a ratio of 1:1:0.2)Discoloration inhibitor (a blend of Cpd-1, 0.182, -3 and -4, each in equal amount)Coupler dispersion medium (Cpd-6) 0.03Coupler solvent (a blend of Solv-1, -2, 0.12and -3, each in equal amount)Fifth layer (Intermediate layer)Gelatin 1.00Color-mix inhibitor (Cpd-7) 0.08Color-mix inhibitor solvent (a blend of Solv-4 0.16and -5, each in equal amount)Polymer latex (Cpd-8) 0.10Sixth layer (Low sensitivity green-sensitive emulsionlayer)Silver bromide emulsion spectral-sensitized by 0.04green-sensitizing dye (ExS-4) (average grainsize: 0.25 .mu.m, grain size distribution:8%, octahedral)Silver chlorobromide emulsion spectral-sensitized 0.06by green-sensitizing dye (ExS-4) (silverchloride: 5 mol %, average grain size:0.40 .mu.m, grain size distribution: 10%octahedral)Gelatin 0.80Magenta coupler (ExM-1) 0.11Discoloration inhibitor (a blend of Cpd-9 0.15and -26, each in equal amount)Stain inhibitor (a blend of Cpd-10, -11, -12, 0.025and -13 in a ratio of 10:7:7:1)Coupler dispersion medium (Cpd-6) 0.05Coupler solvent (a blend of Solv-4 and -6, 0.15each in equal amountSeventh layer (High sensitivity green-sensitiveemulsion layer)Silver bromide emulsion spectral-sensitized by 0.10green-sensitizing dye (ExS-4)(average grainsize: 0.65 .mu.m, grain size distribution: 16%octahedral)Gelatin 0.80Magenta coupler (a blend of ExM-1, -2, 0.11and -3, each in equal amount)Discoloration inhibitor (a blend of Cpd-9 0.15and -26, each in equal amount)Stain inhibitor (a blend of Cpd-10, -11, 0.02512, and -13 in a ratio of10:7:7:1)Coupler dispersion medium (Cpd-6) 0.05Coupler solvent (a blend of Solv-4 and 0.156, each in equal amount)Eighth layer (Intermediate layer)Same as the fifth layerNinth later (Yellow filter layer)Yellow colloidal silver 0.12Gelatin 0.70Color-mix inhibitor (Cpd-7) 0.03Color-mix inhibitor solvent (a blend of 0.10Solv-4 and -5, each in equal amount)Polymer latex (Cpd-8) 0.07Tenth layer (Intermediate layer)Same as the fifth layerEleventh layer (Low sensitivity blue-sensitiveemulsion layerSilver bromide emulsion spectral-sensitized by 0.07blue-sensitizing dyes (ExS-5 and -6)(average grain size: 0.40 .mu.m, grain sizedistribution: 8%, octahedral)Silver chlorobromide emulsion spectral- 0.14sensitized by blue-sensitizing dyes(ExS-5 and -6) (silver chloride: 8 mol %,average grain size: 0.60 .mu.m, grain sizedistribution: 11%, octahedral)Gelatin 0.80Yellow coupler (a blend of ExY-1 and -2, 0.35each in equal amount)Discoloration inhibitor (Cpd-14) 0.10Stain inhibitor (a blend of Cpd-5 and -15 0.007in a ratio of 1:5)Coupler dispersion medium (Cpd-6) 0.05Coupler solvent (Solv-2) 0.10Twelfth layer (High sensitivity blue-sensitiveemulsion layer)Silver bromide emulsion spectral-sensitized by 0.15blue-sensitizing dyes (ExS-5 and -6)(averagegrain size: 0.85 .mu.m, grain sizedistribution: 18%, octahedral)Gelatin 0.60Yellow coupler (a blend of ExY-1 and -2, 0.30each in equal amount)Discoloration inhibitor (Cpd-14) 0.10Stain inhibitor (a blend of Cpd-5 and 0.00715 in a ratio of 1:5)Coupler dispersion medium (Cpd-6) 0.05Coupler solvent (Solv-2) 0.10Thirteenth layer (Ultraviolet absorbing layer)Gelatin 1.00Ultraviolet absorber (a blend of Cpd-2, 0.504, and -16, each in equal amount)Color-mix inhibitor (a blend of Cpd-7 0.03and -17, each in equal amount)Dispersion medium (Cpd-6) 0.02Ultraviolet absorber solvent (a blend of 0.08Solv-2 and -7, each in equal amount)Irradiation-inhibiting dye (a blend of 0.05Cpd-18, -19, -20, -21, and -27 in aratio of 10:10:13:15:20)Fourteenth layer (Protective layer)Fine grain silver chlorobromide emulsion (silver 0.03chloride: 97 mol %, average grain size:0.1 .mu.m)Copolymer of acryl-modified-poly(vinyl alcohol) 0.01(Molecular weight: 50,000)Poly(methyl methacrylate) particle (average 0.05particle size: 2.4 .mu.m) and silicon dioxide(average particle size: 5 KM)(a blend,each in equal amount)Gelatin 1.80Gelatin hardener (a blend of H-1 and H-2, 0.18each in equal amount)Fifteenth layer (Back-side layer)Gelatin 2.50Ultraviolet absorber (a blend of Cpd-2, 0.504, and -16, each in equal amount)Dye (a blend of Cpd-18, -19, -20, 21, 0.06and -27, each in equal amount)Sixteenth layer (Back-side protective layer)Poly(methyl methacrylate) particle (average 0.05particle size: 2.4 .mu.m) and silicon dioxide(average particle size: 5 .mu.m)(a blendeach in equal amount)Gelatin 2.00Gelatin hardener (a blend of H-1 and H-2, 0.14each in equal amount)______________________________________
Preparation of Emulsion EM-1
Aqueous solutions containing potassium bromide and silver nitrate were simultaneously added to an aqueous solution of gelatin with vigorous agitation at 75.degree. C. over 15 minutes, to obtain a silver bromide emulsion of octahedral grains having an average grain size of 0.35 .mu.m. A chemical-sensitizing treatment of the thus obtained emulsion was carried out by adding, in order, 0.3 g/mol.Ag of 3,4-dimethyl-1,3-thiazoline-2-thione, 6 mg/mol.Ag of sodium thiosulfate, and 7 mg/mol.Ag of chloroauric acid (tetrahydrate), and then heating the mixture at 70.degree. C. for 80 minutes. The thus-obtained silver bromide grains were brought up as a core under the same precipitating conditions as the first precipitating process, to obtain a monodisperse core-shell silver bromide emulsion of octahedral-shaped grains having an average grain size of 0.7 .mu.m. The deviation coefficient of the grain size distribution of this emulsion was about 10%. A further chemical sensitization of this emulsion was carried out by adding 1.5 mg/mol.Ag of sodium thiosulfate and 1.5 mg/mol.Ag of chloroauric acid (tetrahydrate), and then heating it at 60.degree. C. for 60 minutes, to obtain an internal latent-image type silver halide emulsion.
In each photosensitive layer, the compounds, ExZK-1 and ExZK-2, in amounts of 13.sup.-3 and 10.sup.-2 weight % to the coating amount of silver halide, respectively, were included as nucleating agents, and 10.sup.-2 weight % of compound Cpd-22 was included as a nucleation accelerator. Further, Alkanol XC (trade name, made by Dupont) and sodium alkylbenzenesulfonate were used as auxiliary agents for the emulsification and dispersion, and succinate ester and Magefac F-120 (trade name, made by Dai Nippon Ink & Chemicals Inc.) were added as coating aids to each layer. In the layers containing silver halide emulsion or colloidal silver, compounds Cpd-23, -24, and -25 were used as stabilizers. Compounds used in the Example are shown below. ##STR137## Solv-1: Di(2-ethylhexyl)sebacate Solv-2: Trinonyl phosphate
Solv-3: Di(3-methylhexyl)phthalate
Solv-4: Tricresyl phosphate
Solv-5: Dibutyl phthalate
Solv-6: Trioctyl phosphate
Solv-7: Di(2-ethylhexyl)phthalate
H-1: 1,2-Bis(vinylsulfonylacetoamido)ethane
H-2: 4,6-Dichloro-2-hydroxy-1,3,5-triazine sodium salt
ExZK-1: 7-(3-Ethoxycarbonylaminobenzamido)-9-methyl-10-propargyl-1,2,3,4-tetrahydroacrylginium trifluoromethanesulfonate
ExZK-2: 2-[4-{3-[3-{-[5-{3-[2-chloro-5-(1-dodecyloxy-carbonylethoxycarbonyl)phenylcarbamoyl]-4-hydroxy-1-naphtylthio}tetrazole-1-yl]phenyl}ureido]benzenesulfonamido}phenyl]-1-formylhydrazine
Samples for comparison and samples of the present invention were prepared by replacing Yellow Couplers ExY-1 and ExY-2 in the low-sensitive blue-sensitive layer and high-sensitive blue-sensitive layer with the couplers for comparison or those of this invention.
These Samples were processed and assessed according to the following procedures and processes.
The prepared silver halide color photographic materials were exposed to light image-wise and were processed by an automatic processor in accordance with the following method continuously until the accumulated replenishing amount of the solution reached three times the tank volume.
______________________________________Processing Temper- Tank ReplenisherSteps Time ature Volume Amount______________________________________Color Development 135 sec 38.degree. C. 15 l 300 ml/m.sup.2Bleach-fixing 40 sec 33.degree. C. 3 l 300 ml/m.sup.2Water washing (1) 40 sec 33.degree. C. 3 l --Water washing (2) 40 sec 33.degree. C. 3 l 320 ml/m.sup.2Drying 30 sec 80.degree. C.______________________________________
Washing was carried out in a so-called countercurrent mode, in which the overflow solution of the tank of washing (2) was led to the tank of washing (1). The amount of carried over bleach-fixing solution by the photographic material from-the bleach-fixing tank to the tank of washing (1) was 35 ml/m.sup.2 and the magnification of replenishing amount to the carried over amount of bleach-fixing was 9.1.
The composition of each processing solution was as follows:
______________________________________ Mother Replen- Solution isher______________________________________Color DeveloperD-Sorbit 0.15 g 0.20 gSodium naphthalenesufonate 0.15 g 0.20 gfolmarin adductEthylenediaminetetrakismethylene 1.5 g 1.5 gphosphonic acidDiethylene glycol 12.0 ml 16.0 mlBenzyl alcohol 13.5 ml 18.0 mlPotassium bromide 0.80 g --Benzotriazole 0.003 g 0.004 gSodium sulfite 2.4 g 3.2 gN,N-Bis(carboxymethyl)hydrazine 6.0 g 8.0 gD-Glucose 2.0 g 2.4 gTriethanolamine 6.0 g 8.0 gN-Ethyl-N-(.beta.-methanesulfonamidoethyl)-3- 6.4 g 8.5 gmethyl-4-aminoaniline sulfatePotassium carbonate 30.0 g 25.0 gFluorescent brightening agent 1.0 g 1.2 g(diaminostyrbene series)Water to make 1000 ml 1000 mlpH (25.degree. C.) 10.25 10.75Bleach-fixing solution(Mother solution andreplenisher are the same)Disodium ethylenediaminetetraacetate 4.0 gIron (III) ammonium ethylenediamine- 70.0 gtetraacetateAmmonium thiosulfate (700 g/l) 180 mlSodium p-toluenesulfinate 20.0 gSodium bisulfite 20.0 g5-Mercapto-1,3,4-triazole 0.5 gAmmonium nitrate 10.0 gWater to make 1000 mlpH (25.degree. C.) 6.20______________________________________
Water Washing Solution
(Mother solution and replenisher are the same)
Tap water was treated by passage through a hybrid-type column filled with an H-type strong acidic cation-exchange resin (Amberlite IR-120B, tradename, made by Rohm & Haas) and an OH-type strong alkaline anion-exchange resin (Amberlite IR-400, tradename, made by the same as the above) so as to make the concentrations of calcium ions and magnesium ions 3 mg/l or less. Then 20 mg/l of sodium dichloroisocyanurate and 1.5 g/l of sodium sulfate were added. The pH of the solution was in a range of 6.5 to 7.5.
In this case the same results as in Example 1 were obtained.
EXAMPLE 8
To 9.15 g of comparative coupler (ExY-1) 10.0 g of tricresyl phosphate, as a high-boiling organic solvent, and 20 ml of ethylacetate were added. The mixture was heated to obtain a solution. The solution was added to 250 g of 10% gelatin solution, 1.2 g of dodecylbenzenesulfonic acid was added to the solution, and the mixture was emulsified and dispersed.
To the emulsified dispersion, 75.7 g of silver chlorobromide emulsion (containing 64.9 g/kg of silver, silver bromide: 70 mol %) and 300 g of 10% aqueous gelatin solution and 153 ml of water were added. After adding of 1.0 g of sodium 1-oxy-3,5-dichloro-s-triazinate, as a hardener, Sample 801 was prepared by coating the dispersion on a prime coated triacetyl cellulose base such that the coating amount of coupler would be 1 mmol/m.sup.2. In this case, 1.66 g/m.sup.2 of gelatin layer was provided on that coated layer, as a protective layer.
Samples 802 to 804 were prepared in the same manner as Sample 801, except that coupler was changed to other comparative couplers and a coupler of the present invention, as shown in Table 6, so as to get an equimolar amount of coated coupler.
The above samples were subjected to an exposure to white light through an optical wedge and then subjected to the processing shown below.
______________________________________Processing Process Temperature Time______________________________________Color development 35.degree. C. 120 sec.Bleach-fixing 33.degree. C. 90 sec.Water washing 30-35.degree. C. 120 sec.Drying 80.degree. C.______________________________________
The composition of each processing solution was as follows:
______________________________________Color developerWater 700 mlEthylenediaminetetraacetic acid 3.0 gDisodium-1,2-dihydroxybenzen- 4.0 g4,6-disulfonateTriethanolamine 12.0 gPotassium bromide 1.5 gPotassium carbonate 27.0 gFluorescent whitening agent (WHITEX 4B, 1.0 gmanufactured by Sumitomo Chem. Co.)Sodium sulfite 0.1 gDisodium-N,N-bis(sulfonatoethyl)- 10.0 ghydroxylamineN-Ethyl-N-(A-methanesulfonamidoethyl)-3- 5.0 gmethyl-4-aminoaniline sulfonate-Water to make 1000 mlpH (25.degree. C.) 10.05Bleach-fixing solutionWater 600 gAmmonium thiosulfate (700 g/l) 100 mlIron (III) ammonium ethylenediamine- 55.0 gtetraacetateEthylendiaminetetraacetic acid 5.0 gAmmonium bromide 40.0 gNitric acid (67%) 30.0 gWater to make 1000 mlpH (25.degree. C.) (adjusted by acetic acid 5.8and aqueous ammonia)______________________________________
Yellow couplers for comparison are as follows: ##STR138##
Thus processed samples were measured the density of colored yellow and the maximum color density Dmax are shown in Table 6.
TABLE 6______________________________________Sample Coupler Dmax Remarks______________________________________801 ExY-1 1.46 Comparative Example802 ExY-2 1.60 Comparative Example803 ExY-3 1.39 Comparative Example804 Y-1 1.90 This Invention______________________________________
The absorption spectra of each sample above-described was measured and the results are shown in FIG. 2.
As is apparent form the results in Table 6, it can be noticed that coupler Y-1 of the present invention give a higher density than those of comparative couplers.
Further, as is apparent from FIG. 2, comparative coupler ExY-2 having a cyclopropane ring in the molecular similarly to the coupler of the present invention has apparently unpreferable absorption at long wavelength side, although it spectral characteristics shows a little increased absorbance. On the other hand, comparative coupler ExY-3 of cyclohexyl ring structure having a methyl group on 1-position is nearly similar to the comparative coupler ExY-1 that is pivaloyl-type coupler in the spectral characteristics and its absorbance is rather reduced.
On the contrary, it can be noticed that, in the case of coupler Y-1 of the present invention, not only the absorbance increases remarkably, but also the absorption at long wavelength side is improved remarkably in the sharpness of down curve. It was quite unexpected that the coupler Y-1 of the present invention would have such an excellent property as shown FIG. 2 even by an analogy from known coupler ExY-2 and ExY-3.
EXAMPLE 9
A multilayer photographic material (901) was prepared by multi-coatings composed of the following layer composition on a paper support which has been both sides polyethylene laminated and subjected to a corona discharge treatment followed by providing a subbing layer coated by gelatin containing sodium dodecylbenzenesulfonate. Coating solutions were prepared as follows:
Preparation of the First Layer Coating Solution
To a mixture of 15.4 g of yellow coupler (ExY-1), 4.8 g of image-dye stabilizer (Cpd-1) 1.3 g of image-dye stabilizer (Cpd-7), 1.3 g of image dye stabilizer (Cpd-9), and 0.3 g of stabilizer -(Cpd-12), 25.0 ml of ethyl acetate and each 3.8 g of solvents (Solv-3) and (Solv-7) were added and dissolved. The resulting solution was dispersed and emulsified in 185 ml of 10% aqueous gelatin solution containing 8 ml of sodium dodecylbenzenesulfonate to obtain emulsified dispersion A. Separately silver chlorobromide emulsion A (cubic grains, 3:7 (silver mol ratio) blend of grains having a 0.88 .mu.m and a 0.7 .mu.m average grain size, and a 0.08 and a 0.10 deviation coefficient of grain size distribution, respectively, each in which 0.3 mol % of silver bromide was located at the surface of grains) was prepared. To this emulsion two kinds of blue-sensitive sensitizing dye A and B were added in such amounts that each dye corresponds 2.0.times.10.sup.-4 mol to the large size emulsion and 2.5.times.10.sup.-4 mol to the small size emulsion, per mol of silver, and then sulfur-sensitized. The chemical ripening of this emulsion was conducted by adding sulfur sensitizing agent and gold sensitizing agent. The thus-prepared emulsion A and the above-obtained emulsified dispersion A were mixed together and dissolved to give the composition shown below, thereby preparing the first layer coating solution.
Coating solutions for the second to seventh layers were also prepared in the same manner as the first-layer coating solution. As a gelatin hardener for the respective layers, H-1 and H-2 were used.
To each layer Cpd-10 and Cpd-11 were added in such amount that respective total amount would be 25.0 mg/m.sup.2 and 50.0 mg/m.sup.2.
As spectral-sensitizing dyes for the respective layers, the following compounds were used:
Sensitizing Dye A for Blue-Sensitive Emulsion Layer ##STR139## Sensitizing Dye B for Blue-Sensitive Emulsion Layer ##STR140## (each 2.0.times.10.sup.-4 mol to the large size emulsion and 2.5.times.10.sup.-4 mol to the small size emulsion, per mol of silver halide.)
Sensitizing Dye C for Green-Sensitive Emulsion Layer ##STR141## (4.0.times.10.sup.-4 mol to the large size emulsion and 5.6.times.10.sup.-4 mol to the small size emulsion, per mol of silver halide)
and Sensitizing Dye D for Green-Sensitive Emulsion ##STR142## (7.0.times.10.sup.-5 mol to the large size emulsion and 1.0.times.10.sup.-5 mol to the small size emulsion, per mol of silver halide)
Sensitizing Dye E for Red-Sensitive Emulsion Layer ##STR143## (0.9.times.10.sup.-4 mol to the large size emulsion and 1.1.times.10.sup.-4 mol to the small size emulsion, per mol of silver halide)
To the red-sensitive emulsion layer, the following compound was added in an amount of 2.6.times.10.sup.-3 mol per mol of silver halide: ##STR144##
Further, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer in amount of 8.5.times.10.sup.-5 mol, 7.7.times.10.sup.-4 mol, and 2.5.times.10.sup.-4 mol, per mol of silver halide, respectively.
Further, to the blue-sensitive emulsion layer and the green-sensitive layer 4-hydroxy-6-methyl-l,3,3a,7-tetrazaubdebe was added in amounts of 1 z 10.sup.-4 mol and 2.times.10.sup.-4 mol per mol of silver halide, respectively.
The following dyes were added to the emulsion were to prevent irradiation. (Figures in parentheses show each coating amount.) ##STR145## (Composition of Layers)
The composition of each layer is shown below. The figures represent coating amount (g/m.sup.2). The coating amount of each silver halide emulsion-is given in terms of silver.
Supporting Base
Paper laminated on both sides with polyethylene (a white pigment, TiO.sub.2, and a bluish dye, ultramarine, were included in the first layer side of the polyethylene-laminated film)
______________________________________First Layer (Blue-sensitive emulsion layer):The above-described silver chlorobromide 0.26emulsion AGelatin 1.54Yellow coupler (ExY-1) 0.48Image-dye stabilizer (Cpd-1) 0.15Solvent (Solv-3) 0.12Solvent (Solv-7) 0.12Image-dye stabilizer (Cpd-7) 0.04Image-dye stabilizer (Cpd-9) 0.03Stabilizer (Cpd-12) 0.01Second Layer (Color-mix preventing layer):Gelatin 0.99Color mix inhibitor (Cpd-5) 0.08Solvent (Solv-1) 0.16Solvent (Solv-4) 0.08Third Layer (Green-sensitive emulsion layer):Silver chlorobromide emulsions (cubic grains, 0.121:3 (Ag mol ratio) blend of grains havinga 0.55 .mu.m and a 0.39 .mu.m average grain size,and a 0.10 and a 0.08 deviation coefficientof grain size distribution, respectively,each in which 0.8 mol % of AgBr was locatedat the surface of grains)Gelatin 1.24Magenta coupler (ExM) 0.20Image-dye stabilizer (Cpd-2) 0.03Image-dye stabilizer (Cpd-3) 0.15Image-dye stabilizer (Cpd-4) 0.02Image-dye stabilizer (Cpd-9) 0.02Solvent (Solv-2) 0.40Fourth Layer (Ultraviolet absorbing layer):Gelatin 1.58Ultraviolet absorber (UV-1) 0.47Color-mix inhibitor (Cpd-5) 0.05Solvent (Solv-5) 0.24Fifth Layer (Red-sensitive emulsion layer):Silver chlorobromide emulsions (cubic grains, 0.231:4 (Ag mol ratio) blend of grains havinga 0.58 .mu.m and a 0.45 .mu.m average grain size,and a 0.09 and a 0.11 deviation coefficientof grain size distribution, respectively,each in which 0.6 mol % of AgBr was locatedat the surface of grains)Gelatin 1.34Cyan coupler (ExC) 0.32Image-dye stabilizer (Cpd-2) 0.03Image-dye stabilizer (Cpd-4) 0.02Image-dye stabilizer (Cpd-6) 0.16Image-dye stabilizer (Cpd-7) 0.40Image-dye stabilizer (Cpd-8) 0.05Solvent (Solv-6) 0.14Sixth layer (Ultraviolet ray absorbing layer):Gelatin 0.53Ultraviolet absorber (UV-1) 0.16Color-mix inhibitor (Cpd-5) 0.02Solvent (Solv-5) 0.08Seventh layer (Protective layer):Gelatin 1.33Acryl-modified copolymer of polyvinyl 0.17alcohol (modification degree: 17%)Liquid paraffin 0.03______________________________________
Compounds used are as follows:
(ExY) Yellow Coupler
ExY-1 The same as in Example 8
ExY-2 The same as in Example 8
ExY-3 The same as in Example 8 ##STR146##
Samples 902 to 913 were prepared in the same manner as sample 901, except that the kind and the coating amount of yellow coupler were changed as shown in Table 7, respectively, provided that the molar ratio of coupler to silver halide in the coating amount was adjusted to be constant (the same as in Sample 901).
Then, these photographic papers were given gradation exposure of a three-color separation filter for sensitometry by using a sensitometer (manufactured by Fuji Photo Film Co., Ltd., FWH model, the color temperature of the source of light being 3200.degree. K.). The exposure was carried out so that the exposure amount would be 250 CMS with an exposure time of 0.1 sec.
After image-wise exposure of the above Photographic Materials, they were continuously processed (running test) by using a paper processor in the following processing steps until the replenishing amount reached a point twice the amount of the tank volume for color development.
______________________________________Processing Replenisher Tanksteps Temperature Time Amount* Volume______________________________________Color Developing 35.degree. C. 45 sec. 161 ml 17 lBleach-fixing 30-35.degree. C. 45 sec. 215 ml 17 lRinsing 1 30-35.degree. C. 20 sec. -- 10 lRinsing 2 30-35.degree. C. 20 sec. -- 10 lRinsing 3 30-35.degree. C. 20 sec. 350 ml 10 lDrying 70-80.degree. C. 60 sec.______________________________________ Note: *Replenisher amount is shown in ml per m.sup.2 of photographic material. Rinsing steps were carried out in 3tanks counterflow mode from the tank o rinsing 3 towards the tank of rinsing 1. The opened surface ratio was changed by changing the size of floating lid.
The compositions of each processing solution were as follows:
______________________________________ Tank Replen- Solution isher______________________________________Color developerWater 800 ml 800 mlEthylenediamine-N,N,N',N'-tetra- 1.5 g 2.0 gmethylenephosphonic acidPotassium bromide 0.015 g --Triethanolamine 8.0 g 12.0 gSodium chloride 1.4 g --Potassium carbonate 25 g 25 gN-ethyl-N-(.beta.-methanesulfonamidoethyl)-3- 5.0 g 7.0 gmethyl-4-aminoaniline sulfonateN,N-bis(carboxymethyl)hydrazine 5.5 g 7.0 gN,N-di(sulfoethyl)hydroxylamine.1Na 4.0 g 5.0 gFluorescent brightening agent 1.0 g 2.0 g(WHITEX-4, made by SumitomoChemical Ind. Co.)Water to make 1000 ml 1000 mlpH (25.degree. C.) 10.05 10.45Bleach-fixing solution(Both tank solution and replenisher)Water 400 mlAmmonium thiosulfate (70%) 100 mlSodium sulfite 17 gIron (III) ammonium ethylenediamine- 55 gtetraacetate dehydrateDisodium ethylenediaminetetraacetate 5 gAmmonium bromide 40 gWater to make 1000 mlpH (25.degree. C.) 6.0______________________________________
Rinsing Solution
(Both Tank Solution and Replenisher)
Ion-exchanged water (Calcium and magnesium each are contained in an amount of 3 ppm or below)
The yellow coupler density of thus processed each Samples was measured, The results are shown in Table 7.
TABLE 7______________________________________ Coating amountNo. Coupler (mmol/m.sup.2) Dmax Remarks______________________________________901 ExY-1 0.6 2.05 Comparative Example902 ExY-2 0.6 2.14 Comparative Example903 ExY-3 0.6 1.98 Comparative Example904 Y-1 0.6 2.45 This Invention905 Y-42 0.6 2.33 This Invention906 Y-43 0.6 2.21 This Invention907 Y-53 0.6 2.44 This Invention908 Y-56 0.6 2.43 This Invention909 ExY-1 0.7 2.27 Comparative Example910 ExY-1 0.8 2.52 Comparative Example911 ExY-1 0.9 2.67 Comparative Example912 Y-1 0.5 2.24 This Invention913 Y-1 0.7 2.69 This Invention______________________________________
As is apparent from the results in Table 7, it can be noticed that, in the comparison of samples at the same coating amount, the couplers of the present invention give higher densities than those of known comparative couplers. In particular, couplers Y-1, Y-53 and Y-56 which have preferable structure of the present invention are excellent.
Further, in order to obtain the similar color density to sample 904 which used coupler Y-1 of the present invention by using the comparative coupler ExY-1, it is needed to increase coating amounts of coupler and silver halide emulsion about 1.3 times. Thus the coupler of the present invention is preferable in view of saving resources.
Although comparative coupler ExY-2 gave a little higher color density among comparative couplers, the hue of this sample cannot be said preferable because the hue being orange by visual observation.
Thus, it can be said that the coupler of the present invention is an excellent coupler because it not only gives a high color density but also brings a preferable color reproduction.
Having described our invention as related to the present embodiments, it is our intention that the invention not be limited by any of the details of the description, unless otherwise specified, but rather be construed broadly within its spirit and scope as set out in the accompanying claims.

Number	Name	Date
RE27848	Weissberger	Dec 1973
4146396	Yokota et al.	Mar 1979
4268591	Tschopp	May 1981
4289847	Ishikawa et al.	Sep 1981
4404274	Arai et al.	Sep 1983
5118599	Lau et al.	Jun 1992
5250406	Yamamoto et al.	Oct 1993
5314797	Yoshioka et al.	May 1994

Number	Date	Country
2213461	Nov 1972	DEX
0161543	Dec 1981	JPX
0164343	Dec 1981	JPX

Silver halide color photographic material containing acylacetamide yellow dye-forming coupler

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Chemical Abstracts, vol 115, No 3, 22252 and 22253 (1991).
Re 27848, Dec. 1973, Weissberger et al.