JP2893097B2 - Silver halide color photographic materials - Google Patents

Description

The present invention relates to a silver halide color photographic light-sensitive material,
In particular, the present invention relates to a silver halide color photographic light-sensitive material having improved storage stability of a yellow color image.

(Prior art) A silver halide photosensitive material is exposed to light and then subjected to color development processing, whereby an aromatic primary amine developing agent oxidized by silver halide reacts with a dye-forming coupler,
A color image is formed.

In this method, a color reproduction method based on a subtractive color method is often used, and yellow, magenta, and cyan color images having complementary colors are formed to reproduce blue, green, and red.

Conventionally, as a coupler with yellow, those which release a phenoxy group, U.S. Pat.No. 3,408,194, those having an imide group as a leaving group known in U.S. Pat.
Nos. 620, 4,057,432, 4,269,936 and 4,404,2
No. 74, and those having a heterocyclic group as a leaving group are known from U.S. Pat. Nos. 4,046,575 and 4,326,024, and the color development speed and the color image fastness have been improved.

However, compared to the advancement of technology for hardening magenta and cyan images, there have been few proposals for hardening of yellow images, and they remain at a low level among yellow, magenta and cyan images, and improvements are strongly desired. I was

(Problems to be Solved by the Invention) As described above, in a color photograph, the fastness of yellow, magenta, and cyan images to light, heat, and humidity is uniformly high, and the fastness levels of the three colors match. It is desirable to have. From these viewpoints, the present inventors have searched for a compound that improves the color image fastness of a wide yellow coupler and does not reduce the color developability.

The use of the epoxy compounds described in U.S. Pat.No.4,239,851 as a method of improving the fastness to heat and humidity of cyan images and the use of U.S. Pat.
It is known to use the epoxy compounds described in 540,657. These U.S. patents also describe the light and heat fastness of a color image obtained from an aryloxy-eliminated yellow coupler, but the effect was small. Also, when applying a cyclic ether compound described in JP-A-62-75450, which is said to be effective in reducing stain generated when treated with a specific stabilizing solution, to a pivaloyl aceto alinide yellow coupler Certainly, the heat fastness of a yellow image, particularly the effect of dark fading when exposed to humidity is great, but the effect of improving light fading is insufficient.

On the other hand, in the field of dispersion technology for dispersing photographic oil-soluble compounds, it is possible to disperse these in an oil-soluble homopolymer or copolymer, for example, U.S. Patent Nos. 3,619,195 and 4,201,589
No. 4,120,725 and the like. Some of these polymers have an effect of improving photofading, but the effect of improving heat fastness, particularly wet heat fastness, is insufficient.

Also, US Pat. No. 4,268,593 proposes a hindered amine compound, but has a problem that if the amount of the hindered amine compound is too large, the color developability decreases. The present inventors have found that the coexistence of the polymer of the present invention and a hindered amine compound in the presence of a yellow coupler allows the wet heat fastness of a yellow color image to be reduced without adversely affecting photographic properties such as a decrease in color development. The present invention was found to improve the light fastness at the same time and unexpectedly.

Therefore, an object of the present invention is to preserve the yellow image,
In particular, it is an object of the present invention to provide a silver halide color photographic light-sensitive material which is improved in light, heat and heat fading or heat retention, and which does not reduce color development.

(Means for Solving the Problems) An object of the present invention is to provide a silver halide color photographic material having at least one silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers is A silver halide color photographic light-sensitive material comprising a yellow coupler represented by the general region (I), a polymer represented by the general formula (II), and a compound represented by the general formula (III). Can be configured.

In the formula, R ₁ represents N- arylcarbamoyl group, Z ₁
Represents a group which can be eliminated in the reaction with an oxidized form of an aromatic primary amine color developing agent.

In the formula, R ² and R ⁵ may be the same or different and represent a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms or a halogen atom.

R ³ and R ⁴ may be the same or different and represent a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group. However,
The total number of carbon atoms of R ³ and R ⁴ is 2 or more, and R ³ and R ₄ may be linked to each other to form a nitrogen-containing heterocycle.

 L represents a divalent linking group.

L 'represents a substituted or unsubstituted hydrocarbon chain which forms a ring together with an oxygen atom and is connected to L.

A represents a repeating unit derived from an ethylenically unsaturated monomer other than the above.

x, y, z represent the weight percentage of each component, x represents 20 to 99, y represents 1 to 80, and z represents 0 to 50.

In the formula, R ⁶ is a hydrogen atom, a hydroxyl group, an oxy radical group, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylsulfinyl group, an arylsulfinyl group, Represents an alkylsulfonyl group, a carbamoyl group, a sulfamoyl group or an arylsulfonyl group.
R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be the same or different and each represents an alkyl group. A represents a nonmetallic atom group necessary to form a 5-, 6- or 7-membered ring. Where R ⁷
And R ⁸ , R ⁹ and R ¹⁰ , R ⁶ and R ⁷ , or R ⁷ and A may be bonded to each other to form a 5- or 6-membered ring.

Next, the yellow coupler of the general formula (I) and the general formula (II)
And the compound of the general formula (III) will be described in detail.

In the general formula (I), preferred substituents on the aryl group (preferably a phenyl group) of the N-arylcarbamoyl group represented by R ₁ include an aliphatic group having 1 to 32 carbon atoms (eg, methyl, allyl, cyclopentyl), To 46 heterocyclic groups (eg, 2-pyridyl, 2-imidazolyl, 2-furyl, 6-quinolyl), aliphatic oxy groups having 1 to 32 carbon atoms (eg, methoxy, 2-methoxyethoxy, 2-propenyloxy), An aromatic oxy group having 6 to 46 carbon atoms (for example,
2,4-di-tert-amylphenoxy, 4-cyanophenoxy, 2-chlorophenoxy), an acyl group having 1 to 46 carbon atoms (eg, acetyl, benzoyl), an ester group having 2 to 36 carbon atoms (eg, butoxycarbonyl, hexa Decyloxycarbonyl, phenoxycarbonyl, dodecyloxy-carbonylmethoxycarbonyl, acetoxy, benzoyloxy, tetradecyloxysulfonyl, hexadecanesulfonyloxy), an amide group having 1 to 46 carbon atoms (for example, acetylamino, dodecanesulfonamide,
-Butoxy-5-tert-octylphenylsulfonamide, α- (2,4-di-tert-pentylphenoxy) butanamide, methanesulfonamide, γ- (2,4-di-ter
(t-pentylphenoxy) butanamide, N-tetradecylcarbamoyl, N, N-dihexylcarbamoyl, N
-Butanesulfamoyl, N-methyl-N-tetradecanesulfamoyl), an imide group having 2 to 36 carbon atoms (eg, succinimide, N-hytantoinyl, 3-hexadecenylsuccinimide), 1 to 36 carbon atoms Ureido groups such as phenylureido, N, N-dimethylureido, N-
(3- (2,4-di-tert-pentylphenoxy) propyl) ureido), an aliphatic sulfonyl group having 1 to 32 carbon atoms or an aromatic sulfonyl group having 6 to 42 carbon atoms (for example, methanesulfonyl, phenylsulfonyl, Dodecanesulfonyl, 2-butoxy-5-tert-octylbenzenesulfonyl), an aliphatic group having 1 to 32 carbon atoms or an aromatic thio group having 6 to 42 carbon atoms (for example, phenylthio, ethylthio, hexadecylthio, 4- (2,4- Di-tert-phenoxyacetamide)
Benzylthio), a hydroxy group, a sulfonic acid group, and a halogen atom (for example, fluorine, chlorine, and bromine). When two or more substituents are present, they may be the same or different.

In the general formula (I), Z ₁ represents a coupling-off group. Preferred examples thereof include a halogen atom (eg, fluorine, chlorine, bromine) and an alkoxy group having 1 to 22 carbon atoms (eg, dodecyloxy, dodecyloxy). Carbonylmethoxy, methoxycarbamoylmethoxy, carboxypropyloxy, methanesulfonyloxy), having 6 to 6 carbon atoms
42 aryloxy groups (e.g., 4-methylphenoxy,
4-tert-butylphenoxy, 4-methanesulfonylphenoxy, 4- (4-benzyloxyphenylsulfonyl) phenoxy, 4- (4-hydroxyphenylsulfonyl) phenoxy, 4-methoxycarbonylphenoxy), carbon number 2 to 32 acyloxy groups (for example, acetoxy, tetradecanoyloxy, benzoyloxy), 1 to 32 carbon atoms sulfonyloxy group (for example, methanesulfonyloxy, toluenesulfonyloxy), and 1 to 32 carbon atoms
32 amide groups (for example, dichloroacetylamino, methanesulfonylamino, triphonylphosphonamide), C2-C32 alkoxycarbonyloxy groups (for example, ethoxycarbonyloxy, benzyloxycarbonyloxy), and C7-42 aryloxy Carbonyloxy group (for example, phenoxycarbonyloxy), having 1 to 1 carbon atoms
32 aliphatic or C6-C42 aromatic thio groups (e.g., phenylthio, dodecylthio, benzylthio, 2-
Butoxy-5-tert-octylphenylthio, 2,5-di-octyloxyphenylthio, 2- (2-ethoxyethoxy) -5-tert-octylphenylthio, tetrazolylthio), having 2 to 32 carbon atoms Imido groups (e.g., succinimide, hydantoinyl, 2,4-dioxooxazolidin-3-yl, 3-benzyl-4-ethoxyhydantoin-1-yl, 3-benzylhydantoin-1-yl,
1-benzyl-2-phenyl-3,5-dioxo-1,2,4-
Triazolidin-4-yl, 3-benzyl-4-ethoxyhydantoin-1-yl), an N-heterocycle having 1 to 42 carbon atoms (for example, 1-pyrazolyl, 1-benzotriazolyl,
5-chloro-1,2,4-triazol-1-yl) and the like. These leaving groups may include photographically useful groups. Examples of the photographically useful group include a group that releases a development inhibitor and an aromatic azo group (for example, phenylazo) when releasing a development accelerator.

B ₁ and Z ₁ of the general formula (I) may form a dimer or a multimer thereof.

Of these preferred as leaving group represented by Z ₁ is an aryloxy group, an imido group or a N- heterocyclic.
Of these, imide groups and N-heterocycles are more preferably
Particularly preferred are leaving groups represented by formulas (IV) to (VI).

In the formula, R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ are each a hydrogen atom, a halogen atom, a carboxylic acid ester group, an amino group, an alkyl group,
Represents an alkylthio group, an alkoxy group, an alkylsulfonyl group, an alkylsulfinyl group, a carboxylic acid group, a sulfonic acid group, an unsubstituted or substituted phenyl group or a heterocyclic ring, and these groups may be the same or different. R _'14
Is a carbamoyl group (eg, N-phenylcarbamoyl)
Represents

Where W ₁ is Together with a non-metallic atom required to form a 5- or 6-membered ring.

A more preferred specific example of the general formula (VI) is the following formula (VII)
To (IX).

In the formula, R ₁₅ and R ₁₆ each represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a hydroxy group, and R ₁₇ , R ₁₈ , and R ₁₉ each represent a hydrogen atom such as an alkyl group or an aryl group. , An aralkyl group or an acyl group, and W ₂ represents an oxygen or sulfur atom.

More preferred yellow couplers of the formula (I) are represented by the following formulas (IA) or (IB).

In the formula, Y represents a group of non-metallic atoms necessary for forming a 5-membered ring. R ₂₀ represents a substituent of a substituted N-phenylcarbamoyl group defined in the formula, among which an aliphatic group, an aliphatic oxy group, an aromatic oxy group, an ester group, an amide group, an imide group, or a halogen atom preferable.

A specific example of the 5-membered ring formed by Y is the above-mentioned general formula (VI
Although they are represented by I), (VIII) and (IX), the general formulas (VII) and (VIII) are particularly preferred. Particularly preferred in the general formula (VII) are those in which one of R ₁₅ and R ₁₆ represents a substituent which is not a hydrogen atom.

In the formula, R ₂₁ represents a halogen atom, an alkoxy group, a trifluoromethyl group or an aryl group, and R ₂₂ represents a hydrogen atom, a halogen atom or an alkoxy group. A is -NH
_{COR 23 -, - NHSO 2 -R} 23, -SO 2 NHR 23, -COOR 23, Represents However, R ₂₃ and R ₂₄ each represent an alkyl group, an aryl group or an acyl group. R _'14 has the formula (V' is the same synonymous).

Next, specific examples of the compound represented by formula (I) are shown, but the compound of the present invention is not limited to these.

Next, the copolymer represented by the general formula (II) will be described in detail.

R ² and R ⁵ may be the same or different and include a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl,
n-propyl, n-butyl) and a halogen atom (eg, a chlorine atom or a bromine atom), of which a hydrogen atom and a methyl group are particularly preferred.

R ³ and R ⁴ may be the same or different and represent a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group, and these hydrocarbon groups may or may not be substituted.

Examples of the aliphatic hydrocarbon group or aromatic hydrocarbon group represented by R ³ and R ⁴ include an aryl group (eg, a phenyl group), a hydroxy group, an alkoxy group having 1 to 6 carbon atoms (eg, a methoxy group), and a halogen atom ( For example, it may be substituted with a chlorine atom), a cyano group or the like.

The total number of carbon atoms of the substituents represented by R ² and R ³ is a coupler,
In particular, 2 to 20 is preferable from the viewpoint of affinity with the hydrophobic coupler.

Nitrogen-containing heterocyclic ring R ² and R ³ are formed by linking each other preferably may contain in addition to the oxygen atom of a plurality of nitrogen atoms or nitrogen atom as a hetero atom in 5- or 6-membered ring, e.g. Rings such as piperidine, morpholine and pyrrolidine can be mentioned.

Among the polymers represented by the general formula [I] used in the present invention, Specific examples of the monomer giving the repeating unit represented by the formula: N-ethylacrylamide, N- (n-propyl)
Acrylamide, N-isopropylacrylamide, N
-(N-butyl) acrylamide, N- (tert) -butyl) acrylamide, N- (n-octyl) acrylamide, N- (isoamyl) acrylamide, N- (tert
-Octyl) acrylamide, N-laurylacrylamide, N-cyclohexylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N-
(1,1-dimethyl-3-hydroxybutylacrylamide), N, N-diethylacrylamide, N, N-dioctylacrylamide, N- (1,1-dimethyl-3-oxobutyl) acrylamide, N-acryloylmorpholine,
N-methyl-N'-acryloylpiperazine, N-ethyl-N'-acryloylpiperazine, N-acryloylpiperazine, N- (β-morpholinoethyl) acrylamide, N- (tert-butyl) methacrylamide, N-
(Tert-octyl) methacrylamide, N-benzylmethacrylamide, N-cyclohexylmethacrylamide, N-phenylmethacrylamide, N, N-diethylmethacrylamide, N, N-dipropylmethacrylamide,
N-methyl-N-phenylmethacrylamide, N-methacryloyl-N'-methylpiperazine, N-methacryloylpiperidine, 4-methacryloyl-2,6-dimethylmorpholine, N-methacryloyl-N'-ethylpiperazine and the like.

L preferably represents a divalent linking group having from 1 to about 20 carbon atoms, _{^{specifically, X 1 p J 1 -X 2}} q J 2 -X 3 r J 3 -X 4 s J ^Four
It is represented by _t . X ¹ , X ² , X ³ , and X ⁴ may be the same or different, and represent —COO—, —OCO—, (R ²¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a substituted alkyl group having preferably 1 to 6 carbon atoms.), —CO—, —SO ₂ —, (R ²¹ is as defined above), (R ²¹ is the same as above, and R ²² preferably has 1 to about 4 carbon atoms.)
Alkylene group), (R ²¹ and R ²² are as defined above; R ²³ is a hydrogen atom, an alkyl group (preferably having 1 to 6 carbon atoms), a substituted alkyl group (preferably having 1 to 6 carbon atoms), —O—, —S— , (R ²¹ and R ²³ have the same meanings as described above).

J ¹ , J ² , J ³ and J ⁴ may be the same or different and represent an alkylene group, a substituted alkylene group, an arylene group, a substituted arylene group, an aralkylene group, or a substituted aralkylene group.

p, q, r, s, and t represent 0 or 1, but they do not become 0 at the same time.

Examples of the substituent that may be further substituted on L include a halogen atom, a nitro group, a cyano group, an alkyl group, a substituted alkyl group, an alkoxy group, a substituted alkoxy group, and a group represented by —NHCOR ²⁴ (R ²⁴ represents an alkyl group, a substituted alkyl group, phenyl group, substituted phenyl group, an aralkyl group, a substituted aralkyl group) ^{_{is, - NHSO 2 R 24 (R}} 24 is as defined above), - SOR ²⁵ (R ²⁵ is as defined above) , −SO ₂ R ²⁵
(R ²⁵ is as defined above), -COR ²⁵ (R ²⁵ is as defined above), (R ²⁶ and R ²⁷ may be the same or different and represent a hydrogen atom, an alkyl group, a substituted alkyl group, a phenyl group, a substituted phenyl group, an aralkyl group, a substituted aralkyl group), (R ²⁶ and R ²⁷ are as defined above), an amino group (which may be substituted with an alkyl group), a hydroxyl group, and a group which forms a hydroxyl group by hydrolysis.

Particularly preferred among the linking groups represented by L are phenylene groups (for example, o-phenylene group, p-phenylene group, m
-Phenylene group), an arylenealkylene group (e.g., Or Such. However R ²⁸ represents an alkylene group which may be substituted preferably 1 to about 12 carbon atoms. ), _{-CO 2 -, - CO 2 -R} 29 -, ( where R ²⁹ each which may be substituted alkylene group, phenylene group, an arylenealkylene group.) -CO ₂ -R ²⁹ -CO ₂ -R ^30- (R ³⁰ is the same as R ²⁹ ), (R ³¹ is synonymous with ^{R 29), - CONH-R} 29 -, ( where R ²⁹ represents the same as above.) (However, R ² and R ²⁹ represent the same as above.), -CONH
—R ²⁹ —COO—R ³⁰ — (R ²⁹ and R ³⁰ represent the same as described above) and the like.

L 'together with an oxygen atom constitutes a ring;
Represents a substituted or unsubstituted hydrocarbon chain.

The ring formed by L 'and the oxygen atom together is preferably a 3- to 8-membered ring, and the formed oxygen-containing ring is substituted by a substituent selected from the same group as described in the description of L. May be.

Of the rings formed by combining L 'and an oxygen atom, particularly preferred are an epoxy ring, a tetrahydrofuran ring and a tetrahydropyran ring.

Hereinafter, in the general formula [I] Examples of monomers giving a repeating unit represented by the following,
It is not limited to this.

Examples of the copolymerizable ethylenically unsaturated monomer represented by A include acrylates, methacrylates, allyl compounds, vinyl ethers, vinyl esters, vinyl heterocyclic compounds, styrenes, Maleic esters, fumaric esters, itaconic esters, crotonic esters, olefins and the like. Specific examples thereof include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, octyl acrylate, 2-chloroethyl acrylate, 2-cyanoethyl acrylate, benzyl acrylate, cyclohexyl acrylate, phenyl acrylate, Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, octyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 3-
Sulfopropyl methacrylate; allyl acetate, allyl caprylate, allyl caproate, allyl laurate, allyl benzoate; allyl butyl ether, allyl phenyl ether; methyl vinyl ether, butyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, 2-chloroethyl vinyl ether, 2-hydroxyethyl vinyl ether, (2-dimethylaminoethyl) vinyl ether, vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl capro Ethate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, repose Vinyl acetate, vinyl naphthoate; styrene, p-acetoxystyrene, p-methylstyrene; methyl p-vinylbenzoate; crotonamide, butyl crotonate, glycerin monocrotonate; methyl vinyl ketone, phenyl vinyl ketone; ethylene, propylene , 1-butene, dicyclopentadiene, 4-methyl-
1-hexane, 4,4-dimethyl-1-pentene, etc .; methyl itaconate, ethyl itaconate, diethyl itaconate, etc .; methyl sorbate, dibutyl maleate, octyl maleate, etc .; dibutyl fumarate, etc .; halogenated olefin Such as vinyl chloride, vinylidene chloride, isoprene and the like; unsaturated nitriles such as
There are acrylonitrile, methacrylonitrile and the like, and two or more of them can be used as needed.

Among these monomers, polymer solubility, lipophilicity,
Acrylic esters, methacrylic esters, and vinyl esters are particularly preferred in terms of affinity with the hydrophobic coupler.

x, y, z represent the weight percentage of each component, x is 20 to 99, preferably 30 to 95, y is 1 to 80, preferably 5 to 70, z is 0 to 50, preferably 0 to 30. Range.

The production of the polymers according to the invention can be carried out by various polymerization methods, such as solution polymerization, precipitation polymerization, suspension polymerization and bulk polymerization. The method of initiating polymerization includes a method using a radical initiator, a method of irradiating light or radiation, and a thermal polymerization method. These polymerization methods and the method of initiating the polymerization are described in, for example, Teiji Tsuruta “Polymer Synthesis Reaction” Revised Edition (published by Nikkan Kogyo Shimbun,
71).

Among the above polymerization methods, a solution polymerization method or a suspension polymerization method using a radical initiator is particularly preferable.

Solvents used in the solution polymerization method, for example, ethyl acetate,
Methanol, ethanol, 1-propanol, 2-propanol, acetone, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, n
-Various organic solvents such as hexane and acetonitrile may be used alone or as a mixture of two or more thereof, or may be used as a mixed solvent with water.

The polymerization temperature must be set in relation to the molecular weight of the polymer to be formed, the type of the initiator, and the like.
Although it is possible to raise the temperature up to or higher, the polymerization is usually carried out in the range of 30 to 100 ° C.

As the radical initiator used for polymerization, for example,
2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-amidinopropane) dihydrochloride, 4,4 '
An azo initiator such as -azobis (4-cyano-pentanoic acid) and a peroxide initiator such as benzoyl peroxide are preferred.

The amount of the initiator is adjusted according to the molecular weight of the polymer, but is preferably in the range of 0.01 to 10 mol%, particularly preferably in the range of 0.01 to 1.0 mol%, based on the monomer.

Preferred examples of the polymer represented by the general formula [II] of the present invention are shown below, but the present invention is not limited thereto (all composition ratios represent weight percentage ratios).

The use ratio (weight ratio) of the polymer represented by the general formula (I) of the present invention to the coupler (in the same layer) is from 1:20.
A range of 20: 1 is preferred, more preferably a range of 1:10 to 1: 1.

The number average molecular weight of this polymer is preferably about 1,000,000 or less, more preferably about 200,000 or less.

To describe the general formula (III) in more detail, R ⁶ represents a hydrogen atom, a hydroxyl group, an oxy radical group, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a chloromethyl group, a hydroxymethyl group, Benzyl group), alkenyl group (for example, vinyl group, allyl group,
An alkynyl group (eg, an ethynyl group, a propynyl group, etc.), an acyl group (eg, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a myristoyl group, a crotonoyl group,
Benzoyl group, toluyl group, furoyl group, 2,4-di-t
-Acylphenoxyacetyl group, etc.), alkyloxycarbonyl group (eg, methoxycarbonyl group, octyloxycarbonyl group, hexadecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, 4-methylphenoxy group) An alkylsulfinyl group (eg, a methylsulfinyl group, an ethylsulfinyl group, etc.), an arylsulfinyl group (eg, a phenylsulfinyl group, a 4-methoxyphenylsulfinyl group, etc.) ), An alkylsulfonyl group (for example, a methanesulfonyl group, an octanesulfonyl group, a 4-phenoxybutanesulfonyl group, etc.), a carbamoyl group, a sulfamoyl group, or an arylsulfonyl group (for example, a benzenesulfonyl group, a 4-methoxybenzenesulfonyl group). ) Represents the.

R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be the same or different and each represents a substituted or unsubstituted alkyl group (eg, a methyl group, an ethyl group, a propyl group, an octyl group, etc.).

A is a non-metallic group necessary to form a substituted or unsubstituted 5-, 6- or 7-membered ring (which may contain multiple suffocating atoms and may contain other heteroatoms) Represents a group of atoms, for example And so on. Here, R ³³ and R ³⁴ may be the same or different and each represents a hydrogen atom, an alkyl group (eg, ethyl, cyclohexyl, octadecyl), an acyl group, a sulfonyl group, a sulfinyl group, an aryl group, a heterocyclic group,
Represents an alkoxycarbonyl group or a carbamoyl group. Further, R ⁷ and R ⁸ , R ⁹ and R ¹⁰ , R ⁶ and R ⁷ , or R ⁷ and A
Are bonded to each other to form a substituted or unsubstituted 5- or 6-membered ring (eg, cyclopentyl, cyclohexyl,
Cyclohexenyl, pyranyl, piperazine, piperidine, morpholine).

From the viewpoint of the effects of the present invention, A is preferably an atom group forming a 5- or 6-membered ring, and particularly preferably 2,2,6,6-tetramethylpiperidine. On the other hand, compounds having no phenolic hydroxyl group in the molecule as a whole are particularly preferable.

Hereinafter, specific examples of the general formula (III) are shown, but the invention is not limited thereto.

These compounds are known as "Synthesis" 1984
894, 122, 1984, 40, 1981, “Journal of the Organic Chemistry (I.Org.Che
m.,) ", Vol. 45, p. 754 (1980)," Journal of
The Chemical Society Section C (J.Chem.S
oc., (C) ", p. 1653 (1971), JP-A-49-53573,
No. 49-7180, No. 49-53575, No. 49-53571, British Patent No. 1,410,846, and the like, and can be synthesized according to them.

The coupler used in the present invention is usually contained in the silver halide emulsion layer in an amount of 0.01 to 2 mol, preferably 0.1 to 1.0 mol, per 1 mol of silver halide.

The polymer used in the present invention is preferably from 5 wt% to 300 wt%, more preferably 10 wt%, based on the yellow coupler.
% To 100% by weight.

Further, the hindered amine compound used in the present invention is preferably 2 mol% to 100 m
ol%, more preferably 5 to 50 mol%.

When the polymer or the hindered amine compound of the present invention is used for the yellow coupler, a high-boiling organic solvent described later may or may not be used. When used, any amount can be used. In the present invention, the compound is preferably contained in the photographic layer as an emulsified dispersion of lipophilic fine particles containing these compounds.

In order to obtain an emulsified dispersion of lipophilic fine particles containing the above-mentioned coupler, high-boiling coupler solvent, hindered amine compound and polymer, it can be preferably prepared by the following method.

After completely dissolving a non-crosslinked linear polymer synthesized by a solution polymerization method, emulsion polymerization or suspension polymerization, a so-called linear polymer, a high boiling coupler, a hindered amine compound and a coupler together in an auxiliary organic solvent, In water, preferably in an aqueous hydrophilic colloid solution, more preferably in an aqueous gelatin solution, with the aid of a dispersant, ultrasound,
It is dispersed in fine particles by a colloid mill or the like and is contained in a silver halide emulsion. Or a dispersing aid such as a surfactant,
Water or an aqueous solution of a hydrophilic colloid such as an aqueous solution of gelatin may be added to an auxiliary organic solvent containing the polymer of the present invention, a high-boiling coupler solvent, a hindered amine compound and a coupler to form an oil-in-water dispersion with phase inversion. After removing the auxiliary organic solvent from the prepared dispersion by a method such as distillation, noodle washing or ultrafiltration, the dispersion may be mixed with a photographic emulsion. The auxiliary organic solvent referred to here is an organic solvent useful at the time of dispersion of an emulsion, and is substantially one which is finally removed from the photosensitive material by a drying step at the time of coating or the above-mentioned method. An organic solvent having a boiling point, or a solvent having a certain solubility in water and removable by washing with water.
As the auxiliary organic solvent, ethyl acetate, acetate of lower alcohol such as butyl acetate, ethyl propionate,
Secondary butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, methyl carbitol acetate, methyl carbitol propionate, cyclohexanone and the like can be mentioned.

Further, if necessary, an organic solvent that is completely miscible with water,
For example, methyl alcohol, ethyl alcohol, acetone, tetrahydrofuran, and the like can be partially used in combination.

These organic solvents can be used in combination of two or more.

The average particle diameter of the lipophilic fine particles thus obtained is
It is preferably from 0.04 μ to 2 μ, more preferably from 0.06 μ to 0.4 μ. The particle size of the lipophilic fine particles can be measured by, for example, a measuring device such as Nanosizer manufactured by Coulter, UK.

The color photographic light-sensitive material of the present invention can be constituted by coating at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer and one red-sensitive silver halide emulsion layer on a support. In general, color printing paper is usually coated on a support in the order described above, but may be in a different order. Further, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned emulsion layers. In these light-sensitive emulsion layers, a silver halide emulsion having a sensitivity in each wavelength region and a dye having a complementary color with the light to be exposed, that is, yellow for blue, magenta for green, and cyan for red are formed. By incorporating a so-called color coupler, the color reproduction by the subtractive color method can be performed. However, the photosensitive layer and the color hue of the coupler may not have the above correspondence.

As the silver halide emulsion used in the present invention, an emulsion composed of silver chlorobromide or silver chloride containing substantially no silver iodide can be preferably used. Here, "contains substantially no silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. The halogen composition of the emulsion may be different or the same between grains. However, when an emulsion having the same halogen composition between grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, grains having a so-called uniform structure having the same composition in any part of the silver halide grains, a core inside the silver halide grains and a shell surrounding the core are used. (Shell) [single or multiple layers] and a so-called stacked structure particle having a different halogen composition, or
Particles having a non-layered structure having a different portion of halogen composition inside or on the surface (in the case of being on the particle surface, a structure in which portions having different compositions are bonded to the edges, corners or surfaces of the particles) are appropriately selected and used. be able to. In order to obtain high sensitivity, it is advantageous to use one of the latter two particles rather than particles having a uniform structure, and this is also preferable from the viewpoint of pressure resistance. In the case where the silver halide grains have the above-described structure, even if the boundary between different portions in the halogen composition is a clear boundary, it is an unclear boundary by forming a mixed crystal due to a composition difference. It is also possible to employ a structure in which a continuous structural change is positively provided.

Regarding the halogen composition of these silver chlorobromide emulsions, any silver halide / silver chloride ratio can be used. Although this ratio can take a wide range according to the purpose, a silver chloride ratio of 2% or more can be preferably used.

Further, a so-called high silver chloride emulsion having a high silver chloride content is preferably used as a photosensitive material suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably at least 90 mol%,
More than 95% mol is more preferable.

Such a high silver chloride emulsion preferably has a structure in which a silver bromide localized phase is formed in a layered or non-layered form inside and / or on the surface of silver halide grains as described above.
The halogen composition of the localized phase is preferably at least 10 mol% in terms of silver bromide content, and more preferably more than 20 mol%. These localized phases can be inside the grains, at the edges, corners, or planes of the grain surfaces. One preferred example is a phase epitaxially grown at the corners of the grains.

On the other hand, in order to minimize the decrease in sensitivity when the photosensitive material is subjected to pressure, even in a high silver chloride emulsion having a silver chloride content of 90 mol% or more, grains having a uniform distribution of the halogen composition in the grains are used. It is also preferably used.

It is also effective to further increase the silver chloride content of the silver halide emulsion in order to reduce the replenishment amount of the developing solution. In such a case, the silver chloride content is 98 mol% to 10 mol%.
Emulsions of substantially pure silver chloride, such as 0 mol%, are also preferably used.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0.1 μm to 2 μm. preferable.

In addition, their particle size distribution has a coefficient of variation (standard deviation of particle size distribution divided by average particle size) of 20%
In the following, a so-called monodispersed one of desirably 15% or less is preferable. At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating.

The silver halide grains contained in photographic emulsions have a regular (regular, cubic, tetradecahedral or octahedral) shape.
r) Those having a crystal form, those having an irregular crystal form such as a sphere or a plate, or those having a complex form thereof can be used. Also,
It may be composed of a mixture having various crystal forms. In the present invention, 50% or more, preferably 70% or more of the particles having the regular crystal form among these,
More preferably, the content is 90% or more.

In addition, emulsions in which tabular grains having an average aspect ratio (diameter / circle diameter in circle) of 5 or more, preferably 8 or more, as projected area exceeds 50% of all grains can be preferably used.

The silver chlorobromide emulsion used in the present invention is described in Chimi by P. Glafkides.
e et Phisique Photographique (published by Paul Montel, 196
7 years), Photographic Emulsion Chemistry by GFDuffin
(Focal Press, 1966), M by VLZelikman et al
aking and Coating Photographic Emulsion (Focal Pre
ss, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halide, any method such as a one-side mixing method, a simultaneous mixing method, and a combination thereof may be used. May be used. A method of forming particles in an atmosphere containing excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used.
According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

In the silver halide emulsion used in the present invention, various polyvalent metal ion impurities can be introduced during the process of forming emulsion grains or physical ripening. Examples of the compound to be used include salts of cadmium, zinc, lead, copper, thallium and the like, or salts or complex salts of Group VIII element iron, ruthenium, rhodium, palladium, osmium, iridium and platinum. it can. Especially above VI
Group II elements can preferably be used. The addition amount of these compounds varies widely depending on the purpose, but is preferably from 10 ^-3 to 10 ^-2 mol per mol of silver halide.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization and spectral sensitization.

As the chemical sensitization method, sulfur sensitization represented by addition of an unstable sulfur compound, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compounds used for chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used.

Spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye that absorbs light in a wavelength range corresponding to the intended spectral sensitivity—a spectral sensitizing dye. As the spectral sensitizing dye used at this time, for example, Heterocyclic compo by FM Harmar
unds-Cyanine deys and related compounds (John Wil
ey & Sons [New York, London], 1964). As specific examples of the compounds, those described in the above-mentioned JP-A-62-215272, page 22, upper right column to page 38, are preferably used.

To the silver halide emulsion used in the present invention, various compounds or their precursors are added for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. be able to. As specific examples of these compounds, those described on page 39 to page 72 of JP-A-62-215272 described above are preferably used. An oxyphenylthiomethyl group, a butanamidomethyl group, a methoxymethyl group and the like can be mentioned.

Preferred examples of the cyan coupler represented by the general formula (CI) or (C-II) are as follows.

In the general formula (CI), preferred R ₁ is an aryl group,
A heterocyclic group, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group,
More preferably, they are aryl groups substituted by a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, or a cyano group.

When R ₃ and R ₂ do not form a ring in formula (CI), R ₂ is preferably a substituted or unsubstituted alkyl group,
It is an aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R ₃ is preferably a hydrogen atom.

In formula (C-II), R ₄ is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In the general formula (C-II), preferred R ₅ has 2 to 15 carbon atoms.
And a methyl group having a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group.

In the general formula (C-II), R ₅ is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms.

Preferred R ₆ in formula (C-II) is a hydrogen atom or a halogen atom, and a chlorine atom and a fluorine atom are particularly preferred. Preferred Y ₁ and Y ₂ in the general formulas (CI) and (C-II) are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a sulfonamide group, respectively.

In the general formula (MI), R ₇ and R ₉ represent an aryl group, R ₈ represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group, and Y ₃ represents hydrogen. Represents an atom or a leaving group. The substituents permitted for the aryl group (preferably phenyl group) of R ₇ and R ₉ are the same as the substituents permitted for the substituent R ₁ , and when there are two or more substituents, they are the same. But they may be different. R ₈
Is preferably a hydrogen atom, an aliphatic acyl group or a sulfonyl group, and particularly preferably a hydrogen atom. Desirable Y ₃ is of a type capable of releasing at any of a sulfur, oxygen or nitrogen atom, and particularly preferred is a type of releasing at a sulfur atom as described in, for example, US Pat. No. 4,351,897 and International Publication WO88 / 04795.

In the general formula (M-II), R ₁₀ represents a hydrogen atom or a substituent. Y ₄ represents a hydrogen atom or a leaving group, particularly preferably a halogen atom or an arylthio group. Za, Zb and
Zc represents methine, substituted methine, = N- or -NH-,
One of the -Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. The case where the Zb-Zc bond is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. When R ₁₀ or Y ₄ forms a dimer or more multimer, Za,
When Zb or Zc is a substituted methine, the case where the substituted methine forms a dimer or more multimer is included.

Among the pyrazoloazole couplers represented by the general formula (M-II), imidazo [1,2-b] pyrazoles described in U.S. Pat. No. 4,500,630 in view of low yellow side absorption of a coloring dye and light fastness. Are preferred, U.S. Pat.
Pyrazolo [1,5-b] [1,2,4] triazole described in JP-A-40,654 is particularly preferred.

In addition, a branched alkyl group as described in JP-A-61-65245 is directly linked to the 2-, 3- or 6-position of the pyrazolotriazole ring to form a pyrazolotriazole coupler.
Pyrazoloazole couplers containing a sulfonamide group in the molecule as described in 65246, JP-A-61-147254
Pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A No. 226,849 and the emulsions used in the present invention described in EP-A-226,849 and EP-A-294,785 have a latent image mainly having a grain surface. Or a so-called internal latent image type emulsion in which a latent image is mainly formed inside the grains.

When the present invention is applied to a color light-sensitive material, the color light-sensitive material is coupled with an oxidized form of an aromatic amine-based color developing agent to form a yellow coupler, a magenta coupler, and a cyan coupler which respectively form yellow, magenta, and cyan. Is usually used.

Cyan coupler preferably used in the present invention,
The magenta coupler has the following general formulas (C-I) and (C-I
(I), (MI) and (M-II).

In the general formulas (CI) and (C-II), R ₁ , R ₂
And R ₄ represents a substituted or unsubstituted aliphatic, aromatic or heterocyclic group; R ₃ , R ₅ and R ₆ represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group or an acylamino group; ₃ may represent a non-metallic atomic group forming a 5- or 6-membered nitrogen-containing ring together with R ₂ . Y ₁ and Y _{2 each} represent a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of a developing agent. n represents 0 or 1.

R ₅ in the general formula (C-II) is preferably an aliphatic group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentadecyl group, a tert-butyl group, a cyclohexyl group, a cyclohexylmethyl group, It is preferable to use a pyrazolotriazole coupler having an alkoxy group or an aryloxy group at the 6-position, such as a phenylthiomethyl group or a dodecyl group.

Formulas (C-I), (C-II), (M-I), and (M-
Specific examples of the coupler represented by II) are listed below.

The couplers represented by the above general formulas (CI) to (M-II) are usually contained in the silver halide emulsion layer constituting the photosensitive layer in an amount of 0.1 to 1.0 mol, preferably 0.1 to 1.0 mol per mol of silver halide.
It is contained in an amount of 1 to 0.5 mol.

In the present invention, various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by an oil-in-water dispersion method known as an oil protection method, and after being dissolved in a solvent, it is emulsified and dispersed in a gelatin aqueous solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water dispersion with phase inversion. Further, the alkali-soluble coupler can be dispersed by a so-called Fisher dispersion method. After removing the low-boiling organic solvent from the coupler dispersion by a method such as distillation, noodle washing or ultrafiltration, it may be mixed with a photographic emulsion.

Dielectric constant (25 ° C) as a dispersion medium for such couplers
It is preferable to use a high-boiling organic solvent having a refractive index of 2 to 20 and a refractive index (25 ° C.) of 1.5 to 1.7 and / or a water-insoluble polymer compound.

As the high-boiling organic solvent, a high-boiling organic solvent represented by the following general formulas (A) to (E) is preferably used.

Wherein W ₁ , W ₂ and W ₃ each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group, and W ₄ represents W ₁ , OW ₁ or SW.
_And n is an integer of 1 to 5, and when n is 2 or more, W ₄ may be the same or different, and in the general formula (E), W ₁ and W ₂ are a condensed ring May be formed).

The high-boiling organic solvent that can be used in the present invention is a compound that is not miscible with water having a melting point of 100 ° C. or less and a boiling point of 140 ° C. or more other than the general formulas (A) to (E). Can be used. The melting point of the high boiling organic solvent is preferably 80 ° C. or higher. The boiling point of the high boiling organic solvent is preferably 160 ° C.
And more preferably 170 ° C. or higher.

Details of these high-boiling organic solvents are described in
No. 215272, page 137, lower right column to page 144, upper right column.

The light-sensitive material prepared in the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative or the like as a color fogging inhibitor.

Various anti-fading agents can be used in the light-sensitive material of the present invention. That is, hydroquinones as organic anti-fading agents for cyan, magenta and / or yellow images,
6-hydroxycoumarones, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols,
Representative examples include hindered phenols, mainly bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, and ether or ester derivatives in which the phenolic hydroxyl group of each of these compounds is silylated or alkylated. Can be Further, a metal complex represented by a (bissalicylaldoximato) nickel complex and a (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Specific examples of the organic anti-fading agent are described in the specifications of the following patents.

Hydroquinones are disclosed in U.S. Pat.Nos. 2,360,290 and 2,4
No. 18,613, No. 2,700,453, No. 2,701,197, No. 2,
No. 728,659, No. 2,732,300, No. 2,735,765, No.
No. 3,982,944, No. 4,430,425, UK Patent No. 1,363,921
No., U.S. Pat.Nos. 2,710,801 and 2,816,028,
6-Hydroxychromans, 5-hydroxycoumarins, and spirochromans are described in U.S. Pat.
No. 3,573,050, No. 3,574,627, No. 3,698,909, No. 3,764,337, JP 52-152225, etc. UK Patent 2,0
No. 66,975, JP-A-59-10539, JP-B-57-19765 and the like, gallic acid derivatives, methylenedioxybenzenes, aminophenols are U.S. Pat.No. 3,457,079, respectively.
Nos. 4,332,886 and JP-B-56-21144, and metal complexes are described in U.S. Pat. Nos. 4,050,938 and 4,241,155 and British Patent 2,027,731 (A), respectively.
These compounds can achieve the object by adding usually 5 to 100% by weight of the corresponding color coupler to the photosensitive layer after co-emulsification with the coupler. In order to prevent the deterioration of the cyan dye image due to heat and particularly to light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent thereto.

Examples of the ultraviolet absorber include benzotriazole compounds substituted with an aryl group (for example, those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (for example, those described in U.S. Pat. Nos. 3,314,794 and 3,352,681),
Benzophenone compounds (for example, those described in JP-A-46-2784) and cinnamate compounds (for example, US Pat.
3,705,805 and 3,707,395), butadiene compounds (described in U.S. Pat. No. 4,045,229),
Alternatively, benzooxide compounds (for example, British Patent No.
3,406,070 and 3,677,672 and 4,271,307) can be used. UV-absorbing couplers (eg, α-naphthol-based cyan dye-forming couplers)
Alternatively, an ultraviolet absorbing polymer or the like may be used. These ultraviolet absorbers may be mordanted to a specific layer.

Above all, a benzotriazole compound substituted with the above-mentioned aryl group is preferable.

It is particularly preferable to use the following compounds together with the above-mentioned coupler. In particular, combination use with a pyrazoloazole coupler is preferred.

That is, the compound (F) which forms a chemically inactive and substantially colorless compound by chemically bonding with the aromatic amine-based developing agent remaining after the color development and / or the aromatic remaining after the color development. The compound (G), which chemically binds to the oxidized form of an aromatic amine-based color developing agent to form a chemically inert and substantially colorless chemical, can be used simultaneously or alone, for example, after storage after processing. It is preferable in order to prevent the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent remaining in the film or the oxidized product thereof and the coupler with the coupler.

Preferred as the compound (F) is a compound having a secondary reaction rate constant k ₂ (in trioctyl phosphate at 80 ° C.) of 1.0 / mol · sec to 1 × 10 ⁻⁵ / mol · sec with the second reaction rate constant with p-anisidine. Compound. The secondary reaction rate constant can be measured by the method described in JP-A-63-158545.

If k ₂ is greater than this range, the compound itself becomes unstable, resulting in decomposition reacts with gelatin or water. On the other hand, if k ₂ is smaller than this range, the reaction with the remaining aromatic amine-based developing agent is slow, and as a result, the side effect of the remaining aromatic amine-based developing agent may not be prevented.

More preferable compound (F) can be represented by the following general formula (FI) or (F II).

In the formula, R ₁ and R ₂ each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0. A represents a group which forms a chemical bond by reacting with an aromatic amine-based developer, and X represents a group which is eliminated by reacting with an aromatic amine-based developer. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y represents that an aromatic amine-based developing agent is added to the compound of the general formula (F II). Represents a promoting group. Here, R ₁ and X, Y and R ₂ or B may be bonded to each other to form a cyclic structure.

Representative methods of chemically bonding with the residual aromatic amine-based developing agent are a substitution reaction and an addition reaction.

Specific examples of the compounds represented by formulas (FI) and (F II) are described in JP-A-63-158545, JP-A-62-283338,
Those described in specifications such as European Patent Publication Nos. 298321 and 277589 are preferable.

On the other hand, the compound (G) which forms a chemically inactive and colorless compound by chemically bonding to an oxidized form of an aromatic amine-based developing agent remaining after the color development processing is more preferably represented by the following general formula (GI) ).

Formula (GI) RZ In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group. Z represents a nucleophilic group or a group which decomposes in the light-sensitive material to release a nucleophilic group. In the compound represented by the general formula (GI), Z is a nucleophilic ⁿ CH ₃ I value of Pearson (RGPearso
n, et al., J. Am. Chem. Soc., 90 , 319 (1968)) or a group derived therefrom is preferred.

Specific examples of the compound represented by the general formula (GI) are described in EP-A-255722, JP-A-62-143048 and JP-A-62-143048.
-229145, Japanese Patent Application Nos. 63-136724 and 62-214681, and European Patent Publications 298321 and 277589 are preferred.

The details of the combination of the compound (G) and the compound (F) are described in EP-A-277589.

The light-sensitive material prepared according to the present invention contains a water-soluble dye or a dye which becomes water-soluble by photographic processing as a filter dye in the hydrophilic colloid layer, or for various purposes such as prevention of irradiation or halation. You may. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, gelatin is lime-treated,
Either one treated with an acid may be used. The details of the method for producing gelatin are described in Arthur Wuice, The Macromolecular Chemistry of Gelatin (Academic Press, 1964).

As the support used in the present invention, a transparent film such as a cellulose nitrate film or a polyethylene terephthalate which is usually used for a photographic light-sensitive material, or a reflective support can be used. For the purposes of the present invention, the use of a reflective support is more preferred.

The term "reflective support" used in the present invention refers to a material which enhances reflectivity and sharpens a dye image formed in a silver halide emulsion layer. Examples include those coated with a hydrophobic resin dispersedly containing a light reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin dispersedly containing a light reflecting substance as a support. For example, baryta paper, polyethylene-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer or combined with a reflective substance, such as a glass plate, polyethylene terephthalate, a polyester film such as cellulose triacetate or cellulose nitrate, Examples include a polyamide film, a polycarbonate film, a polystyrene film, and a vinyl chloride resin.

Other reflective supports include specular or secondary
A support having a seed diffuse reflective metal surface can be used. The metal surface has a spectral reflectance of 0.5 in the visible wavelength range.
The above materials are preferred, and the metal surface is preferably roughened or diffusely reflective using metal powder. As the metal, aluminum, tin, silver, magnesium or an alloy thereof is used, and the surface may be the surface of a metal plate, a metal foil, or a metal thin layer obtained by rolling, vapor deposition, plating, or the like.
Above all, it is preferable to obtain a metal by vapor deposition on another substrate. It is preferable to provide a water-resistant resin, especially a thermoplastic resin layer, on the metal surface. An antistatic layer is preferably provided on the side of the support of the present invention opposite to the side having the metal surface. For details of such a support, see, for example, JP-A-61-210346.
Nos. 63-24247, 63-24251 and 63-24255.

 These supports can be appropriately selected depending on the purpose of use.

As the light-reflective substance, it is preferable to sufficiently knead a white pigment in the presence of a surfactant.
It is preferable to use those treated with a to tetravalent alcohol.

The occupied area ratio (%) per defined unit area of the white pigment fine particles is most typically obtained by dividing the observed area into adjacent 6 μm × 6 μm unit areas and projecting the unit area. It can be determined by measuring the occupied area ratio (%) (R ₁ ) of the fine particles. Variation coefficient of the occupied area ratio (%) is the ratio of the standard deviation s of R _i to the average value of R _i () s /
Can be obtained by The number (n) of the target unit areas is preferably 6 or more. Therefore the coefficient of variation s / Can be obtained by

In the present invention, the occupied area ratio of the pigment fine particles (%)
Is preferably 0.15 or less, particularly preferably 0.12 or less. 0.08
In the following cases, it can be said that the dispersibility of the particles is substantially “uniform”.

The color developer used in the development of the photosensitive material of the present invention is
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as the color developing agent.
Phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N-ethyl-N
-Β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-Β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof.
These compounds can be used in combination of two or more depending on the purpose.

The color developing solution includes a pH buffer such as an alkali metal carbonate or phosphate, a development inhibitor such as a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound or an antifoggant. It is common to include. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, N, N-
Hydrazines such as biscarboxymethylhydrazine,
Various preservatives such as phenylsemicarbazides, triethanolamine, catecholsulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, and dye formation Couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, various chelating agents represented by aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids ,
For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, Ethylenediamine-N, N, N ',
N'-tetramethylenephosphonic acid, ethylenediamine-
Di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as typical examples.

When the reversal processing is performed, color development is usually performed after black-and-white development and reversal processing are performed. In this black and white developer,
Known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone and aminophenols such as N-methyl-p-aminophenol can be used alone or in combination. .

The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 or less per square meter of the light-sensitive material. By reducing the bromide ion concentration in the replenishing solution, 500 m
It can be less than l. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The contact area between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = contact area between treatment liquid and air (cm ² ) / capacity of treatment liquid (cm ³ ) The above-mentioned aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05.

As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-62-241342, Examples of the method include a slit developing method described in JP-A-63-216050.

The reduction of the aperture ratio is preferably applied not only to both the color development and black-and-white development steps but also to the following various steps, for example, all the steps such as bleaching, bleach-fixing, fixing, washing and stabilization.

Further, by using means for suppressing the accumulation of bromide ions in the developer, both replenishment can be reduced.

The time for the color development processing is usually set between 2 and 5 minutes, but the processing time can be further reduced by using a high temperature, a high pH and using a high concentration of the color developing agent.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further processing in two successive bleach-fix baths,
Fixing before bleach-fixing or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, for example, a compound of a polyvalent metal such as iron (III) is used. A typical bleach is iron (II
Organic complex salts of I), for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol ether diaminetetraacetic acid, or citric acid and tartaric acid And complex salts such as malic acid. Of these, aminopolycarboxylate iron (III) complex salts such as ethylenediaminetetraacetate iron (III) complex salt are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually
4.0 to 8.0, but lower for faster processing
It can be treated at pH.

A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their prebaths, if necessary. Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent 1,290,812, JP-A-53-812.
No. 95630, Research Disclosure No. 17.129 (July, 1978), etc .; compounds having a mercapto group or disulfide bond; thiazolidine derivatives described in JP-A-50-140129; described in U.S. Pat. No. 3,706,561 Thiourea derivatives; iodide salts described in JP-A-58-16235; polyoxyethylene compounds described in West German Patent 2,748,430; polyamine compounds described in JP-A-45-8836; bromide ions, etc. Can be used. Among them, a compound having a mercapto group or a disulfide group is preferable in view of a large accelerating effect, and particularly, U.S. Patent No. 3,893,858,
Compounds described in West German Patent No. 1,290,812 and JP-A-53-95630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether-based compounds, thioureas, and a large amount of iodide.The use of thiosulfates is common,
In particular, ammonium thiosulfate can be used most widely. Preservatives for the bleach-fix solution include sulfites and bisulfites, p
-Sulfinic acids such as toluenesulfinic acid or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the material used, such as a coupler), the application, the rinsing water temperature,
It can be set in a wide range depending on the number of washing tanks (number of stages), a replenishment method such as countercurrent flow, forward flow, and other various conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the Society of Motion Picture and T
It can be determined by the method described in elevision Engineers, Vol. 64, pp. 248-253 (May, 1955).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, the method of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively as a solution to such a problem. Also, isothiazolone compounds, thiabendazoles, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles described in JP-A-57-8542, Hiroshi Horiguchi, "Bactericidal and antifungal chemistry," 1986
Year) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Antimicrobial and Antifungal Society, "Encyclopedia of Antimicrobial and Antifungal Agents" (1986) A bactericide can also be used.

In the processing of the light-sensitive material of the present invention, the pH of the washing water is from 4 to
9, preferably 5 to 8. Washing water temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the use, etc., but in general, 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of 30 seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization process, Japanese Unexamined Patent Application Publication No.
Known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can all be used.

Further, after the above-mentioned water washing treatment, a stabilization treatment may be further carried out. For example, a stabilizing bath containing formalin and a surfactant used as a final bath of a color light-sensitive material for photography can be mentioned. . Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.
In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline compounds described in U.S. Patent No. 3,342,597, 3,342,599, Research Disclosure Nos. 14,850 and 15,159, Schaff base type compounds described therein, aldol compounds described in U.S. Patent No. Complex, JP 5
Examples thereof include urethane compounds described in 3-135628.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-1444547, and JP-A-58-144547.
No. 15438.

The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to. Further, in order to save silver of the light-sensitive material, a process using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

(Examples) Hereinafter, the present invention will be described specifically with reference to Examples.
The present invention is not limited to this.

Example 1 A multilayer color photographic paper A having the following layer constitution was produced on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

Preparation of First Layer Coating Solution To 19.1 g of the yellow coupler compound example (I-7), 27.2 cc of ethyl acetate and 8.2 g of a solvent (solv-3) were added and dissolved, and this solution contained 8 cc of 10% sodium dodecylbenzenesulfonate. It was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution. On the other hand, silver chlorobromide emulsion (silver bromide 80.0 mol%, cubic;
With an average grain size of 0.85 μm and a coefficient of variation of 0.08, silver bromide 80.0%, cubic; average grain size of 0.62 μm, a coefficient of variation
A mixture of 0.07 and a ratio of 1: 3 (Ag mole ratio) was sulfur sensitized, and the following blue-sensitizing sensitizing dye was added in an amount of 5.0 × 10 ^-4 mol per mol of silver. did. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the following composition.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

 The following were used as spectral sensitizing dyes for each layer.

The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer per mole of silver halide.
4.0 × 10 ⁻⁶ mol, 3.0 × 10 ⁻⁵ mol, 1.0 × 10 ⁻⁵ mol or 2-methyl-5-t-octylhydroquinone was added to each of 8 × 10 ⁻³ mol and 2 × 10 ⁻ mol per mol of silver halide. ² mol and 2 × 10 ^-2 mol were added.

Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1.2 × 10 ^-2 mol, 1.1 ×
10 ^-2 mol was added.

Further, to the red-sensitive emulsion layer, the following mercaptoimidazoles were added in an amount of 2 × 10 ^-4 mol per mol of silver halide, and the following mercaptothiadiazoles were added in an amount of 4 × 10 ^-4 mol per mol of silver halide.

The following dyes were added to the emulsion layer to prevent irradiation.

(Layer Configuration) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [Polyethylene on the first layer side contains white dye (TiO ₂ ) and bluish dye (ultra blue)] First layer (blue-sensitive layer) Silver chlorobromide emulsion (AgBr: 80 mol%) 0.26 gelatin 1.83 yellow coupler (ExY) 0.83 solvent (Solv-3) 0.36 second layer (color mixture prevention layer) gelatin 0.99 color mixture inhibitor (Cpd-4) 0.08 solvent (Solv-1) 0.16 solvent (Solv-3) 0.08 Third layer (green-sensitive layer) Silver chlorobromide emulsion (AgBr 90 mol%, cubic, average grain size 0.47 μm, variation coefficient 0.12, AgBr90 mol%, cubic, average grain size 0.36 μm, variation coefficient 0.09 0.16 Gelatin 1.79 Magenta coupler (ExM) 0.32 Color image stabilizer (Cpd-1) 0.02 Color image stabilizer (Cpd-2) 0.20 Color image stabilizer (Cpd) -3) 0.01 Color image stabilizer (Cpd-7) 0.03 Color image stabilizer (Cpd-8) 0.04 Solvent (Solv-2) 0.6 5 Fourth layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorbing agent (UV-1) 0.47 Color mixing inhibitor (Cpd-5) 0.05 Solvent (Solv-4) 0.24 Fifth layer (red sensitive layer) Silver chlorobromide emulsion ( AgBr70mol%, cubic, average particle size 0.49μm, variation coefficient 0.08 and AgBr70mol%, cubic, average particle size 0.34μm, variation coefficient 0.10 are mixed in a ratio of 1: 2 (Ag molar ratio) 0.23 Gelatin 1.34 Cyan coupler (ExC) 0.30 Color image stabilizer (Cpd-5) 0.17 Color image stabilizer (Cpd-6) 0.40 Solvent (Solv-5) 0.20 Sixth layer (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorber ( UV-1) 0.16 Color mixture inhibitor (Cpd-4) 0.02 Solvent (Solv-4) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic-modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03 Next, a sample B was prepared in the same manner as the sample A except that the additives shown in Table 1 were added to the emulsified dispersion and the solvent was changed.
~ O was produced.

A sensitometer (Fuji Photo Film Co., Ltd., FWH
Using a mold and a color temperature of a light source of 3200 ° K), a gradation exposure of a three-color separation filter for sensitometry was given. The exposure at this time was performed so that the exposure amount was 250 CMS with an exposure time of 0.1 second.

The sample after exposure was processed using an automatic developing machine using a solution having the following processing step and processing solution composition.

Processing temperature Time Color development 37 ° C 3 minutes 30 seconds Bleaching and fixing 33 ° C 1 minute 30 seconds Washing 24-34 ° C 3 minutes Drying 70-80 ° C 1 minute The composition of each processing solution is as follows.

Color developer Water 800 ml Diethylenetriaminepentaacetic acid 1.0 g Nitrilotriacetic acid 2.0 g Benzyl alcohol 15 ml Diethylene glycol 10 ml Sodium sulfite 2.0 g Potassium bromide 1.0 g Potassium carbonate 30 g N-ethyl-N- (β-methanesulfonamidoethyl) -3- Methyl-4- aminoaniline sulfate 4.5 g Hydroxylamine sulfate 3.0 g Fluorescent whitening agent (WHITEX 4B, manufactured by Sumitomo Chemical) 1.0 g Add water 1000 ml pH (25 ° C) 10.25 Bleaching fixer Water 400 ml Ammonium thiosulfate (700 g /) 150ml Sodium sulfite 18g Ammonium iron (III) ethylenediaminetetraacetate 55g Disodium ethylenediaminetetraacetate 5g Add water 1000ml pH (25 ℃) 6.70 Reflect the yellow dye concentration of each sample obtained through a blue filter through a reflection type densitometer Was measured. Next, when the sample was stored at 80 ° C. and 75% RH for 15 days, and when stored under sunlight for one month, the residual ratio of the initial density of yellow at 2.0 was measured and the results are shown in Table 1.

From Table 1, it can be seen that the light-sensitive material having the polymer of the present invention and the hindered amine compound simultaneously and remarkably improved the light fading and the wet heat fading without lowering the color developing property of yellow as compared with the case where they were individually added. .

Example 2 A multi-layer color photographic paper A having the following layer constitution was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

Preparation of First Layer Coating Solution To 19.1 g of the yellow coupler compound example (I-7), 27.2 cc of ethyl acetate and 8.2 g of a solvent (Solv-1) were added and dissolved.
This solution is 10% sodium dodecylbenzenesulfonate
It was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc.
On the other hand, a silver chlorobromide emulsion (cubic, 3: 7 mixture (average grain ratio) of 0.88 μm and 0.70 μm) (silver molar ratio) The coefficient of variation of the particle size distribution is 0.08 and 0.10, and each emulsion is silver bromide The following blue-sensitive sensitizing dye is contained in the emulsion having a large size per mole of silver.
2.0 × 10 ⁻⁴ mol was added to each of the emulsions, and for small-sized emulsions, 2.5 × 10 ⁻⁴ mol was added and then subjected to sulfur sensitization. The above-mentioned emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the following composition.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardener for each layer, 1-
Oxy-3,5-dichloro-s-triazine sodium salt was used.

 The following were used as spectral sensitizing dyes for each layer.

(Per mole of silver halide, 2.0 × 10 ^-4 mol for large-size emulsion or 2.5 × 10 ^-4 mol for small-size emulsion, respectively) (Per mole of silver halide, for large emulsions
4.0 × 10 ^-4 mol, 5.6 × 10 ^-4 mol for small size emulsion) and (Per mole of silver halide, for large emulsions
7.0 × 10 ^-5 mol, or 1.0 × 10 for small size emulsions
^-5 mol) (Per mole of silver halide, for large emulsions
0.9 × 10 ^-4 mol, and 1.1 × 10 ^-4 for small size emulsions
The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Also, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer per mole of silver halide.
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added.

The following dyes were added to the emulsion layer to prevent irradiation.

(Layer Configuration) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). Silver halide represents a silver equivalent coating amount.

Support Polyethylene laminated paper [The first layer side polyethylene contains white pigment (TiO ₂ ) and bluish dye (ultra blue)] First layer (blue sensitive layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (I -7) 0.82 Solvent (Solv-1) 0.35 Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture inhibitor (Cpd-4) 0.08 Solvent (Solv-1) 0.16 Solvent (Solv-3) 0.08 Third layer (green color) Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of 0.55 μm average grain size and 0.39 μm emulsion (Ag molar ratio). Variation coefficient of grain size distribution is 0.10 and 0.08, AgBr for each emulsion)
0.12 Gelatin 1.24 Magenta coupler (ExM) 0.20 Color image stabilizer (Cpd-1) 0.03 Color image stabilizer (Cpd-2) 0.15 Color image stabilizer (Cpd-3) 0.02 Color image stabilizer (Cpd-8) 0.02 Solvent (Solv-2) 0.40 Fourth layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorbing agent (UV-1) 0.47 Color mixing inhibitor (Cpd-4) 0.05 Solvent (Solv) -4) 0.24 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of 0.58 µm and 0.45 µm in average grain size, Ag molar ratio) Variation in grain size distribution Coefficients are 0.09 and 0.11, AgBr for each emulsion
0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-5) 0.17 Color image stabilizer (Cpd-6) 0.40 Color image stabilizer ( Cpd-7) 0.04 Solvent (Solv-5) 0.15 Sixth layer (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixture inhibitor (Cpd-4) 0.02 Solvent (Solv-4) 0.08 Seventh layer (Protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03 Next, with respect to the coupler emulsified dispersion of the first layer, Samples B to O were prepared in the same manner as Sample A except that the additives shown in Table 2 were added and the coupler and the solvent were changed.

First, each sample was subjected to gradation exposure of a three-color separation filter for sensitometry using a sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K). The exposure at this time was performed so that the exposure amount was 250 CMS with an exposure time of 0.1 second.

The exposed sample was subjected to continuous processing (running test) using a paper processor until the replenishment was twice the tank capacity for color development in the next processing step.

Processing process temperature time replenisher ^* tank capacity color phenomenon 35 ℃ 45 seconds 161ml 17 Bleaching and fixing 30-35 ℃ 45 seconds 215ml 17 rinse 30-35 ℃ 20 seconds -10 rinse 30-35 ℃ 20 seconds -10 rinse 30-35 ℃ 20 sec 350 ml 10 drying 70 to 80 ° C. 60 seconds * replenishment rate (for three tank countercurrent system of the rinsing →.) per photosensitive material 1 m ² is had the following composition of each processing solution.

Bleach-fix solution (same as tank solution and replenisher) Water 400ml Ammonium thiosulfate (700g /) 100ml Sodium sulfite 17g Ammonium iron (III) ethylenediaminetetraacetate 55g Disodium ethylenediaminetetraacetate 5g Ammonium bromide 40g Add water 1000ml pH ( 6.0 rinsing solution (the same as the tank solution and the replenishing solution) Ion-exchanged water (calcium and magnesium are each 3 ppm or less) The yellow dye concentration of each of the obtained samples was measured with a reflection type densitometer through a blue filter. Next, when the sample was stored at 80 ° C. and 70% RH for 30 days and when stored under sunlight for 3 months, the residual ratio of the initial density of yellow at 2.0 was measured and the results are shown in Table 2.

From Table 2, it can be seen that the light-sensitive material having the polymer of the present invention and the hindered amine compound simultaneously and significantly improved light fading and wet heat fading without lowering the yellow color developability as compared with the case where they were added alone. .

(Effect of the Invention) According to the present invention, a color photograph having a high maximum color density and excellent fastness against light and wet heat can be obtained.

Continuation of the front page Judge of the Joint Panel Judge Takanashi Judge Yasuko Eto Judge Koshi Ueno (56) References JP-A-61-6652 (JP, A) JP-A-63-147533 (JP, A) JP-A 62- 75450 (JP, A) JP-A-1-177548 (JP, A) JP-A-64-537 (JP, A)

Claims (1)

(57) [Claims] In a silver halide color photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers is represented by the general region (I). Yellow coupler and general formula (II)
A silver halide color photographic light-sensitive material comprising a polymer represented by formula (III) and a compound represented by formula (III): In the formula, R ² and R ⁵ may be the same or different and represent a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms or a halogen atom. R ³ and R ⁴ may be the same or different and represent a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group. However,
The total number of carbon atoms of R ³ and R ⁴ is 2 or more, and R ³ and R ⁴ may be linked to each other to form a nitrogen-containing heterocycle. L represents a divalent linking group. L 'represents a substituted or unsubstituted hydrocarbon chain which forms a ring together with an oxygen atom and is connected to L. A represents a repeating unit derived from an ethylenically unsaturated monomer other than the above. x, y, z represent the weight percentage of each component, x represents 20 to 99, y represents 1 to 80, and z represents 0 to 50. In the formula, R ⁶ is a hydrogen atom, a hydroxyl group, an oxy radical group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylsulfinyl group, an arylsulfur Represents a nyl group, an alkylsulfonyl group, a carbamoyl group, a sulfamoyl group or an arylsulfonyl group. R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be the same or different and each represents an alkyl group. A represents a nonmetallic atom group necessary to form a 5-, 6- or 7-membered ring. Here, R ⁷ and R ⁸ , R ⁹ and R ¹⁰ , R ⁶ and R ⁷ , or R ⁷ and A may be bonded to each other to form a 5- or 6-membered ring.