JPH03150560A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain an image small in dye stains, superior in color reproducibility, small in variation of photographic performances during storage, and superior in graininess and sharpness by incorporating a specified compound in a photographic constitutent layer. CONSTITUTION:At least one of the photographic constituent layers contains the compound not developing color and being hardly diffuible and represented by formula I in which X is -SO2 or the like; Z is an atomic group necessary to form a ring together with the group of formula II; R1 is H, sulfonyl, or the like; and R2 is H or a substituent, thus permitting the obtained silver halide color photographic sensitive material to be small in dye stains, superior in color reproducibility, small in variation of photographic performance during storage, and superior in graininess and sharpness.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material, and particularly to a silver halide color photographic light-sensitive material containing a novel color stain inhibitor.

[Prior art]

When a multilayer color photographic material containing a color-forming coupler in a silver halide photographic material is developed using a color developing agent such as phenylene diamine, the color developing agent oxide produced during development causes the adjacent images to It is well known that the phenomenon of so-called "color turbidity" (color mixing) occurs, in which undesirable pigments are formed by migration into the forming layer. Furthermore, it is known that during color development, the oxidation of the developing agent, capri of the emulsion, etc. cause an undesirable phenomenon of "R color fog". In the following, this "color turbidity" and "color fog" will be collectively referred to as "color contamination."

In order to prevent color staining, it is recommended to use hydrazide compounds as disclosed in JP-A-62-27731 and JP-A-1-14745.
5, EP-338,785,
The effect cannot be said to be sufficient, and there are also problems such as changes in photographic performance during storage.

[Purpose of the invention]

The purpose of the present invention is, firstly, to provide a photosensitive material with less color staining and excellent color reproducibility, secondly, to provide a photosensitive material with less change in photographic performance during storage, and thirdly, to provide a photosensitive material with little change in photographic performance during storage.
The fourth objective is to provide a photosensitive material with excellent graininess.
An object of the present invention is to provide a photosensitive material with excellent sharpness.

[Structure of the invention]

The above objects of the present invention have been achieved by a silver halide color photographic material having the following structure.

A photograph comprising, on a support, at least one blue-sensitive silver halide emulsion layer each containing a yellow coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a red-sensitive silver halide emulsion layer containing a cyan coupler. In a silver halide color photographic light-sensitive material having constituent layers, at least one of the constituent layers is non-color-forming and diffusion-resistant.
A silver halide color photographic material containing a compound represented by I].

- Formation [I) The atomic group required for R1 is hydrogen atom, sulfonyl group or acyl group, R2 represents a hydrogen atom or a substituent.

Next, a compound represented by one type [I] will be explained in detail.

In the formula, X is preferably -C-1-802-, and 1 More preferably -C-.

The ring formed by 1 Z is preferably a 5- to 7-membered ring, particularly a 5- to 6-membered ring, and the ring may be saturated or unsaturated, or may have a substituent or be fused with another ring. etc.

Examples of the ring formed by Z include those having the following ring structure.

Examples of other rings bonded to the ring formed by Z include a benzene ring, a naphthalene ring, and a heterocycle.

Substituents on the ring formed by 2 include, for example, alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, etc. In addition, halogen atoms and nitro, hydroxyl , cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano,
Alkoxy, aryloxy, heterocyclicoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylulamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio Also included are polygroups, spiro compound residues, bridged hydrocarbon compound residues, and the like.

The alkyl group preferably has 1 to 32 carbon atoms, and may be linear or branched.

As the aryl group, a phenyl group is preferred.

Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group include the above-mentioned alkyl groups and aryl groups.

The alkenyl group preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched.

The cycloalkenyl group has 3 to 12 carbon atoms, especially 5
-7 is preferred.

Sulfonyl groups include alkylsulfonyl groups, arylsulfonyl groups, etc.; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, aryloxyphosphonyl groups, and arylphosphonyl groups. Examples of nearacyl groups include alkylcarbonyl groups, arylcarbonyl groups, etc.; carbamoyl groups include alkylcarbamoyl groups, arylcarbamoyl groups, etc.; sulfamoyl groups include alkylsulfamoyl groups,
Arylsulfamoyl group; As an acyloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc.; As a carbamoyloxy group, an alkylcarbamoyloxy group, an arylcarbamoyloxy group, etc.; As an ureido group, an alkylureido group, an arylureido group, etc.; Examples of the sulfamoylamino group include an alkylsulfamoylamino group and an arylsulfamoylamino group; as the heterocyclic group, a 5- to 7-membered group is preferable; specifically, a 2-furyl group, a 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.; the heterocyclic oxy group preferably has a 5- to 7-membered heterocycle, for example, 3,
4,5.6-tetrahydrobilanyl-2-oxy group, ■
-Phenyltetrazole-5-oxy group, etc.; The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, such as 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1 , 3,5-triazole-6 monothio group, etc.; Siloxy groups include trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; imide groups include succinimide group, 3-heptadecylsuccinimide group, phthalimide group. group, glutarimide group, etc.

The compound represented by general formula (1) has a partial structure in its molecule that promotes adsorption to silver halide grains, or has a diffusion-resistant coupler or the like in the substituent of the ring formed by 2. It is preferable that a diffusion-resistant group (ballast group), which is commonly used in photographic additives, is incorporated.

The ballast group is a group having 8 or more carbon atoms and is relatively inert to photography, such as an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, an ether group, an amide group, etc. group, ureido group, urethane group, sulfonamide group, thioether group, etc., and combinations of these groups.

Partial structures that promote adsorption to silver halide grains include heterocycles containing nitrogen or sulfur atoms (e.g., imidazole, triazole, tetra-1-zole, pyrimidine, indazole, benzimidazole, benzotriazole, oxazole, thiazole,
benzothiazole, tetrazaindene, pentazaindene, etc.), partial structures having a mercapto group (e.g., thiophenol, mercaptoimidazole, mercaptotriazole, mercaptotetrazole, mercaptothiazole, mercaptooxazole, mercaptobenzimidazole, mercaptobenzoxazole, mercaptobenzo) thiazole, mercaptopyridine, mercaptopyrimidine, mercaptothiadiazole, etc.), thiourea,
Examples include thioethers or quaternary ammonium salts (eg, benzimidazolium salts, benzoxacillium salts, benzothiazolium salts, pyridinium salts, etc.).

Examples of the sulfonyl group represented by R1 include an alkylsulfonyl group (preferably a linear or branched one having 1 to 20 carbon atoms), a cycloalkylsulfonyl group, and an arylsulfonyl group (preferably one having 196 to 20 carbon atoms). , specifically phenylsulfonyl, naphthylsulfonyl, etc.).

The acyl group represented by R1 preferably has 1 to 2 carbon atoms.
0 aliphatic carbonyl groups (eg, alkylcarbonyl, etc.), cycloalkylcarbonyl groups, arylcarbonyl groups (eg, benzoyl, etc.), and the like.

The sulfonyl group and acyl group represented by R1 include those having a substituent.

A hydrogen atom is particularly preferred as R□.

Examples of the substituent represented by R2 include an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an amino group, an alkoxycarbonyl group, an aryloxycarbonyl group, and a carbamoyl group. Examples include groups.

The alkyl group represented by R3 preferably has 1 to 30 carbon atoms, and may be linear or branched, and specifically includes methyl, ethyl, butyl, t-butyl, octyl, dodecyl, octadecyl, etc. The cycloalkyl group is, for example, a cycloalkyl group, the aryl group is preferably one with 6 to 30 carbon atoms, specifically phenyl, naphthyl, etc., and the heterocyclic group is preferably one with 1 carbon number. -12, specifically imidazolyl, pyridyl, etc., and the alkoxy group preferably has 1 to 30 carbon atoms, specifically methoxy, ethoxy, octyloxy, dodecyloxy, benzyloxy, etc. Examples of cycloalkyloxy groups include cyclohexyloxy, aryloxy groups preferably have 6 to 30 carbon atoms, specifically phenoxy, naphthyloxy, etc., and amino groups include It preferably has 0 to 30 carbon atoms, specifically amino, methylamino, phenylamino, etc., and the alkoxycarbonyl group preferably has 1 to 30 carbon atoms.
Examples of aryloxycarbonyl include ethoxycarbonyl, octyloxycarbonyl, dodecyloxycarbonyl, benzyloxycarbonyl, etc. Aryloxycarbonyl preferably has 1 to 30 carbon atoms, such as phenoxycarbonyl, naphthyloxycarbonyl, etc. The carbamoyl group preferably has 1 to 30 carbon atoms.
Examples include carbamoyl, N,N-diethylcarbamoyl, and phenylcarbamoyl.

The multiple groups represented by R2 include those having substituents.

Specific examples of the compound represented by general formula (1) are described below, but the present invention is not limited to these. ) (18) (22) (28) (31) (33) (35) (38) (39) 2:3 Next, a synthesis example of the compound according to the present invention will be shown.

Example 1 (Synthesis of Exemplified Compound 7) The synthesis scheme is as follows.

5-amino-6-azacytosine log and pyridine 8+
nQ was suspended in ethyl acetate 100ii4, and 17.5 g of p-nitrobenzoyl chloride was added dropwise to the suspension while stirring at room temperature.

After the reaction, the reaction solution was washed with water, and the separated ethyl acetate layer was concentrated to obtain crude crystals.

The crude crystals were recrystallized from acetonitrile to form compound (I
) 21.5g was obtained.

21.5 g of compound (I) was added to 1.5 g of tetrahydro7ran.
Compound (II) 1 was dissolved in 150 mα of ethanol and subjected to catalytic reduction using 2 g of 5% palladium on carbon as a catalyst.
7.9g was obtained.

17.9 g of compound (n) and 7 ml of pyridine were suspended in 150 ml of acetonitrile, and while stirring at room temperature, the compound (III) was diluted with 30 ml of acetonitrile.
) was added dropwise.

After the reaction, the reaction solution was suspended in 800 mL of water and the precipitated crystals were collected by filtration. The crude crystals were suspended with acetonitrile under heating to obtain 36.2 g of compound (7).

Identification of compounds (1), (n), and (7) was performed using FAB-MA.
Performed by SS spectra, each M'''=262.
M"=231, M"+1=507 were detected.

It was further confirmed by 'HNMR spectrum and IR spectrum.

Example 2 (Synthesis of Exemplified Compound 24) The synthesis scheme is as follows.

Convex 4-aminophthalhydrazide 14.2g and pyridine 7
, 2m4 in ethyl acetate J, 00mff and stirred at room temperature +4? Into the solution, 18.6 g of m-nitrobenzenesulfonyl chloride was added dropwise.

After the reaction, ethyl acetate 1001 was added to the reaction solution, washed with water, and the separated ethyl acetate layer was concentrated to obtain crude crystals. Ethyl acetate, this crude crystal! Recrystallization was performed using a l:l mixed solvent of n-hexane to obtain 25.2 g of compound (I).

25.2 g of Compound (1) was suspended in 300 ml of ethanol, and catalytic reduction was performed using 2.5 g of 5% palladium on carbon as a catalyst to obtain 22.4 g of Compound (II).

22.4 g of compound (II) and 6 mQ of pyridine were dissolved in 200 mQ of acetonitrile, and while stirring at room temperature,
12.7 g of compound (m) was added dropwise.

After the reaction, acetonitrile was distilled off and 300ml of ethyl acetate was added.
12 was added, washed with water, and the separated ethyl acetate layer was concentrated to obtain crude crystals. The crude crystals were recrystallized from acetonitrile to obtain 29.4 g of compound (24).

Identification of compounds (1), (II), (24) was performed using FAB
- performed by MASS spectra, each M + = 3
63. M"+1-334. M"+1=475 was detected.

It was further confirmed by 'HNMR spectrum and IR spectrum.

In addition to the above-mentioned photosensitive silver halide emulsion layer, the photographic constituent layers in the photographic light-sensitive material of the present invention include an intermediate layer located between a plurality of photosensitive silver halide emulsion layers, and a plurality of photosensitive silver halide emulsion layers. a protective layer located on the opposite side of the layer from the support;
Examples include an antihalation layer and an undercoat layer located between the plurality of photosensitive silver halide emulsion layers and the support.

The color stain preventive agent according to the present invention can be added as a color fog preventive agent to an emulsion layer containing a photographic coupler and a photosensitive silver halide or an intermediate layer between emulsion layers having the same color sensitivity. Further, as a color turbidity preventing agent, it is preferable to add it to an intermediate layer provided between emulsion layers having different color sensitivities.

When the compound according to the present invention is used as a color antifoggant, per layer], ox to-'-1,0X 10-
'Mo127m2 is preferable, and when used as a color turbidity preventive agent, per layer], OX 10-
Although it is preferable to use 1.0 x 10-'mo47 m'', the present invention is not limited thereto.

Furthermore, it can be added to both the intermediate layer and the emulsion layer to prevent color fog and color turbidity.

The compound according to the present invention may be used in combination with various color stain inhibitors other than the present invention (for example, hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives, sulfonamide derivatives, etc.).

The compounds according to the invention can be introduced into the photographic constituent layers by various methods, such as those used for introducing couplers into emulsion layers, such as by using high-boiling solvents and/or boiling points of 30°C to 15°C.
It is possible to use a method of dissolving it in a low boiling point solvent at 0°C and then dispersing it in a hydrophilic colloid.

The silver halide photographic material of the present invention can be, for example, color negative and positive films, color photographic paper, and the like.

The silver halide photographic material of the present invention has a structure in which a silver halide emulsion layer containing magenta, yellow, and cyan couplers as couplers and a non-light-sensitive layer are laminated on a support in an appropriate number and layer order. However, the calendar number and layer order may be changed as appropriate depending on the important performance and purpose of use.

The coupler may be 4-equivalent or 2-equivalent.

Furthermore, by coupling with a coupler having a color correction effect, a competitive coupler, and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, and a fogging agent can be produced. Compounds that release photographically useful fragments such as agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers can also be used.

A coupling reaction with an oxidized product of an aromatic primary amine developer is carried out, but a colorless coupler that does not form a dye can also be used in combination.

Preferred yellow couplers include benzoylacetanilide type and piparoylacetanilide type couplers; magenta couplers include 5-pyrazolone type, pyrazoloazole type and indasilone type couplers; and cyan dye-forming couplers include phenol type and naphthol type couplers. Coupler types include pyrazoloquinazolone, pyrazolopyrimidine, pyrazolotriazole, and imidazole couplers.

Next, typical specific examples of yellow couplers are given.
2.163.812, JP 47-26133, JP 48-29432, JP 50-65321, JP 51-
No. 3631, No. 51-50734, No. 51-1026
No. 36, No. 48-66835, No. 48-94432, No. 49-1229, No. 49-10736, Japanese Patent Publication No. 51-33410, No. 52-25733, etc. And it can be synthesized according to the methods described therein.

Next, a typical example of a magenta coupler will be given.

5 -66 - -8 -9 0 -11 2 17 8 -19 =39- 0 3 0 -24 5 -26 -27 In addition to these, examples of magenta couplers include U.S. Patent No. 3,684.514 and British Patent No. 1.183.515
No., Special Publication No. 40-6031, No. 40-6035, No. 44-15754, No. 45-40757, No. 46-
No. 19032, JP-A-50-13041, JP-A No. 53-1
No. 29035, No. 51-37646, No. 55-624
No. 54, US Patent No. 3,725,067, British Patent No. 1,
No. 252.418, No. 1.334,515, Japanese Unexamined Patent Publication No. 1973
No. 9-171956, No. 59-162548, No. 60
-43659, 60-33552, Research Disclosure No. 24626 (1984),
Patent Application No. 59-243007, No. 59-243008, No. 59-243009, No. 59-243012,
Examples include compounds described in Japanese Patent No. 60-70197 and Japanese Patent No. 60-70198, and can be synthesized according to the methods described therein.

A typical example of a cyan coupler is given below.

-4 C-5 1 43 L -8 -9 -10 4 -13 -14 0 to t12L; t12+1J21,4137- 22 7 Other cyan couplers include, for example, U.S. Pat.
, No. 423,730, No. 2,801.171, JP-A-50-112038, No. 50-134644, No. 5
No. 3-109630, No. 54-55380, No. 56-
No. 65134, No. 56-80045, No. 57-155
No. 538, No. 57-204545, No. 58-9873
1, No. 59-31953, etc., and can be synthesized according to the methods described therein.

The silver halide emulsion used in the light-sensitive material of the present invention includes:
Any of the conventional silver halide emulsions can be used.

The emulsion can be chemically sensitized by conventional methods, and can be optically sensitized to a desired wavelength range using a sensitizing dye.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

=48 The emulsion layer and other hydrophilic colloid layers can be hardened, and can also contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process.

A formalin scavenger-1 optical brightener, a matting agent, a lubricant, an image stabilizer, a surfactant, a development accelerator, a development retardant, and a bleach accelerator can be added to the photosensitive material.

As a support, paper laminated with polyethylene, etc.
Polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

To obtain a dye image using the photosensitive material of the present invention, after exposure,
A color development process including a color development step (preferably using an aromatic primary amine color developing agent) can be performed.

〔Example〕

EXAMPLES The present invention will be explained below with reference to examples, but the present invention is not limited only to the following examples.

Example 1 The following layers were sequentially applied from the support side onto a paper support laminated on both sides with polyethylene to obtain multicolor silver halide photosensitive material sample 101.

1st layer: Blue-sensitive silver halide emulsion layer Yellow coupler (Y-9) 6.8mg/loOc
m", blue-sensitive silver chlorobromide emulsion (containing 99.5 mol% silver chloride) 3.2 mg/100 cm" in terms of silver, dibutyl phthalate 3.5 mg/100 cm2, gelatin 13.5
The coating was applied so that the coating amount was mg/100 cm2.

2nd layer: Intermediate layer Comparative compound (a) 0.75 mg/look, dibutyl 7 talate 5 mg/I 00 cm, and gelatin 9.0 mg/100 cm.

Third layer: Green-sensitive silver halide emulsion layer Magenta coupler (M 17) 3.5mg/100
cm'', green-sensitive silver chlorobromide emulsion (containing 99.5 mol% silver chloride), converted to silver, 2.5 mg/100 cm'', dibutyl phthalate 3.0 mg/100 cm'', gelatin 12.
The coating was applied so that the concentration was 0 mg/locm2.

4th layer: Intermediate layer ultraviolet absorber (UV-1) 0.7mg/100c
m”, dibutyl phthalate 6.0 mg/100 cm’,
2.5-di-L-octylhydroquinone (HQ l
) 0.5mg/100cm”, gelatin 12.0m
g/100 cm".

5th layer: Red-sensitive silver halide emulsion layer Cyan coupler (C-3) 4.2mg/100cm"
, red-sensitive silver chlorobromide emulsion (containing 99.5 mol% silver chloride) 3.0 mg/100 cm2 in terms of silver, tricresyl phosphate 3.5 mg/100 cm2, gelatin 11
．． 5 mg/100 cm".

6th layer: Protective layer gelatin was coated at 8.0 mg/100 cm2.

In addition, the comparative compound (a) in the second layer of sample 101 was changed to the color stain preventive agent shown in Table 1 (added in an equimolar amount), and sample 102
~106 were produced.

Each sample obtained above was subjected to imagewise exposure with blue light and processed in the following steps.

Processing process Temperature Time Development color development 3
5.0±0.3°O 45 seconds bleach fixing 35.0±0,
5℃ 45 seconds stabilization 30~34°0 90
Dry for seconds Naturally dry at room temperature (25℃) Color developer Pure water 800ml + Triethanolamine 10gN,N
-Diethylhydroxylamine 5g Potassium bromide 0.02g Potassium chloride 2g Potassium sulfite
0.3g 1-hydroxyethylidene-1-1 diphosphonic acid 1.0g ethylenediaminetetraacetic acid 1.0g catechol-3,5-disulfonic acid disodium salt 1.0gN-
Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5g optical brightener (4.4'
-diaminostilbendisulfonic acid derivative)
1.0g potassium carbonate
Add 27g of water to bring the total volume to 14, and pH = 10.
Adjust to 10.

Bleach-fix solution Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% aqueous solution) 100ml
Ammonium bisulfite (40% aqueous solution) 27.5
Add mff water to bring the total volume to 1Q, and adjust to pH = 6.2 with potassium carbonate or glacial acetic acid.

Stabilizing liquid 5-chloro-2-methyl-4-isothiazolin-3-one 1.0g ethylene glycol 1. Ogl-Hydroxyethylidene-1.1 Diphosphonic acid 2.0g Ethylenediaminetetraacetic acid 1.0g Ammonium hydroxide (20% aqueous solution) 3.0g Ammonium sulfite 3.0g Optical brightener (4,4'
-diaminostilbendisulfonic acid derivative)
Add 1.5 g of water to bring the total volume to 112, and adjust the pH to 7.0 with sulfuric acid or potassium hydroxide.

The treated sample was measured using a densitometer (PDA-65 manufactured by Konica Corporation).
The color mixture value (D c/D a
) are shown in Table 1 with sample 101 set as 100.

Table 1 From Table 1, it can be seen that the sample of the present invention has significantly improved color mixing compared to the comparative sample.

Comparative compound (a) Comparative compound (b) Also, instead of exemplified compound (3) of sample 103, (15)
, (17), (23), and (39), the effects of the present invention were also observed.

Example 2 Each sample used in Example 1 was stored at 60°C in the dark and at a relative humidity of 8
After being left at 0% high temperature and high humidity for 3 days, it was exposed and processed in the same manner as in Example 1. Fog was measured by a conventional method. In addition, in order to observe the variation in color mixture, the above test was a forced deterioration test to check the storage stability of each sample. Correlates with the long-term storage stability of each sample below.

From Table 2, it can be seen that the samples of the present invention have less fog and less variation in color mixture value than the comparative samples, and have good storage stability.

Example 3 A multilayer color film sample 3 old having the layer structure shown below was formed by layering it on a support coated with an antihalation layer.

Layer structure: Pro layer, BH layer, BL layer, YF layer, GH
layer, GL layer, IL layer, RH layer, RL layer, support 56 Next, RL layer, RH layer, GL layer, GH layer, BL layer, B H
The following describes the layers, IL layer, YF layer, and Pro layer. The amount added is shown per 1 m2. Further, the amounts of silver halide and colloidal silver are shown in terms of silver.

RL layer (low sensitivity red-sensitive silver halide emulsion layer) average grain size (
〒) 0.47p m, coefficient of variation (S/r) 0.12,
An emulsion (emulsion I) consisting of AgBr I containing an average of 8 mol % of Agl was color sensitized to red sensitivity.1. Og, average grain size 0.3177 m, coefficient of variation 0.10. Average Agl
Emulsion consisting of AgBr l containing 8 mol% (emulsion 11)
1.0 g and 0.07 g of 1-hydroxy-4-(4
-(1-hydroxy-8-acetamido-3,6-disulfo-2-naphthylazo)phenoxy)-N-[:δ-
(2,4-di-t-amylphenoxy)butyl-2-
Nafamide disodium (referred to as cc-1), 0.4
g of cyan coupler (C-12) and 0.06 g of DI
Contains a dispersion in which R compound (D-1) is dissolved in 1.0 g of tricresyl phosphate (TCP) and emulsified and dispersed in an aqueous solution containing 2.4 g of gelatin. layer.

RH layer (high sensitivity red-sensitive silver halide emulsion layer) average grain size 0
．． 7 p m, coefficient of variation 0.12, average Agl 6 mol%
2.0 g of a red-sensitized emulsion (emulsion ■) consisting of AgBr I containing A layer containing a dispersion obtained by dissolving 0.23 g of TCP and emulsifying and dispersing it in an aqueous solution containing 1.2 g of gelatin.

GL layer (low-sensitivity green-sensitive silver halide emulsion layer) Emulsion ■ sensitized to green sensitivity 1-5gs Emulsion ■ sensitized to green sensitivity 1.5 g and 0.35 g of magenta coupler (M -19), 0.10 g of 1-(2,4,6-dolichlorophenyl)-4-(1-su7tylazo)-3-(
2-chloro-5-octadecenylsuccinimideanilino)-5-pyrazolone (referred to as CM-1) and 0.0
A layer containing a dispersion in which 4 g of DIR compound (D-1) was dissolved and 68 g of TCP was emulsified and dispersed in an aqueous solution containing 264 g of gelatin.

GH layer (high-sensitivity green-sensitive silver halide emulsion layer) 2.0 g of emulsion ■ sensitized to green sensitivity, 0.14 g of magenta coupler (M-19) and 0.45 g of colored magenta coupler (CM) -1) and a dispersion obtained by emulsifying and dispersing 0.27 g of TCP dissolved in an aqueous solution containing 2.4 g of gelatin.

BL layer (low-speed blue-sensitive silver halide emulsion layer) Emulsion I color sensitized to blue sensitivity 0-5g 5 Emulsion ■ color sensitized to blue sensitivity 0.5g and 0.7g yellow coupler (Y -12) and 0.02g of DIR compound (D-1)
and a dispersion obtained by emulsifying and dispersing 0.68 g of TCP dissolved in an aqueous solution containing 1.8 g of gelatin.

BH layer (high sensitivity blue-sensitive silver halide emulsion layer) average grain size 0
．． 80 p m, coefficient of variation 0.14, an emulsion consisting of AgBr I containing 6 mol % on average Agl, 0.9 g of an emulsion sensitized to blue sensitivity and 0.25 g of yellow coupler (
A layer containing a dispersion in which 0.25 g of TCP in which Y-12) was dissolved was emulsified and dispersed in an aqueous solution containing 2.0 g of gelatin.

I L layer (intermediate layer) 0.07 g of dibutyl 7 tallate (referred to as DBP) in which 0.07 g of HQ-1 was dissolved and 0.70 g of gelatin 9
- a layer containing minerals;

YF layer (yellow filter layer) 0.15g yellow colloidal silver, 0.3g comparative compound (
a) dissolved in 0, 11 g of DBP and 1. A layer containing og gelatin.

Pro layer (protective layer) A layer consisting of 2.3 g of gelatin.

D-] Samples 302 to 308 were produced exactly the same as Sample 301, except that the comparative compound (a) in the YF layer of Sample 301 produced in this way was replaced with the color stain preventive agent shown in Table 3 in equimolar amounts. .

After wedge exposure of each sample using blue light, color development was performed according to the processing steps below.

=60- [Processing process] Processing time Color development
38°0 3 minutes 15 seconds Bleach 38°0 6 minutes 30 seconds Wash with water 25-30°C 3 minutes 1
Fix for 5 seconds 38℃
Wash with water for 6 minutes and 30 seconds at 25-30℃
Stabilized for 3 minutes 15 seconds 25-30℃ 1 minute 3
Drying for 0 seconds 75-80°C The composition of the treatment liquid used in each treatment step is as follows.

[Color developer] 4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine l/2 sulfate 2.0 g anhydrous potassium carbonate 37. 5g sodium bromide
1.3g nitrilotriacetic acid trisodium (l hydrate) 2.5g potassium hydroxide
Add 1.0 g of water, close with 1 O, and adjust the pH to 10.6 using sodium hydroxide.

[Bleach solution] Ethylenediaminetetraacetic acid iron ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid
Add 10.0g water and make 1
g, and adjust the pH to -8.0 using aqueous ammonia.

[Fixer] Ammonium thiosulfate 175.0g Anhydrous ammonium sulfite 8.6g Sodium metasulfite 2.3g Water was added to make IQ, and the pH was adjusted to -6.0 using acetic acid.

[Stabilizer] Formalin (37% by weight) 1.5+o
+2 Konidax (manufactured by Konica Corporation) 7.5m
Add Q water to obtain IQ.

For each sample treated above, the color mixture value (D C/D !1) was determined in the same manner as in Example 1, and is shown in Table 3 as a relative value with Sample 301 as 100.

In addition, the samples were subjected to the above development treatment immediately after exposure to white light, and after the exposure, they were left in a dark place at 60°C and 80% relative humidity for 7 days to undergo forced deterioration, and then the above development treatment was performed. The changes in the sensitivity of the red-sensitive layer (the fog of the red density + the logarithm of the reciprocal of the exposure dose at a density of 0°25) of these two types of samples were calculated as the change in sensitivity under forced aging conditions. It is shown in Table-3.

Further, after uniform exposure with red light, exposure was performed with green light in a pattern for measuring the MTF value. The MTF (40 lines/mn+) value of the magenta image was measured using a Konica microdensitometer (Koni 63 Table 3).
1 to 302), color stain prevention according to the present invention.

It was found that those containing the agent had a small color mixture, a small decrease in sensitivity during forced deterioration, and a relatively good sharpness expressed by an MTF value.

Also, instead of exemplified compound (3) of sample 303, (16)
, (38) were also found to have the effects of the present invention.

Example 4 A multilayer color film sample 4 old, which was exactly the same as sample 301 of example 3, was produced, except that the following new intermediate layer was provided between the RL layer and RH layer of sample 301 of example 3.

New intermediate layer A layer containing 0.04 g of DBP and 0.4 g of gelatin in which 0.06 g of comparative compound (a) was dissolved.

Regarding sample 401 prepared in this way, samples 402 to 402, which are exactly the same as sample 401, except that the comparative compound (a) of the newly established intermediate layer was replaced with the compound shown in Table 4 in equimolar amounts.
408 was produced.

Next, the red light sensitivity of each sample and the graininess of the red-sensitive layer (RMS
value) was calculated.

That is, each sample was wedge exposed according to the conventional method,
After performing the same treatment as in Example 3, the optical density with red light was measured using the optical densitometer PAD-65,
Sensitivity was determined from the exposure amount required to give an optical density of "fog +0.5" and was expressed as a relative value with the value of sample 401 as 100.

The RMS value is determined by calculating the standard deviation of the variation in density value that occurs when the minimum density + 1.2 density is scanned through a red filter with a microdensitometer with a circular scanning aperture of 25 μm, and then calculating the value of sample 401 by 100 It is shown as a relative value. The results are also shown in Table 4.

Table 4 As is clear from Table 4, the sample containing the compound of the present invention had the same sensitivity as the comparative sample and was superior in graininess.

Also, instead of exemplified compound (3) of sample 403, (32)
The effects of the present invention were also observed in samples using .

〔Effect of the invention〕

As is clear from the above results, the present invention provides a silver decagenide color photographic light-sensitive material with less color staining, excellent color reproducibility, little change in photographic performance during storage, and excellent graininess and sharpness. I was able to provide it.

Claims (1)

[Scope of Claims] A blue-sensitive silver halide emulsion layer containing at least one yellow coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a red-sensitive halide emulsion layer containing a cyan coupler, each on a support. In a silver halide color photographic light-sensitive material having a photographic constituent layer including a silver emulsion layer, at least one of the photographic constituent layers contains a non-coloring and diffusion-resistant compound represented by the following general formula [I]. A silver halide color photographic material characterized by: General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, There are ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, Z is the atomic group necessary to form a ring with ▲ mathematical formulas, chemical formulas, tables, etc. represents a hydrogen atom or a substituent. ]