JPS6227741A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance stability at the time of development processing and raw storage stability by incorporating a DIR compound to be allowed to release a diffusive development inhibitor or its precursor by the coupling reaction with the oxidation product of a color developing agent in one of silver emulsion layers and further, a photographic useful reagent precursor. CONSTITUTION:The diffusive DIR compound is allowed to release the diffusive development inhibitor or its precursor by the coupling reaction with the oxidation product of a color developing agent and it is represented by formula (1) in which A is a coupler component, n is 1 or 2, and Y is a group combined with the coupling site of A to be allowed to release a diffusive development inhibitor or its precursor by the coupling reaction with the oxidation product of a color developing agent. It is added, preferably in general, in an amount of 2X10<-4>-5X10<-1> mol, especially, 1X10<-3>-1X10<-1> mol per mol of silver halide, preferably to the photosensitive emulsion layer containing the photographic useful reagent precursor. This precursor may be added to any of the silver halide emulsion layers, a subbing layer, a protective layer, interlayers, a filter layer, an antihalation layer, or other assistant layer in the silver halide photographic sensitive material, preferably, to the same layer that contains the diffusie DIR compound.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to silver halide color photographic materials (hereinafter referred to as "photosensitive materials"), and more specifically, to stability during development processing and raw color photographic materials. (This invention relates to a photosensitive material that has improved storage stability during color sensitization before exposure.

[Conventional technology] In recent years, there has been a demand for the development of photosensitive materials with high image quality and uniformity, and at the same time, the development process has become increasingly automated.
and faster. In other words, even if a photosensitive material has high image quality performance, if it does not have sufficient stability during processing, not only will the original performance of the photosensitive material not be brought out, but even a small amount of development will occur. Fluctuations in processing conditions result in photosensitive materials with large variations in performance.
Unable to meet user needs. Known methods for improving processing stability include, for example, a method of controlling the developability of silver halide, a method of using couplers with good development properties, and a method of improving with various additives. Among them, a method of improving processing stability by adding non-photosensitive fine grain silver halide to a non-photosensitive hydrophilic colloid layer is disclosed, for example, in U.S. Pat. No. 3, a 23.02.
No. 2, No. 3 591.382, No. 3.737.317
No., JP-A No. 50-23228, JP-A No. 50-55332, etc., and is known to exhibit remarkable improvement effects.

However, this technique has the drawback of deteriorating the shelf life of the silver halide emulsion layer adjacent to the non-photosensitive hydrophilic colloid layer to which fine-grain silver halide has been added, and is not fully satisfactory. .

On the other hand, although it is common practice to use diffusive DIR compounds to improve image quality, the use of these diffusive DIR compounds deteriorates the storage stability of photosensitive materials, and furthermore, the combination of conventional techniques has led to the use of diffusive DIR compounds. This resulted in deterioration of storage stability.

[Problems to be Solved by the Invention] Therefore, the technical object of the present invention is to provide a photosensitive material with excellent stability during development processing and shelf life.[Means for Solving the Problems] The present invention As a result of intensive research based on the above-mentioned technical background,
In a light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers reacts with an oxidized form of a color developing agent to release a diffusive phenomenon suppressor or its diffusible precursor. DIR
It has been found that the above-mentioned problems can be solved by a photosensitive material containing a compound and a photographically useful reagent precursor.

The present invention will be explained in detail below.

DI which is used in the present invention and which reacts with the oxidized form of a famous color developing agent to release a diffusible development inhibitor or its precursor.
The R compound (hereinafter referred to as a diffusible DIR compound) is represented by the following general formula (1).

The remaining general formula (1) % formula %) In the formula, A represents a coupler component, m represents 1 or 2,
Y represents a group that binds to the coupling position of the coupler component A and leaves by reaction with the oxidized product of the color developing agent, and represents a highly diffusible development inhibitor or a compound capable of releasing a development inhibitor.

A only needs to have the properties of a coupler, and it is not necessary to create a dye by coupling.

In the diffusible DIR compound general formula (1), Y represents the following general formulas (2A) to (5).

General formula of diffusible DIR compound (2A) General formula of diffusible DIR compound (2B) General formula of diffusible DIR compound (2c) General formula of diffusible DIR compound (2E) General formula of diffusible DIR compound (3) Diffusability DIR compound general formula (4) R6 Diffusible DIR compound general formula (5) Above general formulas (2Δ) to (2D), ? '; and (3), R represents an alkyl group, an alkoxy group, anrulamino group, a halogen atom, an alkoxycarbonyl group, a thiazolylideneamino group, an aryloxycarbonyl group, an alkoxy group, a carbamoyl2. %, N, -alkylcarbamoyl group, N, N-i/alkylcarbamoyl group, nitro group, amino group, N-arylcarbamoyloxy group,
Represents a sulfamoyl group, an N-alkylcarbamoyloquino group, a hydroxy group, an alkoxycarbonylamino group, an alkylthio group, an arylthio group, an aryl group, a heterocyclic group, a cyano group, an alkylsulfonyl group, or an aryloxycarbonylamino group. n represents 1 or 2, and when n is 2, R1 may be the same or different, and the total number of carbons contained in n R3 is 0-10.

R in the above general formula (2E) is R8 in (2A) to (2D)
, X represents an oxygen atom, a sulfur atom, or a selenium atom, and in the general formula (4), R7 is an alkyl group,
Represents an aryl group or a heterocyclic group.

In general formula (5), R8 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and 174 represents a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group. group,)'lukanesulponamide group,
Represents a cyano group, a heterocyclic group, an argylthio group, or an amino group.

fl,, R,, R3 or R4 is an alkyl group in Table 4-
In this case, the substitution may be a non-1δ substitution, a linear or branched chain, or a cyclic alkyl group. Substituents include halogen atom, 21-ring group, cyano group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, carbamoyl store, hydroquine group, alkanesulfonyl group, arylsulfonyl group , an alkylthio group or an arylthio group.

When R1, R7, R3 or R4 represents an aryl group, the aryl group may be substituted. Examples of substituents include alkyl groups, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, halogen atoms, nitro groups, amino groups,
Sulfamoyl group, hydroxyl group, carbamoyl group,
Examples include an aryloxycarbonylamino group, an alkoxycarbonylamino group, ananolamino group, a cyano group, and a ureido group.

When R4 represents a heterocyclic group, it represents a 5- or 6-membered monocyclic or fused ring containing a nitrogen atom, an oxygen atom, or a sulfur atom as a heteroatom, and a pyridyl group or a quinolyl group. , furyl group, benzodeazolyl group, oxacylyl group, imidazolyl group, deazolyl group, triazolyl group, benzotriazolyl group, imido group, oxazine group, etc., which are further substituted with the substituents listed for the above aryl group. Moni.

In general formulas (2E) and (4), the number of carbon atoms contained in R3 is 1 to 15.

In the above general formula (5), the total number of carbon atoms contained in R1 and R4 is 1 to 15. In the above general formula (1), Y represents the following general formula (6).

Diffusivity 1) T I? Compound general formula ((1)-'1'
IM E - I N It l B I T formula, ]
"I M E 21% is a group that binds to the coupling position of the coupler and is cleaved by reaction with the color developing agent, and after being cleaved from the coupler, I N HI 13ITW
Pack a package that can be moderately suppressed and released. IN HI B
The IT group is a development inhibitor.

In general formula (6) -'1' I M E-I N
The HI 1311′ group represents the following general formulas (7) to (13).

Use the blank space below.
tmi
−j← ← two = phrase
-≧ Diffusible DIR Compound General Formula (13) In General Formulas (7) to (13), R6 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkoxycarbonyl group, an anilino group, an acylamino group. group, ureido group, cyano group, nitro group,
Represents a sulfonamide group, sulfamoyl group, carbamoyl group, aryl group, carboxy group, sulfo group, hydroxy group, alkanesulfonyl group, and has general formulas (7), (8), (9), (11) and (13)
), Q represents 1 or 2; in general formulas (7), (1[), (12) and (13), k represents an integer from 0 to 2; general formulas (7), (10) and (1[), R8
represents an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group, or an aryl group, and in general formulas (12) and (13), B is an oxygen atom or -N (R
a has the same meaning as already defined R.

represents. ), and the I N HI B I T group is represented by the general formula (2A), (2B
), (3), (4) and (5) have the same meaning as the general formula defined in (5) except for the number of carbon atoms.

However, in general formulas (2A), (2B), and (3), the number of carbon atoms contained in each R1 in the molecule is 1 in total.
~32, and in general formula (4), the number of carbon atoms contained in R3 is 1 to 32, and in general formula (5), R3
The total number of carbon atoms contained in R4 is 0 to 32.

When R6 and RIl represent an alkyl group, the substitution may be unsubstituted, linear or cyclic. Examples of the substituent include the substitution methods listed when Rl''-R4 is an alkyl group.

When R6 and R8 do not represent an aryl group, aryl"l(
should have been replaced. R as a substituent.

- The substituents listed when R9 is an aryl group can be mentioned.

Among the above diffusible DIR compounds, general formula (2% formula% Particularly preferred are those having a releasing group.

The yellow image-forming coupler residue represented by A in general formula (1) includes pivaloylacetanilide type,
Benzoylacetanilide type, malondiester type, malondiamide type, dibenzoylmethane type, benzothiazolylacetamide type, malonester monoamide type, benzothiazolyl, acetate type, benzoxacylylacetamide type, benzoxacylylacetate type, malondiester type, Benzimidazolylacetamide type,
or benzimidazolyl acetate type coupler residues, coupler residues derived from heterocycle-substituted acetamides or heterocycle-substituted acetates contained in U.S. Pat. No. 3,841.880 or U.S. Pat. No. 3,770.446
No. 1,459,171, West German Patent (OLS)
) No. 2.503,009, JP-A-50-139738, and Research Disclosure No. 157:37, coupler residues derived from acylacetamides, or heterozygous compounds described in U.S. Pat. No. 4,046,574. Examples include cyclic coupler residues.

The magenta image-forming coupler residue represented by A includes a 5-oxo-2-pyrazoline nucleus, pyrazolo-(1,5-
a) Coupler residues having a benzimidazole core or an anoacetophenone type coupler residue are preferred. The cyan image-forming coupler residue represented by A includes a coupler residue having a phenol nucleus or an α-naphthol nucleus;
Indacylon or pyrazolotriazole coupler residues are preferred.

Furthermore, the effect as a DIR coupler is the same even if the coupler does not substantially form a dye after coupling with the oxidized form of the main agent and releasing the development inhibitor. Coupler residues of this type represented by A include U.S. Pat.
No. 213, No. 4,088.49, No. 3,632.3
No. 45, No. 3,958.993 or No. 3,961.9
Examples include the coupler residues described in No. 59. Preferred diffusible DIR compounds used in the present invention include, but are not limited to, the following compounds.

'Q qD
-9 C1□H250COCHC00CI2) (25IN
=IN cut 2 t D-18 D-19 t D-26 at at Q QD
-37 o3H dimension riρ ゛ q
D-43 D-44 CO2CH2CH2CN H O2 1
! Q
Q Low glue Q Q? ri=7 H D-5・↓ H D-58 0H H ■ H3 These diffusible DIR compounds of the present invention are disclosed in U.S. Patent No. 4.23.
No. 4,678, No. 3,227,554, No. 3.617
, No. 291, No. 3,958,993, No. 4.149,
No. 886, No. 3,933,500, JP-A-57-56
No. 837, No. 51-13239, British Patent No. 2,072.
363, No. 2,070,266, Research Disclosure No. 21228, December 1981, etc., it can be easily synthesized.

The addition m of the diffusible DIR compound of the present invention is generally from 2 x l O-'' to 5 x I O-'' per mole of silver in the emulsion layer.
'Mole childish, more V childish lXl0-3~
1xlO-'mol.

The addition method will be described later in the photographically useful reagent prep J- of the present invention.
Refer to the 3 and 4 chapters about the.

The diffusible DfR compound of the present invention is preferably added to a light-sensitive emulsion containing the photographically useful reagent precursor of the present invention.

Next, the photographic (T) reagent breaker of the present invention will be explained.

The photographically useful reagent precursor used in the present invention refers to a compound that exists stably under storage conditions and whose blocking group is released at the required timing during processing to release a photographic reagent. Compounds represented by formulas (I) to (IX) can be mentioned.

Go to the blank below χ General formula (Vl) 〇General formula (■) General formula (■) General formula (IX) -e Known photographs in which A is substituted with a heteroatom in formulas (1) to (IX) Antifoggants such as mercaptotetrazoles, mercaptocyanoazoles, benzotriazoles or inguzols, and developing agents such as pyrazolidones, hydroquinones or p-phinidine diamines. Drugs (auxiliary developers), fogging agents or nucleating agents such as hydranones, hydrazides, quaternary salts or acetylenes, silver halide solvents such as thioethers, hypo or rhodanines, azo dyes, and the above as a function of development. It is assumed that the photographic reagent has a redox function by which the photographic reagent is released, for example, it also contains a coloring material for a color diffusion transfer sensitive material.

X in general formulas (1) to ('/[) represents a divalent timing group, which is bonded to the methyl group via an oxygen atom, and after being cleaved as X-A during treatment, A is immediately released. represents a group that As such a linking group, JP-A-54-
British Patent No. 2072363, JP-A-57-1, which releases A by the intramolecular ring-opening reaction described in No. 14513.5.
A by the intramolecular electron mechanism described in No. 154234 etc.
Name those that release A, those that release A with the elimination of carbon dioxide as described in JP-A-57-179842, etc., or the linking group for formalin elimination described in Japanese Patent Application No. 57-20344. I can do it. The structural formulas of the representative Xs described above are shown below.

HA Ding J Margin Shit 1, Ctls　N　　(＾) /′ C.I.

(A) CHl -〇-C-(A) -0CI+, -(A) where m represents O or an integer from 1 to 4, and n represents 0 or 1. 6Q is -C〇- or -8O7- , Z is 5 to 7
Represents the atomic group that forms the sun.

W in general formula (rl) is -CR'R@-1-0-1
It represents S-1-NR7-, forms a 5- or 7-membered ring with Y, and forms a 4-membered ring when Q is 0.

R5, R8, and R7 are each a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 20 carbon atoms, and 6 to 2 carbon atoms.
6 aryl group, an alkogino group having 1 to 16 carbon atoms, and an aryloquine group having 6 to 26 carbon atoms, and may have a substituent.

Y represents a nonmetallic atomic group forming a five-membered ring with W,
Examples of the five-membered ring formed include succinimide F, maleimide, oxazonodinone, thiohyguntoin, hydantoin, urazole, parabanic acid, and the like.

Examples of the 6-membered ring include glutaric imide, 3-oxyglutaric imide, barbylic acid, uracil, and benzoxanonedione.

= yl in the general formula (Vl) is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group,
Alkoxy group, aryloquine group, asoleoquine weir, carbonate ester group, amino group, galbonamide group, ureido group, carboxyne group, oxycarbonyl group, carbamoyl group, acyl group, sulfo group, sulfonyl group, sulfamoyl group, cyano group, nitro group, etc. represents.

In the general formula (■), X' represents a carbon atom or a sulfur atom, D represents an electrophilic group (e.g. carbonyl group, thiocarbonyl group, sulfonyl group, sulfinyl group, allyl group, benol group, etc.), and L represents a linking group bonded to R-C- through a carbon atom, and R represents a substituent bonded to a hydrogen atom or a carbon atom. m+ and nl each represent 1-3, preferably 1-2.

R1 in general formulas (1), (III), (IV) and (V) represents a substituent on the phenyl nucleus.

R2 in general formulas (III) and (V) represents a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, or an aryl group having 6 to 26 carbon atoms, and the alkyl group and aryl group may have a substituent.

R3 and R4 in the general formulas (IV) and (■) are respectively an alkyl group having 1 to 16 carbon atoms, an aryl group having 6 to 26 carbon atoms, a cyclic group having 5 to 10 carbon atoms, and a carbon Ml-
Represents 10 heterocyclic residues, each with one substituent. It's good.

R 7 , R8, and R9 in the general formula (■) each represent a substituent, and at least one of R', R", and R"
One is an electron-withdrawing method that can be generated at the time of the phenomenon in which amino1-nitrogen atoms are bonded via π bonds, and at the same time,
At least one of R7, n8, and R9 is cleaved by an intramolecular nucleophilic reaction of the amide nitrogen atom or an intramolecular electron transfer from the amide nitrogen atom, and a photographic reagent is substituted at the position of S. , 口 represents 0 or an integer from 1 to 4, and m represents an integer from 1 to 3.

In general formula (IX) [ElQ, R11 and R1! each represents a substituent, m3 represents 0.1 or 2, and m3 represents a substituent.

represents 0 or l, and the sum of m3 and 03 is 1-3.

Next, specific examples of photographically useful reagent precursors used in the present invention are shown. However, it is not limited to these.

[Exemplary compounds]

P″″′3.

P-4 H H3 P-1゜ H2 P-15 OOH SO□NH2 P-27 P-29 CH.

P -33 ON2 N P -38 P -40 P -42 H3 These photographically useful reagent precursors are described in, for example, JP-A-Sho 2.
No. 7-135949, No. 59-3434, No. 59-9
No. 3442, No. 59-137945, No. 59-140
No. 445, No. 59-201057, No. 5-2184
No. 39, No. 59-219741, No. 60-41034
It is synthesized by the method described in No.

The photographically useful reagent precursor according to the present invention is silver 1i5
It may be added to any of the silver halide emulsion layer, undercoat layer, protective layer, intermediate layer, filter layer, antihalation layer, and auxiliary layer of the 3tt material.

Preferably, it is added in the same layer as the diffusible DIR compound of the Ashigi invention.

In order to add the photographically useful reagent precursor used in the present invention to these layers, the photographically useful reagent precursor may be added as is or in a solvent that does not adversely affect the photosensitive material in the coating solution for forming the layer. For example, it can be added after being dissolved in water, alcohol, etc. to an appropriate concentration. Alternatively, a photographically useful reagent precursor can be welded to a high-boiling point organic solvent and/or a low-boiling point organic solvent, and added after being emulsified and dispersed during dissolution in water.

Examples of high boiling point solvents include organic compounds with a boiling point of 150°C or higher, such as phenol derivatives, phthalate alkyl esters, phosphate esters, citric acid esters, benzoate esters, alkylamides, fatty acid esters, and trimesic acid esters, which do not react with the oxidized form of the developing agent. A solvent is used.

Examples of high-boiling point organic 78 soot that can be used in the present invention include U.S. Pat.
No. 4, No. 2゜835.579, No. 3,287.134
No. 2,353.262, No. 2.852.383, No. 3,554,755, No. 3.676, No. 137,
3,676゜142, 3.700.454, 3,748.141, 3,779,765, 3
．． No. 837463, British Patent No. 958,441, No. 1,
222゜753, 0LS2,538,889, JP-A-47-i031, JP-A-9-90523, JP-A-50-2
No. 3823, No. 51-26037, No. 51-27!1
No. 21, No. 51-27922, No. 51. -26035
No. 51-26036, No. 50-62832, No. 53-1520, No. 53-1521, No. 53-15
No. 127, No. 54-119921, No. 54-1199
22, No. 55-25057, No. 55-36869, No. 56-19049, No. 56-81836, and Japanese Patent Publication No. 48-29060.

Several low-boiling or water-soluble solvents that can be used with or in place of high-boiling solvents are disclosed in U.S. Pat. No. 2,801,171;
Can you name the one described in No. 2,949,360, etc.? Examples of organic solvents with low boiling points that are substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate-1-, butanol, chloroform l4, carbon tetrachloride, nitromethane, nitromethane, benzene, etc., and water-soluble organic solvents include , acetone, methyl isobutyl ketone, β-ethoxyethyl acetate, methquinoglycol acetate, methanol, ethanol, acetonitrile, dioxane, medylpolamide, dimethyl sulfoxide, hexamethyl phosphoramide, noethylene glycol monophenyl ether, Examples include phenoquinoethanol and the like.

The photographically useful reagent precursor of the present invention may be added at any time during the manufacturing process, but direct coating is generally preferred.

The preferred addition amount of the photographically useful reagent precursor of the present invention varies depending on the type of photographically useful reagent, but it is preferably lXI O-'' to [x10 for river moles, more preferably mekabuto-based Kafuri. Prevention~1 is l x 10-
'~l
It is 10-1 mol.

In the light-sensitive material of the present invention, the same color-sensitive layer may be composed of two or more layers with different sensitivities, and in this case, any of the highest sensitivity layer, middle sensitivity layer, and lowest sensitivity layer may Although it is possible to apply the diffusible DIR compounds and photographically useful precursors of the present invention, it is preferable to apply them to medium to high speed layers.

When the present invention is applied to a multilayer color photosensitive material, a 11" 1B with at least 11" of tone sensitivity, green sensitivity and red sensitivity.

Diffusive Dir? of the present invention in one of the light-sensitive emulsion layers. It is preferable that the diffusible DIII compound of the present invention be contained in the photosensitive emulsion layer, and more preferably in all the photosensitive emulsion layers.

The silver halide composition of the light-sensitive emulsion layer of the present invention is up to one's discretion; for example, silver iodobromide, silver bromide, silver chlorobromide, crude chloroiodide,
Silver chloroiodobromide and the like may also be contained. Furthermore, the present invention can be applied to so-called black-and-white photosensitive materials.

The silver halide grains used in the silver halide emulsion of the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The particles can be grown all at once, or they can be grown after forming seed particles. The method of creating and growing the plants may be the same or different.

A silver halide emulsion may be prepared by simultaneously mixing halide ions and silver ions, and then mixing one of them into a liquid in which the other is present. Further, while taking into consideration the critical growth rate of fine silver halide products, generation of halide ions and silver ions can be avoided by sequentially and simultaneously adding the halide ions and silver ions while controlling the pH and pAg in the mixing pot. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. After growth, a conversion method may be used to change the halogen composition of the particles.

During production of the silver halide emulsion of the present invention, it is possible to control the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains by using a silver halide solvent as necessary. can.

The silver halide grains used in the silver halide emulsion of the present invention are formed by cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (complex salts containing), rhodium salt, Metal ions can be added using at least one selected from salts (complex salts containing) and iron salts (complex salts containing) to contain these metal elements inside the particles and/or on the particle surfaces. Furthermore, by placing the particles in an appropriate reducing atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may remain contained. When removing the salts, research
Disclosure) No. 17643.

The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical or plate shape. It may have a crystalline form.

In these particles, the ratio of the (l OO) and (111) planes can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The average grain size of the silver halide grains of the present invention (representing the diameter of a circle with an area equal to the projected area of the grain → size) is 5 μm.
The thickness is preferably 3 μm or less, particularly preferably 3 μm or less.

The silver halide emulsion of the present invention may have any grain size distribution. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). A particle with a value of 0.20 or less when divided by the average grain size.The grain size is the diameter in the case of spherical silver halide, and the projection of the grain in the case of grains with a shape other than spherical. This indicates the diameter when the image is converted into a circular image with the same area.) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

The silver halide emulsion of the present invention may be a mixture of separately formed silver halide emulsions of 2M or more.

In the present invention, silver halide emulsions may be used, for example, in British Patent No. 8
No. 18,061, No. 1.315,755, No. 1,39
No. 6,696, Japanese Patent Publication No. 15748/1974, U.S. Patent No. 1
, No. 574,944, No. 1,623.499, No. 1,
No. 673.522, No. 2,278,947, No. 2, 3
99°083, 2.410.689, 2.41
No. 9,974, 2.4118. (No. 160, 2, 4
g7,85Q, 2,518.698, 2,52
No. 1,926, No. 2.642.36, No. 2.694
, No. 637, No. 2,128,868, No. 2,739.
No. 06Q, No. 2,7.43,132, No. 2,743,
No. 183, No. 2.933,609, No. 2,983.6
No. 10, No. 3,021.215, No. 3゜026.20
No. 3, No. 3,297,446, No. 3,297,447
No. 3,361.564, No. 3.4, No. 914,
3.554.757, 3,565°631, 3,565.633, 3.591,385, 3
．． No. 656,955, No. 3.76L, No. 267, No. 3,
772. Oat No. 3,857.7L1, No. 3.8
No. 91,446, No. 3,901,714, No. 3,90
No. 4,415, No. 3,930,867, No. 3.984
, No. 249, No. 4.054, 457, No. 4.067.
No. 740, Research, Disclosure (Rese
arch Disclosure) No. 12008, same 1
No. 3452, No. 13654, T, Il, James
s, The Theory of the Photo
graphicProcess, (4th Ed,
It is preferable to carry out sensitization using a chemical sensitizer or sensitization method described in Macmillan, 1977), pages 67 to 76.

Sensitizing dyes include cyanine dyes, merocyanine dyes,
> U-containing anine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes, hemioxanol dyes, etc. are used.

Pigments especially for babies include cyanine pigments, merocyanine pigments,
and a complex merocyanine pigment. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes.

That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, and a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei: and A nucleus in which an aromatic hydrocarbon ring is fused to these nuclei,
These include indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxacillinone-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2°4-dione nucleus, rhodanine nucleus, thiobarbylic acid solution, and the like can be applied.

Useful sensitizing dyes for use in blue-sensitive silver halide emulsion layers include, for example, West German Patent No. 929. (No. 100, U.S. Patent No. 2,231,658, U.S. Patent No. 2,493,748, U.S. Patent No. 2.503,776, U.S. Patent No. 2,519,001, U.S. Pat.
, No. 912,329, No. 3,656,959, No. 3,
No. 672,897, No. 3,694,217, No. 4.0
No. 25,349, No. 4.046.572, British Patent 1
, No. 242,588, Special Publication No. 44-14030, No. 5
Examples include those described in No. 2-24844. Also, useful sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Pat.
No. 2,072.908, No. 2.739,149, No. 2.945.763, British Patent No. 505,979, etc. This can be cited as a representative example. Furthermore, useful sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Pat.
, No. 269.234, No. 2,270,378, No. 2.
No. 442,710, No. 2,454.629, No. 2,7
Cyanine dyes such as those described in No. 76.280, etc.
Typical examples include melonanine dyes and complex cyanine dyes. Furthermore, US Patent 2
．． No. 213.995, No. 2,493,748, No. 2,
Cyanine dyes, merocyanine dyes or semicyanine dyes such as those described in German Patent No. 519,001 and German Patent No. 929,080 can be advantageously used in green-sensitive silver halide emulsions or red-sensitive halogen emulsions.

These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization. Typical examples are Special Publications No. 43-4932, No. 43-4933, No. 4
No. 3-4936, No. 44-32753, No. 45-25
No. 831, No. 45-26474, No. 46-11627
No. 46-181 (No. 17, No. 47-8741, No. 47-11114, No. 47-25379, No. 47-
No. 37443, No. 4g-28293, No. 4g-384
No. 06, No. 48-38407, No. 48-38408, No. 48-41203, No. 48-41204, No. 4
No. 9-6207, No. 5O-11Q662, No. 53-1
No. 2375, No. 54-34535, No. 55-1569
No. 50-33220, No. 50-33828, No. 50-38526, No. 51-107127, No. 51-115820, No. 5L-135528, No. 5
No. 1-151527, No. 52-23931, No. 52-
No. 51932, No. 52-L (No. 14916, No. 52-1)
No. 04917, No. 52-109925, No. 52-11
No. 0618, No. 54-gottg, No. 56-257
No. 28, No. 57-1483, No. 5g-10753,
No. 58-91445, No. 5g-153926, No. 5
No. 9-114533, No. 59-116645, No. 59
-116647, U.S. Patent No. 2,688,545, U.S. Patent No. 2,977.229, U.S. Patent No. 3.397.060, U.S. Patent No. 3
．． 506.443, 3,578.447, 3゜672,898, 3,679,428, 3.7
No. 69,301, No. 3.814.609, No. 3,83
7.862 etc.

Examples of dyes that do not themselves have spectral sensitizing effects, or substances that do not substantially absorb visible light and exhibit supersensitization, are used in sensitizing dyes and tora, such as formaldehyde condensation of aromatic organic acids. products (e.g., U.S. Patent 3,
437,510), cadmium salts, azaindene compounds, aminostilbene compounds substituted with nitrogen-containing heterocyclic groups (e.g., U.S. Pat. No. 2.933.3'9
No. 0, No. 3,635,721), etc. U.S. Patent No. 3,615,613, U.S. Patent No. 3,615.64
No. 1, No. 3,617.295, No. 3,635.721
The combinations described in this issue are particularly useful.

As anti-fogging agents and stabilizers, U.S. Pat. No. 2,713.541, U.S. Pat.
Pentazaindenes described in No. 81, U.S. Patent No. 2,
No. 716.062, No. 2゜444.607, No. 2,4
No. 44,605, No. 2,756,147, No. 2,83
No. 5.581, No. 2,852,375, Research Disclo + - (Research Disclo
azaindenes such as tetrazaindenes described in U.S. Pat. No. 14851, triazaindenes described in U.S. Pat. ;
U.S. Patent No. 2,131,038, U.S. Patent No. 3,342.59
6, quaternary salts such as thiazolium salts described in U.S. Patent No. 3,954,478, biryllium salts described in U.S. Pat. Onium salts; US patent 2.
403゜927, 3.266.897, 3.7
No. 08,303, JP-A-55-135835, JP-A No. 59
Mercaptotetrazoles, mercaptotriazoles, and mercaptodiazoles described in U.S. Pat. No. 71047, mercaptothiazoles described in U.S. Pat. Thiazoles, mercaptobenzimidazoles, mercaptooxadiazoles described in U.S. Pat. No. 2,843.491, U.S. Pat.
Mercapto-substituted heterocyclic compounds such as mercaptothiadiazoles described in US Pat. No. 364,028; US Pat.
, 236,652, catechols described in Japanese Patent Publication No. 43-10256, resorcinols described in Japanese Patent Publication No. 56-44413, and polyhydroxy such as gallic acid esters described in Japanese Patent Publication No. 43-4133. Benzenes: Tetrazoles described in West German Patent No. 1,189.380, triazoles described in US Patent No. 3,157,509, benztriazoles described in US Patent No. 2,704.721, U.S. Patent 3.28743
urazoles described in US Pat. No. 5, pyrazoles described in US Pat. No. 3.106.467, indazoles described in US Pat. Azoles such as polymerized benztriazoles and U.S. patents 3,
pyrimidines described in U.S. Pat. No. 161.515, 3-pyrazolidones described in U.S. Pat. No. 2,751.297, and polymerized pyrrolidones or polyvinylpyrrolidones described in U.S. Pat. Heterocyclic compounds: JP-A No. 54-130929, No. 59-
No. 137945, No. 140445, British Patent No. 1,35
6.142, U.S. Pat. No. 3,575.699, U.S. Patent No. 3,
Various inhibitor breakers described in US Pat. No. 649,267, etc.; sulfinic acids and sulfonic acid derivatives described in US Pat. No. 3,047,393; US Pat. No. 2,566.
No. 266, No. 2,839,405, No. 2,488.7
There are inorganic salts described in No. 09 and No. 2.728゜663.

Gelatin is preferably used as the binder (or protective colloid) for the silver halide emulsion of the present invention, but
Hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can be used.

When gelatin is used as a binder (or protective colloid) for the silver halide emulsion of the present invention, the jelly strength of the gelatin is not limited, but the jelly strength is 250 g or more (
The value measured by the buggy method) is preferable.

The photographic emulsion layer and other water-based colloid layers of the light-sensitive material of the present invention may be hardened by using one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. I can do it. A hardening agent can be added to the processing solution to harden the photosensitive material to such an extent that it is not necessary to add the hardening agent, but it is possible to add a hardening agent to the processing solution.

A plasticizer may be added to the silver halide emulsion layer and/or other shallow water colloid layer of the light-sensitive material of the present invention for the purpose of increasing flexibility.

A dispersion (latex) of a water-insoluble or pheasant-soluble polymer may be contained in the photographic emulsion, distillate, or other hydrophilic colloid layer of the light-sensitive material of the present invention for the purpose of improving dimensional stability.

The emulsion layer of the light-sensitive material of the present invention undergoes a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, p-phenylenediamine derivatives, aminophenol derivatives, etc.) during color development processing to form a dye. A dye-forming coupler is used.

Dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the emulsion layer's sensitive spectrum, with a yellow dye-forming coupler in the blue-sensitive emulsion layer; A magenta dye-forming coupler is used in the green-sensitive emulsion layer, and a dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, photosensitive materials may be produced using different combinations from the above.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Furthermore, even if these dye-forming couplers are 4-functional, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. It may be either 2-equivalent. Dye-forming couplers can be used as development accelerators, bleach accelerators, developers, silver halide solvents, toning agents, hardeners, fogging agents, antifogging agents, and chemical sensitizers by coupling with oxidized forms of developing agents. Compounds that release photographically useful fragments can be included, such as spectral sensitizers, spectral sensitizers, and desensitizers. Colored couplers having a color correction effect may be used in combination with these dye-forming couplers to the extent that the effects of the present invention are not impaired.

As the yellow dye-forming coupler (yellow coupler) used in the present invention, various acylacetanilide couplers can be preferably used. Among these, benzoylacetanilide and pivalo(ruacetanilide) compounds are advantageous. Specific examples of usable yellow couplers include British Patent No. 1077.374, Japanese Patent Publication No. 45-40757, and Japanese Patent Application Laid-open No. 47-1031. , same 47
-26133, 4g-94432, 50-87
No. 650, No. 51-3631, No. 52-115219
No. 54-99433, No. 54-133329,
No. 56-30127, U.S. Patent No. 2.875.057
No. 3,253.924, No. 3,265,506, No. 3゜401', No. 194, No. 3゜551.155
No. 3,551.156, No. 3,664.841, No. 3,725', No. 072, No. 3,730.722, No. 3,891゜445, No. 3.90Q, No. 483 ,
3.929.484, 3,933,500, 3,973,968, 3,990.896, 4
．． No. 012.259, No. 4.022.620, No. 4.
No. 029.508, No. 4.057,432, No. 4.1
No. 06.942, 4. lLS, No. 953, 4, 26
No. 9.936, No. 4.236,053, No. 4.304
No. 445, No. 4,314,023, No. 4゜336.3
No. 27, No. 4.356.258, No. 4,386.15
No. 5, No. 4,401.752, etc.

Also, magenta dye-forming coupler (magenta coupler)
As such, various 5-pyrazolone couplers, pyrazolopenzimidazole couplers, pyrazolotriazole couplers, and open-chain acylacetonitrile couplers can be preferably used. Specific examples of magenta couplers that can be advantageously used are disclosed in Japanese Patent Application Nos. 58-164882 and 58-164882;
No. 8-167326, No. 58-206321, No. 58
-214863, 58-217339, 59-
No. 24653, Special Publication No. 40-6031, No. 40-60
No. 35, No. 45-40757, No. 47-27411, No. 49-37854, JP-A-50-13041,
No. 51-26541, No. 51-37646, No. 51
-105320, 52-42121, 53-1
No. 23129, No. 53-125835, No. 53-12
No. 9035, No. 54-413540, No. 56-292
No. 36, No. 56-75648, No. 57-17950, No. 57-35858, No. 57-146251, No. 59-99437, British Patent No. 1°252.418, US Patent No. 2,800. No. 788, 3. QO5,7
No. 12, 3,062,653%, 3.127.26
No. 9, No. 3,214,437, No. 3,253,924
No. 3,311.476, No. 3,419,391, No. 3.519.429, No. 3.558.319,
3.582,322, 3.615.506, 3.658.544, 3.705.896, 3.
, No. 725.067, No. 3,758,309, No. 3,
No. 823,156, No. 3,834゜908, No. 3.8
No. 91,445, No. 3,907,571, No. 3,92
6.631, 3,928. , No. 044, 3,93
No. 5,015, No. 3,960,571, No. 4.076
．． No. 533, No. 4,133,686, No. 4,237.
No. 217, No. 4,241,168, No. 4,264,7
No. 23, No. 4,301,235, No. 4.310,62
This is what is described in No. 3, etc.

As a cyan dye-forming coupler (cyan coupler),
Various naphthol couplers and phenol couplers can be preferably used. Specific examples of cyan couplers that can be used advantageously are described in British Patent No. 1.038.331;
, No. 543,040, Japanese Patent Publication No. 4g-36894, Japanese Patent Publication No. 59838-1983, No. 50-137137, No. 5
No. 1-146828, No. 53-105226, No. 54
-115230, 5B-29235, 56-1
No. 04333, No. 56-126833, No. 57-13
No. 3650, No. 57-155538, No. 57-204
No. 545, No. 58-118643, No. 59-3195
No. 3, No. 59-31954, No. 59-59656,
No. 59-124341, No. 59-166956, U.S. Patent No. 2,369°929, No. 2,423,730
No. 2,434.272, No. 2,474,293, No. 2,698.794, No. 2.772,162,
No. 2,801,171, No. 2,895.826, No. 3,253,924, No. 3,311,476, No. 3
, 458,315, 3,476.563, 3,
No. 591,383, No. 3.737.316, No. 3,7
58,308, 3,767.411, 3゜79
No. 0.384, No. 3,880,661, No. 3,926
, No. 634, No. 4,004.929, No. 4.009,
No. 035, No. 4,012,258, No. 4,052゜2
No. 12, No. 4,124,396, No. 4,134.76
No. 6, No. 4,138,258, No. 4.146,396
No. 4,149,886, No. 4,178.183, No. 4,205,990, No. 4,254,212,
No. 4,264,722, No. 4,288,532, No. 4,296,199, No. 4,296,200, No. 4
．． No. 299.914, No. 4,333,999, No. 4,
334.011, 4゜386.155, 4.4
It is described in No. 01,752, No. 4,427,767, etc.

As a colored coupler, for example, British Patent No. 937.
No. 621, No. 1.035,959, No. 1.255.1
No. 11, JP-A-48-22028, JP-A No. 52-4212
No. 1, Japanese Patent Publication No. 3g-22335, No. 44-2016, No. 44-15754, U.S. Patent No. 2,449.96
No. 6, No. 2.521.908, No. 2,543.691
No. 2.801.171, No. 2,983,608, No. 3,005,712, No. 3,034,892,
3,061,432, 3,419,391, 3,476.560, 3,476.563, 3
, 481,741, 3,519.429, 3゜583.971, 3,622,328, 3,6
No. 84,514, No. 4,004.929, No. 4.07
0. ．． No. 191, No. 4.138.258, No. 4.13
8゜264, 4,163,670, 4,292
, No. 400, No. 4,369.248, etc. can be used.

° As colorless couplers, U.S. Patent No. 2,998.314, British Patent No. 1,284,649, West German Patent No. 1,168,7 are used to adjust the radius and prevent color turbidity and fogging.
A so-called Weiss coupler described in No. 69 can be used.

Anionic surfactants, nonionic surfactants, Cationic surfactants can be used.

The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsion layers (between the same color-sensitive layers and/or between different color-sensitive layers) of the light-sensitive material of the present invention, causing color fringing or reducing sharpness. A color cast inhibitor can be used to prevent deterioration and graininess from becoming noticeable.

The color fog preventive agent may be contained in the emulsion layer itself, or may be contained in an intermediate layer provided between adjacent emulsion layers.

In the light-sensitive material of the present invention, an image stabilizer can be used to prevent deterioration of the dye image.

The hydrophilic colloid layers such as the protective layer and intermediate layer of the photosensitive material of the present invention contain an ultraviolet absorber in order to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light. May contain.

Compounds that change the developability, such as a phenomenon accelerator and a development retardant, and a bleach accelerator can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material of the present invention. Compounds that can be preferably used as development accelerators are listed in Research Disc.
losure) No. 17643, Section XXIrfiB-D, and the development retarder is the compound described in Section XXIrfiB-D of No. 17643.
It is a compound described in Section I and Section E. A black and white developing agent and/or its precursor may be used to accelerate development or for other purposes.

The photographic emulsion layer of the light-sensitive material of the present invention contains polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholine compounds, quaternary ammonium compounds, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may also contain urethane derivatives, urea derivatives, imiguzol derivatives, and the like.

The photosensitive material of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer, and/or 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 matting agent can be added to the silver halide emulsion layer and/or the hydrophilic colloid layer of the light-sensitive material of the present invention for the purpose of reducing the gloss of the light-sensitive material, improving the ease of writing, and preventing the light-sensitive materials from sticking together.

A lubricant can be added to the photosensitive material of the present invention in order to reduce its sliding friction.

It is possible to add an antistatic agent to the photosensitive material of the present invention for the purpose of preventing static electricity. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and may be used as a hydrophilic colloid other than the emulsion layer and/or the emulsion layer on the side on which the emulsion layer is laminated with respect to the support. It would be nice if it could be used as a layer.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material of the present invention includes improved coating properties, antistatic properties, improved slipperiness,
Emulsification dispersion, adhesion prevention, photographic properties (promotion of development, 8! film formation,
Various surfactants can be used for the purpose of improving (sensitization, etc.).

The support used in the photosensitive material of the present invention includes α-olefin polymers (e.g. polyethylene, polypropylene,
Flexible reflective supports such as paper laminated with ethylene/butene, synthetic paper, etc., semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, etc. These include films made of materials, flexible supports made of these films with reflective layers, glass, metals, ceramics, etc.

The photosensitive material of the present invention can be used directly or after subjecting the support surface to corona discharge, ultraviolet irradiation, flame treatment, etc., as necessary, or to improve the adhesion, antistatic property, dimensional stability, abrasion resistance, etc. of the support surface. It may be applied through one or more subbing layers to improve hardness, antihalation, frictional properties, and/or other properties.

When applying the 11 odd color of the sphere light meter of the present invention, a thickener may be used to improve the coating properties.

Also, for things like hardeners, which are so reactive that if added to the coating solution in advance they will cause gelation before coating, it is best to mix them using a suftic mixer or the like just before coating. preferable.

In preparing the light-sensitive material of the present invention, the silver halide emulsion layer and other hydrophilic colloid layers were prepared in accordance with Research Disclosure.
re) Apply by the method described in No. 17643, x■-8,
It can be dried by the method described in Section B.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material of the present invention has a certain sensitivity. Light sources include natural light, tungsten lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams, X-rays, and γ-rays. , light emitted from a phosphor excited by α rays, etc. can be used.

The exposure time is not only the 1 millisecond to 1 second exposure time normally used in cameras, but also exposure shorter than 1 microsecond, such as LOO nanosecond to 1 microsecond exposure using a cathode ray tube or xenon flash lamp. However, exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently.

Various color developments can be used for the development of the photosensitive material of the present invention. Alternatively, a color image may be formed by an inversion method. When the reversal method is used, a black and white negative development step is performed, followed by a fixing step and white exposure, or a bath containing a fogging agent is used, followed by color development.

(The processing step of providing white light exposure or the step of processing with a fogging agent may be the same as the color development processing step.) In the present invention, the color development processing step is a step of forming a color image; Specifically, it is a process of forming a color image through a coupling reaction between an oxidized color developing agent and a color coupler.

Therefore, in the color development processing process, it is usually necessary to incorporate a color developing agent into the color developing solution, but it is necessary to incorporate the color developing agent into the color photographic material, and use a color developing solution or a color developing agent containing the color developing agent. It also includes treatment with an alkaline solution (activator solution). The color developing agent contained in the color developing agent is an aromatic primary amine color developing agent, and includes aminophenol derivatives and p-phenylezine amine derivatives. These color developing agents can be used as salts of organic acids and inorganic acids; for example, hydrochloric acid, sulfate, P-toluenesulfonate, sulfite, oxalate, benzenesulfonate, etc. can be used. can.

These compounds generally have a color developer IQ of about 0.
19 to about 309, more preferably color developer I
Use a concentration of about 19-15 g for Q. 0.19
A sufficient color density cannot be obtained if the amount added is less than .

Further, the processing solution temperature of the color developing bath is 10°C to 65°C, more preferably 25°C to 45°C.

Examples of the aminophenol-based phenomenon agents include 0-aminophenol, p-aminophenol, 5-aminophenol,
Included are 2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene, and the like.

A particularly useful primary aromatic amine color developer is N-N'
-Dialkyl-p-phenylenediamine type compound, and the alkyl group and phenyl group may be substituted or unsubstituted. Among them, examples of particularly useful compounds include N-N'-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N'-dimethyl-p-phenylenediamine hydrochloride, 2 -Amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β- Hydroxyethylaminoaniline, 4-amino-3-methyl-N,N'-diethylaniline, 4-amino-N-(2-methoxyethyl)
-N-ethyl-3-methylaniline-p-)luenesulfonate and the like.

Further, the above color developing agents may be used alone or in combination of two or more. Furthermore, the above color developing agents may be incorporated into color photographic materials. For example, US Patent 3.
No. 719.492, a method of incorporating a coloring agent into a metal salt, US Pat. No. 3,342,559, and Research Disc.
closure) 1976 No. 15L59, a method of incorporating a color developing agent into a Schiff salt, JP-A-58-65429 and JP-A-58-2413
A method of incorporating a dye precursor as shown in US Pat. No. 7, etc., a method of incorporating a color developing agent precursor as shown in US Pat. No. 3,342,597, etc. can be used. In this case, it is also possible to process the photosensitive material with an alkaline solution (activator solution) instead of a color developing solution, and the bleach-fixing process is carried out immediately after the alkaline solution treatment. The color developing solution used in the present invention contains alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, borax, etc. It can further contain various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, development regulators such as citrazic acid, and preservatives such as hydroxylamine or sulfites. Further, various antifoaming agents and surfactants, and organic solvents such as methanol, dimethylformamide, and dimethylsulfoxide may be appropriately contained.

The PTI of the color developing solution used in the present invention is usually 7 or more, preferably about 9 to 13.

In addition, the color developing solution used in the present invention may optionally contain antioxidants such as diethylhydroquinamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, and pentose. or hexose, pyrogallol-L,
3-dimethyl ether etc. may be contained.

Various chelating agents can be used as metal ion sequestering agents in the color developing solution used in the present invention. For example, as the chelating agent, amine polycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminopentaacetic acid,
Organic phosphonic acids such as I-human axyethylidene-1,l-diphosphonic acid, aminotri(methylenephosphonic acid)
Or aminopolyphosphonic acid such as ethylenediaminetetraphosphoric acid, oxycarboxylic acid such as gluconic acid such as citric acid, phosphonocarboxylic acid such as 2-voshoptane-1,2,4-tricarboxylic acid, hexametaphosphoric acid such as tripolyphosphoric acid, etc. Examples include polyphosphoric acid, polyhydroxy compounds, and the like.

[Effects of the Invention] According to the present invention, as is clear from Examples 1z below, it is possible to provide a photosensitive material with excellent stability during development processing and raw storage stability.

[Examples] Hereinafter, the present invention will be explained in detail with reference to Examples, but the embodiments of the present invention are not limited thereby.

A green-sensitive, low-sensitivity silver halide gelatin emulsion (silver iodobromide emulsion Nk with an average grain size of 0.5 μm and containing 6 mol % of silver iodide) was deposited on a support made of subbed cellulose triacetate.
g (equivalent to 0.5 mol of silver) and the following dispersion were added so that the silver amount was 1.5 g/mt.
It was created.

(Dispersion) Coupler ■30g, Coupler ■9g, Diffusivity DI in Table 1
0.4 g of the R compound and 0.8 g of the photographically useful reagent precursor from Table 1 were dissolved in 80 g of tricresyl phosphate and 120 g of ethyl acetate, and 400 g of 10% gelatin.
and sodium triisopropylnaphthalene sulfonate4.
Mix with 5 g and emulsify and disperse using a colloid mill.

Each sample obtained in this way and each of these samples was
The sample was left in an atmosphere of 5° C. and 20% relative humidity for 3 days, exposed to green light through a wedge, and subjected to the following development process to obtain the results shown in Table 1.

Processing process (37,8°C) Processing time 1, color development
2 minutes 45 seconds and 3 minutes 15 seconds 2, bleaching 6 minutes 30 seconds 3 washing with water 3 minutes 1
5 seconds 4, fixing 6 minutes 30 seconds 5, washing with water 3 minutes 15 seconds 6, stabilization 1 minute 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

[Color developer composition] 4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 14.75 g Anhydrous sodium sulfite 4.25 g Hydroxyamine 1/2 sulfate 2, Og Anhydrous Potassium carbonate 37. ．． 5g Sodium Bromide 1.3g Nitrilotriacetic acid
Add 2.5 g of trisodium salt (l hydrate) and 1.0 g of potassium hydroxide to make 112.

5 Bleach solution composition] Ethylenediaminetetraacetic acid iron ammonium salt 100.
0g Ethylenediaminetetraacetic acid diammonium salt 10.0
g ammonium bromide summer 50.0g water
Acetic acid 10. om
Add Q water, tQ, and adjust to pH 6 using ammonia water.
, adjust to 0.

, fixer composition] Ammonium diosulfate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Water was added to adjust the IQ, and the pH was adjusted to 6.0 using acetic acid.

[Stabilizing liquid composition] Formalin (37% aqueous solution) 1.5 m + 2 Konidax (manufactured by Konishi Photo Industry Co., Ltd.) 7.5 me Water was added to make 2.

As is clear from Table 3, the processing stability and raw storage stability are significantly improved according to the present invention.

Patent applicant: Konishiroku Photo Industry Co., Ltd. Agent: Nobuaki Sakaguchi (and one other person)

Claims (1)

[Claims] In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers is coated with a diffusible development inhibitor or its A silver halide color photographic light-sensitive material, characterized in that it contains a DIR compound that releases a diffusible precursor, and also contains a photographically useful reagent precursor.