JPH077189B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

The present invention relates to a silver halide color photographic light-sensitive material (hereinafter abbreviated as light-sensitive material), more specifically, stability during development processing and raw color light-sensitive material (exposure). (Meaning the previous color light-sensitive material) is simultaneously improved in storability.

[Prior Art] In recent years, there has been a demand for the development of high-quality and uniform photosensitive materials, and at the same time, the development process has become more automated.
And has been speeded up. That is, even if a light-sensitive material having high image quality performance is not sufficiently stable at the time of development processing, not only the original performance of the light-sensitive material cannot be brought out but also a slight development Due to fluctuations in processing conditions, it becomes a photosensitive material with a large variation in performance,
Cannot meet user needs. Known methods for improving the processing stability are, for example, a method of controlling the developability of silver halide, a method of using a coupler having a good developability, and a method of improving with various additives. Among them, a method for improving the processing stability by adding a non-photosensitive fine grain silver halide to the non-photosensitive hydrophilic colloid layer is, for example, U.S. Pat.
1,382, 3,737,317, JP-A-50-23228, 50-5
No. 5332, etc., and is known to exhibit a remarkable improvement effect.

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

On the other hand, it is generally practiced to use a diffusible DIR compound to improve the image quality. However, the use of this diffusible DIR compound deteriorates the raw storability of the light-sensitive material, and with the combination of conventional techniques, it is more and more raw. This caused deterioration of storage stability.

[Problems to be Solved by the Invention] Therefore, it is an object of the present invention to provide a light-sensitive material excellent in stability during development processing and raw storage stability. [Means for solving the problem] As a result of earnest research based on the aforementioned 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 oxidant of a color developing agent to release a diffusible development inhibitor or its diffusible precursor. A photosensitive material containing a DIR compound and containing a reagent precursor, wherein the photographically useful reagent is a development inhibitor and is photographically useful represented by the following general formulas (I) to (IX). It has been found that the above problems can be solved by using a light-sensitive material.

Hereinafter, the present invention will be described in detail.

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

In the general formula (1) AY) m, A represents a coupler component, m represents 1 or 2, and
Y represents a group capable of releasing a development inhibitor having a large diffusibility or a development inhibitor, which is a group which is bonded to the coupling position of the coupler component A and is released by the reaction with the oxidation product of the color developing agent.

It is sufficient that A has the properties of a coupler, and it is not always necessary to form a dye by coupling.

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

Diffusible DIR compound general formula (2A) Diffusible DIR compound general formula (2B) Diffusible DIR compound general formula (2C) Diffusible DIR compound general formula (2D) Diffusible DIR compound general formula (2E) Diffusible DIR compound general formula (3) Diffusible DIR compound general formula (4) Diffusible DIR compound general formula (5) In the above general formulas (2A) to (2D) and (3), R ₁ is an alkyl group, an alkoxy group, an acylamino group, a halogen atom, an alkoxycarbonyl group, a thiazolilideneamino group, an aryloxycarbonyl group, an acyloxy group, carbamoyl. Group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, nitro group, amino group, N-arylcarbamoyloxy group, sulfamoyl group, N-
It represents an alkylcarbamoyloxy 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, when n is 2, R ₁ may be the same or different, and the total number of carbon atoms contained in n R ₁ is 0 to 10.

R _{2 in the} general formula (2E) has the same meaning as R _{1 in} (2A) to (2D), X represents an oxygen atom, a sulfur atom or a selenium atom, and R ₂ in the general formula (4) is an alkyl group. Represents an aryl group or a heterocyclic group.

In the general formula (5), R ₃ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R ₄ represents a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an acylamino group, an alkoxycarbonylamino group, an aryloxy. It represents a carbonylamino group, an alkanesulfonamide group, a cyano group, a hetrocyclic group, an alkylthio group or an amino group. When R ₁ , R ₂ , R ₃ or R ₄ represents an alkyl group, it may be substituted or unsubstituted, linear or branched, or a cyclic alkyl group. The substituent is a halogen atom, a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group,
Examples thereof include an aryloxycarbonyl group, a sulfamoyl group, a carbamoyl group, a hydroxy group, an alkanesulfonyl group, an arylsulfonyl group, an alkylthio group and an arylthio group.

When R ₁ , R ₂ , R ₃ or R ₄ represents an aryl group, the aryl group may be substituted. As the substituent, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, a nitro group, an amino group, a sulfamoyl group, a hydroxy group, a carbamoyl group, an aryloxycarbonylamino group, an alkoxycarbonylamino group, an acylamino group, Examples thereof include a cyano group and a ureido group.

When R ₁ , R ₂ , R ₃ or R ₄ represents a heterocyclic group, it represents a 5-membered or 6-membered monocyclic or condensed ring containing a nitrogen atom, an oxygen atom or a sulfur atom as a hetero atom, and a pyridyl group,
A quinolyl group, a furyl group, a benzothiazolyl group, an oxazolyl group, an imidazolyl group, a thiazolyl group, a triazolyl group, a benzotriazolyl group, an imide group, an oxazine group, etc., which are further substituted by the substituents listed for the aryl group. May be done.

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

In the above general formula (5), the total number of carbon atoms contained in R ₃ and R ₄ is 1 to 15. In the above general formula (1), Y
Represents the following general formula (6).

Diffusible DIR compound General formula (6) -TIME-INHIBIT In the formula, the TIME group is a group that is bonded to the coupling position of the coupler and can be cleaved by a reaction with a color developing agent. After cleavage from the coupler, the INHIBIT group is appropriately cleaved. It is a group that can be suppressed and released. The INHIBIT group is a development inhibitor.

In the general formula (6), the -TIME-INHIBIT group represents the following general formulas (7) to (13).

Diffusible DIR compound general formula (7) Diffusible DIR compound general formula (8) Diffusible DIR compound general formula (9) Diffusible DIR compound general formula (10) Diffusible DIR compound general formula (11) Diffusible DIR compound general formula (12) Diffusible DIR compound general formula (13) In formulas (7) to (13), R ₅ represents 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, a ureido group, a cyano group, a nitro group. , A sulfonamide group, a sulfamoyl group, a carbamoyl group, an aryl group, a carboxy group, a sulfo group, a hydroxy group, and an alkanesulfonyl group, represented by the general formulas (7), (8), (9), (11) and (13) In the general formulas (7), (11), (12) and (13), 1 represents 1 or 2.
k represents an integer of 0 to 2, and in the general formulas (7), (10) and (11), R ₆ represents an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group or an aryl group, ) And (13), B is an oxygen atom or (R ₆ has the same meaning as previously defined.), And the INHIBIT group has the general formula defined by the general formulas (2A), (2B), (3), (4) and (5) and the carbon number. Except the same meaning.

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

When R ₅ and R ₆ represent an alkyl group, they may be substituted or unsubstituted, linear or cyclic. Examples of the substituent include the substituents enumerated when R _{1 to} R ₄ are alkyl groups.

When R ₅ and R ₆ represent an aryl group, the aryl group may be substituted. Examples of the substituent include the substituents enumerated when R _{1 to} R ₄ are aryl groups.

Of the above diffusible DIR compounds, the general formula (2A), (2
Those having a leaving group represented by B) and (2E) to (5) are particularly preferable.

Examples of the yellow image-forming coupler residue represented by A in the general formula (1) include pivaloyl acetanilide type,
Benzoyl acetanilide type, malon diester type, malon diamide type, dibenzoyl methane type, benzothiazolyl acetamide type, malon ester monoamide type, benzothiazolyl acetate type, benzoxazolyl acetamide type, benzoxazolyl acetate type, Malon diester type, benzimidazolyl acetamide type, or benzimidazolyl acetate type coupler residues, heterocyclic-substituted acetamides contained in U.S. Pat.No. 3,841,880 or coupler residues derived from heterocyclic substituted acetates or U.S. Pat.No. 3,770,446, British Patent 1 , 45
9,171, West German Patent (OLS) 2,503,009, JP-A-50-139
Examples thereof include a coupler residue derived from an acylacetamide described in No. 738 or Research Disclosure 15737, or a heterocyclic coupler residue described in US Pat. No. 4,046,574.

Examples of the magenta color image forming coupler residue represented by A include 5-oxo-2-pyrazoline nucleus, pyrazolo- [1,5-
a] A coupler residue having a benzimidazole nucleus or a cyanoacetophenone type coupler residue is preferable. The cyan image forming coupler residue represented by A is preferably a coupler residue having a phenol nucleus or an α-naphthol nucleus, and an indazolone or pyrazolotriazole coupler residue.

Furthermore, the coupler does not substantially form a dye after releasing the development inhibitor by coupling with the oxidized product of the developing agent.
The effect as a DIR coupler is the same. Examples of this type of coupler residue represented by A include U.S. Pat. No. 4,052,213,
4,088,491, 3,632,345, 3,958,993 or
Examples thereof include the coupler residue described in No. 3,961,959.
The preferred diffusible DIR compounds used in the present invention include, but are not limited to, the following compounds.

These diffusible DIR compounds of the present invention are described in US Pat.
No.3, No.3,227,554, No.3,617,291, No.3,958,993,
4,149,886, 3,933,500, JP-A-57-56837, 5
It can be easily synthesized by the method described in 1-13239, British Patents 2,072,363, 2,070,266, Research Disclosure, December 1981, No. 21228, and the like.

The addition amount of the diffusible DIR compound of the present invention is generally preferably 2 × 10 ^{−4 to} 5 × 10 ⁻¹ mol, and more preferably 1 × 10 ⁻³ to 1 × 10 ⁻¹ mol per mol of silver in the emulsion layer. It is a mole.

The addition method can be referred to the description of the photographically useful reagent precursor of the present invention described later.

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

Next, the photographic useful reagent precursor of the present invention will be described.

The photographically useful reagent precursor used in the present invention refers to a compound that stably exists under storage conditions and releases a photographic reagent by releasing a blocking group at a timing required during processing. The compounds represented by formulas (I) to (IX) may be mentioned.

General formula (I) General formula (II) General formula (III) General formula (IV) General formula (V) General formula (VI) General formula (VII) General formula (VIII) General formula (IX) In the general formulas (I) to (IX), A is a known photographic reagent in which a hetero atom is substituted, and concretely, it is represented by mercaptotetrazoles, mercaptothiadiazoles, benzotriazoles or indazoles to prevent fog. Agents, pyrazolidones, hydroquinones or p
-Developing agents typified by phenylenediamines (auxiliary developing agents), hydrazines, hydrazides, quaternary salts, fogging agents such as acetylenes or nucleating agents, thioethers, silver halides such as hypo or rhodanines. It also contains a solvent, an azo dye, and a photographic reagent having a redox function for releasing the photographic reagent as a function of development, for example, a color material for a color diffusion transfer photosensitive material.

X in the general formulas (I) to (VI) represents a divalent timing group, is bonded to a methyl group through an oxygen atom, and is a group that rapidly releases A after being cleaved as X-A during treatment. Represents Examples of such a connecting group include those disclosed in JP-A-54-145135.
Which releases A by the intramolecular ring-opening reaction described in JP-A No. 2072363 and JP-A No. 57-154234 which releases A by intramolecular electron irradiation, JP-A-57-17.
Examples thereof include those which release A with the elimination of carbon dioxide as described in 9842, and the linking group for formalin elimination described in Japanese Patent Application No. 57-20344. The structural formulas of the representative X described above are shown below.

Here, m represents 0 or an integer of 1 to 4, and n is 0 or 1.
Represents Q is -CO- or -SO ₂ - represents, Z represents a group of atoms which form a 5- to 7-membered.

It is W in formula ^{(II) -CR 5 R 6 -} , - O -, - S
-, - NR ⁷ - represents a 5-membered or 7-membered ring is formed together with Y, l (0 or 1) to form a four-membered ring when 0. R ⁵ , R ⁶ and R ⁷ are each a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 26 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, and 6 to 6 carbon atoms. 26
Represents an aryloxy group and may have a substituent.

Y represents a nonmetallic atomic group forming a 5-membered ring with W,
Examples of the 5-membered ring formed include succinimide, maleimide, oxazocydinone, thiohydantoin, hydantoin, urazole, and parabanic acid.
Examples of the 6-membered ring include glutaric acid imide, 3-oxyglutaric acid imide, barbituric acid, uracil, and benzoxazinedione.

Y ¹ in the general formula (VI) is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, a carbonic acid ester group, an amino group, a galbonamide group, a ureido group, a carboxy group. , Oxycarbonyl group, carbamoyl group, acyl group, sulfo group, sulfonyl group, sulfamoyl group, cyano group, nitro group.

In the general formula (VII), X ² represents a carbon atom or a sulfur atom, D represents an electrophilic group (eg, carbonyl group, thiocarbonyl group, sulfonyl group, sulfinyl group, allyl group, benzyl group, etc.), and L Is Represents a linking group that bonds D to D, and R represents a hydrogen atom, an alkyl group, or an aryl group. m ₁ and n ₁ are each 1 to
3 and preferably 1-2.

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

R ² in the 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 the aryl group may have a substituent. Good.

R ³ and R ⁴ in the general formulas (IV) and (V) are each an alkyl group having 1 to 16 carbon atoms, an aryl group having 6 to 26 carbon atoms, an alicyclic group having 5 to 10 carbon atoms, and 1 to 1 carbon atoms. It represents 10 heterocyclic residues, each of which may have a substituent.

In formula (VIII), R ⁷ , R ⁸ and R ⁹ each represent a substituent, and at least one of R ⁷ , R ⁸ and R ⁹ is bonded to the amide nitrogen atom through a π bond during development. At least one of R ⁷ , R ⁸ and R ⁹ is an electron-withdrawing group which may be generated, and at least one of R ⁷ , R ⁸ and R ⁹ is solvated by intramolecular nucleophilic reaction of the amide nitrogen atom or intramolecular electron transfer from the amide nitrogen atom. A photographically useful reagent is substituted at the position where it can be cleaved, n ₂ represents 0 or an integer of 1 to 4, and m ₂ represents an integer of 1 to 3.

R ¹⁰ , R ¹¹ and R ¹² in the general formula (IX) each represent a substituent, m ₃ represents 0.1 or 2, n ₃ represents 0 or 1, m
The sum of ₃ and n ₃ is 1-3.

Specific examples of the photographically useful reagent precursor used in the present invention are shown below. However, it is not limited to these.

[Exemplified compound]

These photographically useful reagent precursors are described, for example, in JP-A-27 / 27.
-135949, 59-3434, 59-93442, 59-137
945, 59-140445, 59-201057, 59-21843
No. 9, No. 59-219741, No. 60-41034, and the like. In the present invention, the above-mentioned photographically useful reagent is a development inhibitor.

The photographic useful reagent precursor according to the present invention is a silver halide emulsion layer, an undercoat layer, a protective layer, an intermediate layer of a silver halide photosensitive material,
It may be added to any of the filter layer, antihalation layer and other auxiliary layers. It is preferably added to the same layer as the diffusible DIR compound of the present invention.

In order to add the photographically useful reagent precursor used in the present invention to these layers, the photographically useful reagent precursor is left as it is in the coating liquid for forming the layer, or a solvent that does not adversely affect the light-sensitive material. , For example water,
It can be added after being dissolved in alcohol or the like at an appropriate concentration. It is also possible to add a photographically useful reagent precursor by welding it to a high boiling organic solvent and / or a low boiling organic solvent, emulsifying and dispersing it in an aqueous solution.

Organic solvents with a boiling point of 150 ° C or higher, such as phenol derivatives, phthalic acid alkyl esters, phosphoric acid esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters, trimesic acid esters, which do not react with the oxidized product of the developing agent as a high boiling point solvent. A solvent is used.

The high-boiling organic solvent that can be used in the present invention,
U.S. Patents 2,322,027, 2,533,514, 2,835,579
No. 3,287,134, 2,353,262, 2,852,383,
Same 3,554,755, same 3,676,137, same 3,676,142, same
3,700,454, 3,748,141, 3,779,765, 3,83
7,863, British Patents 958,441, 1,222,753, OLS2,5
38,889, JP-A-47-1031, 49-90523, 50-238
No. 23, No. 51-26037, No. 51-27921, No. 51-27922
No. 51, No. 51-26035, No. 51-26036, No. 50-62632,
53-1520, 53-1521, 53-15127, 54-1
19921, 54-119922, 55-25057, 55-3686
No. 9, No. 56-19049, No. 56-81836, Japanese Patent Publication No. 48-29060
Those listed in No.

Low-boiling or water-soluble organic solvents that can be used with or instead of high-boiling solvents are U.S. Patent Nos. 2,801,171 and 2,949,3.
Examples include those described in No. 60 and the like. The low boiling point substantially water-insoluble organic solvent includes ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, benzene, etc., and the water-soluble organic solvent includes acetone, Methyl isobutyl ketone, β-ethoxyethyl acetate, methoxyglycol acetate, methanol, ethanol, acetonitrile, dioxane,
Examples include dimethylformamide, dimethylsulfoxide, hexamethylphosphoramide, diethylene glycol monophenyl ether, and phenoxyethanol.

The timing for adding the photographically useful reagent precursor of the present invention may be selected at any time during the production process, but it is generally preferred to be just before coating.

The preferred addition amount of the photographically useful reagent precursor of the present invention varies depending on the kind of the photographically useful reagent, but is preferably 1 × 10 ⁻⁸ to 1 × 10 ⁻¹ mol per mol of silver, and more preferably a mecapto antifoggant. Is 1 × 10 ^-6 to 1 × 10 ^-1 mol, and azole antifoggants such as benzotriazole are 1 × 10 ^-5 〜
It is 1 × 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 having different sensitivities. In this case, any of the highest sensitivity layer, the middle sensitivity layer and the lowest sensitivity layer can be used. Although the diffusible DIR compound and the photographically useful precursor of the present invention can be applied, it is particularly preferably applied to the middle and high sensitivity layers.

When the present invention is applied to a multilayer color light-sensitive material, blue sensitivity,
At least one of the green-sensitive and red-sensitive light-sensitive emulsion layers may contain the diffusible DIR compound of the present invention, but preferably in a plurality of light-sensitive emulsion layers, more preferably in all light-sensitive emulsion layers. That is, it contains the diffusible DIR compound of the present invention.

The silver halide composition of the photosensitive emulsion layer of the present invention is arbitrary, and examples thereof include silver iodobromide, silver bromide, silver chlorobromide, and silver chloroiodide.
Silver chloroiodobromide and the like may be contained. The present invention can also be applied to so-called black-and-white light-sensitive materials.

The silver halide grains used in the silver halide emulsion of the present invention may be those obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after forming seed grains. The method of forming seed particles and the method of growing seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed at the same time, or the other may be mixed in a liquid containing either one. Alternatively, it may be produced by sequentially adding halide ions and silver ions simultaneously while controlling the pH and pAg in the mixing vessel while taking into consideration the critical growth rate of silver halide crystals. By this method, silver halide grains having a regular crystal form and a substantially uniform grain size can be obtained. After the growth, the conversion method may be used to change the halogen composition of the grains.

In the production of the silver halide emulsion of the present invention, the grain size, grain shape, grain size distribution and grain growth rate of silver halide grains can be controlled by using a silver halide solvent, if necessary. it can.

The silver halide grains used in the silver halide emulsion of the present invention are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium in the process of forming grains and / or the process of growing grains. It is possible to add a metal ion using at least one selected from a salt (complex salt containing) and an iron salt (complex salt containing iron) so that these metal elements are contained inside the particle and / or on the surface of the particle. By placing in a suitable reducing atmosphere, reduction sensitizing nuclei can be imparted to the inside and / or the surface of the grain.

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 may be contained therein. When removing the salts, Research. Research Disclosur
e) It can be carried out based on the method described in 17643.

The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal form such as a cube, octahedron or tetradecahedron, or may have an irregular shape such as a sphere or a plate. It may have a crystalline form. In these particles,
Any ratio of {100} plane to {111} plane can be used. Further, it may have a composite form of these crystal forms, and particles of various crystal forms may be mixed.

The average grain size of the silver halide grains of the present invention (the grain size represents the diameter of a circle having an area equal to the projected area) is 5 μm.
m or less is preferable, and 3 μm or less is particularly preferable.

The silver halide emulsion of the present invention may have any grain size distribution. An emulsion having a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion having a narrow grain size distribution (referred to as a monodisperse emulsion. The monodisperse emulsion referred to here is the standard deviation of the grain size distribution. When divided by the average grain size, the value is 0.20 or less, where the grain size is the diameter in the case of spherical silver halide and the projected image in the case of grains other than spherical. The diameter when converted to a circular image of the same area is shown). Further, a polydisperse emulsion and a monodisperse emulsion may be mixed and used.

The silver halide emulsion of the present invention may be used as a mixture of two or more kinds of silver halide emulsions formed separately.

The silver halide emulsion used in the present invention is, for example, British Patent 61.
No. 8,061, No. 1,315,755, No. 1,396,696, Japanese Patent Publication No.44-1
5748, U.S. Patents 1,574,944, 1,623,499, 1,67
3,522, 2,278,947, 2,399,083, 2,410,689
No., No. 2,419,974, No. 2,448,060, No. 2,487,850,
2,518,698, 2,521,926, 2,642,361, 2,6
94,637, 2,728,668, 2,739,060, 2,743,18
No. 2, No. 2,743,183, No. 2,983,609, No. 2,983,610,
3,021,215, 3,026,203, 3,297,446, 3,2
No. 97,447, No. 3,361,564, No. 3,411,914, No. 3,554,75
No. 7, No. 3,565,631, No. 3,565,633, No. 3,591,385,
No. 3,656,955, No. 3,761,267, No. 3,772,031, No. 3,8
57,711, 3,891,446, 3,901,714, 3,904,41
No. 5, No. 3,930,867, No. 3,984,249, No. 4,054,457,
Ibid., 4,067,740, Research. Disclosure (Resea
rch Disclosure) 12008, 13452, 13654, T.
H.James.The Theory of the Photographic Process. (4
th Ed. Macmillan. 1977) p67 to 76 and the like are preferably used for sensitization.

As the sensitizing dye, a cyanine dye, a merocyanine dye,
A complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a steryl dye, a hemioxanol dye and the like are used.

Particularly useful dyes are cyanine dyes, merocyanine dyes,
And a complex merocyanine dye. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei: and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus, that is, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus Nuclei, quinoline nuclei, etc. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-2,
5- to 6-membered heterocyclic nuclei such as 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus can be applied.

Examples of useful sensitizing dyes used in a blue-sensitive silver halide emulsion layer include West German Patent 929,080 and U.S. Pat.
No. 58, No. 2,493,748, No. 2,503,776, No. 2,519,001
No., No. 2,912,329, No. 3,656,959, No. 3,672,897,
Examples thereof include those described in JP-A-3,694,217, JP-A-4,025,349, JP-A-4,046,572, British Patent 1,242,588, JP-B-4414030 and JP-A-52-24844. Further, useful sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Patents 1,939,201, 2,072,908, and 2,
Representative examples thereof include cyanine dyes, merocyanine dyes and complex cyanine dyes such as those described in 739,149, 2,945,763 and British Patent 505,979. Further, useful sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Pat.
No. 4, No. 2,270,378, No. 2,442,710, No. 2,454,629,
Cyanine dyes such as those described in No. 2,776,280,
Typical examples thereof include merocyanine dyes and complex cyanine dyes. Furthermore, US Patent 2,
213,995, 2,493,748, 2,519,001, West German patent 9
Cyanine dyes, merocyanine dyes or complex cyanine dyes such as those described in No. 29,080 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 thereof are Japanese Examined Patent Publication Nos. 43-4932, 43-4933, and 43-4936,
44-32753, 45-25831, 45-26474, 46
-11627, 46-18107, 47-8741, 47-1111
No. 4, No. 47-25379, No. 47-37443, No. 48-28293,
48-38406, 48-38407, 48-38408, 48
-41203, 48-41204, 49-6207, 50-4066
No. 2, No. 53-12375, No. 54-34535, No. 55-1569,
JP-A-50-33220, JP-A-50-33828, JP-A-50-38526,
51-107127, 51-115820, 51-135528,
51-151527, 52-23931, 52-51932, 52-
104916, 52-104917, 52-109925, 52-11
0618, 54-80118, 56-25728, 57-1483
No. 58-10753, No. 58-91445, No. 58-153926, No.
59-114533, 59-116645, 59-116647, U.S. Patents 2,688,545, 2,977,229, 3,397,060, and
3,506,443, 3,578,447, 3,672,898, 3,67
No. 9,428, No. 3,769,301, No. 3,814,609, No. 3,837,862
No. etc.

Examples of dyes that are used together with sensitizing dyes and have no spectral sensitizing effect, or substances that do not substantially absorb visible light and exhibit supersensitization include, for example, aromatic organic acid formaldehyde condensate ( For example, U.S. Pat.
7,510), cadmium salts, azaindene compounds, aminostilbene compounds substituted with nitrogen-containing heterocyclic ring groups (for example, US Pat. Nos. 2,933,390 and 3,635,721).
Those listed in No.). U.S. Patent 3,615,613,
The combinations described in 3,615,641, 3,617,295 and 3,635,721 are particularly useful.

US Pat. No. 2,713,541 as an antifoggant and a stabilizer.
No. 2,743,180, pentazaindenes described in 2,743,181, U.S. Patents 2,716,062, 2,444,607,
2,44,605, 2,756,147, 2,835,581, 2,8
52,375, Research Disclosure (Research D
isclosure) tetrazoindenes described in No. 14851,
Triazaindenes described in U.S. Pat. No. 2,772,164, and azaindenes such as polymerized azaindenes described in JP-A-57-211142; U.S. Pat. No. 2,131,03
U.S. Pat. Nos. 3,342,596 and 3,954,478, thiazolium salts, US Pat. No. 3,148,067, pyrilium salts, and quaternary onium salts such as phosphonium salts described in JP-B-50-40665; Patent 2,403,927
No. 3,266,897, No. 3,708,303, JP-A-55-135835
No. 59-71047, mercaptotetrazoles, mercaptotriazoles, mercaptodiazoles, mercaptothiazoles described in U.S. Pat.No. 2,824,001, mercaptobenzthiazoles described in U.S. Pat. Benzimidazoles, mercaptooxadiazoles described in U.S. Pat.No. 2,843,491, mercapto-substituted heterocyclic compounds such as mercaptothiadiazoles described in U.S. Pat.No. 3,364,028; U.S. Pat.No. 3,236,652, Japanese Patent Publication No. 43-10256 Catechols described, resorcins described in Japanese Patent Publication No. 56-44413, and polyhydroxybenzenes such as gallic acid esters described in Japanese Patent Publication No. 43-4133; tetrazoles described in West German Patent 1,189,380 , The triazoles described in US Pat. No. 3,157,509, US Pat. Benztriazoles described in 4,721, urazoles described in U.S. Patent 3,287,135, pyrazoles described in U.S. Patent 3,106,467, U.S. Patent 2,2
71,229, and indazoles, and JP-A-59-
Polymerized benztriazoles and other azoles described in 90844 and pyrimidines described in US Patent 3,161,515, 3-pyrazolidones described in US Patent 2,751,297, and polymers described in US Patent 3,021,213 Heterocyclic compounds such as polypyrrolidone, that is, polyvinylpyrrolidones; JP-A Nos. 54-130929 and 59-137945
No. 140445, British Patent 1,356,142, US Patent 3,57
5,699, various inhibitor precursors described in 3,649,267 and the like; sulfinic acid and sulfonic acid derivatives described in US Pat. No. 3,047,393; US Pat. No. 2,566,266,
Inorganic salts described in Nos. 2,839,405, 2,488,709, and 2,728,663 are available.

As the binder (or protective colloid) of the silver halide emulsion of the present invention, it is advantageous to use gelatin,
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 homopolymers or copolymers can also be used.

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

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention should be hardened by using one or more hardeners that crosslink binder (or protective colloid) molecules and enhance film strength. You can The hardener can be added in an amount such that the photosensitive material can be hardened to the extent that it is not necessary to add the hardener to the processing liquid, but it is also possible to add the hardener to the processing liquid.

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

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

In the color development processing, the emulsion layer of the light-sensitive material of the present invention undergoes a coupling reaction with an oxidant of an aromatic primary amine developer (for example, p-phenylenediamine derivative, aminophenol derivative, etc.) to form a dye. Dye forming couplers are used. The dye-forming couplers are usually selected so that a dye that absorbs the light of the light-sensitive spectrum of the emulsion layer is formed for each emulsion layer. A magenta dye forming coupler is used in the sensitive emulsion layer and a cyan dye forming coupler is used in the red sensitive emulsion layer. However, the light-sensitive material may be produced by a method different from the above combination depending on the purpose.

It is desirable that these dye-forming couplers have a group called a ballast group, which has a carbon number of 8 or more, which makes the coupler non-diffusible. Further, these dye-forming couplers are required to reduce 4 molecules of silver ions in order to form 1 molecule of dye, but even if they are 4 equivalents, only 2 molecules of silver ions need to be reduced. Either equivalence may be used. Dye-forming couplers include development accelerators, bleaching accelerators, developers, silver halide solvents, toning agents, hardeners, fog agents, antifoggants, and chemical sensitizers by coupling with an oxidized product of a developing agent. , Spectral sensitizers, and compounds that release photographically useful fragments such as desensitizers. Colored couplers having a color correction effect may be used in combination with these dye-forming couplers within a range that does not impair the effects of the present invention.

As the yellow dye-forming coupler (yellow coupler) used in the present invention, various acylacetanilide type couplers can be preferably used. Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous. Specific examples of yellow couplers that can be used include British Patent No. 1,077,874 and Japanese Patent Publication No. 45-4.
0757, JP-A-47-1031, 47-26133, 48-944
No. 32, No. 50-87650, No. 51-3631, No. 52-115219
No. 54-99433, No. 54-133329, No. 56-30127,
U.S. Pat.Nos. 2,875,057, 3,253,924, 3,265,506
No. 3,408,194, 3,551,155, 3,551,156,
3,64,841, 3,725,072, 3,730,722, 3,8
91,445, 3,900,483, 3,929,484, 3,933,50
No. 0, 3,973,968, 3,990,896, 4,012,259,
4,022,620, 4,029,508, 4,057,432, 4,1
06,942, 4,133,958, 4,269,936, 4,286,05
No. 3, No. 4,304,845, No. 4,314,023, No. 4,336,327,
No. 4,356,258, No. 4,386,155, No. 4,401,752, etc.

Also, magenta dye-forming coupler (magenta coupler)
As various types, various 5-pyrazolone-based couplers, pyrazolobenzimidazole-based couplers, pyrazolotriazole-based couplers, and open-chain acylacetonitrile-based couplers can be preferably used. Specific examples of magenta couplers that can be advantageously used include Japanese Patent Application Nos. 58-164882 and 58-167326.
No. 58-206321, 58-214863, 58-217339
No. 59-24653, Japanese Patent Publication No. 40-6031, No. 40-6035
No. 45-40757, 47-27411, 49-37854,
JP-A-50-13041, 51-26541, 51-37646,
51-105820, 52-42121, 53-123129, 5
3-125835, 53-129035, 54-48540, 56-
29236, 56-75648, 57-17950, 57-35858
No. 57-146251, No. 59-99437, British Patent No. 1,25
2,418, U.S. Pat.Nos. 2,600,788, 3,005,712, and
3,062,653, 3,127,269, 3,214,437, 3,25
3,924, 3,311,476, 3,419,391, 3,519,429
No., No. 3,558,319, No. 3,582,322, No. 3,615,506,
3,658,544, 3,705,896, 3,725,067, 3,7
58,309, 3,823,156, 3,834,908, 3,891,44
No. 5, No. 3,907,571, No. 3,926,631, No. 3,928,044,
3,935,015, 3,960,571, 4,076,533, 4,1
33,686, 4,237,217, 4,241,168, 4,264,72
No. 3, No. 4,301,235, No. 4,310,623, 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 advantageously used include British Patents 1,038,331 and 1,543,040.
Japanese Patent Publication No. 48-36894, Japanese Patent Publication No. 48-59838, 50-13
7137, 51-146828, 53-105226, 54-1152
No. 30, No. 56-29235, No. 56-104333, No. 56-126833
No. 57-133650, No. 57-155538, No. 57-204545
No. 58, No. 58-118643, No. 59-31953, No. 59-31954,
59-59656, 59-124341, 59-166956, U.S. Pat.Nos. 2,369,929, 2,423,730, 2,434,272.
No. 2, 2,474,293, 2,698,794, 2,772,162,
2,801,171, 2,895,826, 3,253,924, 3,3
11,476, 3,458,315, 3,476,563, 3,591,38
No. 3, No. 3,737,316, No. 3,758,308, No. 3,767,411,
3,790,384, 3,880,661, 3,926,634, 4,0
04,929, 4,009,035, 4,012,258, 4,052,21
No. 2, No. 4,124,396, No. 4,134,766, No. 4,138,258,
4,146, 396, 4,149,886, 4,178,183, 4,
205,990, 4,254,212, 4,264,722, 4,288,5
32, 4,296,199, 4,296,200, 4,299,914
No. 4,433,999, 4,334,011, 4,386,155,
No. 4,401,752, No. 4,427,767, etc.

As a colored coupler, for example, British Patent No. 937,621
No. 1,035,959, No. 1,255,111, JP-A-48-22028
No. 52-42121, Japanese Patent Publication No. 38-22335, 44-2016
No. 44-15754, U.S. Patent Nos. 2,449,966, 2,521,
908, 2,543,691, 2,801,171, 2,983,608
No. 3, No. 3,005,712, No. 3,034,892, No. 3,061,432,
3,419,391, 3,476,560, 3,476,563, 3,4
81,741, 3,519,429, 3,583,971, 3,622,32
No. 8, No. 3,684,514, No. 4,004,929, No. 4,070,191,
4,138,258, 4,138,264, 4,163,670, 4,2
Those described in Nos. 92,400 and 4,369,248 can be used.

As colorless couplers, U.S. Pat.No. 2,998,314 and British Patent 1,284,649 are used for controlling gradation, preventing color turbidity, and fogging.
The so-called Weiss coupler described in German Patent No. 1,168,769 can be used.

Dissolving a hydrophobic compound in a solvent having a low boiling point solvent alone or in combination with a high boiling point solvent, as a dispersion aid when dispersed in water using mechanical or ultrasonic waves, an anionic surfactant, a nonionic surfactant, Cationic surfactants can be used.

Between the emulsion layers (the same color-sensitive layer and / or different color-sensitive layers) of the light-sensitive material of the present invention, the oxidant of the developing agent or the electron transfer agent moves to cause color turbidity or deterioration of sharpness. In addition, an anti-foggant can be used to prevent the graininess from being conspicuous.

The antifoggant may be contained in the emulsion layer itself,
An intermediate layer may be provided between adjacent emulsion layers and contained in the intermediate layer.

An image stabilizer which prevents deterioration of a dye image can be used in the light-sensitive material of the present invention.

The protective layer of the light-sensitive material of the present invention, a hydrophilic colloid layer such as an intermediate layer is a fog-prevention due to discharge caused by charging of the light-sensitive material due to friction, etc., and an ultraviolet absorber to prevent deterioration of the image by UV light. May be included.

To the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material of the present invention, a compound such as a development accelerator or a development retarder which changes the developability and a bleaching accelerator can be added. Compounds that can be preferably used as the development accelerator are Research. Research Disclosure 176
No. 43, items XXI to D, and the development retarder is a compound, No. 17643, item XXI, item E. A black and white developing agent and / or its precursor may be used for the purpose of promoting development and other purposes.

The photographic emulsion layer of the light-sensitive material of the present invention comprises a polyalkylene oxide or a derivative thereof such as an ether, an ester or an amine, a thioether compound, a thiomorpholine compound, a quaternary ammonium compound, for the purpose of increasing sensitivity, increasing contrast or promoting development. It may include a urethane derivative, a urea derivative, an imidazole derivative, and the like.

The light-sensitive material of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer, and / or an irradiation prevention layer. In these layers and / or in the emulsion layers, dyes which are bleached or bleached from the light-sensitive material during the development processing may be contained.

A matting agent can be added to the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material of the present invention for the purpose of reducing gloss of the light-sensitive material, improving writing properties, and preventing sticking of the light-sensitive materials to each other.

A lubricant may be added to the light-sensitive material of the present invention to reduce its sliding friction.

An antistatic agent for the purpose of antistatic can be added to the light-sensitive material of the present invention. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and is a hydrophilic colloid other than the emulsion layer and / or the emulsion layer on the side of the support on which the emulsion layer is laminated. It may be used in layers.

In the photographic emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material of the present invention, coating property improvement, antistatic property, slip property improvement,
Various surfactants can be used for the purpose of emulsion dispersion, prevention of adhesion, improvement of photographic characteristics (acceleration of development, hardening, sensitization, etc.).

The support used in the light-sensitive material of the present invention includes an α-olefin polymer (for example, polyethylene, polypropylene,
From papers laminated with ethylene / butene copolymer), flexible reflective supports such as synthetic papers, semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide And a flexible support in which a reflective layer is provided on these films, glass, metal, pottery, and the like.

The photosensitive material of the present invention is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support, if necessary, and then directly or on the surface of the support, antistatic property, dimensional stability, abrasion resistance, It may be applied via one or more subbing layers to improve hardness, antihalation properties, friction properties, and / or other properties.

At the time of application of the light-sensitive material of the present invention during production, a thickener may be used in order to improve the application property. For a hardener such as a hardener that causes gelation before coating when it is added to the coating solution in advance because it has a high reactivity, it is recommended to mix it with a static mixer or the like immediately before coating. preferable.

In preparing the light-sensitive material of the present invention, the silver halide emulsion layer and other hydrophilic colloid layers were researched. Research Disclosure 17643 No. XV A
It can be applied by the method described in Section B and dried by the method described in Section B.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in the spectral region where the emulsion layer constituting the light-sensitive material of the present invention has sensitivity. As a light source, natural light (sunlight), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, various laser light, light emitting diode light, electron beam,
Any of light emitted from a phosphor excited by X-rays, γ-rays, α-rays and the like can be used.

The exposure time is, of course, from 1 millisecond to 1 second which is usually used in a camera, and it is also possible to use exposure shorter than 1 microsecond, for example, exposure of 100 nanoseconds to 1 microsecond using a cathode ray tube or a xenon flash lamp. However, exposure longer than 1 second is possible. The exposure may be performed continuously or intermittently.

Various color developments can be used for the development processing of the light-sensitive material of the present invention. Alternatively, a color image may be formed by the inversion method. When the reversal method is used, a black and white negative development step is carried out and white exposure is carried out without a fixing processing step, or a color development processing is carried out by further processing in a bath containing a fogging agent.
(The processing step of providing white exposure or the step of processing with a fog 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 color image, and specifically, Specifically, it is a step of forming a color image by a coupling reaction between an oxidized product of a color developing agent and a color coupler.

Therefore, in the color development processing step, it is usually necessary to include a color developing agent in the color developing solution, but the color developing agent is incorporated in the color photographic material, and the color developing solution containing the color developing agent or Treatment with an alkaline solution (activator solution) is also included. The color-developing agent contained in the color-developing solution is an aromatic primary amine color-developing agent, and includes aminophenol-based and p-phenylenediamine-based derivatives. These color developing agents can be used as salts of organic acids and inorganic acids, for example, salt acid, sulfate, P-toluenesulfonate, sulfite, oxalate,
Benzene sulfonate and the like can be used.

These compounds are generally about 0.1 g per color developer 1.
To about 30 g, more preferably about 1 g to 15 g for Color Developer 1. If the amount added is less than 0.1 g, sufficient color density cannot be obtained.

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

Examples of the aminophenol-based developer include o-aminophenol, p-aminophenol, 5-amino-2-
Oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene and the like are included.

A particularly useful primary aromatic amine color developer is NN'-
It is a dialkyl-p-phenylenediamine compound, and the alkyl group and the phenyl group may be substituted or may not be substituted. Among them, particularly useful compound examples include NN'-dimethyl-p-phenylene diamine 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
-Toluene sulfonate etc. can be mentioned.

The color developing agents may be used alone or in combination of two or more kinds. Furthermore, the color developing agent may be incorporated in a color photographic material. For example, US Pat.
A method of incorporating a color developing agent such as 9,492 into a metal salt and incorporating it therein, U.S. Pat. No. 3,342,559 and Research. As disclosed in Research Disclosure No. 15159 in 1976, a method of forming a Schiff salt and incorporating a color developing agent therein, as a dye precursor as shown in JP-A-58-65429 and 58-24137. It is possible to use a method of incorporating a finger, a method of incorporating a color developing agent precursor such as that shown in US Pat. No. 3,342,597, and the like. In this case, the light-sensitive material can be processed with an alkaline solution (activator solution) instead of the color developing solution, and the bleach-fixing process is performed immediately after the alkaline solution process.
The color developing solution used in the present invention may contain an alkaline agent usually used in a developing solution, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate or borax. And further contains various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, or development modifiers such as citrazinic acid, and preservatives such as hydroxylamine or sulfite. May be. Further, various antifoaming agents and surfactants, and an organic solvent such as methanol, dimethylformamide or dimethylsulfoxide, etc. may be appropriately contained.

The pH of the color developer used in the present invention is usually 7 or higher, preferably about 9-13.

In the color developing solution used in the present invention, if necessary, diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, an aromatic secondary alcohol, hydroxamic acid, bentose or an antioxidant is used. Hexose, pyrogallol-1,3
-Dimethyl ether and the like may be contained.

Various chelating agents can be used as a sequestering agent in the color developing solution used in the present invention. For example, as the chelating agent, ethylenediaminetetraacetic acid, amine polycarboxylic acid such as diethylenetriaminopentaacetic acid,
Organic phosphonic acids such as 1-hydroxyethylidene-1,1'-diphosphonic acid, aminopolyphosphonic acids such as aminotri (methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acids such as citric acid or gluconic acid, 2-phosphonobutane- Examples thereof include phosphonocarboxylic acid such as 1,2,4-tricarboxylic acid, polyphosphoric acid such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compound.

[Effects of the Invention] According to the present invention, as is apparent from the following examples, it is possible to provide a light-sensitive material excellent in stability during development processing and raw storage stability.

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

Green-sensitive low-sensitivity silver halide gelatin emulsion (average grain size
Silver iodobromide emulsion containing 0.5 mol of 6 mol% silver iodide) 1 kg
(Amount of silver 0.5 mol) Add the following dispersion
Samples A to H were prepared by coating so as to be 1.5 g / m ₂ .

(Dispersion) 30 g of coupler, 9 g of coupler, diffusible DIR compound of Table 1
0.4 g and 0.8 g of the photographically useful reagent precursor in Table 1 were dissolved in 80 g of tricresyl phosphate and 120 g of ethyl acetate, mixed with 400 g of 10% gelatin and 4.5 g of sodium triisopropylnaphthalenesulfonate, and then mixed in a colloid mill. Emulsify and disperse.

Each sample thus obtained and each of these samples
The sample left to stand in an atmosphere of 20 ° C and 20% relative humidity for 3 days is exposed to green through a wedge, and the following development processing is performed.
The results shown in Table 1 were obtained.

Processing process (37.8 ℃) 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 15 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 processing solution used in each processing step is as follows.

[Color developer composition] 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline sulfate 4.25 g anhydrous sodium sulfite 2.0 g hydroxyamine 1/2 sulfate 2.0 g anhydrous potassium carbonate 37.5 g Odor Sodium chloride 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1.

[Bleaching liquid composition] Ethylenediaminetetraacetic acid iron ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 ml Add water to adjust the pH to 6.0 using ammonia water.

[Fixer composition] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.6 g Sodium metasulfite 2.3 g Water is added to adjust the pH to 1 using acetic acid to adjust the pH to 6.0.

[Stabilizing solution composition] Formalin (37% aqueous solution) 1.5 ml Conidax (Konishi Photo Industry Co., Ltd.) 7.5 ml Add water to make 1.

As is clear from Table 3, according to the present invention, it is well understood that the processing stability and the raw storability are remarkably improved.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one of said silver halide emulsion layers reacts with an oxidant of a color developing agent. A silver halide color photographic light-sensitive material containing a DIR compound which releases a diffusible development inhibitor or a diffusible precursor thereof, and a photographic useful reagent precursor represented by the following general formulas (I) to (IX). A silver halide color photographic light-sensitive material, wherein the photographically useful reagent is a development inhibitor. General formula (I) General formula (II) General formula (III) General formula (IV) General formula (V) General formula (VI) General formula (VII) General formula (VIII) General formula (IX) Here, in the general formulas (I) to (IX), A is a photographic reagent substituted with a hetero atom. X in the general formulas (I) to (VI) represents a divalent timing group, is bonded to a methyl group through an oxygen atom, and is a group that rapidly releases A after being cleaved as X-A during treatment. Represents M in the general formulas (I) to (IX) represents 0 or an integer of 1 to 4, and n represents 0 or 1. Q is -CO- or -SO ₂
Represents-, and Z represents an atomic group forming 5 to 7 members. It is W in formula ^{(II) -CR 5 R 6 -} , - O -, - S
-, - NR ⁷ - represents a 5-membered or 7-membered ring is formed together with Y, l (0 or 1) to form a four-membered ring when 0. R ⁵ , R ⁶ and R ⁷ are each a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 26 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, and 6 to 6 carbon atoms. 26
Represents an aryloxy group and may have a substituent Y represents a non-metal atom group forming a 5-membered ring or a 6-membered ring with W. Y ¹ in the general formula (VI) is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, a carbonic acid ester group, an amino group, a galbonamide group, a ureido group, a carboxy group. , Oxycarbonyl group, carbamoyl group, acyl group, sulfo group, sulfonyl group, sulfamoyl group, cyano group, nitro group. In the general formula (VII), X ² represents a carbon atom or a sulfur atom, D represents an electrophilic group, and L represents Represents a linking group that bonds D to D, and R represents a hydrogen atom, an alkyl group, or an aryl group. m ₁ and n ₁ are each 1 to
Represents 3. R ¹ in the general formulas (I), (III), (IV) and (V)
Represents a substituent on the phenyl nucleus. R ² in the 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 the aryl group may have a substituent. Good. R ³ and R ⁴ in the general formulas (IV) and (V) are each an alkyl group having 1 to 16 carbon atoms, an aryl group having 6 to 26 carbon atoms, an alicyclic group having 5 to 10 carbon atoms, and 1 carbon atom. To 10 heterocyclic residues, each of which may have a substituent. In formula (VIII), R ⁷ , R ⁸ and R ⁹ each represent a substituent, and at least one of R ⁷ , R ⁸ and R ⁹ is bonded to the amide nitrogen atom via a π bond during development. At least one of R ⁷ , R ⁸ and R ⁹ is an electron-withdrawing group that may be generated and is cleaved by an intramolecular nucleophilic reaction of the amide nitrogen atom or an intramolecular electron transfer from the amide nitrogen atom. A photographically useful reagent is substituted at a possible position, n ₂ represents 0 or an integer of 1 to 4, and m ₂ represents an integer of 1 to 3. R ¹⁰ , R ¹¹ and R ¹² in the general formula (IX) each represent a substituent, m ₃ represents 0, 1 or 2, n ₃ represents 0 or 1, and the sum of m ₃ and n ₃ is 1 ~ 3.