JPH0558536B2 - - Google Patents

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material in which fluctuations in photographic performance during storage over time are improved.

[Prior art]

In recent years, advances in silver halide photographic materials (hereinafter referred to as "photosensitive materials") have been remarkable, and high-sensitivity fine-grain technology has been developed that harmonizes the contradictory properties of sensitivity and graininess. ,
It has demonstrated its effectiveness as a photosensitive material for printing. However, with the introduction of small format photosensitive materials for photography (e.g. 110 film, disk film, etc.), enlarged prints from negative film suffer from image roughness (graininess) and deterioration of sharpness. It is also true that the image quality is significantly degraded. Conventionally, various techniques for improving sharpness have been known, and among them, many methods have been disclosed that use couplers that can release a development inhibitor or its precursor during a coupling reaction with an oxidized developing agent, so-called DIR couplers. As a useful DIR coupler, Japanese Patent Publication No. 55-34933, Japanese Patent Publication No. 57-93344,
U.S. Patent No. 3227544, U.S. Patent No. 3615506, U.S. Patent No. 3617291,
It is described in No. 3701783, etc. Especially diffusive
It is known that when a compound such as a DIR coupler is used, which has an effect on so-called distant emulsion layers, interimage effects (IIE) are further emphasized and color reproducibility is improved. However, diffusive DIR has the drawback that it is susceptible to fluctuations in photographic performance during storage over time, and in particular, fog is likely to increase, so it has not yet been fully satisfied.

[Purpose of the invention]

The present invention has been made in view of the above circumstances, and its object is to provide a photographic material in which fluctuations in photographic performance, particularly increases in fog, are prevented during storage over time.

[Structure of the invention]

The above object is to provide a photographic material having a photographic constituent layer including at least one light-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer on a support.
At least one of the silver halide emulsion layers contains at least one coupler capable of reacting with an oxidized developing agent to release a diffusible development inhibitor or its precursor, and at least one of the photographic constituent layers Consisting of a photosensitive material containing at least one compound represented by the following general formula [] or a water-soluble salt thereof as an inhibitor in an amount of 1 x 10 ^-7 to 1 x 10 ^-2 mol per mol of silver halide. It was done. General formula [] In the formula, X represents a hydroxyl group or an amino group. R ₁ and R ₂ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, or an alkoxysulfonyl group,

The group is located in the ortho or para position of X. R ₁ and R ₂ may be bonded to each other to form a heterocycle with the nitrogen atom. Y represents a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, an unsubstituted or alkyl-substituted amino group, an acylamino group, or a sulfo group (including salts), and n is 0 to
Represents an integer of 4. When n is 2 or more, the plurality of Y's may be the same or different, Y's at the ortho position may bond with each other to form a carbon ring, or Y's at the ortho position and R ₁ or / and Y and R ₂ may be bonded to each other to form a heterocycle. The present invention will be described in more detail below. Among the compounds represented by the above general formula [],
There is a compound that can reduce silver halide and is well known in the photographic field as a silver halide developing agent (hereinafter simply referred to as a developing agent). Generally, techniques have also been disclosed for accelerating development, improving graininess, increasing sensitivity, improving gradation, etc. by incorporating a developing agent, which is a well-known compound, into a light-sensitive material. There is. For example, according to Japanese Patent Publication No. 47-51259, black and white developing agents are added to color photosensitive materials per mole of silver halide.
By adding 750 mg to 4.9 g and using it in combination with a polyvinyl heterocyclic compound, the effect of improving graininess and color fog has been obtained. Furthermore, in JP-A-56-89739, a blue-sensitive photosensitive layer contains 10 g or more of a black and white developing agent (not containing a primary amino group) per mole of silver halide.
Improves the developability of coarse particles during color development processing and the gradation of yellow images. However, the addition of a large amount of developing agent as described above is not effective against, for example, increasing fog and decreasing sensitivity during storage of photosensitive materials, and when applied to color reversal films, etc. It also has the disadvantage of causing increased desensitization. Furthermore, by adding a small amount (130 mg or less per mole of silver halide) of a black and white developing agent, photographic properties (especially sensitivity and fog) during storage of light-sensitive materials can be improved.
A technique for improving the stability of photographic materials is disclosed in JP-A-58-176637, but there is no suggestion of a technique for preventing fluctuations in photographic performance during storage by using diffusible DIR as in the present invention. In the general formula [], the substituents that the substituted alkyl groups represented by R ₁ and R ₂ may have include a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, an acylamino group, a sulfonamide group, and a hetero group. Examples of substituents that the substituted alkyl group represented by Y may have include cyclic groups, etc.
Examples include hydroxyl group, alkoxy group, acylamino group, and sulfonamide group. The compound of the general formula [] used in the present invention is:
Preferably, it can be represented by the following general formulas [], [][] and [V]. General formula []

【formula】 General formula []

【formula】 General formula []

【formula】 General formula []

[Formula] In general formulas [] to [V], R ₁ and R ₂ are respectively synonymous with R ₁ and R ₂ in general formula [],
R ₃ to _{R 18} have the same meaning as explained for Y in the general formula []. Also, R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and
R ₆ , R ₆ and R ₁ , R ₂ and R ₇ , R ₇ and R ₈ , R ₉ and R ₁₀ , R ₁₀
and R ₁ , R ₂ and R ₁₁ , R ₁₁ and R ₁₂ , R ₁₂ and R ₁₃ , R ₁₃ and
R ₁₄ , R ₂ and R ₁₅ , R ₁₅ and R ₁₆ , R ₁₆ and R ₁₇ and R ₁₇
Each R ₁₈ may be bonded to each other to form a ring. General formulas [] to [V] also include water-soluble salts, and preferred examples include hydrochloride, sulfate, and p-toluenesulfonate. Below, the general formula used in the present invention [] ~
Specific compound examples of [V] are shown below, but the present invention is not limited thereto.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

[Table] The amount of the compound [ ] of the present invention added varies depending on the photosensitive material and the type of compound, but it is an amount that allows these compounds to substantially act as a fog suppressant. 1 per mole of silveride
A range of ×10 ^-7 to 1 ×10 ^-2 mol is sufficient, and more preferably a range of 1 × 10 ^-6 to 5 × 10 ^-3 mol. The compound [ ] according to the present invention can be added to any layer, but preferably it is a layer containing the DIR coupler of the present invention or a layer adjacent thereto. Most preferred is a layer containing the DIR coupler of the invention. The addition time is preferably before the application of each layer, but
It is also possible to use a method such as impregnating the coating layer with a solution of the compound after coating. Any method can be used for addition, but water,
It is preferable to add it by dissolving it in methanol, fluorinated alcohol, dimethylformamide, acetone, or a mixed solvent thereof. Next, a DIR coupler that releases a diffusible development inhibitor or its precursor will be explained. In order to emphasize IIE, it is preferable that the action distance of the inhibitor group of the development inhibitor is large. That is, it is preferable that the so-called diffusivity is high. In the present invention, the diffusibility of the inhibiting group can be evaluated by the following method. Photosensitive material samples (A) and (B) consisting of layers having the following compositions on a (transparent) support were prepared. Sample (A): A sample having a green-sensitive silver halide emulsion layer Spectrally sensitized silver iodide (silver iodide 6 mol%, average grain size 0.48 μm) and a magenta coupler with the following structure per mol of silver. , a gelatin coating solution containing 0.07 mol was applied so that the amount of coated silver was 1.1 g/m ² and the amount of gelatin applied was 3.0 g/m ² , and a protective layer was applied thereon; chemical sensitization and spectral sensitization were applied. A gelatin coating solution containing silver iodobromide (silver iodide 2 mol %, average grain size 0.08 μm) was coated with a silver amount of 0.1 g/m ² ,
It was applied so that the amount of gelatin applied was 0.8 g/m ² . Sample (B): The same as the above sample (A) except that silver iodobromide was removed from the protective layer. In addition to the above, each layer contains a gelatin hardening agent and a surfactant. Samples (A) and (B) were exposed to white light using a wedge and then processed in accordance with the processing method described in Example 1 below, except that the developing time was 2 minutes and 40 seconds. The sensitivity of sample (B) was 60% (−△logE=0.22 in logarithmic representation) for the developer.
One was used in which various types of development inhibitors were added in an amount that suppressed the amount of development inhibitor, and one was used in which no development inhibitor was added. Sensitivity of sample (A) without development inhibitor added
So, the sensitivity of sample (B) is So', the sensitivity of sample (A) when a development inhibitor is added is S _A , and the sensitivity of sample (B) is S _B. Sensitivity △So=So′−S _B ′ Desensitization of sample (B) △S=So−S _A ′ Diffusivity=△S/△So. However, all sensitivities were set as the logarithm (-logE) of the reciprocal of the exposure amount at the density point of fog density +0.3. The value obtained by this method was used as a measure of diffusivity. The table illustrates the diffusibility of several types of development inhibitors.
It is preferable that the diffusivity exceeds 0.34, and in the present invention, it is more preferable that the diffusivity is 0.4 or more. magenta coupler

【table】

[Table] The diffusible DIR compound of the present invention can be represented by the following general formula. General formula (1) A-(Y) _n In the formula, A represents a coupler component, and m is 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 (2A) General formula (2B) General formula (2C) General formula (2D) General formula (2E) (X; O, S or Se) General formula (3) General formula (4) 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 thiazolylideneamino group, an aryloxycarbonyl group, an acyloxy group, or a carbamoyl group. basis,
N-alkylcarbamoyl group, N,N-dialkylcarbamoyl group, nitro group, amino group, N-arylcarbamoyloxy group, sulfamoyl group, N-alkylcarbamoyloxy group, hydroxy group, alkoxycarbonylamino group, alkylthio group, arylthio group , represents 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, 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 above general formula (2E) is (2A) to (2D)
R ₁ has the same meaning, X represents an oxygen atom or a sulfur atom, and in general formula (4), R ₂ is an alkyl group,
Represents an aryl group or a heterocyclic group. In general formula (5), R ₃ is a hydrogen atom, an alkyl group,
Represents an aryl group or a heterocyclic group, R ₄ is a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkanesulfonamide group, a cyano group, a heterocyclic group,
Represents 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 cyclic alkyl. Substituents include halogen atom, nitro group, cyano group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, carbamoyl group, hydroxy group, alkanesulfonyl group, arylsulfonyl group, alkylthio group Or an arylthio group, etc. When R ₁ , R ₂ , R ₃ or R ₄ represents an aryl group, the aryl group may be substituted. Substituents include alkyl groups, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, halogen atoms, nitro groups, amino groups, sulfamoyl groups, hydroxy groups, carbamoyl groups, aryloxycarbonylamino groups, alkoxycarbonylamino groups, acylamino groups, cyano group or ureido group. When R ₁ , R ₂ , R ₃ or R ₄ represents a heterocyclic group, it represents a 5- or 6-membered monocyclic ring or fused ring containing a nitrogen atom, oxygen atom, or sulfur atom as a hetero atom, and a pyridyl group, quinolyl group, furyl group,
selected from benzothiazolyl group, oxazolyl group, imidazolyl group, thiazolyl group, triazolyl group, benzotriazolyl group, imido group, oxazine group, etc., and these may be further substituted with the substituents listed for the above aryl group. . In 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). General formula (6) -TIME-INHIBIT In the formula, the TIME group is a group that binds to the coupling position of the coupler and can be cleaved by reaction with a color developing agent, and after being cleaved by the coupler, the INHIBIT group is released under appropriate control. This is a possible group.
The INHIBIT group is a development inhibitor. In the general formula (6), the -TIME-INHIBIT group represents the following general formulas (7) to (13). General formula (7) General formula (8) General formula (9) Compound general formula (10) Compound general formula (11) Compound general formula (12) General formula (13) In general formulas (7) to (13), R ₅ is a hydrogen atom,
Halogen atom, alkyl group, alkenyl group, aralkyl group, alkoxy group, alkoxycarbonyl group, anilino group, acylamino group, ureido group,
Represents a cyano group, nitro group, sulfonamide group, sulfamoyl group, albamoyl group, aryl group, carboxy group, sulfo group, hydroxy group, alkanesulfonyl group, and has general formulas (7), (8), (9), (11) ) and (13),
l represents 1 or 2, and in general formulas (7), (12), (12) and (13),
k represents an integer from 0 to 2, and in the general formulas (7), (10) and (11), R ₆ represents an alkyl group, alkenyl group, aralkyl group, cycloalkyl group, or aryl group, and the general formula (12 ) and (13), B is an oxygen atom or

[Formula] (R ₆ represents the same meaning as defined above), and the INHIBIT group is the general formula defined in general formulas (2A), (2B), (3), (4) and (5). and have the same meaning except for the number of carbon atoms. However, in general formulas (2A), (2B) and (3), the total number of carbons contained in each R ₁ in one molecule is 1 to 32, and in general formula (4), the number of carbons contained in R ₂ is 1 to 32 in total. The number of carbon atoms is 1 to 32, and in the general formula (5), the total number of carbon atoms contained in R ₃ and R ₄ is 0 to 32
It is. When R ₅ and R ₆ represent an alkyl group, it may be substituted or unsubstituted, chain-like or cyclic. Examples of the substituent include the substituents listed 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. R ₁ as a substituent
- The substituents listed when R ₄ is an aryl group can be mentioned. Among the above diffusible DIR compounds, those having leaving groups represented by general formulas (2A), (2B), (2E) to (4) are particularly preferred. The yellow image-forming coupler residue represented by A in general formula (1) includes piparoylacetanilide type, benzoylacetanilide type, malondiester type, malondiamide type, dibenzoylmethane type, benzothiazolylacetamide type, Coupler residues of malone ester monoamide type, benzothiazolylacetate type, benzoxazolyl acetamide type, benzoxazolyl acetate type, malon diester type, benzimidazolylacetamide type or benzimidazolylacetate type, included in U.S. Pat. No. 3,841,880 Coupler residues derived from heterocycle-substituted acetamides or heterocycle-substituted acetates or U.S. patents
Coupler residues derived from acylacetamides described in No. 3770446, British Patent No. 1459171, West German Patent (OLS) No. 2503099, JP-A-50-139738 or Research Disclosure No. 15737, or US Patent No. 4046574 Examples include the heterocyclic coupler residues described in . The magenta image-forming coupler residue represented by A is a coupler residue having a 5-oxo-2-pyrazoline nucleus, a pyrazolo-[1,5-a]benzimidazole nucleus, or a cyanoacetophenone type coupler residue. preferable. The cyano image-forming coupler residue represented by A is preferably a coupler residue having a phenol nucleus or an α-naphthol nucleus, or an indazolone or pyrazolotriazole coupler residue. 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 developing agent and releasing the development inhibitor. This type of coupler residue represented by A includes U.S. Pat.
Examples include coupler residues described in No. 3632345, No. 3958993, and No. 3961959. Specific examples of the diffusible DIR compound of the present invention are listed below, but the invention is not limited thereto. D-1 D-2 D-3 D-4 D-5 D-6 D-7 D-8 D-9 D-10 D-11 D-12 D-13 D-14 D-15 D-16 D-17 D-18 D-19 D-20 D-21 D-22 D-23 D-24 D-25 D-26 D-27 D-28 D-29 D-30 D-31 D-32 D-33 D-34 D-35 D-36 D-37 D-38 D-39 D-40 D-41 D-42 D-43 D-44 D-45 D-46 D-47 D-48 D-49 D-50 D-51 D-52 D-53 D-54 D-55 D-56 D-57 D-58 D-59 D-60 D-61 D-62 These compounds are described in U.S. Pat. No. 4,234,678;
No. 3227554, No. 3617291, No. 3958993, No.
No. 4149886, No. 3933500, JP-A-57-56837,
Special Publication No. 51-13239, U.S. Patent No. 2072363, same
No. 2070266, Research Disclosure 1981
It can be easily synthesized by the method described in December No. 21228, etc. The amount of the diffusible DIR compound added in the present invention varies depending on the photosensitive material and the type of compound, but is 2×10 ^-4 to 5× per mole of silver in the silver halide emulsion layer.
It is preferably used in a range of 10 ^-1 mol, more preferably 1 x 10 ^-3 to 1 x 10 ^-1 mol. A non-diffusive DIR coupler can also be used in combination, as long as it does not impede the effects of the present invention. It is preferable to use a high-speed coupler in order to provide the light-sensitive material of the present invention with excellent photographic performance (especially sensitivity and graininess). The following describes the high speed yellow coupler, high speed magenta coupler and high speed cyan coupler that are preferably used in the present invention. The high-speed 2-equivalent yellow coupler used in the present invention refers to a 2-equivalent yellow coupler with a fast coupling reaction, for example, the following general formulas (14) to (17).
It is a coupler represented by General formula (14) General formula (15) General formula (16) General formula (17) In general formulas (14) to (17), R ¹ is 1
It represents a valence group, l represents an integer from 1 to 3, and when l is 2 or more, R ¹ may be the same or different. R ² represents a substitutable group on the benzene ring, m represents 1 or 2, and when m is 2, R ²
may be the same or different. R ³ represents a halogen atom, an alkoxy group or an aryloxy group, Z represents a group that can be eliminated during a coupling reaction with an oxidation product of a color developing agent, and R ⁴ represents a tert-
Represents a butyl group or a phenyl group. There are no particular restrictions on the monovalent group represented by R ¹ ,
For example, halogen atoms (e.g. fluorine, chlorine, bromine, iodine, etc.), alkyl groups (e.g. methyl, ethyl, tert-butyl, tert-pentyl, etc.), aryl groups (phenyl, naphthyl, etc.), alkoxy groups (methoxy, ethoxy, pentoxy, dodecyloxy, hexadecyloxy, etc.), aryloxy groups (phenoxy, etc.), alkylthio groups (methylthio, ethylthio, octylthio, etc.), arylthio groups (phenylthio, etc.), acylamino groups (acetamide, butanamide, heptadecylcarbonylamino, benzamide) ), carbamoyl group (N
-methylcarbamoyl, N-phenylcarbamoyl, etc.), acyl groups (acetyl, benzoyl, etc.), alkylsulfonyl groups (dodecylsulfonyl, etc.),
Sulfonamide group (methanesulfonamide, benzenesulfonamide group), sulfamoyl group, nitrile group, acyloxy group (acetoxy, benzoxy, etc.), alkyloxycarbonyl group (methyloxycarbonyl, dodecyloxycarbonyl, etc.)
etc. Examples of the group represented by R ² include a halogen atom (e.g., fluorine, chlorine, bromine, iodine, etc.), R ⁵ −,
R ⁵ O-,

【formula】

[Formula] R ⁵ −COO−, R ⁵ −OCO−,

【formula】

【formula】

Examples include [Formula]. Here, R ⁵ , R ⁶ and R ⁷ are each a hydrogen atom,
an alkyl group each optionally having a substituent,
It represents an aryl group or a heterocyclic group, preferably an alkyl group or a heterocyclic group, each of which may have a substituent. Examples of the above-mentioned substituents include the same groups as the group represented by R ¹ . The halogen atom represented by R ³ is fluorine,
Examples include chlorine, bromine, iodine, etc. Among these, fluorine and chlorine are particularly preferred. The alkoxy group represented by R ³ preferably has 1 to 18 carbon atoms, such as methoxy, ethoxy, hexadecyloxy, and the like. Among these, methoxy is particularly preferred. Examples of the aryloxy group represented by R ³ include phenoxy and naphthyloxy. Examples of the group represented by Z include a halogen atom (e.g. fluorine, chlorine, bromine, etc.), ^-SR8 [where ^R8 is an alkyl group (e.g. methyl, ethyl, ethoxyethyl, ethoxycarbonylmethyl, etc.)], an aryl group ( For example, phenyl, 2-methoxyphenyl, etc.)
It represents a heterocyclic residue (eg, benzoxazolyl, 1-phenyl-5-tetrazolyl, etc.) or an acyl group (eg, ethoxycarbonyl, etc.). ], −OR ⁹
[Here, R ⁹ is an alkyl group (e.g., carboxymethyl, N-(2-methoxyethyl)carbamoylmethyl, etc.), an aryl group (e.g., phenyl, 4-carboxyphenyl, 4-(4-benzyloxybenzenesulfonyl)phenyl, etc.) ), Teherocyclic groups (e.g. 1-phenyl-5-tetrazolyl, isoxazolyl, 4-pyridinyl, etc.) or acyl groups (e.g. ethoxycarbonyl, N,N-diethylcarbamoyl, phenylsulfamoyl, N-phenylthiocarbamoyl, etc.) ). ], or

[Formula] [Here, R ¹⁰ represents a nonmetallic atomic group necessary to form a 5- to 6-membered ring together with -N, and is preferably selected from C, N, O, and S, and these rings are It may have a substituent. Examples of what these rings represent are:

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】 【formula】

【formula】

[Formula] etc. The phenyl group represented by R ⁴ may have a substituent represented by -(R ¹ )l (wherein R ¹ and l are as defined above). Among the couplers represented by the general formulas (14) to (17), the coupler represented by the general formula (14) is particularly preferred since it has high coloring properties. Typical specific examples of high speed 2-equivalent yellow couplers used in the present invention are shown below, but the present invention is not limited thereto. Y-1 Y-2 Y-3 Y-4 Y-5 Y-6 Y-7 Y-8 Y-9 Y-10 Y-11 Y-12 Y-13 Y-14 Y-15 Y-16 Y-17 Y-18 Y-19 Y-20 Y-21 Y-22 Y-23 Y-24 Y-25 Y-26 Y-27 Y-28 Y-29 Y-30 Y-31 Y-32 Y-33 Y-34 Y-35 Y-36 Y-37 Y-38 Y-39 Y-40 Y-41 Y-42 Y-43 Y-44 Y-45 Y-46 Y-47 Y-48 Y-49 Y-50 Y-51 Y-52 Y-53 Y-54 Y-55 Y-56 Y-57 Y-58 Y-59 Y-60 Couplers represented by general formulas (14) to (17) can be synthesized by known methods.
No. 66835, No. 51-102636, No. 49-122335, No.
No. 50-34232, No. 53-9529, No. 53-39126, No. 53-39126, No.
No. 53-47827, No. 53-105226, Special Publication No. 49-13576
No. 51-89729, No. 51-75521, U.S. Pat.
You can refer to No. 4059447 and No. 3894875. The content of the high speed 2-equivalent yellow coupler used in the present invention is from 1×10 ³ to 1 mol of silver halide contained in the silver halide emulsion layer containing the coupler.
A range of 1×10 ⁻¹ mol, particularly 1×10 ⁻² to 8×10 ⁻¹ mol is preferred. The silver halide emulsion layers of this invention can contain yellow couplers other than fast 2-equivalent yellow couplers. In this case, the ratio of fast 2-equivalent couplers to total yellow couplers is at least 15
Preferably it is mol%. As the high speed magenta coupler, a coupler represented by the following general formula (18) can be preferably used. General formula (18) In the formula, z ₁ represents a nonmetallic atom group necessary to form a nitrogen-containing heterocycle, and the ring formed by z ₁ may have a substituent. X ₁ represents a substituent that can be eliminated by reaction with the oxidized product of the color developing agent. Moreover, R represents a hydrogen atom or a substituent. Examples of the substituent represented by R in the general formula (18) include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, and a sulfinyl group. group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclicoxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group,
Examples include sulfonamide group, imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, heterocyclic thio group, etc. . Examples of the halogen atom include a chlorine atom and a bromine atom, with a chlorine atom being particularly preferred. The alkyl group represented by R has 1 to 1 carbon atoms.
32 is preferable, and as the alkenyl group and alkynyl group, those having 2 to 32 carbon atoms are preferable, and as the cycloalkyl group and cycloalkenyl group,
Those having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, are preferable, and the alkyl group, alkenyl group, and alkynyl group may be linear or branched. In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups are substituents (e.g., aryl, cyano, halogen atoms, heterocycles, cycloalkyl, cycloalkenyl, spiro compound residues, bridged hydrocarbon compounds) In addition to residues, those substituted via a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl, and those substituted via a heteroatom (specifically, hydroxy, alkoxy, aryloxy, heterocycles substituted via an oxygen atom such as oxy, siloxy, acyloxy, carbamoyloxy;
Nitro, amino (including dialkylamino, etc.),
Those substituted through a nitrogen atom such as sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfonamide, imide, ureido, alkylthio,
arylthio, heterocyclic thio, sulfonyl, sulfinyl, sulfamoyl, etc., substituted via a sulfur atom; phosphonyl, etc., substituted via a phosphorus atom, etc.)). Specifically, for example, methyl group, ethyl group, isopropyl group, t-butyl group, pentadecyl group, heptadecyl group, 1-hexylnonyl group, 1,1'-
Dipentylnonyl group, 2-chloro-t-butyl group, trifluoromethyl group, 1-ethoxytridecyl group, 1-methoxyisopropyl group, methanesulfonylethyl group, 2,4-di-t-amylphenoxymethyl group , anilino group, 1-phenylisopropyl group, 3-m-butanesulfonaminophenoxypropyl group, 3,4′-{α-[4″(p-hydroxybenzenesulfonyl)phenoxy]dodecanoylaminophenylpropyl group, 3-[4′-(α
-2″,4″-di-t-amylphenoxy)butanamido]phenyl}-propyl group, 4-[α-(o-
Chlorphenoxy)tetradecanamidephenoxy]propyl group, allyl group, cyclopentyl group,
Examples include cyclohexyl group. The aryl group represented by R is preferably a phenyl group, which may have a substituent (eg, an alkyl group, an alkoxy group, an acylamino group, etc.). Specifically, phenyl group, 4-t-butylphenyl group, 2,4-di-t-amyl phenyl group, 4
-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4'-[α-(4''-t-butylphenoxy)tetradecanamido]phenyl group, etc. The heterocycle represented by R includes 5- A 7-membered group is preferred, and may be substituted or fused.Specifically, 2-furyl group, 2-
Examples include thienyl group, 2-pyrimidinyl group, and 2-benzothiazolyl group. Examples of the acyl group represented by R include acetyl group, phenylacetyl group, dodecanoyl group, α
-2,4-di-t-amylphenoxybutanoyl group and other alkylcarbonyl groups, benzoyl groups, 3
Examples include arylcarbonyl groups such as -pentadecyloxybenzoyl group and p-chlorobenzoyl group. Examples of the sulfonyl group represented by R include methylsulfonyl group, alkylsulfonyl group such as dodecylsulfonyl group, benzenesulfonyl group, p-
Examples include arylsulfonyl groups such as toluenesulfonyl groups. The sulfinyl group represented by R includes ethylsulfinyl group, octylsulfinyl group, 3
- an alkylsulfinyl group such as a phenoxybutylsulfinyl group, a phenylsulfinyl group, m
Examples include arylsulfinyl groups such as -pentadecyl phenylsulfinyl group. The phosphonyl group represented by R includes an alkylphosphonyl group such as a butyloctylphosphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group, an aryloxyphosphonyl group such as a phenoxyphosphonyl group, and a phenylphosphonyl group. and arylphosphonyl groups. The carbamoyl group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as N-methylcarbamoyl group, N,N-dibutylcarbamoyl group, N
-(2-pentadecyloctylethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoyl group, N-{3-(2,4-di-t-amylphenoxy)propyl}carbamoyl group, and the like. The sulfamoyl group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-propylsulfamoyl group, an N,N-diethylsulfamoyl group,
Examples include N-(2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, and N-phenylsulfamoyl group. Examples of the spiro compound residue represented by R include spiro[3,3]heptan-1-yl. The bridged hydrocarbon compound residue represented by R is, for example, bicyclo[2,2,1]heptane-1
-yl, tricyclo[3,3,1,1,3,7]
Examples include decane-1-yl-7,7-dimethyl-bicyclo[2,2,1]heptan-1-yl. The alkoxy group represented by R may be further substituted with the substituents listed above for alkyl, such as methoxy group, propoxy group, 2
-methoxyethoxy group, pentadecyloxy group,
Examples include 2-dodecyloxyethoxy group and phenethyloxyethoxy group. The aryloxy group represented by R is preferably phenyloxy, and the aryl nucleus may be further substituted with any of the substituents or atoms listed above for the aryl group, such as a phenoxy group,
Examples include pt-butylphenoxy group and m-pentadecylphenoxy group. The heterocyclic oxy group represented by R is 5
Those having a ~7-membered heterocycle are preferred, and the heterocycle may further have a substituent, for example, 3,4,5,6-tetrahydropyranyl-2
-oxy group, 1-phenyltetrazole-5-oxy group, and the like. The siloxy group represented by R may be further substituted with an alkyl group, and examples thereof include a trimethylsiloxy group, a triethylsiloxy group, a dimethylbutylsiloxy group, and the like. The acyloxy group represented by R includes, for example, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc., and may further have a substituent, specifically an acetyloxy group, an α-
Examples include chlorcetyloxy group and benzoyloxy group. The carbamoyloxy group represented by R may be substituted with an alkyl group, an aryl group, etc.
For example, N-ethylcarbamoyloxy group, N,N
-diethylcarbamoyloxy group, N-phenylcarbamoyloxy group, and the like. The amino group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an ethylamino group, an anilino group,
Examples include m-chloroanilino group, 3-pentadecyloxycarbonylanilino group, and 2-chloro-5-hexadecaneamideanilino group. Examples of the acylamino group represented by R include an alkylcarbonylamino group, an arylcarbonylamide group (preferably a phenylcarbonylamide group), and may further have a substituent,
Specifically, acetamido group, α-ethylpropanamide group, N-phenylacetamide group, dodecanamide group, 2,4-di-t-amylphenoxyacetamide group, α-3-t-butyl-4- Examples include hydroxyphenoxybutanamide group. Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group, which may further have a substituent. Specifically, methylsulfonylamino group, pentadecylsulfonylamino group, benzenesulfonamide group, p-toluenesulfonamide group, 2-
Examples include methoxy-5-t-amylbenzenesulfonamide group. Even if the imide group represented by R is a closed type,
It may be cyclic and may further have a substituent, such as a succinimide group, a 3-heptadecylsuccinimide group, a phthalimide group, a glutarimide group, and the like. The ureido group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-ethylureido group, an N
-Methyl-N-decylureido group, N-phenylureido group, N-p-tolylureido group, and the like. The sulfamoylamino group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as N,N-dibutylsulfamoylamino group, N-methylsulfamoylamino group, etc. group, N-phenylsulfamoylamino group, and the like. The alkoxycarbonylamino group represented by R may further have a substituent, such as a methoxycarbonylamino group, a methoxyethoxycarbonylamino group, an octadecyloxycarbonylamino group, and the like. The aryloxycarbonylamino group represented by R may have a substituent, and examples thereof include a phenoxycarbonylamino group and a 4-methylphenoxycarbonylamino group. The alkoxycarbonyl group represented by R may further have a substituent, such as a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group, an octadecyloxycarbonyl group, an ethoxymethoxycarbonyloxy group, a benzyloxycarbonyl group, etc. Can be mentioned. The aryloxycarbonyl group represented by R may further have a substituent, such as a phenoxycarbonyl group, p-chlorophenoxycarbonyl group, m-pentadecyloxyphenoxycarbonyl group, etc. It will be done. The alkylthio group represented by R may further have a substituent, such as an ethylthio group, a dodecylthio group, an octadecylthio group, a phenethylthio group, a 3-phenoxypropylthio group, and the like. The arylthio group represented by R is preferably a phenylthio group, and may further have a substituent, such as a phenylthio group, a p-methoxyphenylthio group,
Examples thereof include a 2-t-octylphenylthio group, a 3-octadecylphenylthio group, a 2-carboxyphenylthio group, and a p-acetaminophenylthio group. The heterocyclic thio group represented by R is 5 to 7
A membered heterocyclic thio group is preferable, and may further have a condensed ring or a substituent. Examples include 2-pyridylthio group, 2-benzothiazolylthio group, and 2,4-diphenoxy-1,3,5-triazole-6-thio group. Examples of substituents that can be separated by reaction with the oxidized product of the color developing agent represented by X ₁ include halogen atoms (chlorine, bromine, fluorine atoms, etc.), carbon atoms, oxygen atoms, sulfur atoms, or nitrogen atoms. Examples include groups substituted via In addition to the carboxyl group, examples of the group substituting via a carbon atom include general formula (19) (R ₁₁ has the same meaning as the above R, Z ₂ has the same meaning as the above Z ₁ , and the ring formed by Z ₃ and Z ₄ described below may be further fused with another ring (for example, a 5- to 7-membered cycloalkene). For example, in general formula (24),
R ₂₅ and R ₂₆ are R ₂₇ and R ₂₈ in general formula (25)
and may be bonded to each other to form a ring (eg, 5- to 7-membered cycloalkene, benzene). More specifically, the magenta coupler represented by the general formula (18) is, for example, the following general formula (21) to
It is expressed by (27). General formula (21) General formula (22) General formula (23) General formula (24) General formula (25) General formula (26) In the general formulas (23) to (26), R ₂₁ to
R ₂₈ and X ₁ are each synonymous with the above R and X ₁ ,
R ₂₁ to R ₂₈ or X ₁ may form a dimer or more multiplex. Among the magenta couplers represented by the general formula (18), preferred are those represented by the following general formula (27). General formula (27) In the formula, R ₂₁ , X ₁ and Z ₄ have the same meanings as R, X ₁ and Z ₁ in general formula (18), respectively. Among the magenta couplers represented by the general formulas (21) to (27), particularly preferred is the magenta coupler represented by the general formula (21). The high speed 2-equivalent magenta coupler used in the present invention also includes a coupler represented by the following general formula (28). General formula (28) R ₃₁ represents an amino group, an acylamino group or a ureido group, and X ₂ represents a group that can be eliminated by reaction with an oxidized product of a color developing agent. Ar represents a phenyl group, which may be substituted with one or more substituents, and examples of the substituents include a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, a cyano group, a carbamoyl group, and a sulfamoyl group. , a sulfonyl group or an acylamino group. To explain in more detail, examples of the amino group represented by R ₃₁ include anilino, 2-chloroanilino, 2,4-dichloroanilino, 2,5-dichloroanilino, 2,4,
5-trichloroanilino, 2-chloro-5-tetradecanamideanilino, 2-chloro-5-(3
-octadecenylsuccinimide) anilino, 2
-chloro-5-tetradecyloxycarbonylanilino, 2-chloro-5-(N-tetradecylsulfamoyl)anilino, 2,4-dichloro-5-
Tetradesyloxyanilino, 2-chloro-5-
(tetradesiloxycarbonylamino)anilino,
2-chloro-5-octadecylthioanilino, 2
-chloro-5-(N-tetradecylcarbamoyl)
Anilino, or 2-chloro-5-[α-(3-tert
-butyl-4-hydroxy)tetradecanamide]anilino, dimethylamino, diethylamino, dioctylamino, pyrrolidino, and the like. Examples of the acylamino group of R ₃₁ include acetamide, benzamide, 3-[α-(2,4-di-
tert-amylphenoxy)butanamide]benzamide, 3-[α-(2,4-di-tert-amylphenoxy)acetamide]benzamide, 3-
[α-(3-pentadecylphenoxy)butanamide]benzamide, α-(2,4-di-tert-amylphenoxy)butanamide, α-(3-pentadecylphenoxy)butanamide, hexadecaneamide, isostearoylamino , 3-(3-
octadecenyl succinimide) benzamide,
Or pivaloylamino etc. can be mentioned. Examples of the ureido group represented by R ₃₁ include 3-{(2,4-di-tert-amylphenoxy)acetamide} phenylureido, phenylureido, methylureido, octadecylureido, 3
-tetradecanamidophenylureide, N,N
- Examples include dioctylureide. Examples of X ₂ include halogen atoms (e.g. fluorine, chlorine, bromine, etc.),
−SCN, −NCS, R ₃₂ SO ₂ NH− (e.g.

[Formula]), R ₃₂ CONH− (e.g. CF ₂ CONH−, Cl ₂ CCONH−, etc.), R ₃₂ OCONH
- (e.g. CH ₂ OCONH-), R ₃₂ O- (e.g.

[Formula] HO ₂ CCH ₂ O-,

[Formula], etc.), R ₃₂ SO ₃ − (e.g.

【formula】),

[Formula] (for example

[Formula]), R ₃₂ CO ₂ − (e.g.

【formula】

[Formula], etc.),

[Formula] (for example

[Formula]), R ₃₂ COCO ₂ − (e.g. CH ₃ COCO ₂ −),

[Formula] (for example

【formula】),

[Formula] (for example

[Formula]), R ₃₂ S- (e.g. HO ₂ CCH ₂ S-,

[Formula], etc.), or

[Formula] [R ₃₄ represents a nonmetallic atomic group necessary to form a 5- to 6-membered ring together with -N, preferably C,
It consists of at least one selected from N, O and S, and these rings may have appropriate substituents.

For example, what can be expressed by [formula] is Ba

【formula】

【formula】

【formula】

【formula】

【formula】 【formula】

Examples include [Formula]. Substituents include alkyl, alkenyl, alicyclic hydrocarbon residue, aralkyl, aryl, heterocyclic residue, alkoxy, alkoxycarbonyl, aryloxy, alkylthio, carboxy, acylamino, diacylamino, ureido, alkoxycarbonylamino, amino, Acyl, sulfonamide, carbamoyl, sulfamoyl, cyano, acyloxy, sulfonyl, halogen, sulfo, and the like. ], etc. Here, R ₃₂ and R ₃₃ may be the same or different and represent an aliphatic group, an aromatic group, or a heterocyclic residue. R ₃₂ and R ₃₃ may be substituted with a suitable substituent. Further, R ₃₃ may be a hydrogen atom. The aliphatic groups for R ₃₂ and R ₃₃ include linear or branched alkyl groups, alkenyl groups,
Examples include an alkynyl group and an alicyclic hydrocarbon group. The alkyl group has 1 to 32 carbon atoms, preferably 1 to 20 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl, octadecyl, isopropyl, and the like. As an alkenyl group,
It has 2 to 32 carbon atoms, preferably 3 to 20 carbon atoms, such as allyl and butynyl. The alkenyl group has 2 to 32 carbon atoms, preferably 2 to 20 carbon atoms, such as ethynyl and propargyl. The alicyclic hydrocarbon group has 3 or more carbon atoms.
32, preferably 5 to 20, such as cyclopentyl, cyclohexyl, 10-camphor, etc. The aromatic group represented by R ₃₂ and R ₃₃ is
Examples include phenyl group and naphthyl group. As the heterocyclic group represented by R ₃₂ and R ₃₃ ,
A 5- or 6-membered ring containing a carbon atom and at least one heteroatom selected from nitrogen, oxygen, and sulfur, which may be fused with a benzene ring, such as pyridyl, pyrrolyl, pyrazolyl,
triazolyl, triazolidyl, imidazolyl,
Examples include triazolyl, thiazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, quinolinyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, and the like. Examples of substituents for R ₃₂ and R ₃₃ include alkyl groups (e.g., methyl, ethyl, tert-octyl, etc.), aryl groups (e.g., phenyl, naphthyl, etc.), nitro, hydroxyl, cyano, Sulfo group, alkoxy group (e.g., methoxy group, ethoxy group, butyroxy group, methoxyethoxy group, etc.), aryloxy group (e.g., phenoxy group, naphthyloxy group, etc.), carboxyl group, acyloxy group (e.g., acetoxy group, benzoxy group, etc.), Acylamino group (e.g. acetylamino group,
benzoylamino group, etc.), sulfonamide group (e.g., methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (e.g., methylsulfamoyl group, phenylsulfamoyl group, etc.), halogen atom (e.g., fluorine, chlorine, etc.) or bromine, etc.), carbamoyl groups (N-methylcarbamoyl group, (N-2-methoxyethylcarba 2-moyl), N-phenylcarbamoyl, etc.), alkoxycarbonyl groups (e.g., methoxycarbonyl group, ethoxycarbonyl group, etc.), acyl groups (e.g., acetyl group, benzoyl group, etc.), sulfonyl groups (e.g., methylsulfonyl group, phenylsulfonyl group, etc.), sulfinyl groups (e.g., methylsulfinyl group, phenylsulfinyl group, etc.), heterocyclic groups (e.g., morpholino group, etc.). group, pyrazolyl group, triazolyl group, tetrazolyl group, imidazolyl group, pyridyl group, benzotriazolyl group, benzimidazolyl group, etc.), amino group (e.g. unsubstituted amino group,
(methylamino group, ethylamino group, etc.), alkylthio groups (eg, methylthio group, ethylthio group, carboxymethylthio group, etc.), and arylthio groups (eg, phenylthio group, etc.).
These substituents may be further substituted with the substituents described above. Specific examples of high speed 2-equivalent magenta couplers used in the present invention are shown below, but the present invention is not limited thereto. M-1 M-2 M-3 M-4 M-5 M-6 M-7 M-8 M-9 M-10 M-11 M-12 M-13 M-14 M-15 M-16 M-17 M-18 M-19 M-20 M-21 M-22 M-23 M-24 M-25 M-26 M-27 M-28 M-29 M-30 M-31 M-32 M-33 M-34 M-35 M-36 M-37 M-38 M-39 M-40 M-41 M-42 M-43 M-44 M-45 M-46 M-47 M-48 M-49 M-50 M-51 M-52 M-53 M-54 M-55 M-56 M-57 M-58 M-59 M-60 M-61 M-62 M-63 M-64 M-65 M-66 M-67 M-68 M-69 M-70 M-71 M-72 M-73 M-74 M-75 M-76 M-77 M-78 M-79 M-80 M-81 M-82 M-83 M-84 M-85 M-86 M-87 M-88 M-89 M-90 M-91 M-92 M-93 M-94 M-95 M-96 M-97 M-98 M-99 M-100 M-101 M-102 M-103 M-104 M-105 M-106 M-107 M-108 M-109 M-110 M-111 M-112 M-113 M-114 M-115 M-116 M-117 M-118 M-119 M-120 M-121 M-122 M-123 M-124 M-125 M-126 M-127 M-128 M-129 M-130 M-131 M-132 M-133 M-134 M-135 M-136 M-137 M-138 M-139 M-140 M-141 M-142 M-143 M-144 M-145 M-146 M-147 M-148 M-149 M-150 M-151 M-152 M-153 M-154 M-155 M-156 M-157 M-158 M-159 M-160 M-161 M-162 M-163 M-164 M-165 M-166 M-167 M-168 M-169 M-170 M-171 M-172 M-173 M-174 M-175 M-176 M-177 M-178 M-179 M-180 M-181 M-182 M-183 M-184 M-185 M-186 M-187 M-188 M-189 M-190 M-191 M-192 M-193 M-194 M-195 M-196 M-197 M-198 M-199 M-200 M-201 M-202 M-203 M-204 The above-mentioned high speed 2-equivalent magenta coupler can be synthesized by a known method. The coupler represented by the general formula (18) was published in the Journal of the Chemical Society and Perkin (Journal of the Chemical Society).
Society, Perkin) (1977), 2047-2052, U.S. Patent No. 3725067, JP 59-9437 and JP
It can be synthesized by referring to No. 58-42045. In addition, the coupler expressed by the general formula is
−122935, No. 56-126833, JP-A-56-38043
No. 56-46223, No. 52-58922, No. 51-
No. 20826, No. 49-122335, No. 50-159336, Japanese Patent Publication No. 51-10100, No. 50-37540, Japanese Patent Publication No. 1977-
No. 112343, No. 53-47827, No. 53-39126, Japanese Patent Publication No. 15471-1971, U.S. Patent No. 3227554 and Research Disclosure
It can be synthesized by referring to Disclosure) 16140. The content of the high speed 2-equivalent magenta coupler used in the present invention is 1×10 ^-3 to 1 mol of silver halide contained in the silver halide emulsion layer containing the coupler.
1 mol, especially in the range of 1 x 10 ^-2 to 8 x 10 ^-1 mol is preferred. As the high speed 2-equivalent cyan coupler, a coupler represented by the following general formula (29) is preferably used. General formula (29) (A-) _n Z where A represents an image-forming coupler residue having a naphthol or phenol nucleus. m represents 1 or 2. Z represents a group that is bonded to the coupling position of the above coupler residue and can be eliminated during the coupling reaction with the oxidation product of the aromatic primary amine developing agent, such as a halogen atom (e.g. F, Cl, etc.), - SCN,−
NCS, −NHSO ₂ R ₁ , −NHCOR ₁ ,

[Formula] −OSO ₂ R ₁ , −OCONR ₁ R ₂ , −OCOR ₁ , −OCSR ₁ , −OCOCO−R ₁ , −OCSNR ₁
Represents R ₂ , -OCOOR ₁ , -OCOSR ₁ or -SR ₁ .
However, when m is 2, Z represents a corresponding divalent group. Here, R ₁ and R ₂ each represent an aliphatic group, an aromatic group, or a heterocyclic group, which may be substituted with a corresponding substituent. R ₂ may be a hydrogen atom. Examples of the aliphatic groups represented by R ₁ and R ₂ include linear or branched alkyl groups, alkenyl groups, alkynyl groups, and alicyclic hydrocarbon groups. The alkyl group has 1 to 32 carbon atoms, preferably 1 to 20 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl, octadecyl, isopropyl, and the like. The alkenyl group has 2 to 32 carbon atoms, preferably 3 to 20 carbon atoms, such as allyl and butenyl. The alkyl group has 2 to 32 carbon atoms, preferably 2 to 20 carbon atoms, such as ethynyl and propargyl. The alicyclic hydrocarbon group has 3 to 32 carbon atoms,
Preferably, the number is 5 to 20, such as cyclopentyl, cyclohexyl, and 10-camphor. Examples of the aromatic group represented by R ₁ and R ₂ include a phenyl group and a naphthyl group. The heterocyclic group represented by R ₁ and R ₂ is a 5- or 6-membered ring containing a carbon atom and at least one hetero atom selected from nitrogen, oxygen, and sulfur, and is fused with a benzene ring. Examples include pyridyl, pyrrolyl, pyrazolyl, triazolyl, triazolidyl, imidazolyl, tetrazolyl, thiazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, quinolinyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, and the like. Substituents for R ₁ and R ₂ include, for example, alkyl groups (such as methyl, ethyl, propyl, butyl,
octyl, etc.), aryl groups (e.g. phenyl, naphthyl, etc.), nitro groups, hydroxyl groups, cyano groups, sulfo groups, alkoxy groups (e.g. methoxy,
ethoxy, methoxyethoxy, etc.), aryloxy groups (e.g., phenoxy, naphthyloxy, etc.), carboxyl, etc., acyloxy groups (e.g., acetoxy, benzoxy, etc.), acylamino groups (e.g., acetylamino, benzoylamino, carboxypropionylamino, etc.), sulfonamide groups ( For example, methanesulfonamide, benzenesulfonamide, etc.), sulfamoyl group (for example, methylsulfamoyl, phenylsulfamoyl, etc.), halogen atom (for example, fluorine, chlorine, bromine, etc.), carbamoyl group (N-methylcarbamoyl group ( N-2-methoxyethylcarbamoyl, etc.),
N-phenylcarbamoyl, etc.), alkoxycarbonyl groups (e.g., methoxycarbonyl, ethoxycarbonyl, phenylmethoxycarbonyl, etc.),
Acyl groups (e.g. acetyl, benzoyl, etc.), sulfonyl groups (e.g. methylsulfonyl, phenylsulfonyl, etc.), sulfinyl groups (e.g. methylsulfinyl, phenylsulfinyl, etc.), heterocyclic groups (e.g. morpholino, pyrazolyl, triazolyl, Tetrazolyl, imidazolyl, pyridyl,
benzotriazolyl, benzimidazolyl, etc.),
Amino groups (e.g. unsubstituted amino, methylamino,
ethylamino, etc.), alkylthio groups (e.g. methylthio, ethylthio, carboxymethylthio, etc.)
Alternatively, examples include arylthio groups (eg, phenylthio, etc.). These substituents may be substituted with the substituents described above. Among the couplers represented by the general formula (29), a particularly useful coupler is represented by the following general formula (30). General formula (30) (R ₃ −A ₁ −) _n Z where m represents 1 or 2, and A ₁ is a cyan image-forming coupler residue having a phenol nucleus or α-
Represents a cyan imaging coupler residue with a naphthol core. Z is a group that is bonded to the coupling position of the above coupler residue and is eliminated when a dye is formed by oxidative coupling with an aromatic primary amine developing agent, and has the same meaning as Z in general formula (29). . R ₃ is a hydrogen atom, or an alkyl group having 30 or less carbon atoms, especially an alkyl group having 1 to 20 carbon atoms such as methyl, isopropyl, pentadecyl, and eicosyl, or an alkoxy group having 30 or less carbon atoms, especially methoxy, isopropoxy, pentadecyloxy,
An alkoxy group having 1 to 20 carbon atoms such as icosyloxy, or an aryloxy group such as phenoxy or p-tert-butylphenoxy, the following formula (1')
It is selected from acylamino groups shown in ~(4') or carbamyl groups shown in the following formulas (5') and (6'). -NH-CO-X (1') -NH-SO ₂ -X (2') −NHCONH−X (4′) −CONHX (5′) In the formula,
Naphthyl, etc.). Here, the above alkyl group and aryl group include a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, an amino group (e.g., amino, alkylamino, dialkylamino, anilino, N-alkylanilino, etc.), an alkyl group (e.g. methyl, ethyl, propyl, cyanomethyl, etc.), aryl group, alkoxycarbonyl group,
Acyloxycarbonyl group, amide group (e.g., acetamide, methanesulfonamide, etc.), imide group (e.g., succinimide, etc.), carbamoyl group (e.g., N-butylcarbamoyl, N,N-dihexylcarbamoyl, etc.), alkylsulfonyl group (e.g., methylsulfonyl, perfluoromethylsulfonyl), sulfamoyl group (e.g. N,
N-diethylsulfamoyl, etc.), alkoxy groups (e.g. methoxy, ethoxy, octadecyloxy, etc.), aryloxy groups (e.g. phenoxy,
p-tert-butylphenoxy, 4-hydroxy-
(3-tert-butylphenoxy, etc.), an acyloxy group (eg, acetoxy, tert-butylcarbonyloxy, etc.), or the like. Y and
Y' represents one selected from the above X, -OX, _-NH1 -X and -N(X) ₂ . In addition to the above substituents, R ₃ is
It may also contain commonly used substituents. Among the compounds represented by the general formula (30),
More preferred are the following general formulas (31) and (32)
This is a compound represented by General formula (31) General formula (32) m, Z and R ₃ are m, Z and R ₃ of general formula (30)
is synonymous with R ₄ is a hydrogen atom, an alkyl group having 30 or less carbon atoms,
In particular, it is selected from an alkyl group having 1 to 20 carbon atoms, or a carbamoyl group represented by the formula (5') or (6') shown in _R3 of the general formula (30). R ₅ , R ₆ ,
R ₇ , R ₈ and R ₉ are each a hydrogen atom, a halogen atom,
Represents an alkyl group, aryl group, alkoxy group, alkylthio group, heterocyclic group, amino group, carbonamide group, sulfonamide group, sulfamyl group, or carbamyl group, and W is necessary to form a closed 5- to 6-membered ring. represents a group of nonmetallic atoms. For example R ₅
represents any of the following groups. hydrogen atoms, primary, secondary or tertiary alkyl groups having 1 to 22 carbon atoms, such as methyl,
Propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, hexyl, dodecyl, 2-chlorobutyl, 2-hydroxyethyl, 2-phenylethyl, 2-(2,4,6-trichlorophenyl)
ethyl, 2-aminoethyl, etc., and allyl groups, such as phenyl, 4-methylphenyl, 2,4,6
-Trichlorophenyl, 3,5-dibromophenyl, 4-trifluoromethylphenyl, 2-trifluoromethylphenyl, 3-trifluoromethylphenyl, naphthyl, 2-chloronaphthyl, 3
-ethylnaphthyl, etc., and heterocyclic groups such as benzofuranyl, furanyl, thiazolyl, benzothiazolyl, naphthothiazolyl, oxazolyl, benzoxazolyl, naphthoxazolyl, pyridyl, quinolyl, etc. R ₅ also represents: That is, amino groups such as amino, methylamino, diethylamino, dodecylamino, phenylamino, tolylamino, 4-(3
-sulfobenzamide) anilino, 4-cyanophenylamino, 2-trifluoromethylphenylamino, benzothiazolylamino, etc., and carbonamide groups such as ethylcarbonamide, decylcarbonamide, phenylethylcarbonamide, etc. Alkylcarbonamide groups such as phenylcarbonamide, 2,4,6-trichlorophenylcarbonamide, 4-methylphenylcarbonamide, 2-ethoxyphenylcarbonamide,
3-[α-(2,4-di-tert-amylphenoxy)acetamide]benzamide, allylcarbonamide group such as naphthylcarbonamide, thiazolylcarbonamide, benzothiazolylcarbonamide, naphthothiazolylcarbonamide ,
Heterocyclic carbonamide groups such as oxazolylcarbonamide, benzoxazolylcarbonamide, imidazolylcarbonamide, benzimidazolylcarbonamide, etc., and sulfonamide groups such as butylsulfonamide, dodecylsulfonamide, phenylethylsulfonamide Alkylsulfonamide groups such as phenylsulfonamide, 2,4,6-trichlorophenylsulfonamide, 2-methoxyphenylsulfonamide, 3-carboxyphenylsulfonamide, naphthylsulfonamide, etc. groups, heterocyclic sulfonamide groups such as thiazolylsulfonamide, benzothiazolylsulfonamide, imidazolylsulfonamide, benzimidazolylsulfonamide, benzimidazolylsulfonamide, pyridylsulfonamide, etc., and propylsulfamyl, octylsulfonamide, etc. Alkyl sulfamyl groups such as phamyl, pentadecyl sulfamyl, octadecyl sulfamyl, etc., phenyl sulfamyl, 2,4,6-trichlorophenyl sulfamyl, 2-methoxyphenylsulfamyl, naphthylsulfamyl Allylsulfamyl groups such as amyl, heterocyclic sulfamyl groups such as thiazolylsulfamyl, benzothiazolylsulfamyl, oxazolylsulfamyl, benzimidazolylsulfamyl, pyridylsulfamyl groups, etc., ethyl carbamyl, octylcarbamyl,
Alkylcarbamyl groups such as pentadecylcarbamyl, octadecylcarbamyl, etc., allylcarbamyl groups such as phenylcarbamyl, 2,4,6-trichlorophenylcarbamyl, etc., and thiazolylcarbamyl, benzothiazolyl Heterocyclic carbamyl groups such as carbamyl, oxazolylcarbamyl, imidazolylcarbamyl, benzimidazolylcarbamyl and the like. R ₆ , R ₇ , R ₈ and R ₉ each represent any of the groups defined by R ₅ and R ₃ also represents -NHCONH-X. W represents a nonmetallic atom necessary to form a 5- or 6-membered ring as shown below. That is, benzene ring, cyclohexene ring, cyclopentene ring, thiazole ring, oxazole ring, imidazole ring, pyridine ring, pyrrole ring, tetrahydropyridine ring, etc. Among the compounds represented by the general formula (30), particularly preferred compounds are those represented by the following general formula (33) or (34).
This is a compound represented by General formula (33) General formula (34) Here, R ₅ , R ₆ , R ₇ , Z and m are general formulas []
and R ₁₀ is -NHCONH-X
(X has the same meaning as in formula (4') above.) Specific examples of high speed 2-equivalent cyan couplers are shown below, but the present invention is not limited thereto. C-1 C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-11 C-12 C-13 C-14 C-15 C-16 C-17 C-18 C-19 C-20 C-21 C-22 C-23 C-24 C-25 C-26 C-27 C-28 C-29 C-30 C-31 C-32 C-33 C-34 C-35 C-36 C-37 C-38 C-39 C-40 C-41 C-42 C-43 C-44 C-45 C-46 C-47 C-48 C-49 C-50 C-51 C-52 C-53 C-54 C-55 C-56 C-57 C-58 C-59 C-60 C-61 C-62 C-63 C-64 C-65 C-66 C-67 C-68 C-69 C-70 C-71 C-72 C-73 C-74 C-75 C-76 C-77 C-78 C-79 The coupler represented by the general formula (29) can be synthesized by a known method.
No. 27147, No. 56-1935, JP-A-50-117422,
No. 47-37425, No. 54-48237, No. 53-52423,
No. 53-105226, No. 53-45524, No. 53-47827
No. 53-39745, No. 50-10135, No. 50-
No. 120334 and US Pat. No. 3,476,563 can be referred to. The content of the high speed 2-equivalent yellow coupler used in the present invention is 1×10 ^-3 to 1 mol of silver halide contained in the silver halide emulsion layer containing the coupler.
1 mol, especially in the range of 1 x 10 ^-2 to 0.8 x 10 ^-1 mol is preferred. The silver halide emulsion layers of this invention can contain cyan couplers other than fast 2-equivalent cyan couplers. In this case, the ratio of fast 2-equivalent couplers to total cyan couplers is at least 20 mol%
It is preferable that For example, for general black and white, for X-ray recording, for plate making, for color positive, for color negative, for color paper,
Although it can be used for color reversal, direct positive, and heat development photosensitive materials, it is particularly advantageous to apply it to color photosensitive materials with a multilayer structure. The silver halide emulsion of the present invention includes silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide,
Any of those used in conventional silver halide emulsions, such as and silver chloride, can be used. The silver halide grains used in the silver halide emulsion may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different. In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Further, while taking into account the critical growth rate of silver halide crystals, halide ions and silver ions may be generated by sequentially and simultaneously adding them while controlling the PH and/or pAg in the mixing tank. With this method,
Silver halide grains with a regular crystal shape and nearly uniform grain size can be obtained. After growth, a convergence method may be used to change the halogen composition of the particles. When producing a silver halide emulsion, a silver halide solvent can be used as necessary to control the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains. In the process of grain formation and/or growth, silver halide grains are produced using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts (complex salts). metal ions can be added using at least one selected from the group consisting of
Further, by placing the particles in an appropriate reducing atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces. Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, Research Disclosure (hereinafter abbreviated as RD) 17643
It can be carried out based on the method described in the item. Even if a silver halide grain has a uniform silver halide composition distribution within the grain, the core/silver halide composition differs between the inside and surface layer of the grain.
They may also be shell particles. The silver halide grains may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grain. The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of {100} planes to {111} planes can be used. or,
The particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed. Silver halide emulsions having any grain size distribution may be used. 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). When divided by the average particle size, the value is
0.20 or less. In the case of spherical silver halide, the grain size is the diameter thereof, and in the case of grains having a shape other than spherical, the grain size is the diameter when the projected image is converted into a circular image of 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 may be a mixture of two or more separately formed silver halide emulsions. Silver halide emulsions can be chemically sensitized by conventional methods. That is, a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a noble metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination. Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too. As the sensitizing dye, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes, and hemioxanol dyes are used. Particularly useful dyes are cyanine dyes, merocyanine dyes, and complex merocyanine dyes. 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, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus,
Tetrazole nucleus, pyridine nucleus, nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei, and nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus , benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus,
benzoselenazole nucleus, benzimidazole nucleus,
Such as quinoline nucleus. These nuclei may be substituted on carbon atoms. The merocyanine dye or composite merocyanine dye includes a nucleus having a ketomethylene structure such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, A 5- to 6-membered heteroartic ring nucleus such as a thiobarbituric acid nucleus can be applied. Useful sensitizing dyes used in blue-sensitive silver halide emulsion layers include, for example, West German Patent No. 929080;
U.S. Patent No. 2231658, U.S. Patent No. 2493748, U.S. Patent No. 2503776,
Same No. 2519001, No. 2912329, No. 3656959, Same No.
No. 3672897, No. 3694217, No. 4025349, No. 3672897, No. 3694217, No. 4025349, No.
No. 4046572, British Patent No. 1242588, Special Publication No. 1977-
Examples include those described in No. 14030 and No. 52-24844. In addition, useful sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Pat.
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in US Pat. No. 2,945,763 and US Pat. No. 5,059,79. Furthermore, useful sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Pat.
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in Japanese Patent No. 2454629, No. 2776280, and the like. Furthermore, U.S. Patent No. 2213995,
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in No. 2493748, No. 2519001, West German Patent No. 929080, etc. 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 Publication No. 43-4932 and No. 43-4932.
No. 4933, No. 43-4936, No. 44-32753, No. 45-
No. 25831, No. 45-26474, No. 46-11627, No. 46
−18107, No. 47-8741, No. 47-11114, No. 47
-25379, 47-37443, 48-28293, 47-37443, 48-28293,
No. 48-38406, No. 48-38407, No. 48-38408,
No. 48-41203, No. 48-41204, No. 49-6207,
No. 50-40662, No. 53-12375, No. 54-34535,
No. 55-1569, JP-A No. 50-33220, No. 50-33828
No. 50-38526, No. 51-107127, No. 51-
No. 115820, No. 51-135528, No. 51-151527, No. 115820, No. 51-135528, No. 51-151527, No.
No. 52-23931, No. 52-51932, No. 52-104916,
No. 52-104917, No. 52-109925, No. 52-110618
No. 54-80118, No. 56-25728, No. 57-1438
No. 58-10753, No. 58-91445, No. 58-153926
No. 59-114533, No. 59-116645, No. 59-
116647, U.S. Patent No. 2688545, U.S. Patent No. 2977229, U.S. Patent No.
No. 3397060, No. 3506443, No. 3578447, No.
No. 3672898, No. 3679428, No. 3769301, No. 3672898, No. 3679428, No. 3769301, No.
It is described in No. 3814609 and No. 3837862. Examples of dyes that do not themselves have a spectral sensitizing effect, or substances that do not substantially absorb visible light and exhibit supersensitization, are used with sensitizing dyes, such as aromatic organic acid formaldehyde condensates ( Examples include those described in U.S. Pat. No. 3,473,510), cadmium salts, azaindene compounds, and aminostilbene compounds substituted with nitrogen-containing heterocyclic groups (for example, those described in U.S. Pat. Nos. 2,933,390 and 3,635,721). . U.S. Patent No. 3,615,613,
The combinations described in No. 3615641, No. 3617295, and No. 3635721 are particularly useful. Silver halide emulsions are used in the manufacturing process of photosensitive materials,
During chemical ripening, at the end of chemical ripening, and/or until the silver halide emulsion is applied after chemical ripening, for the purpose of preventing fog during storage or photographic processing, or to keep photographic performance stable. In addition, compounds known in the photographic industry as antifoggants or stabilizers can be added. U.S. patented antifoggant and stabilizer
Pentazaindenes described in No. 2713541, No. 2743180, and No. 2743181, U.S. Patent No. 2716062,
Same No. 2444607, No. 2444605, No. 2756147, Same No.
Tetrazaindenes described in No. 2835581, No. 2852375, and RD14851, triazaindenes described in U.S. Pat.
Azaindenes such as the polymerized azaindenes described in US Pat. No. 211142; US Pat.
Quaternary onium salts such as thiazolium salts described in No. 3342596 and No. 3954478, pyridium salts described in U.S. Pat. No. 3148067, and phosphonium salts described in Japanese Patent Publication No. 1983-40665; U.S. patents
No. 2403927, No. 3266897, No. 3708303, JP-A-Sho
Mercaptotetrazoles, mercaptotriazoles, and mercaptodiazoles described in No. 55-135835 and No. 59-71047, U.S. Patent No. 2824001
mercaptodiazoles described in US Patent No. 3,397,987, mercaptobenzimidazoles described in US Patent No. 2,843,491, mercaptooxadiazoles described in US Patent No. 3,364,028 Mercapto-substituted heterocyclic compounds such as mercaptothiadiazoles; US Pat. No. 3,236,652, Japanese Patent Publication No.
Catechols listed in No. 43-10256,
Polyhydroxybenzenes other than the present invention such as resorcinols described in Japanese Patent No. 56-44413 and gallic acid esters described in Japanese Patent Publication No. 43-4133; tetrazoles described in West German Patent No. 1189380, US Patent No. 3157509 triazoles described in US Pat. No. 2,704,721, urazoles described in US Pat. No. 3,287,135, pyrazoles described in US Pat. No. 3,106,467, and triazoles described in US Pat. indazoles, azoles such as polymerized benzotriazoles described in JP-A No. 59-90844, and pyrimidines described in U.S. Pat. No. 3,161,515;
Heterocyclic compounds such as 3-pyrazolidones described in U.S. Pat. No. 2,751,297 and polymerized pyrrolidones or polyvinylpyrrolidones described in U.S. Pat. No. 3,021,213;
−137945, 140445, British Patent No. 1356124,
Various inhibitor precursors described in U.S. Pat. No. 3,575,699, U.S. Pat. No. 3,649,267; sulfinic acid and sulfonic acid derivatives described in U.S. Pat.
There are inorganic salts described in No. 2488709 and No. 2728663. It is advantageous to use gelatin as a binder (or protective colloid) for silver halide emulsions, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, single Alternatively, hydrophilic colloids such as synthetic hydrophilic polymer sugars such as copolymers can also be used. The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention can be hardened by using one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. can. The hardening agent can be added to the processing solution in an amount sufficient to harden the photosensitive material to the extent that it is not necessary to add the hardening agent, but it is also possible to add the hardening agent to the processing solution. A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of increasing flexibility. Preferred plasticizers are the compounds described in section A of RD 17643. The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material may contain a dispersion (latex) of a water-insoluble or poorly soluble synthetic polymer for the purpose of improving dimensional stability. The emulsion layer of the photosensitive material contains a dye-forming compound that undergoes a coupling reaction with an oxidized product of an aromatic primary amine developer (for example, p-phenylenediamine derivatives, aminophenol derivatives, etc.) to form a dye during color development processing. A coupler is used. The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive 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, depending on the purpose, silver halide color photographic 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. Dye-forming couplers can be used as development accelerators, bleaching accelerators, developing agents, silver halide solvents, toning agents, hardeners, fogging agents, antifogging agents, and chemical sensitization by coupling with oxidized forms of developing agents. Compounds that release photographically useful fragments such as agents, spectral sensitizers, and desensitizers are included. A colorless coupler (also called a competitive coupler) which undergoes a coupling reaction with an oxidized aromatic primary amine developer but does not form a dye can also be used in combination with a dye-forming coupler. As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. As magenta dye-forming couplers, 5-pyrazolone couplers, pyrazolobenzimidazole couplers, open-chain acylacetonitrile couplers, indazolone couplers, and the like can be used together with the couplers of the present invention. Phenol or naphthol couplers are generally used as cyan dye-forming couplers. Dye-forming couplers, DIR couplers, DIR compounds that do not need to be adsorbed onto the surface of silver halide crystals,
Among image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc., hydrophobic compounds are processed using solid dispersion methods,
Latex dispersion method, oil-in-water emulsion dispersion method, etc.
The dispersion can be carried out using various methods, which can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler. For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, and usually a high boiling point organic solvent with a boiling point of about 150°C or higher is mixed with a low boiling point and/or Dissolve in a water-soluble organic solvent and emulsify using a surfactant in a hydrophilic binder such as an aqueous gelatin solution using a dispersion means such as a stirrer, homogenizer colloid mill, flow mixer, or ultrasonic device. After being dispersed, it may be added to the desired hydrophilic colloid liquid. A step of removing the low boiling point organic solvent may be included after or simultaneously with the dispersion. 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. Low boiling or water-soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Organic solvents with low boiling points and substantially insoluble in water include ethyl acetate,
Propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, benzene, etc., and water-soluble organic solvents include acetone, methyl isobutyl ketone, β-ethoxyethyl acetate, methoxyglycol acetate, methanol, and ethanol. , acetonitrile, dioxane, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric triamide, diethylene glycol monophenyl ether, phenoxyethanol and the like. When dye-forming couplers, DIR couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. have acid groups such as carboxylic acid or sulfonic acid, they are treated as hydrophilic colloids in an alkaline aqueous solution. It can also be introduced inside. Anionic surfactants, nonionic surfactants, Cationic surfactants and amphoteric surfactants can be used. The oxidized form of the developing agent or the electron transfer agent migrates between the emulsion layers of the light-sensitive material (between the same color-sensitive layers and/or between different color-sensitive layers), causing color turbidity, deterioration of sharpness, and graininess. A color antifoggant can be used to prevent the color from becoming noticeable. The color antifoggant 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 using the silver halide emulsion of the present invention, an image stabilizer can be used to prevent deterioration of the dye image. Examples of image stabilizers include phenol derivatives and their bis forms, hydroxycoumarans and their spiro forms, hydroxycoumarans and their spiro forms,
Preferred are hydroxychroman and its spiro derivative, piperidine derivatives, aromatic amine compounds, benzodioxane derivatives, benzdioxole derivatives, silicon atom-containing compounds, thioether compounds, and the like. Specific examples include British Patent No. 1410846, Japanese Patent Application Publication No. 49-134326, Japanese Patent Application Publication No. 52-35633, and Japanese Patent Application Publication No. 52-35633.
No. 147434, No. 52-150630, No. 54-145530, No. 52-150630, No. 54-145530, No.
No. 55-6321, No. 55-21004, No. 55-124141,
No. 59-3432, No. 59-5246, No. 59-10539,
Special Publication No. 48-31625, No. 49-20973, No. 49-
No. 20974, No. 50-23813, No. 52-27534, U.S. Patent No. 2418613, No. 2710801, No. 2735765,
Same No. 2816028, No. 3069262, No. 3336135, Same No.
No. 3432300, No. 3457079, No. 3573050, No. 3432300, No. 3457079, No. 3573050, No.
No. 3574627, No. 3698909, No. 3700455, No.
No. 3764337, No. 3935016, No. 3982944, No.
No. 4013701, No. 4113495, No. 4120723, No.
No. 4155765, No. 4159910, No. 4254216, No. 4155765, No. 4159910, No. 4254216, No.
No. 4268593, No. 4279990, No. 4332886, No. 4268593, No. 4279990, No. 4332886, No.
Examples include No. 4360589, No. 4430425, and No. 4452884. 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 the photosensitive material being charged due to friction, etc., and to prevent image deterioration due to UV light. May contain. In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used in the light-sensitive material. When containing dyes, ultraviolet absorbers, etc. in the hydrophilic colloid layer of a photosensitive material, they may be mordanted with a mordant such as a cationic polymer. Compounds that change the developability, such as development accelerators and development retarders, and bleaching accelerators can be added to the silver halide emulsion layer and/or other hydrophilic colloid layers of the light-sensitive material. Compounds that can be preferably used as development accelerators are listed in Items B to D of RD17643.
The development retardant is a compound described in Section E of No. 17643. The emulsion layer of the light-sensitive material contains polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development.
It may also contain quaternary ammonium compounds, urethane derivatives, urea derivatives, imidazole derivatives, and the like. A fluorescent whitening agent can be used in the photosensitive material for the purpose of emphasizing the whiteness of the white background and making the coloration of the white background less noticeable. Compounds that can be preferably used as fluorescent sensitizers are described in Section V of RD17643. The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out of the light-sensitive material or bleached during the development process. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like. Reducing the gloss of the photosensitive material in the silver halide emulsion layer and/or other hydrophilic colloid layer of the photosensitive material;
A matting agent can be added to improve the ease of writing and to prevent photosensitive materials from sticking to each other. A lubricant can be added to the photosensitive material to reduce sliding friction. An antistatic agent can be added to the photosensitive material 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 the protective colloid layer other than the emulsion layer on the side on which the emulsion layer is laminated with respect to the emulsion layer and/or the support. May be used for. Preferably used antistatic agents are
This is a compound described in RD17643. The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material has various properties such as improving coating properties, preventing static electricity, improving slipperiness, dispersing emulsions, preventing adhesion, and photographic properties (promoting development,
Various surfactants can be used for the purpose of improving (high contrast, sensitization, etc.). The support used in the photosensitive material of the present invention includes α
- Flexible reflective supports such as paper laminated with olefin polymers (e.g. polyethylene, polypropylene, ethylene/butene copolymer), synthetic paper, etc., cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, Films made of semi-synthetic or synthetic polymers such as polyamide, flexible supports with reflective layers on these films, glass,
Includes metals, ceramics, etc. The hydrophilic colloid layer of the photosensitive material can be applied directly or after applying corona discharge, ultraviolet irradiation, flame treatment, etc. to the surface of the support as necessary, or to improve the adhesion, antistatic property, dimensional stability, and abrasion resistance of the support surface. The coating may be coated through one or more subbing layers to improve properties such as hardness, hardness, antihalation, friction properties, and/or other properties. When coating the photosensitive material, a thickener may be used to improve coating properties. Also, for things like hardeners, which are so reactive that if added to the coating solution in advance they will gel before coating, it is best to mix them using a static mixer or the like just before coating. preferable. Particularly useful coating methods are extrusion coating and curtain coating, which allow two or more layers to be applied simultaneously.
Depending on the purpose, packet application may also be used. or,
The application speed can be selected arbitrarily. 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 is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps,
Xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, various laser lights, light emitting diode lights, electron beams, X-rays, γ
Any known light source can be used, such as light emitted from a phosphor excited by radiation, alpha radiation, or the like. Exposure times include not only exposure times of 1 millisecond to 1 second, which are normally used in cameras, but also exposure times shorter than 1 microsecond, such as those using cathode ray tubes or xenon flash lamps.
Exposures of 100 nanoseconds to 1 microsecond can be used, and exposures longer than 1 second are also possible.
The exposure may be performed continuously or intermittently. A known method can be used to develop the photosensitive material of the present invention. The processing temperature used is between 18°C and 50°C, and depending on the purpose, black and white photographic processing, lithographic development processing, or color photographic processing to form a dye image can be applied. Black-and-white photographic processing uses dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone), aminophenols (e.g. N-methyl-
(p-aminophenol), ascorbic acid, etc. can be used alone or in combination. The developing solution contains other known preservatives, alkaline agents, PH moderators, capri inhibitors, etc., and, if necessary, solubilizers, color toners, development accelerators, surfactants, antifoaming agents, etc. It may also contain water softeners, hardeners, etc. The present invention can also be applied to a so-called developer-containing type photosensitive material in which a developing agent is contained in the photosensitive material in a developable amount and processed in an alkaline bath. Next, when forming a dye image, an alkaline aqueous solution containing a color developing agent is used. As the color developing agent, a known primary aromatic amine developer such as phenylene diamines can be used. Color developers also contain PH compounds such as alkali metal sulfites, carbonates, borates, and acid salts.
laxatives, halogen salts, and organic antifoggants,
It may contain water softeners, preservatives, organic solvents such as benzyl alcohol and ethylene glycol, and development accelerators such as quaternary ammonium salts and amines. Processing after color development is usually a bleaching process.
The bleaching solution may be applied simultaneously with the fixing process or separately. As bleaching agents, compounds of polyvalent metals such as iron (), cobalt (), chromium (), copper (), persulfates, etc. are used. For example, ferrocyanide, dichromate, iron,
Cobalt organic complex salt, ethylenediaminetetraacetic acid,
Nitrilotriacetic acid, persulfate, permanganate,
etc. can be used.

【Example】

Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. Example 1 An antihalation layer (0.40 g of black colloidal silver) was applied to a subbed cellulose triacetate film.
and 3.0g of gelatin. ) Sample 1 was prepared by sequentially coating each of the following layers on a transparent support having: The amounts of additives added are shown in amounts per 1 m ² of light-sensitive material, and the amounts of silver halide emulsions are shown in amounts converted to silver. Layer 1...1.4 g of low-sensitivity red-sensitive silver iodobromide (containing 7 mol% silver iodide) emulsion color-sensitized to red sensitivity and
1.2 g gelatin and 0.8 g cyan coupler A (exemplary coupler C-48) and 0.075 g 1-hydroxy-4-[4-(1-hydroxy-δ-acetamido-3,6-disulfo-2-naphthylazo) phenoxy]-N-[δ-(2,4-di-
A low-speed red-sensitive emulsion layer containing 0.65 g of tricresyl phosphate (TCP) in which disodium t-amylphenoxy)butyl-2-naphthamide (a type of colored cyan coupler) is dissolved. Layer 2...1.3g of highly sensitive red-sensitive silver iodobromide emulsion (containing 6 mol% silver iodide), 1.2g of gelatin and
0.21 g of cyan coupler used in layer 1 and 0.02
A high-sensitivity red-sensitive emulsion layer containing 0.23 g of TCP in which the colored cyan coupler used in layer 1 of g. Layer 3: 0.04 g of n dissolved in 0.07 g of 2,5-di-t-octylhydroquinone (antifouling agent)
- Interlayer containing dibutyl phthalate (DBP) and 0.8 g gelatin. Layer 4...0.80 g of low-speed silver iodide (containing 6 mol % silver iodide) emulsion color sensitized to green sensitivity, 2.2 g of gelatin, and 0.8 g of magenta coupler B (exemplary coupler M-1) and 0.15 1-(2,4,
0.95 g of TCP in which 6-trichlorophenyl)-4-(1-naphthylazo)-3-(2-chloro-5-octadecenylsuccinimideaniline)-5-pyrazolone (a type of colored magenta coupler) is dissolved. A low-sensitivity green-sensitive emulsion layer containing Layer 5...1.8 g of high-sensitivity green-sensitive silver iodobromide (containing 3 mol% silver iodide) emulsion color-sensitized to green sensitivity, 1.9
g of gelatin and 0.60 g of DBP in which 0.20 g of the magenta coupler used in layer 4 and 0.049 g of the colored magenta coupler used in layer 4 were dissolved.
A high-sensitivity green-sensitive emulsion layer containing Layer 6...0.15g of yellow colloidal silver 0.2g of anti-fouling agent (same as contained in layer 3) dissolved in 0.11g
of DBP and 1.5 g of gelatin. Layer 7: 0.2 g of low-sensitivity silver iodobromide (containing 4 mol% silver iodide) emulsion sensitized to blue sensitivity, 1.9 g of gelatin, and 1.5 g of yellow coupler C (exemplified coupler Y-52). Low speed blue sensitive emulsion layer containing 0.6g dissolved TCP. Layer 8: 1.0 g of high-sensitivity silver iodobromide (containing 2 mol% silver iodide) emulsion sensitized to blue, 1.5 g of gelatin, and 1.30 g of the yellow coupler used in layer 7 dissolved in 0.65 g. Highly sensitive blue-sensitive emulsion layer containing g TCP. Layer 9...protective layer with 2.3 g of gelatin. The emulsion layer of this example was a monodispersed emulsion, and was prepared as follows. First, an ammonium silver nitrate aqueous solution, potassium iodide and potassium bromide aqueous solutions were added to a reaction vessel in which silver halide seed particles and a gelatin aqueous solution were previously charged, while controlling the pAg and PH in the reaction vessel. and were added in proportion to the increase in surface area during particle growth. Next, a Demol N aqueous solution manufactured by Kao Atlas Co., Ltd. and a magnesium sulfate aqueous solution were added to perform precipitation and desalting, and gelatin was added to obtain an emulsion with pAg 7.8 and pH 6.0. Furthermore, sodium thiosulfate, chloroauric acid, and rhodan ammonium were added, and chemical ripening was performed to produce 4-hydroxy-6-
Methyl-1,3,3a,7-tetrazaindene was added and gelatin was further added to obtain a monodisperse silver iodobromide emulsion. Here, the particle size was changed by changing the amounts of ammoniacal silver nitrate and potassium halide. A core-shell type emulsion was produced by the method described in Japanese Patent Application Laid-Open No. 54-48521. Samples 2 to 13 were prepared in the same manner as Sample 1 except that the diffusible DIR of the present invention as shown in Table 1 and the compound represented by the general formula [] of the present invention were added to Layer 1 and Layer 2 of Sample 1. Created. Further, Samples 14 to 25 were prepared in the same manner as Sample 1 except that the diffusible DIR and compound [ ] of the present invention as shown in Table 1 were added to Layer 4 and Layer 5 of Sample 1. Furthermore, Samples 26 to 33 were prepared in the same manner as Sample 1, except that the diffusible DIR and compound [ ] of the present invention as shown in Table 1 were added to Layer 7 and Layer 8 of Sample 1. Using film samples Nos. 1 to 33 prepared as described above, a forced aging test was conducted under the following conditions in order to observe long-term natural aging changes in a short period of time. Forced aging test conditions Room temperature storage 3 days 60℃ dry 3 days 50℃ 80% relative humidity 3 days After this, each of these samples was given neutral exposure through an optical wedge and then treated with the following processing steps. A dye image was obtained. Processing process Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying The composition of the processing solution used in each processing step is It is as follows. (Color developer) 4-amino-3-methyl-N-ethyl N-(β
-hydroxyethyl)aniline sulfate 4.75g Anhydrous sodium sulfite 4.25g Hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate)
2.5g Potassium hydroxide 1.0g Add water to make 1. (Bleach solution) Ethylenediaminetetraacetic acid iron ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml Add water to make 1, and adjust the pH using aqueous ammonia.
Adjust to 6.0. (Fixer) Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to make 1, and adjust the pH to 6.0 using acetic acid. (Stabilizing liquid) Formalin (37% aqueous solution) 1.5ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5ml Add water to make 1. The cyan, magenta, and yellow coloring densities are measured using a densitometer, and from this the fog density (Fog) data and the relative sensitivity (S ₂ ) data (measured at the exposure amount that gives a density of fog + 0.3) are tabulated. Shown in 1. However, sample 1 showed data on the color density of three colors, samples 2 to 13 showed data on cyan color density, samples 14 to 25 showed data on magenta color density, and samples 26 to 33 showed data on yellow color density. The data shown in the table is for the coupler according to the present invention, and is for sample No. 2 without a fog suppressant.
The other S ₂ are expressed relative to each other with S ₂ as 100.

【table】

【table】

Claims (1)

[Scope of Claims] 1. A silver halide photographic light-sensitive material having a photographic constituent layer including at least one light-sensitive silver halide emulsion layer and at least one light-insensitive hydrophilic colloid layer on a support, At least one of the silver halide emulsion layers contains at least one coupler capable of reacting with an oxidized form of a developing agent to release a diffusible development inhibitor or its precursor, and at least one of the photographic constituent layers is characterized by containing at least one compound represented by the following general formula [] or a water-soluble salt thereof as an inhibitor in an amount of 1×10 ^-7 to 1×10 ^-2 mol per mol of silver halide. Silver photographic material. General formula [] [In the formula, X represents a hydroxyl group or an amino group. R ₁ and R ₂ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, or an alkoxysulfonyl group, and the [Formula] group is located at the ortho or para position of X. R ₁ and R ₂ may be bonded to each other to form a heterocycle with the nitrogen atom. Y represents a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, an unsubstituted or alkyl-substituted amino group, an acylamino group, or a sulfo group (including salts), and n is 0 to
Represents an integer of 4. When n is 2 or more, the plurality of Y's may be the same or different, Y's at the ortho position may bond with each other to form a carbon ring, or Y's at the ortho position and R ₁ or / and Y and R ₂ may be bonded to each other to form a heterocycle. ]