JPS61102647A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve graininess and sharpness b incorporating a coupler. CONSTITUTION:The coupler to be added is represented by the formula shown there in which A is a coupler residue to be cleft from X by reacting with the oxidation product of a color developing agent; X is 0 or S; R1 is an aliphatic, aromatic, or heterocyclic group; R2 is a substituent; n2 is 0, 1, or 2 and when n is 2, each of R2 may be different or combine with each other to form a divalent cyclic group. Such a coupler releases an aromatic alcohol or thiol substd. SO2NH2 or OH group upon the reaction with the oxidation product of a color developing agent, and this released compd. reduces said product by its own strong reducing power. The substitution of SO2NH2 or OH group properly enhances solubility and diffusitivity of the released compd. in an emulsion. The dimensions of the substituents R1. R2 can control the diffusivity, thus permitting the obtained photographic sensitive material to be prevented from mottles, enhanced in graininess, and improved in sharpness.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material containing a photographic coupler for improving sharpness and graininess.

(Prior art) By color-developing a silver halide color photographic material, an oxidized aromatic-amine color developing agent and a coupler react to form indophenol, indoaniline,
It is known that indamine, azomethine, phenoxazine, phenazine and similar dyes can be produced to form color images. In this method, a subtractive color method is usually used for color reproduction.
Magenta, and cyan color image forming agents are used. To form a yellow image, for example, an acylacetanilide or diindiylmethane coupler is used; to form a magenta image, a pyrazolone, virazolobenrymidazole, cyanoacetophenone or indacylon coupler is used, and a cyan Primarily phenolic couplers, such as phenols and naphthols, are used to form color images.

In recent years, high image quality has become more important than ever in silver halide photographic materials, particularly in photosensitive materials with the spread of disk cameras and 110-sized cameras. In particular, it is important to improve sharpness and graininess.

It has been known that couplers are used not only to form dye images but also to release photographically useful groups. Compounds that release photographically useful groups are used for various purposes such as improving color reproducibility, improving graininess, improving sharpness, or increasing sensitivity.

Now, couplers have been proposed that can release a compound that traps an oxidized color developing agent upon coupling of the coupler. For example, Japanese Patent Publication Showa JX-XR3IR, same!
7-///! 37. Compounds described in No. 17-/JlrtJt and the like are known. These couplers are used for the purpose of improving graininess or controlling gradation, but their effects are weak and further improvements have been desired. It has also been found that the scavengers for the oxidized developing agent released by these known couplers not only have a weak scavenging ability but also have low diffusivity. Therefore, it was not possible to improve the sharpness, and it was also not possible to obtain a multilayer effect by diffusing into other layers.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to reduce graininess by incorporating a novel coupler that releases a compound that captures an oxidized developing agent upon reaction with the oxidized developing agent. An object of the present invention is to provide a color photographic material that is excellent in sharpness or color reproducibility due to a multilayer effect.

(Means for Solving the Problems) The above object has been achieved by a silver halide color photographic light-sensitive material containing a coupler represented by the following general formula [I].

General formula [E] In the formula, human represents a coupler residue that cleaves with X upon reaction with an oxidized developing agent, X represents an oxygen atom, and represents a sulfur atom, and R1 represents an aliphatic group, an aromatic group, or a sulfur atom. represents a heterocyclic group, R2 represents a substituent, and n is 0. / or represents co, and when n is 2, the λ R2s may be different substituents, or each of the R2s may become a covalent group and connect to form a cyclic structure.

The couplers of the present invention release aromatic alcohols or aromatic thiols substituted with sulfonamide groups and hydroxyl groups upon reaction with oxidized developing agent. These released compounds have a strong reducing effect.
, reducing the oxidized developing agent. In addition, the hydroxyl group and sulfonamide group as substituents moderately increase the water solubility and increase the diffusibility of the compound released from turnip 2- in the emulsion. Further, by adjusting the sizes of the substituents represented by R1 and R2, the diffusivity can be easily adjusted. In other words, it has strong reducing properties, moderate water solubility, and easy adjustment of diffusivity.
It is believed that two things exactly explain the superior performance of the present invention. This is because when using the coupler of the present invention,
Excess oxidized developing agent generated during development processing can be reduced and effectively removed. This prevents individual pigment clouds from growing beyond a certain level, prevents the occurrence of mottles, and improves graininess. When using Turnip 2- of the present invention, an edge effect and a multilayer effect were observed when the reducing agent released from the turnip 2- had a high diffusivity. This effect was particularly noticeable in color reversal sensitive materials. For example, conventional couplers that release development inhibitors (DIR couplers) ft
It is known to be used for edge effects and multilayer effects. However, in color reversal photosensitive materials, conventional DI
At present, R couplers cannot be used because they do not have the effect of inhibiting development. This is because conventional DIR couplers use a base inhibitor that adsorbs to silver halide, which does not have a development inhibitory effect in color reversal processing with high development activity. However, the coupler of the present invention showed excellent graininess improvement effects and sharpness improvement effects even when used in color reversal sensitive materials. That is, in the second development of the color reversal process, the compound released from the coupler of the present invention functions as a scavenger for the oxidized developing agent and consumes the oxidized developing agent. As a result, developable silver is consumed and color development is eventually suppressed, which is probably why the DIR effect is exhibited.

In general formula CI), when R1 represents an aliphatic group, the number of carbon atoms is 1 to 3λ, preferably 1 to /r, and it is a substituted or unsubstituted, linear or branched, chain or cyclic, saturated or unsaturated hydrocarbon group. - It may be a deviation. Permissible substituents for these groups include, for example, those listed below: halogen atom, aryl group, alkoxy group, aryloxy group, arylthio group, alkoxycarbonyl group, hydroxyl group, acylamino group, cyano group, nitro group. group, carbamoyl group, sulfamoyl group, sulfonamido group, acyloxy group, alkylthio group, amine group, sulfonyl group, acyl group, ureido group, or aryloxycarbonyl group. When these substituents include an aliphatic group, the number of carbon atoms is /-/, 4, linear or branched, chain chain is cyclic, saturated or unsaturated, substituted or unsubstituted. Good too. Further, when the above-mentioned substituent includes an aromatic group, it has 6 to 10 carbon atoms, and is preferably a substituted or unsubstituted phenyl group.

In the general formula ("I), when R represents an aromatic group, the number of carbon atoms is t to 10, and it is preferably a substituted or unsubstituted phenyl group. Substituents include an aliphatic group, an aromatic group,
Heterocyclic group, halogen atom, alkoxy group, aryoloxy group, arythio group, alkoxycarbonyl group, hydroxyl group, acylamino group, cyano group, nitro group, carbamoyl group, sulfamoyl group, sulfonamide group,
Examples include acyloxy group, alkylthio group, amino group, sulfonyl group, ureido group, aryloxycarbonyl group, carboxyl group, acyl group, alkoxycarbonylamino group, and sulfamoylamino group.

When these substituents contain an aliphatic group, the number of carbon atoms is 1.
~J, preferably /-/4, linear or branched,
It may be linear or cyclic, saturated or unsaturated, substituted or unsubstituted. Further, when the above-mentioned substituent includes an aromatic group, the number of carbon atoms is from O to 1O, and it is preferably a substituted or unsubstituted phenyl group. In addition, when the above substituent contains a heterocycle, for example, imidazole, pyrrole,
It has a ring structure such as thiophene, tetrahydrofuran, benzimidazole, pyridine, triazole, virazoleimidazolidine, and ≠-dione.

When R1 represents a heterocyclic group in the general formula [E], the hetero atom is selected from a nitrogen atom, a sulfur atom, an oxygen atom, or a selenium atom! Preferably a heterocyclic group having 0 to 7 members, such as imidazole, pyrazole &/1
λ, triazole, thiophenfucine, benzimidazole, pyridine, tetrahydrofuran, etc., which have a ring structure, and these may have a substituent, and preferred substituents include an aliphatic group, an aromatic group, an acylamino group, and a sulfonamide group. group, alkoxy group, halogen 10, aryloxycarbonyl group, alkoxycarbonyl group, alkylthio group, ureido group, cyano group, amino group, aryloxy group, etc. When these substituents include an aliphatic group moiety, the number of carbon atoms is 1 to 3-1, preferably / to 16, and may be linear or branched, chain or cyclic, saturated or unsaturated, substituted or unsubstituted. It may be. When the above substituent includes an aromatic group, the number of carbon atoms is t~
10, preferably a substituted or unsubstituted 7-enyl group.

In general formula CI] VC, preferred substituents for R2 include aliphatic group 5 aromatic group, aliphatic oxy group, aliphatic or aromatic thio group, aliphatic or aromatic acyl group, aliphatic or aromatic oxycarbonyl group, aliphatic or aromatic sulfonyl group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted sulfamoyl group,
fat! or an aromatic acylamino group, an aliphatic or aromatic oxycarbonylamino group, a substituted or unsubstituted ureido group, a substituted or unsubstituted carbamoyloxy group, a halogen atom, a cyano group, a formyl group, or a nitro group, and n is 2, R2 may be the same or different. Also, when n is 2, it is good.

When these substituents include an aliphatic group, the number of carbon atoms is 7.
~32, preferably 7 to 16, straight chain or branched,
It may be linear or cyclic, saturated or unsaturated, substituted or unsubstituted.

When R3 includes an aromatic group, the number of carbon atoms is 4-1
0, preferably a substituted or unsubstituted phenyl group. Further permissible substituents for R2 are the same as those for R, aliphatic or aromatic groups.

A preferred example is when X in general formula (I) is an oxygen atom.

Particularly preferred couplers are those in which the OH group and the NH30211 group are in the 2-position with respect to X in the general formula (I).

In general formula CII, A is specifically represented by the following general formula (II
), (III), (Ilil'), (Vl, (1, (■
) or (■) is a turnip 2-residue.

General formula (I[] R4CCHCNH-R5 General formula (III) General formula [■] General formula [v] General formula (V[] In the above formula, the free bond derived from the coupling position is a coupling-off group (X in general formula CI)
represents the bonding position of In the above formula, R4・R5・
R6h R? -RBb R9・R1,
・R11h R12, Rt sb R14, R1
If s or R16 contains a diffusion-resistant group, it is selected such that the total number of carbon atoms is r ~ 32, preferably 10 ~ λ; otherwise, the total number of carbon atoms is preferably less than or equal to l. .

Next, R4 to R16 and IVc of the general formulas (It) to (■) will be explained.

In the formula, R4 represents an aliphatic group, an aromatic group, an alkoxy group, or a heterocyclic group, and R5 represents an aromatic group or a heterocyclic group.

In the formula, the aliphatic group represented by R4 preferably has 1 carbon number.
-22, which may be substituted or unsubstituted, linear or cyclic. Preferred substituents for the alkyl group 1 include an alkoxy group, an aryloxy group, an amino group, an acylamino group, and a halogen atom, which may themselves have further substituents. Specific examples of aliphatic groups useful as R4 are: inoprobyl, isoamyl, tert-butyl, isoamyl, tert-amyl, i,i-dimethylbutyl, / , /-dimethylhexyl group, l, /-diethylhexyl group, dodecyl group, hexadecyl group, octadecyl group, cyclohexyl group, /-methoxyinpropyl group, /-phenoxyisopropyl group, /-pte
r t-7' tylphenoxyisopropyl group, α-aminoisopropyl group, α-(diethylamino)isopropyl group, α-(succinimide)inpropyl group, α-(
These include phthalimido) isopropyl group, α-(ininsulfonamido) isopropyl group, and the like.

When R4 or R5 is an aromatic group (especially phenyl group), the aromatic group may be substituted.
Guy 0 Fang 8n 賎1゛2 1.

0 alkyl group, alkenyl group, alkoxy group, a
1-rukoxycarbonyl group, alkoxycarynylamino group, aliphatic amide group, alkylsulfamoyl group, alkylsulfonamide group, alkylureido group,
May be substituted with an alkyl-substituted succinimide group, etc.
In this case, the alkyl group may have an aromatic group such as phenylene interposed in the chain. Phenyl group is also aryloxy group,
It may be substituted with an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamide group, an arylureido group, etc., and the total number of carbon atoms in the aryl group of these substituents may be substituted with one or more alkyl groups of /-22.

The phenyl group represented by R4 or R5 is further
It may be substituted with an amino group, a hydroxy group, a carboxy group, a sulfo group, a nitro group, a cyano group, a thiocyano group, or a halogen atom, including those substituted with a lower alkyl group having carbon number/-4.

R4h or R5 may represent a substituent in which a phenyl group is fused with another ring, such as a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a r-r5nyl group, or a tetrahydronaphthyl group.

These substituents may themselves have further substituents.

When R4 represents an alkoxy group, the alkyl moiety represents a linear or branched alkyl group, an alkenyl group, a cyclic alkyl group, or a cyclic alkenyl group having 1 to 32 carbon atoms, preferably 1 to λ, These may be substituted with a halogen atom, an aryl group, an alkoxy group, or the like.

When R4 or R5 is a heterocyclic group, the heterocyclic group is connected to the carbon atom of the carbonyl group of the acyl group or the nitrogen atom of the amide group in alpha-acylacetamide through two of the carbon atoms forming the ring, respectively. Join. Such heterocycles include thiophene, furan, biran, virol, pyrazole, pyridine, pyrazine, pyrimidine, biritazine, indolizine, imidazole, thiazole, oxazole, triazine, thiadiazine.

An example is oxazine. These further have a substituent on the ring.

In the general formula CI[], R6 is a linear or branched alkyl group (e.g., methyl, isopropyl, tert-butyl, hexyl, dodecyl group, etc.), an alkenyl group, preferably having a carbon number of 1 to 3λ. (e.g. allyl group), bicyclic alkyl group (e.g. cyclopentyl group, cyclohexyl group, norbornyl group, etc.), aralkyl group (e.g. hahenzyl, β-phenylethyl group, etc.), cyclic alkenyl group (e.g. evacyclopentenyl, cyclohexenyl group, etc.) ), and these represent a halogen atom, a nitro group, a cyan group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl group, an alkylthiocarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and a sulfonyl group. group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, thiourethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group , dialkylamino group, anilino group, N
-arylanilino group, N-alkylanilino group, N-
It may be substituted with an acylanilino group, a hydroxy group, a mercapto group, etc.

Furthermore, R6 may represent an aryl group (eg, phenyl group, α- or β-naphthyl group, etc.). The aryl group may have one or more substituents, such as an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group, a cyano group, and an aryl group. group, alkoxy group, aryloxy group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, sulfonamide group, heterocyclic group , arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group.

It may have an anilino group, an N-alkylanilino group, an N-arylanilino group, an N-acylanilino group, a hydroxy group, and the like. More preferred as R6 is phenyl in which at least one ortho position is substituted with an alkyl group, an alkoxy group, a halogen atom, etc. This is because the coloration of the coupler remaining in the film due to light or heat is more preferable. It is useful because there are few.

Furthermore, R6 is a heterocyclic group (for example, a !- or t-membered heterocyclic group containing a nitrogen atom, an oxygen atom, or a sulfur atom as a hetero atom, a fused heterocyclic group, such as a pyridyl group, a quinolyl group, a furyl group, a benzothiazolyl group, oxasilyl group, imidazolyl group, naphthoxacylyl group, etc.), a heterocyclic group substituted with a substituent listed in b for the above aryl group, an aliphatic or aromatic acyl group, an alkylsulfonyl group, an arylsulfonyl group, It may also represent an alkylcarbamoyl group, an arylcarbamoyl group, an alkylthiocarbamoyl group or an arylthiocarbamoyl group.

In the formula, R7 is a hydrogen atom, carbon number / to 32, preferably 1
22 straight chain or branched alkyl, alkenyl, cyclic alkyl, aralkyl, cyclic alkenyl group (these groups may have the substituents listed for R6 above), aryl group 2 and heterocyclic group (these groups) may have the substituents listed above for R6), an alkoxycarbonyl group (for example, a methoxycarbonyl group, an ethoxycarbonyl group, a stearyloxycarmenyl group) 1,
Aryloxycarbonyl groups (e.g., phenoxycarbonyl group, naphthoxycarbonyl group), aralkyloxycarbonyl groups (e.g., benzyloxycarbonyl group, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, heptadecyloxy group, etc.), Aryloxy groups (e.g., phenoxy, tolyloxy, etc.), alkylthio groups (e.g., ethylthio, dodecylthio, etc.), arylthio groups (e.g., phenylthio, α-naphthylthio, etc.), carboxy groups, acylamino groups (e.g., acetylthio, etc.), Amino group %J-((,2,≠-G t
er t-amylphenoxy)acetamide] benzamide group, etc.), diacylamino group, N-alkylacylamino group (e.g. N-methylpropionamide group, etc.)
, N-arylacylamino group (e.g. N-phenylacetamide group, etc.), ureido group (e.g. ureido, N-
aryl ureido, N-alkylureido group, etc.), urethane group, thiourethane group, arylamino group (e.g. phenylamino group, N-methylanilino group, diphenylamino group, N-acetylanilino group, 2-chloro-
tetradecaneamide anilino group, etc.), alkylamino group (e.g. n-butylamino group, methylamino group, cyclohexylamino group, etc.), cycloamino group (e.g. piperidino group, pyrrolidino group, etc.), bicyclic amino group (e.g. ≠- pyridylamino group, λ-benzoxasilylamino group, etc.), alkylcarbonyl group (e.g. methylcarbonyl group, etc.), carbonyl group (e.g. phenylcarbonyl group), sulfonamide group (e.g. eva-alkylsulfonamide group, carbamoyl group (e.g. ethylcarbamoyl group,
dimethylcarbamoyl group, N-methyl-phenylcarbamoyl, N-phenylcarbamoyl, etc.), sulfamoyl group [IJ, tba N-alkylsulfamoyl, N,
Any of N-dialkylsulfamoyl group, N-arylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N,N-diarylsulfamoyl group, cyano group, and hydroxy group It represents something.

In the formula, R8 represents an aliphatic group or an aromatic group.

The aliphatic group preferably has 1 to 22 carbon atoms and may be substituted or unsubstituted, linear or cyclic. Preferred substituents include an alkoxy group, an alkylthio group, an aryloxy group, a carboxyl group, a halogen atom, and an acylamino group.

etc., and these themselves may further have substituents.

Specific examples of aliphatic groups useful as R8 include the following: nidodecyl, hexadecyl, dodecyloxypropyl, cyclohexyl, tert-butyl, butyl, J-(x, j≠ -di-tert-acylphenoxy)propyl group, /'-(co,≠-di-tert)
t-acylphenoxy)propyl group, etc.

When R8 represents an aromatic group, it may have the substituents listed above when R4 is an aryl group.

In the formula, R9 is an aliphatic group (e.g. methyl group, ethyl group, etc.), a halogen atom (e.g. chlorine atom, fluorine atom),
It represents an alkoxy group (eg, methoxy group, ethoxy group) or an aromatic group (eg, phenyl group).

In the formula, &11G and R11 each represent a hydrogen atom, an aliphatic group, or an aromatic group. When R10 or R11 represents an aliphatic group, the number of carbon atoms is /~3λ, preferably /-
/r may be substituted or unsubstituted, and the chain chain may be cyclic. Preferable substituents include an aryloxy group, an alkoxy group, a halogen atom, an aryl group, and a hydroxyl group.

A carboxyl group, a cyan group, a nitro group, an alkoxycarbonyl group, an acylamino group, a sulfonamide group, an acyloxy group, etc., and these may further have a substituent. Specific examples of useful aliphatic groups for R10 or R11 are as follows: nidodecyl group, hexadecyl group,
dodecyloxyprobyl group, cyclohexyl group, ter
t-ethyl group, 3-(co,≠-di-tert-acylphenoxy)propyl group, 1-(co,≠-di-tert-
acylphenoxy)propyl group, λ-carmexyethyl group, etc. RLO''i Next, when R11 represents an aromatic group, the number of carbon atoms is A-10%. Preferably, the substituted or unsubstituted phenyl group is an unsubstituted phenyl group. Preferred substituents include an alkoxy group, an aliphatic group, an acylamino group, and an alkoxycarbonyl group. group, halogen atom, sulfonamide group, sulfamoyl group, carbamoyl group, carboxyl group, hydroxyl group, cyano group, nitro group, etc. Rlo is R1
Specific examples of useful aromatic groups of 1 are as follows: 2-tetradecyloxyphenyl group, hetetradecyloxyphenyl group, 3-dodecyloxycarbonylphenyl group, cochloroododecyloxy group. Carbonylphenyl group, phenyl group, ≠-carboxyphenyl group, etc.

In the formula, R12 is a halogen atom, an acylamino group (e.g., acetamido group, 2,4L-di-tert-acylphenoxyacetamide group), a sulfonamide group (e.g., methanesulfonamide group, hexadecylsulfonamide group), an alkoxy group (e.g. methoxy group, dodecyloxy group), or an aliphatic group (eg, methyl group, ethyl group).

In the formula, l represents O%l or ko, and when l is 2, 2
The two substituents may be the same or different.

R13tti7! J-carbonyl group, carbon number 2-3
an alkanoyl group, an arylcarbamoyl group, preferably having 2 to 7 λ carbon atoms, an alkanecarbamoyl group having λ to 3 λ carbon atoms, preferably 1 to 3 carbon atoms, preferably 1-λ
λ represents an alkoxycarbonyl group or an aryloxycarbonyl group, which may have a substituent, and examples of the substituent include an alkoxy group, an alkoxycarbonyl group, an acylamino group, an alkylsulfamoyl group, an alkylsulfonamide group, and an alkyl group. Examples include a succinimide group, a halogen atom, a nitro group, a carboxyl group, a nitrile group, an alkyl group, and an aryl group.

R14 is an arylcarmenyl group, an alkanoyl group having 2 to 3 carbon atoms, preferably 2 to 2, or an arylcarbamoyl group, having λ to 3 carbon atoms, preferably 2 to . 2.2 alkanecarbamoyl group, an alkoxycarbonyl group or aryloxycarbonyl group having 1 to 3 carbon atoms, preferably / to -2 carbon atoms, an alkanesulfonyl group or arylsulfonyl group having 1 to 3λ carbon atoms, preferably / to 2-carbon atoms; Aryl group!
or t-membered heterocycle fr (hetero atoms are selected from nitrogen atom, oxygen atom, sulfur atom, for example triazolyl group, imidazolyl group, phthalimide group, succinimide group, furyl group, pyridyl group or benzotriazolyl group) ), which may have the substituent described above for R4a.

In the general formula (■), R15 represents an aliphatic group, an aromatic group, a heterocyclic group or an IJ group. Regarding the aliphatic group, aromatic group and heterocyclic group, the explanation for R4 applies. When Rlg represents an anilino group, the phenyl group may have the substituents listed when R6 represents a phenyl group. Preferred examples of R15 include interfluoropropyl group, /, l, 2,2.
! .

3-hexafluoropropyl group, p-cyanoanilino group, 3. ≠-dichloroanilino group, p-propanesulfonylanilino group, coethanesulfonamidophenyl group,
Examples include.

In the formula, R16 represents an aliphatic group or an aromatic group.

The explanation for R4 applies to these. Preferred examples of R16 include tert-butyl group, t-(Z
, a-di-tert-amylphenoxy)propyl group, t-(z, ta-di-tert-amylphenoxy)pentyl group, isoamyl group, 1-(co,≠-di-te)
Examples include rt-octylphenoxy)heptyl group.

Examples of the compounds used in the present invention include, but are not limited to, the following compounds.

-39: h 0H (”)　　　　　　　.8 0H υh α OH OH (c) Jfl An example of synthesis of a coupler according to the present invention will be shown.

Synthesis example (11 Synthesis of exemplified compound (1) It was synthesized using the following synthetic route.

Exemplary compound (1) CsHu(t) ■ Synthesis of compound ~: SOt of compound O, compound 1 of older brother
0. ≠2 and 6 t of triethylamine were added to 00 ml of acetonitrile and heated under reflux for 3 hours. After cooling to room temperature, ethyl acetate/l was added and washed with water. After neutralization with dilute hydrochloric acid, the water washing was repeated and the oil layer was separated and concentrated. The residue was crystallized using a mixed solvent of ethyl acetate and hexane to obtain the compound jf.

■ Compound synthesis: 200ml of 1K compound containing caustic potassium jt.

Jft- and stirred at room temperature for 5 hours. ethyl acetate 1tt
- After addition and washing with water, neutralization was performed using acetic acid. After washing with water, the oil layer was separated and concentrated. By crystallizing the residue using a mixed solvent of ethyl acetate and hexane, the compound
2. I got tt.

■ Synthesis of exemplified compound (1): Compound 12.4? ,
Hirisin tth and benzenesulfonyl chloride 3. !
The mixture was added to 100 mt of chloroform and heated under reflux. After 3 hours, the mixture was cooled, washed with dilute hydrochloric acid, and then washed with water. After separating the oil layer, the solvent was distilled off and the residue was crystallized using a mixed solvent of ethyl acetate and hexane to obtain the desired coupler.
I got y.

Synthesis Example (2) Synthesis of Exemplified Compound (2) Synthesis Example (in Step 11, 6)
-Hydroxy-2-tert-butylbenzoxazole was used, but the same method as in Synthesis Example (1) was used to synthesize Nyoshi coupler (2).

Synthesis Example (3) Synthesis of Exemplary Compound (3) Synthesis was carried out by the following synthetic route.

α 0H Exemplary Compound (3) ■ Synthesis of Compound 〜: In addition to +/S′ of Compound 〜 and sodium methoxide, 221″lcN, N-dimethylformamide λooml, add the compound 7. to this solution at room temperature. 11 was added. After heating to !0°C and reacting for t hours, post-treatment was carried out by a conventional method to obtain compound ≠rt.

■ Synthesis of compound ~: +ry of compound ~, λ-tetradecyloxyaniline 3≠, 7? N, N'-zinchlorohexylcarbodiimide 23. By performing a dehydration condensation reaction using ≠t, the compound ~ is converted to jO0λ? Obtained.

(2) Synthesis of compound ~: J-0,2t of compound ~ was hydrolyzed in 4L00 mL of methanol using caustic potash 209 to obtain ≠2.32 of compound ~.

■ Synthesis of exemplified compound (3): Compound 2.32,
Benzenesulfonyl chloride l-2, lr? Exemplary compound (3) was obtained by heating and refluxing in chloroform using , pyridine//, jt, xr, 3.

The coupler of the present invention is preferably used in combination with commonly used photographic couplers. For the dye-forming cabranomole used in the same layer / 0-2 to l.

The desired effect of the present invention can be obtained by using the amount in the range of 0 mole, preferably 0.01 NO.

Kashitsu of the present invention or Kashitsu 2- which can be used in combination as described below
can be introduced into the photosensitive material by various known dispersion methods,
Typical examples include a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method. In the oil-in-water dispersion method, the boiling point is 1
After dissolving in either a high boiling point organic solvent of 7j'c or more and a low boiling point so-called auxiliary solvent, or a mixture of both, finely dispersed in an aqueous medium such as water or an aqueous gelatin solution in the presence of a surfactant. do. Examples of high-boiling organic solvents are U.S. Patent No. λ,! , No. 22.027, etc. Dispersion may be accompanied by phase inversion, and if necessary, auxiliary solutions may be removed or reduced by distillation, noodle washing, ultrafiltration, etc. before use for coating.

Specific examples of high boiling point organic solvents include phthalate esters (dibutyl phthalate, dicyclohexyl heptatarate,
esters of phosphoric or phosphonic acids (triphenyl phosphate, tricresyl phosphate, etc.)
Raw ethylhexyl diphenyl phosphate, tricyclohexyl phosphate), )! J-2-Ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, Z-low ethylhexylphenyl phosphonate, etc.), benzoic acid esters (low-ethylhexyl benzoate, dodecyl benzoate, λ-ethylhexyl-p)
-hydroxybenzoate, etc.), amides (diethyldodecanamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (stearyl alcohol, λ,lA-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, instearyl lactate, trioctyl citrate, etc.), aniline derivatives (N,N-dibutyl-2-butoxy-j-tert-
octylanily, etc.), hydrocarbons (), rough-in,
(dodecylbenzene, diisopropylnaphthalene, etc.), and as an auxiliary solvent, solvents with a boiling point of about 300
to about /40°C, typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, λ-nitoxyethyl acetate, dimethylformamide, and the like.

The process and effects of latex dispersion methods and specific examples of latex for impregnation are disclosed in U.S. Pat.

No. 363, OLS No. 1, j4ti, No. 7, and OL
It is described in S No. λ, J Hiro/, No. 230, etc.

゛・Various color couplers can be used in the present invention. In other words, a color coupler is a compound that can react with an oxidized product of an aromatic primary amine developer to produce a dye. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolone or pyrazoloazole compounds, and open chain or heterogeneous ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that may be used in the present invention are found in Research Disclosure (RD)/74 Hiro J (/7 in 2011) Section VII-D and RD/1717 (/P
7P year l/month).

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a pallast group or being polymerized. A two-equivalent color coupler substituted with a leaving group is preferable to a four-equivalent color coupler in which the coupling active position is a hydrogen atom. Couplers in which the color-forming dye has adequate diffusivity, non-color-forming couplers, or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is US Patent No. 2. Hiro 0
No. 7,210, same No. 2. ♂7j, No. 017 and No. 3, 2t! , jOt issue, etc. The use of two-equivalent yellow couplers is preferred for the present invention, and US Pat. or, tya issue, same No. J, 4 (Hiroshi 7
, Octopus issue, same No. J, PJJ,! No. 01 and No. ≠,
022゜420, etc., or Japanese Patent Publication No. 1-10732.

U.S. Patent No.≠, IAO/, 7yo2, U.S. Patent No.≠, 32t,
No. 024c, RD/lrO,! ;3 (/979≠month).

British Patent No. 1. ≠No. 21.020, West German Application Publication No. 2,
21 Ri, Ri No. 17, Sai No. 2, 2 Otsu l, No. 361, Sai No. 2
, No. 322, 117 and No. 2≠33. A typical example is the nitrogen atom dissociator yellow coupler described in I/, No. 1, etc. The .alpha.-piparoylacetanilide coupler has excellent color fastness, particularly light fastness, while the a-benzoylacetanilide coupler provides a high color density.

The magenta coupler that can be used in the present invention is preferably an oil-protected indacylon or cyanoacetyl coupler! - Pyrazoloazole couplers such as pyrazolone and pyrazolotriazoles are mentioned. ! The -pi2zolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye. J//, No. 01.2, No. λ.

3'lJ, No. 703, No. 2,400,710, No. 2. RiO♂,! No. 73, No. 3, 0 Otsu 2, 6! 3,
Same 3rd. /yo No. 2,196 and same No. 3゜ri 36,0/
It is written in the evening edition etc. A two-equivalent pyrazolone type Kab 2- is preferred because it can provide high color density and high sensitivity with a small amount of coated silver, and is used as a leaving group in U.S. Pat.
The nitrogen atom leaving group described in No. 0r or U.S. Patent No. ≠.

3! The arylthio groups described in / and I-7 are particularly preferred. Also, European Patent No. 73. The pallast group described in No. 3 has the effect of increasing the color density even for Yoichi pyrazolone type Kab 2-. As the pyrazoloazole type Kab 2-, pyrazolobenzimidazoles described in U.S. Pat.
1. Pyrazolo Crtl-c]ci described in No. 047
tco,≠]triazoles, pyrazolotetrazoles and R described in RD J Hiroko 20 (/rig≠year to month)
Examples include pyrazolopyrazoles described in Dco≠230 (/ri≠June). Imidazo [l] described in European Patent No. 1/1, No. 7 Hiro 1, in terms of low yellow side absorption of the coloring dye and light fastness.

[Cob] pyrazoles are preferred, and European Patent No. 11,
Pyrazolo C/,,z-b)(/t
J r≠]triazole is particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected 7-tall couplers and phenol-based couplers, preferably the 7-tall couplers described in U.S. Pat. US Patent No.≠,
No. 2.272 to O, same No. ≠.

Typical examples include the oxygen atom dissociative type divalent naphthol couplers described in No. 14tt, J Ribu No., No. 3, No. 2 Ko I, No. JJJ, and No. Specific examples of phenolic couplers include U.S. Patent Nos. 2,36, 5P2,
It is described in No. 26 etc. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention and are described, for example, in U.S. Patent No. J, 772.002.
Phenolic cyan couplers described in U.S. Pat.

3or No. 44. /24. J Riwo No., same No. 1 Hiroshi.

J31A, No. 01, No. 1, 327. /No. 73, West German Patent Publication No. 3, 3-? , 7 Kota issue and Tokugan Sho J-, 5
'-Ko 2671, etc., λ, J'-diacylamino substituted phenolic couplers and US Patent No. j,
lI-≠Otsu, ≦22, No. 333, Tatata, No. 11.4'J-/, jr and No. 27
, No. 767, etc., has a phenylureido group at the co-position and! These include phenolic couplers having an acylamino group at the - position.

Dye-forming couplers are used in amounts of p, o, ooλ to 0.15 moles per mole of light-sensitive silver halide in the layer to which they are added. Photographic power 2 - In photosensitive materials, 7 moles of photosensitive silver halide, yellow oak 2 - 0, 0/@ 0
, 1 mol, azentacap 2- is 0.003 to 0.2
1 mol, and cyan turnip 2- is 0.002 to 0.1
2 mol is often used, and in color photosensitive materials for printing such as Color E/g-, yellow, agenta and cyan couplers are used per 1 mol of photosensitive silver halide (7,/ to 0.2 mol). However, it is possible to design photosensitive materials outside this range.

The coupler of the present invention and the couplers described above can be used in combination of two or more types in the same layer in order to satisfy the characteristics required for a photosensitive material, or the same metal compound can be added to two or more different layers. , of course it doesn't matter.

In order to correct unnecessary absorption in the short wavelength region of the magenta and cyan coupler chromophores, it is preferable to use a colored coupler in combination with the color photosensitive material for photographing. U.S. Patent No.
Yellow-colored magenta couplers described in US Pat. No. 3241-1J, etc. or US Pat.
I-, /31.2jI and British Patent No. 7. /≠4
Typical examples include magenta-colored shear/couplers described in , Jtlr, and the like.

These color couplers may form comer or higher polymers. Typical examples of polymerized couplers are described in U.S. Patent No. 3. ≠J-/, rco-O and the same year.

oro, No. 211. Polymerization 1'
A specific example of a magenta coupler is described in British Patent No. 2.
i.

Ko, No. 173 and U.S. Patent No. ≠, El, 7. It is described in No.

In addition, various undiffused couplers can be used in combination to improve graininess, and such couplers are described in U.S. Pat.
344. 37 and British Patent No. 2/2! ,! Specific examples of magenta couplers are given in European Patent No. 9'g,
! No. 73 and West German Patent Publication (OLS) j I J1
4'+! 33) Specific examples of K include yellow, magenta, and cyan.

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

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. Preferred silver halide is silver iodobromide containing silver iodide of /j molti or less. Particularly preferred is an iodine containing silver iodide at a concentration of 72 mol 1 from λmolti.
It is 1° silver oxide.

Silver halide grains in photographic emulsions can be cubic, hexagonal, or
It may have a regular crystal shape such as a -dihedron or a 14L-hedron, it may have an irregular crystal shape such as a spherical shape, or it may have a composite shape of these crystal shapes.

In addition, tabular grains with a thickness of o, r microns or less, a diameter of at least 096 microns, and an average aspect ratio of 5 or more, as described in Resate Disclosure Co., Ltd. 2!3≠, occupy a large proportion of the total projected area % or more may be used.

The crystal structure may be uniform, the inside and outside may have different compositions, it may have a layered structure, or silver halides with different compositions may be joined by epitaxial bonding, and various crystal structures may be used. It may also consist of a mixture of particles in crystalline form.

Further, the latent image may be formed mainly on the surface of the particle or may be formed inside the particle.

The grain size of the silver halide may be fine grains of 0.07 microns or less or large grains with a projected area diameter of up to 3 microns, and may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution.

The photographic emulsion used in the present invention is P, GIafkides.
Written by Chimie et Physique Photo
graphique (published by Paul Monte1,
IP67 Ng, F.

Photographic Emuls by Duffin
ionChemistry ('rhe Focal
P, ress, 1946), V, L, Zelik
Making and Coa by Man et al.
ting Photographic Emulsion
('rhe Focal Press) / 2 Otsuhiroten), etc. can be used for adjustment. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used.

According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be allowed to coexist.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example H, Fr1eser! @D
ie Grundlagender Photog
raphischenprozesse mit S
ilber-halogeniden” (Akadem
ische Verlagsgesellschaft
+/ritr) t7J- ~ The method described on page 73≠ can be used.

That is, a sulfur sensitization method using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); noble metal compounds (e.g., total complex salts, Pt, I
A noble metal sensitization method using complex salts of metals of group 1 of the periodic table such as r, Pd, etc. can be used alone or in combination.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, beromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzi
l Midazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (
%/-phenyl-mercaptotetrazole); dimercaptopyrimidines; mercaptotriazines:
thioketo compounds such as oxadorinthione;
Azaindenes, such as triazaindenes 1, tetraazaindenes (particularly Hiro-hydroxy substituted (1, J,
Ja, 7) Tetraazaindenes), Pentaazaindene Nato: Adding many compounds known as antifoggants or stabilizers such as inzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. be able to.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives,
It may also contain urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

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

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

The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and 5-myoxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyania dyes, and complex merocyania dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterochronic ring nucleus for these dyes.

Although these sensitizing dyes may be used alone, they may be used in combination (combinations of sensitizing dyes are often used, especially for the purpose of supersensitization).

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminostyl compounds substituted with nitrogen-containing heterocyclic groups (for example, U.S. Pat.
7 Co. No. 1, aromatic organic acid formaldehyde condensates (for example, those described in U.S. Pat. No. 3,7≠3,310), cadmium salts, azaindene compounds, and the like. The invention is also applicable to multilayer, multicolor photographic materials having at least λ different spectral sensitivities on the support. A multilayer natural color photographic material usually has at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other water-based colloid layers.

For example, activated vinyl compounds (/, j.

! -triacryloyl-hexahydro-S) riazine,
l,3-vinylsulfonyl-cofuro, B-nor, etc.)
, active halogen compounds (2, Hiro-dichloro-Δ-hydroxy-5-)riazinato), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), and the like can be used alone or in combination.

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant.

The photosensitive material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, U.S. Pat. No. 3, J-, 33
, 7F Hiro issue, same≠, 23 Otsu, , 0/J issue, special public Akiyo/-At Hiro O issue and European patent! 7. Benzotriazoles substituted with an ary group described in ltO, etc., U.S. Patent No. ≠, O≠j0,2
No. 22 and same≠, /7! , U.S. Patent J, 70! .

Gos issue and 3.707.37! Cinnamic acid esters described in US Pat. No. 3,2/! , 630 and British Patent Nos. 1, J, 2/, 3! Benzophenones described in U.S. Patent No. 3,7j/, U7J and U.S. Pat. , If! /, A polymer compound having an ultraviolet absorption residue as described in the issue is used. U.S. Patent No. 3. ≠Tata, No. 762 and same j,
700, Hiro! ! The ultraviolet a-absorbing fluorescent brighteners described in this issue may also be used. A typical example of a UV absorber is Rf
)24t23ri (/PI≠June), etc.

The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known anti-fading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives 1'' bisphenols, and the like.

The color photographic emulsion layer forming the dye image layer according to the present invention is coated on a flexible support such as plastic film, paper, or cloth commonly used in photographic light-sensitive materials. Useful flexible supports include films of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose acetate butyrate, polystyrene, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polymers (e.g. polyethylene, polypropylene), etc. Paper coated or laminated with The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light.

When these supports are used for reflective materials, it is preferable to add a white pigment to the support or laminate layer. White pigments include titanium dioxide, barium sulfate,
Examples include zinc oxide, zinc sulfide, calcium carbonate, antimony trioxide, silica white, alumina white, titanium phosphate, etc., and titanium dioxide, barium sulfate, and zinc oxide are particularly useful.

The surface of these supports is generally treated with an undercoat to improve adhesion with photographic emulsions and the like. The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment.

When these supports are used for reflective materials, a hydrophilic colloid layer containing a high density of white pigment may be further provided between the support and the emulsion layer to improve the whiteness and sharpness of the photographic image. can.

In the reflective material having the magenta coupler of the present invention, a paper support laminated with a polymer is often used as the support, but if a synthetic resin film kneaded with a white pigment is used, smoothness, gloss, sharpness, In addition to improving the degree of
This is particularly preferable since it provides photographic images with particularly excellent saturation and depiction of dark areas. In this case, the synthetic resin film raw material is
Polyethylene terephthalate and cellulose acetate are particularly useful as white pigments, and barium sulfate and titanium oxide are particularly useful.

In addition to the above, various photographic additives known in this field, such as stabilizers, antifoggants, surfactants, antistatic agents, developing agents, etc., may be added to the color photographic material of the present invention as necessary. An example of this can be found in Research Disclosure/7j4Lj.

Furthermore, depending on the case, a fine-grain silver halide emulsion having substantially no photosensitivity (for example, silver chloride, silver bromide, or chloride with an average grain size of 0.20 μm or less) may be included in the silver halide emulsion layer or other hydrophilic colloid layer. A silver oxide emulsion) may also be added.

The color developing solution that can be used in the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As a color developing agent, ≠-amino-N, N-diethylaniline, J-)f-amino-N, N-diethylaniline, ≠-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-Hiroshi. -Amino/-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-Hiro-amino-N-ethyl-N-β
-methanesulfamide ethylaniline, ≠-amino-3
Typical examples include -methyl-N-ethyl-N-β-methoxyetheranili 7.

The color developer may contain pH buffering agents such as alkali metal sulfites, carbonates, salts, borates, and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants. can include. Also, if necessary,
water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol,
Development accelerators such as polyethylene glycols, quaternary ammonium salts, amines, dye-forming couplers, competitive turnips 2-
Turnips like sodium boron hydride.

Racers, auxiliary developers such as /-phenyl-3-pyrazolidone, viscosity-imparting agents, US Patent ≠, 013.

The polycarboxylic acid chelating agent described in No. 723, the antioxidant described in OLS Kotto 6λλ, and YRO may be included.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Examples of bleaching agents include iron (■),
Compounds of polyvalent metals such as cobalt (■), chromium (■), and copper (n), peracids, quinones, nitroso compounds, and the like are used. For example, ferricyanide, dichromate,
M complex salts of iron(III) or cobalt(III), such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, /,
Aminopolycarboxylic acids such as 3-diamino-λ-propatoltetraacetic acid; complex salts of organic acids such as citric acid, tartaric acid, and malic acid; persulfates, manganates; nitrosophenols, and the like can be used.

Of these, potassium 7-erythyanide, sodium iron(III) ethylenediamine acetate, and ammonium iron(III) ethylenediaminetetraacetate are particularly useful. The ethylene diamide/iron tetraacetate (III tri-complex salt) is useful in both stand-alone bleach solutions and -bath egg white fixers.

It may be washed with water after color development or white fixing.

Color development is /r'c! It can be carried out at any temperature between 0C and 0C. Color development is preferably carried out at jQ'(:' or higher, particularly preferably at 3!0C or higher).

The development time is preferably as short as about 3 minutes to about 1 minute. Liquid replenishment is preferable for continuous development processing, processing area/per square meter. j) Replenish with the following solution: j j OCr, 1 tocr, preferably 1 oocr: Benzyl alcohol in the developer is 20ml/l
Below, /Ornl/ is preferably 13 or less.

Bleach-fixing can be carried out at any temperature from /roc to jo 0c, but temperatures above jo 0c are preferred. j j' (If the value is above, the processing time can be reduced to 1 minute or less. 1.
It is also possible to reduce the amount of liquid replenishment. The time required for washing with water after color development or bleach-fixing is usually within 3 minutes, but washing can also be carried out within 1 minute using a stabilizing bath.

Colored pigments not only deteriorate due to light, heat, or temperature, but also deteriorate and fade due to mold during storage. Shea seven-color images are particularly susceptible to severe deterioration due to mold, so it is preferable to use a mold preventive agent. Specific examples of anti-mold agents are disclosed in Japanese Patent Application Laid-open No. 7-17-177/J7-J4.
There are 6 coachazolylbenzimidazoles as described in c≠. The antifungal agent may be incorporated into the photosensitive material, or may be added externally during the development process, or may be added at any process if it coexists with the processed photosensitive material.

The present invention includes color negative film, force 2-eper, color positive film, color reversal film for slides, color reversal film for movies, and color 1) for TV.
It can be used in general silver halide color light-sensitive materials such as versal films. In particular, when used in color negative films that require high sensitivity and high image quality, especially color reversal films, remarkable effects can be obtained in improving sharpness and graininess.

The present invention can be applied to light-sensitive materials that use a single black coupler system or a mixed three-color coupler system. A detailed description of the black coupler one-way system is provided in U.S. Patent No. 3,6 here, 6.2.
No. J, 731/L, 7J! number, room clerk, l coro
r 4' 6 / issue, Tokai Show rz-i.

j2≠7, same jko≠272! No. and same! ! -10
j2≠ is written in the issue, and the three-color turnip 2-mixing method is in Re5earch Disclosure/7/
There is a detailed explanation in .

Example 1 The emulsion layer and the auxiliary layer were coated on a cellulose 93 acetate support in the following order to obtain a sample (/) 90 1st layer Low-sensitivity red-sensitivity emulsion layer The cyan coupler λ-(heptafluorobutyramide)-7-(2'-(λ“, μl-di-t-amylphenox7)butyramide)phenol (coupler ■>1
Oott tricresyl phosphate) / 00oc and ethyl acetate 10 (1; dissolved in Icc, lO tizelatin aqueous solution / 9, surfactant dodecylbenzenesulfonic acid sodium 1O1) An emulsion obtained by stirring at high speed.
Add and mix red-sensitive, low-sensitivity silver iodobromide emulsion/yu (silver halide grain size O, Jμ silver 70? gelatin 6 Off, natural change content 3 mol), gelatin, water, stabilizer, coating aid, etc. , 7'Co (silver amount 0, Af/m2)K layer was coated to have a film thickness of 2 μm after drying. Emulsion of the cyan coupler used in the first layer of the core red-sensitive emulsion layer/kliFe,
Red-sensitive medium-sensitive silver iodobromide emulsion / 9 (average grain size of silver halide grains Q, evening μ Silver 70f Gelatin 60f
Add and mix gelatin, water, stabilizers, coating aids, etc., and coat to a dry film thickness/μ. (Silver amount O1 reference f/m2) 3rd layer Highly sensitive red-sensitive emulsion layer 9' is added to the emulsion of the coupler used in the 7th layer to red-sensitive and highly sensitive silver iodobromide emulsion/kII (silver halide grains). Average particle size 0.6μ silver 70f gelatin 60fk (contains #3 mol%) mixed with gelatin, water, stabilizers, coating aids, etc. and coated to a dry film thickness of 1μ.
O, 4'f/m2) Third layer Intermediate layer λ, Targy 5eC-octylhydroquinone λ009
Dissolve 200 CCVC in ethyl acetate, add 10% aqueous solution/9 and 20% sodium dodecylbenzenesulfonate.
? f. The emulsion obtained by high-speed stirring is mixed with gelatin, water,
Mix with coating aids, etc. to form a dry film thickness of 1μ = coating friend.

No.! Layer Low green sensitivity emulsion layer Magenta coupler An emulsion obtained in the same manner as the emulsion of the first layer was used as a green-sensitive, low-sensitivity silver bromide emulsion/9 (XF), average grain size 0.3 μ, silver 7 oy, gelatin content, legal content 3 mol. %), gelatin, water, a stabilizer, and a coating aid were mixed and coated to a dry film thickness of μ. (Amount of silver 0.7?/m2) 6th layer Core green emulsion layer! The magenta coupler emulsion/k19 used in the layer was green-sensitive, the central silver iodobromide emulsion/9 ("F average grain size o
, Yuμ Silver 70f Gelatin Aotk Contains Natural T3
mol%) and gelatin, water, stabilizers, coating aids, etc., and coated to a dry film thickness of lμ (& high silver content 0).
, 'A? /m 2) 7th layer Highly sensitive green sensitive emulsion layer! Emulsion of magenta coupler used in layer 9, green-sensitive, highly iodine-sensitive silver bromide emulsion/yellow (average grain size 0.7 μm)
So silver 702, gelatin 60? Gold content: 3 molt)
The mixture was mixed with gelatin, water, a stabilizer, a coating aid, etc., and coated to a dry film thickness of lμ. (Coated silver amount O1 Hiro1
/TL2) r-th layer Mix the emulsion ' h t used in the intermediate layer, gelatin, water, and a coating aid, and coat to a dry film thickness of 0.5 μm.

2nd Layer Yellow Filter 1st layer Yellow colloidal silver and gelatin were mixed and coated to a dry film thickness/μ.

io layer Low-sensitivity blue-sensitivity emulsion layer Yellow coupler, α-(hibaroyl)-α-(/-benzyl-terethoxy-3-hydantoinyl)-2-chloro-5-dodecyloxycarbonylacetanilide, is added to the cyan coupler of the first layer. Instead, use tricresyl phosphate)'i/2OCC, ethyl acetate/20cc
Emulsion prepared by changing VC/kg't-1 Blue-sensitive low-sensitivity silver iodobromide emulsion/kg (average grain size O6 μ, silver 70t, contains ceratin 601, natural change content 3 mol%)
The mixture was mixed with gelatin, water, a stabilizer, and a coating aid, and coated in two coats to a dry film thickness of μ. (Coated silver amount O, +r/
m2) 1st/layer Core blue-sensitive emulsion layer Emulsion of yellow coupler used in 1st O layer/'Kg'
1 kg of blue-sensitive core silver iodobromide emulsion (average grain size o,
tμ, silver 70f, gelatin 60? , Tenhen Kaiji 3 Morchi)
Then, mix gelatin, water, stabilizers, coating aids, etc., and coat to a dry film thickness of lμ.

(Amount of coated silver: O0?/m) 72nd layer High-sensitivity back emulsion layer An emulsion of a yellow coupler used in the 70th layer is mixed with a blue-sensitive high-sensitivity silver iodobromide emulsion/yu (average grain size 0). .7μ
, silver 701, gelatin jaO9, legal content 3 mol%), gelatin, water, stabilizer, coating aid, etc. are mixed,
Dry film thickness /μ
Hiro r/m2) 13th layer λ protective layer Kabuji Kawa JHC UV absorber,! −Chloro λ−(
2-Hydroxy-3,tert-butylphenyl)-
2H-benzotriazole ivy.

. 2-(2-Hydroxy-rt-i-y-ruphenyl)-2fl-benzotriazole JOf, Co(λ-b
Droxy 3-3ec-butyl-! -t-bunalphenyl)-2H-benzotriazole? , dodecyl-r
-(N,N-diethylamino)-λ-benynesulfonyl-λ, Hiro-pentadienoate 7001, dissolved in tricresyl phosphate 200Ω, acetic acid ether-ooccvc, dodecylbenzenesulfone 20f, /θ tizelatin jklil, high speed The emulsion obtained by stirring is mixed with 1 kgk % gelatin, water, coating aids, etc. to form a dry film thickness of λμ: coating material.

(Total UV absorber coating to, rt/m2) 1st ≠ layer 1st protective layer Fine-grained silver iodobromide emulsion (grain size o
Contains iμ, silver 70f, gelatin zoy, natural connotation
1 molt) Gold, gelatin, water, stabilizer, coating aid, etc. were mixed and coated to give a dry film thickness of /μ. (silver iii
O,jg/1rL2) The obtained multilayer coating film is designated as sample &l.

An emulsion was prepared by replacing the l/co vinegar of the cyan coupler used in the first to third layers with an equimolar amount of the compound of the present invention. Sample points 2 to 1 were prepared using this emulsion according to the sample preparation method.

Comparison compound NHCaHy (i) Sample Ji/ NA/ /f After exposure through a pattern for grain size measurement, sample 1 after Cassie reversal treatment, RMS granularity is measured by density measurement using a micro-grainness measuring device t0 image density 1
．． O and λ, the granularity at O is shown.

Sample &/~A//t-MT Fijl11 After exposure and color reversal processing, sample 1 was measured using a microdensity meter, and the pMTF value was determined by calculation.

As for the sharpness, the grain sharpness was greatly improved in sample muko-t using the compound of the present invention compared to the comparative compound of io lines/mmb 2θ lines/mm.

Processing process Time Temperature 1st development t' 3t0C (±0.3) Water washing λ' Reversal λ' Color development t' Adjustment λ' Standard White t' Fixation Reference' Water washing Reference' Stable 7' Regular Wet and dry first developing water 700
Sodium gotetrapolyphosphate 2 and sodium sulfite CO? Hydroquinone monosulfonate 30? Sodium carbonate (l hydrate) 3091-phenyl-
≠-Methyl-≠-Hydroxymethyl-3 1 Pyrazolidone 2? Potassium bromide, J′? Potassium thiocyanate /, λt Potassium diiocyanate (0,
1% solution) Add λgo water
1000rrt1 reverse water 700
rnl nitrilo・N-N-N-1 rimethylenephosphonic acid・t Na salt 3 to stannous chloride (l hydrate)/l p-aminophenol 0. / Sodium hydroxide ry Glacial acetic acid
Add 11ml water
10oovt1 color developing water 700
m1 Sodium tetrapoly11phosphate 2? Sodium sulfite 7f Sodium phosphate (dihydrate, salt) 34? potassium bromide
it Potassium iodide (0, no solution) Ta-O-sodium hydroxide
3t citradinic acid i,
ztN-Ethyl-N-(β-methanesulfonamidoethyl) -3-methyl-Hiro-aminoaniline sulfate //1 Add water to ethylenediamine 3
1000 go adjusted water 700
11Ll Sodium sulfite 121
Sodium ethylenediaminetetraacetate (hydrohydrate) r? Thioglycerin O,4A glacial acetic acid
Add 3ml water
100100O bleaching water roo
TILl Sodium ethylenediaminetetraacetate (cohydrate salt) Of ethylenediaminetetraacetic acid.

Iron (II) ammonium (λ water salt 1 /20.O? Potassium bromide 100.Of water added
i, ol fixing water roo
txt-ammonium thiosulfate IO, Or
Sodium sulfite! , O? Sodium bisulfite j, Of water added
/, 01 stable water 100
ml formalin (37% by weight) j, 0rr
cl surfactant solution (product name Dryfel)! , 0 and add water i, ol Example 2 A multilayer color photosensitive material (lO7
)It was created.

1st layer; antihalation layer black colloidal silver... old... 0 , /
rf/rrt2 ultraviolet absorber U-/ ・0.
01t/rrt2 same U-λ...0
．． Gelatin layer containing t/m'' λth layer; Intermediate layer Co, t-bentaterylhydroquinone...0.1117m2 Coupler C-/......0.//f /r
3rd layer of gelatin layer containing rt2; 1st red-sensitive emulsion layer Silver iodobromide Silver iodide Hiromorchi (average grain size O0≠μ) ...... L, Cot/m2 Sensitization Pigment processing: 7.4/- per mole of silver
×lO mole same ■ ・・・・・・・・・0 for 1 mole of silver, #
X10 mol sensitizing dye■ ・・・・・・r for 1 mol of silver,
txio' molar same ■ ...... For silver l-E-nyl, oxio-' molar coupler C-x ...... 0. ≠!
? / m ”Coupler C-J-・-・-0, OJ!f
/n2 coupler C-≠ ・・・・・・・・・ Gelatin layer 3rd layer containing 0.0 coj f/m″; 2nd red-sensitive emulsion layer ・・・・・・・・・ /, Of ?/m2 sensitizing dye I ・
... Old... For 1 mole of silver! , koX/σ
Molar sensitizing dye ■ ・・・・・・・・・・・・ i, zxto molar same for 1 mole of silver ■ ・・・・・・・・・・・・ λ, / for 1 mole of silver XIO mole same ■ ・・・・・・・・・・・・ For 1 mole of silver / , jXlo Molar coupler 〇-2・・・・・・・・・ o, orot/m
2 turnip 2-C-z ・・・・・・・・・ o, oyo
t/m2 coupler C-J ・・・・・・・・・ 0.
034t? Gelatin layer containing /m2! Layer: Middle layer, j-t-pentadecylhydroquinone...0.01rt7m"
Sixth layer of gelatin layer containing; first green-sensitive emulsion layer...0.1017m" sensitizing dye V.
・・・・・・・・・・・・ ≠ -0×1 for 1 mole of silver
0 'mole sensitizing dye ■ ・・・・・・・・・・・・ J for 1 mole of silver, 0x10 mole same ■ ・・・・・・・・・・・・ For 1 mole of silver / , Coupler C-4 to 0XIO'%...O1≠!
t/m2 coupler C-7・・・・・・・・・・・・
・0.139/rrt2 coupler cr...
・・・・・・・・・ O0Oλt / m2 coupler C
-u ・・・・・・・・・・・・ O', 011t/
7th layer of gelatin layer containing m2 '; 2nd green-sensitive emulsion layer average grain size o, rμ 0.1197 m2 Sensitizing dye ■ 2.7X10 per 7 moles of silver 'Mole is the same ■ ・・・・・・・・・・・・ i, rxio for 1 mole of silver ■ ・・・・・・・・・・・・ 7, for 1 mole of silver! X10 molar coupler C-j ・・・・・・・・・ o, oyzt
/m2 Coupler C-7・・・・・・・・・ 0.0/!
Gelatin layer 2nd layer containing t/m2; yellow filter layer yellow colloidal silver ・・・・・・・・・・・・ 0.01
17m2λ,! 2nd layer of gelatin layer containing decylhydroquinone...o, yot/n''; 1st blue emulsion layer----0,37t/m'' sensitizing dye ■・・・・・・・・・・・・ For 1 mole of silver ≠, 4cxlO mol coupler C-ta ・・・・・・・・・・・・ 0.7/
f/m2 coupler C-≠ ・・・・・・・・・・・・
0.07t/m2 10th layer; Blue-sensitive emulsion layer average grain size O62μ ...... o, zrt/m" Sensitizing dye ■ ...... Silver 1 J-OXlo 'mole coupler c-y for mole... Old... 0.23f
Gelatin layer ii layer containing /m2; first protective layer ultraviolet absorber U-/...0. /≠9
/ m 2 U-2・・・・・・・・・0
．． Gelatin layer containing λ t/m 2 First layer: Second protective layer Average particle size 0.07μ ・・・・・・・・・ 0. λj S'/m'' polymethacrylate particles (diameter i, zμ) ... gelatin layer containing a, 10f?/n2 Each layer was coated with gelatin hardener H-7 and a surfactant in addition to the above composition. .

(Sample IO~10e) 10 mol% of coupler C-2 in the second layer of sample IO7 is made up of the coupler of the present invention! Sample 1 except that it was replaced with O mole
In the same way as 0/, I created ~70 samples.

These samples were exposed to light for sensitometry through a blue filter and subjected to color development processing as described below. Further, exposure for conventional 1MS measurement was carried out, and color development was carried out in the same manner. Photographic properties and graininess of the obtained sample were measured using a blue filter. 4Arμ was used as an a/cer for grain size measurement. The nine couplers of the invention used and the photographic results are all shown in Table 2.

The development used here was carried out using IcJ♂0C as described below.

1 Color development...3 minutes! seconds 2 m
White...6 minutes JO seconds 3, water wash...
・・・・・・3 minutes it seconds 4 Fixation・・・・・・・
... for 30 seconds 5 minutes Wash with water for 3 minutes/
6 seconds Stable...3 minutes 1j seconds The composition of the treatment liquid used in each step is as follows.

Color developer Sodium nitrilotriacetate I, ot Sodium sulfite Hiroshi, Of Sodium carbonate
JO, Of? potassium bromide
/,≠thydroxylamine sulfate
-2 ginseng-(N-ethyl-N-β-hydroxyethylamino)-2 monomethylaniline sulfate Hiroshi! ? Add water and 11゜Bleach solution ammonium bromide /lO, Ot7mm =
Ryosui (2rh az, ocr: ethylenediamine-tetraacetic acid sodium iron salt /J0.O?glacial acetic acid
Add i4c, o rice water
/1 Fixer Nato2 Sodium polyphosphate 2.0? Sodium sulfite μ, oy thiosulfate 7 ammonium A (771) /7J-, OCC sodium bisulfite d, add 4f water
Add il stabilizer formalin r, occ water il Table 2 8 Relative sensitivity: Relative value with sample ioi as ioo with the reciprocal of the exposure that gives turn 88 Graininess: Value at concentration o, rVc 1st From the table, it can be seen that samples 102 to 10 of the present invention clearly have excellent graininess.

Structure of the compound used in the example C-/U-λ C-λ -J SO3Na 5OaNa -z -A 〃- Q(2-c1+-3Oz-a(2-CONHLCHz
l 2 parts) 2H5 C2H sensitizing dyestuff.

■ Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment September 1985 (0 days 1, Incident indication Showa!2 year patent application No. 2 #697 2, Name of invention Silver halide color photographic light-sensitive material 3
, Relationship with the case of the person making the amendment Patent applicant 4, Subject of the amendment The description in the "Detailed Description of the Invention" column 5 of the specification and the "Detailed Description of the Invention" column of the description of the contents of the amendment are as follows: Correct as shown below.

The description in lines 1 to 6 of page 6 of Hiromu is as follows: ``The coupler of the present invention is preferably used in the silver halide emulsion layer or a layer adjacent thereto, and is preferably used in combination with an ordinary photographic color power teller. Preferable.The amount of the coupler of the present invention used (the ratio of the coupler of the present invention/ordinary photographic color coupler) is !/ri!
~/00/0 is preferred, lQ/rio-,,6.

/≠O is more preferable. ” and correct it.

Claims (1)

[Scope of Claims] A silver halide color photographic material containing a coupler represented by the following general formula. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, A represents a coupler residue that cleaves with X upon reaction with the oxidized developing agent, X represents an oxygen atom or a sulfur atom, and R_1 is an aliphatic group. , represents an aromatic group or a heterocyclic group, R_2 represents a substituent, n represents 0, 1 or 2, and when n is 2, the two R_2 may be different substituents, and the two R_2 may each become a divalent group and connect to form a cyclic structure.