JPS6186751A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photographic sensitive material enhanced in the sharpness and graininess of an image considerably by incorporating a specified coupler in a photosensitive material layer. CONSTITUTION:The red-sensitive emulsion layer or its adjacent layer of the silver halide color photographic sensitive material contains the coupler capable of reducing the excess of the oxidation product of a developing agent produced at the time of development processing in combination with other couplers and effectively removing it, and it is represented by the formula shown there in which A is coupler residue to be cleft from X by a reaction with the oxidation product of a developing agent; X is O or S; R1 and R2 are each an aliphatic, aromatic, or heterocyclic group; and R3 is a substituent. As a result, the color photographic sensitive material by which a color development is effectively controlled, and superior in the sharpness and graininess, especially, a color reversal film high in sensitivity and high image quality is obtd.

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-grade amine color developing agent and a coupler react to form indophenol, indoaniline,
It is known that indamine, azomethine, phenoxazine, phenazine and similar dyes are produced and color images are formed. In this system, subtractive color reproduction is usually used for color reproduction, with yellow, magenta, and cyan color image-forming agents having a complementary color relationship with a silver halide emulsion that is reductively sensitive to blue, green, and red, respectively. is used. To form a yellow image, for example, an acylacetanilide or dibenzoylmethane coupler is used, and to form a magenta image, a pyrazolone, pyrazolobenzimidazole, cyanoacetophenone or indacylon coupler is mainly used. , Cyan Color Painting II? Primarily phenolic couplers, such as phenols and naphthols, are used for the formation.

In recent years, with the spread of disc cameras and /10 size cameras in silver halide photographic materials, especially color photographic materials, high image quality has become more important than ever. In particular, it is important to improve sharpness and graininess.

It has been known that couplers are used not only to form dyes 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, a coupler has been proposed that can release a compound that captures oxidized color developing agent gold from the coupling position of the coupler. For example, JP-A Showjλ-λtsit, JP-A-J
7-///137, j7-/JttJt, etc. 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 these known couplers not only have a weak ability to scavenge the oxidized developing agent released by the scavenger, 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, for the purpose of the present invention, by incorporating a novel coupler that releases a compound that captures the sound of oxidized developing agent by reaction with oxidized developing agent, graininess and sharpness can be improved. Another object of the present invention is to provide a color photographic material that is excellent in color reproducibility due to a multilayer effect.

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

General formula [I) N1(SO2R2 [In the formula, A represents all the coupler residues that are cleaved with X upon reaction with the oxidized developing agent, X represents an oxygen atom or a sulfur atom, and %R1 and R2 each represent a fatty acid. represents a group group, an aromatic group or a heterocyclic group, and R3 represents a substituent,
n represents 0% l or ko, and when n is λ, λ R
3 may be a different substituent, and λ of R1 s R2 and R3 may be divalent groups and linked to form a cyclic structure.] In the uninvented compound, the oxidized developing agent and By this reaction, an aromatic alcohol or an aromatic thiol having two (or more) sulfonamide groups bonded to it is released. One of the sulfonamide groups must be in the para position to XK. It is believed that this precisely explains the superior performance of the present invention. That is, from A, bissulfonamidophenol 4 [, <t:E When bissulfonamidothiophenol is separated, these compounds exhibit a strong reducing action and reduce the oxidized developing agent. Moreover, the λ sulfonamide groups moderately increase water solubility and increase diffusibility. Furthermore, the diffusivity can be easily adjusted by adjusting the size t of Ri, R2, or R3. A coupler in which sulfonamide groups are bonded to the 2nd and 3rd positions relative to It had a fatal flaw: it caused a coupling reaction. For this reason, there were problems in that the reducibility was weak (and color turbidity occurred due to the dye produced by the coupling reaction). Such defects are not observed in the compounds of the present invention.

Furthermore, US Pat. This coupler is used for the purpose of improving color density, and particularly for reducing the amount of developed silver (equivalence) t- per amount of dye produced. For this purpose, it shows a certain degree of performance, and a dye is produced with an amount of silver close to the theoretically required 2 equivalents of silver. The inventive couplers do not function as coequivalent couplers. This is because the compound released from the coupler exhibits strong reducing properties and reduces the oxidized developing agent. In other words, in order to obtain the same color density, a large amount of silver is required. [It is impossible to use.

When the coupler of the present invention is used, excess oxidized developer generated during development can be reduced and effectively removed. This prevents individual pigment clouds from growing beyond a certain level, prevents malt formation, and improves graininess. Edge effects and interlayer effects were also observed with the couplers of the present invention when the reducing agent released therefrom was highly diffusive. This effect was particularly noticeable in color reversal sensitive materials. For example, conventional couplers that release development inhibitors (DIR
Coupler) is known to be used for all edge and layer effects. However, the current situation is that conventional DIR couplers cannot be used in color reversal sensitive materials because they do not have the effect of inhibiting development. This is the conventional D
This is because the IR coupler uses a type of inhibitor that adsorbs to silver halide, and the development inhibitory effect is not effective in color reversal processing where development activity is high. 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 of the present invention released by the coupler functions as a scavenger for the oxidized developing agent and consumes the oxidized developing agent. This consumes developable silver and ultimately suppresses color development, resulting in DI
It probably shows the R effect.

The invention will be described in detail below.

In general formula CI), XIr1 is preferably an oxygen atom.

General formula (when R and R2 represent an aliphatic group in IJ, the number of carbon atoms is /~3, preferably 1~/l, substituted or unsubstituted, linear or branched, chained or cyclic, saturated or unsaturated) Examples of substituents include those listed below: halogen atom, aryl group, alkoxy group, acyloxy group, arylthio group, alkoxycarbonyl group, hydroxyl group, acylamino group, cyano group, nitro group. group, carbamoyl group, sulfamoyl group, sulfonamido group, acyloxy group, alkylthio group, amino group, sulfonyl group, acyl group, ureido group, or aryloxycarbonyl group.When these substituents contain a portion of an aliphatic group, carbon number, ha/~
It may be linear or branched, chain or cyclic, saturated or unsaturated, substituted or unsubstituted.

In addition, when the above substituent includes an aromatic group, the number of carbon atoms is r
s≦10, preferably a substituted or unsubstituted phenyl group.

In general formula (I), when R1 and R2 represent an aromatic group, the number of carbon atoms is 6 to 10, and preferably a substituted or unsubstituted phenyl group. Substituents include aliphatic groups, aromatic groups, heterocyclic groups, -, rogen atoms, alkoxy groups, acyloxy groups, arylthio groups, alkoxycarbonyl groups, hydroxyl groups, acylamino groups, cyano groups, nitro groups, carbamoyl groups, and sulfamoyl groups. group, sulfonamide group, acyloxy group, alkylthio group, amino group,
Examples include a sulfonyl group, a ureido group, an aryloxycarbonyl group, a carboxyl group, an acyl group, an alkoxycarbonylamino group, and a hasulfamoylamino group. When these substituents include an aliphatic group moiety, the number of carbon atoms is ij/~32, preferably H/~/l, linear or branched, chained or cyclic, saturated or unsaturated, substituted or It may be unsubstituted. Also, the above t
(e) When the substituent contains an aromatic group, the number of carbon atoms is 6 to IO, and it is preferably a phenyl group substituted with C1 or unsubstituted. In addition, when the above substituent contains a heterocycle, for example, imidazole, pyrrole, thiophene, tetrahydrofuran,
It has a ring structure such as benzimidazole, pyridine, tri/-, pyrazole imidazolidine-2,4L-dione.

When R1 and R2 represent a heterocyclic group in the general formula (IJ), the heteroatom is preferably a j- to 7-membered heterocyclic group selected from a nitrogen atom, a sulfur atom, an oxygen atom, or a selenium atom. For example, imidazole, Pyrazole%'tλ, Hirotriazole, thiophenefuran, benzimidazole, pyridine, tetrahydrofuran, etc. All of these substituents may be substituted, and preferred substituents include aliphatic groups, aromatic groups, acylamino groups, and sulfonamide groups. , alkoxy group, halogen atom, aryloxycarbonyl group, alkoxycarbonyl group, argylthio group, ureido group, cyano group, aamino group, aryloxy group, etc.When these substituents include an aliphatic group, the number of carbon atoms [/~32, preferably i/-/4,
Linear or branched, chain or cyclic, saturated or unsaturated,
It may be substituted or unsubstituted. When the above-mentioned substituent includes an aromatic group, it has a carbon number of Ha to 10, and is preferably a substituted or unsubstituted phenyl group.

General formula ([In J, R3 is preferably an aliphatic group, an aromatic group, a heterocyclic group] - rogene atom, alkoxy group, aryloxy group, arylthio group, alkoxycarbonyl group, thioureido group, acylamino group, cyano group, Nitro group, carbamoyl group, sulfamoyl group, sulfonamide group, alkoxy group, argylthio group, amino group, sulfonyl group, ureido group, aryloxycarbonyl group, alkoxycarbonylamino group, sulfamoylamino group, acyl group, or tffn is 2. When these substituents are part of an aliphatic group, the number of carbon atoms is 7 to 3, preferably /-74, straight chain or branched, chain or cyclic, -unsaturated or unsaturated, unsubstituted. It may be either transshipment or transshipment.

When R3 includes an aromatic group, the number of carbon atoms is 6 to 1.
0 and is preferably a phenyl group that can be purchased or purchased at no cost.

One role formula (IJ, AH details are the following general formula (II
), (1), (If/), (V), i), ('vll
) or (■).

General formula ([J One-part formula (III) General formula CIt/J 〇 General formula (V) General formula (■J 〇 General formula [■] R14-C)i-Rts General formula [■] The more derived free bond represents the bonding position of the coupling-off group (X in general formula (H). In the above formula, R5, R6s R7
s IL 8 s R9% RIO% R1
1-R12s R13s R14% Rts % R
If R17 carries a diffusion-resistant fund, it is selected so that the total number of carbons is 1 to 3, preferably Bio to λ; otherwise, the total number of carbons is preferably /j or less. .

+lCm6E General formula CII ) ~(VIA) (D
Rs to R17 and l will be explained.

In the formula, R5H represents an aliphatic group, an aromatic group, an alkoxy group or a heterocyclic group, and R6 represents an aromatic group or a heterocyclic group.

In the formula, the aliphatic group represented by R5 preferably has a carbon number/
-2, which may be substituted or unsubstituted, linear or cyclic. Preferred substituents for the alkyl group include an alkoxy group, an aryloxy group, an amino group, an acylamino group, and a halogen atom, which may themselves have further substituents. Typical examples of aliphatic groups useful as R5 are: inpropyl, isobutyl, tert-butyl, isoamyl, te.
rt-amyl group, /, /-dimethylbutyl group, /, l-
dimethyl to middle syl M, t, i-') ethylhexyl group,
Dodecyl group, hexadecyl group, octadecyl group, cyclohexyl group, l-methoxyinpropyl group, l-phenoxyisopropyl group, /I) tert-butylphenoxyisopropyl group, α-aξtwinpropyl group, α-(diethylaminocoisopropyl group, α-(succinimido)inopropyl group, α-(phthalimido)isopropyl group, α-(benzenesulfonamido)isopropyl group, and the like.

When R5 or R6 is an aromatic group (particularly a phenyl group), the aromatic group may be substituted. Aromatic groups such as phenyl groups include alkyl groups having 32 or less carbon atoms, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, alkoxycarbonylamino groups, 41 aliphatic amide groups, alkylsulfamoyl groups, alkylsulfonamido groups, and alkyl groups. In this case, the alkyl group may be substituted with an aromatic group such as phenylene in the chain.The phenyl group may also be substituted with an aryloxy group, an aryloxycarbonyl group, It may be substituted with an arylcarbamoyl group, an arylamide group, an arylsulfamoyl group, an arylsulfonamide group, an arylureido group, etc. may be substituted with one or more alkyl groups.

15% In addition, the phenyl group represented by UR6 can further include an amino group, a hydroxy group, a carboxy group, a sulfo group, including those substituted with a lower alkyl group having a carbon number of
It may be substituted with a nitro group, a cyano group, a thiocyano group or a halogen atom.

In addition, R5, URe'rX, and a phenyl group may represent a substituent formed by condensing another ring, such as a heptyl group, a quinolyl group, an isonoryl group, a chromanyl group, a chromanyl group, and a tetrahydronaphthyl group.

These substituents may themselves have further substituents.

When R5 represents an alkoxy group, the alkyl moiety has 1 to 3 to 2 carbon atoms, preferably a linear or branched alkyl group, an alkenyl group, a cyclic alkyl group, or a cyclic alkenyl group. These may be substituted with an I.rogen atom, an aryl group, an alkoxy group, or the like.

When R5 or tdRs represents a heterocyclic group, each of the heterocyclic groups is connected via one of the carbon atoms forming the ring to the carbon atom of the carbonyl group of the acyl group in alpha-acylacetamide, and the nitrogen atom of the amide group. Combine with. Such heterocycles include thiophene, 7rane, pyran,
Examples include virol, pyrazole, pyridine, pyrazine, pyrimidine, pyritazine, indolizine, imidazole, thiazole, oxazole, triazine, thiadiazine, oxazine, and the like. These may further have a substituent on the ring.

Monofunctional formula (R7 in IIIJ, straight chain or branched alkyl group having 7 to 32 carbon atoms, preferably 117 to -22 carbon atoms (e.g. methyl, isopropyl, tert-butyl,
hexyl, dodecyl, etc.), alkenyl groups (e.g. allyl group, etc.), cyclic alkyl groups (e.g. cyclopentyl group, cyclohexyl group, norbornyl group, etc.), aral group (e.g. benzyl, β-phenylethyl group, etc.)
, cyclic alkenyl 4 (e.g. cyclopentenyl, cyclohexenyl group, etc.) f: Represents a halogen atom, nitro group, cyano group, aryl group, alkoxy group, aryloxy group, carboxy group, alkylthiocarbonyl group, arylthiocarbonyl group , alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, thiourethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, hearylanilino group, hearylanilino group, hearylanilino group, hydropoxy group, etc.

Furthermore, R7B 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,
Aralyl group, cyclic alkenyl group, halogen atom, nitro group, cyano group, aryl group, alkoxy group, aryloxy group, carboxyl 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, anilino group, It may have an N-alkylanilino group, an N-arylanilino group, a heacylanilino group, a hydroxy7 group, and the like. Ino, which is more preferable as R7, is phenyl in which at least one ortho position is R-substituted with an alkyl group, alkoxy group, . In addition, R7 is a heterocyclic group (for example, a heterocyclic group containing a nitrogen atom, an oxygen atom, a sulfur atom as a hetero atom, a !-membered or H+-membered heterocyclic group, a fused heterocyclic group, and a pyridyl group). , quinolyl group, furyl group, benzothiazolyl group, oxasilyl group, imidazolyl group, naphthoxacylyl group, etc.); Alkylsulfonyl group, arylsulfonyl group, alkylcarbamoyl group, arylcarbamoyl group, arylthiocarbamoyl group
Alternatively, it may represent an arylthiocarbamoyl group.

In the formula, Rstl hydrogen atom, a linear or branched alkyl, alkenyl, cyclic alkyl, aralkyl, cyclic alkenyl group having carbon atoms of 1 to 32, preferably 1 to 1 (these groups have the substituent groups listed for both R7) ), aryl groups and heterocyclic groups (with the above-mentioned R7
Alkoxycarbonyl groups may have the substituents listed above, such as ethoxycarbonyl groups, ethoxycarbonyl groups, stearyloxycarbonyl groups, aryl dicarbonyl groups (e.g. phenoxycarbonyl groups, nandodicarbonyl groups, etc.). , aralkyloxycarbonyl groups (e.g. benzyloxycarbonyl group, etc.), alkoxy groups (e.g. (e.g., tolylthio group, tert-amylphenoxy)acetamide] benzamide group, etc.), diacylamino group, N-alkylacylamino group (e.g., hemethylzolopionamide group, etc.), hearylacylamino group (e.g., hephenylacetamide group, etc.) )
, ureido groups (e.g. ureido, hairarylureido, ~-alkylureido groups, etc.), urethane groups, thiourethane groups, arylamino groups (e.g. phenylamino,
Hemethylanilino group, diphenylamino group, N-acetylanilino group, cochloro=! -tetradecanamide anilino group, etc.), alkylamino groups (e.g. n-butylamino group, methylamino group, cyclohexylamino group, etc.), cycloamino groups (e.g. piperidino group, pyrrolidino group, etc.), heterocyclic amino groups (e.g. pyridylamino group, -1penzoxazolylamino M, etc.), alkylcarbonyl group (e.g. methylcarbonyl group, etc.)
, arylcarbonyl group (e.g., phenylcarbonyl group, etc.), sulfonamide group (e.g., alkyl sulfonamide group, arylsulfonamide group, etc.), carbamoyl group (e.g., ethylcarbamoyl group, dimethylcarbamoyl group, N-methyl-phenylcarbamoyl group, hephenylsulfonamide group, etc.). A/force/l/bamoyl, etc.), sulfamoyl group (
For example, hair alkyl sulfamoyl, N,N-dialkyl sulfamoyl group, hair arylsulfamoyl group,
~-alkyl-arylsulfamoyl group, N, N
- diarylsulfamoyl group, etc.), cyano group, or hydroxyl group.

In the formula, R9tl represents an aliphatic group or an aromatic group. The aliphatic group preferably has carbon atoms of -22, and may be substituted or unsubstituted, and may be chain-like or twisted-cyclic. Preferred substituents include an alkoxy group, an aryloxy group, a carboxyl group, a halogen atom, and an acylamino group, which may themselves have further substituents. Specific examples of aliphatic groups useful as R9 include the following: nidodecyl, hexadecyl, dodecyloxypropyl, cyclohexyl, t
ert-butyl group, butyl group, 3-(=.

Hiroji-tert-amylphenoxy]propyl group, /
-(,2,44-di-tert-abarphenoxy)propyl group, and the like.

When R9 represents an aromatic group, it may have the substituents listed above when R5 is an aryl group.

In the formula, RioH is an aliphatic group (e.g. methyl group, ethyl group, etc.), a rogen atom (e.g. chloro atom, furano atom), an alkoxy group (e.g. methoxy group, ethoxy group) or an aromatic group (e.g. phenyl group). represent.

In the formula, %R11 and l'hzld each represent a hydrogen atom, an aliphatic group, or an aromatic group. R11 or HR12
When represents an aliphatic group, the number of carbon atoms is 1 to 3λ, preferably /-/I, and it may be substituted or unsubstituted, chain or cyclic. Preferred substituents include an aryloxy group, an alkoxy group, a rogen atom, an aryl group,
These include a hydroxyl group, a carboxyl group, a cyano 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 R11 or UR12 include nidodecyl groups,
They include a hexadecyl group, a dodecyloxypropyl group, a cyclohexyl group, a tert-butyl group, a J-(2,4cm di-tert-amylphenoxydinepropyl group), a l(λl-di-tert-amylphenoxydinpropyl group), and the like.

When R11 or R12 represents an aromatic group, the number of carbon atoms is t~
10, preferably a substituted or unsubstituted phenyl group. Preferred substituents include an alkoxy group, an aliphatic group, an acylamino group, an alkoxycarbyl group, a halogen atom, a sulfonabad group, a sulfamoyl group, a carbamoyl group, a carboxyl group, a hydroxyl group, a cyano group, a nitro group, and the like. . Examples of useful aromatic groups for R11 or fl R12 are as follows: 2-tetradecyloxyphenyl group, μm tetradecyloxyphenyl group, 3-dodecyloxycarbonylphenyl group,
Examples include carbonyl phenyl group, phenyl group, tercarboxyphenyl group, and the like.

In the formula, R13t'! Halogen atoms, acylamino groups (e.g., acetamide groups, λ9μm di-tert-amylphenoxyacetamide groups), sulfonamide groups (e.g., methanesulfonamide groups, hexadecylsulfonamide groups), alkoxy groups (e.g., methoxy groups, dodecyloxy groups), Or it represents an aliphatic group (eg methyl group, ethyl group).

In the formula, l is 0. / or λ, and when l is 2, λ
The two substituents may be the same or different.

R14fdArylcarbonyl group, alkanoyl group with 2 to 3 carbon atoms, preferably 2 to 2 carbon atoms, arylcarbamoyl group, alkanecarbamoyl group with 2 to 32 carbon atoms, preferably 2 to λ carbons a/~3λ, preferably/~ here It represents an alkoxycarbonyl group or an aryloxycarbonyl group, and these may be substituent groups (substituents include an alkoxy group, an alkoxycarbonyl group, an acylamino group, an alkylsulfamoyl group, an alkylsulfonamide group, an alkylsuccinyl group). These include an imide group, a 10-gen atom, a nitro group, a carbonyl group, a nitrile group, an alkyl group, and an aryl group.

R15 is an arylcarbonyl group, an alkanoyl group with 2 to 3 carbon atoms, preferably 2 to 2 carbon atoms, an arylcarbamoyl group, an alkanecarbamoyl group with λ to 3-2 carbon atoms, preferably λ#2, and an alkanecarbamoyl group with 2 to 32 carbon atoms; Preferably, an alkoxycarbonyl group having 7 to 2 carbon atoms, preferably an aryloxycarbonyl group, an alkanesulfonyl group having 1 to 32 carbon atoms, preferably 1-carbon, an arylsulfonyl group, an aryl group!
membered or double-membered heterocyclic group (the petro atom is selected from nitrogen atom, oxygen atom, sulfur atom, such as triazolyl group, imidazolyl group, phthalimide group, succinimide group, furyl group, pyridyl group or benzotriazolyl group) (which is a group), and these may be substituted radicals as described above for R14.

In the general formula [■], R16H 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 μR5 applies. When R□6 represents an anilino group, the phenyl group may have the substituents listed above when R7 is a phenyl group. Preferred examples of R16 include pentafluoropropyl group, /, /, co, 2
．． J, 3-hexafluoropropyl group, p-cyanoanilino group, -11≠-dichloroanilino group, p-pronozonesulfonylanilino group, coethanesulfonamidophenyl group, and the like.

In the formula, 117 represents an aliphatic group or an aromatic group.

What has been explained about these iRs applies. Preferred examples of R17 include titer t-butyl group, /-(2,4(-di-tert-amylphenoxy)propyl group, /-(2,II-di-tert-amylphenoxy)pentyl group, and isoalε). group, /-(2,
Examples include Hiro-di-tert-octylphenoxy)heptyl group.

The coupler of the present invention is preferably used in combination with other conventional couplers, and has a ratio of l×/0-2mo to the main coupler.
1% ~/00mo1% Preferably Hj-jOmo
Used in 1.

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

OH cry cooc, □H25 Nt-1802Cr2 Hl 7 NH302C161-133 N) isO2c16H33 ■ Compound This synthesis/, To a solution of tA-dihydroxy-1-naphthoic acid 204AI dissolved in 100 ml of dimethylformamide, add a methanol solution of sodium methoxide (2 g %) 31
rtgf was added. After stirring for 10 minutes, this reaction solution was
300 ml of a dimethylformamide solution of λ,1L-dinitrofluorobenzene irtg was added dropwise at room temperature. 2
After stirring for an hour, add 10/≠g of concentrated hydrochloric acid to the reaction solution.
Added gradually.

The precipitated crystal 'kF was collected, washed with water, and dried to obtain compound 227≠g.

■ Synthesis of compound t Compound 3.274Lg, Q-tetradecyloxyaniline 22Ag, dimethylformamide 2. jl mixture,
Dicyclohexylcarpodiimide (DC
00 ml of a chloroform solution of C)/40.49 was added dropwise. After stirring for μ hours, the reaction solution was filtered, and 2 O of water was added to the f solution.
oml was slowly added dropwise. Crystal kiP that has precipitated
By taking and drying, the older compound λy was obtained.

■ Synthesis of exemplified compound (1) Reduced iron soog, ammonium chloride 309, acetic acid l 0
tnl, water j j Oml isopropyl alcohol co.

Yo! The mixture was reduced for t-10 minutes. The compound Dakota 2I was gradually added to this reaction solution under reflux. After 30 minutes, the reaction solution was filtered and the p-liquid gold was concentrated. The concentrate was added dropwise to 1 liter of tetrahydrofuran or 7 isit of benzenesulfonyl chloride at room temperature. Furthermore, pyridine 3! - After dropping 1 g, it was stirred for 72 hours. The reaction solution was extracted with ethyl acetate, and the entire organic layer was washed with water. After drying over IJ sulfuric acid, the solvent was distilled off, and the resulting concentrate was recrystallized from a mixed solution of acetonitrile and ethyl acetate to obtain 273.2 it of Exemplified Compound (1). (m, p, /&7゜o
"c) Synthesis of Exemplified Compound (2) In step (1) of Synthesis Example (1), methanesulfonyl chloride kumquat was used instead of benzenesulfonyl chloride. (m-p-/4'4.0°C) The coupler of the present invention is preferably used in combination with a commonly used photographic coupler. -2~l.

It is preferably 0 mole, and can be used in the range of B, o, I-0.1 mole to obtain the desired effect of the present invention.

The coupler of the present invention or the coupler that can be used in combination as described below can be introduced into the light-sensitive 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 t
After dissolving either a high boiling point organic solvent of yzoc or higher and a low boiling point so-called auxiliary solvent alone or a mixture of the two, finely dispersed in an aqueous medium such as aqueous gelatin solution in water in the presence of a surfactant. do. Examples of high boiling point organic solvents are described in U.S. Pat. No. 2,322,027 and others. Dispersion may be accompanied by μ phase inversion (or, if necessary, the auxiliary solvent 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 phthalate,
Ziro ethylhexyl phthalate, didodecyl phthalate, etc.), phosphoric acid phosphonic acid noesters (triphenyl phosphate, lJ cresyl phosphate,
λ-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, triloethyl phosphate, tridodecyl phosphate, tryptonyl diethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate, etc.)
, benzoic acid esters (2-ethylhexyl benzoate, dodecyl benzoate, monoethyl p-
Hydrogen dibenzoates, amides (diethyldodecaneamide, hetetradecylpyrrolidone, etc.), alcohols or phenols (stearyl alcohol, co-, 4C-di-tert-alphenol, etc.)
, aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributate, instearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl phthaltoxyj-tert-octyl aniline, etc.), carbonization Examples include hydrogens (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and as the auxiliary solvent, those having a boiling point of about 300 to about /100c can be used. Typical examples include ethyl diacetate, butyl acetate, ethyl propionate, Examples include methyl ethyl ketone, cyclohexanone, coethyl ethyl acetate, and dimethyl formamide.

The process and effects of latex dispersion methods and examples of latex materials for impregnation are described in U.S. Patent No. μ,/Tata.

No. 363, OLS No. J, j4L/, λ7 Hiroshi and OLS Happy! It is described in Kol, No. 230, etc.

Various color couplers can be used in accordance with the present invention. The term "color coupler" as used herein refers to a compound capable of producing a dye by reacting with an oxidized product of an aromatic amine developer. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolone or pyrazoloazole compounds, and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that may be used in the present invention include Research Disclosure (RD) 774 Ko3 (IP71).
month) ■-D and the same /Ir7/7 (/ri7P year/1
month) K is described in the cited patents.

The color coupler incorporated in the light-sensitive material is preferably made of a pallast group or polymerized so that it has diffusion resistance. A two-equivalent color coupler transferred with a leaving group is preferred to an equivalent color coupler in which the coupling active position is a hydrogen atom. Couplers in which the color-forming dye has appropriate diffusivity, non-color-forming couplers, DIR couplers that release a development inhibitor upon coupling reaction, or couplers that release all of the development accelerator 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 U.S. Pat.
ny, No. 21 O, No. J,, r7! , No. 0!7 and No. 3,263. It is written in the jtO≦ issue.

The use of two-equivalent yellow couplers is preferred for the present invention, as described in U.S. Pat. Hiro Or, / YlL No. J,
4C! 7, Ri Jr. No. 3.233.101 and No. 022.

420, etc., or Japanese Patent Publication No. Sho Jr. No. 107J, U.S. Patent No. 01.712, U.S. Pat. 021
A, RD/1rOjJ (/P7 <April), British Patent No. 7. ll-2j, 0coO, West German Application Publication No. 2
, 2/ri, ri 17th, ko, koti, st1, ri, ri, ri, 132, ! ? No. 7 and No. 7.

A representative example thereof is the nitrogen atom separation type yellow coupler described in Kou 33, r/, No. 2, etc. α
- Pivaloylacetanilide couplers have excellent color fastness, particularly light fastness, while α-benzoylacetanilide couplers provide high color density.

The magenta coupler that can be used in the present invention is preferably an oil-protected type indacylon type or a cyanoacetyl type coupler. - Pyrazoloazole couplers such as pyrazolone and pyrazolotriazoles may be mentioned. The j-pyrazolone 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 coloring density of the coloring dye, and representative examples thereof include U.S. Pat. No. 2゜3, No. 3,703, No. -, too, ytr, No. 2.2 Or, 173, No. J, No. 012,413,
The same No. s, isλ, t, and the same No. 3 Els, 0
/j issue etc. Two equivalents! - Pyrazolone couplers are preferred because they provide high color density and high sensitivity with a small amount of coated silver, and are used as leaving groups in U.S. Pat.
10. U.S. Patent No. ≠ over the nitrogen atom leaving group described in No.

The arylthio group described in No. 3jlIIr27 is particularly preferred. It also has the effect of increasing the coloring density for the ballast group [j-pyrazolone couplers described in European Patent No. 73.474. Examples of pyrazoloazole couplers include pyrazolobenzimidazoles described in U.S. Pat.
Pyrazolo ('e/
cJ(/.

λ, u) Triazoles, RD, 2 μ2.20 (/ri r
Pyrazolotetrazoles and RD described in ≠June
Examples include pyrazolopyrazoles described in 21A2JO (/PI Ko, June 2013). European Patent No. 1/74 in terms of low yellow side absorption and light fastness of the coloring dye.
Imidazo (/.

j-)) J pyrazoles are preferred, pyrazolo(/, j-k)3(/,
, 2. μ] Particularly preferred for triazoles.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, and are disclosed in US Patent No. λI Hong 74c.

Naphthol couplers as described in US Pat. No. 223, preferably US Pat. No. 012.272, No. μ.

/Hiroshi 4. Typical examples include the two-equivalent naphthol-based couplers of the oxygen atom dissociation type described in J-RI No. 2, No. 1A, 221, 2.33, and No. μ, 2-A, 200; Specific examples of couplers include U.S. Pat. , / 2nd issue, 2nd issue. I? ! ,1
．． 2 is written in the number etc. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention;
A typical example is U.S. Patent No. J, 77.2.0.
Phenolic cyan coupler described in US Pat. No. 2,772.712, US Pat. No. 3,7jlr.

No. 301, No. 1I, /26. J Riwo No., same No. 1 Hiromu.

334c, No. 071, Hiroshi J, 27, / 73, West German Patent Publication No. 3, 32, No. 72, and Patent Application Sho J
No. 1-17247/, etc., and J-diacyl amino substituted phenolic couplers, and U.S. Pat.
1st bow, t2.2, 333, Tatata, 1st Hiroshi, Hiroshi Jr/,! It has a phenylureido group at the 2-position as described in No. J, ≠, ≠ 27.747, etc., and! These include phenolic couplers that have an acylamino group in the - position.

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

0.00 to 065 moles are used per mole of light-sensitive silver halide in the layer added to the dye-forming coupler. In color photosensitive materials for photography, yellow couplers Bo, oi to 06 per mol of photosensitive silver halide are used.
5 moles, magenta coupler dO,003 to θ, λ!
Mol, also cyan coupler r4o, oos or 017
2 moles are often used (and in color photosensitive materials for printing such as color paper, yellow, magenta, and cyan couplers are often used in amounts of 0.1 to 5 moles per 1 mole of photosensitive silver halide. There are many, but
It is possible to design photosensitive materials outside this range.

In order to correct unnecessary absorption in the short wavelength region of the magenta and cyan coupler chromophores, it is preferable to use all colored couplers together in the color sensitive material for photographing. U.S. Patent No.≠, /Aj, 470 and Japanese Patent Publication No. 7-37
≠Yellow colored magenta coupler described in No. 13 etc. U.S. Patent No. 13! , 004c, 922 same No. a, i, y
r, 2rt and British Patent No. 1. Typical examples include the magenta-colored cyan coupler described in J.P./μt, No. 341, etc.

These color couplers may form a dimer or more polymer. Typical examples of polymerized couplers include U.S. Pat. Hiro! /, tλO and the same.

010.2// issue. ,t? A specific example of the IJ mom-magenta coupler is British Patent No. 2,10λ,
No. 773 and US Pat. No. 367.21.

In addition, the graininess can be completely improved by using a chromophoric diffusive coupler, and such couplers are disclosed in US Pat.
364,237 and British Patent No. λ.

/2! ,! Specific examples of 70VC magenta couplers are also disclosed in European Patent No. 24.1r73 and West German Patent Publication (OL).
S)j, 32μ,! No. 33 describes specific examples of 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.

The photographic emulsion layer of the photographic light-sensitive material used in the present invention...
Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used as silver halide. Preferable-・
It is silver iodobromide containing silver iodide having a molar coefficient of silver rhodanide of 1d/j or less. Particularly preferred is silver iodobromide containing from 1 to 7 moles of silver iodide.

Silver halide grains in photographic emulsions are cubic, hexagonal,
It may have a regular crystalline shape such as a spheroid, an irregular crystalline shape such as a spherical shape, or a composite of these crystalline shapes. In addition, as described in Research Disclosure 2-213μ, tabular grains with a thickness of 0.1 micron or less, a small diameter (also 00 microns, and an average aspect ratio of 5 or more) account for 0.4 or more of the total projected area. There may also be an emulsion that accounts for .

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

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

Grain size Td of silver halide, 0. The emulsion may be fine grains with a diameter of less than /i micron or large grains with a projected area diameter of up to 3 microns (or 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, G1afkides.
Written by Chimie et Physique Photo
ographique (published by Paul Monte1, /947) by G-F-Duffin Photogr
aphic Emulsion Chemistry (T
Published by Focal Press, 1966), V
Making by L., Zelikman et al.
and Coating Photography
cEmulsion (The Focal Pres.
It can be adjusted using the method described in ``S'', / 6 Koen, etc. 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...rogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. It's okay.

It can also be used in a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one form of the simultaneous mixing method, a method of keeping the pAge constant in the liquid phase in which silver halide is produced, ie, a similar Chondral 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 and physical ripening, gold salts such as cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or their complex salts, rhodium salts or their complex salts, iron salts, iron complex salts, etc. may be present. Good silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example, H. Fr1eser ed.
Die Grundlagender Photogr
aphischenProzesse mit Sil
ber-halogeniden” (Akademis
che Verlagsgesellschaft.

/961)≦7j to 73 Hiroshi pages can be used.

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

The photographic emulsion used in the present invention can contain various compounds for the purpose of completely preventing fogging during the manufacturing process, storage, or photographic processing of the light-sensitive material, or completely stabilizing the photographic performance. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, beromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially /-phenyl-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds, such as oxadorinthion; azaindenes, e.g. Antifogging agents such as triazaindenes, tetraazaindenes (specially vc4cm hydroxy-substituted (/+3+32+7) tetraazaindenes), pentaazaindenes, etc.; benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. Compounds known as additives or stabilizers can be added.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains polyalkylene oxide, derivatives thereof such as ethers, esters, and amines, thioether compounds, thiomorpholines, etc., for the purpose of increasing sensitivity, increasing contrast, or promoting development. 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 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 hemioxonol dyes. Particularly useful dyes are those belonging to the 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.

These sensitizing dyes may be used singly or in combination (combinations of sensitizing dyes are often used particularly 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. No. 3313-0, U.S. Pat.
Described in 7 Co. No. 1.

), aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3,7 Ko 3,110), cadmium salts, azaindene compounds, and the like.

The present invention is also applicable to multilayer, multicolor photographic materials having a small number of different spectral sensitivities on a support. Multilayer natural color photographic materials usually have a red-sensitive emulsion layer, a green-sensitive emulsion layer, , and a blue-sensitive emulsion layer, and the order of these layers can be arbitrarily selected according to need. The blue-sensitive emulsion layer usually contains all of the yellow-forming couplers, but different combinations may be used depending on the case.

In the photographic material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers may entirely contain an inorganic or organic hardener.

For example, activated vinyl compounds (/, j.

! -Triacryloyl-hydro-s-triazine, t,s-vinylsulfonyl-2-pro/1! active halogen compound (2, Hiro-dichloro-6-
Hydroxy-s-triazinato), mucohalogen acids (mucochloric acid, mucophenoxychloric acid, etc.), and the like can be used alone or in combination.

The photosensitive material produced using the inventive film may contain hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, ascorbic acid, i54 derivatives, etc. as color antifogging agents.

The photosensitive material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, US Pat. No. J, J33.
7th grade, 2nd grade, 2nd grade, 0/3 grade, Tokko Akira! /-1t
benzotriazole substituted with an aryl group as described in μθ and European Patent No. 7.160;
U.S. Patent No. Hiroshi, O≠! 0.22 No. and staff, /
Pj, butadines described in Tatata, U.S. Pat.
! -30 and the benzophenones described in British Patent Nos. 1 and 3, Jjtj, and US Patent No. 3. Full 7.
Polymer compounds having ultraviolet absorbing residual properties such as those described in No. 27λ and Kou No. 31, No. 7 can be used. U.S. Patent No. 3. ≠Tata, 76λ and the same J
, 700, ≠! Ultraviolet-absorbing fluorescent brighteners described in item j may also be used. Typical examples of UV absorbers are:
It is described in RD Cog 23 (Lri rμ June 2013).

Photosensitive material ICI' made using the present invention! The hydrophilic colloid layer may contain a water-soluble dye 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, osasonol dyes; hemioquinol dyes and merocyania? fees 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 λ or more. Known anti-fading agents include . . . idrogonone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, hibisphenols, etc. Colors forming the dye image layer according to the present invention The photographic emulsion layer is coated on a flexible support such as plastic film, paper, or cloth that is commonly used in photographic light-sensitive materials. Useful flexible supports include films composed of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose acetate butyrate, polystyrene, polyethylene terephthalate, polycarbonate, and alpha-olefin polymers (e.g. polyethylene, polypropylene) with baryta layers. ) or other fully coated and laminated paper. 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 subjected to an undercoat treatment for adhesion with photographic emulsions, etc. Before or after the undercoat treatment, the support surface may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. .

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 completely improve the whiteness and sharpness of the photographic image. In the reflective material containing the magenta coupler of the present invention, a paper support fully laminated with a polymer is often used as the support, but if a synthetic resin film kneaded with a white pigment is used, smoothness and gloss can be improved. - In addition to improving sharpness, photographic images with particularly excellent saturation and continuous shooting of dark areas can be obtained, which is particularly preferable. In this case, polyethylene terephthalate and cellulose acetate are particularly useful as raw materials for the synthetic resin film, and barium sulfate and titanium oxide are particularly useful as white pigments.

In addition to the above, the color photographic material of the present invention may contain various photographic additives known in this field, such as stabilizers, antifoggants, surfactants, antistatic agents, photosensitive agents, etc., as necessary. An example of this is described in Research Disclosure/7AILJ.

Further, depending on the case, fine grains having substantially no photosensitivity may be contained in the silver halide emulsion layer or other hydrophilic colloid layer. silver chlorobromide emulsion) may 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, 3-methyl-≠-amino-N, N-diethylaniline, ≠-aminoheethylhe β-hydroxyethylaniline, 3-methyl-≠
-Aminohe12thiruhe β-hydroxyethylaniline, 3-Methyl-Hiro-aminohe ethylhe β-
Methanesulfamide ethylaniline, ≠-amino-3-
Typical examples include methyl, ethyl, and β-methodiethylaniline.

The color developer may contain pH slowing agents such as alkali metal sulfites, carbonates, 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 glycol, quaternary ammonium salts, and amines, dye-forming cazolers, and competitive couplers. ,
Turnip racer such as sodium boron/1 hydride,/
- Auxiliary developers such as phenyl-3-pyrazolidone, viscosity-imparting agents, US Pat.

The polycarboxylic acid chelating agent described in No. 723, the antioxidant described in OLS No.

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 (II), peracids, quinones, and nitroso compounds are used. For example, ferricyanide, dichromate, iron(1)-cobalt(III) organic complex salts, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, l,3
Aminopolycarboxylic acids such as diamino-pro, C-noltetraacetic acid, or complex salts of organic acids such as citric acid, tartaric acid, and malic acid: persulfates, manganates; nitrosophenols, etc. can be used.

Of these, potassium ferricyanide, sodium iron(III) ethylenediaminetetraacetate, and ammonium iron(In) ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron(I[I) complex salt can be added to a separate bleaching solution.
It is also useful in -bath bleach-fix solutions.

It may be washed with water after color development or bleach-fixing treatment.

Color development can be carried out at any temperature between /ff'c and tt'c. Preferably HJO'C or higher, particularly preferably j
, t0c or more, the time required for development is preferably as short as about 3 minutes to about 1 minute. For continuous development processing, it is preferable to replenish the solution, and it is preferably 33 oaa to ttoaa per square meter of processing area, preferably tooca.
Replenish the following fluids. The benzyl alcohol B in the liquid is preferably 20 rttl/l or less, preferably 7i or less.

Bleach-fixing B can be carried out at any temperature from IR'C to TO'C, but preferably JO'C or above. When the temperature is 3j'C or more, the processing time can be reduced to t-1 minutes or less, and the amount of liquid replenishment can be reduced. The time required for washing with water after color development or bleach-fixing is usually within 3 minutes, and washing can also be carried out within 7 minutes using a stabilizing bath.

Colored pigments not only deteriorate due to light, heat, and temperature, but also deteriorate and fade due to mold during storage. Cyan color images are particularly prone to deterioration due to mold (it is preferable to use a mold preventive agent. Specific examples of mold preventive agents include cochiazo as described in There are rilbenzimidazoles.Fungicides may be incorporated into the photosensitive material.
It may be added externally during the development process (as long as it coexists with the processed photosensitive material, it can be added at any step).

The present invention can be used in general silver halide color photosensitive materials such as color negative film, color paper, color positive film, color reversal film for slides, color reversal film for movies, color reversal film for TV, etc. 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. Otsuλ2. tλri issue, same J, 73g, 733 issue, same≠, /kot,≠6
No. 7, Tokukai Shojyo-10j KotA No. 7, same! λ-IA2
7th issue and the same! ! -10j2ulr, and the three-color coupler mixing method is described in Re5earch
A detailed explanation can be found in Disclosure/71.

The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 On a triacetyl cellulose support provided with an undercoating layer,
The emulsion layer and the auxiliary layer were coated in the following order to obtain sample (/J).

4-(heptafluorobutyramide)--1-(λ'-(2", V"-di-t-amylphenoxy)butyramide)phenol (coupler ■), which is a cyan coupler in the low-sensitivity red-sensitivity emulsion layer I
009f tricresyl phosphate dissolved in 1OOCC and ethyl acetate 1OOCA, 10% aqueous gelatin solution 1K
P, surfactant sodium dodecylbenzenesulfonate 10
Emulsion ZOOG2 red-sensitive low-sensitivity silver iodobromide emulsion / KP (-average grain size of silver halide grains O93μ silver 70fi gelatin tog-@containing content 3 molt) and gelatin, water , stabilizers, loading aids, etc. were added and mixed, and coated to a film thickness of 1 μm after drying. (Amount of silver O0≦g/door) λth layer Intermediate blue-sensitive emulsion layer 7th layer cyan coupler emulsion tKyy2, red-sensitive medium-sensitivity silver iodobromide emulsion/KP (-average grain size of silver halide grains O0jμ silver 70i gelatin tog
2 containing 3 moles], gelatin, water, a stabilizer, a coating aid, etc. were added and mixed, and coated to a dry film thickness of lμ. (Silver i10,4c, lil/m) Third layer Highly sensitive red-sensitive emulsion layer Emulsion of the coupler used in the first layer tKp@Red-sensitive high-sensitivity silver iodobromide emulsion/Ky (-Average of silver halide grains Particle size 0.6μ silver 70i gelatin 60g total iodine content 3 mo/I/%] was mixed with gelatin, water, stabilizers, coating aids, etc. and coated to give a dry film thickness/μ. (Silver amount Q, Hiroshi g/n) 1st A layer Intermediate layer 2, j-G 5ec-octylhydroquinone 200i
200 t-ethyl acetate (dissolved in AK, mixed with 17% aqueous gelatin solution/KP and dodecylbenzenesulfonic acid, emulsion obtained by stirring at high speed, gelatin, water, coating aid, etc.) The coating was applied to a dry film thickness of lμ.

5th layer Low green sensitivity emulsion layer Magenta coupler /-(J, u, ≦-trichlorophenyl)-s-(j-(J, Hiroshi t-amylphenoxyacetamide)benzamide)-j-pyrazolone, etc. is an emulsion r obtained in the same manner as the emulsion of the first layer.
o o g@, green-sensitive, low-sensitivity silver bromide emulsion/KP (average grain size 0.3μ, silver 70y, gelatin top@contains, moderate content 3 molt), gelatin, water, stabilizer, coating aid, completely mixed, and dried. It was coated to have a film thickness of λμ. (Amount of silver 0.7y/m2) 4th layer Intermediate blue-sensitive emulsion layer Emulsion of magenta coupler used in 5th layer / Kg is green-sensitive, solid silver iodobromide emulsion / KP (average grain size 0
．． jtμ Silver 709 gelatin toy'@containing iodine content 3 mol%) was mixed with gelatin, water, a stabilizer, a coating aid, etc., and coated to a dry film thickness of lμ. (Amount of silver coated
0. ≠9/m) 7th layer Highly sensitive green-sensitive emulsion layer The magenta coupler emulsion/KP used in the 5th layer was mixed into a green-sensitive, highly iodobromide emulsion i Ky (average grain size 0).
．． 7μ, 70g of silver, gelatin t01” containing iodine tj
Morti), gelatin, water, stabilizers, coating aids, etc. were mixed and coated to a dry film thickness/μ. (Amount of silver coated
0. U,! 71/m) Rth layer The emulsion/Kyt- used in the μth intermediate layer, gelatin, water, and a coating aid were mixed and coated to a dry film thickness of O0jμ.

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

10th layer Low-sensitivity blue-sensitivity emulsion layer Yellow coupler, α-(pivaloyl)-α-(/-benzyl-!-ethyl-3-hydantoynyl)-1-chloro-y-dodecyloxycarbonylacetanilide as the 7th layer. Used instead of cyan coupler in the layer, tricresyl phosphate /2OCa, ethyl acetate /20CCV
Emulsion prepared by changing C/KPt-1 Blue-sensitive, low-sensitivity silver iodobromide emulsion/KP (average grain size O0jμ, silver 70j9
．． Contains 40 g of gelatin (iodine content: 3 mol%), mixed with gelatin, water, stabilizer, and coating aid, dry film thickness λμ
It was applied so that (Coated silver amount 0.4g/rn2)
1st/Layer Intermediate blue-sensitive emulsion layer Emulsion of the yellow coupler used in the 1st O layer lKi Blue-sensitivity Blue-sensitive solid silver iodobromide emulsion Ky (average grain size o, t
70 g of silver, gelatin tog, iodine content 3 mol %), gelatin, water, stabilizers, coating aids, etc. were mixed and coated to a dry film thickness of 1 μ.

(Amount of coated silver '-"l/") 1st λ layer Emulsion of yellow coupler used in 70 highly sensitive blue-sensitive emulsion layers/Kg gold,
Blue-sensitive high-sensitivity silver iodobromide emulsion/Ky (average grain size 0.7μ, containing silver 70II, gelatin 6og, legal content 3 mol%) is mixed with gelatin, water, stabilizers, coating aids, etc. , and was applied to a dry film thickness of lμ. (Coated silver amount Q, Hirofj/m2) 1st ≠ layer 3rd protective layer UV absorber instead of coupler! -Kuroro 2-(2
-Hydropalm-3,j-di-t-butylphenyl)-2
H-benzotriazole/! i.

λ-(2-hydroxy-z-t-butylphenyl)-2
H-benzotriazole JOG, J-(cohydroxy-j-5eC-butyl-1-1-butylphenyl)-J
) L-benzotriazole 3!9°dodecyl-1-(N
, N-diethylamino)-λ-henzensulfonyl-9μm pentagenoate ioog dissolved in tricresyl phosphate-〇0CC% ethyl acetate ooccvc,
/Kpt of the emulsion obtained by stirring at high speed dodecylbenzenesulfonate λog, to% gelatin JKp
-, mixed with gelatin, water, coating aids, etc., and coated to a dry film thickness of μ.

(Total UV absorber application II O, 1117m2) 1st!
Layer 7th protective layer Chemically sensitized fine-grain silver iodobromide emulsion (grain size 0)
．． 1μ, silver 70g, gelatin tog2 content, legal content
1 mol %) t-, gelatin, water, stabilizers, coating aids, etc., and coated to a dry film thickness of lμ. (Amount of silver
0. Jji/m2) The obtained multilayer coated film was used as sample 7.
Let it be g6/.

An emulsion was prepared by replacing the l/co amount of the cyan coupler used in the seventh to third layers with the compound of the present invention (equivalent mole number).

Using this emulsion, prepare sample/comparison compound +I) COOCt-t3 Sample 4/-4/ is exposed to light through an IR turn for grain size measurement, and after color reversal processing, the RMS granularity of the sample is determined by density measurement using a microdensity meter. Measurements were made.

The granularity at image density/, 0 and λ, O is shown.

Sample A/-4/ was exposed to light through a pattern for MTF measurement, and after color reversal processing, sample t was measured using a microdensity meter and the MTF value was determined by calculation.

Sharpness ('I'F 70 lines/mm20 lines/mW
Show by value.

Compared to the comparative compound, the sample using the compound of the present invention/
Graininess and sharpness are greatly improved at 16co-r.

Processing process Time Temperature 1st development A' JroC (±0.3) Water washing λ' Reversal, 21 Color development t' Adjustment λ' Bleaching 6' Fixing φ' Water washing μ' Stable l' Constant Warm dry 7th developing water 700
m1 Sodium tetrapolyphosphate λy Sodium sulfite 209 Hydrogyf non-monosulfonate 3017 Sodium carbonate (/hydrate) 30g1-Phenyl-Hiroshi-methyl- ≠-Hydroxymethyl-3 One pyrazolidone, 2g Potassium bromide λ, j9 Thiocyan Potassium acid /, 29 Potassium iodide (0, /
97. Solution)-M Add water 1
000trt reverse water 70
0M nitrilo, he, N, N-)rimethylenephosphonic acid/tNa salt, 311 stannous chloride (dihydrate)/1p-aminophenol 0. /ji sodium hydroxide
rg glacial acetic acid
/jrttl add water
/ 000 Go color developing water 700
Sodium gotetrapolyphosphate 2Il Sodium sulfite 7g Sodium tertiary phosphate (cohydrate) 3'g Potassium bromide 1g Potassium iodide (0.1% solution/y,) TaQ Sodium hemp hydroxide 3I citradinic acid
/, jp to ethyl-(β-methanesulfonamidoethyl) -3-methyl-φ-aminoaniline sulfate iig ethylenediamine 3I Add water
ioooml adjusted water 700
Sodium sulfite 1.2g Sodium ethylenediaminetetraacetate (cohydrate) II Thioglycerin O0 Hiro-Glacial acetic acid
Add 3d water
10100O bleaching water ro
orniSodium ethylenediaminetetraacetate (dihydrate) 2.09Ethylenediaminetetraacetate iron (n) ammonium (dihydrate) /20.0g Potassium bromide ioo, og Add water
/, Ol fixing water 100
ammonium gothiosulfate to, og sodium sulfite z, op sodium bisulfite z, og add water
/ , 01 stable water ♂00
rnl formalin (37 wt es) 6.0
Surfactant solution (trade name Drywell) r, omt Add water /, Ol Example 2 A multilayer color photosensitive material consisting of each layer having the composition shown below on a transparent triacetyl cellulose film support (
iot)-@Created.

1st layer; -Ration prevention layer black colloidal silver 0.11
777m2 Ultraviolet absorber U −/ =-0, 019
Gelatin layer λ layer containing 7 m2 U-2-0, / 2 g/m2; intermediate layer λ, j-G-t- is quinone containing tadecyl hyde...Q, ltg/rIL2 coupler C-/ --- 0,11177m2 Total gelatin layer 3rd layer; 1st red-sensitive emulsion layer Silver iodobromide (silver iodide reference mol%) (Average grain size o, uμ) ....../, 2g/m2 Sensitizing dye I ・・・・・・・・・・・・・per 1 mole of silver /, 4
AX10 mole same ■ ・・・・・・・・・O0 per mole of silver X10 mole coupler C-2-・-・-0,010/i/m2 coupler C-1----・-0, 070ji/m2 coupler C-J...0.0J, t9/wind 2nd gelatin layer containing gold! The middle class! -D-t-pentadecylhydroquinone-・・・・0, Ot g/
The gelatin layer containing m2; the first green-sensitive emulsion layer---0, r09/m2 Sensitizing dye■ ・・・・・・・・・・・・ For 1 mole of silver te ψ, oxt o mole is the same ■ ・・・・・・・・・・・・ j for 1 mole of silver, O×10 mole is the same ■ ・・・・・・・・・・・・・ for 7 mole of silver te/, 0x10 molar coupler C-6-...-0. uZi/m2
Coupler C-7・・・・・・・・・ 0. /39/m
2 sensitizing dye ■ ・・・・・・・・・・・・ Same mole of s, txio for 1 mole of silver ■ ・・・・・・・・・・・・ 0x10 mole coupler for 1 mole of silver C-co -・・・・・・ o, 4c yo g/
rIL2 coupler C-J ・・・-・-・-0,O
Jjg/rn2 coupler C-a-・・・・・0,
02j gelatin layer containing fl 7 m2 φ layer; second red-sensitive emulsion layer --- / , 0, lit / rn2 Sensitizing dye I ...... 7 moles of silver For 1 mole of silver, i, zxio moles are the same ■ ・・・・・・・・・・・・・・・・ 2 for 1 mole of silver, /x10 moles ■ ・・・・・・・・・・・・ For 1 mole of silver, /, jt×10 Molar coupler C-1------・-・・0 ,0297m2
Coupler C-u ・・・・・・・・・ O0O≠g
7th layer of gelatin layer containing /m 2; 2nd green-sensitive emulsion layer...0, r j & /71L2 sensitizing dye ■...... Silver 7 mol to 7×10 mol ■ ・・・・・・・・・・・・ 1.1rxlO mol to 1 mol silver ■ ・・・・・・・・・・・・ Silver 7.1XIO-5 moles for 7 moles Coupler C-4-=・0.091 g/m2 Coupler C-7...0.0/! Gelatin layer containing i/m2; Yellow filter layer Yellow colloidal silver 0.01
11/m2, gelatin layer containing j-t-pentadecylhydroquinone-0.0797m2; first blue emulsion layer...0.379/rn2 sensitization Pigment ■
・・・・・・・・・・・・ Hiro, μX for 1 mole of silver
IO molar coupler C-ta 0.7/i/
m2 coupler C-II =-...-0,07g/m
2 1st O layer; 2nd blue-sensitive emulsion layer... o, 55g7rn2 sensitizing dye V
1N ・・・・・・・・・J for 7 moles of silver, OX/ 0 mole coupler C-ta ・・・・・・・・・O, KO Jfi
Gelatin layer 1st/layer containing /m2; 1st protective layer ultraviolet absorber [J-/...0.7μ9
/rn2 same U-λ...0.
12th gelatin layer containing 2λg/m2; 2nd protective layer...0,2! /l/m2 Polymethacrylate particles (diameter/, jμ) Each layer of gelatin layer containing 0.10 g/m2 vcl-j In addition to the above composition, gelatin hardening agent H-/
or a surfactant was applied.

(Same as sample 10/ except that the couplers (1) and (6) of the present invention were replaced with 4CO mole% of coupler C-2 in the third layer of sample io, 2, IO sample 10/ Samples ioλ and 1O3t were then prepared.These samples were exposed to light for sensitometry through a red filter, and color development was performed as described below.Also, exposure for conventional RMS measurement was carried out, and the same The photographic properties and graininess of the obtained sample were measured using a red filter.Grainness measurement was carried out using a Guza μ.

The development process used here was carried out at JJ''C as described below.

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

Color developer Sodium nitrilotriacetate i, og Sodium sulfite μ, O! 9 Sodium carbonate J (7, OII Potassium bromide
/-up Hydroxylamine sulfate Co, Reference I≠-(N-ditylhe β-hydroxyethylamino)-2-methylaniline sulfate Hiroshi・j9 Add all water /1 Bleach solution Ammonium bromide /lO,09 Ammonia Water (waving λ) 2! , OQC ethylenediamine-tetraacetic acid sodium iron salt /30.09 glacial acetic acid
lμ, add OCa water
/1 Fixer Sodium Tetrapolyphosphate 2. Op Sodium sulfite μ, Oy Ammonium thiosulfate (70%) / 7 J, 000 Sodium bisulfite ≠, B Water gold plus
/ l stabilized formalin r, add oca water l no 1st table Relative sensitivity 2 fog 10, Jt - relative value of sample 1O7f7r:lOQ with reciprocal of exposure amount + 4) Graininess: concentration o, r From the values in Table 7, it can be seen that sample 102.101d of the present invention clearly has excellent graininess.

Structure of compounds used in examples U-/ hmm -i α −1 0.3 -J C-j(-da C-jc-4 OCR2C)12SCH2COO)l C2H5 ■ 2H5 2H5 ■ (()12)38s3 ■ C21 (5 Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment

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 by reaction with the oxidized developing agent, X represents an oxygen atom or a sulfur atom, and R_1 and R_2 are each aliphatic group,
represents an aromatic group or a heterocyclic group, R_3 represents a substituent, n represents 0, 1 or 2, and when n is 2, two R_3 may be different substituents, and R_1,
Two of R_2 and R_3 may become divalent groups and connect to form a cyclic structure. ]