JPS61102646A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve graininess and sharpness by incorporating a coupler. CONSTITUTION:The silver halide color photographic sensitive material superior in graininess, sharpness, and color reproducibility due to the interlayer effect can be obtained by forming on a support at least one photosensitive silver halide emulsion layer contg. a coupler capable of releasing a compd. capable of capturing the oxidation product of a color developing agent at the time of reaction with said oxidation product of a color developing agent. The coupler is represented by the formula shown on the right 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; Y is an aliphatic, aromatic, aliphatic or aromatic oxy, aliphatic or aromatic acyl group, or oxycarbonyl, sulfocarbonyl, halogen, cyano, formyl, nitro, or the like, each may be same or different when n is 2; and n is 1 or 2.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material containing the following photographic coupler which improves 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, etc.
It is known that indamine, azomethylene, phenoxazine, phenazine and similar dyes can be produced to form color images. In this system, subtractive color reproduction is usually used for color reproduction, using silver halide emulsions that are selectively sensitive to blue, green, and red, and color image-forming agents of yellow, magenta, and cyan, which are complementary colors, respectively. be done. To form a yellow image, for example, an acylacetanilide or dibenzoylmethane coupler is used, and to form a magenta image, a pyrazolone, pyrazolobenzimidazole, or cyanoacetophenone muff is mainly an indacylon cazoler. Phenolic couplers, such as phenols and naphthols, are primarily used to form cyan images.

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

It is conventionally known that couplers are used not only to form dye images, but also to release photographically useful materials. 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, Tokukai Akira! λ-ko13/l, same j
7-///yo37, same! Compounds described in No. 7-IJrtJt 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 scavenging agents for the oxidized developing agent released by these couplers are not only weak in 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 improve graininess and freshness by incorporating a novel coupler that releases a compound that captures an oxidized developing agent by reaction with the oxidized developing agent. Another object of the present invention is to provide a color photographic material with excellent color reproducibility due to a multilayer effect.

(Means for Solving the Problems) An object of the present invention is to have at least one photosensitive silver halide emulsion layer on a support, and to contain at least one coupler represented by the following general formula (1). This was achieved using silver halide color photographic materials.

General formula CI) [Formula C1 represents all the coupler residues that are cleaved with X by reacting with the oxidized form of the developing agent, X represents an oxygen atom, and Y represents a sulfur atom, Y represents an aliphatic group, an 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, aliphatic or aromatic acylamino group, aliphatic or aromatic oxycarbonylamino group,
It represents 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, n represents 1 or co, and when n is 2, Y is the same or different. It's okay. ] When the substituent represented by Y in general formula (T) contains an aromatic group moiety, it has 4 to 10 carbon atoms and is preferably a substituted or unsubstituted phenyl group. Substituents include halogen atoms, acylamino groups (e.g. acetamido groups, butanamide groups), hydroxyl groups, alkoxy groups (e.g. methoxy groups, butoxy groups), nitro groups, sulfonamide groups (e.g. benzenesulfonamide groups, methanesulfonamide groups). group), carbamoyl group, carboxyl group, etc.

When the substituent represented by Y in general formula CI) contains an aliphatic group moiety, the number of carbon atoms is /-70, and 7~! It is preferably in the range of , and may be linear or cyclic, linear or branched, saturated or unsaturated, substituted or unsubstituted. Permissible substituents include halogen atoms, alkoxy groups (e.g. methoxy group, ethoxy group 1!'), human c2-
? Examples include syl group, sulfonamide group (for example, methanesulfonamide group, benzenesulfonamide group, etc.), carboxyl group, acylamino group (for example, acetamide group, benzamide group, etc.).

In general formula CI), the OH group is preferably located at the 2-position or the hi-position with respect to X.

A preferred example is when X in general formula (1) is an oxygen atom.

In general formula (CI), a person can use the following general formula (II) in detail.
), (1), (If/), (V), (VI:) or [
②] This is a coupler residue represented by .

General formula (II) General formula (III) R3 General formula (IV) General formula [v] General formula (VI) υ General formula [■] General formula [■] Free bond derived from the coupling position in the above formula The hand represents the attachment position In of the coupling-off group. In the above formula, a□, R2, R3, Raaaaaa
R 5% 6% l 8% 91
If 10 1 11%R□2 or "t3 contains a diffusion-resistant group, it is selected such that the total number of carbon atoms is 1 to 3, preferably 70-, otherwise,
The total number of carbons is /! The following are preferred.

Next, steps a to R of the general formulas (II) to [■].

and l will be explained.

In the formula, R+1 represents an aliphatic group, an aromatic group, an alkoxylic group, or a heterocyclic group, and R+2 represents an aromatic group or a heterocyclic group.

In the formula, the aliphatic group represented by ao preferably has a carbon number l
N 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. Specific examples of aliphatic groups useful as a□ are: isoprobyl, isobutyl, tert-butyl, isoamyl, te.
rt-amyl group, l,/-dimethylbutyl group, /, /-
Dimethylhexyl group, i, t-diethylhexyl group, dodecyl group, decyl group, octadecyl group, cyclohexyl group, l-methoxyisozorobyl group, l-phenoxyisopropyl group, /-p-tert-butylphenoxy Isozorobyl group, α-aminoisozorobyl group, α-(
These include diethylamino)isopropyl group, α-(succi/imido)isopropyl group, α-(phthalimido)inpropyl group, α-(benzenesulfonamido)inzolobyl group, and the like.

When a or R2 represents an aromatic group (particularly a phenyl group), the aromatic group may be substituted. Aromatic groups such as phenyl groups include alkyl groups having 3 or less carbon atoms, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, alkoxycarbonylamino groups, aliphatic amide groups, alkylsulfamoyl groups, alkylsulfonamido groups, and alkyl groups. It may be substituted with a ureido group, an alkyl-substituted succi/imide group, etc., and in this case, the alkyl group has a phenine/imide group in the chain.
An aromatic group such as the like may also be present. The phenyl group may be substituted with an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamide group, an arylsulfamoyl group, an arylsulfonamide group, an arylureido group, etc., and the aryl of these substituents The radical moieties may be further substituted with one or more alkyl groups having a total of /-22 carbon atoms.

The phenyl group represented by R or R2 may further include an amine group, a hydroxy group, a carboxyne group, a sulfo group, a nitro group, a cyano group, a thiocyano group, or a halogen group, including those substituted with a lower alkyl group having a carbon number of -4. May be substituted with atoms.

Further, R1'C may represent a substituent in which a phenyl group is fused with another ring, such as a naphthyl group, a quinolyl group, an inquinolyl group, a chromanyl group, a chromanyl group, a tetrahydronaphthyl group, etc. These substituents may themselves have further substituents.

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

When R or R12 is a heterocyclic group, the heterocyclic group is bonded to the carbon atom of the carbonyl group of the acyl group in alpha acylacetamide or the nitrogen atom of the amide group, respectively, through one of the carbon atoms forming the ring. do. Such heterocycles include thiophene, furan, pyran, pyrrole, pyrazole, pyridine, pyrazine, pyrimidine,
Examples include pyritazine, indolizine, imidazole, thiazole-oxazole, triazine, thiadiazine, oxazine and the like. These may further have a substituent on the ring.

In the general formula (I[I), R3 represents 1 to 3 carbon atoms,
Preferably 1 to 22 linear or branched alkyl groups (e.g., methyl, isopropyl, tert-butyl, hexyl, dodecyl, etc.), alkenyl groups (e.g., allyl groups, etc.), cyclic alkyl groups (e.g., cyclopentyl, cyclohexyl, etc.). , norbornyl group), aralkyl group (e.g. evabenzyl, β-phenylethyl group)
, ', these are noroge/atom, nitro group, cyano group, aryl group, alkoxy group, aryloxy group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group , diacylamino group, riV
Ido group, urethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-arylanilino group, N
It may be substituted with a '-alkylanilino group, an N-acylanilino group, a 'hydroxy group, etc.

Furthermore, R13 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,
Aralkyl group, cyclic alkenyl group, halogen atom, nitro group, cyano group, aryl group, alkoxy group, aryloxy group, carboxy group, alkoxycarbonyl group, 7
1J-ruoxycarbonyl 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, N-alkylanilino group, N-arylanilino group, N-acylanilino group, hydroxy group, etc. Very preferable as R3 is at least one alkyl group at the ortho position,
Phenyl substituted with an alkoxy group, halogen atom, etc.
It is useful because it does not change color due to light or heat.

Furthermore, R3 is a heterocyclic group (for example, a Δ-membered heterocyclic ring containing a nitrogen atom, an oxygen atom, or an ioc atom as a petro atom, or a fused σ heterocyclic group, such as a pyridyl group, a quinolyl group, a furyl group, or a benzothiazolyl group). group, oxasilyl group, imidazolyl group, naphthoxacylyl group, etc.), as mentioned above.
a heterocyclic group, an aliphatic or aromatic acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbamoyl group substituted with the substituents listed for the group;
It may also represent an arylcarbamoyl group or an alkylthiocarbamoyl group.

In the formula, R4 is a hydrogen atom, a linear or branched alkyl, alkenyl, cyclic alkyl, aralkyl, or cyclic alkenyl group having 1 to 3.2 carbon atoms, preferably 1 to 22 carbon atoms (these groups are substituted with the substituents listed above for R3). ), aryl groups and heterocyclic groups (these may have the above R3
), alkoxycarbonyl groups (e.g. methoxycarbonyl group, ethoxycarbonyl group, stearyloxycarzenyl group),
Aryloxycarbonyl groups (e.g., phenoxycarbonyl group, naphthoxycarbonyl group, etc.), aralkyloxycarbonyl groups (e.g., benzyloxycarbonyl group, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, heptadecyloxycarbonyl 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, aclaramino groups (e.g. acetylamino group, 5-C(x,≠-di-tert-amylphenoxy)acetamide]benzamide group, etc.), diacylamino group, N-alkylacylamino group (e.g., N-methylzoμ pionamide group, etc.), N-aryl- Ruaflamino group (e.g. N-phenylacetamide group, etc.)
, ureido groups (e.g. frayed, N-arylfreido, N-alkylureido groups, etc.), urethane groups, thiourethane groups, arylamino groups (e.g. phenylamino,
N-methylanilino group, diphenylamino group, N-acetylanilino group, λ-chloro! -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, -1be/zo-nazolylamino group, etc.), alkylcarbonyl group (e.g. methylcarbonyl group, etc.),
Arylcarbonyl group (e.g., phenylcarbonyl group, etc.), sulfonamide group (e.g., alkylsulfonamide group, arylsulfonamide group, etc.), carbamoyl group (e.g., ethylcarbamoyl group, dimethylcarmemoyl group, N-mef-phenylcarbamoyl, N -phenylcarbamoyl group), sulfamoyl group (e.g. N-
alkylsulfamoyl, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group, N-furkyl-N-arylsulfamoyl group, NlN-diarylsulfamoyl group, etc.), cyan group, hydroxyl group Represents either.

In the formula, R+5 represents an aliphatic group or an aromatic group.

The aliphatic group preferably has 7 carbon atoms, and may be substituted or unsubstituted, chain or cyclic. Preferred substituents include an alkoxy group, an alkylthio 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 R5 are as follows: nidodecyl, hexadecyl, dodecyloxpropyl, cyclohexyl, tert-butyl, butyl, 3-(co.

≠-di-tert-acylphenoxy)propyl group, /
-(2,44-di-tert-acylphenoxy)propyl group, and the like.

When R5 represents an aromatic group, it may have the same substituents as those listed above when R is an aryl group.

In the formula, R+6 is an aliphatic group (e.g. methyl group, ethyl group, etc.), a halogen atom (e.g. chlorine atom, fluorine atom)
, represents an alkoxy group (eg, methoxy group, ethoxy group) or an aromatic group (eg, phenyl group).

In the formula, R7 and R8 each represent a hydrogen atom, an aliphatic group or an aromatic group, and when R7 or R8 represents an aliphatic group, the number of carbon atoms is 1 to 32, preferably /-/r,
Substituted or unsubstituted, the chain-like chain may be cyclic. Preferred substituents include an aryloxy group, an alkoxy group, a gen atom, an aryl group, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxycarbonyl group, an aclaramino group, a sulfonamide group,
These may further have a substituent such as an alkoxy group. Specific examples of useful aliphatic groups for R7 or R8 are as follows: nidodecyl group, hexadecyl group,
dodecyloxyprobyl group, cyclohenocyl group, ter
t-7'tilts, 3-(2,4cm di-tert-acylphenoxy)propyl group, /-(co, hiro-gite)
rt-acylphenoxy)propyl group, etc. When R8 represents an aromatic group, R8 is preferably a substituted or unsubstituted phenyl group having 4 to carbon atoms.

Preferred substituents include an alkoxy group, an aliphatic group, an acylamino group, an arylcarbonyl group, a halogen atom, a sulfonamide group, a sulfamoyl group, a carbamoyl group,
These include carboxyl group, hydroxyl group, cyano group, nitro group, etc. Specific examples of useful aromatic groups for R7 or R8 are: 2-tetradecyloxyphenyl group, tertetradecyloxyphenyl M, 3
-)"decyloxycarbonyl phenyl group, cochloro-j-)"y' syloxycarbonylphenyl group, phenyl group, ≠-carboxylic diphenyl group, and the like.

In the formula, R19 is a halogen atom, an acylamino group (e.g. acetamido group, J,4L-di-tert-amylphenoxyacetamide group), a sulfonamide group (e.g. methanesulfo/amide group, hexadecylsulfonamide group)
, represents an alkoxy group (eg, methoxy group, dodecyloxy group) or an aliphatic group (eg, methyl group, ethyl group).

In the formula, l represents OX/ or co, and when l is 1, the two substituents may be the same or different.

&,. is an arylcarbonyl group, has 2 to 3 λ carbon atoms, and is better <r! λ~2 alkanoyl group, arylcarbamoyl group, carbon number λ~32, preferably Colcoco alkanecarbamoyl group, carbon a7-32, preferably 1--
2 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,
Examples include an acylamino group, an alkylsulfamoyl group, an alkylsulfonamide group, an alkylsuccinimide group, a halogen atom, a nitro group, a carboxyl group, a nitrile group, an alkyl group, and an aryl group.

R engineering is an arylcarbonyl group, carbon number λ~32, preferred!
, L, < is a colcoco alkanoyl group, an arylcarbamoyl group, having 2 to 3-2 carbon atoms, preferably a colcoco alkanecarbamoyl group, a/~32 carbon atoms, preferably 1
~λλ alkoxycarbonyl group or arylodicarbonyl group, carbon number 1 to 32, preferably /N2
alkanesulfonyl group, arylsulfonyl group, IJ'' group, !-membered or t-membered heterocyclic group (petero atom is selected from nitrogen atom, oxygen atom, and iodine atom, such as triazolyl group, imidazolyl group, phthalimide group) , a succinimide group, a furyl group, a pyridyl group, or a benzotriazolyl group), and these may have the substituents described in &□ above.

In the general formula [■], "12" represents an aliphatic group, an aromatic group, a heterocyclic group, or an aniline group.For the aliphatic group, aromatic group, and heterocyclic group, the explanation for R is applicable. When a□2 represents an anilino group, the phenyl group may have a substituent as listed when RJ3 represents a phenyl group.A preferable example of "12" is pentafluorozolobyl. base, /,,l,ko,
co, 3°3-hexafluorozolobyl group, p-cyanoanilino group, 3. Examples include ≠-dichloroanilino group, p-propanesulfonylanilino group, and λ-ethanesulfonamidophenyl group.

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

For these, the same as described for Ro is applicable. Preferred examples of "13" include tert-butyl group, /-(co,≠-di-tert-amylphenoxy)propyl group,
/-(2,≠-di-1ert-amylphenoxy)pebutyl group, ゛isoamyl group, /-(J, 4L-di-tert
Examples include t-octylphenoxy)butyl group.

The compounds used in the present invention include the following seven compounds, but are not limited to these.

H COQC4) 1゜H OH OH (8) OH OH ]
CHO(t)c 5i-i Engineering 1 〇)( C,2H2500CCHCOOC,2H25H C(JOC4H.

ct (21) C) k4OH OH OH OH Synthesis Example (1) Synthesis of Exemplary Compound (1) Synthesis was carried out using the following synthetic route.

ocOC(CH3)3λOH Exemplary Compound (1) ■Synthesis of Compound A: 309 of Compound I, J-acetyl-Hiro-piparoyloxyphenol, 144.2f and triethylamine t2 were added to acetonitrile at 200 dK and heated to reflux. After reacting for 5 hours, cool and add ethyl acetate JOO.
mlt-addition water washing, dilute hydrochloric acid washing, and further water washing were performed in this order.

The oil layer was separated, the solvent was distilled off under reduced pressure, and the residue was recrystallized from hexane and ethyl acetate to obtain compound 232.

■Synthesis of Exemplary Compound (1): Compound 7. ! 10% water-containing methanol including ff, 200
The mixture was dissolved in Jl and stirred at room temperature for 1 hour. The desired coupler (1) was obtained by post-processing in the same manner as in step (3) above.

Synthesis example (2) Synthesis of exemplified compound (5) It was synthesized using the following synthetic route.

α CH3 CH3 Exemplary Compound (5) The synthesis of compound Hiro is a special request! It was synthesized by the synthesis method described in No. 2-123!03 and Japanese Patent Application Sho Star No. 12λ≠60. The synthesis route is shown in the reaction formula above. Compound j below
The method for synthesizing exemplified compound (5) will be specifically shown.

(2) Synthesis of compound: Compound ≠ 2j9 was added to acetonitrile λoo7, and anhydrous butafluorobutyric acid 31f was added dropwise at room temperature.

After 2 hours of reaction, the reaction mixture was concentrated under reduced pressure and the solvent was distilled off. The residue was used in the next step.

■Synthesis of compound B: Compound obtained in the previous step! Jr2 was added to acetic acid≠oosl containing 0g1fc of Mizuhiro and heated to OoC. Iron powder was gradually added to this solution over a period of 0 ft-JO minutes. The mixture was allowed to react for 10 minutes without exceeding ioo'c, and then cooled to room temperature. Insoluble materials were filtered out, the filtrate was poured into water, and the precipitated fc crystals were filtered out to remove silica compounds. (After drying) Tokutomo.

■Synthesis of Compound 7: Compound 7 was added to 300-proof acetonitrile and heated under reflux.
t-amylphenoxy)hexanoyl chloride2. t,
79't-dropwise. After reacting at this temperature for 3 hours, the mixture was cooled to room temperature, and 5 oz. of ethyl acetate was added thereto and washed with water. The oil layer was separated and concentrated, and the residue was crystallized using a mixed solvent of ethyl acetate and acetonitrile to obtain compound 7.
22 Tokuji.

■Synthesis of exemplified compound (5): 200m dichloromethane
1 to 31 of compound 7,? f was dispersed and boron tripromide Jjf was added dropwise at o'C. After the dropwise addition, the mixture was allowed to react for a period of time at 10 oC or less, and the temperature was gradually returned to room temperature. This was gradually poured into 100 liters of sodium hydrogen carbonate while stirring. The oil layer was transferred to a separatory funnel and washed with water repeatedly. After separating the oil layer, the solvent is distilled off under reduced pressure and the residue remains! The desired coupler (5) tJ7 was obtained by recrystallizing ' from ethyl acetate and hexane.
．． I got 02.

The coupler of the present invention can be used in combination with commonly used photographic couplers. IO to 2.0 moles, preferably o, for every 7 moles of dye-forming coupler used in the same layer.
The desired effect of the present invention can be obtained by using it in the range of o, zo, r moles.

The coupler of the present invention or the couplers 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 ys'C or higher and a low-boiling point so-called auxiliary solvent in a mixed solution, it is dissolved in an aqueous medium such as water or an aqueous gelatin solution in the presence of a surfactant. Finely disperse. Examples of high boiling point organic solvents are U.S. Pat. It is described in J Co. λ, No. 027, etc. Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, or the like before use for coating.

Specific examples of high-boiling organic solvents include phthalate esters (dibutyl phthanate, dicyclohexyl phthalate,
G-ether hexyl phthanate, didodeclophthalate, etc.), phosphoric acid or fc is esters of phosphonic acid (
triphenyl phosphate, tricresyl phosphate, coethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-, z-ethylhexyl phosphate, tridodecyl phosphate, drift xyethyl phosphate, trichloropropyl phosphate, sheath-ethylhexyl phenyl phosphate, etc.), benzoin Acid esters (λ-ethylhexyl benzoate, dodecyl benshade, λ-, Tf-ruhexyl p-hydroxy-7penzoate, etc.), amides (diethyl dodeca/amide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (instearyl alcohol, λ, e-tert-amylphenol, etc.), aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, instearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutel-cobutoxyt-
tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), etc. As the auxiliary solvent, those having a boiling point of about 300 to about 1 to 0 C can be used, and typical examples include ethyl acetate, Examples include butyl acetate, ethyl zoropionate, methyl ethyl ketone, cyclohexanone, coethoxyethyl acetate, dimethylformamide, and the like.

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

JtJ No., OLS No. 1, jul, Core No. 4L and OLS No. 1,! It is described in Hiroshi/, No. 230, etc.

A variety of color couplers can be used in the present invention. Here, color coupler refers to aromatic 1
A compound that can generate a dye by reacting with an oxidized form of a primary amine developer. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolone or pyrazoloazole compounds, and open chain or heteroartic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that may be used in the present invention are provided in Research Disclosure (RD)/7A.
44j (/7 December 2012)■-D section and /171
7 (1975'//).

It is preferable that the color coupler incorporated in the light-sensitive material is made into a polymer having all pallast groups, so that it has diffusion resistance. A two-pixel color coupler substituted with a leaving group is preferred over a four-equivalent color coupler in which the coupling active position is a hydrogen atom. It is also possible to use couplers in which the color-forming dye assumes adequate diffusivity, non-color-forming couplers or f) IR couplers which release a development inhibitor upon coupling reaction, or couplers which release a development accelerator.
1. Typical examples of yellow couplers that can be used in the present invention include oil-protected acylacetamide couplers. Specific examples thereof include U.S. Pat. No. 2,4407,210 and U.S. Pat. Ir7j, 0
JrV and No. 3. It is described in Kobu J', No. 104, etc. The use of a two-pixel yellow coupler is preferred for the present invention, and US Pat. Hiro≠7. Octopus No. 3. 3J, No. 10 and No. ≠, O here.

The oxygen atom dissociative yellow coupler described in No. t, 2θ, etc. or Japanese Patent Publication No. Sho JLR-1073, US Patent No. ≠, 4cd/, 7! No. ko, No. μ, 3 t, 0
No. 2, F4. D/10! ! (/ri7ri φ month), British Patent No. 1.≠2, No. 020, West German Published Application No. 1, 2/
Ri, Ri No. 17, Same No. -, Koro 1.3t No. 1, Same No. λ, 3
Kota! Typical examples include the nitrogen atom separation type yellow couplers described in No. 17 and No. 2゜Hiroshi No. 33.112. α-pivaloylacetanilide couplers have excellent color fastness, particularly light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include oil-protected indazolo/cyanoacetyl couplers, preferably pyrazoloazole couplers such as pyrazolone and pyrazolotriazoles. ! - As for the pyrazolone couplers, couplers in which the 3-position is substituted with an arylamino group or an acylamino group are preferable from the viewpoint of the hue and coloring density of the coloring dye. No.-1
No. 3143,703, No.-, too, yrr, No. 2,901,173, No. J, 042, J
IS No. 3.7! ko, rribu issue and same number 3゜'1
It is described in lJt, No. 0/z, etc. two pixel j
- 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. Patent No. ≠, 310. fc nitrogen atom leaving group or US Pat.

The arylthio group described in No. 31/, No. 127 is particularly preferred. Also, European Patent No. 73. The ballast group described in the above publication has the effect of increasing color density even with pyrazolone couplers. As the bigroazole couplers, pyrazolobenzimidazoles described in U.S. Pat.
Pyrazolo (j, /-c) (/
.

Co, ≠] triazoles, RDλ≠ virazolonato 2-azoles and RID2 described in Coco O (June 1999)
Examples include pyrazolopyrazoles described in 1fi, 2JO (/9rll - year as month). European Patent No. 1/7 in terms of low yellow side absorption and light fastness of the coloring dye
Imidazo [l.

[Cob] pyrazoles are preferred, and European Patent No. 11,
Pyrazolo (/, j-b) (/,, 2.
[Hiroshi] triazole is particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, and US Pat. ≠7≠.

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

Typical examples include the oxygen atom elimination type two-equivalent naphthol couplers described in Ir4, Ir4, Ir4A, 221,233 and Ir200. Specific examples of phenolic couplers include U.S. Pat. ! rO/, /71
No. J, 772, /6-, No. 1. rij, Ir2 are described in the No. 1, etc. Humidity and temperature robust cyan couplers are preferably used in the present invention and are typically described in U.S. Pat. No. 3,772.
, phenolic cyan coupler described in No. 002,
U.S. Patent No. 2,772. / No. 1, No. J, 7! I
.

No. 301, No. 4c, /2t, No. J Riwo, No. Hiroshi.

334L, oii No. 4L, 3λ7. /7J, West German Patent Publication No. 3,322,722 and % Gansho jlr
-4.247/, etc., and U.S. Patent No. J,
444LA, Bu-1, same No.≠, 333, Tatata No. 4c, 4A11,...! r! No. 9 Oyobi No. ≠
These include phenolic couplers having a phenylcundide group at the λ-position and an azilua or mino group at the first position, which are described in Japanese Patent Application Publication No. 27,747.

The dye-forming coupler is used in an amount of from 0.00 to 0.005 moles, depending on the 7 moles of light-sensitive silver halide in the layer to which it is added. In color photosensitive materials for photography, 1 mole of photosensitive silver halide is 7'C4), and yellow couplers are o, oi
to O0j0/, magenta couplers are often used in amounts of 0.003 to 0.2/mol, and cyan couplers are often used in amounts of 0.00 to 0,872 moles, and in color photosensitive materials for printing such as color paper, yellow, magenta and Both cyan couplers are photosensitive/10.0. It is often used in an amount of 1 to 0.05 mol, but 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 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 2 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.
≠73, etc., or U.S. Pat. No. 4A, OOA, No. 229, No. 1T,
/31,2J″1 and British Patent No. 1./≠t, 3t
A typical example is the magenta-colored cyan coupler described in No. y.

These color couplers may form a polymer having λ-mer or more. Typical examples of polymerized couplers are described in U.S. Patent No. 3. φ11,120 and the same≠.

No. 010.2/7. Specific examples of polymerized magenta cazolers are given in British Patent Nos. 2 and 10, 773.
No. 367.21 and US Pat. No. 367.21.

The granularity can be improved by using a coupler with various diffusion types, and such couplers are disclosed in U.S. Patent No.
, 3&t, 237 and British Patent No. 1゜lco! ,! 70
A specific example of a magenta coupler is given in European Patent No. 2≦,
? No. 73 and West German Patent Publication (OL8), ? , J co 4L
, 33) describes specific examples of yellow, maze/red, and cyan.

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

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. The preferred silver halide is /! Silver iodobromide containing silver iodide of 2 to 12 moles is particularly preferred.

Silver halide grains in photographic emulsions are cubic, hexagonal, l
It may be a regular crystal such as a λ-hedron or an l≠-hedron, or may have an irregular crystal shape such as a spherical shape, or a composite of these crystal shapes. Also, Research Disk Coger Coco! As described in 3≠, the thickness is 0.2 microns or less and the diameter is at least o.
, 4 microns and an average aspect ratio of 5 or more may be an emulsion in which tabular grains occupy jO% or more of the total projected area.

The crystal structure may be uniform, the inside and outside may have different compositions, it may have a layered structure, or silver halides of different compositions may be joined by Evita-Kikuyaru bonding. 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.

Silver halide grains may be fine grains with a grain size of v-1, o, i microns or less, or large grains with a projected area diameter of up to 3 microns2, monodisperse emulsions with a narrow distribution, or wide distribution. It may also be a polydisperse emulsion with

The photographic emulsion used in the present invention is P, Glafkides.
Written by Chimie et Physique Pboto
graphique (published by Paul Monte1,
/9.47 years) G, F.

Photographic Emuls by Duffin
ionChemistry (The Focal
Press, 1996), V, L, Ze
Making and by likman et al.
Coating Photographic Em
ulsion (The Focal Press
It can be adjusted using the method described in, for example, published in 1999, published by J.D. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the methods for reacting the soluble silver salt and soluble halogen salt include the one-sided mixing method, the simultaneous mixing method,
Any combination thereof may be used.

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 form of the simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, ie, the 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.

The emulsions may be formed separately and one or more fc silver halide emulsions may be used as a complete mixture.

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

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, see for example “Die Grundlagender Photo” edited by H. Frleser.
graphischenProzesse mjt
Silber-halogeniden” (Akade
mische Verlagsgesellschaf
t.

The method described in pages 7j to 73≠ can be used.

Namely, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (such as thiosulfates, thioureas, mercapto compounds, and rhodanines); reducing substances (e.g., stannous salts); , amines, dorazine conductor, formamidine sulfur 7rllS silane compound)
t-reduction sensitization method: The t-reduction sensitization method using noble metal compounds (e.g. complex salts of metals of group II of the periodic table such as Pt, Ir, Pd, etc. in addition to total complex salts) is used alone or in combination. be able to.

The photographic emulsion used in the present invention can contain various compounds *t- for the purpose of preventing fog during the manufacturing process, storage or photographic processing of the light-sensitive material, or for stabilizing the photographic performance. That is, azoles, such as penzothiazolicum salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, beromobenzimidazoles, mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially nophenyl-!-mercaptotetrazoles, etc.; mercazotopyrimidines; mercaptotriazine) thioketo compounds, such as oxadolinthione; azaindenes, such as triazaindenes, tetraazaindenes (particularly ≠-hydroxy-substituted (/, 3.3a, 7) tetraazaindenes), pentaazai/ A number of compounds known as antifoggants and stabilizers can be added, such as henzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc.

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, for the purpose of increasing sensitivity, increasing contrast, or accelerating development, for example, polyalkylene esters or derivatives thereof such as ethers, esters, and amines, thioether compounds, thiomorpholines, etc. Quaternary ammonium salt compound, V-tan derivative,
It may also contain urea derivatives, imidazole derivatives, 3-pyrazolidoes, 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 L-sfuryl dyes, and hemioxonol dyes. In particular, Ishikawaka pigment is a pigment belonging to cyanine pigments, merocyania pigments, and complex merocyanine pigments. 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 alone or in combination, and 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.
2/), aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3.7≠3,610), cadmium salts, azaindeno compounds, and the like. The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer, and one blue-sensitive emulsion layer M 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.
Different combinations may be used depending on the case.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

For example, activated vinyl compounds (1, J.

! -triacryloylhexahydro-s-triazine, l,3-vinylsulfonyl-1-furopanol, etc.)
, active norogen compounds (2,≠-dichloro-t-hydroxy-5-)riazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. can be used alone or in combination.

The photosensitive material made from kumquats of the present invention may contain a hydroquinone derivative, an aminephenol salt conductor, gallic acid 84, 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. Patent No. J, J-JJ;
No. 7944, U, No. 234, 0/3, Special Publication No. 1983-.
67≠θ and European patent! 7.140 etc.) IJ Azoles, U.S. Pat. , listed in Tatata issue, nine butadiens, US special FF3.70! .

♂0! No. and J, 707, . 37! Cinnamic acid esters described in the issue, US patent! ,214r,! No. 30 and British Patent No. i, 3 Co/, 3! ! It is possible to use benzophenones described in US Pat.

U.S. Patent No. 3. ≠ri2.7≦λ No. and same J, 700
．． Ultraviolet absorbing fluorescent brighteners described in No. ≠jj may also be used. Typical examples of ultraviolet absorbers are R, D, 2≠
232 (/r≠yearΔmonth).

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 oxynol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxynol dyes; hemioxonol dyes and merocyanine dyes are useful.

When carrying out the present invention, the following known antifading 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.

As a known anti-fading agent, Pad°
Examples include toquinone derivatives, gallic acid derivatives, p-alkoxyphenol U, p-oxyphenol derivatives, and bisphenols.

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, polyethylene, polyethylene terephthalate, polycarbonate, baryta layers or alpha-on-fibers/polymers (e.g. Paper coated or laminated with polyethylene, polypropylene, etc. 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 gold such as zinc oxide, zinc sulfide, calcium carbonate, antimono trioxide, silica white, alumina white, titanium phosphate, etc., and titanium dioxide, pallium 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, it is possible to further improve the whiteness and sharpness of photographic images by providing a hydrophilic colloid I6 containing a white pigment in high density between the support and the emulsion layer. 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 material is used, smoothness and・In addition to improving sharpness,
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 (IIFC) acid and titanium oxide are particularly useful.

In addition to the above, the color photographic light-sensitive material of the present invention may contain various photographic additives known in this field, such as stabilizers, antifoggants, surfactants, antistatic agents, developing agents, etc., as necessary. Examples are given in Research Disclosure/74≠3.

Furthermore, depending on Yang Kai, a fine-grain silver halide emulsion having substantially no photosensitivity (for example, silver chloride, silver bromide, salt, etc. with an average grain size of 0.20μ or less) is used in the silver halide emulsion layer or other hydrophilic colloid layer. Silver bromide 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 color developing crude drugs, Hiro-amino-f'J, N-diethylaniline, 3-methyl-≠-amino-N, N-diethylaniline, p-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl- -Amino/-N-ethyl-N-β-hydroxyethylaniline, 3-methylder-amino-N-ethyl-N-
β-methanesulfamide ethylaniline, ≠-ami/-
Representative examples include J-methyl-N-ethyl-N-β-methoxyethylaniline.

The color developer may contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and acid salts, development inhibitors such as bromides, iodides, and organic anti-capri agents, and 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 couplers, and competitive couplers. ,
Fogging agents such as sodium boron hydride, l-
Auxiliary developers such as phenyl-3-virazolid/viscosity-imparting agents, US patent≠, 17. S'J.

The polycarboxylic acid chelating agent described in No. 723, the antioxidant described in West German Opening Publication (OL8), No. 6, and No. 910 may also 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. As a bleaching agent, for example, iron (III
), cobalt ('I[), chromium (Vl), copper (II)
Compounds of polyvalent metals such as, peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromate, iron(III) or cobalt c? M)
organic complex salts, such as aminopolycarboxylic acids such as ethylvindiaminetetraacetic acid, nitrilotriacetic acid, J-diamino-2-niproanoltetraacetic acid, citric acid, tartaric acid,
Complex salts of organic acids such as malic acid; persulfates, manganates; nitrosophenols, etc. can be used.

Among cholera, potassium ferricyanide, sodium iron(III) ethylenediaminetetraacetate, and ammonium iron(lil) ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron (, 2) complex salts are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

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

What about color development? It can be carried out at any temperature between 0C and jj'C. Preferably 30°C or higher, particularly preferably 3!
Perform all color development at 00 or higher.

The development time is preferably as short as about 3 minutes to about 1 minute. For continuous development processing, liquid replenishment is preferred, with jjOcc to /&Occ per square meter of processing area,
Preferably, 100 cc or less of the liquid is replenished. The benzyl alcohol in the developer is 20. t/l or less, preferably t
It is preferably less than osl/Ij.

Bleach-fixing can be carried out at any temperature from /1°C to 30°C, preferably 3°C or higher. If it is 3!00 or more, the processing time can be reduced to 7 minutes or less, and the liquid replenishment can be reduced by 1 gold. The time required for washing with water after color development or bleach-fixing is usually 3 minutes or less, and washing can be done within 1 minute using a stabilizing bath.

In addition to being degraded by light, heat, or temperature, the colored pigment frames can also deteriorate and fade due to mold during storage. Cyan images are particularly susceptible to severe deterioration due to mold, so it is preferable to use a mold preventive agent. Specific examples of antifungal agents are disclosed in Japanese Patent Application Laid-Open No. 7-7-/7λ.
There are more 2-thiazolylbenzimidazoles described in ≠Hiroshi.

The antifungal agent may be built 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 is applicable to color negative film, color paper, color positive film, color reversal film for slides, color reversal film for movies, and Ocolor for TV.
It can be used in general silver halide color light-sensitive materials such as reversal 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. Pat. No. 3,622. Bu-
Ta, 3.73≠, 735, room clerk, /26.4At
No. 1, Tokukai Akira! j-1012147, 32-412
7Jj issue and the same! ! -10!2≠ is written in the issue, Mayu three-color coupler mixing method 1 unit, aesearch
A detailed explanation can be found in Dis, closure/7/2, etc.

Example 1 Sample (1) was obtained by coating an emulsion layer and an auxiliary layer in the following order on an undercoated cellulose 93-acetate support.

1st layer Low-sensitivity red-sensitivity emulsion layer cyan coupler co(heptafluorobutyramide)-1-(-'-(-", 4c"-di-t-amylphenoxy7)butyramide] phenol (coupler ■) i
Dissolve ooy in 100 cc of tricresyl phosphate and 100 cc of ethyl acetate, and make 1 k of 10% gelatin aqueous solution.
g, surfactant sodium dodecylbenzenesulfonate lO
2 and the emulsion j00f obtained by high-speed stirring was mixed into a red-sensitive low-sensitivity silver iodobromide emulsion/# (average grain size of silver halide grains 0° 3μ, silver 702, gelatin tOft-contained (natural content 3 mol%)) and gelatin, water, stabilizers, coating aids,
Akira.

etc. and mix until the film thickness after drying becomes .mu.
(It was coated. (Amount of silver: Olbf/m2)
Second layer Central red-sensitive emulsion layer The emulsion of the cyan coupler used in the first layer was converted into red-sensitive medium-sensitive silver iodobromide emulsion / # (/- average grain size of silver halide grains O0jμ, silver 70f). , gelatin tOf
ft containing iodine content 3 mol%), gelatin, water, stabilizer,
Add a coating aid, etc., mix, and coat to a dry film thickness of 1μ. Red-sensitive high-sensitivity silver iodobromide emulsion / kg (average grain size of silver halide grains o, tμ, silver 70?, gelatin 109'f: contains iodine content 3 mol%), gelatin, water, stabilizer, It was mixed with a coating aid and the like and coated to a dry film thickness of lμ. (Silver fO
0≠f/m”)th φ layer Intermediate layer Ko,!-G5ec-Octylhydroquinone-〇Of
was dissolved in 00 cc of ethyl acetate, 10 tizelatin aqueous solution/kLi and sodium dodecylbenzenesulfonate 2
An emulsion obtained by stirring at a high speed of 0ff was mixed with gelatin, water, a coating aid, etc., and coated to a dry film thickness of lμ.

3rd layer Low green sensitivity emulsion layer Magenta coupler /-(ko, hiro, 6-drichlorophenyl)-J-(j-(ko, 4c di-t-amylphenoxyacetamide)benzamide)-! - Emulsion 5 obtained in the same manner as the emulsion of the seventh layer except that pyrazolone was used.
oot, a green-sensitive, low-sensitivity iodine silver bromide emulsion (average grain size 0.3μ, silver 70f1 gelatin content, iodine content 3 mol%), gelatin, water, stabilizer, and coating aid. The mixture was mixed and coated to a dry film thickness of μ. (Silver to,
717 m2) 6th layer Central green-sensitive emulsion layer Emulsion of the magenta coupler used in the first layer / to 9 green-sensitive, central silver iodobromide emulsion / kg (average grain size O0
! μ, silver 70? , contains gelatin tOf, iodine content 3-
Mix gelatin, water, stabilizers, coating aids, etc., and coat the mixture to a dry film thickness of lμ. (Amount of silver coated
o, 4A (7 m2) 7th layer Highly sensitive green-sensitive emulsion layer 1 kg of the emulsion of the magenta coupler used in the 3rd layer was mixed into a green-sensitive, highly sensitive silver iodobromide emulsion/kg (average grain size 0
．． A film containing 7 mol of silver and 1 mol of gelatin (containing 7 mol of silver and 1 mol of gelatin), gelatin, water, 1 stabilizer, coating aid, etc. was mixed and coated to a dry film thickness/μ. (Amount of silver coated
Q, μf/m 2) R-th layer The emulsion 1kQ used in the third intermediate layer was mixed with gelatin, water, and a coating aid, and coated to a dry film thickness of O0jμ.

Second layer Yellow filter First layer Yellow colloidal silver and gelatin were mixed and applied to a dry film thickness/μ.

10th layer Low-sensitivity blue-sensitivity emulsion layer Yellow coupler, α-(hibaroyl)-α-(/-benzyl-!-ethoxy-3-hydantoinyl)-cochrolow!-dodecylox7carponylacetanilide, is added to the 1st j-cyan coupler. , add tricresyl phosphate/coOcc, ethyl acetate to lcocc
An emulsion prepared by changing the emulsion/' to 9k, a blue-sensitive low-iodophilic silver bromide emulsion/kli (average grain size 0.jp, silver 70
9. Contains gelatin 740'f, legal content 3 mol%);
Gelatin, water, a stabilizer, and a coating aid were mixed and coated to a dry film thickness of λμ. (Coated silver amount 0.1,77m
) 1st/Layer Emulsion of yellow coupler used in middle window blue-sensitive emulsion layer 1st ior@
Night-sensitivity medium-sensitivity silver iodobromide emulsion/kg (average grain size o, 6μ, silver 701, gelatin: yA O?, iodobromide content 3)
Morti), gelatin, water, stabilizers, coating aids, etc. were mixed and coated to a dry film thickness of lμ.

(Amount of coated silver O1≠7m) 72nd layer The yellow coupler emulsion lkq used in the 10th layer of high-sensitivity emulsion layer was mixed into a light-sensitive high-sensitivity silver iodobromide emulsion/kg (average grain size 0.7μ, @70f, gelatin toyt-containing, natural change-containing t3 morch] was mixed with gelatin, water, a stabilizer, a coating aid, etc., and coated to a dry film thickness of lμ. (Amount of silver coated: O1≠?/m2) 1st J @ 2nd protective layer UV absorber instead of coupler, !-chloro2-(cohydroxy-3.!-di-t-butylphenyl)-cohybenzotriazole/If1.2-(2-tJ”roxy z-t-7'tylphenyl)-2H-benzotriazole J Of, co(cohydroxy-J-s
ec-Butyl-1-1-butylphenyl)-cohybenzotriazole 31f.

Dodecyl-z-(N,N-diethylamino)-cobenzenesulfonylluco,≠-pentagenoate 100f
200cc of t-tricresyl phosphate, dissolved in 00cc of ethyl acetate, sodium dodecylbenzenesulfonic acid, 1096 kg of gelatin gold, emulsion obtained by high speed stirring /kqt, mixed with gelatin, water, coating aid, etc., and dried. The film was coated to a film thickness of μ.

(Total UV absorber coating - II o, sr/m2) 7th Hiro layer 1st protective layer Fine grain silver iodobromide emulsion (grain size 0
．． 1μ, contains 701 silver, gelatin toy, natural content 1
(mol%), gelatin, water, stabilizers, coating aids, etc. were mixed and coated to a dry film thickness of lμ. (Amount of silver: 0.3 7 m2) The obtained multilayer coated film is designated as sample A/.

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

Using this emulsion, Sample Muko/I was prepared according to the method for preparing Sample I.

Hinu Compound N HCa H7 (1) Sample A/=A/ /' is exposed through a pattern for grain size measurement, and after color reversal processing, the Rms granularity is measured by measuring the density of the sample using a micro density meter. Image#degree/,
The granularity at 0 and λ, O is shown.

The sample shop / -& / / was exposed through the MTF measurement pattern, and after color reversal processing, the sample was measured using a Miku o (i1 degree measuring machine, and the 5 MTF value was determined by calculation. 90 sharpness IT, 10 lines/m m and 20 pieces/mm
' MTF value.

Compared to the comparative compound honey, the constant sample &2 using the compound of the present invention
It is clear that the graininess and sharpness are greatly improved at ~r.

Processing process Time Warm first development 3♂0C (±0.3) water washing 2/7 Reversal 2' 〃 Color development t' 〃 'toning
, 2/ 〃 Bleaching 6' 〃 Fixing
≠I 〃Water washing reference' 〃Stable l' Normally wet and dry First developing water 700
,/sodium tetrapolyphosphate λ2 Sodium sulfite 20f Hydroquinone monosulfonate 3oy Sodium carbonate (l hydrate) 3011-Phenyl-
φ-Methyl≠-Hydroxymethyl-3 1 Pyrazolidone 22 Potassium bromide 2.52 Potassium thiocyanate 1. Jf potassium iodide (0,
/% bath solution by adding 2d water
1oooyit inversion water 700
．． 1 Nitrilo・N-N-N-)limethinphospho/acid-6 atxJf Stannous chloride (cohydrate)/2 p-aminophenol 0. /f Sodium hydroxide If Glacial acetic acid
Add 1zzl water
1000 color development water 700
Goteto, sodium laboriphosphate Sodium disulphite 72 Sodium tertiary phosphate (λ hydrate) JAW Potassium bromide
12 Potassium iodide (0,/
% Solubility fL) Ta Omt Sodium hydroxide
3t citradinic acid
/, 51N-ethyl-N-(β-methanesulfontemidoethyl) -3-methyl-≠-aminoaniline sulfate //f ethylenediamine 32 Add water
1000 Shoulder Adjustment Water 70
0rttl Sodium sulfite l
λt Sodium ethylenediaminetetraacetate (λ hydrate) it Thioglycerin 0.44xi Glacial acetic acid
J g1 Add water
/ 000 Shoulder bleaching water 700
GLethy7indiaminetetodiacetate sodium (cohydrate salt) 2.0? Ethylenediaminetetraacetate iron (') ammonium (λ water salt) l co0.Of potassium bromide ioo, ay add water
1. Op fixing water r o
o,z ammonium thiosulfate 10. Of
Sodium sulfite 3.02 Sodium bisulfite j, Of Add water
/, OA stable water 100
xl formalin (37% by weight) j, 0go surfactant solution tL (product name Drywell)! ,0ytxt
Add water /, O1 Example 2 Multilayer color photosensitive material (10/
)It was created.

1st layer; antihalation layer black colloidal silver 0,16
97m2 Ultraviolet ray absorber U-/-0,0197m2
Gelatin layer λ layer containing U-2...o, ico2/m2; Intermediate layer 2, j-di-t-pentadenolhydroquinone...0.1197m2 Coupler C-/...・・・・・・・・・ 0,1197
Gelatin layer 3j containing m2; 1st red-sensitive emulsion layer ...... /, 2f/m2 Sensitizing dye I ......... 1 mole of silver On the other hand, 1, Hiro x lO mole sensitizing dye ■ ・・・・・・・・・・・・ 0.4tX70 per mole of silver Molkabu-7-C-2・-----・・-o, 0109/m
Gelatin layer j layer containing 2 Kazolar C-1-・kawa-0,07Of7m" coupler C-3--0,0 Jjf/m2; intermediate layer co,!-G-t-pentadecyl Hydrokino/... 0, Or f/
Gelatin layer containing m2 Layer: 1st green-sensitive emulsion layer"----0, !r Oj 7m 2 sensitized color fibers V ・
・・・・・・・・・・・・ For 1 mole of silver,
u・0X10 -%A/
Same ■ ・・・・・・・・・−・ # J for 1 mole
, 0x10 moles ■ ・・・・・・・・・・− per 1 mole of silver /
, Ox/ (7-'%A/ Turnip 7-C-A ・・・・・・・・・・・・ O0≠
z f / m 2 turnip: 7-C-7---------
−−−−0,/3f/m2 sensitizing dye ■・・・・・・−・
...for 1 mole of silver! , 1X10 4 moles same ■ ・・・・・・・・・・・・ Hiroshi for 1 mole of silver, 0X10 4 moles coupler IC-2・・・・・・・・・ O0≠s 9
/ m2 Casoler C-J ・-----・-・-0
,03! f/m2 Kazolar c-e --------
Gelatin layer φ layer containing o, okoz f/m2; second red-sensitive emulsion layer... i, oy7m2 Sensitizing dye I......・ For 1 mole of silver, j, AXlo mole is the same. -Co, 1xlO-4 mol per mol of silver sensitizing dye ■ ・-・・・・・・・・・・・・／, jXIO' mol coupler C-t ・・・・・・・・・・...-0,029
7m” coupler C-Hiroshi -・・・・・・・・・・・ o,
7th gelatin layer containing opi f/m2; 2nd green-sensitive emulsion layer = .= ...0, I! f / m "Sensitizing dye V - 7 x IO' mole per mole of silver ■ ...................................... 1 mole of silver For i, rxio mole same ■ ・・・・・・・・・・・・ 7 for 1 mole of silver, ! C-7-...-= First layer of gelatin layer containing 0.0/If/m2; Yellow filter layer, yellow colloidal silver...0. or
Gelatin layer containing t/m"J,j-di-t-pentadecylhydroquinone...o,oyoy7m"; first nurturing emulsion layer---0,j7f /FF! 2 Sensitizing dye■ ...---------≠ per mole of silver, #
X/ 0 Molcazolar C-ta --------・----0, 7/
97m 2 Coupler C-1----------------------0
, 07f/m" io layer; th blue-sensitive emulsion layer ° -------- o, try/m2 sensitizing dye ■
・・・・・・・・・・・・J for 1 mole of silver,
OX/0 Molcazolar C-ta ----------0, J J
11th layer of gelatin layer containing f/m 2; 1st protective layer of gelatin layer 1 containing ultraviolet absorber U-/... o, i 2/m2 U-co-0,221/m'';λth protective layer・・・・・・Q1cojf/m Gelatin layer containing "polymethacrylate particles (diameter/, jμ) ・-0,/097m" In addition to the above composition, each layer contains Apply gelatin hardening agent) 1-1 and surfactant to Structure of compound used in Examples -t C-/U-CoC-J C-Hiro-j C-≦ Sensitizing dye ■ (CH2) 4803Na (CH, t3803Na 2H5 Chronic comparison coupler (4) (Samples 102 to 104) !0 molch of coupler C-2 in the second layer of sample 10 with the coupler of the present invention or comparative coupler (4) Sample 1O was prepared in the same manner as sample 10/ except for replacing
- Created ~/a& friend.

These samples were exposed to light for sensitometry through a tan color filter, and then subjected to color development processing as described below. At t7, exposure for conventional RM8 measurement was carried out, followed by similar color development. The obtained sample was measured for X-ray properties and graininess using a blue filter. An aperture of 4Llrμ was used for grain size measurement. The couplers of the present invention used and the photographic properties are shown in Table 1.

The development process used here is as follows: to 1 Color development...3 minutes 15 seconds 2
White...----3 minutes JO seconds Wash with water...
...3 minutes! Second 4 Stable...
・6 minutes 30 seconds 5 Washing with water・・・・・・3 minutes is
Second 6 Stable...3 minutes! The composition of the treatment liquid used in each step is as follows.

Force 2 - Developer Sodium Nitrilotriacetate /, Of Sodium Sulfite ≠, 02 Sodium Carbonate! 0.02 potassium bromide
/, 4L? Hydroxylamine sulfate, φV Hiro-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate 44.79 Add water and l! Bleach solution ammonium bromide lbuo, oya/%Nia water C2r%) 2z, Occ ethylenediamine-tetraacetic acid sodium iron salt /JO1Of glacial acetic acid
lhiro, add occ water
IL Fixer Sodium Tetrapolyphosphate, Of Sodium Sulfite, Of Ammonium Thiosulfate (7°) /71.0cc Sodium Bisulfite, Add Water
il stabilizer formali 7 f, Occ
From Table 1, it can be seen that Samples 102-ioz of the present invention clearly have excellent graininess.

Although the comparative sample/at had poor color development and low relative sensitivity, its graininess was worse than that of the sample containing the coupler of the present invention.

This procedural amendment (on the side of March 1985/R Nihon) Mr. Commissioner of the Japan Patent Office 1, Indication of the case, Showa! 2nd year patent application No. 1
No. 2, Title of the invention I. Silver halide color photographic light-sensitive material 3, Relationship to the case of the person making the amendment Patent applicant name Title (520
) Fuji Photo Film Co., Ltd. 4. Date of amendment order: February 1st, 1930 to 1930 (shipment date) & Subject of amendment: Column 6, "Detailed Description of the Invention" of the specification, Contents of amendment (1) No. 1! rP from page/line to page j7, line 6,
Chimie etPhysi by Glafkides
que Photographique (Paul M.
onte1, 1267) G, F, Duffin!
Photographic Emulsion Chem
istry (published by The Focal Pras+s, 1996), V, L.

Making a by Zvlikman et al.
ndCoating PhotographicEmu
lsion (published by The Focal Pleas,
/rit≠year)'' to ``P. Grafkide, 1 Shimmy Technique Physique Photographic'' (Ball Montell Publishing, 1267)
1 Photographic Emulsion Chemistry by G.F. Daafin (Published by Focal Press, /P.
1 Making and Coating Photographic Emulsion # (Published by Focal IV, / ? & 2011) by V. L. Zelikman et al.
Chimia etPh7giq by Glafkides
ue Photographique (Paul Mo
nte1 Publishing%/967) G, F, Duff i
Photographa Emulsion C by n
hemiatr7 (published by The Focal Press, 1946), V, L.

Making an by Zelikman et al.
dCoating PhotographicEmul
sion (published by The Focal Press, / 4A).

(2) No. rH,F from page 7 line to // line
r1eaerli @Die Grundlagend
erPhotographlschen Prozes
se mitSilber-halogeniden'
(Akadsmiache Verlagsgeael
lachaft.

/961) pages 471-7j4c” [H, Freezer Edition 1 Die Grundlagender
Photography, Production, Mitsut, Zilper, Halogenyden 1 (Academy, 7 Engineering, Ararksha, / Published in 941) Pages 471-7J4A (H, Frte
aar edition”’Die GrundlagenderP
photographischen Prozesse
mit Silber-halogeniden'(
Akademiache Verlagsgesellschaft, /ritr)
Otsu 7! (page 73)”.

Procedural amendment 1, case display Showa! Patent Application No. 28-94 2, Title of Invention Silver Halide Color Photographic 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.

Hirohiro page 1, line ≠ page - It is preferable to use it in combination with Capsy.The amount of the coupler of the present invention to be used (the ratio of the coupler of the present invention/ordinary photographic color coupler) is preferably from 5 to 00/0, 1O/100/0.
-60/4t0 is more preferable. ” he corrected.

Claims (1)

Claims: A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support and containing at least one coupler represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A represents a coupler residue that cleaves with X by reacting with the oxidized form of the developing agent, X represents an oxygen atom or a sulfur atom, and Y represents an aliphatic group. , 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, aliphatic or aromatic acylamino group, aliphatic or aromatic oxycarbonylamino group,
Represents a substituted or unsubstituted ureido group, substituted or unsubstituted carbamoyloxy group, halogen atom, cyano group, formyl group or nitro group, n represents 1 or 2, and when n is 2, Y may be the same or different. Good too. ]