JPS60218646A - Silver halide color photographic material - Google Patents

Abstract

PURPOSE:To elevate a color picture density and improve the sharpness of a picture image by using a polymer coupler consisting of a dye-forming monomer unit and a monomer unit contg. a sulfonic acid group. CONSTITUTION:The polymer coupler consisting of monomer units capable of forming a dye by coupling with an oxidized body of a developing agent comprising an aromatic amine, and monomer units having sulfinic acid groups, as constituting components, is incorporated in an emulsion layer of a photosensitive silver halide. The monomer unit having an sulfinic acid group is exemplified by the formula wherein R is H, or 1-6C alkyl; L is a divalent jointing group having 1-20 carbon atoms; Y is a sulfinic acid group or a salt thereof; r is 0 or 1.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention is directed to the production of a silver halide compound containing an aromatic-grade amine drug acid (?), a novel polymeric cassillator which forms a dye by physical coupling. It relates to color photographic materials.

(Background technology) Silver halide color photography m. In the field of m-materials, oxidized aromatic compounds are produced by color development after exposure.
It was well known that amine developers and couplers are inversely oxidized aromatic-grade amine developers to give dye images.

reacts with a coupler to give indophenol, indoaniline, inda, amine, azomethine, phenol, phenazine, and similar dyes, and a dye image is formed. In this method, subtractive color method is usually used, blue, green.

A silver halide emulsion selectively sensitive to red and dye image forming agents of yellow, magenta, and cyan, which are related to each other as residual colors, are used.

As the yellow dye image forming agent, for example, acylacetanilide or benzylmethane coupler is used, and as the 1 zenta dye image forming agent, for example, Virazone is used. Pyrazolobenzimidazole, cyanoacetophenone, or indacylon couplers are used, and as the cyan dye image forming agent, for example, phenol or naphthol couplers are used.

By the way, in multilayer color photographic materials, in order to reduce color mixture and improve color reproducibility, it is necessary to fix each coupler in a separate layer, and to make the coupler resistant to diffusion. , many methods are known.

One method is to introduce a long chain aliphatic group into the coupler molecule to prevent diffusion.

Couplers produced by this method are immiscible with gelatin aqueous solutions, so it is necessary to solubilize them in an alkali and add them to the gelatin aqueous solution, or to dissolve them in a high boiling point organic solvent and emulsify and disperse them in the gelatin aqueous solution for coating. It is.

However, in this method, coupler crystals tend to precipitate in the emulsion layer, and when a high-boiling organic solvent is used, a large amount of gelatin is required to soften the emulsion layer, resulting in a decrease in the quality of the dye image. There was a problem in that sharpness deteriorated.

Another method of making couplers diffusion resistant is to polymerize them. “The
Theory of the Photo, rap
hicProcess J 4! th Ed,,/ri7
7゜Macmillan, New York, 34
! The hydrophilic polymer coupler described on page 7 does not have sufficient diffusion resistance, tends to cause color mixing, and in even worse cases has the problem of leakage during development. For this solution, U.S. Patent No. 07,1
0ri No., same ll co/j, /ri No. 5.

Dohiro, Hirokol,? LJ issue, Tokukai Sho 1! -27132,
same! t-2F? A polymer cassillator having a phenolic hydroxyl group or an active methylene group as described in No. 4I has been proposed, but this type of polymer has insufficient color development and the density of the resulting dye image is low. Another problem is that the resulting dye image does not have sufficient stability against light, temperature, humidity, etc.

(Object of the Invention) Therefore, an object of the present invention is to provide a color photographic material in which the density of a dye image obtained by development processing is sufficiently high and the sharpness thereof is excellent.

Another object of the present invention is to provide a color photographic material in which a dye image obtained by development is stable against light, temperature, humidity, etc. for a long period of time.

(Structure of the Invention) The object of the present invention is to have a monomer unit capable of forming a dye by coupling with an oxidized product of an aromatic-grade amine developer and a seven-unit monomer unit having a sulfinic acid group as constituent components. This was achieved by a color photographic material characterized by containing a polymer cassillary in a silver halide emulsion layer.

A preferred example of the monomer unit capable of forming a dye by coupling with the oxidized product of an aromatic-grade amine developer used in the present invention is represented by the general formula (A).

General formula (A) 几■ [In the general formula (A), 几 represents a hydrogen atom or an alkyl group having /~ carbon atoms. Y represents 几 -co, -, or 10, 0N- (where 几 represents a member selected from the same group as mentioned above). A
is an alkylene group having /, /2 carbon atoms.

Or represents an arylene group. X is 10-1 liters Yomogi -Co-, -CO-, -802-, -CON-.

し几 represents something selected from the same group as mentioned above. Q is cyan, magenta, or
It is a yellow dye-forming coupler residue (however, the bond with X is other than the 1st position of the coupling link). m and n are each 0 or /.

Preferred structures will be explained below.几 is a hydrogen atom,
or carbon number/, 1 alkyl group 1 e.g. methyl group,
Ethyl group, n-propyl group, is.

-zolopyl group, n-butyl group, tert-butyl group, l
5o-dityl group, 5ee-butyl group, tn-amyl group, t
It represents an ert-amyl group, an n-hexyl group, etc., and a hydrogen atom, a methyl group, and an ethyl group are particularly preferred.

几Y is 100□-9 or 100N- (however, 几 represents an item selected from the same group as mentioned above).

For example -eONfl-, -CON-, -C(JN-.

etc., -Co2-, -CONt(+, -CON
−.

A is an alkylene group having 7-t carbon atoms, such as a methylene group, an ethylene group, a methylmethylene group, a dimethylmethylene group, a trimethylene group, or a tetramethylene group. Pentamethylene group, hexamethylene group.

Octamethylene group, decamethylene group, arylene group Examples include O-phenylene group, m-phenylene group.

Represents p-phenylene group, naphthylene group, etc.

In addition, some of the hydrogen atoms of the algylene group or arylene group represented by A are aryl groups (e.g., phenyl group, tolyl group, etc.), nitro group, hydroxyl group, cyano group, alkoxy group (e.g., methoxy group, etc.), aryloxy group. (e.g. phenoxy group), acyloxy group (e.g. acetoxy group), acylamino group (e.g. acetylamino group), sulfonamide group (e.g. methanesulfonamide group), sulfamoyl group (e.g. methylsulfamoyl group), carboxyl group, carbamoyl group (e.g., methylcarbamoyl group), alkoxycarbonyl group (e.g., methoxycarbonyl group), sulfonyl group (e.g., methylsulfonyl group), halogen atom (e.g., fluorine, chlorine, bromine atom, etc.). .

For humans, methylene group, ethylene group, methylmethylene group, dimethylmethylene group, trimethylene group, tetramethylene group, pentamethylene group, m-phenylene group, p-phenylene group, etc. are preferred.

X is -0-, -CO-, -CO+, -so□-9, etc.)
It represents -o+, -〇〇+, -CO2-, etc.

-802-, -CONH+, -Nf(CONH+.

-NHCO□- and the like are particularly preferred.

Q represents a coupler residue capable of forming a dye by coupling with an aromatic-grade amine developer, and as a cyan dye-forming coupler residue, a phenol type expressed by Ll general formula (1), or a phenol type represented by general formula (II) The naphthol type represented by is preferred. Below, the marks indicate the bonding positions with crab.

General formula (1), General formula (II) [General formula (1), (u) K-ite, R1#'i alkyl group, alkenyl group, alkoxy group, alkoxycarbonyl group, halogen atom, alkoxycarbamoyl group, aliphatic It represents an amide group, an alkylsulfamoyl group, an alkylsulfonamide group, an alkylureido group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamide group, or an arylfreido group. p represents an integer from O to J, and q represents an integer from O to Hiro.

zl is a hydrogen atom, a halogen atom, a sulfo group, an acyloxy group, an alkoxy group, or an aryloxy group.

It represents a heterocyclic oxy group, an alkylthio group, an arylthio group, or a heterocyclic thio group, and these groups may be substituted. Examples of the substituent include an aryl group (for example, a phenyl group), a nitro group, and a hydroxyl group.

Cyano group, sulfo group, alkoxy group (eg methoxy group), aryloxy group (eg phenoxy group), acyloxy group (eg acetoxy group).

Acylamino group (e.g. acetylamino group), alkylsulfonamide group (e.g. methanesulfonamide group),
Alkylsulfamoyl groups (e.g. methylsulfamoyl group), halogen atoms (e.g. fluorine, chlorine, bromine, etc.), carboxy groups, alkylcarbamoyl groups (e.g. methylcarbamoyl group), alkoxycarbonyl groups (e.g. methoxycarbonyl group, etc.), Alkylsulfonyl group (e.g. evamethylsulfonyl group, etc.), alkylthio group (
For example, β-carboxyethylthio group, etc.). When there are λ or more substituents, they may be the same or different.

The magenta dye-forming coupler residue has the general formula ([1
) to (X), pyrazolone type, pyrazolotriazole type, and imidazopyrazole type are preferred.

General formula (1) General formula (IV) 2 General formula (■) 2 2 General formula (IK) General formula (X) General 2〇a) General formula (kari) 2 Tatami general formula (X[[[) General formula 0GV) In the ceremony, 几2 is Kopishizorin! Substituents of known types in the 7-position of the -on coupler, such as alkyl groups, substituted alkyl groups (e.g. haloalkyl such as fluoroalkyl,
cyanoalkyl, benzylalkyl, etc.), aryl group, #-substituted aryl group [Substituents include alkyl group (eg, methyl group).

ethyl group, etc.), alkoxy group (e.g., methoxy group, ethoxy group, etc.), aryloxy group (e.g., phenyloxy group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group), acylamino group (e.g., acetylamino group), carbamoyl group. group, an alkylcarbamoyl group (eg, methylcarbamoyl group, ethylcarbonyl group).

Dialkylcarbamoyl group (e.g. dimethylcarbamoyl group), arylcarbamoyl group (e.g. phenylcarbamoyl group), alkylsulfonyl group (e.g. methylsulfonyl group), arylsulfonyl group 11. ttf phenylsulfonyl group), alkylsulfonamide group (eg methanesulfonamide group), arylsulfonamide group (eg phenylsulfonamide group), sulfamoyl group.

Alkylsulfamoyl group (e.g. ethylsulfamoyl group), dialkylsulfamoyl group (e.g. dimethylsulfamoyl group), alkylthio group (e.g. methylthio group), arylthio group (e.g. phenylthio group), cyano group, nitro group, Examples include halogen atoms (for example, fluorine, chlorine, bromine, etc.), and when there are co or more substituents, they may be the same or different.

Particularly preferred substituents include a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, and a cyano group. ] represents 1R3, R4, R5, R6, 71"81,.

R101, and 2 are each a hydrogen atom.

1 In addition to the hydroxyl group, each unsubstituted or substituted alkyl group (preferably one having a carbon number of 1-0).

For example, methyl group, propyl group, t-butyl group.

trifluoromethyl group, tridecyl group, etc.), teryl group (preferably one with t-20 carbon atoms, e.g., phenyl group, ≠-t-i tylphenyl group + 'ta-di-t-amylphenyl group) , l-methoxyphenyl group, etc.), heterocyclic group (e.g., cofuryl group).

cochenyl group, 2-pyrimidinyl group, 2-he7zothiazolyl group, etc.), alkylamino group (preferably one with carbon number/-20; for example, methylamino group, diethylamino group, t-butyl'rmino group, etc.) .

Acylamino group (preferably one with a carbon number of λ to -0, e.g., acetylamino group, propylamide group, benzamide group, etc.), anilino group (e.g., phenylamino group, cochloroanilino group, etc.), alkoxycarbonyl group (preferably is one having a carbon number of - to co0 (for example, a methoxycarbonyl group, a butoxycarbonyl group, a coethylhexyloxycarbonyl group, etc.), an alkylcarbonyl group (preferably one having a carbon number of λ to co0; for example, an acetyl group).

dithylcarbonyl group, cyclohexylcarbonyl group, etc.)
, arylcarbonyl group (e.g., preferably carbon number 7
~Co0 things. Benzoyl group, 4! -1-butylbenzoyl group, etc.), alkylthio groups (preferably those having 1-0 carbon atoms, such as methylthio group, octylthio group, cophenoxyethylthio group, etc.), arylthio groups (preferably those having 6 to 0 carbon atoms), For example, phenylthio group,
-2-boudo #5t-s-t-octylphenylthio group, etc.).

Carbamoyl group (preferably one having 1 to 20 carbon atoms; for example, N-ethylcarbamoyl group, N,N-dibutylcarbamoyl group, N-methyl-N-butylcarbamoyl group, etc.), sulfamoyl group (preferably one having 1 to 20 carbon atoms) For example, N-ethylsulfmoyl group, N,N-diethylsulfamoyl group, N,N-dipropylsulfamoyl group, etc.) or sulfonamide group (preferably one having 1 to 0 carbon atoms). For example, methanesulfonamide group.

(benzenesulfonamide group, p-toluenesulfonamide group, etc.).

Z2 is a hydrogen atom, a halogen atom, or an oxygen atom.

It represents a leaving group bonded to the coupling position with a nitrogen or sulfur atom, and when z2 is bonded to the coupling position with an oxygen, nitrogen, or sulfur atom, these atoms are an alkyl group, an aryl group, an alkyl group, etc. It is bonded to a sulfonyl group, arylsulfonyl group, alkylcarbonyl group, arylcarbonyl group, or a heterocyclic residue. Furthermore, when a nitrogen atom is bonded to the coupling position, it contains the nitrogen atom and forms a j- or l-membered ring (for example, an imidazolyl group, a pyrazolyl group, a triazolyl group).

(such as a tetrazolyl group).

The yellow dye-forming coupler residue has the general formula (XV
) Acylacetanilide type.

Alternatively, benzoylacetanilide compounds represented by the general formulas 0(■) and (Xllllll) are preferred.

General formula (XV) 14 General formula (XVI) General formula (X■) In the formula, R, 几, R05 and R□6 are each hydrogen atom or a well-known substituent of the yellow color-forming coupler residue, such as an alkyl group. , an alkenyl group.

Alkoxy group, alkoxycarbonyl group, halogen Jl
Carpamoyl group, aliphatic amide group, alkylsulfamoyl group, alkylsulfonamide group, alkylureido group, alkyl-substituted succinimide group, aryloxy group, aryloxycarbonyl group, arylcarbamoyl group.

Arylamide group, arylsulfamoyl group.

Arylsulfonamide group, aryl freido group.

Carboxy group, sulfo group, nitro group, cyano group.

It represents a thiocyano group, etc., and these substituents may be the same or different.

Z3 is a hydrogen atom or the following general formula 〇M), (XK).

Represents a group represented by (n) or (XXI).

■0几17'X■) 几 and 4 represent an optionally substituted aryl group or heterocyclic group.

R08, 几0. are hydrogen atoms and halogen atoms, respectively.

Carboxylic acid ester group, amine group, alkyl group.

Alkylthio group, alkoxy group, alkylsulfonyl group, alkylsulfinyl group, carbonic acid group.

It represents a heterocycle spanning a sulfonic acid group or an unsubstituted or substituted phenyl group, and these groups may be the same or different.

Represents a nonmetallic atom required to form a membered ring or a t-membered ring.

Among the general formula (XXI), preferably (XXII) ~
(XXIV).

In the formula L24, R24 and R24 each represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a hydroxy group, and R21 and R22 each represent a hydrogen atom, an alkyl group, or an aryl group.

W2 represents an aralkyl group or an acyl group; W2 represents an oxygen atom; and W2 represents a sulfur atom.

Preferred specific examples of the monomer unit represented by general formula (1) of the present invention are shown below.

Monomer units that form cyan dye H α Cl-13 CL(3 (-CH2-C+ exposure OH OH3 place OH3 CH.

Monomer unit forming magenta dye H3 匡CH2CH20N (-OH2-C-← C) 120F3 +CH2-C-← α CH3 802CE (3 +CH2-c÷ ko+CH2-CH← CH3 α (-OH2-CH→ CH3 ÷0H2 -C-← ■ α CH3 (-OH2-C-)-・ (-C)12-CH-+- α CH3 +CH2-C→ ■ +C(1□-CH) 1 (-OH2-CH+ (-CH2- C→ α +CH2-CH+ CH3 1 (-CH2-C-masu(-CH2-C→ ■ α Monomer unit forming yellow dye +C*42-C→ (-CH, -CH-← ÷CH2-C-+ ■ CH3 + cti ).

General formula (XXV) +C)I 2-C (L).

[In the general formula (XXV), R represents one selected from the group defined in the general formula (1).

L represents a divalent linking group having 1,20 carbon atoms. Y represents a sulfinic acid group or a sulfinic acid group forming a salt. r is 0 or l. ] In the monomer unit represented by the general formula (XXV), R is particularly preferably a hydrogen atom, a methyl group, or an ethyl group.

L is a divalent linking group having /-20 carbon atoms, such as an alkylene group (e.g. methylene group, ethylene group, trimethylene group, hexamethylene group, etc.) + phenylene group (
For example, 0-phenylene group.

p-phenylene (JLm-phenylene group nato), ri-ren alkylene group C example u-J' 几-5 几25 represents an alkylene group having /-/co carbon atoms. )
, -CO-, -Co□-几26- (provided that R26t represents an alkylene group, phenylene group, or arylene alkylene group), -CONH-几26- (however, R26 represents the same as above).

几-CO-N-几26- (However, 几 and 几26 represent the same as above), Cfl□- CH- -CONF (CHCH=CEICH, - etc. are particularly preferred; Y is sulfine; Represents a sulfinic acid group forming an acid group or a salt.The cationic acid group forming the sulfinic acid group is preferably a monovalent to trivalent one, and when it has a covalence or more, the paired anion is represented by the general formula (XXV). Other anions may be used in addition to the seven units represented by the formula. Preferred cations include ammonium ions and metal ions, with alkali metal ions (eg, sodium ions and potassium ions) being particularly preferred.

Preferred specific examples of the monomer unit represented by general formula (XXV) are shown below.

Preferred polymers used in the present invention include a monomer unit represented by the general formula (1) capable of forming a dye by coupling with an oxidized product of an aromatic-grade amine developer, and a monomer unit represented by the general formula (XXV). , may contain one seven-piece unit other than one seven-piece unit having a sulfinic acid group.

Preferred examples of this seven-unit unit include ethylene, propylene, l-zotene, l-vinylimidazole, and styrene.
monoethylenically unsaturated esters of aliphatic acids (e.g. vinyl acetate, allyl acetate, etc.).

), monoethylenically unsaturated amides of aliphatic acids (e.g. N
- Hinylacetamide, N-vinylpyrrolidone, etc. )
, ethylenically unsaturated monocarboxylic or dicarboxylic acid esters (e.g. methyl acrylate) + ethyl acrylate, hydroxyethyl acrylate, methyl methacrylate, n-butyl methacrylate, benzyl acrylate, 2-ethylhexyl acrylate, cyclohexyl methacrylate, furfuryl acrylate, Diethyl maleate, diethyl itaconate, etc. ).

Ethylenically unsaturated monocarboxylic acid amides (e.g. acrylamide, dimethylacrylamide, methacrylamide, diacetone acrylamide, acryloylmorpholine, acrylamide-co-methylpropane sulfonate, methacryloylmorpholine, etc.) Monoethylenically unsaturated compounds - (e.g. acrylonitrile), or dienes (e.g. zotadier, isozoley, etc.)
Among these, those with high hydrophilicity are particularly preferred.

The polymer cassillator of the present invention preferably contains 20 to 1% of monomer units capable of forming a dye by coupling with an oxidized product of an aromatic-grade amine developer, particularly 30 to 0w1%. A range of is preferred. Furthermore, the monomer unit having a sulfinic acid group is λ~, tOvy
Preferably, it contains about ttlj, especially
AOw is preferably in the range of 1%. The content of monomer units other than those mentioned above is preferably 70 wt% or less.

The molecular weight of the polymer cassiller of the present invention is 5xio3 to 1x
IO is preferred. If the molecular weight is too small, the polymer will not move easily, and if the molecular weight is too large, it may cause problems in coating. Preferably 1xio' to λx
It is io.

Preferred specific examples of the polymer cassiller used in the present invention are shown below.

MP-z MP-4 S02 Suni Shadow The monomer capable of forming a dye by coupling with the oxidized product of an aromatic-grade amine developer, which is used in the synthesis of the polymer cassillator of the present invention, is disclosed in Japanese Patent Application Laid-open No. Sho SS-Co. 5ost issue, same s
s-kota troz, same jj-42 guyogu, same jj-
It is synthesized according to the method described in No./102≠3.

Synthesis Example 1 Poly[co'-((/-hydroxy-conaphthoylamino)ethyl]acrylanilidocovinylbenzenesulfine 1nlJ-2-acrylamide λ-methylzolo/sodium honeysulfonate) (CP-4
Synthesis of A) In a reaction vessel of 3oojW/, co'-((/-hydroxy-conaphthoylamino)ethylcoacrylanilide/I1.Of, vinylbenzenesulfinic acid force') 7
-' f
, /, thoroughly degassed with nitrogen gas, and then heated to 0c.

λ'-azobisisobutyronitrile 0. /7jrf was added and heating continued for an hour. After cooling the reaction sample to room temperature,
The precipitate was added to 400 ml of acetone, and the precipitate was collected by filtration and dried under vacuum to obtain a J/, tf polymer. (
Yield t) Synthesis Example 2 Poly(/-(co,j-dichlorophenyl)-
Synthesis of 3-methacryloylamino)-copyrazolin-j-one-covinylbenzenesulfinic acid currycoacrylamidocomethylzolononosulfonate/sodium acid) (MP-/) In a 300xl reaction vessel, /-
(co,j-dichlorophenyl)-3-methacryloylami/-J-pyrazolin-j-one10. jf, vinylbenzenesulfinic acid potassium A, Of, coacrylamidocomethylpronognesulfonic acid/J, jf.

D M F A Omls Methanol AOmtXjN Sodium hydroxide aqueous solution/$, 1 was added, thoroughly degassed with nitrogen gas, heated to t00CK, and 0.1! f was added and heating was continued for an hour. After cooling the reaction sample to room temperature, it was added to 100 ml of acetone, the precipitate was collected by filtration, and dried under vacuum.
．． % of polymer of jf.

(Yield HiroPti) Synthesis Example 3 Poly(l-(λ, Hiro, 6-drichlorophenyl)-1-(Cauchloro J-7-Rylamidebenzamide)-Copyrazolin-5-one-Covinylbenzenesulfinic acid Kariko 2-acrylamide-2-
Synthesis of Sodium Methylpropanesulfonate) (MP-7)/-(Co, G, Mono-Trichlorophenyl)-3-(-1 Chloro-3-Acrylamide Be/Zuamide)-1-1 Birazoli/-! Synthesis was carried out in the same manner as in Synthesis Example 2 using -one. (Yield s3) Synthesis Example 4 Poly(p/-chloro-3'-(α-(≠-
Synthesis of methoxycarbonylphenoxy)-α-piparoylacetamide] acrylanilide-co-vinylbenzenesulfinic acid curry-co-acrylamide-co-methylzorono-resistant sodium sulfonate) (YP-J) In a 300-proof reaction vessel, μ'-chloro3 ′-(n r
a J yas, so+n-d -s--yw 1xz
t % -α-piparoylacetamide] acrylanilide to, zt, vinylbenzenesulfinic acid potassium 6° Ofl 2-acrylamide co-methylzolonone sulfonic acid/J, j f % D MF 40 m
l % methanol 40 ml/, j N sodium hydroxide aqueous Blunt was added, thoroughly degassed with nitrogen gas, heated to 60 °C, λ, 2'-azobisisozotyronitrile O0/11 was added, Continue heating for an hour. After cooling the reaction sample to room temperature, it was added to 600 ml of acetone, the precipitate was collected by filtration, and dried under vacuum. 7.21
of polymer was obtained. (Yield SS%) Two or more kinds of the BoIJ-r-coupler of the present invention can be contained in the same layer. Furthermore, the same polymer coupler may be contained in four or more different layers.

In order to introduce the polymer Cassiller of the present invention into the silver halide emulsion layer, if it is water-soluble, it can be added to the silver halide emulsion as an aqueous solution, or if it is water-insoluble, it can be dispersed in a hydrophilic colloid to the silver halide emulsion. In addition to this, this can be achieved by applying it.

The amount of the polymer coupler of the present invention to be used is preferably 0.001 mol or less, particularly in the range of o, or mol to o, oooi mol, based on 1 mol of #I in terms of a portion of the coupler.

The silver halide color photographic light-sensitive material of the present invention can be applied not only to monochrome color photographs but also to multilayer natural color photographs.

Examples include color negative film, color reversal film, color positive film, color photographic paper, color reversal photographic paper, and the like.

The silver halide color photographic light-sensitive material using the present invention includes:
One or more known gelatin hardening agents may be used. Examples of such known curing agents include:
Aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclobentanedione, bis(cochloroethylurea), -
Monohydroxyda, t-dichloro-/,! , j-) Reazine, et al., U.S. Pat. Compounds containing reactive halogens described in JO No. 7 etc., divinyl sulfone, j-acetyl-7,3-diacryloylhexahydro-t,s,
z-t IJ Asin, et al. U.S. Patent No. J, tJ1.7
No. 1I, 3°-3, No. 7/3, British Patent No. 2,
r4ri issue.

Compounds with reactive olefins such as those described in U.S. Pat. Methylol compounds, incyanates described in U.S. Patent No. J, 103.4 (37, etc.); Aziridine compounds, U.S. Patent No. 2.7, 221, 2.71
j, acid derivatives described in Kota J, etc., carbodiimide compounds described in U.S. Pat. Epoxy compounds, US Patent No. 3
．． 3 Co/, No. 313, J, Jt Reference 3゜ Cotaco, inoxazole compounds, halogenocarmexaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane, dichlorodioxane, JP-A Akira! Dihydroxyquinoline compounds described in No. o-3rsao, JP-A-Sho! I-//Compound having a phosphorus-halogen bond described in JPJP, JP-A-Shoj, 2-93
N-sulfonyloxyimide compounds described in 'fi70, N-acyloxyimino compounds described in Japanese Patent Publication No. 1983-220119, JP-A-417. -44N-carbonyloxyimide compound described in No. 44JJjJ, JP-A-74
Cosulfonyloxypyridinium salts described in JP-A-110742, JP-A-Sho≠2-jl Risan j and JP-A-J/-1
Examples include N-carpamoylpyridinium salts described in No. 942j. Examples of inorganic compound hardeners include chromium moepan and zirconium sulfate. In addition, instead of the above compounds, compounds in the form of precursors, such as alkali metal bisulfite aldehyde adducts, methylol derivatives of hydantoin, primary aliphatic ditroalcohols, mesyloxyethylsulfonyl compounds, chloro It may be used in combination with ethylsulfonyl compounds and the like.

As the curing agent used in the silver halide color photographic light-sensitive material of the present invention, vinylsulfonyl compounds are particularly preferred.

A compound that accelerates the hardening of gelatin can also be used in combination with these gelatin hardening agents.

Such curing accelerators include West German patent (published),
u/7. Non-zotetratonic solvent described in JTT issue, JP-A-1973
Betaine type surfactants, tertiary amines or salts thereof (e.g., JP-A No. 4-104A
J issue, same! Norta No. 11, West German patent (published) 2. IJt
, No. 301, British Patent No. 1. 6), various inorganic salts, polyhydric alcohols, etc.

In the manufacturing process, the gelatin used in the silver halide color photographic material of the present invention is
So-called alkaline-treated (lime-treated) gelatin that is soaked in an alkaline bath, acid-treated gelatin that is soaked in an acid bath, and double-soaked gelatin that has undergone both treatments, or [Bu
ll, 8oc.

Sci, Photo, Japan JA/4
Any enzyme-treated gelatin such as that described in J0, page 1 (lfAA) may be used. The compound of the present invention can also be applied to low molecular weight gelatin which has been partially hydrolyzed by heating the gelatin in a water bath or by treating it with a proteolytic enzyme.

Gelatin to which the compound of the present invention is applied may optionally contain colloidal albumin, casein, cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, sugar derivatives such as agar, sodium alginate, and starch derivatives, and synthetic hydrophilic colloids. For example, it can be changed to 1N@ with polyvinyl alcohol, bo17 N-vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide, or derivatives/partial hydrolysates thereof, etc. In addition, it can be converted to 1N@ with so-called gelatin conductor, that is, with a buffer in the molecule. amino groups, imino groups, hydroxyl groups, and carboxyl groups as functional groups treated and modified with a reagent that has one group that can react with them, or bonded with molecular chains of other polymeric substances. A graft polymer may be used instead.

Reagents for making the above derivatives include, for example, isocyanates, acid chlorides, acid anhydrides, as described in U.S. Pat.
r, acid anhydrides listed in 'ytt issue, Special Publication Showa 3
Bromoacetic acids shown in No. 9-11/≠, Special Publication No. 44.
Phenylglycidyl ethers described in No. 2-2 trus, U.S. Patent No. 3.13, vinyl sulfone compounds described in Tag No. 3, British Patent No. 1t/
, al≠, N-allyl vinyl sulfonamides described in U.S. Patent No. 3. /It, maleimide compounds described in No. 44A, US% fraud, jri≠,
Acrylonitrile as shown in Coco No. 5', polyalkylene oxides as described in US Pat. U.S. Patent No. 743.
Esters of acids such as those shown in British Patent No. I, o33. Examples include alkanesultones described in No. i (R).

In addition, the nucleus crystal molecules grafted onto gelatin are disclosed in U.S. Patent No.
2,74J, 4.2/No., same, 13), 7 East t7,
Same co, rijt, tt≠ issue or Polymer L
etters, j,! Ris(iri47), Photo
, 8ci, Eng, , 1111 (/941),
J, Polymer 8ci, a A-/,
There are many descriptions in ri, 31ri 9 (lri 7/), etc.
Acrylic acid, methacrylic acid or derivatives thereof such as esters, amides, and nitriles, and polymers or copolymers of styrene and other compounds commonly called vinyl heptamers can be used in a wide range of ways. However, hydrophilic vinyl polymers that are moderately compatible with gelatin, such as polymers or copolymers of acrylic acid, acrylamide, methacrylamide, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, are particularly desirable.

In the photographic emulsion 1- and other layers of the photographic light-sensitive material of the present invention, synthetic polymers other than those mentioned above, such as latex-like water-dispersed vinyl compound polymers, especially compounds that increase the speed stability of the photographic material may be used. etc. may be included alone or in combination, or in combination with a hydrophilic water-permeable colloid.

The photographic material of the present invention may contain a matting agent. The matting agent is preferably a water-insoluble fine particle of an organic or inorganic compound with an average diameter of from 0.0μ to ioμ, particularly preferably from 0.3μ to jμ.

The compounds of this invention are present in the blue-sensitive emulsion layer in the case of yellow dye-forming polymer couplers, in the green-sensitive emulsion layer in the case of magenta dye-forming polymer couplers, and in the red-sensitive emulsion layer in the case of cyan dye-forming polymer couplers. Usually, they are added to the same amount, but different combinations may be used depending on the case. The same applies when a dye-forming coupler other than the compound of the present invention is used in combination. Couplers other than those of the present invention when used in combination include polymer cassillars not containing monomer units represented by the general formula (XXV), and those represented by the general formulas (1) to Q The moiety includes a coupler to which a group selected from the group defined in general formula (1) is bonded.

These couplers may be either g-equivalent or di-equivalent to silver ions. It may also be a colored coupler that has a color correction effect or a 11% DIR cazoler that releases a development inhibitor during development.

In addition to DI couplers, there are also colorless DI couplers in which the product of the coupling reaction is colorless and releases a development inhibitor.
It may also contain an R coupling compound. In addition to DIR couplers, compounds that release a development inhibitor during development may also be used.

In the present invention, to introduce a coupler other than the polymeric cassillary into the silver halide emulsion, known methods such as those described in US Pat. No. 83,027 can be used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (such as acetyl tributyl citrate), Benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (e.g. tributyl trimesate), etc.
or an organic solvent with a boiling point of 30°C to /jO°C, such as lower alkyl acetate such as ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate,
After being dissolved in methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid.

The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination.

Also, Tokko Akira! It is also possible to use the dispersion method using a polymer as described in Japanese Patent Application Laid-open No. 113-113 and JP-A-5I-J Tata San No. 3.

When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

Examples include gelatin conductors, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carbodimethyl cellulose, cellulose sulfate esters, sodium alginate, starch derivatives, etc. Sugar-induced
Conductor: Various types of synthetic hydrophilic materials such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, boria chloramide, polyvinylimidazole, polyvinyl pyrazole, etc. There is a polymeric substance. Silver halide used in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, or silver chloride. It's okay.

The average grain size of the silver halide grains in a photographic emulsion (grain diameter for spherical or near-spherical grains).

In the case of cubic particles, the edge length is used as the particle size, and the projected area is also expressed as an average. ) is not particularly limited, but it is preferably 3μ or more.

The particle size distribution may be narrow or wide.

The silver halide grains in the photographic emulsion may have regular crystal bodies such as ', cubic, or hexagonal, or may have irregular crystal bodies such as spherical or plate-shaped, or may have irregular crystal bodies such as spherical or plate-shaped. It may be a composite form of the crystal form. It may also consist of a mixture of particles of various crystalline forms.

Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of three times or more the grain thickness occupy at least jO- of the total projected area.

The silver halide grains may have different phases inside and on the surface. Further, the particles may be particles in which a latent image is mainly formed on the surface, or may be particles in which a latent image is mainly formed inside the particles.

The photographic emulsion used in the present invention is P, Glafkide.
Written by Chimie at Physique Photo
ographique (published by Paul Monte1,
7267), G, F.

Photographic Emulsi by Dufme n
onChemistry (The Focal Pr.
ess, 1946), V, L, Zelikman
Making and Coa. et al.
Photographic Emulsion (The
It can be adjusted using the method described in Focal Press, Vol. 44C). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good.

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

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

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

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

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

After forming a precipitate or physically ripening the emulsion, soluble salts are usually removed; methods for this purpose include the long-known Tardel water washing method, which involves gelling gelatin; Good too.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example, H. Frleser ed.”
Die Grundlagender Photogr
aphischenprozesse mit 8i1
berhalogenjden” (Akademisc
be Ver l agsgese 1lshaft
.

/941) The method described on pages A7s to 73 can be used.

That is, a sulfur sensitization method using a sulfur-containing compound capable of reacting with active gelatin or silver, a reduction sensitization method using a reducing substance, a noble metal sensitization method using a noble metal compound, etc. can be used alone or in combination.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing the photographic property ki3.

That is, many compounds known as antifoggants or stabilizers can be added, such as azoles, mercaptopyrimidines, mercaptotriazines, thimecarbonyl compounds, azaindenes, thiosulfonic acids, sulfinic acids, sulfonamides, etc. .

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced using the present invention contains coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast). Various surfactants may be included for various purposes such as oxidation, sensitization, etc.

For example, nonionic surfactants such as saponins (steroids), alkylene oxide derivatives, glycide derivatives, polyhydric alcohol fatty acid esters, sugar alkyl esters, acidic groups such as carboxyl groups and sulfo groups, etc. Anionic surfactants containing anionic surfactants, amphoteric surfactants such as aminoalkylsulfonic acids and alkyl betaines, and cationic surfactants such as alkylamine salts and quaternary ammonium salts can be used.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary Ammonium salt compound, urethane haze conductor,
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. For example, the monomer component is alkyl (meth)acrylate, (meth)acrylamide, styrene, etc. alone or in combination, or a combination of these with (meth)acrylic acid, hydroxyalkyl (meth)acrylate, styrene sulfonic acid, etc. Polymers can be used.

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 hemioxynol 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. That is, pyrroline nucleus, oxazinone nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus,
Pyridine nuclei, etc.; Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei; Applicable examples include a neutral nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, and a quinoline nucleus. These nuclei may be substituted on 4 carbon atoms.

Pyrazoline-! as a core having an L ketomethylene structure in merocyanine dyes or composite merocyanine dyes. -one nucleus, thiohydantoin nucleus, 2-thioxazolidine-2
, dione nucleus, theazolidine nucleus, dione nucleus, rhodanine nucleus, thio/(rubituric acid nucleus, etc.)
Heterotic ring nuclei can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

A sensitizing dye and (4) 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.
, 7coI), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 74AJ, J10), cadmium salts, azaindene compounds, and the like.

In the photosensitive material produced using the present invention, when the hydrophilic colloid layer contains dyes, ultraviolet absorbers, etc.
They may be mordanted, such as by cationic polymers.

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

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (e.g.
tertiazolidone compounds (e.g., those described in U.S. Pat.
,3! Ko.

bri), benzophenone compounds (e.g., those described in JP-A-414-Core I4!), cinnamate ester compounds (e.g., U.S. Pat. No. 3,701.101)
Same issue! 707.37jt), butadiene compounds (e.g., U.S. Pat. No. 707.37jt);

No. 0471.2 Kota No. 4), or benzoxidol compounds (e.g., U.S. Pat.
ss) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These ultraviolet absorbers may be mordanted in specific layers.

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

In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known anti-fading agents include hydroquinone sieve conductors (for example, the compounds described in JP-A-1-1-1-3), gallic acid derivatives, p-alkoxyphenols and bisphenols.

Photographic processing of layers comprising photographic emulsions made using the present invention includes, for example, Research Disclosure No. 176 No. 2
Any of the known methods and known treatment liquids as described in Sections 3 to 30 can be applied. The processing temperature is usually chosen between 1lr0C and jooC, but i
The temperature may be lower than t 0c or above zooc.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylene diamines (for example, ≠-
Amino-N, N-diethylaniline, 3-methyl-V-
Amino-N, N-diethylaniline, Amino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-amino-N-ethyl-N-β-hydroyaethylaniline, 3-methyl-≠-amino-N-ethylaniline
-β-methanesulfamide ethylaniline, ≠-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

Other photos by L, F, A, Mason
graphicProcessing Chemises
try (Published by FocalPress, 1996)
Ko J4-λ-ta, U.S. Patent Ko, Iris, OIS No., Same Ko, J Octopus.

36≠, those described in Japanese Patent Application Laid-open No. 4'ff-14'933, etc. may be used.

Color developers may also contain pE such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or antifoggants such as buffers, bromides, iodides, and organic antifoggants. 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, competitive couplers, fogging agents such as sodium boron hydride, auxiliary developers such as l-phenyl-3-pyrazolidone, tackifying agents, polycarboxylic acid chelating agents, antioxidants, and the like 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 (lit)
), cobalt (Ill), chromium (■), and polyvalent metal compounds such as it (it), peracids, quinones, nitron compounds, etc. are used.

For example, ferricyanide, dichromate, organic complex salts of iron(1) or cobalt(If), such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, l.

Aminopolycarboxylic acids such as 3-diamino-2-proAnortetraacetic acid; complex salts of organic acids such as citric acid, tartaric acid, and malic acid; persulfates, permanganates; nitrosophenols, and the like can be used. Among these, potassium ferricyanide, iron ethylenediaminetetraacetate (1)
Sodium and iron(1) ammonium ethylenediaminetetraacetate are particularly useful. Iron ethylenediaminetetraacetate (
lli) Complex salts are useful both in stand-alone bleach solutions and in -bath bleach-fix solutions.

(Example) The present invention will be explained below with specific examples.
The present invention is not limited to these examples in any way.

Example 1 Sample A was prepared by coating each layer having the following composition on a cellulose triacetate film support.

t Silver halide emulsion layer Red-sensitive silver iodobromide emulsion...Silver coating amount /, 2f/m2 Gelatin 1.097m"
Polymer Casilar 0p-2 ・・・・・・・・・・・・ 0.4397m”2 Protective layer gelatin ・・・・・・・・・・・・ /SOf/m2
Hardener 112 l・・・・・・・・・ 0.13
97m2 Samples B to 1 (
It was created.

The obtained sample was wedge-exposed with white light having a color temperature≠100°, and then subjected to the treatment described below, and the density of the resulting color image was measured.

Next, the sample was irradiated with a fluorescent light (20,000 lux) for one day, and the fastness of the color image to light was evaluated from the difference in density of the color image before and after irradiation.

Table 1 shows the maximum densities of samples A to H and the dye residual rates at concentrations i and o.

Hardener H-/CH2=CH-802-CH2-CONH-CH2C)
1 = CH-80, -0H2-CONH-CH2 As is clear from Table 1, the polymeric couplers having sulfinic acid groups of the present invention are disclosed in the US Patent ≠.

≠Compared to the polymer cassillars having active methylene groups described in Koi, Tis, and JP-A No. 11-217, it has a higher maximum density and excellent light fastness (especially magenta dye). There is.

Example 2 A multilayer color photosensitive material was prepared on a cellulose triacetate film support, comprising layers having the composition shown below.

1st layer: antihalation layer black gelatin layer containing colloidal silver 2nd layer: interlayer coupler C-7 and 2. Gelatin layer 3rd M containing an emulsified dispersion of j-di-t-octylhydroquinone = First red-sensitive emulsion silver iodobromide emulsion (silver iodide: j moles qb) Silver coating amount /, 417 m2 Sensitizing dye l φ , 5xio mol/silver 1 mol sensitizing dye 1
/,! ×10 mol/silver 1 mol coupler C-co o,
op mol/silver 1 mol Kacapu C-Jo, 003 mol/silver 1 mol Casolar C-≠ o, ooo 4 mol/silver 7 mol 2nd layer = 2nd red-sensitive emulsion layer Silver iodobromide emulsion (-silver iodide: lO mol ) Silver coating amount /,
717m" Sensitizing dye I JXIO mol/silver 7 mol Sensitizing dye 1 JXIO' mol/silver 1 mol coupler c-2
o,oo 2 mol/silver 7 mol coupler C-jO002 mol/silver 1 mol Casolar C-Jo, 00/ot mol/silver 1 mol J layer: Intermediate layer co,! - Gelatin layer 6th layer containing an emulsified dispersion of di-t-octylhydroginone: First green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; reference mol ts) Silver coating amount 1. -y /-2 Sensitizing dye 11 1X10 '&ni/Silver/Moni sensitizing dye■
Co x 10 mol/silver J mol Polymer Casiler MP-1 0.07 mol/silver 1 mol (coupler equivalent) Coupler C-/0.001-r Nyl/silver/% Coupler C-u o, oo/z Mol/silver/-Tk 7th layer;
First green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide: 1 mol) Silver coating amount i, 3y7m" Sensitizing dye [I JX/17 mol/silver 1 mol sensitizing dye■
1. JXIO'mol/Silver! Molar coupler C-40,0
/7 mol/silver 1 mol Casolar C-7o, oθ 3 mol/silver! Molar coupler C-Reference o, oo θ 3 mol/silver 1 mol Layer: yellow filter layer 0.0. and an emulsified dispersion of t-di-t-octylhydroquinone.

2nd layer: 7th blue-sensitive emulsion layer Monodispersed silver iodobromide emulsion (silver iodide: 6 mol%) Silver coating amount 0
,7f/m2 Coupler C-Reference 〇, 0/j mol/silver 1 mol 10th layer:
2nd blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide: lJ morch) Silver coating amount 0.417 m'' Coupler C-40.0 t mol/silver 1 mol 11th layer: 1st protective layer iodobromide Silver emulsion (silver iodide; 1 mol, average grain size 0.07μ)
) Silver coating amount 0 #f/m" Ultraviolet absorber UV-/gelatin dispersion 1st co-layer: Co-protective layer gelatin dispersion of polymethyl methacrylate particles (average particle size 1.2μ) Each layer contains the above-mentioned In addition to the composition, gelatin hardener H-/, surfactant, gelatin, etc. were added.

Compounds used in Examples Coupler C-/Coupler C-3 (J4(Coupler C-g Coupler C-j Coupler c-7 Coupler cr-r c' Sensitizing dye 1 Sensitizing dye ■ (C)12) 3803H- N(C2H,)3 sensitive dye■ NaS03(CH2)3(OCH2CH2)2UV-/CN x/y=7/J (Jusagi ratio) After imagewise exposure of the obtained sample to white light with a color temperature of uroo ° , development processing was performed.

The development process used here was carried out at 31r0C as described below.

1 Color development・・・・・・・・・・・・3 minutes
! 2 seconds Bleach...... for 3 minutes
0 seconds 3 Water ・Wash... Old... Old... 3 minutes/J seconds 4 Fix......... minutes 30 seconds 5 Water Wash...・・・・・・・・・・・・3 minutes 13 seconds 6 Stable・・・・・・・・・・・・3 minutes/j seconds The processing liquid composition used in each step is as follows. That's right.

Color developer sodium nitrilotriacetate / , Of sodium sulfite μ, oy Sodium carbonate 30 , Of potassium bromide 1. μV Hydronodylamine sulfate tto, oy Ammonia water (t%) Coj, Occ Ethylenediamine-tetraacetic acid sodium iron salt Iio, oy Glacial acetic acid /4c, Occ Add water ll Fixer Sodium tetrapolyline J, Ofsodium sulfite G,oy Ammonium thiosulfate (70%) ) /7j, Occ Sodium bisulfite Il, At Add water /1 Stabilizing liquid formalin 1.0cc Add water /1 In this way, color images with excellent color separation can be obtained even in multilayer color photography systems. did it.

Patent applicant: Fuji Photo Film Co., Ltd. Procedural amendment to the Commissioner of the Japan Patent Office 1, Indication of the case: Showa JP Patent Application No. 747μ 2, Title of invention: Silver halide color photographic light-sensitive material 3, Person making the amendment Relationship with the case Patent applicant name (520) Fuji Photo Film Co., Ltd. 4. Subject of amendment Specification 5. I will submit the details of the amendment, 1111Ff) engraving (no changes to the content).

Procedural amendment book Showa! Director General of the Japan Patent Office on the 3rd, Indication of the case: Japanese Patent Application No. 7414μ of 1939 2, Title of the invention: Silver halide color photographic light-sensitive material 3, Relationship with the person making the amendment: Patent applicant: 4, Subject of amendment The description in column 5 of ``Detailed Description of the Invention j'' of the specification and column ``Detailed Description of Invention'' of the description of contents of the amendment is amended as follows.

(11 page 2 line 77 "Naftol" string "Naphthol" and correct it.

(2) Page 14, line 3 "Ethyl carbonyl" "Ethylcarbamoyl" and correct it.

(3) On the bottom line of page 1 "R eye" chu R47J and correct it.

(4) Line 1 of page No. 1 rR24VcJ rR2itiJ and correct it.

(5) Structure 2 in the center of page μ3 [Cha and correct it.

(6) [Cp −/J, rCp-ko”, rcp-JJ, “C
p-da”, “cp-jJ, rCp-bu”, and rCp
-7J as "Cp-/J,rcp-ko" and "Cp-J", respectively.
J, rCp-4′J, “cp-JJ.

“cp-bu” and “Cp-7J and correct it.

(7) On page 71, after “British Patent No. 44,142,” “Research
Insert "Disclosure, A/7azr".

(8) Page 73, line 3, “vinylsulfonyl compound l tv rc “or its precursor” Of course, insert it.

(9) Insert the following sentence between Hiroyuki and line j on page 73.

[As vinylsulfonyl compounds, for example, Japanese Patent Publication No. 419-13163, U.S. Patent No. 3゜139, Jst
U issue or Research Disclosure, A/7
Examples include those described in ψsr et al. The vinylsulfonyl compound or its precursor preferably has the following general formula (
B) or (C).

General formula (B) (C112=C)l-802噌A General formula (C) (XCH2C)12-8σ FriendIn the above formula, ν represents AJ, a divalent linking group 5c, and
represents a monovalent organic group that can be separated from the compound represented by the general formula (C) as IX) to give the compound represented by the general formula CB).

Examples of A include alkylene, phenylene, etc. When representing alkylene, there is an ether bond in the chain,
It may have an amide bond or the like.

Alkylene and phenylene may have a substituent.

Ati, preferably alkylene, particularly preferably -CH2-1-C)120CH, -1-CH2CH
CH2-1 and -CH2CONH Changju CH2→; NHCOCH2 (niltλ or Jl
l-representation).

xh A halogen atom, an acyloxy group, and a sulfonyloxy group are preferred, and a chlorine atom, an acetoxy group, and a methanesulfonyloxy group are particularly preferred.

Specific examples of preferred gelatin hardeners are shown below, but the invention is not limited thereto.

H-/CHsa=CH-8C)2CHmUCH2-s
o2cH=CH2 2 Insert the following sentence before the 3rd line on page 10.

[In the present invention, gelatin may be lime-treated or
Either one processed using sour grapes is fine. For details on the method of manufacturing gelatin, see The Macromolecular Chemicals of Gelatin, by Arthur Vuis.
Academic Press, Published in 1999) K is listed.

The above-mentioned hydrophilic colloid that can be used aυ page 10 line "Sugar derivative;" "Sugar derivatives," and correct it.

a2 Tari I row "Cp-2"t rcp-2” and correct it.

(Above) Procedural amendment written in 1 month, Showa era] 7E1! 1. Mr. Stomach 'I'J"J Secretary 1. IG's Showa J Patent Application No. 7616 ≠ No. 2
, Title of the invention Relationship to the case of the person filing silver halide color photographic light-sensitive material 3, Supplement 11 Patent applicant 4 - Arrival 4, Subject of amendment ``Detailed description of the invention'' column 5 of the specification , the statement in the "Detailed Description of the Invention" column of the Description of Contents of the Amendment is amended as follows.

(1) No. 1! page/! The structural formula of the row is [R 1+CH2-C+ Correct as (Y), n(A) n-(X) lQJ.

(2) Page 6, line 6 After "-5o2-1" "R 10CO-1-S-1-0CON-1 -NSO2-J Insert.

(3) 1-m2-yohin from the 73rd line to the 1st line on page 73 represents O or l, respectively. " is corrected to "l, n, 2, and l independently represent θ or 11, but m, n, and l are never O at the same time."

Claims (1)

[Claims] A polymer coupler having as constituent components ζ a monomer unit capable of forming a dye by clinking with an oxidized product of an aromatic-grade amine developer and a sulfinic acid group-containing monomer unit; A silver halide color photographic material containing silver halide in a silver halide emulsion layer.