JPS61165757A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having a high coloring property and high light and formalin resistances by incorporating a specific magenta coupler to at least one of silver halide emulsion layers. CONSTITUTION:In the titled material having at least one of the silver halide emulsion layers provided on a substrate, the magenta coupler shown by formulas I and or II wherein R and R' are each a hydrogen atom or a substituent. R1 is each an alkyl, an aryl, an alkoxy, an aryloxy, an amino or a heterocyclic ring group, R2 is a bivalent org. group. Y and Y' are each an oxygen or a sulfur atom, Z and Z' are each a non-metallic atom capable of forming a nitrogen contg. heterocyclic ring is incorporated to at least one of the silver halide emulsion layers. The additional amount of the magenta coupler in the titled material is preferably 1.5X10<-3>-7.5X10<-1>mol. per one mol of silver.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention provides a silver halide photographic photosensitive material containing a magenta coupler that forms a magenta dye image with high color development and improved storage stability, especially light fastness. Regarding materials. More specifically, the present invention relates to a silver halide color photographic material containing a novel magenta coupler.

(Prior art) In conventional silver halide color photographic materials, exposed silver halide grains are reduced with an aromatic primary amine color developing agent, and the oxidized product of the color developing agent produced at this time and Dye images can be obtained by coupling with couplers that form yellow, magenta and cyan dyes.

The coupler that has been put to practical use in the past to form the magenta dye is a pyrazolone type coupler, but this has unfavorable side absorption and is said to have poor storage stability, especially resistance to formalin gas (formalin resistance). It has its drawbacks.

In order to improve the above drawbacks, various 1-pyrazolo[3,2-CF-s-triazole-based magenta couplers have been proposed. For example, U.S. Patent 3,725
, No. 067, British Patent No. 1,252,418, 1.3
No. 34,515. The compounds described in both patents are, of course, superior to pyrazolone magenta couplers in terms of side absorption, but improvements in formalin resistance are insufficient, and little improvement has been shown in terms of color development and light fastness of images. do not have.

Research D 1 closure 1244
The compound described in No. 3 cannot be put to practical use at all in terms of color development. 1H-pyrazolo [
Although 3,2-Cl-3-triazole type magenta couplers have been significantly improved in terms of formalin resistance and color development, there has been little improvement in light resistance.

Also, JP-A-59-99437, JP-A No. 59-125732
Although the coupler described in the issue has also been improved in color development,
There continues to be no improvement in the lightfastness of dye images based on the described couplers.

In the latter case, the light resistance of the image is simply improved by the additive used in combination. However, for the former coupler of Compound Example 19 described in the specification, although the light resistance is slightly improved, it is still not sufficient.

In other words, 1H-pyrazolo[3], which has attracted attention for its lack of side absorption and high formalin resistance,
, 2-CF-s-triazole-based magenta couplers, it can be said that little improvement has been made in terms of the light resistance of dye images.

(Objective of the Invention) An object of the present invention is to provide a silver halide color photographic light-sensitive material that has good light resistance and formalin resistance, and has high color development.

(Structure of the Invention) The object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which at least one of the silver halide emulsion layers has the following general formula: This is achieved by a silver halide color photographic light-sensitive material containing a magenta coupler represented by [I] and/or [ff].

General formula [I] General formula [II] In the formula, R and R' are each a hydrogen atom or r! 1j
fI! represents a group. R1 represents an alkyl group, aryl group, alkoxy group, aryloxy group, amine group or heterocyclic group, and R2 represents a divalent organic group. Y and Y' each represent an oxygen atom or a sulfur atom. 2
and 2' each represent a group of nonmetallic atoms that can form a nitrogen-containing heterocycle. (However, the nitrogen-containing heterocycle represented by Z and 2' does not further form a condensed ring.) In the case of a bis body, it is preferable that each Z', R' and Y' are the same. may be different.

Hereinafter, unless otherwise specified, the group represented by -8-C-R of the compound represented by the general formula [I], the group represented by the general formula [Ir]
For convenience, the group represented by Y' in the compound represented by Y' is simply represented by X.

Specifically, the substituents represented by R and R' include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group,
heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group,
Cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, peterocyclic oxy group, siloxy group, acyloxy group, carbamoyl oxide group, imide group, ureido group, sulfamoylamino group,
Alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonylamino group, aryloxycarbonyl group, alkylthio group, arylthio group,
Or it is a heterocyclic thio group.

Next, the magenta coupler represented by the general formula [I] or [II] of the present invention will be explained in more detail.

In the general formula [I] or [II], examples of the halogen atom represented by R or R' include a chlorine atom and a bromine atom, with a chlorine atom being particularly preferred.

The alkyl group represented by R or R' includes one having 1 to 32 carbon atoms, an alkenyl group, an alkynyl group having 2 to 32 carbon atoms, a cycloalkyl group, and a cycloalkenyl group having 3 to 12 carbon atoms, In particular, those having 5 to 7 are preferred, and the alkyl group, alkenyl group, or alkynyl group may be straight or branched.

Also, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups are substituted! ! [
For example, aryl, cyanide, halogen atom, heterocycle, cycloalkyl, cycloalkenyl, spiro compound residue,
In addition to bridged hydrocarbon compound residues, those substituted via a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl, and those substituted via a hetero atom, specifically hydroxy , alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, which are substituted via an oxygen atom, nitro, amino (including dialkylamino, etc.), sulfamoylamino, alkoxycarbonylamino, aryloxycarbonyl Those substituted via a nitrogen atom such as amino, acylamino, sulfonamide, imide, and ureido; those substituted via a sulfur atom such as alkylthio, aryldio, heterocyclic thio, sulfonyl, sulfinyl, and sulfamoyl;
[substituent via a phosphorus atom such as phosphonyl].

Specifically, for example, a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a pentadecyl group, a heptadecyl group,
1-hexylnonyl group, 1.1'-dipentylnonyl group, 2-chloro-t-butyl group, trifluoromethyl group,
1-ethoxytridecyl group, 1-methoxyisopropyl group, methanesulfonylethyl group, 2,4-di-t-amylphenoxymethyl group, anilino group, 1-phenylisopropyl group, 3-l-butanesulfonaminophenoxyprobyl group, 3-4'-(α-[4"(+1-hydroxybenzenesulfonyl)phenoxycododecanoylamino)phenylpropyl group, 3-(4'-[α-(2",
Examples thereof include 4''-di-t-amylphenoxy)butanamido]phenyl)-brobyl group, 4-[α-(0-chlorophenoxy)tetradecanamidophenoxy]propyl group, allyl group, cyclopentyl group, and cyclohexyl group.

The aryl group represented by R or R' is preferably a phenyl group, and this aryl group may have a substituent (eg, an alkyl group, an alkoxy group, an acylamino group, etc.).

Specifically, phenyl group, 4-t-butylphenyl group,
2.4-di[-amylphenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4'
-[α-(4″-t-butylphenokidine tetradecanamide 1 phenyl group) and the like.

The heterocyclic group represented by R or R' is 5 to 7
Preferably, these are substituted or fused. Specifically, 2-furyl group, 2
-chenyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.

Examples of the acyl group represented by R or R' include acetyl group, phenylacetyl group, dodecanoyl group, α-
Examples include alkylcarbonyl groups such as 2,4-di-t-amylphenoxybutanoyl group, arylsulfnyl groups such as benzoyl group, 3-pentadecyloxybenzoyl group, and p-chlorobenzoyl group.

Examples of the sulfonyl group represented by R or R' include alkylsulfonyl groups such as methylsulfonyl group and dodecylsulfonyl group, and arylsulfonyl groups such as benzenesulfonyl group and p-1-luenesulfonyl group.

Examples of the sulfinyl group represented by R or R' include an alkylsulfinyl group such as an ethylsulfinyl group, an octylsulfinyl group, and a 3-phenoxybutylsulfinyl group, an arylsulfinyl group such as a phenylsulfinyl group, and a m-pentadecylphenylsulfinyl group. Can be mentioned.

The phosphonyl group represented by R or R' includes an alkylphosphonyl group such as a butyloctylphosphonyl group,
Examples include alkoxyphosphonyl groups such as octyloxyphosphonyl groups, aryloxyphosphonyl groups such as phenoxyphosphonyl groups, and arylphosphonyl groups such as phenylphosphonyl groups.

The carbamoyl group represented by R or R' may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-methylcarbamoyl group, N,
N-dibutylcarbamoyl group, N-(2-pentadecyloctylethylmoyl group, N-ethyl-N-dodecylcarbamoyl group, N-(3-(2.4-di-t-amylphenoxy)propyl)carbamoyl group, etc. can be mentioned.

The sulfamoyl group represented by R or R' may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-propylsulfamoyl group, an N. Examples include N-diethylsulfamoyl group, N-(2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, and N-phenylsulfamoyl group.

The spiro compound residue represented by R or R' is
Examples include spiro[3.3]hebutan-1-yl and the like.

Examples of the bridged carbonized compound residue represented by R or R' include bicyclo[2.2.1]hebutan-1-yl,
tricyclo[3.3.1.1 ]]decan-1-yl7,7-dimethyl-bicyclo[2.2.1]hebutane-
1-yl and the like.

The alkoxy group represented by R or R' may be further substituted with the substituents listed above for the alkyl group, such as methoxy group, propoxy group, 2-ethoxyethoxy group, pentadecyloxy group, 2 -dodecyloxyethoxy group, phenethyloxyethoxy group, etc.

As the aryloxy group represented by R or R',
Phenyloxy is preferred, and the aryl nucleus may be further substituted with the substituents or atoms listed above for the aryl group, such as phenoxy group, pt-butylphenoxy group, m-pentadecylphenoxy group etc.

As the heterocyclic oxy group represented by R or R',
Those having a 5- to 7-membered heterocycle are preferred, and the heterocycle may further have a substituent, for example, 3.4.
Examples include 5.6-tetrahydrobilanyl-2-oxy group and 1-phenyltetrazol-5-oxy group.

The siloxy group represented by R or R' may be further substituted with an alkyl group, such as a trimethylsiloxy group, a triethylsiloxy group, a dimethylbutylsiloxy group, and the like.

Examples of the acyloxy group represented by R or R' include an alkylcarbonyloxy group and an arylcarbonyloxy group, which may further have a substituent, specifically an acetyloxy group, an α -chloroacetyloxy group, benzoyloxy group, etc.

The carbamoyloxy group represented by R or R' may be substituted with an alkyl group, an aryl group, etc., such as N-ethylcarbamoyloxy group, N,N-diethylcarbamoyloxy group, N-7enylcarbamoyloxy group etc.

The amine group represented by R or R' may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as ethylamino group, anilino group, monochloroanilino group, 3-pentadecyloxycarbonyl group. Examples include anilino group, 2-chloro-5-hexadecaneamide anilino group, and the like.

Examples of the acylamino group represented by R or R' include an alkylcarbonylamino group, an arylcarbonylamino group (preferably a phenylcarbonylamino group), and may further have a substituent, specifically an acetamido group, α-ethylpropanamide group, N-phenylacetamide group, dodecanamide group, 2,4-di-t-amylphenoxyacetamide group, α-3-t-butyl-4
-hydroxyphenoxybutanamide group and the like.

The sulfonamide group represented by R or R' is
Examples include an alkylsulfonylamino group and an arylsulfonylamino group, and may further have a substituent. Specific examples include a methylsulfonylamino group, a pentadecylsulfonylamino group, a benzenesulfonamide group, a p-toluenesulfonamide group, and a 2-methoxy-5-t-amylbenzenesulfonamide group.

The imide group represented by R or R' may be open-chain or cyclic, and may have a substituent, such as succinimide group, 3-heptadecylsuccinimide group, phthalimide group, etc. group, glutarimide group, etc.

The ureido group represented by R or R' is an alkyl group,
It may be substituted with an aryl group (preferably a phenyl group), etc., such as an N-ethylureido group, an N-methyl-N-decylureido group, an N-phenylureido group,
N-1)-tolylureido group and the like.

The sulfamoylamino group represented by R or R' is
It may be substituted with an alkyl group, an aryl group (preferably an engineering group), etc., for example, N.

Examples include N-dibutylsulfamoylamino group, N-methylsulfamoylamino group, and N-phenylsulfamoylamino group.

The alkoxycarbonylamino group represented by R or R' may further have a substituent, such as a methoxycarbonylamino group, a methoxy-1-oxycarbonylamino group, an octadecyloxycarbonylamino group, and the like.

The aryloxycarbonylamino group represented by R or .R' may have a substituent, such as phenoxycarbonylamino group and 4-methylphenoxycarbonylamino group.

The alkoxycarbonyl group represented by R or R' may further have a substituent, such as methoxycarbonyl group, butyloxycarbonyl group, dodecyloxycarbonyl group, octadecyloxycarbonyl group, ethoxymethoxycarbonyloxy group, benzyloxy Examples include carbonyl group.

The aryloxycarbonyl group represented by R or R' may further have a substituent, such as phenoxycarbonyl group, p-chlorophenoxycarbonyl group, m-
Examples include pentadecyloxyphenoxycarbonyl group.

The alkylthio group represented by R or R' may further have a substituent, for example, an ethylthio group, a dodecylthio group, an octadecylthio group, a phenethylthio group,
-phenoxypropylthio group.

The arylthio group represented by R or R' is preferably a phenylthio group, and may further have a substituent, such as a phenylthio group, p-methoxyphenylthio group, 2-t-
Examples include octylphenylthio group, 3-octadecylphenylthio group, 2-carboxyphenylthio group, and p-acetaminophenylthio group.

The heterocyclic thio group represented by R or R' is 5
A ~7-membered heterocyclic thio group is preferred, and may further have a condensed ring or a substituent. For example, 2-pyridylthio group, 2-benzothiazolylthio group, 2.4-
Diphenoxy-1°3.5-triazole-6-thio group is mentioned.

Examples of the nitrogen-containing heterocycle formed by Z or Z' include a pyrazole ring, imidazole ring, triazole ring, and tetrazole ring.

In addition, general formula [I] or [II] and general formula [I] described below
Substituents on the heterocycle in [I] to [IX] (e.g. R
3 to R5°) is a moiety (herein, Rn and 2″ are general formulas [I] or [II
] has the same meaning as R or R' and 2 or 2', and X is as described above. ), it forms a so-called screw-type coupler, which is, of course, included in the present invention.

More specifically, those represented by the general formula [I] or [II] are represented by, for example, the following general formulas [II[] to [■].

General formula [■] General formula [rV] General formula [Vl] General formula [VI] General formula [■] General formula [■] In the general formula [I [[] ~ [■], R3 ~ Rho
and X is R or R of the above general formula [I] or [II]
', and X is as described above.

Also, preferred among general formula [I] or [I] are:
It is represented by the following general formula [IX].

General formula [rX] where R, X and 2] are R3,X in general formula [II]
and general formula CI].

Among the magenta couplers represented by the general formulas [I[I] to [■], particularly preferred are the magenta couplers represented by the general formula [I1].

Regarding the substituents on the heterocycle in general formulas [II[] to [rX], R in general formula [II], R' in general formula [II] and R' in general formula [I11] to [
IX], it is preferable that R3 satisfies the following condition 1, more preferable is the case that the following conditions 1 and 2 are satisfied, and particularly preferable is the case that the following conditions 1.2 and 3 are satisfied.

Condition 1: The root atom directly connected to the heterocycle is a carbon atom.

Condition 2: Only one hydrogen atom or no hydrogen atom is bonded to the carbon atom.

Condition 3 All bonds between the carbon atom and adjacent atoms are single bonds.

The most preferred substituents R and R' on the heterocycle are those represented by the following general formula [X].

General formula [In the formula "II, R12 and R13 are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group" group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group group, amino group, acylamino group, sulfonamide group, imide group, ureido group, sulf7moylamino LL alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, heterocycle It represents a thio group, and at least two of R11, R12 and R1 are not hydrogen atoms.

Furthermore, two of the R11, R1□ and R,3, for example R1, and R+2, may be combined to form a saturated or unsaturated ring (for example, cycloalkane, cycloalkene, heterocycle), Furthermore, R+3 may be bonded to the ring to constitute a bridged hydrocarbon compound residue.

The group represented by R11 to R1 may further have a substituent, and specific examples of the group represented by R11 to R13 and the substituent that the group may have include the above-mentioned general formula [II Specific examples of the group represented by R or R' in [II] and substituents are listed.

Also, for example, a ring formed by combining R11 and R1□ and R
Specific examples of the bridged hydrocarbon compound formed by -R,3 and the substituents it may have include:
R or R in the above general formula [II or [II]
Specific examples of cycloalkyl, cycloalkenyl, and heterocyclic groups represented by ' and their Wl substituents are listed.

Among the general formula [X], (i) when two of R,1 to R+'5 are alkyl groups, one of (++)R,, to R13, for example R11, is a hydrogen atom When the other two RI2 and R+3 combine to form a cycloalkyl group with the root carbon atom, then the following is true.

Furthermore, it is preferable among (i) that two of R to R13 are alkyl groups and the other one is a hydrogen atom or an alkyl group.

Here, the alkyl and the cycloalkyl may further have a substituent. Specific examples of the alkyl, the cycloalkyl, and the substituent thereof include those of the general formula [II or [II]
Specific examples of alkyl, cycloalkyl, and substituents thereof represented by R or R' are mentioned.

In the general formula [I], R) represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, or a heterocyclic group. Examples of the alkyl group represented by R1 include methyl group, ethyl group, etc. group, 1-butyl group, octadecyl group, benzyl group, etc.

Examples of the aryl group represented by R1 include phenyl group and naphthyl group. Examples of the alkoxy group represented by R1 include methoxy group, ethoxy group, and propoxy group.

Examples of the aryloxy group represented by R3 include a phenoxy group. Examples of the amino group represented by R1 include a methylamine group, a butylamino group, an octylamino group, a dimethylamino group, a diethylamino group, a methylethylamino group, a methylphenylamino group, and the like.

Examples of the heterocyclic group represented by R1 include a morpholino group, a vivezino group, and a piperazino group. R4
Alkyl group, aryl group, alkoxy group represented by
The aryloxy group and the heterocyclic group may have a substituent, and these substituents include a halogen atom, a nitro group,
Cyano group, hydroxy group, sulfone group, carboxy group,
Alkyl group, alkenyl group, aryl group, alkoxy group, aryloxy group, acylamino group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfamoyl group, sulfonamide group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a dialkylamino group, a ureido group, and the like.

In the general formula [II], 21i represented by R2
Specifically, the organic group of 1[i includes, for example, an alkylene group (e.g., methylene group, ethylene group, hexylene group, etc.), an arylene group (e.g., phenylene group, etc.), an alkylene arylene group (e.g., methylene phenylene group, etc.)
, arylene alkylene groups (e.g. 0-methylphenylene ethylene group, etc.), alkylene arylene alkylene groups (e.g. methylene phenylene methylene group, etc.), arylene alkylene arylene groups (e.g. phenylene methylene phenylene group, etc.), heterocyclic groups (e.g. divalent triazine ring, piperidine ring, etc.).

In general formula [I] or [II], YSY' represents an oxygen atom or a sulfur atom. Hereinafter, the general formula [I
] or [II], but the present invention is not limited thereto.

Margin below Exemplary compound H3 23)S )I S-C0CzHs These compounds are e.g. Also, Y’ Y’ It can be synthesized by

However, in the formula, R, R, Y, Y' are the general I
2 R, R2, Y, Y' represented by formula [I] or [n]
R and R+ are synonymous with R in the general formula [I[[]
, R+.

Synthesis Example-1 (Exemplary Compound-4) 3-(1-methyl-2-dodecylsulfonyl)ethyl-
5-sec butyl-1H-pyrazolo[3°2-C] -
8.8 g of s-triazole and 2.4 g of di(ethoxythiocarbonyl) disulfide were dissolved in 1 ooom, P dimethylformamide, 1.1 g of sodium carbonate was added, and after stirring at air temperature for 5 hours, the reaction solution was poured into water. Pour and extract with ethyl acetate. After washing with water and drying, the solvent was distilled off, and the residue was purified by column chromatography to obtain a candy-like target product. (
The desired substance was confirmed by NMR, Mas, and s spectra. ) Synthesis Example-2 (Exemplary Compound-17) 3-(1-methyl-2-dodecylsulfonyl)ethyl-
9.4 g of 6-isopropyl-7-mercabuto 1H-pyrazolo[3,2-C]-s-triazole and 1.9 g of phthaloyl chloride were dissolved in 1 ml of acetonitrile, and 1.1 g of sodium carbonate was added. Reflux for 2 hours while stirring. The reaction solution was poured into ice water and extracted with ethyl acetate. After washing with water and drying, the solvent is distilled off to obtain a candy-like substance. Purification was performed by column chromatography to obtain a yellow candy-like target product. (Confirmed by NMR1Mass spectrum).

The magenta coupler according to the present invention is added to the photographic light-sensitive material according to the present invention in an amount per mole of silver.

The silver halide photographic light-sensitive material of the present invention can be, for example, a color negative film, a positive film, or a color photographic paper. In particular, when a color photographic paper intended for direct viewing is used, the method of the present invention can be used. The effects of this will be effectively demonstrated.

The silver halide photographic material of the present invention, including this color photographic paper, may be one for monochrome use or one for multicolor use. In the case of multicolor silver halide photographic materials, in order to perform subtractive color reproduction, a photographic coupler is usually used.
It has a structure in which silver halide emulsion layers containing magenta, yellow, and cyan couplers and a non-light-sensitive layer are laminated on a support in an appropriate number of layers and in a temperature order. It may be changed as appropriate depending on the important performance and purpose of use.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes conventional silver halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any of those used in emulsions can be used.

The silver halide grains used in the silver halide emulsion of the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are produced. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halogen ions and silver ions may be mixed simultaneously, or one may be mixed in the presence of the other. In addition, while considering the critical growth rate of silver halide crystals, we added halide ions, silver ions, etc.
It may also be produced by controlling and sequentially adding H and PAQ simultaneously. After growth, a conversion method may be used to change the halogen composition of the particles.

When producing the silver halide emulsion of the present invention, the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains can be controlled by using a silver halide solvent as necessary.

The silver halide grains used in the silver halide emulsion of the present invention are prepared in the process of forming and/or growing the grains such as cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt, rhodium salt or complex salt. Metal ions can be added to the interior of the particles and/or on the surface of the particles using iron salts or complex salts, and can be reduced to the interior of the particles and/or on the surface of the particles by placing them in an appropriate reducing atmosphere. Can provide sensitizing nuclei.

In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

The silver halide grains used in the silver halide emulsion of the present invention may consist of a uniform layer inside and on the surface, or
It may consist of different layers.

The silver halide grains used in the silver halide emulsion of the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grains.

The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal shape or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of the [I, 0, 0] plane to the [I, 1, 1] plane can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The silver halide emulsion of the present invention may be a mixture of two or more separately formed silver halide emulsions.

The silver halide emulsion of the present invention is chemically sensitized by a conventional method. That is, compounds containing sulfur that can react with silver ions,
A sulfur sensitization method using activated gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination.

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Also good.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
For the purpose of preventing fog during storage or photographic processing and/or keeping photographic performance stable, silver halide emulsions are used during and/or at the end of chemical ripening, and/or after the end of chemical ripening. Compounds known in the photographic industry as antifoggants or stabilizers can be added prior to coating.

Gelatin is advantageously used as a binder (or protective colloid) for the silver halide emulsion of the present invention, but
In addition, hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of light-sensitive materials using the silver halide emulsion of the present invention can be formed by using a hardening agent alone or in combination to crosslink binder (or protective colloid) molecules and increase film strength. It is hardened. It is desirable to add the hardening agent in an amount that can harden the photosensitive material to the extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution.

A plasticizer can be added for the purpose of increasing the flexibility of the silver halide emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention.

A dispersion of a water-insoluble or sparingly soluble synthetic polymer (
latex).

In the emulsion layer of the silver halide color photographic light-sensitive material of the present invention, an aromatic primary amine developer (
For example, a dye-forming coupler is used that forms a dye by performing a coupling reaction with an oxidized product of p-phenylenediamine derivatives, aminophenol derivatives, etc.). The dye-forming couplers are typically selected such that for each emulsion layer a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, and a yellow dye-forming dye is formed for the blue light-sensitive emulsion layer. A magenta dye-forming coupler is used in the green light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red light-sensitive emulsion layer.

However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

Examples of yellow dye-forming couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivaloylacetanilides), and magenta dye-forming couplers include, in addition to the couplers of the present invention, 5-pyrazolone couplers, pyrazolobenzimidazole couplers, and pyrazolo couplers. Examples include triazole, open-chain acylacetonitrile couplers, and cyan dye-forming couplers include naphthol couplers and phenol couplers.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Furthermore, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either 2-equivalence may be used.

Hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the silver halide crystal surface can be treated with various methods such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion. can be appropriately selected depending on the chemical structure of the hydrophobic compound, etc. The oil-in-water emulsion dispersion method can be applied to a previously unknown method of dispersing hydrophobic additives such as couplers. Usually, a high boiling point organic solvent with a boiling point of about 150°C or higher is mixed with a low boiling point and/or as needed. Or, by dissolving it in combination with a water-soluble organic solvent, using a surfactant in a hydrophilic binder such as an aqueous gelatin solution, and using a dispersion means such as a stirrer, homogenizer, colloid mill, 70-jit mixer, or long sonic device. After being emulsified and dispersed, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

High boiling point oils include phenol derivatives, phthalate esters, phosphate esters, which do not react with the oxidized form of the developing agent,
Boiling point 15 of citric acid ester, benzoic acid ester, alkyl amide, fatty acid ester, trimesic acid ester, etc.
An organic solvent having a temperature of 0° C. or higher is used.

Anionic active agents, nonionic surfactants, Cationic surfactants can be used.

Between the emulsion layers of the color photographic light-sensitive material of the present invention (between the same color-sensitive layers and/or between different color-sensitive layers), the oxidized form of the developing agent or the electron transfer agent may migrate, causing color turbidity or sharpness. Color antifoggants are used to prevent deterioration and graininess from becoming noticeable.

The color antifoggant may be used in the emulsion layer itself, or may be used in a film intermediate layer by providing an intermediate layer between adjacent emulsion layers.

In the color light-sensitive material using the silver halide emulsion of the present invention, an image stabilizer can be used to prevent deterioration of the dye image.

Ultraviolet absorbers are added to hydrophilic colloid layers such as the retaining layer and intermediate layer of the photosensitive material of the present invention to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light. May contain.

A color light-sensitive material using the silver halide emulsion of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer and/or an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material or are bleached during development.

The silver halide emulsion layer and/or other hydrophilic colloid layer of a silver halide light-sensitive material using the silver halide emulsion of the present invention is used to reduce the gloss of the light-sensitive material, to improve the ease of writing, and to prevent mutual pecking of the light-sensitive materials. A matting agent can be added to achieve this goal.

A lubricant can be added to reduce the wear friction of a photosensitive material using the silver halide emulsion of the present invention.

An antistatic agent for the purpose of preventing static electricity can be added to a light-sensitive material using the silver halide emulsion of the present invention.

Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated with respect to the support. It may also be used in a colloid layer.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion of the present invention may include improved coatability,
Various surfactants are used for the purposes of preventing static electricity, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (such as accelerating development, increasing contrast, and sensitization).

The light-sensitive material using the silver halide emulsion of the present invention has a photographic emulsion layer, and other layers include a baryta layer or a flexible reflective support such as paper laminated with α-olephne polymer, synthetic paper, cellulose acetate, nitric acid, etc. cellulose, polystyrene,
It can be applied to films made of semi-synthetic or synthetic polymers such as polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, as well as rigid bodies such as glass, metal, and ceramics.

The silver halide material of the present invention can be used directly or (adhesiveness, antistatic property, dimensional stability, resistance The coating may be applied via one or more subbing layers (to improve abrasion, hardness, antihalation, frictional properties, and/or other properties).

When coating a photographic light-sensitive material using the silver halide emulsion of the present invention, a thickener may be used to improve coating properties. Particularly useful coating methods are ex-dulsion coating and curtain coating, which allow two or more layers to be applied simultaneously.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, xenon arc lamps, carbon arc lamps,
xenon flash lamp, cathode m tube flying spot,
Various laser lights, light emitting diode lights, electron beams, X-rays, T
Any known light source can be used, such as light emitted from a phosphor excited by rays, alpha rays, or the like.

Exposure times include not only exposure times of 1 millisecond to 1 second commonly used in cameras, but also exposure times shorter than 1 microsecond, such as exposure times of 100 microseconds to 1 microsecond using cathode ray tubes and xenon flash lamps.
Microsecond exposures can be used, and exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently.

The silver halide photographic material of the present invention can form an RFIJ image by color development as known in the art.

The aromatic primary amine color developing agents used in the color developing solution of the present invention include known ones that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Additionally, these compounds generally have a concentration of about 0.1 g to about 3,017 g per color developer 11, preferably about 1 g to about 1.5 g per color developer 11≦.
Use at a concentration of g.

Examples of aminophenol-based developers include 0-7 minophenol, p-7 minophenol, 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1°4-dimethylbenzene and the like.

Particularly useful primary aromatic amino color developers are N, N'
-Dialkyl-〇-phenylenediamine type compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include N,N'-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,
N'-dimethyl-〇-phenylenediamine store! ! shop,
2-amino-5-(N-ethyl-N-dodecylamino)
-Toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoanilinelii! I
Sunshio, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N.

N'-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-o-
Examples include toluene sulfonate.

In addition to the above-mentioned primary aromatic amine color developer, the color developer used in the process of the present invention further contains various components that are normally added to color developers, such as sodium hydroxide and sodium carbonate. , alkaline agents such as potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickening agents, etc. may be optionally contained. can. The rlH value of this color developer is usually 7 or more, most commonly about 10.
〜about 13.

In the present invention, after color development processing, processing is performed with a processing liquid having a fixing ability, but if the processing liquid having a fixing ability is a fixing liquid, a bleaching treatment is performed before that. As the bleaching agent used in the bleaching process, a gold Jl complex salt of an organic acid is used, and the metal complex oxidizes the gold horse silver produced by development and converts it into silver halide, and at the same time colors the uncolored part of the color former. It has a composition of aminopolycarboxylic acid, oxalic acid, citric acid, etc., in which metal ions such as iron, cobalt, copper, etc. are coordinated.

The most preferred organic acids used to form such metal complexes include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific representative examples of these include the following.

[I] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [6-coethylenediaminetetraacetic acid tetrasodium salt [7] Nitrilotriacetic acid The bleaching agent used in the sodium acetate salt contains the above-mentioned organic acid complex salt as a bleaching agent, and may also contain various additives. As additives, it is particularly desirable to include rehalogenating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide, gold a salts, and chelating agents.

Also, DH such as octate, oxalate, acetate, carbonate, phosphate, etc.
1m''#J agent, alkylamines, polyethylene oxides, and other substances known to be added to ordinary bleaching solutions can be added as appropriate.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Sulfites such as potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, lj2 potassium acid, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid,
pH consisting of various salts such as sodium acetate and ammonium hydroxide! It may contain one or more types of buffering agents.

When the process of the present invention is carried out while replenishing the bleach-fix replenisher in the bleach window IFM (bath), the bleach-fix solution (bath) may contain thiosulfate, thiocyanate, sulfite, etc. These salts may be added to the bleach-fixing replenisher to replenish the processing bath.

In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank, if desired, or an appropriate oxidizing agent may be added. For example, dissipated hydrogen, bromine a salt, persulfate, etc. may be added as appropriate.

[Examples] Next, the present invention will be specifically explained using Examples, but the present invention is not limited thereto.

[Example 11] The magenta coupler of the present invention and the comparative coupler shown in Table 1 were each taken in an amount of 0.1 mole per mole of silver, and 1 times the amount of tricresyl phosphate and 3 times the amount of the coupler iut were added. of ethyl acetate was added and heated to 60°C to completely dissolve. This solution was mixed with 1 part of a 5% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont).
The mixture was mixed with 1200+n length of a 5% gelatin aqueous solution containing 20-20-20-20-20-20-20-2, and emulsified and dispersed using an ultrasonic dispersion machine to obtain an emulsion. Thereafter, this dispersion was mixed into a green-sensitive silver iodobromide emulsion (silver iodide 6
Mol% content) to 4! Added to J as l' film agent 1.2-
A 2% solution of bis(vinylsulfonyl)ethane (water:methanol-1:1>120111) was added and coated onto the subbed transparent polyester base and dried to form sample 1-
1 to 1-10 were created. (Coated silver amount 20mg/10
0 cmz) The sample thus obtained was subjected to wedge exposure according to a conventional method, and then subjected to the following development treatment. The results are shown in Table 1.

[Development processing step] In each processing step, the composition of the processing solution used is as follows.

[For color development @liquid composition] [Carbonic acid")')!a
30gIt! ,,+) Sea urchin 2
．． 5゜[Bleaching solution composition] 1'' Ethylenediaminetetraacetate iron [Fixer composition] [Stabilizing solution composition Table-1 1) Specific sensitivity is the reciprocal of the exposure amount that gives a density of fog density + 0.1, and comparative coupler 1 ) sample N001 was set as 100.

2) 30°C, 62% RH1:! III, a The sample was placed in a sealed container to which 6 cc of 2H Saleta 0.9% formalin aqueous solution was added for 3 days, and then color development was performed. For comparison, a sample not treated with formalin is also developed.

In addition, formalin resistance was calculated|required according to the following formula.

3) The sample after the color development process was irradiated with a xenon fade meter for 5 days, and the percentage of dye remaining at the initial density of -1.0 was shown.

The following is the specific gravity of gold white (Coupler 1) Ct Comparative coupler 2) From Table 1, it is clear that the couplers of the present invention are excellent in color development, formalin resistance, and light resistance.

[Example-2] Samples 1-1 to 1-10 in Example-1 were wedge exposed to the same ti, and the following development treatments were performed.

These results are shown in Table 2. Insensitivity and light resistance were measured using the same method as in Example-1.

[Development process] Color development 38℃ 3 minutes 30 seconds Bleach fixing
33℃ 1 minute 30 seconds stabilization treatment/or water washing treatment 25-30℃ 3 minutes drying
75-80°C for 2 minutes The composition of the treatment liquid used in each treatment step is as follows.

[Color developer] Benzyl alcohol is d ethylene glycol 15 m Potassium sulfite 2.0 g Potassium bromide
0.70 Sodium Chloride
0,2 Q charcoal potassium
30. OQ hydroxylamine i old j! A3.
Og polyphosphoric acid (PP5) 2.5Q
3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfur mfM 5.5g Fluorescent brightener 4,4'-diaminostilbenzsulfonic acid derivative) 1. Oa potassium hydroxide 2. Add OQ water to make all layers one layer and adjust to p) -110,20.

[Bleach fixing 8! ] Ethylenediaminetetraacetic acid ferric ammonium dihydrate so gEthylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100n+1
Ammonium sulfite (40% solution > 27.5 +
Adjust the pH to 7.1 with nQ potassium carbonate or glacial acetic acid, and add water to bring the total pH to 11.

[Stabilizing liquid 5-chloro o-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol IQ gU, as is clear from the results in Table 2 of Shimokanpaku, the coupler of the present invention It can be seen that Samples 2-4 to 2-10 containing the above are superior in sensitivity, color development, and light resistance compared to the comparative samples.

[Example 3] A silver halide color photographic material was prepared by sequentially coating the following layers on polyethylene resin coated paper containing 7-natase type titanium oxide.

The amounts added below are per 100 cn+''.

(1) 20 na gelatin, 5 mg of silver as a blue-sensitive silver chlorobromide emulsion, and 3ff1 g of di-octyl phthalate coupler in which 8 mg of yellow coupler and 0.1 mg of 2,5-di-t-octylhydroquinone were dissolved. Layer containing solvent (2) 12 na gelatin, 0.5 mg 2.5-di-
Interlayer comprising 2+11 CI of dibutyl phthalate UV absorber solvent in which t-octylhydroquinone and 1 g of 4II UV absorber were dissolved.

(3) 18 na gelatin, a green-sensitive silver chlorobromide emulsion with a silver content of 4 n+g, and 2.5 mg of dioctyl phthalate coupler in which 5 mg of magenta coupler and 0.2 zg of 2,5-di-t-octylhydroquinone were dissolved. Layer containing solvent.

(4) An intermediate layer containing the same composition as (2).

(5) 16++o+ gelatin, a red-sensitive silver chlorobromide emulsion with a silver content of 4IIg, and a 2,Oa+g trifluoride in which 3.5mg of cyan coupler and 0.1mg of 2,5-di-t-octylhydroquinone were dissolved. II containing cresyl phosphate coupler solvent.

(6) Gelatin protective layer containing 9 mg gelatin.

Coating aids are added to each layer (1) to (6), and (
A gelatin crosslinking agent was added to layers 4) and (6).

As the ultraviolet absorber (2) and (4), t of the following structure is used.
A mixture of JV-1 and LIV-2 was used.

The above multilayer photosensitive material was treated in the same manner as in Example-2. Table 3 shows the yellow coupler, magenta coupler, and cyan coupler used in each layer and the results.

Each sample was measured for magenta density after exposure to white light.

Further, measurements of specific sensitivity and light resistance were carried out in the same manner as in Example 1.

It is clear from Table 3 that the light fastness of the dye image of the coupler of the present invention is excellent, and it is also clear that it can be further improved by using an ultraviolet absorber.

Margin below UV absorber UV-1 UV-2 Y-coupler C-coupler t Margin below

Claims (1)

[Scope of Claims] In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has the following general formula [I
] and/or [II]. A silver halide color photographic material containing a magenta coupler represented by [II]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R and R' each represent a hydrogen atom or a substituent. R_1 represents an alkyl group, aryl group, alkoxy group, aryloxy group, amino group or heterocyclic group, and R_2 represents a divalent organic group. Y and Y' each represent an oxygen atom or a sulfur atom. Z and Z' each represent a group of nonmetallic atoms capable of forming a nitrogen-containing heterocycle. (However, the nitrogen-containing heterocycles represented by Z and Z' do not further form a condensed ring.)