JPS61166547A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To form a silver halide color photographic sensitive material good in light resistance and formalin resistance and high in color formation performance by incorporating a specified magenta coupler in a silver halide emulsion layer. CONSTITUTION:At least one of the silver halide emulsion layers contains a magenta coupler, preferably, in the amt. of 1X10<-2>-5X10<-1>mol per mol of silver, represented by formula 1, above all, preferably, formula 2, and in formulae 1, 2, R is H or a substituent; A is an atomic group necessary to form a 5- or 6-membered hetero ring; and Z, Z1 are each a nonmetallic atomic group capable of forming an N-contg. hetero ring.

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 Ra developing agent produced at this time is oxidized. Dye images can be obtained by coupling the bodies 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 has poor storage stability, especially resistance to formalin gas (formalin resistance). It has the following drawbacks.

In order to improve the above drawbacks, various 1-pyrazolo[3,2-C]-s-triazole magenta couplers have been proposed. For example, U.S. Patent 3,725,0
No. 67, British Patent No. 1,252,418, British Patent No. 1.334
, No. 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.

Res, arch D 1 closure 124
The compound described in No. 43 cannot be put to practical use at all in terms of color development. The 1H-pyrazolo[3,2-c]-s-triazole type magenta coupler described in JP-A No. 58-42045 has been significantly improved in terms of formalin resistance and color development, but it still has improved light resistance. has hardly been done.

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, in the case of the coupler of Compound Example 19 described in the specification of the former, the light resistance is improved slightly but still sufficiently. It can not be said.

In other words, 1H-pyrazolo[3], which has attracted attention for its lack of side absorption and high formalin resistance,
, 2-C]-s-triazole type 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 which has good light fastness and formalin resistance, and has good 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].

General formula [I] In the formula, R represents a hydrogen atom or a substituent, and A is 5 to 6
Represents a group of atoms necessary to form a member heterocycle. 2 represents a nonmetallic atomic group capable of forming a nitrogen-containing heterocycle. (However, the nitrogen-containing heterocycle represented by 2 does not further form a condensed ring.) Hereinafter, unless otherwise specified, the groups represented by -N-q and A of the compound represented by the general formula [I] is simply represented by X here for convenience.

Specifically, the substituent represented by R is a halogen atom,
Alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, 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, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamide group, imide group, ureido group , sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, or heterocyclic thio group.

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

In the general formula [I1, the halogen atom represented by R includes, for example, a chlorine atom and a bromine atom, with a chlorine atom being particularly preferred.

The alkyl group represented by R has 1 to 32 carbon atoms, and the alkenyl group and alkynyl group have 2 to 32 carbon atoms.
32 carbon atoms, cycloalkyl groups, and cycloalkenyl groups preferably have 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms,
Further, the alkyl group, alkenyl group or alkynyl group may be linear or branched.

In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups are substituents [e.g., aryl, cyano, halogen atoms, heterocycles, cycloalkyl, cycloalkenyl, spiro compound residues, bridged hydrocarbon compounds] In addition to residues, those substituted via a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl, and those substituted via a heteroatom, specifically hydroxy, alkoxy, and aryloxy. , heterocyclic oxy,
Those substituted via an oxygen atom such as siloxy, acyloxy, carbamoyloxy, nitro, amine (including dialkylamino, etc.), sulfylmoylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfonamide, imide, ureido, etc. substituted through the nitrogen atom, alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl,
Substitution via a sulfur atom such as sulfamoyl, substitution via a phosphorus atom such as phosphonyl, etc.] may also be present.

Specifically, for example, a methyl group, an ethyl group, an isoprobyl group, a t-butyl group, a pentadecyl group, a heptadecyl group,
1-hexylnonyl group, 1.1'-dipentylnonyl group, 2-chloro-1-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" (p-hydroxybenzenesulfonyl)phenoxy]dodecanoylamino)phenylpropyl group, 3-(4'-[α-(2"
, 4"-di-t-amylphenoxy)butanamido]phenyl)-propyl 1,4-[α-(O-chlorophenoxy)tetradecanamidophenoxy]propyl group, allyl group, cyclopentyl group, cyclohexyl group, and the like.

The aryl group represented by R is preferably a phenyl group, and this aryl group has a substituent group (for example, an alkyl group,
(alkoxy group, acylamino group, etc.).

Specifically, phenyl group, 4-t-butylphenyl group,
2.4-di-t-amylphenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4'
-[α-(4″-t-butylphenoxy)tetradecanamido]phenyl group and the like.

The heterocyclic group represented by R is preferably a 5- to 7-membered one, which may be substituted or fused. Specific examples include 2-furyl group, 2-chenyl group, 2-pyrimidinyl group, and 2-benzothiazolyl group.

Examples of the acyl group represented by R include acetyl group, phenylacetyl group, dodecanoyl group, α-2,4-
Examples include alkylcarbonyl groups such as di-t-amylphenoxybutanoyl group, arylcarbonyl groups such as benzoyl group, 3-pentadecyloxybenzoyl group, and p-chlorobenzoyl group.

Examples of the sulfonyl group represented by R include alkylsulfonyl groups such as methylsulfonyl group and dodecylsulfonyl group, aryl sulfonyl groups such as benzenesulfonyl group and p-toluenesulfonyl group.

The sulfinyl group represented by R includes an alkylsulfinyl group such as an ethylsulfinyl group, an octylsulfinyl group, a 3-phenoxybutylsulfinyl group, an arylsulfinyl group such as a phenylsulfinyl group, and a -1pentadecyl phenylsulfinyl group. Examples include groups.

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

The carbamoyl group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as N-methylcarbamoyl group, N,N-dibutylcarbamoyl group, N-(2-pentadecyl group), etc. Examples thereof include octylethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoyl(3-(2.4-di-t-amylphenoxy)propyl)carbamoyl group, and the like.

The sulfamoyl group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as N-pro and Rusulf 7-moyl groups, N. N-
Examples include diethylsulfamoyl group, N-(2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, and N-phenylsulfamoyl group.

Examples of the spiro compound residue represented by R include spiro[3.3]heptan-1-yl.

Examples of the bridged carbonized compound residue represented by R include bicyclo[2.2.1]hebutan-1-yl, tricyclo[3.3.1.1]]decan-1-yl7.7-dimethyl-bicyclo [2.2.

11-heptane-1-yl and the like.

The alkoxy group represented by 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. group, phenethyloxyethoxy group, and the like.

The aryloxy group represented by R is ), u,,
Oya, 7o, ah! J-/lz. G Yoko. The 21' aryl group may be substituted with the substituents or atoms listed above, such as phenoxy group, pt-butylphenoxy group, -1pentadecylphenoxy group, and the like.

The heterocyclic oxy group represented by R preferably has a 5- to 7-membered heterocycle, and the heterocycle may further have a substituent, for example, 3, 4, 5, 6. -tetrahydrobilanyl-2-oxy group and 1-phenyltetrazole-5-oxy group.

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

The acyloxy group represented by R may have, for example, an alkylcarbonyloxyloxy group, specifically an acetyloxy group,
Examples include α-chloroacetyloxy group and benzoyloxy group.

The carbamoyloxy group represented by R is an alkyl group,
It may be substituted with an aryl group, and examples thereof include N-ethylcarbamoyloxy group, N,N-diethylcarbamoyloxy group, N-phenylcarbamoyloxy group, and the like.

The amino group represented by 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-pentadecyloxycarbonylanilino group, 2-
Examples include chloro-5-hexadecaneamide anilino group.

Examples of the acylamino group represented by R include an alkylcarbonylamino group, an arylcarbonylamino group (preferably a phenylcarbonylamino group), and may further have a substituent, specifically an acetamido group, an α-
Examples include an ethylpropanamide group, an N-phenylacetamide group, a dodecanamide group, a 2,4-di-t-amylphenoxyacetamide group, and an α-3-t-butyl-4-hydroxyphenoxybutanamide group.

Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group, which 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 may be open-chain or cyclic, and may have a substituent, such as succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutarinide group, etc. Examples include imide groups.

The ureido group represented by R may be substituted with an alkyl group, 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-o-
Examples include tolylureido group.

The sulf7moylamino group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as N,N-dibutylsulfamoylamino group, N-methylsulfamoylamino group, N-methylsulfamoylamino group, -phenylsulfamoylamino group and the like.

The alkoxycarbonylamino group represented by R may further have a substituent, such as a methoxycarbonylamino group, a methoxyethoxycarbonylamino group, an octadecyloxycarbonylamino group, and the like.

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

The alkoxycarbonyl group represented by R may further have a substituent, such as a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group, an octadecyloxycarbonyl group, an ethoxymethoxycarbonyloxy group, < y v / L/Okiha 2. Boyu 2. Examples include groups. The aryloxycarbonyl group represented by 11″R may further have an l!!! group, such as a phenoxycarbonyl group, p-
Examples include chlorphenoxycarbonyl group, I-pentadecyloxyphenoxycarbonyl group, and the like.

The alkylthio group represented by R may further have a substituent, for example, an ethylthio group, a dodecylthio group,
Examples include octadecylthio group, phenethylthio group, and 3-phenoxypropylthio group.

The arylthio group represented by R is preferably a phenylthio group, and may further have a substituent, such as a phenylthio group, p-methoxyphenylthio group, 2-t-octylphenylthio group, 3-octadecylphenylthio group, 2
-carboxyphenylthio group, p-acetaminophenylthio group, etc.

The heterocyclic thio group represented by R is preferably a 5- to 7-membered heterocyclic thio group, and may further have a fused ring (
It may also have a substituent. Examples include 2-pyridylthio group, 2-benzothiazolylthio group, and 2,4-diphenoxy-1,3,5-triazole-6-thio group.

Examples of the nitrogen-containing heterocycle formed by 2 include a pyrazole ring, an imidazole ring, a triazole ring, and a tetrazole ring.

In addition, the substituents (for example, R to R,) on the heterocycle in general formula [I] and general formulas [II] to [■] described later are moieties (herein, R' and 2' are general formulas [I ] in R,
It has the same meaning as Z, 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, what is represented by the general formula [I] is represented by, for example, the following general formulas [I] to [■].

The following are blank general formula [IN General formula [I1 [] General formula [rV] General formula EV] General formula [VI] General formula [■] In the above general formulas [II] to [■], R-R and X
has the same meaning as R in the general formula [I], and X is as described above.

Moreover, among the general formula [I], the following general formula [
■].

General formula [■] In the formula, R, X and zl are Rl in the general formula [II]
It has the same meaning as X and 2.

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

Regarding the substituents on the heterocycle in general formulas [I] to [■], R in general formula [I] and R in general formulas [II] to [■] satisfy the following condition 1. It is preferable that the following conditions 1 and 2 are satisfied, and more preferable that the following conditions 1 and 2 are satisfied.
The following condition 1. is particularly preferable.
This is a case where conditions 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 substituted IR on the heterocycle is represented by the following general formula [IX].

General formula [IX] R1 u C- R%0 where R,,R,. and R11 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, a sulfinyl group, a phosphonyl group, a carbamoyl group, and a sulfamoyl group. group, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamide group, Represents an imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, heterocyclic thio group, and RI? , RIo and R1+ are not hydrogen atoms.

Moreover, two of the above Rq, R10 and Ro, for example, R
9 and RIQ may be bonded to form a saturated or unsaturated ring (e.g., cycloalkane, cycloalkene, heterocycle), and R11 is further bonded to the ring to constitute a bridged hydrocarbon compound residue. It's okay.

The group represented by R9-R11 may further have a substituent, and specific examples of the group represented by R9 to R1+ and the substituents that the group may have include the above-mentioned general formula [
Specific examples and substituents of the group represented by R in [I] are listed.

Also, for example, a ring formed by combining R9 and RIQ and R9
Specific examples of the bridged hydrocarbon compound residue formed by ~R0 and the substituents it may have include specific examples of the cycloalkyl, cycloalkenyl, and heterocyclic groups represented by R in the above general formula [I]. Examples and substituents thereof are listed.

Among the general formulas [IX], (t) R9-R
When two of 51 are alkyl groups, (li) R9 to R
When one of 1+, for example R9, is a hydrogen atom, and the other two R1° and Ro combine to form a cycloalkyl group with the root carbon atom, the following is true.

Furthermore, in (1), it is preferable that two of R9 to R11 are alkyl groups and the other one is a hydrogen atom or an alkyl group.

Here, the alkyl and cycloalkyl may further have a substituent. Specific examples of the alkyl, the cycloalkyl, and the substituent thereof include the alkyl, cycloalkyl, and its substituent represented by R in the general formula [I]. Specific examples of substituents are listed.

The heterocycle formed by A in the general formula [I] can preferably be represented by the following general formula [X].

General formula [X]
, 1.・RI! Here, A2 represents a nonmetallic atom group necessary to form a 5- to 6-membered nitrogen-containing heterocycle, and 11RI2 represents an alkyl group, an aryl group, or an acyl group. Typical specific examples of the heterocycle represented by the above general formula [X] are illustrated below.

Vilorinylidene, Vilorinylidene, Imidarylidene,
pyridylidene, quinolilidene, imidazolylidene,
imidazolylidene, pyrazolinylidene, benzimidazolylidene, pyrimidinylidene, quinolilidene, brnylidene, triazolilidene, tetrazolylidene, oxazolilidene, oxazolilidene, benzoxazolilidene, thiazolidinylidene, thiazolilidene, benzthiazolilidene, oxadiazolilidene, Examples include thiadiazolilidene and furazanilidene.

These heterocycles include one substituent such as an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, a nitro group, a cyano group, a hydroxyl group, a thio group, a halogen atom, a carboxylic acid group, a sulfonic acid group, etc. These heterocycles include those substituted as above, and also include those in which these heterocycles form a condensed ring (for example, a condensation of a heterocycle or an aromatic ring) at an appropriate position.

Specific examples of the magenta coupler of the present invention represented by the general formula [E] will be shown below, but the present invention is not limited thereto.

Below is the margin [IHIfu HJ Shiyama〇Hs [IHI? A typical method for synthesizing the Mazenk coupler of the present invention is shown below.

Method (1) Method (2) In the formula, B is an alkyl group or a substituted alkyl group, and Y
e represents an acid anion. R, R, , R52, and A2 each have the same meaning as the above general formula [I[] or [X]. Moreover, various types of quaternary upper life 1 can be used depending on the target R12.

Next, specific synthesis examples of these compounds will be shown.

Journal of the Chemica
l 5ociety, Perkinl, 20
47-2052 (1977), British Patent No. 3,725
, No. 067, JP-A-58-102232, JP-A-59.
Synthesis was carried out with reference to No.-99437 and the like.

Synthesis of compound example <4) The reaction scheme is as follows.

δ mountain synthesis example [Compound example (4)] 1.3-dimethylimidazolidine-2-thione 13C1
and 20 g of ethyl bromoacetate were stirred for 3 hours while heating to 120°C. After cooling, the reaction solution was washed with ethyl acetate to obtain oily 1,3-dimethyl-2-ethoxycarbonylmethylthioimidazolidinium bromide 22[I.

The bromine salt 22o and 7-amino-6-methyl-3-[
(2-dodecylsulfonyl-1-methyl)ethyl]-1
H-pyrazolo[3,2-C]-s-triazole3
0(+ was dissolved in 50 oz of ethanol, 20-! of triethylamine was added to a colander, and heated under reflux for 2 hours under a nitrogen stream. After cooling, the solvent was distilled off under reduced pressure. The residue was dissolved in ethyl acetate, and further The organic layer was washed with 1N hydrochloric acid, concentrated under reduced pressure, and purified by silica gel column chromatography using a hexane/ethyl acetate warm solvent. 28 g of the target product was obtained. The structure of the target product was confirmed by NMR, IR, and mass spectroscopy. It was done by spectrum.

The amount of the magenta coupler according to the present invention added to the photographic light-sensitive material of the present invention is 1.5 x 10-3 per mole of silver.
The range is preferably from 7.5 x 10 moles to 7.5 x 10 moles, more preferably from 1 x 10 moles to 5 x io moles.

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 calendar number and order of temperature. 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 acidic method, neutral method, and ammonia method. After the particles are created, they may be grown. 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, halide ions and silver ions were
It may be produced by sequentially and simultaneously adding H and PA while controlling the amount. 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 may be formed by cadmium salt, zinc salt, Senba salt, thallium salt, iridium salt or complex salt, rhodium salt or complex salt, rhodium salt or complex salt, etc. in the process of forming and/or growing the grains. It is possible to add metal ions using iron salts or complex salts and encapsulate them inside the particles and/or on the particle surfaces.By placing them in an appropriate reducing atmosphere, metal ions can be added to the inside of the particles and/or on the particle surfaces. It can give you a feeling of emotion.

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 or plate shape. In these particles, [I,0,01 plane and C1,1,1]
Any surface ratio 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,
Sulfur sensitization method using activated gelatin, selenium sensitization method using selenium compounds, reduction sensitization method using reducing substances,
A noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination.

8 Ef. ga>, □112, □yooi 1'te,
Using a dye known as a sensitizing dye, it is possible to optically sensitize to a desired wavelength range. 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. The hardener is li! in the processing solution. Ii! photosensitive material to the extent that there is no need to add a discipline agent! ! Although it is desirable to add a hardening agent to the processing solution, it is also possible to add a 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-7 enylene diamine derivative, aminophenol derivative, etc.). The dye-forming couplers are selected one for each emulsion layer so that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, and a yellow dye is selected for the blue-light sensitive emulsion layer. As for the forming couplers, 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.

Yellow dye-forming couplers include acylacetamide couplers (e.g. benzoylacetanilides,
In addition to the coupler of the present invention, magenta dye-forming couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazoles, open-chain acylacetonitrile couplers, etc., and cyan dye-forming couplers include: These 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 812 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, and is usually used in a high-boiling organic solvent with a boiling point of about 150°C or higher, and if necessary, in a low-boiling point and/or Also
,,,.

is dissolved using a water-soluble cloth Iam medium, and the gelatin is dissolved in water.
After emulsifying and dispersing a surfactant in a hydrophilic binder such as liquid using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or long sonic device, the desired hydrophilic colloid layer is formed. A step of removing the low-boiling 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.

A UV absorber is added to the hydrophilic colloid layers such as the protective layer and intermediate layer of the photosensitive material of the present invention in order to prevent capri due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light. It may be included.

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 photosensitive material using the silver halide emulsion of the present invention reduces the gloss of the photosensitive material, improves the ease of writing, and prevents the photosensitive materials from sticking to each other. 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-olephin 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. As coating methods, ex-doulsion (coating) and curtain coating, which allow two or more layers to be applied at the same time, are particularly useful.

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 lamps, cathode ray tube flying spots, various laser beams, light emitting diode lights, electron beams, X-rays,
Any known light source can be used, such as light emitted from a phosphor excited by γ rays, α rays, etc.

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.

It's okay to be ignored.

The silver halide photographic material of the present invention can be used to form an 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 amine phenol and p-phenylene diamine 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 30 (l) per color developer 11, preferably about 1 g to about 1 g per color developer 1f!
．． Use at a concentration of 5g.

Examples of aminophenol-based developers include 〇-aminophenol, p-aminophenol, and 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-p-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 hydrochloride,
2-amino-5-(N-ethyl-N-dodecylamino)
-Toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N
-ethyl-N-β-hydroxyethylaminoaniline,
4-amino-3-methyl-N.

N'-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-
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. , an alkali agent such as potassium carbonate, an alkali metal sulfite, an alkali metal bisulfite, an alkali metal thiocyanate, an alkali metal halide, benzyl alcohol, a water softener and a thickening agent. The I)H 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. A metal complex salt of an organic acid is used as a bleaching agent in the bleaching process, and the metal complex salt has the effect of oxidizing the metallic silver produced during development and converting it into silver halide, and at the same time coloring the uncolored areas of the coloring agent. It has a structure in which metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid. The most preferred organic acids used to form such metal complexes of organic acids 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] Ethylenediaminetetraacetic acid tetrasodium salt [7] Nitrilotriacetic acid Sodium acetate The bleaching agents used are as mentioned above! In addition to containing a metal complex salt of 1R as a bleaching agent, it can also contain various additives. As additives, it is particularly desirable to include rehalogenating agents, metal salts, and chelating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide.

Also, the pH of borates, oxalates, acetates, carbonates, phosphates, etc.
! 1. Buffers, 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, carbonic acid 1) Hall agents consisting of various salts such as potassium, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. may be contained alone or in combination.

When carrying out the process of the present invention while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, 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, hydrogen peroxide, bromate, 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-1] The magenta coupler of the present invention and the comparative coupler shown in Table 1 were each taken in an amount of 0.1 mol per mol of silver, and tricresyl phosphate was added in an amount of 1 times the weight of the coupler and 3 times the weight of the coupler. of ethyl acetate was added and heated to 60°C to completely dissolve. This solution was mixed with 1z of a 5% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont).
The mixture was mixed with a 5% gelatin aqueous solution 1200-A containing oJ' and emulsified and dispersed using an ultrasonic disperser to obtain an emulsion. Thereafter, this dispersion was added to 4ko green-sensitive silver iodobromide emulsion (containing 6 mol% silver iodide), and a 2% solution of 1,2-bis(vinylsulfonyl)ethane (water:methanol) was added as a hardening agent. -1:1) 12011 was added, coated and dried on the undercoated transparent polyester base, and samples 1-1 to 1-9
It was created. (Amount of coated silver: 20 ma/1000 m') The sample thus obtained was subjected to wedge exposure according to a conventional method, and then subjected to the following development treatment. Table 1 shows the results.

[Development process] 81″!IP!G″8°NT゛*rqvt″’fi!
l Iff fi j, t 1''...

[Color developing solution composition] Potassium carbonate 30 G [Bleach solution composition] [Fixer composition] [Stabilizing solution composition 1 Table 1 below in margin) Specific sensitivity is the reciprocal of the exposure that gives a density of Capri density + 0.1 Sample N001 using comparative coupler 1) was set as 100.

2) 0.9% temperature and humidity controlled to 30℃, 62%RH
After the sample was placed in a sealed container containing 6 cc of formalin aqueous solution for three days, 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 margins: 1 Comparative coupler 1) Comparative coupler 2) From Table 1, the couplers of the present invention have color development, formalin resistance,
It is clear that it has excellent light resistance.

[Example-2] Samples 1-1 to 1-9 in Example-1 were similarly exposed to wedge light and subjected to the following development treatment.

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
In the 75-80°C 2-minute combination treatment step, the composition of the treatment liquid used was as follows.

[Color developer] Benzyl alcohol 15m/ethylene glycol 15-! Potassium sulfite 2.0g Potassium bromide
0.7g sodium chloride
0.2g potassium carbonate
3G, Og hydroxylamine sulfate 3
．． 0g polyphosphoric acid (TPPS) 2.5
173-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 5.5g Optical brightener (4,4'-diaminostilbenzsulfonic acid derivative) 1.0g water Add 2.0g of potassium oxide water to make everyone 1/1 and adjust to E) H10.20.

[Bleach-fix solution] Ferric ammonium ethylenediaminetetraacetate dihydrate 60 Q ethylenediaminetetraacetic acid II 3Q ammonium thiosulfate (70% solution) 100m+/ammonium sulfite (40% solution) 27.5 ml pH 7 with potassium carbonate or glacial acetic acid, Adjust to 1 and add water to bring the total volume to 1.

[Stabilizing liquid] 5-chloro-2-methyl-4-isothiazolin-3-one 1° Oa ethylene glycol 10 G or less As is clear from the results in Table 2, the coupler of the present invention It can be seen that samples 2-4 to 2-9 containing the above samples 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 anatase-type titanium oxide.

The amounts added below are per 100 cm.

(1) Gelatin of 20so, blue-sensitive silver chlorobromide emulsion with silver content of 51(+), and di-octyl of 3so in which yellow coupler of 81111 and 0.1g of 2,5-di-t-octylhydroquinone were dissolved. Layer (2) containing phthalate coupler solvent 121G gelatin, 0.5mg 2.5-di-
medium containing 2 mg of dibutyl phthalate UV absorber solvent in which t-octylhydroquinone and 41 (It) UV absorber are dissolved.

(3) 181 G of gelatin, 4 Ia of green-sensitive silver bromide emulsion, 5 Il of 1 g of magenta coupler and 2.5 mg of dioctyl dissolved in monooctyl hydroquinone with 0.2 mg of 2,5-di. Layer containing phthalate coupler solvent.

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

(5) 16+o gelatin, 41 g of silver as a red-sensitive silver chlorobromide emulsion, and 2,0 tephole in which 3.5 mg of cyan coupler and 0.1 mg of 2.5-di-t-octylhydroquinone were dissolved. layer containing a tricresyl phosphate coupler solvent.

(6) Gelatin protective layer containing 9m(+) 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), U with the following structure is used.
A mixture of V-1 and UV-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.

Below - Margin 1′ UV absorber UV-1 UV-2 Y-coupler L

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
A silver halide color photographic material containing a magenta coupler represented by the following. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R represents a hydrogen atom or a substituent, and A is 5 to 6
Represents a group of atoms necessary to form a member heterocycle. Z represents a nonmetallic atomic group capable of forming a nitrogen-containing heterocycle. (However, the nitrogen-containing heterocycle represented by Z does not further form a condensed ring.)