JPS61177456A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve resistances to light and formalin and to enhance color formation performance by incorporating a specified magenta coupler in at least one silver halide emulsion layer. CONSTITUTION:At least one silver halide emulsion layer formed on the support of a silver halide color photographic sensitive material contains a magenta coupler represented by the general formula, R being H or a substituent, R' being H, halogen, alkyl, aryl, cycloalkyl, or heterocyclic, Y being a nonmetallic atomic group necessary for forming a 5- or 7-membered hetero ring together with an N atom, and Z being a nonmetallic atomic group capable of forming an N-contg. hetro ring. The magenta coupler is added, preferably, in an amt. of 1.5X10<-3>-7.5X10<-1>, especially, 1X10<-2>-5X10<-1>mol per mol of silver halide.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention provides a silver halide photographic photosensitive material containing a magenta coupler that forms magenta dye images with high color development and improved storage stability, particularly 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 general, in silver halide color photographic light-sensitive materials, exposed silver halide grains are reduced with an aromatic primary amine color developing agent, and the oxidized product of the color developing agent and yellow, magenta A dye image can be obtained by coupling with a coupler forming each of cyan and cyan dyes.

The coupler that has been put into practical use in the past to form the magenta dye is a pyrazolone coupler.
This has the disadvantage of having unfavorable side absorption and poor storage stability, especially resistance to formalin (formalin resistance).

In order to improve the above drawbacks, various IH-pyrazo o[3,2cl-s-triazole type magenta couplers have been proposed.
No. 7, British Patent No. 1,252,418, No. 1, 334
.

It is described in No. 515. The compounds described in both patents are superior to pyrazolone magenta couplers in terms of side absorption, but the improvement in formalin resistance is insufficient.
Furthermore, little improvement has been shown in terms of color development and light fastness of images.

Research D 1 closure 12
The IH-pyrazo o[3,2e]-9-)+771-type magenta coupler described in JP-A No. 58-42045, in which the compound described in No. 443 cannot be put to practical use at all in terms of color development, is formalin-resistant. Although significant improvements have been made in terms of color development and color development, there has been little improvement in light resistance.

Also, JP-A-59-99437 and JP-A No. 59-12573
Although the color forming properties of the coupler described in No. 2 have been improved, there is still no improvement in the light fastness of dye images based on the coupler described.

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, IH-pyrazolo [3], which has attracted attention for its lack of side absorption and high formalin resistance,
, 2-cl-s-) lyazole type magenta couplers, it can be said that little improvement has been made in terms of the light resistance of dye images.

[Purpose of the invention]

An object of the present invention is to provide a silver halide color photographic material that has good light fastness and formalin resistance and 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 contains the following general compounds. This is achieved by a silver halide color photographic light-sensitive material containing a magenta coupler represented by formula [I].

General formula (1) In the formula, R represents a hydrogen atom or a substituent, and R' is a hydrogen atom, a hydrogen atom, an alkyl group, a cycloalkyl group,
Represents an aryl group or a heterocyclic group.

Y represents a nonmetallic atomic group necessary to form a 5- to 7-membered heterocycle with a nitrogen atom, and Z represents a nonmetallic atomic group capable of forming a nitrogen-containing heterocycle (provided that Z The nitrogen-containing heterocycle represented does not further form a fused ring,
) Hereinafter, unless otherwise specified, it is represented by the general formula [I]. For convenience, Uni is simply represented by Q.

Specifically, the substituent represented by R is a halogen atom,
Furkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulf77moyl group, cyano group,
Spiro compound residue, endowed hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amine 7 group, acyl 7 mi 7 group, sulfone 7 mido group, imide group, ureido group, sul77moylamino group, alkoxycarbonylamino group, 7lyloxycarbonyl group, flukoxycarbonyl group, aryloxycarbonyl group, furkylthio 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 general formula (1), 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, the alkenyl group, and the alkynyl group has 2 to 3 carbon atoms.
2, dichlorofurkyl group, and cycloalkenyl group preferably have 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and 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 through a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and 7-aryloxycarbonyl, and those substituted through a heteroatom (specifically, hydroxy, alkoxy, and aryl) Oxy, heterocyclic oxy,
Those substituted via an oxygen atom such as siloxy, acyloxy, carbamoyloxy, nitro, 7mino (including dialkylamino, etc.), sul77moylamino, alkoxycarbonylamino, aryloxycarbonyl7mihaacylamino, sulfonamino, sulfonamide , imide, ureido etc. substituted via nitrogen atom, alkylthio, arylthio, heterocyclic thio, sulfonyl,
sulfinyl, sulfonyl, etc.; phosphonyl, etc., substituted via a phosphorus atom; etc.); specifically, for example, a methyl group, Ethyl group, isopropyl group, t-butyl group, pentadecyl group, heptadecyl group,
1-hexylnonyl group, i,i'-nopentylnonyl group, 2-chloro-t-butyl group, 1-fluoromethyl group, 1-ethoxytridecyl group, 1-nodoxyisopropyl group, methanesulfonylethyl group , 2,4-note t-7
Milphenoxymethyl group, anilino group, 1-phenylisopropyl group, 3-Il-butanesulfonaminophenoxyprobyl group, 3-4'((2-(4''(p-hydroxybenzenesulfonyl)phenoxy)dodecanoyl 7mino ,) phenylpropyl group, 3-(4'-(ff
-(2”,4”-di-t-7milphenoxy)butane 7
Mido]phenyl)-propyl group, 4-(ff-(.

-chlorophenoxy)tetradecanamidophenoxypropyl group, 7lyl group, cyclopentyl group, cyclohexyl group, and the like.

The 7-aryl group represented by R is preferably a phenyl group, which may have a substituent (for example, an alkyl group, an alkoxy group, an acylamide 7 group, etc.).

Specifically, phenyl group, 4-t-butyl 7-enyl group,
2,4-di-t-7mylphenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4'
-(a-(4″-t-butylphenoxy)tetradecanamide) phenyl group, and the like.

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

Examples of the 7-syl group represented by R include acetyl group, phenylacetyl group, dodecanoyl group, a-2,4-di-
Examples thereof include a furkylcarbonyl group such as a t-amylphenoxybutanoyl group, a 7-arylcarbonyl group such as a benzoyl group, a 3-pentadecyloxybenzoyl group, and a ρ-chlorobenzoyl group.

The sulfonyl group represented by R includes a methylsulfonyl group, a light alkylsulfonyl group such as a dodecylsulfonyl group,
Examples include 7lylsulfonyl groups such as benzenesulfonyl group and p-)luenesulfonyl group.

Examples of the sulfinyl group represented by R include ethylsulfinyl group, octylsulfinyl group, furkylsulfinyl group such as 3-phenoxybutylsulfinyl group, phenylsulfinyl group, and chiarylsulfinyl group such as -1pentadecyl phenylsulfinyl group. etc.

The phosphonyl group represented by R includes an alkylphosphonyl group such as a butyloctylphosphonyl group, a phenylphosphonyl 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.
For example, N-methylcarbamoyl group, N,N-cyphthylcarbamoyl group, N-(2-pentadecyloctylethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoyl group, N-(3-(2,4-nor Examples include t-7 milphenoxy)propyl)carbamoyl group.

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

Examples of the bridged hydrocarbon compound residue represented by R''ch include bicyclo[2,2,1]heptan-1-yl, tricyclo[3,3,1,1'']decane-1-yl, 7,7
-nomethyl-bicyclo[2,2,1]hebutan-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 a methoxy group, a propoxy group, a 2-ethoxyethoxy group,
Examples include pentadecyloxy group, 2-dodecyloxyethoxy group, and 7enethyloxyethoxy group.

The aryloxy group represented by R is preferably a 7-enyloxy group, and the 7-aryl nucleus may be further substituted with any of the substituents or atoms listed above for the 7-aryl group, such as a phenoxy group, p -t-butylphenoxy group,
- Bentadecyl phenoxy group and the like.

The heterocyclic oxy group represented by R preferably has 5 to 7 heterocycles, and the heterocycle may further have a substituent, for example, 3゜4.5.6-tetrahydro Examples include pyranyl-2-oxy group, 1-phenyltetrazol-5-oxy group, and the like.

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

Examples of the acyloxy group represented by R include furkylcarbonyloxy group, arylcarbonyloxy group, etc., and may further have a substituent, specifically, acetyloxy group, a-chromitusetyloxy group, etc. group, benzoyloxy group, etc.

The carbamoyloxy group represented by R may be substituted with an alkyl group, an aryl group, etc. Examples include N-ethylcarbamoyloxy group, N,N-noethylrupamoyloxy M, and N-phenylcarbamoyloxy group. It will be done.

The amide group represented by R may be substituted with an alkyl group, a 7-aryl group (preferably a phenyl group), etc., such as an ethylamino group, anilino group, a -monororoanilyl group,
Examples thereof include 3-pentadecyloxy group, 2-chloro-5-hexadecaneamide anilino group, and the like.

Examples of the acyl 7-mi 7 group represented by R include furkylcarbonyl amine 7 groups, arylcarbonyl amine 7 groups (preferably phenylcarbonyl amine 7 groups), etc., and may further have a substituent. acetamido group, a-ethylpropanamide group, N-phenyl 7cetamido group,
Examples thereof include a dodecanamide group, a 2,4-di-t-7-methylphenoxyacetamide group, and a 5a-3-t-butyl-4-hydroxy-7e/xybutanamide group.

Examples of the sulfone 7 mido group represented by R include an alkylsulfonylamino group, an arylsulfonylamino group, and may further have a substituent.

Conformally, there are 7 methylsulfonylamino groups, a bentatecylsulfonylamino group, a benzenesulfonamide group, p-)
Examples include a luenesulfone 7mido group and a 2-methoxy-5-t-7 milbenzenesulfonamide group.

The imide group represented by R may be open-chain or cyclic, and may have a substituent, such as a succinimide group, a 3-heptadecylsuccinimide group, a 7-talimide group, Examples include glutarimide group.

The ureido group represented by R is a furkyl group, an aryl group (
(preferably phenyl group), etc., such as N-ethylureido group, N-methyl-N-decylureido group, N-7! Examples thereof include a nylureido group, an Np-)lylureido group, and the like.

The sul77moylamide7 group represented by R is an alkyl group,
It may be substituted with an aryl group (preferably a phenyl group), and examples thereof include N,N-diptylsul7amoylamy7 groups, N-methylsul7amoylamy7 groups, N-phenylsulfTmoylamy7 groups, and the like.

The alkoxycarbonylamide 7 group represented by R is,
It may further have a substituent, for example, 7 methoxycarbonylamide groups, 7 methoxyethoxycarbonylamide groups,
Examples include 7 octadecyloxycarbonylamide groups.

The aryloxycarbonyl group represented by R may have a substituent, and examples thereof include a phenoxycarbonylamino group and a 4-methylphenoxycarbonylamino group.

The alkoxycarbonyl group represented by R may further have a substituent, such as a nodoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group, an octadenyloxycarbonyl group, an ethoxymethoxycarbonyloxy group, Examples include benzyloxycarbonyl group.

The 717-ruoxycarbonyl group represented by R may further have a substituent (for example, phenoxycarbonyl group, p-chlorophenoxycarbonyl group, l-pentadecyloxyphenoxycarbonyl group, etc.). .

, the furkylthio group represented by R may further have a substituent (e.g., ethylthio group, dodecylthio group,
Examples include octadecylthio group, 7enethylthio group, and 3-phenoxypropylthio group.

The 7-arylthio group represented by R is preferably a phenylthio group and may further have a substituent, for example, a phenylthio group,
p-/)xyphenylthio group, 2-octylphenylthio group, 3-occudecylphenylthio group, 2-carboxy7erthio group, p-7ceto7minophenylthio group, and the like.

The heterocyclic thio group represented by R is preferably a 5- to 7-membered heterocyclic thio group, which may further have a condensed ring or a substituent, such as 2-pyrinorthio group, 2-benzothiazolylthio group, and 2,4-diphenoxy-1,3,5-toI77sol-6-thio group.

Examples of the nitrogen-containing heterocycle formed by Z include a pyrazole ring, imidazole ring, triazole ring, or tetrazole ring, and examples of the substituents that the ring may have include those described for R above. .

In addition, the substituents (for example, R1R1 to R1) on the heterocycle in general formula (1) and general formulas (If) to [■] described later are moieties (herein, RII and Z' are in general formula (1)). R in
, Z, and Q 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 [■]].

General formula [■] General formula (III) General formula [■] N -N -NH General formula (V) General formula [VI] General formula [■] In the general formula (If) to [■], R3 to R, and Q
has the same meaning as R and Q above.

Also, among the general formula (1), the following general formula [
■].

General formula [■] In the formula, R+-Q and Z have the same meanings as RlQ and Z in the general formula (I).

Among the magenta couplers represented by the general formulas (II) to [■], particularly preferred is the magenta coupler represented by the general formula (n).

Regarding the substituents on the heterocycle in general formulas [1] to [■], R in general formula [■] and R3 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.
The following conditions 1 and 1 are particularly preferred.
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 substituents R and R3 on the heterocycle are those represented by the following general formula (ff).

General formula CI 1oC- R in the formula R,,R,. and R1 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, sul77 moyl group,
Cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, 7-syloxy group, carbamoyloxy group, 7-mino group, acylami 7 group, sulfonamide group , imido group, ureido group, sul77moylamino group, alkoxycarbonylami7 group, aryloxycarbonyl7mi7 group, alkoxycarbonyl group, 7lyloxycarbonyl group, alkylthio group, arylthio group, heterocyclic thio group, RstRlo and at least two of R11 are not hydrogen atoms.
and R16 may be bonded to form a saturated or unsaturated ring (e.g. dichloroflucan, cycloalkene, heterocycle), and R11 may be bonded to the chain ring to form a bridged hydrocarbon compound residue. good.

The groups represented by R9 to R11 may have a substituent, and specific examples of the group represented by R9 to R1+ and the substituents that the group may have include those in the general formula CI) described above. Specific examples of the group represented by R and substituents are listed.

Also, for example, a ring formed by combining R9 and R10 and R5
Specific examples of the bridged hydrocarbon compound residue formed by -R1 and its optional substituents include specific examples of cycloalkyl, cycloalkenyl, and heterocyclic groups represented by R in the aforementioned general formula CI). and its substituents.

Among the general formulas (ff), (i) R=~R
When two of 1 are alkyl groups, (ii) R* to R1
When one of +, for example, R8, is a hydrogen atom, and the other two, R9 and R10, combine to form a cycloalkyl with the root carbon atom, the following is true.

Furthermore, it is preferable among (i) that two of R1 to RI+ are furkyl 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 the alkyl represented by R in the general formula (1), cycloalkyl R/ Examples of the halogen atom represented include a chlorine atom and a bromine atom.

Alkyl groups (e.g. methyl group, ethyl group, i-propyl group a4), cycloalkyl groups (e.g. cyclohexyl group etc.), aryl groups (e.g. phenyl group etc.) and heterocyclic groups (e.g. imidazolyl group, thiazolyl group) represented by R1 ) further includes a halogen atom, nitro group, cyano group, hydroxy group, sulfo group, carboxy group, alkoxy group, aryloxy group, acylamino group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfamoyl group, sulfonamide may be substituted with a group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylamino group, or a ureido group.

As a 5- to 7-membered heterocycle formed by Y and a nitrogen atom,
For example, cyclic amines such as cyclic amide compounds, cyclic imide compounds, cyclic urea compounds, imidazole, pyrazole, triazole, lactam compounds, piperidine, pyrrolidine, pyrroline, bifour, morpholine, pyrazolidine, and pyrazoline are mentioned.

Next, specific examples of the magenta coupler represented by the general formula [I] of the present invention are shown below, but the present invention is not limited thereto.

CM.

c, 11 cn.

Suga CI horse 3 01゜ C1 bird 0) C.B.

Next, 5. of the present invention. A typical synthesis method for magenta couplers will be described. Journal of the Chemistry
cal 5ociety.

Perkinl 1977, 2047-2052
, U.S. Patent No. 3,725,067, JP-A-59-9
The synthesis was carried out with reference to No. 9437, JP-A No. 58-42045, etc.

Furthermore, a method for introducing a hydroxy group into the 7-position of an IH-pyrazolo(3,2-e)-;m-)lyazole compound (general formula (I)) is shown in U.S. Pat. No. 3,419,391. It can be obtained by ayonotation at the 7-position so that the 7-position is diazotized and heated in an aqueous hydrochloric acid solution.The 7-hydroxy-1■-pyrazolo (3,2-
6)-1-) Exemplary compounds can be synthesized by reacting a lyazole compound with an α-substituted alkyl halide. The α-substituted alkyl halide was synthesized with reference to JP-A-52-90932.

In the above reaction formula, Y and R' are the same as those shown in general formula [1], and Hae represents a halide. Obtain letter α
-Substituted alkyl halide in a solvent such as alcohol, a7ton, dioxane, tetrahydrofuran, ether, benzene, dimethylformamide, sodium alcoholade, sodium hydroxide, potassium carbonate, pyridine,
An exemplary triethylamine compound was obtained.

Next, a specific synthesis example will be shown.

Synthesis Example 1 (Exemplary Compound 1) 5.5-dimethylhydantoin and formalin were heated on a water bath for 2 hours to obtain 5.5-dimethyl-3-hydroxymethylhydantoin. Next, this was reacted with thionyl chloride under heating, and excess thionyl chloride was removed under reduced pressure to obtain 5°5-dimethyl-3-dimethylhydantoin. Separately, 3-(3-(4-(4-dodecyloxyphenylsulfonamido)phenyl)pu-buil]-6-methyl-7-hydroxy-IH-vilazo (3
, 2-f]-i was dissolved in triazole alcohol, added with an equivalent amount of sodium alcohol, and heated on a water bath under nitrogen atmosphere. Next, the alcohol was removed under reduced pressure, dimethylformamide was added, and the previously obtained dimethylformamide solution of 5,5-dimethyl-3-chloromethylhydantoin was added dropwise while stirring at room temperature. After stirring for 1 hour, the reaction was carried out at 50'C for 2 hours, the reaction mixture was poured into ice water, and the resulting brown viscous substance was dissolved in ethyl acetate. The ethyl acetate solution was washed with water, dried over sodium sulfate, and then the solvent was removed under reduced pressure. The oil was purified by silica gel column chromatography. The candy-like substance obtained by mixing the solvent was confirmed to be Exemplified Compound [I] from the results of mass spectrometry.

Synthesis Example 2 (Exemplary Compound 11) 5,5-dimethylhydantoin in Synthesis Example 1 was replaced with morpholine, and 3-(3-(4-(4-dodecyloxyphenylsulfonamido)phenyl)propyl]-6-methyl-7- Hydroxy j 1 ) 1-pyrazolo(3,2-
6)-1-) lyazole to 3-(1-methyl-2-dodecylsulfoethyl)-6-methyl-7-hydroxy-I
Synthesis was carried out in exactly the same manner as in Synthesis Example 1, except that H-pyrazolo(3,2-c)-.■-triazole was used, to obtain a pale yellow candy-like substance. This product was confirmed to be Exemplified Compound (11) from the mass spectrum results.

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 to 1 mole of silver.
-3%/I/ to 7.5 x to"" %4 is preferred, more preferably I x to -2 mol to s
The silver halide photographic light-sensitive material of the present invention can be, for example, a color negative film or a color photographic paper, and a color photographic paper used for direct viewing. When used, the effects of the method of the present invention are effectively exhibited.

The silver halide photographic light-sensitive materials of the present invention, including this color photographic paper, may be for single color or multicolor.In the case of multicolor silver halide photographic materials, subtractive color reproduction is possible. In order to do this, it usually has a structure in which a silver halide emulsion layer containing magenta, yellow and cyan couplers as photographic couplers and a non-light sensitive layer are laminated on a support in an appropriate number and order of layers. However, the calendar number and layer order 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 halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any used in silver 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 method for producing and growing the 0-type particles may be the same or different.

Silver halide emulsions can be prepared by mixing halide ions and silver ions at the same time, or by mixing one in the presence of the other. ions and silver ions in a mixing pot
Growth may be performed by sequentially and simultaneously adding HspAg in a controlled manner, or the silver halide composition of the grains may be changed using a convergence method after growth.

When producing the silver halide 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 formed by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts, etc. or complex salts, iron salts or complex salts,
Metal ions can be added and incorporated into the particles and/or on the particle surfaces, and by placing them in a suitable reducing atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

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 unnecessary soluble salts may be left in the silver halide emulsion.
This 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 also 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. Any ratio of the (1007 planes and (1111 planes) can be used. In addition, particles with various crystal forms may be mixed.

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

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 dye may be used alone or in combination of two or more, and together with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect, or a compound that does not substantially absorb visible light. In addition, a supersensitizer that enhances the sensitizing action of the sensitizing dye may be included in the emulsion.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
During chemical ripening for the purpose of preventing capri during storage or photo processing and/or maintaining stable photographic performance,
and/or at the end of the chemical ripening, and/or after the end of the chemical ripening and before coating the silver halide emulsion, compounds known in the photographic industry as anti-capri agents or stabilizers can be added.

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 such an 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, p-phenylenediamine! A dye-forming coupler is used that forms a dye by performing a coupling reaction with an oxidized form of a conductor or a 7-minofenol derivative. The dye-forming couplers are typically selected for each emulsion layer to form a dye that absorbs light in the emulsion layer's sensitive spectrum, with a yellow dye-forming coupler for the blue light-sensitive emulsion layer. However, 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 acylaceto 7-mido couplers (e.g., benzoylacetanilides, piparoylacetanilides), and magenta dye-forming couplers include, in addition to the couplers of the present invention, 5-pyrazolone couplers, vilazolobenlimigzole couplers, and pyrazolone couplers. Examples include zolotriazole, open-chain acylaceto 7-mido couplers, and cyan dye-forming couplers such as lotus 7-tall couplers and phenol couplers.

It is desirable that these dye-synthesizing couplers have a group called a belast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms.Also, these dye-forming couplers have 4 molecules in order to form one molecule of dye. Either 4-isomerism, in which 100 silver ions need to be reduced, or 2-isomerism, in which only 2 molecules of silver ions need to be reduced, may be used.

For dye-forming hydrophobic compounds such as couplers that do not need to be adsorbed onto the silver halide crystal surface, various methods such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion can be used. can be appropriately selected depending on the chemical structure of the hydrophobic compound, etc. The oil-in-water emulsion dispersion method can be applied using conventionally known methods for dispersing hydrophobic additives such as couplers, and is usually mixed with a high boiling point organic solvent having a boiling point of about 150°C or higher, and if necessary, a low boiling point and/or a high boiling point organic solvent. Alternatively, it is dissolved using a water-soluble organic solvent, and a surfactant is used in a hydrophilic binder such as an aqueous gelatin solution using a stirrer, homogenizer, colloid mill, 70-jet mixer,
It may be emulsified and dispersed using a dispersion means such as an ultrasonic device, and then added to the desired hydrophilic colloid layer. A step of removing the low-boiling organic solvent may be included simultaneously with the dispersion or dispersion (1° high boiling, α-oil agents include phenol derivatives, heptatarates, phosphates, etc. that do not react with the oxidized form of the developing agent,
Boiling point 15 of citric acid ester, ambrocomatate ester, alkyl amide, fatty acid ester, trinosinate ester, etc.
An organic solvent having a temperature of 0° C. or higher is used.

7-Nionic surfactants, nonionic surfactants, cations are used as dispersion aids when dissolving a hydrophobic compound in a low boiling point solvent alone or in combination with a high boiling point solvent and dispersing it in water using a machine or ultrasound. A surfactant 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 anti-capri agents are used to prevent deterioration and noticeable graininess.

The color antifoggant may be used in the emulsion layer itself, or in an intermediate layer provided between adjacent emulsion layers.

In the color light-sensitive material using the silver halide emulsion layer 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. 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 ylene-ageing prevention layer.

These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the color light-sensitive material during development.

The silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photosensitive material using the silver halide emulsion of the present invention reduces the gloss of the photosensitive material, increases the retouchability, and sticks the photosensitive materials together. A matting agent can be added for prevention purposes.

A lubricant can be added to reduce the sliding friction of the light-sensitive material using the silver halide emulsion of the present invention.

An antistatic agent for the purpose of preventing static electricity can be added to the light-sensitive material containing 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 as protective colloids in the emulsion layer and/or the emulsion layer on the side on which the emulsion layer is laminated with respect to the support. It may also be used as a 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,
Antistatic, improved slipperiness, emulsification and dispersion, prevention of adhesion, and (
Various surfactants are used for the purpose of improving photographic properties (such as accelerating development, increasing contrast, sensitization, etc.).

The photographic emulsion layer of the light-sensitive material using the silver halide emulsion of the present invention, and other layers include a baryta layer or a visible reflective support such as paper laminated with an a-olefin polymer, synthetic paper, cellulose acetate, cellulose nitrate, It can be applied to films made of semi-synthetic polymers such as polystyrene, polyvinyl chloride, polyethylene tere-7-thalerate, polycarbonate, and polyamide, as well as rigid bodies such as plastic, metal, and ceramics.

The silver halide photosensitive material of the present invention is prepared by subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary.
1* or 2 or more to improve adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, antihalation properties, friction properties, and/or other properties directly or on the surface of the support. It may be applied through a subbing layer.

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. Roots B coatings and curtain coatings 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, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams,
Any known light source can be used, such as light emitted from a phosphor excited by X-rays, gamma rays, AG, 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, or longer exposures of 1 second or more are possible. The exposure may be performed continuously or intermittently.

An image can be formed using the silver halide photographic material of the present invention by color development as known in the art.

Aromatic No. 11 used in the color developer in the present invention!
The amine color developing agents include those known and widely used in various color photographic processes.

These developers include aminophenol and I)-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 are generally used in color developer IQ at approximately 0.5%. tg to about 30 g, preferably about 1 g to about 1 for color developer IQ.
．． Use at a concentration of 5g.

Examples of aminophenol-based developers include 〇-7minophenol, p-aminophenol, and 5-amino-2-
Oxytoluene, 2-7 minnow 3-oxytoluene, 2
-Oxy-3-7 minnow 1°4-tmethylbenzene and the like are included.

Particularly useful primary aromatic 7-mino color developers include N, N'
-Nofurkyl-9-phenylenenoamine compound, in which the alkyl group and phenyl group may be substituted with any substituent.Among them, the most useful compound is N,N'-diethyl-p- Phenylenecyamine hydrochloride, N-methyl-p-phenylene dihumine monochloride, N,
N'-nomethyl-p-phenylenenoamine hydrochloride, 2-
7mi/-5-(N-ethyl-N-dodecylamido/)-toluene 1, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-7 minoaniline sulfate, N-
Ethyl-N-β-hydroxyethylaminoaniline, 4
-7 minnow 3-methyl-N,N'-noethylaniline,
Examples include 4-7minor N-(2-methoxyethyl)-N-ethyl-3-methyl7nyline-p-)luenesulfonate.

In addition to the above-mentioned primary aromatic amine color developer, the color developer used in the process of the present invention contains various components normally added to color developers, such as sodium hydroxide, sodium carbonate, Alkaline agents such as potassium carbonate, alkali metal sulfites, alkali metal bisulfites,
Alkali metal thiocyanates, alkali metal halides, benol alcohol, water softeners, thickeners, and the like may optionally be included. 9 of this color developer
The H value is usually 7 or higher, most commonly about 10 to 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, copper, etc. are coordinated with 7 minoboricarboxylic acid or an organic acid such as oxalic acid or citric acid. There are 8 like this! The most preferred organic acids used to form the metal complex salts of 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.

[1] Ethylenenoaminetitraacetic acid [2] Nitrilotriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid nonodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [6] Ethylenedi7minetetraacetic acid tetrasodium salt Salt (7) 2) Lyrotriacetic acid sodium salt The bleaching agent used contains the above-mentioned metal complex salt of an organic acid as a bleaching agent, and may 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.
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 It may contain one or more pH buffers consisting of various salts such as potassium, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide.

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. By including these salts in the bleach-fixing replenisher, 1! May be added to the 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 as desired (or an appropriate oxidation Agents such as hydrogen peroxide, bromates, persulfates, 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 a 5% aqueous solution of Flukanol B (alkylnaphthalene sulfonate, manufactured by DuPont).
Mix with 1200ml of 5% gelatin aqueous solution containing
The mixture was 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%).
4, and a 2% solution of 1,2-bis(vinylsulfonyl)ethane (water:methanol=
1:1) Add 120 Ugly/Stand, apply and dry on the undercoated transparent polyester base, and prepare sample 1-1-1.
-10 was created. (Coated silver amount 20mg/100cv2
) The samples thus obtained were 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.

[Color developing solution composition] [Bleach solution composition J [Fixer composition 1 [Stabilizing solution composition] , -\ 1) Specific sensitivity is the reciprocal of the exposure that gives a density of fog density + 0.1, and comparative coupler 1) Sample No. 1 used was 1
It was set as 00.

2) 0.9% temperature and humidity controlled to 30℃, 62%RH
After placing the sample in a sealed container containing 6 cc of formalin aqueous solution for 3 days, color development is 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 color development treatment was irradiated with a xenon fade meter for 5 days, and the percentage of dye remaining at the initial density = 1.0 was measured.
showed that.

Comparative Couplers (1) Comparative Couplers (2) (Exemplary Compounds of Japanese Patent Publication No. 48-30895) From Table 1, it is clear that the couplers of the present invention are excellent in color development, formalin resistance, and light resistance.

[Example 21 Samples 1-1 to 1-10 in Example 1 were similarly exposed to wedge light and subjected to the following development treatment. These results are shown in Table 2. The measurements of specific sensitivity and light resistance are shown in Example-
The same method as 1 was used.

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

[Color developing solution] [Bleach-fixing solution] [Stabilizing solution] As is clear from the results in Table 2, samples 2-4 to 2-10 containing the couplers of the present invention had better sensitivity, color development, and It can be seen that it has excellent light resistance.

[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 100ca+2.

(1) 20 mg of gelatin, 5 mg of silver as a blue-sensitive silver chlorobromide emulsion, and 3B di-octyl 7 in which 8 mg of one yellow coupler and O, 1 mg of 2,5-not-t-octylhydroquinone were dissolved. Layer (2) containing tallate coupler solvent; intermediate containing 12 g gelatin, 0.5 mg 2,5-not-t-octylhydroquinone and 2 mg dibutyl 7-thaleate UV absorber solvent dissolved in 4B UV absorber; layer.

(3) 18 mg gelatin, 4B green-sensitive silver chlorobromide emulsion as 1 silver, and 5 g magenta coupler 1
A layer containing 2.5 mg of dioctyl 7-thaleate coupler solvent in which 0.2 mg of 2,5-di-t-octylhydroquinone was dissolved.

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

(5) 2,0eiH in which 16 mg of gelatin, 4 mg of silver as a red-sensitive silver chlorobromide emulsion, and 3.5 mg of cyan coupler and 0.1-g of 2,5-di-t-octylhydroquinone were dissolved. A layer containing a tricresyl phos 7 ethocabler solvent.

(6) Gelatin preserves containing 9mg of gelatin! l
1 layer.

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.

Cut external ray absorber UV-1 0 ■ UV-2 H A clear dye image with excellent spectral absorption characteristics, good color tone, and wide color reproduction gamut is formed, and the light fastness of the magenta dye can be improved.

Applicant Roku Konishi Photo Industry Co., Ltd. Procedural amendment (method) % formula % 2. Name of the invention Silver halide color photographic light-sensitive material 3. Relationship with the person making the amendment Patent applicant address 1 Nishi-Shinjuku, Shinjuku-ku, Tokyo No. 26-2 Konishiroku Photo Industry Co., Ltd. (Telephone 0425-83-1521) Patent Department 4, Date of amendment order 5, “Detailed description of the invention” column 6 of the specification subject to amendment, Contents of amendment 1 ) Page 3, line 15 of the specification [Research D 1 closure J] [Research ψ disclosure (Research
D Correct it to 1 closure month.

2) Page 32, lines 18 to 19 of the specification [Jour
nal of the chemical 5
ociety, PerkinI 1977.2047
〜2052J and ``Journal of the Chemical Society, Perkin Edition I (J, Chem,
Soc, Perkin Trans, I
), 19 Fufu year 92047-2052 ￥L" is corrected.

Procedural amendment April 10, 1986

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: General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc.
Represents an aryl group or a heterocyclic group. Y represents a nonmetallic atomic group necessary to form a 5- to 7-membered heterocycle together with a nitrogen atom, and 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.)]