JPH0365532B2 - - Google Patents

Description

[Detailed description of the invention]

(Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material with improved color development. More specifically, 1H-pyrazolo[1,5
-b] [1,2,4] It relates to a silver halide color photographic light-sensitive material containing a triazole magenta coupler. (Prior Art) In silver halide color photographic light-sensitive materials, so-called dye-forming couplers (hereinafter simply referred to as couplers) react with a light-sensitive silver halide emulsion and an oxidized product of an aromatic primary amine developer to form a dye. A method using a yellow coupler, a cyan coupler, and a magenta coupler is usually used. Among these, 5-pyrazolone couplers, which are frequently used as magenta couplers, have major problems in color reproduction, such as the fact that the azomethine dye has sub-absorption near 430 nm and the tail of the absorption spectrum is poorly cut off on the long wavelength side. It was hot. In order to solve this problem, 1H-pyrazolo[1,5-b][1,2,4]triazole couplers were developed. However, although this family of couplers has solved the above-mentioned problems regarding hue, the couplers cannot be developed when developed under conditions that generate a sufficient amount of oxidized aromatic primary amine developer in the silver halide emulsion layer. It has been found that there is a problem in that the maximum color density (hereinafter simply referred to as Dmax) decreases due to the low conversion rate from azomethine to azomethine dye (hereinafter simply referred to as coloring efficiency). (Objective of the Invention) The first object of the present invention is to produce 1H-pyrazolo[1,5-b][1,2,
4] To provide a silver halide color photographic light-sensitive material with improved color development using a triazole coupler. The second object of the present invention is to improve the sensitivity of 1H-
An object of the present invention is to provide a novel highly sensitive silver halide color photographic light-sensitive material using a pyrazolo[1,5-b][1,2,4]triazole coupler. (Means for Solving the Problems) The above object is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which a substituted or unsubstituted alkyloxy group is present at the coupling active position. or 1H bound to a substituted or unsubstituted heterocyclic oxy group
- A silver halide color photographic light-sensitive material characterized by containing at least one type of pyrazolo[1,5-b][1,2,4]triazole magenta coupler. The coupler preferably has the following general formula []
It is expressed as General formula [] (However, in the formula, R ¹ and R ² represent a hydrogen atom or a substituent. ^{R 3} represents an alkyl group or a heterocyclic group. Also, R ¹ , R ² or R ³ form a double or higher polymer. In the general formula, a multimer means one having two or more groups represented by the general formula [] in one molecule, and includes bis-form polymer couplers. Here, the polymer coupler may be a homopolymer consisting only of a monomer having a moiety represented by the general formula [] (preferably one having an ethylenically unsaturated bond, hereinafter referred to as vinyl monomer), or an aromatic primary amine A copolymer may be made with a non-color-forming vinyl monomer that does not couple with the oxidized form of the developer.) In the general formula [], R ¹ and R ² are hydrogen atoms, halogen atoms, aliphatic groups, or aryl groups. , heterocyclic group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imide group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, carbamoyl group, acyl group, sulfamoyl group, sulfonyl group, sulfinyl group, alkoxycarbonyl group , represent an aryloxycarbonyl group, and may be the same or different. The case where R ¹ or R ² becomes two groups and forms a bis body is also included. In addition, when the moiety represented by the general formula [] is in the vinyl monomer,
R ¹ or R ² represents a simple bond or linking group,
The moiety represented by the general formula [] and the vinyl group are bonded through this. More specifically, R ¹ and R ² are hydrogen atoms, halogen atoms (e.g., chlorine atoms, bromine atoms, etc.),
Aliphatic groups (e.g., straight-chain, branched-chain alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups having 1 to 32 carbon atoms), which include oxygen atoms, nitrogen atoms, sulfur atoms, It may be substituted with a substituent linked to a carbonyl group, a hydroxy group, an amino group, a nitro group, a carboxy group, a cyano group, or a halogen atom,
For example, methyl group, propyl group, t-butyl group,
Trifluoromethyl group, tridecyl group, 2-methanesulfonylethyl group, 3-(3-pentadecylphenoxy)propyl group 3-{4-{2-[4-(4
-Hydroxyphenylsulfonyl)phenoxy]
dodecanamido}phenyl}propyl group, 2-ethoxytridecyl group, trifluoromethyl group, cyclopentyl group, 3-(2,4-di-t-amylphenoxy)propyl group, etc.), aryl group (e.g., phenyl group, 4-t-butylphenyl group,
2,4-di-t-amyl phenyl group, 4-tetradecanamidophenyl group, etc.), heterocyclic group (e.g., 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.) , cyano group, alkoxy group (e.g. methoxy group, ethoxy group, 2-methoxyethoxy group, 2-dodecyloxyethoxy group, 2-methanesulfonylethoxy group, etc.), aryloxy group (e.g. phenoxy group, 2-methylphenoxy group) , 4-t-butylphenoxy group, etc.), heterocyclic oxy group (e.g., 2-benzimidazolyloxy group, etc.), acyloxy group (e.g., acetoxy group, hexadecanoyloxy group, etc.), carbamoyloxy group (e.g. , N-phenylcarbamoyloxy group,
N-ethylcarbamoyloxy group, etc.), silyloxy group (e.g., trimethylsilyloxy group,
etc.), sulfonyloxy groups (e.g., dodecylsulfonyloxy groups, etc.), acylamino groups (e.g., acetamido group, benzamide group, tetradecanamide group, α-(2,4-di-t-amylphenoxy)butyramide group, γ- (3-t-butyl-4-hydroxyphenoxy)butyramide group, α-{4-(4-hydroxyphenylsulfonyl)phenoxy}decaneamide group, etc.), anilino group (e.g. phenylamino group, 2-chloroanilino group, 2-chloro-5-tetradecanamide anilino group, 2-chloro-5-dodecyloxycarbonylanilino group, N-acetylanilino group, 2
-chloro-5-{α-(3-t-butyl-4-hydroxyphenoxy)dodecaneamide}anilino group, etc.) ureido group (e.g., phenylureido group, methylureido group, N,N dibutylureido group, etc.), imide groups (e.g., N-succinimide group, 3-benzylhydantoynyl group, 4-
(2-ethylhexanoylamino)phthalimide group, etc.), sulfamoyl group (e.g., N,N-
dipropylsulfamoylamino group, N-methyl-N-decylsulfamoylamino group, etc.), alkylthio group (e.g. methylthio group, octylthio group, tetradecylthio group, 2-phenoxyethylthio group, 3 -phenoxypropylthio group, 3
-(4-t-butylphenoxy)propylthio group,
etc.), arylthio groups (e.g., phenylthio groups,
2-butoxy-5-t-octylphenylthio group, 3-pentadecylphenylthio group, 2-carboxyphenylthio group, 4-tetradecanamidophenylthio group, etc.), heterocyclic thio group (e.g.
2-benzothiazolylthio group, etc.), alkoxycarbonylamino group (e.g., methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), aryloxycarbonylamino group (e.g., phenoxycarbonylamino group, 2,
4-di-tert-butylphenoxycarbonylamino group, etc.), sulfonamide group (e.g., methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, octadecanesulfonamide group, 2-methyloxy-5-t-butylbenzenesulfonamide group, etc.), carbamoyl group (e.g., N-ethylcarbamoyl group, N,N-dibutylcarbamoyl group, N-(2-dodecyloxyethyl)carbamoyl group, N -methyl-N-dodecylcarbamoyl group, N-{3-(2,4-di-tert
-amylphenoxy)propyl}carbamoyl group, etc.), acyl group (e.g. acetyl group, (2,
4-di-tert-amylphenoxy)acetyl group,
benzoyl group, etc.), sulfamoyl group (e.g.
N-ethylsulfamoyl group, N,N-dipropylsulfamoyl group, N-(2-dodecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N,N-diethylsulfamoyl group moyl group, etc.), sulfonyl group (e.g., methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.),
Sulfinyl groups (e.g., octanesulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, etc.), alkoxycarbonyl groups (e.g.,
methoxycarbonyl group, butyloxycarbonyl group, dodecyloxycarbonyl group, octadecyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g. phenoxycarbonyl group, 3
-pentadedylphenoxycarbonyl group, etc.). When R ¹ or R ² becomes a divalent group to form a bis body, this divalent group can be described in more detail as a substituted or unsubstituted alkylene group (for example,
methylene group, ethylene group, 1,10-decylene group,
_{-CH2CH2 -} O- _CH2CH2- , etc.), substituted or unsubstituted phenylene groups ( _e.g. , 1,4-phenylene group, 1,3-phenylene group,

【formula】

[Formula], etc.), -NHCO-R ⁵ -CONH- group (R ⁵ represents a substituted or unsubstituted alkylene group or phenylene group)
Examples include. When the moiety represented by the general formula [] is present in the vinyl monomer, the linking group represented by R ¹ or R ² is an alkylene group (a substituted or unsubstituted alkylene group, such as a methylene group or an ethylene group). ,
1,10 _- decylene _group , _{-CH2CH2OCH2CH2- ,}
), phenylene group (substituted or unsubstituted phenylene group, such as 1,4-phenylene group, 1,3
-phenylene group,

【formula】

[Formula] etc.), -NHCO-, -CONH-, -O-, -OCO- and aralkylene groups (e.g. etc.). Note that the vinyl group in the vinyl monomer may have a substituent other than those represented by the general formula []. Preferred substituents are a hydrogen atom, a chlorine atom, or a lower alkyl group having 1 to 4 carbon atoms. Examples of non-color-forming ethylene-like monomers that do not couple with the oxidation products of aromatic primary amine developers include acrylic acid, α-chloroacrylic acid, α-alacrylic acid (such as methacrylic acid), and derivatives of these acrylic acids. ester or amide (e.g. acrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propylacrylate, n-butylacrylate,
t-Butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n
-butyl methacrylate and β-hydroxy methacrylate), methylene dibis acrylamide,
vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (e.g. styrene and its derivatives),
vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid,
Citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic acid, maleic anhydride, maleic esters, N-vinyl-2-pyrrolidone, N-vinylpyridine, and 2- and 4-
Examples include vinylpyridine. It also includes cases where two or more of the non-color-forming ethylenically unsaturated monomers used herein are used together. In the general formula [], the alkyl group or heterocyclic group represented by ^R3 is an alkyl group having 1 to 18 carbon atoms (e.g., methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group). , i-butyl group, t-butyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-octadecyl group, etc.), alkenyl group having 1 to 18 carbon atoms (e.g.
propenyl group, butenyl group, octenyl group, etc.)
Aralkyl groups having 1 to 18 carbon atoms (e.g., benzyl group, phenylethyl group, etc.), aralkenyl groups having 1 to 18 carbon atoms (e.g., phenylpropenyl group, etc.), cycloalkyl groups (e.g., cyclopentyl group, cyclohexyl group, methyl cyclohexyl group, cycloheptyl group, etc.), or a 5- or 6-membered heterocyclic group (the hetero atom is selected from a nitrogen atom, an oxygen atom, or a sulfur atom. Examples of the heterocyclic group include a tetrahydrofuryl group, (imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, thiazolyl group, piperazyl group, etc.). Here, the alkyl group, alkenyl group, aralkyl group, aralkenyl group, cycloalkyl group, and heterocyclic group represented by R ³ each have a substituent such as a halogen atom (such as fluorine, chlorine, or bromine), a cyano group, a hydroxyl group, Alkoxy groups (e.g., methoxy, ethoxy, propyloxy, butoxy, octyloxy, etc.), aryloxy groups (e.g., phenoxy), acyloxy groups (e.g., acetyloxy, propionoyloxy, etc.) butyroyloxy group, benzoyloxy group, etc.), acylamino group (e.g., formamino group, acetylamino group, propionoylamino group, benzoylamino group, etc.), sulfonamide group (e.g., methylsulfonamide group, octylsulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (e.g., unsubstituted sulfamoyl group, methylsulfamoyl group, ethylsulfamoyl group, propylsulfamoyl group, phenylsulfamoyl group, etc.), sulfonyl group (e.g., methylsulfonyl group), group, ethylsulfonyl group, octylsulfonyl group, benzenesulfonyl group, etc.), carboxy group, sulfo group, nitro group,
arylthio group (e.g. phenylthio group etc.),
Alkylthio groups (e.g., methylthio group, ethylthio group, etc.), carbamoyl groups (e.g., ethylcarbamoyl group, phenylcarbamoyl group, etc.),
Alkoxycarbonyl groups (e.g., methoxycarbonyl group, ethoxycarbonyl group, etc.), sulfinyl groups (e.g., methylsulfinyl group, phenylsulfinyl group, etc.), heterocyclic groups (e.g.,
pyrazolyl group, triazolyl group, etc.). These substituents may be further substituted with these substituents, or two or more substituents may be substituted at the same time, and in this case, the substituents may be the same or different. In addition, when R ³ becomes a divalent group to form a bis body, this divalent group is described in more detail as follows:
Substituted or unsubstituted alkylene groups (e.g., methylene group, ethylene group, 1,10-decylene group, -
CH ₂ CH ₂ -O-CH ₂ CH ₂ -, etc.), substituted or unsubstituted divalent heterocyclic groups (e.g.

【formula】 【formula】

[Formula], etc.), or a group represented by the following general formula []. General formula [] -A ¹ -B-A ² (However, in the formula, A ¹ , A ² and B represent a divalent group.
Specifically, A ¹ and A ² represent a substituted or unsubstituted alkylene group or a heterocyclic group, and B represents a substituted or unsubstituted alkylene group or a heterocyclic group, an aryl group, an oxygen atom, an amino group, a sulfur atom,

【formula】 【formula】

Represents a divalent group such as [Formula] or a simple bond. ) Specific examples of typical magenta couplers according to the present invention are shown below, but the present invention is not limited thereto. Next, a general method for synthesizing the coupler of the present invention will be described. The synthesis of the 1H-pyrazolo[1,5-b][1,2,4]triazole skeleton and the connection of the ballast group are carried out by the methods described in Japanese Patent Application No. 59-27745, Japanese Patent Application No. 59-53443, etc. be able to. (1) After halogenating the coupling active site (bromination, chlorination, etc.), the halogen atom is
How to replace with R ³ O [X represents a halogen atom (bromine atom, chlorine atom, etc.). ] For halogenation of the coupling active position, 1 equivalent of bromine, N-bromosuccinimide, sulfuryl chloride, N-chlorosuccinimide, or other halogenating agent is applied to 4-equivalent coupler (A) in an inert solvent such as dichloromethane. This can be easily done by doing this. Next, this halogenated compound (B) is placed in an aprotic polar solvent such as dimethylformamide (DMF), dimethylsulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), N-methyl-2-pyrrolidone, etc. Appropriate R ³ −
OM, (R ³ -O) ₂ M' or (R ³ -O) ₃ M'' (R ³ represents an alkyl group or a heterocyclic group. M, M' and M'' are monovalent, divalent, and represents a trivalent metal ion) to obtain (C) in which an alkyloxy group or a heterocyclic oxy group is introduced into the desired coupling active position. Preferably, the halogenated compound (B) is added in an equivalent to 50 times the amount (by weight) of the above solvent, and an equivalent to 20 times the amount (molar ratio) of an appropriate aliphatic alcohol or a sodium salt of a hydroxy-substituted heterocyclic compound. Or it is preferable to react with potassium salt at a temperature of 50°C to 150°C. Further, this reaction may be accelerated by the addition of a quaternary ammonium salt such as tetrabutylammonium bromide or an alkali metal halide such as cesium bromide. (2) After introducing an alkyloxy group or a heterocyclic oxy group into the active methylene of β-ketonitrile, 1H-pyrazolo[1,5-b][1,2,
4] Method for forming triazole skeleton Halogenated product obtained by treating 3-oxonitrile (D) with a halogenating agent such as bromine or sulfuryl chloride in an inert solvent such as dichloromethane.
When (E) is treated with an appropriate R ³ -OH in the presence of a tertiary amine or with a metal salt such as R ³ -OM mentioned above in (1), the corresponding alkyloxy form or heterocyclic ring can be obtained. Oxygen (F) is obtained. The target coupler (I) of the present invention can be synthesized from the aminopyrazole (G) obtained by reacting this with hydrazine hydrate in a solvent such as ethanol by the method described in Japanese Patent Application No. 70146/1982. . 3-Oxonitrile (D) is US Patent No. 4411753, German Patent (Publication) No. 3209472
Synthesis, 472 (1977) and the like. Specific synthesis examples of typical couplers according to the present invention are shown below. Synthesis Example 1 (Synthesis of exemplary coupler (M-1)) (1) Synthesis of intermediate (B) 100ml of tetrahydrofuran and dichloromethane
6-methyl-2-(3-
[4-{2-(2,4-di-t-amylphenoxy)octanamide}phenyl]propyl)-
50.0 g of 1H pyrazolo[1,5-b][1,2,4]triazole (A) was dissolved. To this, 13.8 g of N-bromosuccinimide (NBS) was added at room temperature and stirring was continued for 30 minutes. This reaction mixture
After washing three times with 500 ml of water, it was dried over anhydrous magnesium sulfate. The oil obtained by distilling off the solvent under reduced pressure was subjected to silica gel column chromatography (elution solvent: hexane: ethyl acetate =
3:1) and the eluate was concentrated to dryness to obtain 49.3 g (87%) of Intermediate (B). Elemental analysis values C (%) H (%) N (%) Calculated value 65.88 7.86 10.11 Measured value 65.77 7.88 10.04 (2) Synthesis of exemplary coupler (M-1) 15.0 g of the above intermediate (B), sodium 2- 10.0 g of (methylthio)ethoxide was added to 75 ml of dimethyl sulfoxide, and the mixture was stirred for 8 hours while heating to 120-130° C. under a nitrogen stream.
After cooling the reaction mixture, it was dissolved in 300 ml of ethyl acetate and washed three times with 300 ml of saturated brine. After drying the organic layer over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was subjected to silica gel column chromatography (eluent:
The eluate was fractionated using hexane:ethyl acetate=3:1) and the eluate was concentrated to obtain 7.0 g of the desired product (M-1). Elemental analysis value C (%) H (%) N (%) Calculated value 69.95 8.73 9.95 Measured value 69.68 8.69 9.79 Synthesis example 2 (Synthesis of exemplary coupler (M-32)) 15.0 g of intermediate (B) and 10.0 g of sodium tetrahydrofuran-3-oxide (prepared from 8.0 g of 3-hydroxytetrahydrofuran and 2.1 g of sodium metal) were added to 75 ml of dimethyl sulfoxide, and the mixture was heated at 120-130°C under a nitrogen stream. The mixture was stirred for 8 hours while heating to . After cooling this reaction mixture
It was dissolved in 300 ml of ethyl acetate and washed three times with 300 ml of saturated saline. After drying the organic layer over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was fractionated using silica gel column chromatography (elution solvent: hexane: ethyl acetate = 3:1).
Concentrate the eluate to obtain the target product (M-32) 7.9g (52%)
I got it. Elemental analysis value C (%) H (%) N (%) Calculated value 72.07 8.78 10.00 Measured value 72.30 8.92 9.78 1H pyrazolo[1,5-b][1,2,4]triazole represented by the above general formula [] The magenta coupler is usually added to the green-sensitive layer, but may be added to other photosensitive layers or non-photosensitive photographic layers depending on the purpose. The magenta coupler represented by the general formula [] of the present invention has a content of 1×10 ^-3 to 5 per mole of silver halide.
×10 ^-1 mol, preferably 1 × 10 ^-2 mol to 5 ×
Used in a proportion of 10 ^-1 mole. The silver halide color photographic light-sensitive material according to the present invention can be used as a color negative film, a color positive film, a color reversal film, a color paper, or a reversal color paper. In the present invention, the coupler can be introduced into the silver halide emulsion layer using known methods, such as those disclosed in the US Pat.
The method described in No. 2322027 is used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, etc.)
dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate),
benzoic acid esters (e.g. octyl benzoate),
Alkylamides (e.g. diethyl laurylamide, fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (e.g. tributyl trimesate), etc., or organic solvents with a boiling point of about 30°C to 150°C, e.g. acetic acid. Lower alkyl acetates such as ethyl, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-
After being dissolved in ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination. Further, the dispersion method using a polymer described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-open No. 51-59943 can also be used. When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution. Binders or protective colloids that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention include:
Although gelatin is advantageously used, other hydrophilic colloids can also be used alone or in conjunction with gelatin. In the present invention, the gelatin may be either lime-treated or acid-treated. For more information on how to make gelatin, see The Macromolecular Chemistry of Gelatin (Academic Press) by Arthur Vuis.
Published in 1964). Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. The preferred silver halide is silver iodobromide containing up to 15 mole percent silver iodide. Particularly preferable is 2
Silver iodobromide containing from mol% to 12 mol% silver iodide. The average grain size of silver halide grains in photographic emulsions (the grain size is defined as the grain diameter for spherical or approximately spherical grains, and the edge length for cubic grains, expressed as an average based on the projected area) is particularly important. No, but 3μ
The following are preferred. The particle size may be narrow or wide. Silver halide grains in photographic emulsions may have regular crystal structures such as cubic or octahedral shapes, or may have irregular crystal structures such as plate shapes, or may have irregular crystal structures such as plate shapes. It can also be a composite form. It may also consist of a mixture of particles of various crystalline forms. Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of five times or more the grain thickness occupy 50% or more of the front projected area. The silver halide grains may have different phases inside and on the surface. Further, the particles may be particles in which a latent image is mainly formed on the surface, or may be particles in which a latent image is mainly formed inside the particle. The photographic emulsion used in the present invention is written by P. Glafkides.
Chimie et Physique Photographique (Paul
Montel Publishing, 1967), GFDuffin
Photographic Emulsion Chemistry (The Focal
Press, 1966), VLZelikman et al.
Making and Coating Photographic Emulsion
(The Focal Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).
One type of simultaneous mixing method is a method of keeping pAg constant in the liquid phase in which silver halide is produced, that is,
A so-called controlled double jet method may also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained. Two or more types of silver halide emulsions formed separately may be mixed and used. In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be allowed to coexist. Silver halide emulsions are usually chemically sensitized.
For chemical sensitization, see, for example, “Die
Grundlagender Photographischen Prozesse
mit Silberhalogeniden” (Akademische
Verlagsgesellschaft, 1968) pages 675-734 can be used. That is, a sulfur sensitization method using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, Reduction sensitization method using amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds):
Noble metal compounds (e.g., gold complex salts, Pt, Ir,
A noble metal sensitization method using complex salts of metals of the periodic table group such as Pb can be used alone or in combination. The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptoazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc.: mercaptopyrimidines; mercaptotriazines ; thioketo compounds such as, for example, oxadolinthione; azaindenes, such as triazaindenes, tetraazaindenes (particularly 4-hydroxy substituted (1,3,
3a, 7) Tetraazaindenes), pentaazaindenes, etc.; Many compounds known as antifoggants or stabilizers such as benzenethiosulfones, benzenesulfinic acid, benzenesulfonic acid amides, etc. Compounds can be added. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced using the present invention contains coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast , sensitization)
Various surfactants may be included for various purposes. The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholins, and quaternary ammonium salts for the purpose of increasing sensitivity, increasing contrast, or accelerating development. compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylate, alkoxyalkyl (meth)
Acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid, methacrylic acid, α,β-unsaturated dicarboxylic acid, Hydroxyalkyl (meth)
Polymers containing a combination of acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as monomer components can be used. The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments,
Included are complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. Namely, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc. Nuclei in which alicyclic hydrocarbon is fused to these nuclei:
and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, i.e., an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxadol nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus , benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms. Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, as a nucleus having a ketomethylene structure. A 5- to 6-membered heteroartic ring nucleus such as a thiobarbituric acid nucleus can be applied. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostyl compounds substituted with nitrogen-containing heterocyclic groups (e.g.,
2933390 and 3635721), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3743510), cadmium salts, azaindene compounds, and the like. The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. A multilayer natural color photographic material usually has at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. In the same or other photographic emulsion layer or non-light-sensitive layer of the photographic light-sensitive material prepared using the present invention, in addition to the coupler represented by the above general formula [], other dye-forming couplers, i.e., color development treatment Aromatic primary amine developer (e.g., phenylenediamine derivative, aminophele derivative, etc.)
Compounds that can develop color by oxidative coupling with the compound may also be used. Typical examples of color couplers include naphthol or phenolic compounds, pyrazolone or pyrazoloazole compounds, and open-chain or heterocyclic ketomethylene compounds. Specific examples of cyan, magenta and yellow couplers that can be used in the present invention include RD17643 (December 1978) - Section D;
18717 (November 1979). These couplers preferably have ballast groups or are polymerized and diffusion resistant. The coupling position is preferably substituted with a leaving group rather than a hydrogen atom. Couplers in which the chromophore has suitable diffusivity, colored couplers, colorless couplers, or couplers which release a development inhibitor or accelerator upon the coupling reaction can also be used. A representative example of the yellow coupler that can be used in combination with the present invention is an oil-protected acylacetamide coupler. Specific examples thereof are described in US Pat. No. 2,407,210, US Pat. No. 2,875,057, and US Pat. No. 3,265,506. Two-equivalent yellow couplers can be preferably used in the present invention,
U.S. Patent No. 3408194, U.S. Patent No. 3447928, U.S. Patent No.
Oxygen atom separation type yellow couplers described in No. 3933501 and No. 4401752, etc.
58-10739, U.S. Pat. No. 4,022,620;
No. 4326024, RD18053 (April 1979), British Patent No.
No. 1425020, West German Published Application No. 2219917, same no.
Typical examples thereof include nitrogen atom separation type yellow couplers described in Japanese Patent Nos. 2261361, 2329587, and 2433812. α-pivaloylacetanilide couplers are characterized by the fastness of color-forming dyes, while α-benzoylacetanilide couplers are characterized by good color-forming properties. Magenta couplers that can be used in the present invention include oil-protected indazolone or cyanoacetyl couplers, preferably 5-pyrazolone couplers and pyrazoloazole couplers such as pyrazolotriazoles other than those of the present invention.
The 5-pyrazolone coupler is preferably one in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the color development rate of the chromophore, and typical examples thereof are U.S. Pat.
No. 2600788, No. 2908573, No.
It is described in No. 3062653, No. 3152896, No. 3936015, etc. A 2-equivalent 5-pyrazolone coupler is preferred, as described in U.S. Pat.
Preferred are nitrogen leaving groups as described in US Pat. No. 4,310,619 or arylthio groups as described in US Pat. No. 4,351,897. Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73636 has high color reactivity. Examples of pyrazoloazole couplers include pyrazolobenzimidazoles described in U.S. Pat. No. 3,369,897, preferably pyrazolo[5,1-c][1,2,4]triazoles described in U.S. Pat. No. 3,725,067; Pyrazolotetrazoles described in RD24220 (June 1984), RD24230 (June 1984)
Pyrazolopyrazoles and patent application 1982-
Examples include imidazopyrazoles described in No. 45512. Cyan couplers that can be used in the present invention include:
Oil-protected naphthol-based and phenolic couplers are listed, and U.S. Patent No.
The naphthol couplers described in US Pat. No. 2,474,293 are preferably
Typical examples include highly active 2-equivalent naphthol couplers of the oxygen atom elimination type described in Nos. 4,228,233 and 4,296,200. Specific examples of phenolic couplers are disclosed in U.S. Pat. No. 2,369,929;
It is described in No. 2423730, No. 2772162, No. 2801171, No. 2895826, etc. Cyan couplers that are robust to heat, humidity, and temperature are preferably used in the present invention; typical examples include the phenolic cyan couplers described in U.S. Pat. No. 3,772,002;
2,5-diacylamine-substituted phenolic couplers described in No. 3758308, No. 4126396, No. 4334011, No. 4327173, West German Patent Publication No. 3329729, and Japanese Patent Application No. 1983-42671, and U.S. patents. No. 3446622, No. 4333999, No. 4451559
These include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, which are described in No. 4,427,767 and the like. The above couplers and the coupler of the present invention can be used in combination of two or more types in the same layer, or the same compound can be added in two or more different layers, in order to satisfy the characteristics required for a photosensitive material. It is done. In order to correct unnecessary absorption in the short wavelength region of the magenta and cyan coupler chromophores, it is preferable to use a colored coupler in combination with the color photosensitive material for photographing. Yellow-colored magenta couplers described in U.S. Patent No. 4163670 and Japanese Patent Publication No. 57-39413, or U.S. Pat.
Typical examples include magenta-colored cyan couplers described in No. 4138258 and British Patent No. 1146368. These color couplers that can be used in combination may also form a dimer or more polymer. Typical examples of polymerized couplers are U.S. Pat. No. 3,451,820 and
Described in No. 4080211. Examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and US Pat. No. 4,367,282. In addition, chromophoric diffusive couplers can be used in combination to improve graininess; examples of such couplers are described in US Patent No. 4366237 and British Patent No. 2125570, and European Patent No.
Specific examples of yellow, magenta and cyan are described in No. 1 and OLS 3324533. The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.),
Dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,3-dihydroxydioxane, etc.), (4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), and the like can be used alone or in combination. In the photosensitive material produced using the present invention, when dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like. The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant. The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (such as those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (such as those described in U.S. Pat.
3314794 and 3352681), benzophenone compounds (for example, those described in JP-A-46-2784), cinnamic acid ester compounds (for example, those described in U.S. Pat. No. 3705805 and 3707375), butadiene Compounds such as those described in US Pat. No. 4,045,229 or benzoxide compounds (such as those described in US Pat. No. 3,700,455) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These ultraviolet absorbers may be mordanted in specific layers. The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include
Included are oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols. For the photographic processing of the layer consisting of the photographic emulsion produced using the present invention, any of the known methods and known processing solutions, such as those described in Research Disclosure No. 176, pages 28-30, can be applied. can do. The treatment temperature is usually chosen between 18°C and 50°C, but it may also be lower than 18°C or above 50°C. Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylenediamines (e.g., 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino- N-ethyl-N-
β-hydroxyethylaniline, 3-methyl-4
-amino-N-ethyl-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-
N-β-methanesulfamide ethylaniline, 4
-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used. Other Photography by LFAMason
Processing Chemistry (Focal Press, 1966)
P226-229, U.S. Patent No. 2193015, U.S. Patent No. 2592364
JP-A No. 48-64933, etc. may be used. Color developers may also contain other pH-based compounds such as alkali metal sulfites, carbonates, borates, and phosphates.
Development inhibitors or antifoggants such as buffers, bromides, iodides, and organic antifoggants can be included. Also, if necessary, hardening and softening agents,
Preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol,
Polyethylene glycol, quaternary ammonium salt,
Development accelerators such as amines, dye-forming couplers,
Competitive couplers, fogging agents such as sodium boron hydride, auxiliary developers such as 1-phenyl-3-pyrazolidone, tackifying agents, polycarboxylic acid chelating agents, antioxidants, and the like may also be included. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As a bleach,
For example, iron (), cobalt (), chromium (),
Compounds of polyvalent metals such as copper, peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromate, organic complex salts of iron () or cobalt (), such as ethylenediaminetetraacetic acid, nitrilotriacetic acid,
Complex salts of aminopolycarboxylic acids such as 1,3-diamino-2-propanoltetraacetic acid or organic acids such as citric acid, tartaric acid, and malic acid: persulfates,
Permanganate; nitrosophenol, etc. can be used. Of these, potassium ferricyanide, sodium ferric ethylenediaminetetraacetate, and amminium ferric ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron() complex salts are useful in both stand-alone bleach solutions and single bath bleach-fix solutions. As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent. (Example) The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto. Example 1 Exemplary compound M-28.6 as a magenta coupler
g of tri(2-ethylhexyl) phosphate 20
ml, add 25 ml of ethyl acetate and dissolve with heating, add 10 g of gelatin, sodium dodecylbenzenesulfonate.
A fine emulsified dispersion was obtained by adding it to 100 ml of an aqueous solution containing 1.0 g and stirring at high speed. The entire amount of this emulsified dispersion was added to 100 g of silver chlorobromide emulsion (containing 6.5 g of Ag) consisting of 50 mol% of Br, and 2% of 2,4-dihydroxy-6-chloro-s was added as a hardener.
- A sample was prepared by adding 100 ml of triazine sodium salt and coating it on a paper support laminated with polyethylene on both sides so that the silver coating amount was 200 mg/m ² .A gelatin layer was provided on top of this coated layer to prepare a sample. This is designated as sample A. Next, magenta coupler M-2 was replaced with 8.8 g of exemplified compounds M-3, 9.0 g of -10, and 7.9 g of M-29, and 19 ml, 17 ml, 16 ml of tri(2-ethylhexyl) phosphate, and 25 ml of ethyl acetate were added, respectively. was added to prepare an emulsified dispersion in the same manner, and samples were prepared by using the same emulsion in the same amount and coating it on the same support so that the amount of Ag coated was the same. These samples are designated as samples B, C, and D, respectively. Furthermore, the compounds shown below as comparative samples
8.9 g was mixed with 18 ml of tri(2-ethylhexyl) phosphate and 25 ml of ethyl acetate according to the method described above. Exactly the same coating sample was prepared. This sample will be used as a comparison sample. Including these comparison samples, samples A to D contain 1000C.
MS wet exposure was applied and the sample was treated with the following processing solution. Developer Benzyl alcohol 15ml Diethylenetriaminepentaacetic acid 5g KBr 0.4g Na ₂ SO ₃ 5g Na ₂ CO ₃ 30g Hydroxyamine sulfate 2g 4-Amino-3-methyl-N-β-(methanesulfonamide)ethylaniline 3/
2H ₂ SO ₄・H ₂ O 4.5g Make up to 1000ml with water PH10.1 Bleach-fix solution Ammonium thiosulfate (70wt%) 150ml Na ₂ SO ₃ 5g Na [Fe (EDTA)] 40g EDTA 4g Make up to 1000ml with water pH6. 8 Processing Steps Temperature Time Developer 33°C 3 minutes 30 seconds Bleach-fix 33°C 1 minute 30 seconds Water Washing 28-35°C 3 minutes Each sample thus obtained is a clear, highly saturated magenta image. It was hot. When the photographic characteristics of these color images were measured, the following results were obtained.

[Table]
As a result, it has been found that the alkyloxy group- or heterocyclic oxy group-eliminating coupler of the present invention exhibits superior characteristics in terms of sensitivity, gradation, and maximum density compared to the halogen atom-eliminating coupler. This is because the introduction of an alkyloxy group or a heterocyclic oxy group leaving group increases coupling activity and color development efficiency. Example 2 As described in Table 2, a color photographic material EFG was prepared by sequentially coating from the first layer (bottom layer) to the seventh layer (top layer) on a paper support laminated with polyethylene on both sides. . At this time, the composition of the coating solution containing the emulsified dispersion and emulsion of the magenta coupler used in the third layer was prepared according to Example 1.

【table】

[Table] These samples E, F, and G were attached with a B-G-R3 color separation filter and exposed in the same manner as in Example 1.
The processing was exactly the same except that the color development time was changed to 2 minutes, 3 minutes and 30 seconds, and 6 minutes. The changes in photographic characteristic values when the color development time was changed were as shown in Table 3.

[Table] These results show that even in multilayer samples of natural color photographs, the alkyloxy group or heterocyclic oxy group separation type coupler of the present invention has better color development than the halogen atom separation type coupler in terms of sensitivity, gradation, and maximum density. It was shown to be an excellent coupler that exhibits small dependence on development time and exhibits photographic properties with small fluctuations even in short development times. In this way, the fact that it shows higher activity and color development efficiency than conventional pyrazoloazole couplers is advantageous in terms of product design, and it has been found that it is a coupler with excellent characteristics. Example 3 Samples E, F, and G prepared in Example 2 were treated with B-G-
A three-color separation filter of R was attached, and the exposure and processing described in Example 1 were performed to obtain various colored images. One part of these samples was heated at a high temperature of 100℃ for 7 days.
The other part was exposed to high temperature and high humidity at 60℃ and 90% RH for 6 weeks, and the other part was exposed to light in a fluorescent lamp bleacher (15,000 lux) for 4 weeks to improve the solidity of the magenta dye image. A sex test was conducted. The results are shown in Table 4.

[Table] Values are magenta density values after fading test
The values in parentheses are the density values measured using a blue filter for non-colored areas.
Tein)
Table 4 shows that the couplers of the present invention show almost no change in color image at high temperatures of 100°C and 60°C and 90% RH, and are more robust to light than comparative compounds. Moreover, in all of the fading tests, it was revealed that there was little staining due to residual coupler. From this, the couplers of the present invention having an alkyloxy group or a heterocyclic oxy group leaving group are sensitive to heat, humidity, and
It has become clear that light does not exhibit any adverse effects.

Claims (1)

[Scope of Claims] 1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which a substituted or unsubstituted alkyloxy group or heterocyclic oxy group is bonded to the coupling active position. 1H-pyrazolo [1,5-b] [1,2,
4] A silver halide color photographic material containing at least one triazole magenta coupler.