JPS62209457A - Color image forming method - Google Patents

Abstract

PURPOSE:To obtain a magenta coupler which exhibits high sensitivity and is improved in gradation by developing a silver halide photosensitive material with a developing soln. contg. an arom. primary amine in the presence of at least one kind of specific couplers. CONSTITUTION:The silver halide photosensitive material is developed with the developing soln. contg. the arom. primary amine in the presence of at least one kind of the specific couplers expressed by formula (I) and (II). In formulas, R1 denotes an alkyl group, aryl group or heterocyclic group, R2 denotes a hydrogen atom or substituent, and R'2 denotes an alkyl group, aryl group, alkylthio group, arylthio group or heterocyclic thio group. X denotes a hydrogen atom or coupling eliminating group. The coupler may be added to the photosensitive material and may be added to a color developing bath. The amt. of the coupler to be added to the photosensitive material is 2X10<-3>-5X10<-1>mol, more preferably, 1X10<-2>-5X10<-1>mol per mol of silver halide.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for processing silver halide color photographic light-sensitive materials. -Relates to a method for processing silver halide color photographic materials. More specifically, /H-pyrazolo[/,z
-b]-/, 2. In the presence of 'I-triazole and /H-pyrazolo[:j, / -C)-/,2.4t-) lyazole magenta couplers, a silver halide color photographic light-sensitive material is processed into a developer containing an aromatic primary amine. The invention relates to a color image forming method in which development is performed using a color image forming method.

(Prior art) Using exposed silver halide as an oxidizing agent, the oxidized aromatic 7th class amine color developing agent and coupler react to form indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine and It is well known that similar pigments can be produced and color images can be formed.

Of these, to form a magenta color image! −
Pyrazolone, cyanoacetophenone, indasilone, pyrazolobenzimidazole, and pyrazolotriazole couplers are used.

Hitherto, most of the pyrazolones have been widely used and researched as magenta image-forming couplers. however! - It was known that unnecessary absorption having a yellow component exists near 3 onm of the dye beam formed from the pyrazolone coupler, causing color turbidity.

Virazolobenzimidazole bone core is described in British Patent No. 10417,6/2 as a magenta imaging bone core that reduces this yellow component, and US Patent J770. &4t7
Indacylon osteonucleus described in US Patent No. 3.7
Pyrazolo described in No. 26.067 [Yu, /-c,
] -/, 2, ri-triazole bone cores have been proposed.

However, the magenta couplers described in these patents, when mixed into silver halide emulsions in dispersed form in hydrophilic protective colloids such as gelatin,
They may give unsatisfactory color images, have low solubility in high-boiling organic solvents, be synthetically difficult, have relatively low coupling activity in common developers, or Some of them are still unsatisfactory due to extremely low robustness.

The inventor of this invention is! - As a result of searching for various new types of magenta color image couplers that do not exhibit sub-absorption in the vicinity of 4t3θnm, which is the biggest drawback in terms of hue of pyrazolone couplers, we have found that they do not exhibit sub-absorption on the short wavelength side and have improved color image fastness. Tokukaisho, which is expensive and easy to synthesize! Day/2/ri! Party B and US patent! <to, disclosed in atg/H
-Pyrazolo[/,z-b:]-/,s,4-monotriazole magenta coupler was found. These couplers have excellent color reproduction and excellent synthesis, and by introducing a leaving group into the coupling active position, so-called 2
It had the characteristics of being able to reduce the amount of silver used and reduce the amount of silver used. However, when the coupling-off group (X) is a halogen, alkylthio, arylthio, etc. that is easy to synthesize, the sensitivity and gradation (γ)K may be slightly lowered! −
There was a problem that it was not as good as pyrazolone magenta couplers.

So, Tokugansho! It has been found that a coupler in which X is an aryloxy group, as shown in No. 3/7/53j2, is one means of solving this problem.

However, although this aryloxy breakaway coupler solves the above-mentioned problems, it has drawbacks such as low synthesis yield, unsuitability for large-scale synthesis, and low stability.

Furthermore, the pyrazolotriazoles disclosed in the aforementioned US Pat. An object of the present invention is to solve these problems and provide a magenta coupler that exhibits even higher sensitivity and improved gradation (r).

(Means to Solve the Problem) The above problem is solved by using a silver halide light-sensitive material containing an aromatic primary amine in the presence of at least one coupler represented by the general formulas (I) and (It). The problem was solved by a color image forming method characterized by developing with a developer.

General formula <1) In the formula, R1 represents an alkyl group, an aryl group or a heterocyclic group, and R2 represents a hydrogen atom or a substituent.

General Formula (II) In the formula, R1 represents the same group as above, and R'2 represents an alkyl group or an aryl group. X represents a hydrogen atom or a coupling-off group.

More specifically, R1 is a methyl group, an ethyl group, an inpropyl group, a t-butyl group, a trifluoromethyl group, a phenylmethyl group, a methoxyethyl group, a -monophenoxyethyl group, a 2-methylsulfonylethyl group, a cohydroxethyl group. group, 313,3-trifluoropropyl group, cofluoroethyl group, cochloroethyl group, λ-bromoethyl group, cocyanoethyl group, alkyl group such as 3-oxobutyl group, or phenyl group, goomethylphenyl J
, &-t-7'tylphenyl group, couacylaminophenyl group, couhalogenphenyl group, coualkoxyphenyl group, aryl group such as hicofuryl group, coachenyl group, cobyrimidinyl group, -1penzothiazolyl group, -1pyridyl group , 3-pyridyl group, goupyridyl group, and other heterocyclic groups.

R2 is a hydrogen atom,...a rogene atom (for example, a chlorine atom,
bromine atom, etc.), alkyl groups [e.g. sulfonamide-substituted alkyl groups (sulfonamide methyl group, /-sulfonamidoethyl group, -1-sulfonamidoethyl group, /-methyl-1-sulfonamidoethyl group, 3-sulfonamide propyl group, etc.), acylamino group-substituted alkyl group,
(A-/-acylaminomethyl group, /-acylaminoethyl group, co-acylaminoethyl group, /-methyl-co-acylaminoethyl group, 3-acylaminozorobyl group, etc.),
Sulfonamide-substituted phenylargyl group (+)-sulfonamidophenylmethyl group, p-sulfonamidophenylethyl group, /-(I)-sulfonamidophenyl)ethyl group, p-sulfonamidophenylpropyl group, etc.)
, acylamino-substituted phenylalkyl group (p-acylaminophenylmethyl group, p-acylaminophenylethyl group, /-(p-acylaminophenyl)ethyl group, p
-acylaminophenylpropyl group), alkylsulfonyl-substituted alkyl group (,2-dodecylsulfonylethyl group, /-methyl-2-tadecylsulfonylethyl group, octadecylsulfonylpropyl group, etc.), phenylsulfonyl-substituted alkyl group ( j-(,2-butyl-
j-t-'octylphenylsulfonyl) furoyl group,
-substituted alkyl groups such as -(cudodecyloxyphenylsulfonyl)ethyl group and unsubstituted alkyl groups such as methyl group, ethyl group, hexyl group and dodecyl group],
Aryl groups (e.g., substituted aryl groups such as sulfonamidophenyl group, acylaminophenyl group, alkoxyphenyl group, aryloxyphenyl group, substituted alkylphenyl group, sulfonamidonaphthyl group, acylaminonaphthyl group, and phenyl, naphthyl group, etc.) (unsubstituted aryl group), Peter term group (e.g., caufuryl group, -
monothenyl group, λ-pyrimidinyl group, cobenzothiazolyl group, etc.), cyano group, alkoxy group (e.g. methoxy group, ethoxy group, co-methoxyethoxy group, co-tethylethoxy group, co-methanesulfonylethoxy group, etc.) , aryloxy group (e.g., phenoxy group, comethylphenoxy group, 9-t-butylphenoxy group, etc.)
, acylamino group (e.g., acetamide group, benzamide group, tetradecanamide group, α-(2,9-di-t)
-amylphenoxy)butyramide group, γ-(3-t-
butyluda-hydroxyphenoxy)butyramide group,
α-(a-(g-hydroxyphenylsulfonyl)phenoxy)decaneamide group, etc.), anilino group (e.g. phenylamino group, -1chloroanilino group, cochrochloride-tetradecanamideanilino group, cochrochloride-dodecyloxycarbonyl anilino group, N-acetylanilino group, cochloro!-(α-(3-t-butyl-
q-hydroxyphenoxy)dodecanamido)anilino group, etc.), ureido group (e.g., phenylureido group,
methylureido group, N, N dibutylureido group, etc.)
, sulfamoylamino group (e.g. 1.N, N-dipropylsulfamoylamino group, N-methyl-N-decylsulfamoylamino group, etc.), alkylthio group (
For example, methylthio group, octylthio group, tetradecylthio group, 2-)Futsukidiethylthio group, 3-phenoxyprobylthio group, j-(4t-t-butylphenoxy)
propylthio group, etc.), arylthio group (e.g., phenylthio group, 2-butoxy-1-1-octylphenylthio group, 3-pentadecylphenylthio group, λ-carboxyphenylthio group, gutetradecanamidophenylthio group, etc.) ), alkoxycarbonylamino groups (e.g., methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), sulfonamide groups (e.g.,
methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, P-)luenesulfonamide group, octadecanesulfonamide group, comethyloxy-jt-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,g-di-t
ert-amylphenoxy)propyl)carbamoyl group, etc.), sulfamoyl group (e.g., N-ethylsulfamoyl group, N,N-dipropylsulfamoyl group, N
-(2-)'7'Syloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, Nl
N-diethylsulfamoyl group, etc.), sulfonyl group (
For example, methanesulfonyl group, octanesulfonyl group,
benzenesulfonyl group, toluenesulfonyl group, etc.),
It represents an alkoxycarbonyl group (for example, a methoxycarbonyl group, a butyloxycarbonyl group, a dodecylcarbonyl group, an octadecylcarbonyl group, etc.), and among these, preferably an alkyl group, an aryl group, an alkylthio group, an arylthio group, and more. Preferred are alkyl groups and aryl groups.

R'2 is a sulfonamido-substituted alkyl group (e.g., sulfonamidomethyl group, /-sulfonamidoethyl group, cosulfonamidoethyl group, /-methyl-cosulfonamidoethyl group, 3-sulfonamidopropyl group, etc.),
Acylamino-substituted alkyl group, (e.g., acylaminomethyl group, /-acylaminoethyl group, 2-acylaminoethyl group, /-methyl-coacylaminoethyl group,
3-acylaminopropyl group, etc.) sulfonamido-substituted phenylalkyl group (e.g. p-sulfonamidophenylmethyl group, p-sulfo/amidophenylethyl &, /
(P-sulfonamidophenyl)ethyl group, p-sulfonamidophenylpropyl group, etc.), acylamino-substituted phenylalkyl group (e.g. p-acylaminophenylmethyl group, p-acylaminophenylethyl a, i
(p-acylaminophenyl)ethyl group, p-acylaminophenylpropyl group, etc.), alkylsulfo=/L
[[Lfurkyl group<2-dodecylsulfonylethyl group,
/-methyl-λ-pentadecylsulfonylethyl group, octadecylsulfonylpropyl group), phenylsulfonyl-substituted alkyl group (3-(2-7'thyl-, t=t
-octylphenylsulfonyl)propyl group, -1(4
t-dodecyloxyphenylsulfonylethyl group, etc.)
Substituted alkyl groups such as , and unsubstituted alkyl groups such as methyl group, ethyl group, hexyl group, dodecyl group, and sulfonamidophenyl group, acylaminophenyl group, alkoxyphenyl group, aryloxyphenylene A4, fi
Substituted aryl groups such as lt-substituted furkylphenyl group, sulfonamide naphthyl group, and acylaminonaphthyl group, unsubstituted aryl groups such as phenyl and naphthyl groups, and alkylthio groups (e.g., methylthio group, octylthio group,
Tetradecylthio group, cophenoxyethyltheo group, 3
-phenoxypropylthio group, J-(4t-t-butylphenoxy)propylthio group, etc.), arylthio group (
For example, phenylthio group, λ-butoxy! -t-octylphenylthio group, 3-ntadecylphenylthio group, λ-carboxyphenylthio group, gutetradecanamidophenylthio group, hetero-terminal thio group (e.g. -1penzothiazolylthio group, co, 4t -Di-phenoxy-/
, 3. j-triazole-6-theo group, cobiridylthio jL, etc.).

Among these, substituted alkyl groups and substituted aryl groups are preferred, and substituted alkyl groups are particularly preferred.

X is a hydrogen atom, a halogen atom (e.g., chlorine atom, bromine atom, iodine atom, etc.), a carboxy group, or a group linked with an oxygen atom (e.g., acetoxy group, propanoyloxy group, benzoyloxy group, 2.'l - dichlorobenzoyloxy 7 group, ethoxyoxaroyloxy group, pyruvinyloxy group, cinnamoyloxy group, phenoxy group, goucyanophenoxyl group, goomethanesulfonamidophenoxy group, coumethanesulfonylphenoxy group,
α-Naphthoxy group, 3-tadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, λ-cyanoethoxy group, benzyloxy group, copheneteroxy group, copheneoxyethoxy group,! -phenyltetrazolyloxy group, copenzothiazolyloxy group, etc.), groups linked through nitrogen atoms (e.g., benzenesulfonamide group, N-ethyltoluenesulfonamide 5, -=
Butafluorobutanamide group, co, j, &,! , 4-hentafluoropenzamide group, octanesulfonamide group, p-cyanophenylureido group, N.

N-diethylsulfamoylamine group, /-piperidyl group,! ,! -dimethylruco, cudioquine-3-oxazolidinyl group, /-benzyl-ethoxy-3-hydantoinyl group, 2N-/, /-dioxo-3(,2H)-oxo-7,2-benzisothiazolyl group, -monoxo /, 2-dihydro/-hyridinyl group, imidazolyl group, pyrazolyl group, 3. ! -diethyl/, 2. 'l-triacy/L/-/-yl, 'tfc halofuromobenzotriazol-/-yl, !-methyl-/, co.

3.4t-tetrazol-/-yl group, benzimidazolyl group, etc.) Groups linked by a sulfur atom (e.g., phenylthio group, 2-carboxyphenylthio group, λ-methoxy5-t-octylphenylthio group, group) Methanesulfonylphenylthio group, 9-octanesulfonamidophenylthio group, benzylthio group, λ-cyanoethylthio group, /-ethoxylponyltridecylthio group, !-phenyluco, !,'l,j-tetrazolylthio group, 2 −
benzothiazolyl group, etc.).

R1s R2% When R'2 or X becomes a covalent group to form a bis body, Rls Silene group, -CH2CH2-0-
CH2CH2-1, etc.), a substituted or unsubstituted phenylene group (for example, /, 4t-phenylene group, /, 3-phenylene group) represents a divalent group at an appropriate position.

When the vinyl monomer contains those represented by the general formulas (N and (II)), the linking group in which either R2 or R'2 is an alkylene group (substituted or unsubstituted alkylene group) For example, methylene group, ethylene group, /, 10-decylene group, -CH2CH20CH
2CH2-1, etc.), phenylene group (substituted or unsubstituted phenylene group, e.g. Eva, 7.4t-phenylene a, i
, 5-phenylene group, -CONH-1-〇-1-OCO-, and aralkylene group (eg, etc.).

Preferred linking groups include the following.

-C112CH20-CH2CH2-NHCO-1 The vinyl group may have substituents other than those shown in general formula (I), and preferred substituents are hydrogen atom, chlorine atom, or lower alkyl having carbon number/~q. Represents a group (eg, methyl group, ethyl group).

Monomers including those of general formulas (I) and (II) may be copolymerized with non-chromogenic ethylene-like monomers that do not couple with the oxidation products of aromatic primary amine developers. good.

Acrylic acid, α
- Chloroacrylic acid, α-alkylacrylic acid (such as methacrylic acid) and esters or amides derived from these acrylic acids (such as acrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylamide, Methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, 1so-butyl acrylate, coethylhexyl 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, hinylbrobionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (e.g. Styrene and derivatives of hiso, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (e.g. vinyl ethyl ether), maleic acid, anhydride Maleic acid, maleic ester, N-vinyl-
Examples include 2-pyrrolidone, N-vinylpyridine, and -1 and q-vinylpyridine. The non-color-forming ethylenically unsaturated monomer used here can also be used in combination with 2'si or more. Examples include n-butyl acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, methyl acrylate and diacetate/acrylamide, and the like.

As is well known in the polymeric color coupler art, non-chromogenic ethylenically unsaturated monomers for copolymerization with solid water-insoluble monomeric couplers depend on the physical and/or chemical properties of the copolymer formed, e.g. solubility, compatibility of the photographic colloidal composition with binders such as gelatin, its flexibility,
It can be selected so that thermal stability etc. are favorably influenced.

The polymer coupler used in the present invention may be water-soluble or water-insoluble, but polymer coupler latex is particularly preferred.

Next, specific examples of typical magenta couplers in the present invention will be shown, but the present invention is not limited thereto.

12F'25 (−ko) (2yo) 3) Shi611t3 (-'111123 (3g) (3♂) (4tg) Shi8”17 (gubu) x:y==:! 0:!　θ (Same for weight ratio and below) (t, t7) (q♂) x: y=gt: it (G9) x: y=t θ,! 0 (!Q) x:y=da! ;! ! (!/) Next, a method for synthesizing the coupler of the present invention using a general formula will be described.

Is the inventor JP-A-60-/76♂? /H-pyrazolo (/
, j-b]-/, 2. Although the method for synthesizing <-triazole has been shown in detail, the coupler of the present invention (general formula (■)) can also be synthesized by basically the same method, although the starting materials are different. The synthesis scheme is shown below.

(R1, R2, and X have the same meanings as above.
' represents an alkyl group or an aryl group. ) The substituent X may be introduced from the beginning as described above, or the synthesis may be carried out with X=H, and various substituents X may be introduced after the skeleton synthesis, as will be described later.

/H-pyrazolo(I,/-(ri-/, co, 4t-triazole coupler, (general formula (■)), Tokkosho &
/-3079! 3-alkoxy (or aryloxy)-! -Can be synthesized using hydrazinopyrazole as a starting material.

Regarding synthesis methods of polymer couplers, solution polymerization and emulsion polymerization will be described, but first, solution polymerization is described in U.S. Pat.
It can be synthesized by the method described in No. tj, and includes a monomeric coupler containing a moiety represented by general formula (I) and a non-chromogenic ethylene-like monomer (for example, acrylic acid, α-chloroacrylic acid, methacrylic acid). alkyl acrylic acid or an ester or amide derived from the acrylic acid (e.g. acrylamide, n-butylacrylamide, n-butyl methacrylate, methyl methacrylate, ethyl methacrylate, etc.)) in an appropriate ratio with a soluble organic Polymerization is initiated by dissolving or mixing in a solvent (e.g., dioxa/, methylcellosolve, etc.) at an appropriate temperature (30 to 7000 degrees) (physical action, such as ultraviolet rays, high energy radiation, etc., or chemical action, persulfate). (initiated by generation of free radicals with initiators such as , hydrogen peroxide, pendiylonitrile, azobisalkylonitrile, etc.). After the polymerization reaction is completed, the polymer can be isolated by extrusion into an organic solvent, concentration, or pouring into water. Regarding the emulsion polymerization method, US Patent J, 370, ? It can be synthesized by the method described in No.j, No. 2.

A general method for introducing a coupling-off group will be described.

(I) Method for linking oxygen atoms The g-equivalent mother coupler of the present invention is formed into a dye by the method shown in Examples, which is hydrolyzed in the presence of an acid catalyst to form a ketone body. The 7-hydroxy compound can be synthesized by hydrogenation using pd-carbon as a catalyst, reduction with Zn-acetic acid, or reduction with sodium borohydride.

By reacting this with various halides, the desired coupler connecting oxygen atoms can be synthesized. (U.S. Patent 3. Wa 2/
(2) Method of connecting nitrogen atoms There are roughly three methods for connecting nitrogen atoms. The first method is to nitrosate the coupling active site with a suitable nitrifying agent as described in U.S. Pat.
For example, a hydrogenation method using pd-carbon as a catalyst, a chemical reduction method using stannous chloride, etc.), and 7-amino and 1
By reacting with various halides in step 7, amide compounds can mainly be synthesized.

The second method is described in U.S. Patent No. J, 7.24-. 067, namely; halogenating the 2-position with a suitable halogenating agent, such as sulfuryl chloride, chlorine gas, bromine, N-chlorosuccinimide, N-bromosuccinimide, etc.; 4tjlJj, the nitrogen heterocycle is reacted with a suitable base catalyst, triethylamine, sodium hydroxide, zaazabicyclo [co,
[lambda], 2] In the presence of octane, anhydrous potassium carbonate, etc., it is possible to substitute and synthesize a coupler linked by a 2-position pressure nitrogen atom. Among compounds linked by oxygen atoms, compounds having a phenoxy group at the 2-position can also be synthesized by this method.

The third method is effective when introducing a π or /θπ electron system aromatic nitrogen heterocycle into the 7th position.
- more than twice the molar amount of π based on the 2-halogen compound synthesized by the first method as described in JLT No. 77.
Or add a 10π-electron aromatic nitrogen heterocycle! θ°
Heating without solvent at ~/ro0C or in an aprotic polar solvent such as dimethylformaldehyde, sulfolane or hexamethylphosphotriamide at 30°~/! θ°
By heating at , an aromatic nitrogen heterocyclic group connected via a nitrogen atom can be introduced into the 2-position.

(3) Method for linking sulfur atoms A coupler in which an aromatic mercapto or heterocyclic mercapto group is substituted at the 7-position is described in US Pat. ．． 227°! ! The method described in item q, i.e., aryl mercaptans, peterocyclic mercaptans and their corresponding disulfides are dissolved in a rhodanized hydrocarbon solvent, converted to sulfenyl chloride with chlorine or sulfuryl chloride, and dissolved in an aprotic solvent. It can be synthesized by adding it to an equivalent coupler. A method for introducing an alkylmercapto group into the 7-position is the method described in U.S. Pat. and S-(alkylthio)isothiourea, a method in which it is synthesized in one step using hydrochloride (or bromine hydrochloric acid) is effective.

Trimethylorthocyanoacetic acid ester (I) (S, M
, -7 Ri x Ruhei 7 (Me Elvain) et al.
Journal of American Chemical Society
5ociety), Volume 77, No.
The manufacturing method is described in 2013) 4t, 2g (01,
29 mole) and hydrazine hydrochloride 2/,, rg (o.

After heating and refluxing J2mole in 100 ml of methanol for 20 hours, the solvent was removed using an evaporator, and recrystallization from methanol yielded 3-amino! -3 methoxypyrazole hydrochloride (II).

Cog (obtained in yield ?11. Melting point /'73-/!θ0 Nuclear magnetic resonance spectroscopy (CDce3, hydrochloride free:
) δ 3゜, ro(3H,s) , riθ(/H,S)! ,30~t,riθ(,2~JH,br)(n)<t
r, og (0, jmole) was dissolved in methanol, and a sodium methoxide timethanol solution (SM-,
2/) neutralized with t6ml (0,jjmole),
10.6 g (θ, jmole) of methyl 3-phthalimidopropionimide ester hydrochloride was added thereto, and the mixture was stirred at room temperature for 7 hours.

In it, a hydroxylamine aqueous solution (hydroxylamine hydrochloride θ, ri g(θ, jmole) and SM-, 2/
40.7m7 (prepared from O, JmOle)) was added and stirred at room temperature for 3 hours. The precipitated crystals were separated, washed with water and acetonitrile, and dried to give ([1)]
/, 7g (yield 7.2g) was obtained.

Melting point/Riotsu~/Tata0 (decomposition) Nuclear magnetic resonance spectrum (DMSO-da) δ Ko,! ~
λ,♂(,2H) 3.70(3H,s) 3.6~3.9(λ)l)! ,3(JH,br,s,) 7,/,2(gH,5)(In) 72g (0,2-mole) of acetonitrile/! P-toluenesulfonylchloride') 4t/7g (0,2,2mo
le)! A solution dissolved in 0 ml of acetonitrile was added dropwise at room temperature over about 7 hours. After the dropwise addition, the mixture was stirred for about 30 minutes, and then 20 ml of pyridine (0,2Q mole
) and stirred for about 30 minutes.

The reaction solution was poured into ice water, and the precipitated crystals were separated and washed with acetonitrile. (IV) yield ♂θ, θg (yield 7!
, Otsuchi). This (II/)/j, 2g (0゜jjmol
e) with methanol-kJOOml and pyridine-0ml (
When the mixture was heated and refluxed for about 2 hours in θ, θ3 mole), crystals were precipitated. The precipitated crystals were separated, washed with methanol, and dried to obtain 2.0 g (yield 6/, male%) of (V).

Melting point 2.2! ~2210 Nuclear magnetic resonance spectrum (IJMsO-d 6 ) δ 3
．． o3(,2H,t,J=2.0)3.70(tH,s
) 3, ♂7 (,2H,t, J=7, o)j, 1
0 (/H,S) 7, rO(gH,S) i, 2.4to(/H,brS) (V) Add hydrazine mono to a methanol (zooml) solution of 4tO, 7g (O, /3 mole). hydrate 7
．． 9 g (O,/, 4 mole) was added and heated under reflux for about 3 hours. After separating the precipitated crystals, the crystals were again dissolved in methanol and dissolved in concentrated hydrochloric acid 27. J-ml (mole) was added, stirred, and filtered to remove insoluble crystals (phthalhydrazide). When the r solution was evaporated to dryness, crude crystals of (M) were obtained.

Add acetonitrile to this and filter and wash (M). g (Yield! Wa, Taste) was able to be obtained. Melting point/1J--/7θ0 (decomposed) nuclear magnetic resonance spectrum (D
MSO-da) δ 3.0-3.3 (gH) j, 7j (JH, S) ♂, 3j (~jH, br) (M) t, 0g (θ, θ coθmole) jc dimethylacetamide jOml Then, at room temperature, triethylamine yy, tml (O, otymole) was added, stirred and cooled with ice water, and -1octyloxy-4-t
-Octylbenzenesulfonyl chloride, sg
An acetonitrile solution of (o, θ mole) was added dropwise. It was extracted with ethyl acetate and recrystallized from a mixed solvent of n-hexane and ethyl acetate (■
) was obtained (yield: 2 pieces).

Melting point/7θ-/7ko0 (■) 2.0g (θ, θ/g mole) in ethyl acetate/
74 tg (0,0/jmol) of N-chlorosuccinimide was added thereto in 2 to 3 portions at room temperature. Extracted with ethyl acetate, dried,
After concentration, the exemplary coupler (6) was reconstituted from a mixed solvent of n-hexane and ethyl acetate, r, rg (yield: 44t).
, 7%).

Melting point/! ! ~/! 6゜Mass spectrometry (FD) rri6 (M) Elemental analysis CHN Calculated value jF, 4t4t 7.7λ //, 7/ Analysis value j♂, 3/ 7.7.2 //, J-7 Synthesis Example 2
(Exemplary coupler α■), 2-7”) + C!~t-octyl-disulfide 6
．． 6 g (0,009! mole) in dichloromethane 20
Dissolve sul7lyl chloride in m1 at room temperature, jg
(0,009! mole) and stirred for 30 minutes.
When the solvent is removed using an evaporator, -one poxy! -Octylsulfenyl chloride was obtained. Dissolve this again in dichloromethane/θml and (■)/θ
, DMF (qoml
) solution at room temperature, and then stirred for 7 hours at
Illustrative coupler (I5) as powder j, , <g (yield 2
θ%) was obtained.

Mass spectrometry (FD) ♂t4t (M) elemental analysis
C, HN Calculated value t6. /2 ♂, 75'? , 27 analysis value 6j, 9/♂,? ! ♂, O♂ The light fastness of the magenta color image formed from the magenta coupler used in the present invention is improved by using it in combination with a color image stabilizer represented by the following general formula.

However, Rlo represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, and R11, R12, R3, R14,
R15 each represents a hydrogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group, an acylamino group, an alkoxycarbonyl group, or a sulfonamide group, and R13 represents an alkyl group, a hydroxy group, an aryl group, or an alkoxy group. Also, RIO and R11 are closed to each other! @ or may form a 6-membered ring, and further RIO and R11
may be ring-closed to form a methylene dioxy ring. Furthermore, Ri3 and R14 are ring-closed again! A negative hydrocarbon ring may also be formed.

These compounds are described in U.S. Pat. No. 3,933-. 0/ as number,
Same 3,9♂ko, ri 4t4, same gu 0.2! Gu.

, 2/Otsu issue specification, JP-A-13-13-2/, 00g issue, same!
Goo/4t, J30 Specification, British Patent Publication 2,
077, 4t! tJ-No., same s, ot, z, trr,
r specification, U.S. Patent No. 3.76, No. 337, U.S. Patent No. 3.4
t32.300, same j, J-74t, 22nd,
Same J, j73, OjO specification, JP-A-Sho! λ-/
! No. 222, No. j3-20322, No. 20322, No. 222, No. 222, No. 3-77.
No. 729, No. 61-63.2/specification, British patent/
, 34t? , J-16, British Patent Publication Co., Ltd., 0go6
．． Specification No. 7j, Tokuko Sho! Gu/2, No. 337, 4tJ'-3/, No. 4-2/ specification, U.S. Patent No. 312
0θ, ri! ! No. specification, JP-A-67-ta 0/! ! Also includes compounds described herein.

A preferred embodiment of the present invention is a silver halide color light-sensitive material containing the coupler of the present invention.

The coupler of the present invention may be added to a light-sensitive material or may be used by being added to a color developing bath. The amount added to the photosensitive material is 2X10-3 mol per 1 mol of silver halide! ×10
-1 mol, preferably /X 10-2~! ×/θ−1
In the case of a polymer coupler, the amount of the polymer coupler to be added may be adjusted so that the above amount of the color forming portion is included, and when used by adding it to a color developer, the bath 70
0.0θ/~0.1 mol, preferably θ per 00cc
, θ/~θ, θ! Moles are appropriate.

The pyrazoloazole coupler of the present invention can be introduced into the photosensitive material by various known dispersion methods, such as solid dispersion method, alkaline dispersion method, preferably latex dispersion method, and more preferably oil-in-water dispersion method. It can be mentioned as follows. In the oil-in-water dispersion method, after dissolving either a high-boiling point organic solvent with a boiling point of /7t0c or higher and a low-boiling point so-called auxiliary solvent alone or in a mixture of the two,
Finely dispersed in an aqueous medium such as water or an aqueous gelatin solution in the presence of a surfactant. Examples of high-boiling organic solvents are U.S. Pat. ! 2.2,027, etc. Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, or the like before use for coating.

Specific examples of high-boiling organic solvents include phthalate esters (dibutyl phthalate, dicyclohexyl phthalate,
(di-2-ethylhexyl phthalate, decyl phthalate, etc.), phosphoric acid or phosphonic acid esters (triphel phosphate, tricresyl phosphate, λ-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tryptoxyethyl phosphate, trichloropropyl phosphate, cicoethylhexyl phenine phosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, -monoethylhexyl-p-hydroxybenzoate, etc.), Amides (diethyldodecanamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol,
aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, isostearyl lactate,
trioctyl citrate, etc.), aniline derivatives (N,
N-dipyl-λ-butoxyj-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like. In addition, as an auxiliary solvent, the boiling point is about 5o0c or more,
Preferably! Organic solvents having a temperature of 0° C. or more and about /600° C. or less can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, λ-ethoxyethyl acetate, and dimethylformamide.

The process and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat. ? .

3 Go No. 3, West German Patent Application (OLS) No. 3, r<ti.

Core 4 is described in No. 64T7, 230 of the same.

In addition to silver chloride and silver bromide, the silver halide emulsions used in the present invention typically include mixed silver halide, such as silver chlorobromide, silver chloroiodobromide, and silver iodobromide. . The silver halides preferably used in the present invention are silver chloroiodobromide, silver iodochloride, or silver iodobromide, and silver chloride, silver bromide, or silver chlorobromide containing 3 or less moles of silver iodide. The silver halogenide grains may have different phases inside and on the surface, may have a multiphase structure such as a bonded structure, or may consist of a uniform phase throughout the grain. Moreover, they may be mixed.

The average grain size of the silver halide grains used in the present invention (in the case of spherical or near-spherical grains, the grain diameter is taken as the grain size, and in the case of cubic grains, the average length is taken as the grain size, and the projected area is also calculated as the average grain size. Hail) is less than 2μ and 0. /μ
The above is preferable, but especially preferable is θ less than /μ, /!
μ or more. The particle size distribution may be narrow or wide.

More than 90% of all particles are within <10% of the average particle size in terms of particle number or weight, especially Ri! A so-called monodisperse silver halide emulsion having a narrow grain size distribution containing more than 10% of grain size can be used in the present invention. Furthermore, in order for the light-sensitive material to satisfy the target gradation, the emulsion layers having substantially the same color sensitivity have different grain sizes. 2! More than one type of monodispersed silver halide emulsion can be mixed in the same layer or coated in separate layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, dodecahedral, dodecahedral, etc.).
), may have an irregular crystal shape such as a spherical shape, or may have a composite shape of these crystal shapes. Tabular grains may also be used, with a special VC length/thickness ratio value! Especially the above! An emulsion in which the above tabular grains account for 50% or more of the total projected area of the grains may be used. An emulsion consisting of a mixture of these various crystal forms may also be used. These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the grains.

The photographic emulsion used in the present invention is described by Glafkides [Chemistry and Physics of Photography J] by Glafkides.

Chimie et Physique Photo
graphique (published by Paul Monte1, 7
967)], Duffin, “Photographic Emulsion Chemistry J [G.
Photographic Em by F. Duff in
ulsion Chemistry (Focal Pr.
ESS, 79≦Otsu)], by Zelikman et al. [Manufacturing and Coating of Photographic Emulsions J [V, L.

Zelikman et al @ Making a
ndCoating Photographic Em
ulsin (published by Focal Press, /96q)
It can be prepared using the method described in ]. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one form of the simultaneous mixing method, a method in which PAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

...In the process of silver halide grain formation or physical ripening, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or iron complex salts, etc. may coexist. .

The emulsion of the present invention is usually used which has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are Research Disclosure A/7
641j and Tie/17/l, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the two Research Disclosures mentioned above, and their locations are shown in the table below.

Additive type RD/2+Da3 RD/17/l/
Chemical sensitizer,! Page 3 4&/Page right column 2 Sensitivity increasing agent Same as above Brightening agent - Page 23 2 Anti-stinting agent, 2! Page right column Otsu! Page 0 left to right column Dye image stabilizer, 2! Page 2 Hardener, 2≦page Otsu! /page left column 1
0 Binder 2g page Same as above // Plasticizer,
Lubricant - Page 2 Otsu! θRight column Various color couplers can be used in the present invention, specific examples of which can be found in the aforementioned Research Disclosure (RD) A/
It is described in the patents listed in 76g3, ■-〇～G. As dye-forming couplers, couplers that provide the three primary colors (i.e., yellow, magenta, and cyan) in subtractive color development are important;
Specific examples of g-equivalent or co-equivalent couplers are as described above with RD/2g.
In addition to Turnip 2- described in the patents described in 4t3, ■-C and D, the following can be preferably used in the present invention.

A representative example of the yellow coupler that can be used in the present invention is a hydrophobic acylacetamide coupler having a ballast group. A specific example is US Patent No. 2.
θ7. ．． No. 210, same No.

♂7j, 0!7 and 3.2g! ,! It is described in No. 06 etc. In the present invention, it is preferable to use a two-wheel yellow coupler, as disclosed in U.S. Pat. 33. !
θ/No. and the same No. gu, θ here.

Oxygen atom separation type yellow coupler described in No. 62θ etc. or Tokuko Sho! ! -10739, U.S. Patent No. g, 4tθ/, 7-t, 2, U.S. Patent No. q, 32t, oλ
No. RD/10!3 (September 1979), British Patent No. 1, 4t2j, No. 020, West German Publication No.
2/9, 9/7 No. 2, No. 261,367, No. 2
,32ri,! / No. 2 and No. 2゜1433, t/, 2
A representative example of this is the nitrogen atom dissociative yellow coupler described in No. α-piparoylacetanilide couplers have excellent color fastness, particularly light fastness, while α-benzoylacetanilide couplers provide high color density.

Examples of the magenta coupler that can be used in combination with the pyrazoloazole coupler in the present invention include indacylon or cyanoacetyl couplers, preferably yoichi pyrazolone couplers, which have a ballast group and are hydrophobic. ! - Pyrazolone-based cazolers are preferably couplers in which the 3-position is substituted with an arylamine group or an acylamino group from the viewpoint of the hue and coloring density of the coloring dye. No. 2, No. 3, 3 da 3゜203
No. J, AOo, No. 7/f, No. 2゜9 (:#
, No. 173, 3.06.2. No. 13, No. 3.
7 Yoko, /9g issue and same issue j, 936°07! It is written in the number etc. Two cars! - As the leaving group of the pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat.
The arylthio group described in European Patent No. 73, t3 is particularly preferred. Also, the !-pyrazolone coupler having a ballast group as described in European Patent No. 73, t3 provides high color density.

Cyan couplers that can be used in the present invention include hydrophobic, diffusion-resistant naphthol and phenolic couplers, such as those described in US Pat. No. 2, Q74t.

Naphthol couplers as described in US Pat. No. 293, preferably U.S. Patent No. DA, θ! λ,, No. 2/2, same issue.

Typical examples include the oxygen atom-eliminating type two-equivalent naphthol couplers described in Kota Otsu No. 1.2θO, Kota No. q, Kota Otsu No. 1.2θO. Further, specific examples of phenolic couplers include U.S. Pat.
No. 1, No. 2,772, /g2, No.-, /9j,
/, 2. <It is written in the number etc.

Cyan couplers that are stable against humidity and temperature are preferably used in the present invention, and a typical example thereof is as described in U.S. Pat. A phenolic cyan coupler having U.S. Patent No. 2. ? ? 2, / Go No. 2, Go No. 3.2! ♂.

30/No., same No. 3, /24. Jri No. 3, same No. 4t.

3j4t, No. 071, Same No. G...? No. 27.173,
West German Patent Publication No. 3,3 Kota, 7.29 and European Patent No. 12/, 3≦! Ko, which is written in the issue etc. - Diacylamino-substituted phenolic couplers and U.S. Patent No. j
, g4tJ, No. 4.2, No. G, No. 333.9, No. D, <13-/, No. 61, and No. Q,
It has a phenylureido group at the co-position as described in No. 4t27.747 and! These include phenolic couplers having an acylamino group at the - position.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such a coupler is
U.S. Patent No. 9,366.237 and British Patent No. 2.
Specific examples of magenta couplers are given in European Patent No. 96,570 and German Published Application No. 3, .
2J4t, No. 333 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. Typical examples of polymerized dye-forming couplers are described in U.S. Patent No. J, '76/
, No. 220 and No. G, θ♂θ.

It is described in issue 2//. Specific examples of polymerized magenta couplers are given in British Patent No. 2,10.2,173 and US Patent No. TL,3O7,2L! '2 (described in ).

Couplers that release photographically useful residues upon camping are also preferably used in the present invention. The DIR cazolers that release development inhibitors are the aforementioned RD/7t4ti,
The patented couplers described in sections (1) to (F) are useful.

The color photographic light-sensitive material according to the present invention includes the aforementioned RD, Ni/7&'13, page 2/~kota and the same, Alt7/6.
6! Development processing can be carried out by the usual methods described in the r/left column to right column.

The color photographic material of the present invention is usually subjected to water washing or stabilization treatment after development, bleach-fixing or fixing.

In the washing process, it is common to use countercurrent washing in tanks larger than one to conserve water. For stabilization treatment, use Tokukaisho instead of the water washing process! A typical example is a multistage countercurrent stabilization treatment as described in No. 2-Zaj'13. In the case of this process, λ~
A countercurrent column for the tank is required. Various compounds are added to this stabilizing bath for the purpose of stabilizing images. For example, membrane pH
Various buffering agents (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, ammonia water monocarboxylic acid) to adjust pH (e.g. pH ~♂) , dicarboxylic acid, polycarboxylic acid, etc.) and formalin are representative examples. In addition, water softeners (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), disinfectants (benzisothiazolinone, isothiazolone, 9-thiazoline benzimidazole, etc.) as necessary. , halogenated phenols, etc.), surfactants, fluorescent brighteners, hardeners, and the like may be used, and two or more compounds for the same or different purposes may be used in combination.

In addition, ammonium chloride,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal film.

(Examples) The present invention will be explained below using examples, but the present invention is not limited by these examples.

Example/ As a magenta coupler, exemplified compound (6) 10, θg
lclJ(-2-ethylhexyl)phos7A'p,)
, Oml, and 26 ml of ethyl acetate were added and dissolved by heating, and the mixture was added to 700 ml of an aqueous solution containing 10 g of gelatin and 0 g of sodium dodecylbenzenesulfonate, and stirred at high temperature to obtain a fine emulsified dispersion. The total amount of this emulsified dispersion is Brr.

100 g of silver chlorobromide emulsion consisting of Morch (Age.

! In addition, 10 ml of flathead, 4-mono-dihydroxy-6-chloro-8-triazine sodium salt was added as a hardening agent, and both sides were laminated with polyethylene so that the silver coating amount was 2 oomg/m2. A sample was prepared by coating a gelatin layer on a paper support and providing a gelatin layer on top of this coated layer. This is designated as sample A.

Next, the magenta coupler, M-6, was converted to the exemplified compound (r)/
l, sg, (/s)/<t, 3g, (xq)70.0g
and tri(2-ethylhexyl) phosphate at 1ml and 17ml, respectively.

An emulsified dispersion was prepared in the same manner by adding 71 ml of ethyl acetate and 2 ml of ethyl acetate, and the same amount of the same emulsion was used.
Coating Ag! on the same support! Samples were prepared by applying the same amount of t. These samples were sample B and C%D, respectively.
shall be.

In addition, the compounds shown below are used as comparative samples! .

? gft! Exactly the same coating sample was prepared by the method described above using 2 ml of ethyl acetate (comparative compound) and 2 ml of ethyl acetate. This sample will be used as a comparative sample.

Including these comparison samples, samples A and D have /θ00C,M,
S, wedge exposure was applied, and the sample was processed with the following processing solution.

Developer benzyl alcohol /jml diethylenetriaminej vinegar I! I12! gKBr
θ, 4tgN a 2 S O3!
g Na2CO330g Hydroxyamine sulfate 2g Guamino-3-methyl-N-β-(methanesulfonamide) Ethylaniline・3/2H2SO4・H2O4t, tg Make up to 1000ml with water pH 10, / Bleach-fix ammonium thiosulfate (7wt%) 160ml1N a
2 S O3j g Na(Fe (EDTA)) 4tO
gDTA pH adjusted to 70θθmil with water, ♂ Treatment process temperature Time: Developing solution: 33°C, 3 minutes and 30 seconds Bleach-fixing solution: 33°C, 7 minutes and 30 seconds Water washing: ♂~3r0cs minutes Each sample obtained in this way was a clear, highly saturated magenta image. When the photographic characteristics of these color images were measured, the following results were obtained.

Table ■ Relative values of exposure that give a density of 100 (Capri 10, !i). The comparative sample was used as the standard (I00).

-++ The ε (molar extinction coefficient) of the dye of the coupler of the present invention is approximately to, oo θ, and that of the comparative coupler (ε in! 6. θ
θQ), the Dm value is still small in the case of molar application.

As a result, it was found that the coupler of the present invention exhibits superior characteristics in both sensitivity and gradation compared to couplers having an alkyl group at the 6-position. This is because the introduction of an alkoxy group or an aryloxy group at the 6-position increases the coupling activity and the color development efficiency.

Example C As described in Table H, the first layer (lowest layer) to the seventh layer (top layer) were coated on a paper support laminated with polyethylene on both sides, and color photographic materials E, F, I created G.

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 a solution prepared according to Example.

A B-G-R7 color separation filter was attached to these samples E, F, and G, and exposure was performed in the same manner as in Example/, but the color development time was changed to 2 minutes, 3 minutes 30 seconds, and 6 minutes. Other than that, the same treatment was applied.

The changes in photographic characteristic values when the color development time was changed were as shown in Table 3.

These results show that even in multilayer samples of natural color photographs, the couplers of the present invention have less dependence on color development time in terms of sensitivity, gradation, and maximum density than the Rodan atom separation type couplers, and have a shorter development time. It was shown to be an excellent coupler that exhibits photographic properties with small fluctuations.

In this way, exhibiting higher activity and coloring efficiency than conventional pyrazoloazole couplers is advantageous in terms of product design.
It turned out to be a coupler with excellent characteristics.

Example 3 As a magenta coupler, 70.0 g of exemplified compound
Add 2 oml of tri(2-ethylhexyl) phosphate and tml of ethyl acetate to (/6.lmm01), dissolve by heating, and add to an aqueous solution/θamal containing gelatin/θg and sodium dodecylbenzenesulfonate/0g at high temperature. A fine emulsified dispersion was obtained by stirring.

The whole emulsified dispersion was added to 100 g of silver chlorobromide emulsion (including Ag, <, and tg) consisting of Br3θmolti,
2% as hardener; 2. 10 ml of googedihydroxy-g-chloro-s-triazine sodium salt was added and coated on a paper support laminated with polyethylene on both sides so that the silver coating amount was 200 mg/m2, and a gelatin layer was placed on top of this coated layer. A sample was prepared using the following equipment. Sample I
~(A).

Next, the magenta coupler (≦) is added to the exemplified compound (♂), (
/θ), (/2), (,2t), (,2/), (30)
, (3/), (36), (32), (4t2), (Q&
), (4tt), (4t9) and (j/), an emulsion dispersion was prepared in the same manner, the same amount of the same emulsion was used, and the same amount of Ag was coated on the same support. A sample was prepared by applying the same amount. These samples are designated as samples I-B to 1-0, respectively.

Furthermore, the comparative compounds shown below as comparative samples ■/,
Exactly the same coating sample was prepared by the method described above using tri(2-ethylhexyl)phosfeld/lrml as tag (/, <, J'mmol) and 2jml of ethyl acetate. This sample is referred to as comparative sample (■).

(Comparative compound ■) (European Patent Publication No. 726.♂O4 is listed in the number) Similarly, the following comparative compound ■,! Comparative sample (2) was prepared using the following.

(Comparative Compound ■) (Described in European Patent Publication No. 76.10q) Including these comparative samples ■ and ■, sample 1-A~! -10ooc on 〇, M
, s, and processed with the following processing solution.

Developer solution benzyl alcohol /! ml diethylenetriamine! Acetic acid! gKBr
O,4tgN a 2 S 03
3 gNa2CO330
g Hydroxyamine sulfate 2g Teramino-3-methyl-N-β-(methanesulfonamide) Ethylaniline 3/2H2SO4H2O4t, tg Make up to 7000ml with water 1) H/θ, / Bleach-fix ammonium thiosulfate (2θwt %) /romlNa
2 S 03 YugNa
[Fe (EDTA)] 4tOgD
TA Make /θθOmjl with water.

pH 6, / Treatment process temperature Time Developer: 33°C 3 minutes 30 seconds Bleach-fixer: 33°C 7 minutes 30 seconds Water washing Coll~3t0c,? Each sample thus obtained had a clear, highly saturated magenta image. When we measured the X-characteristics of these color images, the table below shows ■
I got a result like this.

Table ■ *Relative sensitivity represents the relative value when the sensitivity of comparative sample ■ of color development 3'30'' is set to 10θ.

※※Gradation (γ) is density 0.1~ko,! It represents the slope of sensitometry up to.

As a result, as in Example 1, it was found that the couplers of the present invention exhibited superior characteristics in terms of sensitivity, gradation, and color density compared to couplers having an alkyl group at the 3-position.

EXAMPLE A multilayer color photographic paper having the layer structure shown in Table 1 was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

Preparation of first layer coating solution: Add and dissolve ethyl acetate/θml and solvent (c) u, Oml to 70g of yellow coupler (a) and 2.7g of color image stabilizer (b), and dissolve this solution in /% dodecylbenzenesulfone. Contains sodium chloride 101/θ
It was emulsified and dispersed in 90 ml of a tizelatin aqueous solution. On the other hand, a blue-sensitive dye shown below was added to a silver chlorobromide emulsion (silver bromide!θ mole, containing 70 g/kg of Ag) per mole of silver chlorobromide at 2.
．． 2! ×10-4 mole added to make blue-sensitive emulsion? jg
I made it. The emulsified dispersion and the emulsion were mixed and dissolved, and the concentration was adjusted with gelatin to give the composition shown in Table I to prepare a coating solution for the first layer.

The coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. As a gelatin hardening agent for each layer /-oxy-3
, terdichloro-3-triazine sodium salt was used.

The following spectral sensitizers were used in each emulsion.

Blue-sensitive emulsion layer; Green-sensitive emulsion layer; 5O3H-N(C2Hs)a Red-sensitive emulsion layer; The following dyes were used as anti-irradiation dyes in each emulsion layer.

Green-sensitive emulsion layer; Red-sensitive emulsion layer: The structural formulas of the compounds used in this example, such as couplers, are as follows.

(a) Yellow coupler (b) Color image stabilizer (C) Solvent (Cg H1g O+-P= 0 (d) Color mixing inhibitor Ut-t (e) /:/ mixture of solvents (molar ratio) (f) Ultraviolet light /:!:3 mixture (molar ratio) of absorbent (g) cyan coupler (h) color image stabilizer (i) /:2 mixture of solvent Silver halide color photographic light-sensitive materials can be created (multilayer coating is done simultaneously after adjusting the lance).

When preparing the third layer coating solution, the general formula (I) or (I) of the present invention is
Using the coupler represented by I) and the comparative coupler, samples were prepared in which only the structure of the third layer was different, as shown in Table ■.
-A to 11-N were made.

These silver halide color light-sensitive materials were wedge exposed in a conventional manner and processed according to the processing steps and processing solution formulations shown below.

Sensitome l)-evaluation was performed on the obtained sample. The results are shown in Table ■.

〔Processing method〕

Process Temperature Time Bleach-fixing 33
°C 7 minutes 30 seconds Water washing 33 °C 3 minutes [Processing solution composition] (Color developer) Water ♂θOm
l Sodium tetrapolyphosphate 2.0 g Benzyl alcohol / g, Omll diethylene glycol / 0,0 m4 Sodium sulfite 2.0 g Potassium bromide
0.5g sodium carbonate
30.0g N-ethyl-N-(β-methanesulfo/amidoethyl)-3-methyl-quaaminoaniline sulfonate 5.0g hydroxylamine sulfate <t, og water added
7000ml pH (2j'C)
10, 20 (bleach-fix solution) water 900m
l ammonium thiosulfate (70%) isθml sodium sulfite /♂g ethylenediaminetetraacetic acid iron (I [I) ammonium jig ethylenediaminetetraacetic acid/2Na sg Add water to 7000ml 1 pH
'C) 7. o.

As is clear from Table 1, samples [-B to 11-N using the couplers of the present invention have improved sensitivity and gradation (γ), and exhibit high color density.

Example! Using the samples ①-A to ll-N prepared in Example 4t, the samples were exposed to wedge light according to a conventional method and processed according to the processing steps and processing solution formulations shown below.

Sensitometric evaluation was performed on the obtained sample. The results are shown in <Table ■>.

〔Processing method〕

Process Temperature Time Bleach fixing 3z0c/min 30 second rinse 2♂～
3!0C 7 minutes 30 seconds [Processing liquid composition] (Color developer) Water ♂00C
c diethylenetriaminepentaacetic acid /, 0g sodium sulfite θ, 2gN, N-diethylhydroxylamine &, Jg potassium bromide 0. Tog Sodium Chloride /,! gtriethanolamine
! , Og potassium carbonate
30 g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-y-aminoaniline sulfate.

Add 2.0g of 4t'-diaminostilbene-based fluorescent brightener (Jumin Chemical Whitetex<t) at /θ00cc KOH pH/θ・-2 (bleach-fix solution formulation) Ammonium thiosulfate (!g) wt%) /romlNa2
SO371g NH4(Fe (l[) (EDTA)]j !g
EDTA-, 2Na 4tg
Add 7.61g of glacial acetic acid water and make a total of 1000ml (pHj, 4t) (Rinse liquid formulation) Add EDTA-2Na-2H200, t, tg water and make a total of 10θOml (pH 7,0) It is clear from Table ■〉 Similarly, samples using the coupler of the present invention [-B to l-N have improved sensitivity and gradation (γ),
It can be seen that the color density is high.

(For Examples) Samples ■-A1 and A were coated with two layers starting from the first layer on a paper support laminated on both sides with polyethylene.
2 was created. The first coated side of polyethylene contains titanium white as a white pigment and a trace amount of ultramarine blue as a positive dye.

(Photosensitive layer composition) The components and coating f expressed in g/m2 are shown below. Regarding silver halide, the coating amount is shown in terms of silver.

1st layer (gelatin layer) Gelatin...7.30 2nd layer (
Antihalation layer) Black colloidal silver...0.70 Gelatin...0.70 3rd layer (low sensitivity red sensitive layer) Iodine spectrally sensitized with red sensitizing dye (Kaoru 1 Shichikaoru 2) Silver bromide (silver iodide!, Q mole ratio, average grain size 0.<1μ)
...θ, /! gelatin
.../, θ0 cyan coupler (Kaoru 3) ・
... θ, /& cyan coupler (+4) ...
・0.07 anti-fading agent (-3+s, -X-a and +7)・
・0.70 coupler solvent (bitter 8 and lol 9)...0. θ
66 No. 9 (high sensitivity red-sensitive layer) Silver iodobromide (silver iodide 6.θ morch, average grain size 0.7μ) spectrally sensitized with red sensitizing dyes (yellow 1 and winter 2)
...θ, /! gelatin
.../, θO cyan coupler~ (Kaoru 3)...
...0.20 cyan coupler (arrow 4) ...0
．． 10 Anti-fading agent (≠5, Yoshi 6 and -14-7)...O1
/! Coupler solvent (Kaoru 8 and Fuyu 9)...0.10th!
1 Eel (middle layer) Magenta colloid silver --- 0.02 Gelatin .../, θθ color mixture prevention agent (-%
to) ... θ, 0♂ Color mixing prevention agent solvent (≠
11 and -1+12)・0.76 volumer latex (+
t3)...0. /θ 6th layer (low sensitivity green sensitive layer) Silver iodobromide spectrally sensitized with green sensitizing dye (≠14) (silver iodide 2.!molti, grain size O0yμ)
...θ, /θ gelatin
・・・・O1♂O magenta coupler=(-%t s )・
... θ, 10 anti-fading agent (-+16) ...
・θ, 10 stain inhibitor (-%t7) ...0
．． 07 Stain inhibitor (+X S )...0.0
0/Coupler solvent (bitter 11 and yellow 19)...O0/! Second
Layer (high sensitivity green sensitive layer) Silver iodobromide (
Silver iodide 36! Molch, particle size 0゜μ)
・・・ ・0. /θ gelatin
...0. ? θ magenta coupler (fts)・
...0. /θ anti-fading agent (%xa)...
・θ, /θ stain prevention agent (+17) ・・・θ
, 0/stain inhibitor (-1+1g)...θ, θ
0/Coupler solvent (bitter 11 and yellow 19)...θ, /J-1st layer (yellow filter single layer) Ixo-:+oi)'Silver...-0,. 20 gelatin.../, θ0 color mixture prevention agent (+1
0) ...0.01 color mixing inhibitor solvent (-+1
1 and bitterness 12)・θ, /! Polymer latex (+X 3
)...0010th layer (low sensitivity blue sensitive layer) Silver iodobromide (silver iodide λ, !molch, grain size θ) spectrally sensitized with a blue sensitizing dye (-+2o).

! μ) ...Q, /! gelatin
...O0!0 yellow coupler (
+z 1)...0.20 stain inhibitor (+18
)...θ, 00/Coupler solvent (Kaoru 9) ・
...0.01 First θ layer (high sensitivity blue-sensitive layer) Silver iodobromide spectrally sensitized with a blue sensitizing dye (-p+2o) (silver iodide 2.! morch, grain size/.

-μ) ...0.2 gelatin
.../, θ0 yellow coupler (+21)...θ, //l.

Anti-staining agent (-%ts)...O3θ02
Coupler solvent (-1+9)...θ, 10th 1st/layer (ultraviolet absorption layer) Gelatin.../,! θ UV absorber (bitter 22, yellow 6 and bitter 7) ・ ・ ・ ・ ・ / , θ θ Color mixing inhibitor (+2 a) ・・・・θ, θg゛ Color mixing inhibitor solvent (arrow 9) ・・・・0 .7! Anti-irradiation dye (Kaoru24)・・・・・O, θ
2 Anti-irradiation dye (arrow 25) ・ ・ ・ ・
0, 02 72nd layer (holding layer) Fine grain silver chlorobromide (silver chloride 27 mol ratio, average size 0.2
μ) ...0.07 gelatin
・・・／、! 0 gelatin hardener (Kaoru 26)
...0. /2 arrow t t, t'-dichlor-3,
3'-di(3-sulfobutyl)-terethylthiacarbonylcyanine Na salt +2) ethyl ammonium-3-C,2-(x-[
3-(3-sulfopropyl)naphtho(/,2-d)thiazoline-coindenmethyl]-/-butenyl)-3-
naphtho(/,2-d)thiazolino]propanesulfonate 32-[α-(,+Z,1lt-di-t-amylphenoxy)hexanamide:l-<t,t-dichloro-!
-Ethylphenol+4.2-[,2-chlorobenzoylamide coke-chloro-! -[α-(2-Chloro-g t-amylphenoxy)octanamidocouphenol 5J-(2-hydroxy-3-sec-!-t-butylphenyl)benzotriazole 62-(2-hydroxy-r- (t-butylphenyl) penztriazole yellow? 2-(2-Hydroxy-3,!-di-butylphenyl)6-chlorobenztriazole aroma 8 Dioctyl phthalate yellow 9 Trinonyl phosphate +10j, J--di-t-octylhydroquinone-1
+11) Recresyl phosphate Kaoru 12 Diptyl phthalate + 13 Polyethyl acrylate bitter 14 3/-Diphenyl-terethyl-3゜3'-
Disulfopropyl oxacarbocyanine Na salt % 15 Comparative coupler ■ (Sample III-AI) (European Patent Publication/26.!Q< is listed) Comparative coupler ■ (Sample l1l-A2) Yellow 163, 3.3 ',! '-Tetramethyl-! , Otsu.

z/,4/tetrapropoxy-/,/'-bisspiroindane 1% 173-(2-ethylhexyloxycarbonyloxy)-/-(3-hexadecyloxyphenyl)-copyrazoline 418.2-methyl-j -t-octylhydroquinone% 19) Lioctyl phosphate Kaoru 20 Triethylammomylum-3-(,2-(3-
Benzylrhodanine! -i+)f:y)-3=benzoxasolinyl]furo/R sulfonate%21 α-pivaloyl-α-[(2,'l-dioxo/-benzyl!-ethoxyhydantoin-3-yl)- 2-chloro-! -(α-,3,4t-di[-amylphenoxy)butanamide]acetanilide yellow 22! -chlororuco-(2-hydroxy-3-t-7
”-IF-ruj-t-octyl)phenylbenztriazole 232.!-G5ec-octerno1hydroquinone 24 25 +26/, &-bis(vinylsulfonylacetamide)
Ethane Next, the comparison magenta coupler (-+tS) of this sample 1-AI or A2 was added to the example coupler (6) (♂) (/θ) (
/7) (24>(,2♂)(3θ)(3/)(3g)(
37) Samples n1A2 to [1-N
It was created. These samples 1-A to 11-N were wedge exposed in a conventional manner and processed according to the processing steps and processing solution formulations shown below.

Sensitometric evaluation was performed on the obtained sample. The results are shown in <Table ■>.

Processing step - Development (black and white development) 3♂0C2 seconds water washing 3♂0C? θ seconds inversion exposure
1001ux or more Color development for 0 seconds or more
3♂'C136 seconds water wash 3♂
'Ca evening bleach fixing 3!0C haU second water washing 3cr 0c/3
Dry for seconds Composition of processing solution (first developer) Nitrilo-N,N,N-trimethylenephosphonic acid, pentasodium salt θ, +g diethylenetriamine/pentaacetic acid, pentasodium salt g,og potassium sulfite 3θ, 0g thiocyanide Potassium acid / 2g Potassium carbonate
! ! , Og hydroquinone monosulfonate potassium salt, 2t, 0g diethylene glycol /! , θml/-phenyl-hydroxydimethylnige-methyl-3 pyrazolidone 2.0g potassium bromide 0.5g potassium iodide
Add t, o mg water
/ 1 (pH 9, 20) (Color developer) Benzyl alcohol / j, Oml diethylene glycol / 2, 0 m13.
3-dithia-/,/-octanediol θ, 2g nitrio-
N,N,N-trimethylenephosphonic acid, pentasodium salt 0.6g diethylenetriaminepentaacetic acid, pentasodium salt, θ2 sodium sulfite, og potassium carbonate
2j, θg hydroxylamine sulfate
, OgN-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-guaminoaniline sulfate! , θg potassium bromide o, zg potassium iodide
/ , add Omg water
/ 1 (pH 10.4to,) (White paper fixer) Komel Capto/13. Coutriazole /, θg ethylenediaminetetraacetic acid disodium dihydrate! , θg ethylenediaminetetraacetic acid, Fe (l[[), ammonium-hydrate salt ♂θ, θg sodium sulfite /j, 0g sodium thiosulfate (700gll liquid) /≦θ, Oml glacial acetic acid! , add θml water / 1 (pH 6, jθ) Table ■ *) Gradation (r) represents the slope of sensitometry from concentration 0.6 to 2.0.

※※) The highest density represents magenta density.

As is clear from Table 1, Samples 111-B to 111-N using the couplers of the present invention have improved gradation (γ) and exhibit high color density.

(Example 2) On the triacetate film base, the first
Samples fV-Al and A2 were created by applying the ~72nd layer.

1st layer; antihalation layer UV absorber (2-hydroxy-3,
! -di-t-butylphenyl)-,2H-benzotriazole/zg, ,2-(,2-hydroxy,t-t-
phthylphenyl)-2H-penztriazole 30g1
Co(2-hydroxy-3-8eQ-butyl-1-1
-butylphenyl)-coH-benzotriazole 3! g
1 and dodecyl t-(N,N-diethylamino)
-2-benzenesulfonyl, 2,4t--! 'ntadienoate 100g and tricresyl phosphate 2
θOml.

An emulsion obtained by stirring an aqueous solution of ethyl acetate, sodium dodecylbenzenesulfonate, and ios gelatin at high speed (hereinafter referred to as emulsion (a)) was prepared by
% gelatin, black colloidal silver, water, and a coating aid, and coated to a dry film thickness of 2 μm.

2nd layer: gelatin intermediate layer λ, j-d-t-octylhydroquinone was dissolved in 100 cc of dibutyl phthalate and 700 cc of ethyl acetate, and an emulsion obtained by stirring at high speed with a 10% aqueous solution of gelatin/kg (hereinafter referred to as emulsion) (referred to as item (b)), 2 kg is l
It was mixed with O gelatin/tkg and coated to a dry film thickness/μ.

3rd layer; low-sensitivity red-sensitive emulsion layer containing 2-(heptafluorobutyramide)-j-(λ'-(2", 4t"-di-t-aminophenoxy)butyramide)-phenol/θθg, which is a cyan coupler. , tricresyl phosphate 100 cc and ethyl acetate 10
Emulsion (hereinafter referred to as emulsion (C)) obtained by dissolving in 0 cc and stirring at high speed with 10 tisgelatin aqueous solution/kg (hereinafter referred to as emulsion (C)) 1
00 g was mixed with a red-sensitive silver iodobromide emulsion/kg (containing 70 g of silver and 0 g of gelatin, and the iodine content was gmol %) and coated to give a dry film thickness of /μ. (Amount of silver 0, tg
/m2) th layer; Highly sensitive red-sensitive emulsion layer
Contains g1 gelatin tOg, iodine content is 2.5 mol%
) and dry film thickness λ,! It was applied so that it was μ.

(Silver i-0, ♂g/m2)th! Layer: Intermediate layer emulsion (b)/kg was mixed with /θtizelatin/kg and coated to give a dry film thickness of /μ.

6th layer: low-sensitivity green-sensitivity emulsion layer Comparative magenta coupler (instead of cyan coupler)
An emulsion (hereinafter referred to as emulsion (d)) obtained in the same manner as the third layer emulsion except that sample fV-At) and comparative magenta coupler (sample N-A2) were used (hereinafter referred to as emulsion (d)) 3θθg
was mixed with a green-sensitive silver iodobromide emulsion/kg (containing 70 g of silver and 0 g of gelatin, and the iodine content was 3 molty) to obtain a dry film thickness.

It was applied so that θμ. (Silver flc0, 7 g/
m2) Comparative magenta coupler〇Comparative magenta coupler■ (Both are described in European Patent Publication /2, /θy) 7th layer: Highly sensitive green-sensitive emulsion layer Emulsion (d) 1000g was mixed with green-sensitive silver iodobromide. emulsion/
kg (contains 70 g of silver, θg of gelatin, and iodine)
, :tco,tmolti) and coated to give a dry film thickness of θμ. (Amount of silver 0.7 g/m2) 1st layer: 7 kg of gelatin intermediate layer emulsion (b) is mixed with /θ% gelatin/kg,
Dry film thickness 0. It was applied so that it became sμ.

2nd layer: yellow filter A layer of yellow emulsion containing colloidal silver was coated to a dry film thickness/μ.

70th layer; low sensitivity back emulsion layer α- which is yellow coupler instead of cyan coupler
An emulsion ( 7000 g of emulsion (hereinafter referred to as emulsion (e)) is used as a blue-sensitive silver iodobromide emulsion/kg (70 fg of silver, gelatin contains Og, and the iodine content is λ,!
(molch) and applied to a dry film thickness of /, jμ. (Silver amount θ, 4 g/m2) 1st/layer: Highly sensitive back-sensitive emulsion layer emulsion (e)/θoog, blue-sensitive silver iodobromide emulsion/k
g (contains 70 g of silver, tog of gelatin, iodine content is λ
,! (mol%) and coated to a dry film thickness of 3 μm. (Silver ta/-/g/m2) 12th layer: Protective layer emulsion (a) was mixed with /θ tizelatin, water, and a coating aid, and coated so that the dry film thickness was λμ. .

73rd layer: Fine grain emulsion covered with the surface of the first protective layer (grain size 0°06μ,
A 70% aqueous gelatin solution containing 1M silver iodobromide emulsion) was applied to a silver coating amount of 0. /g/m2, dry film thickness o, trμ.

A gelatin hardener/4t-bis(vinylsulfonylacetamido)ethane and a surfactant were added to each layer, respectively.

Next, use the comparative magenta coupler of this sample Y-As or A2 as an example coupler (Otsu) (j-) (I0) (/7) (
z) (2♂) (3o) (J/) (3O) (37) (Gu 2) (g4t) (4tt) (Gu?) and (j/) were replaced in the same manner except that Sample ■-B~■-
I created P.

These samples 1-A to 2-P were exposed to light through a neutral gray sensitometric wedge, and then subjected to the following reversal process.

Processing process Process Time Temperature First development 6 minutes 3♂0C Wash with water 2 minutes Reversal 2 minutes Color development 3 minutes Adjustment - minutes Bleached white 6 minutes Fixed arrival time Wash with water 9 minutes Stable for 7 minutes at room temperature drying The composition of the treatment liquid used is as follows.

-Developer water 2θθ
ml NitriloN, N, N-)rimethylenephosphonic acid pentathrium salt 2g Sodium sulfite 20g Hydroquinone monosulfonate 30g Sodium carbonate (-hydrate salt) 30g/-phenyl-damethyl-monohydroxymethyl-3-pyrazolidone Cog Potassium bromide 2.3g Potassium thiocyanate / 2g Potassium iodide (Q, 7
% solution) Add 2ml water
1000m1 inverted liquid water 700
m1 Nitrilo-N,N,N-trimethylenephosphonic acid pentasodium salt 3g Seventh chloride
Tin (trihydrate) /gp-aminophenol 0.1g Sodium hydroxide
2g glacial acetic acid
Add 13ml water and 1000m
1 color developer water 200
m1 Nitrilo-N,N,N-)rimethylenephosphonic acid pentasodium salt 3g Sodium sulfite 7g Sodium triphosphate (/λ hydrate) 36g Potassium bromide 7g Potassium iodide (0
17% solution) 90ml sodium hydroxide
3g citradinic acid
/・! gN-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-q-amine aniline sulfate //g3.6-cythiaoctane/.

♂-Diol 7g Add water 10100O Adjusted liquid water 700
m1 Sodium sulfite /2g Sodium ethylenediaminetetraacetate (trihydrate) 2g Thioglycerin 0.4tml Glacial acetic acid
Add j ml water
10100O bleach solution water 1
00g Sodium ethylenediaminetetraacetate (trihydrate) λgIron(I) ammonium ethylenediaminetetraacetate (trihydrate) 120g Potassium bromide 700g Add water
10100O fixer water ♂θ
Oml sodium thiosulfate tro, 0g
Sodium sulfite! , θg sodium bisulfite j, add 0g water
10100O stable liquid water 200
m1 formalin (32% by weight) s, o
ml Fuji Drywell (surfactant manufactured by Fuji Film ■)! , θml Add water /θ00ml Table X *Gradation D) represents the slope of sensitometry from concentration O06 to 2.0.

Brown *The highest density represents magenta density.

As is clear from <Table

(Example/) A multilayer color photosensitive material having each layer having the composition shown below was prepared on a triacetylcellulose film support and designated as Samples V-A1 and A2.

1st layer: antihalation layer black gelatin layer containing colloidal silver λ layer; intermediate layer λ,! - Gelatin layer containing an emulsified dispersion of D-t-octylhydroquinone 3rd layer: 1st red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide: j morch)...Silver coating amount /, gg/m2 increase Sensitive dye■...G for 1 mole of silver! ×/θ−
4 moles of sensitizing dye■ ...for 1 mole of silver/! ×/θ−
4 mole coupler EX-/... O for 7 moles of silver, O4t mole coupler EX-3... o for 1 mole of silver, oo 3 mole coupler EX-2... 0 for 1 mole of silver, θθO mole q Layer: First red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide: 70 mol%) ...Silver-gold cloth* /-tg/m2 Sensitizing dye ■ ...E per 1 mole of silver x 10-4 mol sensitizing dye ■...for 1 mol of silver/ x 10-4 mol coupler EX-/... 0.002 mol for 1 mol of silver Coupler EX-2... for 7 mol of silver 0.02 mole coupler EX-3...0 per mole of silver, Qθ/mole number! Layer: Intermediate layer The same layer as the second layer; First green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide: 4t morch) ... Silver coating amount /, 2 g / m2 Sensitizing dye ■ ... ...for 7 moles of silver! ×/θ-4 mol Sensitizing dye ■...2 x 10-4 mol per mol of silver Magenta coupler for comparison ■ or ■...0001 mol per mol of silver 7th layer: 1 red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide: 1 mol) ... Silver coating amount 7.3 g/m2 Sensitizing dye ■ ... 3X10-4 mol sensitization per 1 mol silver Dye ■.../2 x 10- per mole of silver
4 mol comparison magenta coupler ■ or ■... 0.0/7 mol per mol of silver 1st layer ``Yellow filter'' Yellow colloidal silver and 2. ! -G-t-
Gelatin layer containing an emulsified dispersion of octylnohydroquinone 9th layer: 71st sensitive emulsion layer Silver iodobromide emulsion (silver iodide: mol %) ... Silver coating amount 0.7 g/m2 Coupler EX -Q...0.2/mole for 1 mole of silver Coupler EX-t...O0θ/! for 1 mole of silver! Mole 1st layer: 2nd blue-sensitive emulsion layer Silver iodobromide (silver iodide; 3 mol%)...Silver coating amount θ, gg/m2 Coupler EX-Q...7 moles of silver, θ, 06 mol 1st/layer: First protective layer silver iodobromide (1 mol silver iodide, average grain size θ, 07 μ)
...Silver coating amount θ, sg/m2 Ultraviolet absorber Ultraviolet absorber UV-containing gelatin layer 72nd layer: Second protective layer polymethyl methacrylate particles (diameter approx./.

! Apply a gelatin layer containing μ).

In addition to the above composition, gelatin hardener H-7 and a surfactant were added to each layer.

(Structural formula of the compound used in Example ♂) % Formula % Comparative magenta coupler ■ (Sample V-At) Comparative magenta coupler ■ (Sample V-A2) 8ti17(t) H-/ (CH2=CH802CII2CONHCI- 12-)
-UV-/ (weight ratio) Sensitizing dye I Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ Next, use the magenta coupler for comparison of this sample V-A1 and A2 as example coupler (4) (I) (io )(/7)(2g
) Lz, r) (3o) (,?/) (to J) (37) (4
t, 2) (g4t) (gt) (4t9) and (!/)
Samples V-B to ■
-P was created. These samples V-A to -P were wedge exposed in a conventional manner and processed according to the processing steps and processing solution formulations shown below.

The development used here was carried out at 3♂0C as described below.

/ Color development ・・・・・・・・・ 3 minutes/!
Second 2 Bleaching ・・・・・・・・・・・・ 6 minutes 3
0 seconds 3 Wash with water ・・・・・・・・・ 3 minutes/
! Second fixation ・・・・・・・・・ Otsubu 3
0 seconds evening water washing ・・・・・・・・・ 3 minutes/
! Seconds 6 Stable ・・・・・・・・・ 3 minutes/
The composition of the treatment liquid used in each step is as follows.

Color liquid retention solution Sodium nitrilotriacetate /, 0g Sodium sulfite, 0g Sodium carbonate 30, 0g Potassium bromide
7.4tg hydroxylamine sulfate 2. l1g goo (N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate, add rg water / l bleach solution ammonium bromide /6θ, Og a / monia ammonium) Ko! , θcc ethylenediamine-tetraacetic acid sodium iron salt /3θ, og glacial acetic acid
/“・Add Occ water
/ lFixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 9.0g Ammonium thiosulfate (70%) /7! , θCC sodium bisulfite
11. , add gg water
/ l Stabilized liquid formalin! , θcc water was added/l. Sensitometric evaluation was performed on each sample thus obtained. The results are shown in <Omotekari>.

Relative sensitivity with Sample V-AI set to 700 with the reciprocal of the exposure that gives a density of Turnip +) As is clear from the density at log E ), samples V-B and V-P using the couplers of the present invention have improved sensitivity and gradation (γ),
It can be seen that the color density is high.

These results show that in silver salt color photography, the coupler of the present invention has less dependence on color development time in terms of sensitivity, gradation, and maximum density than the 6-position alkyl type coupler, and shows less variation with a short development time. It was shown to be a coupler with excellent photographic properties. As described above, it was found that the coupler exhibiting higher activity and coloring efficiency than conventional pyrazoloazole couplers is advantageous in terms of product design, and has excellent characteristics.

Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment 1985//Month% Date 1, Case Indication 1988 Patent Application No.-4AJ7
/λ No. 2, Title of invention Color image forming method 3,
Relationship with the case of the person making the amendment Patent applicant's office 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Subject of amendment Column 5 of "Detailed Description of the Invention" in the specification, "Details of the Invention" in the description of the contents of the amendment The description in the "Explanation" section has been amended as follows.

l) Page λ/, 2nd line After "aryloxy group" "or heterocyclic oxy group" Insert.

c) Insert all ", alkylthio group, arylthio group, heralocyclic thio group" after "aryl group" on page 7, line 1.

3) Page 71r, line λ "Halogen atom separation type" "Methyl type at 6th position" and correct it.

Hiroshi) Attachment 7 after the structural formula of compound (jl) on page 36 2H5 (!the law of nature QC4He (j7) (sr) (jri)

Claims (1)

[Claims] A silver halide photosensitive material is developed with a developer containing an aromatic primary amine in the presence of at least one coupler represented by formulas (I) and (II). Color image forming method. General Formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In the formula, R_1 represents an alkyl group, aryl group, or heterocyclic group, and R_2 represents a hydrogen atom or a substituent. General Formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In the formula, R_1 represents the same group as above, and R'_2 represents an alkyl group, an aryl group, an alkylthio group, an arylthio group, or a heterocyclic thio group. X represents a hydrogen atom or a coupling-off group.