JPS6291948A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photographic sensitive material having superior color reproducibility and sensitivity and developing high density color by forming a silver halide emulsion layer contg. a specified pyrazoloazole type coupler on a support. CONSTITUTION:A silver halide emulsion layer contg. a pyrazoloazole type coupler represented by formula I is formed on a support. In the formula, R1 is H or a substituent, X is H or a group eliminable by a coupling reaction with the oxidized product of an aromatic primary amine developing agent and each of Za, Zb and Zc is methine, substituted methine, =N- or -NH-. The coupler represented by the formula I is preferably used by 5X10<-2>-5X10<-1>mol per 1mol silver halide in the silver halide emulsion layer.

Description

[Detailed Description of the Invention] (Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material, which is excellent in dust, dark color reproduction, sensitivity, and processing characteristics. be.

(Prior art) Using oxidized silver halide as an oxidizing agent, the oxidized aromatic/grade amine thread color developing main mulberry and coupler react to produce indophenol, indoaniline, indamine, azomethine, phenoxazine, It is well known that fenazi/and similar dyes can be produced and color images can be formed.

Up until now, most of the magenta color image forming couplers have been widely used and researched! - It was a pyrazolone. ! - Pyrazolone couplers have excellent fast IW and efficiency in forming dyes, and the formed azomethine dyes have excellent fastness to light and heat. It has been said that this is the cause of the color becoming muddy.

Magenta color that reduces this yellow component 1. [! The pyrazolobenzimidazole bone nucleus described in British Patent No. 1,0≠7.1,12 as the iI image cedar bone nucleus, and the pyrazolobenzimidazole bone nucleus described in British Patent No. 1,0≠7.1,12! , pyrazolotriazole bone nucleus described in OA7 No. 8, pyrazoloimidazole bone nucleus described in U.S.A.
Pyrazolopyrazole bone core described in No. J9, European Patent No. 1
/? ,! The pyrazolotriazole bone core described in No. 4OA has been developed.

The dyes formed by these materials are superior to those formed by conventional j-pyrazolones in terms of absorbing unnecessary yellow components, and they also have a higher absorption spectrum on the long wavelength side. It is also a preferable coupler in terms of color reproduction in that the absorption of

(Problems to be Solved by the Invention) However, while these birazoloazole couplers have the excellent points mentioned above, they also have undesirable properties (r'ff) as described below. found out.

In other words, when these couplers coexist with silver halide to be used as an oxidizing agent for an aromatic primary amine developing agent necessary for the color-forming reaction, more specifically, the emulsion dispersion of these couplers and the halogenated A silver saponified emulsion is mixed with a silver emulsion to prepare a coated product, and its photographic properties 1. Next, the feeling of color decreases, and then the color develops and becomes darker (
This behavior shows a behavior in which the This can be confirmed, for example, by preparing all the coatings incorporating the S-pyrazolone coupler KRAT and comparing them with the 'fc results obtained by color development or black and white development. In addition, a part of the phenomenon can be understood by comparing the results obtained by preparing a coating of only a silver halide emulsion without adding any coupler and developing it in black and white.

Originally, couplers used in silver halide color photographic light-sensitive materials do not have any effect on the silver halide emulsion, except for couplers that provide special functions such as development inhibitor-releasing couplers or development accelerator-releasing couplers. Gold is also not expected to have any effect, especially on the photosensitization process.
It is undesirable to compromise the benefits of sensitization by 15 rupees or the sense of work effect.

Conventionally, it has been widely used as a magenta image forming coupler! - It was found that such an effect on silver halide was hardly observed with pyrazolone couplers, but was observed in a broad manner with pyrazoloazole couplers.

The pyrazoloazole coupler is a coupler having a pyrazolobenzimidazole ring and a pyrazolotriazole bone core '4f. Compounds with all these residues have stronger interactions with silver ions or silver ions, i.e., with the -b complex. We confirmed that it has a secondary effect with formation or adsorption.

It has also been confirmed that such interactions cause sensitization and deterioration of color development of emulsions.All samples were prepared in which a silver halide emulsion and a pyrazoloazole coupler were coated on a support. When examining changes in interactions depending on the halogen species in the emulsion, it was found that silver chloride emulsions are more likely to cause deterioration in color development than silver bromide emulsions. On the other hand, it has also been found that a silver iodobromide emulsion containing silver iodide is less likely to cause a decrease in color development than a silver bromide/silver emulsion (4-4 silver bromide emulsion). In other words, in the emulsion of silver chlorobromide thread, the interaction with pyrazoloazole couplers in reducing color development is greater than in the emulsion of silver iodine thread. It was more difficult to introduce all azole couplers.

One way to solve such problems is to
Although the method of controlling the pk-1 of a coating film is disclosed in No. -/J Cor. It contains such inadequacies. In other words, even if it is possible to cut the coating film as it is by setting pHk: 414, it is possible to cut the coating film as it is, but in order for the coating film to develop color, it must go through a development process. ,
When the film is immersed in a developer having a pH of about 2 to 12, the pH in the film increases significantly, and new interactions occur in the treated layer, causing the film to break. J This interaction is also positive for silver chlorobromide.

In any case, it is important to cut off this effect on halogenators, especially silver chlorobromide, and improvements are expected.

Therefore, the first object of the present invention is to provide a halogenated urine photographic light-sensitive material which is excellent in color development, sensitivity and color density.

A second object of the present invention is to provide a silver halide photographic material containing a pyrazoloazole coupler and capable of providing high sensitivity and sufficient color development.

(Means for Solving the Problem) The object of the present invention is to produce a silver halide color photographic light-sensitive material having a silver halide emulsion/# containing a pyrazoloazole coupler represented by the general formula [I] on a support. I'm afraid I'll be mistaken.

In the general formula CI:), 几represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. Za is methine, substituted methine, ;N- or -N
Represents H-. zb and ZC are also methine, substituted methine, =
He or -NH-Th & Suga, at least one of Zb-Zc (•) is a substituted methine having -C-tt3 as a substituent. When zb is f-substituted methine, either Za or Zc is -N)l-, and the other is 7thine, substituted methine, =he, or 1''L is Zc. When is the above IiE-converted methine, Z3 is -N
H-, and zb is methine, substituted methine or =N-. l(+2 represents either an alkyl group or a halogen atom, 3, i(,4 represents a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an ano group, a hydroxyl group, an alkoxy group, an acyloxy group) , heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, amino-tawara, ureido group, imide group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, carboxycarbonyl group, carbamoyl group, acyl group, sulfamoyl group, sulfonyl group, sulfinyl group, alkoxycarbonyl group, aryloxycarbonyl group 'kffwasu.

Among the pyrazoloazole magenta couplers represented by the general formula [I], preferred are the general formulas (II) to F'
(Vl).

(u) (1) (IV) (V) lt2 is a straight-chain alkyl group and may be a 43t+-branched alkyl group, such as methyl shield, ethyl group, propyl group, butyl group, ethyl group, hexyl group, hezotyl group, etc. On the left, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl blue, eicosyl group, cyclopentyl group, cyclopentyl group, etc.

These alkyl groups and substituents such as alkyl groups, alkoxy groups, and aryl groups described below may further contain one or more lL
The substituent may include a halogen atom (for example, a fluorine atom, a chlorine atom, etc.), an alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.).
Co, 2-dimethylpropyl group, n-butyl group, t-butyl group, trifluoromethyl fluoride, tridecyl &, j-Cλ
, ≠-di-t-amylphenoxy)propyl group, allyl group, λ-dodecyloxyethyl group, 3-phenokizib a
Bill light, λ-hexylsulfonyl-ethyl group, cyclopentyl group, be/zyl group, etc.), alkenyl light (e.g.
vinyl, etc.), alkynyl groups (e.g. /-propynyl, etc.), aryl groups (e.g. λ, phenyl, group),
-7'tylphenyl 7i, 2, 41-cy t-amylphenyl group, Hiroshi-tetradecanamidophenyl, etc.), heterocyclic group (e.g., 2-furyl shield, 2-chenyl, -1pyrimidinyl group, 2- benzothiazolyl group, etc.), cyano end, hydroxyl group, alkoxy group (e.g., methoxy group, ethoxy group, comethoxy group,
codedecyloxyethoxy group, λ-methanesulfonyl ethoxy group, etc.), aryloxy group (e.g.
phenoxy group, 2-methylphenoxy7 group, Hiroshi-1-butylphenoxy group, etc.), heterocyclic oxy group (e.g. 2
-benzimidazolyloxy scrap, etc.), alkini group (e.g., acetoxy group, hexadecanoyloxy group, etc.)
, carbamoyloxy group (flLt, hephenylcarpamoyloxy group, heethylcarbamoyloxy7 structure, etc.), silyloxy group (e.g., trimethylsilyloxy group, e), sulfonyloxy group (e.g., dodecylsulfonyloxy group, etc.), acylamino groups (e.g.
Acetamito group, benzamide group, tetradecanamide group, α-(λ.

μm di-t-amylphenoxy)butyramide group, r-
(J-t-7” Chiruhiro-hydroxyphenoxy)butyramide group, α-(<<-(e-hydroxyphenylsulfonyl)phenoxy)tecanamide group, anilino group (e.g., phenylamino group, cochloroaniline group) υ) group, -1 taroro 1 tet 2 decanamide anilino group, λ
- Kuroro! -dodecyloxycarbonylanilino group,
Ha acetylanilino group, cochroro! −(α−(3
-1-butyl-Hiro-hydroxyphenoxy) dodecanamide 1anilino L, etc.), amino-R5 (e.g., ethylamine group, dimethylamino group, methyloctylamino group, etc.), ureido group (e.g., phenylureido group, methylureido group, etc.) group, N, N-dibutylureido group, etc.),
imido groups (e.g., hesuccinimide, 3-be/zylhydantoinyl, ≠-(coethylhexanoylamino)phthalimide, etc.), sulfamoylamino groups (e.g., N,N-dibutylhydantoinyl, etc.); rufamoylamino group, N-methyl-N-decylsulfamoylamino group, etc.), alkylthio group (e.g. methylthio group, octylthio group, tetradecylthio group, -monophenoxyethylthio group, 3-phenocoylate group) Zolopyrthio, 3-(≠-t-
butylphenoxy)propylthio group, etc.), arylthio group (e.g., phenylthio group, λ-dutoxyj-t
-octylphenylthio, 4, J--<ntadecylph;
nylthio group, λ-carboxyphenylthio group, kutetradecanamidophenylthio L5, etc.), heterocyclic thio group (e.g., cobenzothiazolylthio group, etc.), alkoxycarbonylamino group (e.g., methoxycarbonylamino group, tetra decyloxycarbonylamino group, etc.), aryloxycarbonylamino group (e.g., phenoxycarbonylamino group, co,≠-di-tert-butylphenoxycarbonylamino group, etc.), sulfonamide group (e.g., methanesulfonamide group) , hexadecane sulfonamide group, benzenesulfonamide group, p-
toluenesulfonamide group, octadecanesulfonamide group, comethoxy-1-1-butylbenzenesulfonamide group, etc.), carboxyl group, carbamoyl group (y
+I, heethylcal/9moyl-i, N, N-dibutylcarbamoyl group, N-(codedecyloxy7ethyl)carbamoyl#N-)thiruhedodeflucarbamoyl group, he-1-<2. ≠-di-tert-amylphenoxy)propyl 1 carbamoyl group, 4), acyl group (
For example, acetyl group, λ, ILA-di-tert-amylphenoxy-acetyl group, benzoyl group, etc.), sulfamoyl group (for example, N-ethylsulfamoyl group,
N,N-dipropylsulfamoyl&,N-(-2-dodecylox7ethyl)sulfamoyl group, ~-ethyl-N-dodecylsulfamoyl group, N,N-diethylsulfamoyl M, 4%L sulfonyl group (e.g. C, methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.), sulfinyl-
4 (IflJ, octane sulfinyl M,)"f silsulfinyl, phenylsulfinyl i, etc.),
Alkoxycarbonyl group (e.g., methoxycarbonyl group, butyloxycarbonyl group, dodecylcarbonyl group, octadecylcarbonyl group, etc.), aryloxycarbonyl group (e.g., t, phenyloxycarbonyl group,
3-bentadefluoroxy-carbonyl group, etc.). Historically, halokene atoms can be cited as 几2.

and lt4 are halogen atoms, alkyl groups, aryl groups, heterocyclic groups, cyano groups, human mixyl groups, alkoxy groups, aryloxy groups, peterocyclic groups, acyloxy groups, carbamoyloxy groups, silyloxy groups, and sulfonyloxy groups. group, acylamino group, anilino group,
Amino group, ureido group, imide group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, carboxyl group, carbamoyl group , acyl-1, sulfamoyl group, sulfonyl group, sulfinyl group,
Alkoxycarzenyl group represents aryloxycarbonyl group. More specifically, R3 and lt4 are halogen atoms (e.g., fluorine atom, chlorine atom, etc.), alkyl groups (e.g., methyl group, ethyl group, propyl group 1,
2. --dimethylzoa-pyl group, n-butyl group, t-butyl group, trifluoromethyl group, tridecyl4. J-(2
゜μm di-t-amylphenoxy)propyl group, allyl group, λ-dodecyloxyethyldi, 3-phenoxyprobyl group, cohexylsulfonyl-ethyl group, cyclopentyl group, benzyl M, 4), aryl group ( For example, phenyl group, +-1-butylphenyl i, J, μm di-t
-amylphenyl group, μm tetradecane amidophenyl group, etc.], heterocyclic group (e.g. '-7'J group, λ-
Chenyl sai, cobyrimidinyl group, λ-benzothiacyly A4,%), cyano group, hydroquinyl group, alkoxy, etc. (e.g., methoxy group, ethoxy group, -1methoxyethoxy7 group, λ-dodefluoxyethoxy group, comethanesulfonyl group) ethoxy group, etc.), aryloxy group (e.g., phenoxy group, 2-methylphenoquino group, μmt-butylphenoxy group, 4% heterocyclic oxy group (e.g., 2-benzimidazolyloyl group, etc.) , acyloxy groups (for example, acetoxy group, hexadecanoyloxy M, etc.), carbamoyloxy groups (for example, hephenyl group, N-ethylcarbamoyloxy group, silyloxy group (for example, trimethylsilyloxy group, ), sulfonyloxy groups (e.g., dodecylsulfonyloxy, etc.), acylamino groups (e.g., acetamido group, benzamide group, tetradecanamide group, α-(x,t,t-di-t-amylphenoxy)butyramide) group, r-<3-t-butyl-μm hydroxyphenoxy)butyramide group, α-14cm (≠
-hydroxyphenylsulfonyl) phenoxy1-decaneamide scales, etc.), anilinofi (e.g., phenylamino group, λ-chloroanilino group, λ-chloro!-tetradecanamideanilino group, cochloro!-dodecyloxycarbonylanilino group, acetylanilino group,
Cokemilo-yo-(α-(J-t-butyl-μmhydroxyphenoxy)dodecaneamide 1 anilino group, '4?
), amino groups (e.g. ethylamino group, dimethylamino group, methyloctylamino,
N,N-dibutylureido group, etc.), imide group (e.g., hesuccinimide group, 3-penzylhydantoinyl group, μm (2-ethyl to 1+?mylamine)7 talimide group, etc.), sul7 Amoylamino fS (e.g., N
, N-dipropylsul7 amoylamino group, N-methyl-N-decylsul7 amoylamino group, etc.), alkylthio group (e.g. methylthio group, octylthio-containing tetradecylthio group, λ-phenoxyethylthio group, 3-phenoxypropylthio group) , j-(≠-1-butylphenoxy)zolopylthio group, etc.), arylthio fs (e.g., phenylthio group, 2-butoxy-jt-octylphenylthio group, 3-pentadecylphenylthio group, λ-
(e.g., 2-benzothiazolylthio group, etc.), alkoxycarbonylamino group (e.g., methoxycarbonylamino group, tetradecyl oxycarbonylamino group, etc.), cycarmenylamino group in aryl group (e.g., phenoxycarbonylamino group, 21 μm di-tart-butylphenoxycarbonylamino group, etc.), sulfonatomytono & (e.g., methanesulfone oxide group, etc.), hexadecanesulfonamide group, benzenesulfone 7mitoh i, l)-1' luenesulfonamide group, octadecanesulfonasF'' group, comethoxyz-t-7' thylbenzenesulfonamide group, etc.), carboxylic group, carbamoyl Group (fl
For example, N-ethylcarbamoyl group, N,N-dibutylcarbamoyl! , N-(7ethyl in 2-dodecyl)carbamoyl, N-methyl-N-dodecylcarbamoyl group, N-(J-(J, u-di-tert-amylphenoxy)propyl)carbamoyl group, etc.), acyl group ( For example, acetyl Ti5.2,4t-di-tert-amylphenoxyacetyl group, benzoyl group, etc.), sulfamoyl group (e.g., 8-ethylsulfamoyl group,
N, N-dipropylsulfamoyl group, N-(λ-dodecyloxyethyl)sulfamoyl group, H-ethyl-N
-dodefursulfamoyl group, N,N-diethylsulfamoyl group, etc.), sulfonyl group (e.g., methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl &, %), sulfinyl! (
For example, octane sulfinyl group, dodecyl sulfinyl group, phenyl sulfinyl group %#)% alkoxycarbonyl group (e.g., methoxycarbonyl group, butyl ox 7 carbonyl group, dodenyl carbonyl group, octadecyl carmenyl group, etc.), arylo oxy 7 carbonyl group Group (
Example 1-1', phenyloxycarbonyl group, 3-pentadecyloxy-carbonyl group, etc.).

General formula (III), ([V) and [■]].

is a hydrogen atom′! ! The word "nen" represents a substituent group, and the substituent groups are those described above and are represented by "f/:", "bon", and "bon".

In the general formulas CI) and (Ill) to (Vl),
is a hydrogen atom and represents a substituent, and the substituent is the one represented by IL and l(3, lt) explained above, and 1'
6 Dust, also represented by -〇-几, can also be around 8. Here, 几 is a substituent represented by 2, which is the same as that described above. Furthermore, 7.1t is a substituent which is substituted by R3 and R4, and is the same as that described above. However, lt6, lt7, E are IL 2,
Unlike the case of 几3 and R4, only one of them can be hydrogen atom gold. In the present invention, it is more preferable that R1 is -Ct, and it is most preferable that none of R1, R7 and R8 are hydrogen atoms.

In particular, in silver halide having silver chloride f&: 10 mol or more, the following is true.

Silver bromide, especially silver bromide containing silver iodide, shows excellent performance.

In addition, the general formula C
II) Couplers with t=P and [■] are particularly preferred.

Specific examples of typical Mai/Takashira according to the present invention will be shown, but the present invention is not limited thereto.

M-/-J Shiba (-Mohe)
[2
Shishiba 2shi
2 drinks
Sa elo
to 2
＜= ■ False ＼
P1) 2 ΣIs the coupler of the present invention disclosed in Japanese Patent Application Publication No. 2003-100000-1'? No. 0772 and the same 0-/
It can be synthesized by applying the method of No. 7trr.

Synthesis example? Shown below.

Synthesis Example> (Synthesis of Exemplary Compound lν1-/) 3-Amino-Yo-Methylpyrazole Tough? and 2゜λ-dimethyl-3-phthalimidopropionimidate methyl salt 11!2
Stir 7v of Dankota in methanol at room temperature for about an hour, then add hydroxylamine hydrochloride 7θ1 and sodium acetate 12
? Add a mixed aqueous solution of and heat under reflux for about 2 hours. The reaction solution was pressed into water to precipitate N-[J-(coH-7-metelpyrazolyl)]-]-, cordimethyl-3-7thalimidopropanamide oxycum? Door, acetonitrile and water/
Washed with 1:1 mixed solvent. Yield % t7tAf (yield j/division), melting point //θ-//amide oxime/00 f'j (acetonitrile 7
00rd, and while stirring at room temperature, an acetonitrile solution of p-toluenesulfonyl chloride r6f? It dripped slowly. After extraction, pyridine 2J! ml was added, and the mixture was further stirred for 1 hour. Then, it was poured into ice water SL, and the precipitated crystals were separated and subjected to ffC# with a mixed solvent of acetonitrile and water. The crystals were added to methanol/E without drying, a pyridine λλ cage was added, and the crystals were heated under reflux for about 2 hours after death. After that, methanol was distilled off under reduced pressure, and about 2
After concentrating to 0.001 Lt, it was poured into about 200 ml of water and stirred for a while. The precipitated crystal 'kF was separated, washed with acetonitrile, and dried to give 6-methyl-j.
(2, colamethyl-2-phthalimidoethyl)-/H
-Pyrazolo (/, j-b) -/, Ko.

l-triazole 66? (yield 70 cm).

100 tt of methanol to pyrazolotriazole JOf with melting point 197-/9P'
& and tj% hydrazichtrad Wtd'fc plus approx. 2
Avoid heating and refluxing for a while. Into this solution 10 Ornl of water and #
Add hydrochloric acid λOrd, separate the precipitated phthalhydrazide, concentrate the solution, and recrystallize the residue from ethanol to obtain t-methyl-λ-(/,/-dimethyl-co-aminoethyl)-/H-pyrazolo. CI, z-b) -
t, 2. IL-triazole dihydrochloride gold 372 (yield 7!) was obtained.

F! ! ! I1. a ~ t t j'C (Dt [middle).

This fh modified m 3ofq dimethylacetamide 60ml
K @Kashi, triethylamine/! , add 7 ml of water, cool with ice water, and stir well. Two drops of an acetonitrile solution of 1-1-octyl-jn-octyloxybenzenesulfonyl chloride 4A72 were added into the solution. The reaction solution was poured into water, extracted three times with ethyl acetate, and the extract was dried over magnesium sulfate/rum and then dried under reduced pressure. Obtained solid f
By recrystallizing from a mixed solvent of n-hexane and ethyl acetate, 6-medel-2-(/l/-dimethyl-,2
-(j-t-octyl-λ-n-octylbenzenesulfonamido)ethylj-/)i-pyrazolo(/, j-b
)-/, co,≠-triazole to 4Lr,rr (yield 7
j 俤) (8 melting point/JO-/Pyrazolotriazole jOf'3) dichlorometh/≠
Dissolved in O- at room temperature, N-chlorosuccinimide 7,
After stirring for 9 times, after about 3θ minutes, reaction a was added twice with water.
After washing once with saturated saline and drying with magnesium sulfate,
By concentrating to dryness and recrystallizing from a mixed solvent of n-hexane and ethyl acetate, the exemplary compound (M-/) was obtained as 2r,
AP (yield: Ochi) could be obtained. Melting point //j-/
/7°C Other exemplified compounds are also 3-amino-! -Okimu pyrazole and methyl nonaimide hydrochloride having a substitution region that can be derived into the desired coupler were combined and synthesized using the above method.

The coupler of the present invention represented by the general formula [I] is from /×10 −3 mol to 1 mol of silver halide present in the same layer.
1 mol, preferably z x 1o-2 mol to rxio
Add to the emulsion layer in molar proportions. Nine or more couplers of the invention may be added to the same emulsion layer.

In the present invention, cyan and yellow couplers can be used in addition to the My/Takashira.

Typical examples of these are naphthol or phenolic compounds and open-chain or heterocyclic ketomethylene compounds. Specific examples of these cyan and yellow couplers that can be conveniently used in the present invention are given in Research Disclosure (RD)/76μ3 (/7?/February) ■-D Section and RD/17/7 (/7/76μ3) The invention is described in patents cited in

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized. Does our color coupler with a leaving group substituted with a coupling active position have a higher amount of coated silver than a four-equivalent color coupler with a hydrogen atom in the coupling active position? Can be reduced. Also useful are color-forming couplers, non-color-forming couplers, or DIR couplers that release all of the development inhibitor or couplers that release a development accelerator along with the coupling reaction, such that the coloring dye has adequate diffusivity. can.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is the US Percentage 2. ≠0
7. Ko No. 10, No. 2, 17! , No. 017 and (b)
No. 3,243. It is described in J04 issue etc. For the present invention, the use of two-hit yellow couplers is preferred and is described in US Pat. tau
7. Yxr No. J, No. 133.101 and No. 1! , 02 co.

6λQ, etc., and is a type of oxygen atom separation type IE coupler or Tokkosho! ? -1073, U.S. Patent No. q, Hiroσ/, 7! Ko No., fiii No. 324, 02
1fi issue, l is also I)/10! ! (/979≠Monday, British Patent No. 1. Hiroko!, OkoO No., West German Application Publication No. 2, 2
/ Ri, Ri No. 77, @ko, 24/, No. 361, No. 2,
3 pieces! r7 and (same No. 2゜41JJ, r/-
A representative example of this is the nitrogen atom dissociative coupler described in the above issue. - Benzoylacetanilide couplers provide high color density.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, as described in US Patent No. λ, ≠7 Hiro.

223, preferably U.S. Pat.

Typical examples include two-equivalent naphthol couplers of the self-annihilated oxygen atom dissociating type in No. 414.3?4, No. 414.3, No. 221.2JJ, No. , Examples of crosspieces of phenolic couplers are disclosed in U.S. Pat.
/71, same No.-, 77u, 762, same No. 2. It is described in rjij, issue 12, etc. Cyan couplers, which are robust against humidity and temperature, are preferably used in the present invention, and examples of their ring types include rice 1fi 1% porcelain 3.
, 772,002, an alkyl group greater than ethyl group &'! is present at the meta-position of the phenol nucleus. ], enol-based cyan coupler, U.S. Pat. No. 1, 772. /A- No., same name j, 7j1! , No. 301, No. 1t, /24
,3? No. -j≠, 33≠, 077, same No. &, J
core.

No. 773, West German Patent Publication No. 3132, No. 72 and Patent Application Akira! λ described in T-Hiroshi 247/issue etc.,! -Diacylamino-substituted phenolic couplers and U.S. Patent No. 3. ≠4L Otsu, LU No., +5j No. μ, 3.33, P
Puri issue, same issue≠, Hirozi, itri issue and same issue≠, ≠2
These include phenolic couplers which are described in No. 7,747 and have a phenylureido group at the fc2-position and an aclaramino group at the 1-position.

The various couplers used in the present invention have the characteristics required for photosensitive materials. *In order to increase
that's all? It is also possible to use them together, and all of the same primary
It is also possible to introduce more than 21 VCs.

The coupler used in the present invention can be incorporated into the light-sensitive material by various known fractional methods, such as solid dispersion method, alkaline dispersion method, preferably veratex dispersion method, and more preferably oil-in-water dispersion method. This can be cited as an example. In oil-in-water + defeat method, the boiling point is /7! After dissolving in a single solution or a mixture of both,
Dispersed in an aqueous medium such as water or an aqueous gelatin solution in the presence of a surfactant. Examples of high boiling point organic solvents are described in U.S. Patent No. 322.027 and others.

Typical usage # for color couplers ranges from 1 mole to 1 mole of photosensitive silver halide, preferably from 0.0 to 1 mole for yellow couplers.
3 moles, and 0.00 to 0.0 moles for cyan couplers.
It is 3 moles.

The silver halide emulsion used in the present invention is usually prepared by combining a water-soluble silver salt (for example, silver nitrate) solution and a water-soluble halogen @ (for example, potassium or sodium chloride alone or a mixture thereof) solution with a highly water-soluble material such as gelatin. Silver halides produced by mixing in the presence of a molecular solution include silver chlorobromide, pure silver chloride, pure silver bromide, or all of them containing some silver iodide. Things are like clothes.

The silver halide preferably used in the present invention is silver chloroiodobromide, which does not contain or contains silver iodide and has a molar concentration of not more than 3 molar fractions, and silver iodochloride is silver iodobromide. More preferred is silver chlorobromide having a silver chloride ratio of t mol or more.

The silver halide grains may have different phases inside and in the overlapping layer, may have a multiphase structure such as a bonded structure, or may have a uniform phase throughout the grain. Moreover, they may be mixed. For example, for silver chlorobromide grains having different phase t-, there may be a core richer in silver bromide than the average halogen composition, or a grain with M in single or multiple layers throughout the grain. Alternatively, the particles may have a core or layer or a plurality of layers that are richer in silver chloride than the average halogen composition. The reason why the coupler of the present invention is more advantageous than other birazoloazole couplers in terms of not softening the gradation is that it contains less silver iodide and has a lower silver chloride content than the other salts. This is the case with silver bromide emulsions. The average grain size of silver halide grains (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 ridge length is taken as the grain size and the projected area is calculated as the average): It is preferably less than or equal to 0.7μ, and particularly preferably less than or equal to /μ, and more than or equal to itμ. The particle size distribution may be narrow or wide.

A so-called monodisperse silver halide emulsion having a narrow grain size distribution in which yos or more, especially 91% or more of all grains are within ±410% of the average grain size in terms of grain number or weight can be used in the present invention. . In addition, in order to satisfy the target gradation of a light-sensitive material, one or more monodisperse silver halide emulsions with different grain sizes are mixed in the same emulsion layer with substantially the same color sensitivity. Can be applied in multiple 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 used in combination.

The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, dodecahedral, dodecahedral, etc.).
), or may have irregular crystal engravings such as spherical shapes, or may have a composite shape of these crystal shapes. Tabular grains may also be used, and in particular, tabular grains with a length/thickness ratio of 1 or more, especially r or more, have a total projected area of ! An emulsion having a density of 0 or more may be used. An emulsion consisting of a mixture of these crystalline forms may also be used. These various emulsions may be either a six-sided latent image type in which a latent image is formed on a human being as a latent image, or an internal image type in which a latent image is formed inside the grain.

The photographic emulsion used in the present invention is P, Gla fkfd
“Chemistry and Physics of Photography J” (Chimie et
Physique Photographique
) (Published by PaulMonte 1, /P
47), G., F. Duffin, “Chemistry of Photographic Emulsions J”
n Chemistry) (111ocal Pres.
s, 1966), V., L., Zelikman
``Manufacture and Coating of Photographic Emulsions J'' (Maki
ng andCoating Photography
ic Emulsion) (Focal Pres.
It can be prepared using the method described in, for example, 1999, published by J.S. 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 halokene salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good.

A method of forming particles under an excess of total silver ions (so-called back mixing method) can also be used. Conversion methods can also be used in which more rhodan salts are added to form less soluble silver halides. As one type of simultaneous mixing method) pAg'tl'' in the liquid phase generated by So silver
It is also possible to use a method of keeping it constant, that is, a method of keeping it constant, that is, a method of keeping it constant. According to this method, a Rogge/Silver Cide 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 salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron f4
Or you can coexist with VC complex salts etc. Ha.

After grain formation, the silver halide emulsion is subjected to physical ripening, desalting and chemical ripening before being used for coating.

Known silver halide solvents (91I, ammonia, Rodankali or U.S. Pat. No. J, 27/, /J)
i7, JP-A-Sho t /'-/ J j 40, JP-A-Sho j J-rxaor, %, JP-A 13-/1LL413
/'? No., Tokukai Akira! 41-1007/7 or Tokukai Sho t≠-7! thioethers and thione compounds described in JR Co., Ltd., etc.) can be used in precipitation, physical ripening, and chemical ripening.

In order to remove soluble fissures from the emulsion after physical ripening,
Nudel water washing, flochieration sedimentation method and ultraleak method etc. are followed.

The silver halide emulsion used in the present invention is a compound or substance that can react with active gelatin or silver and contains sulfur (for example, thiosulfates, thioureas, mercapto compounds, rhodanines).
l-Sulfur sensitization using; Reduction Note 1: Reduction sensitization using sulfur (e.g., stannous, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); Metal compounds (e.g., total complex salts, etc.) , Pt, Ir%Pd, R
A complex salt of a metal part of group (I) of the periodic table such as h, Fe, etc.) can be used alone or in combination.

The photographic emulsion used in the present invention is spectrally sensitized with a photographic sensitizing dye. The dyes used include 7-anine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicuanine dyes, styryl dyes, and hemioxonol dyes, but these sensitizing dyes may be used alone. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself has no partial sensitizing effect or a substance that does not substantially absorb visible light,
The supersensitizing gold may be included in the entire emulsion. for example,
Aminostilbene compounds substituted with nitrogen-containing heterocyclic groups (
Kutoe is U.S. Patent No. 2, 33.32O, same! , 63
3,72/), aromatic acid formaldehyde condensates (e.g. U.S. Pat. Nos. 3,7≠7, 11)
0), cadmium salts, azaindene compounds, etc.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fogging during the IR production process, storage, or photographic processing of the light-sensitive material, or for stabilizing the photographic performance. The light-sensitive material of the present invention may contain hydroquinone derivatives, amine phenol derivatives, amines, gallic acid derivatives, natechol derivatives, ascorbic acid derivatives,
It may also contain all of the colorless coupler, sulfonamide phenol visiting conductor, and the like.

Various anti-fading agents can be used in the light-sensitive material of the present invention.

In the photosensitive material of the present invention, an ultraviolet absorber can be added to each hydrophilic bit colloid.

The light-sensitive material of the present invention is used for a variety of purposes such as a feeding aid, antistatic property (E), improvement of slipperiness, emulsification dispersion, prevention of adhesion, and improvement of photographic properties (e.g., development acceleration, hard MJ, sensitization). Super-superactive surfactant-t=a may also be used.

In addition to the above-mentioned additives, the photosensitive material of the present invention further contains various stabilizers, anti-staining agents, developing mulberry or its precursor,
Current 1 Ice accelerated cutting or before that, blade body, lubricant, mordant,
A matting agent? Various additives useful for photographic light-sensitive materials may be added, such as F, Masanori Denbo, plasticizers, and some other additives useful for photographic materials.Representatives of these additives are Research Disclosure /741LJ December) and same/, l
6 self-published in '7/, 4 (/775'/July).

The present invention provides at least two spectral features on a support, l
It is also applicable to multi-color photographic materials with f.

Multilayer natural color photographic materials usually consist of one layer of red-sensitive emulsion, one layer of green-sensitive emulsion, and one layer of green-sensitive emulsion on the support. All of the r-sensitive emulsion layers each have at least one. The order of these layers can be arbitrarily selected as required. Furthermore, each of the above emulsion layers has a different sensitivity.
The photosensitive material according to the present invention may be made of two or more emulsions jm, and a non-photosensitive f- may be present in +Vj of two or more emulsion layers having a photosensitive layer. Materials/Engineering, /S Loge/In addition to the emulsion layer, VC1 protection 1-1 intermediate layer,
It is preferable to provide an auxiliary layer such as a single filter layer, a layer with a thickness of 1 m, and a back layer.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are formed of a flexible support such as plastic film, paper, or cloth, or a flexible support such as glass, ceramic, or metal, which is commonly used in photographic light-sensitive materials. is applied to.

Among the supports used in the present invention, preferred are baryta paper and polyethylene laminated supports containing a white pigment (for example, titanium oxide) in the polyethylene support.

The silver halide color photographic photosensitive material of the present invention is suitable for use mainly in electrosensitive materials for direct image #A festivals, such as color base/q- and color reversal paper, color reversal film, and color positive film for movies.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, a p-7 unilene diamine compound is preferably used, and representative examples thereof include 3-methyl-μm amino- to N
-diethylaniline I) 7.3-Methyl-hiro-aminoh-ethyl-N-β-hydroxylethylaniline, 3-methyl-μmamino-h-ethyl-N-β-methanesulfonamidoethylaniline, j-mef- Examples include .mu.-amino-to-ethyl-to-1.beta.-methoxyethylaniline and their sulfates, hydrochloric acid groups, p-toluenesulfonates, and the like.

Color developing solutions include not only alkali metal sulfates and hydroxylamine, but also alkali metal carbonates,
It typically includes pH buffering agents such as borates or phosphates; development inhibitors or antifoggants such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. In addition, the organic solvent flit may contain a development accelerator such as benzyl alcohol, diethylene glycol, etc.), polyethylene glycol, quaternary ammonium salt, and amine.

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. Examples of bleaching agents include iron (III)
), compounds of polyvalent metals such as cobalt (lit), chromium (■), copper (II), peracids, quinones, nitroso compounds, etc. are used. Ferricyanide as a typical bleaching agent; dichromium IIi! 2 salts; organic complex salts of lit or cobalt (I'll), aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, /, 3-diamino-11-α-panoltetraacetic acid, or Complex salts of organic acids such as citric acid, tartaric acid, and malic acid; persulfates; mankan salts; nitrosophenols, etc. can be used. Among these, ethylenediaminetetraacetic acid ill salt and persulfate are preferred from the viewpoint of rapid processing and environmental pollution. Furthermore, ethylenediaminetetraacetic acid iron(1) complex salts are sometimes useful both in independent circulation solutions and in -containing solutions.

Do you use each type of whitening solution and bleach-fixing solution as necessary? 'll promoter may be used in combination.

qF': After the fixing process or the fixing process, a washing process is usually performed. In the water washing process (CR), various known compounds may be added for the purpose of preventing precipitation and saving water. For example, in order to prevent precipitation, inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphorus Water softeners such as acids, bactericidal agents and anti-spill agents that prevent the growth of various bacteria, algae, and algae, hardening agents such as magnesium salts and aluminum salts, and dust that reduces drying load and unevenness. It is possible to add surfactants, etc. to prevent corrosion if necessary.
Needle.

E. West, “Water Quality Judgment Criteria J”
ity Cr1teria), “Science and Engineering of Photography J (Photo, 8ci, Eng,), Vol. 4, 31
Lμ~3! ? Compounds described in Page (/Ribuya) etc. may be added. In particular, the addition of chelating agents and anti-/ζ-cutting agents is ■
It is effective.

In the water washing step, it is common to use 1a gold countercurrent water washing of λ class or higher to save water. , Furthermore, 7-r in % Kaisho for 1 liter of the water washing process! A multi-stage countercurrent stabilization treatment process as described in ltJ may be performed. Various compounds are added to the stabilizing bath for the purpose of total image stabilization. For example, membrane pl-i-
(r- Various buffering agents for adjusting (e.g. pH 3 to t) (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, Typical examples include monocarboxylic acid [used in combination with dicarboxylic acid, polycarmenic acid, etc.] and formalin2, as well as water softeners (inorganic phosphoric acid, aminopolycarmenic acid, organic phosphorus, etc.) as needed. acids, aminopolyphosphonic acids, phosphonocarzenic acids, etc.)
, tillicides (benzointhiazolinone, illithiazolone, μm thiacili/benzimidazole, halogenated phenols, etc.), surfactants, fluorescent brighteners, hardeners, etc.! The jiI additive may be used conveniently, or two or more compounds for the same or different purposes may be used in combination.

After treatment, ammonium chloride was used as a pH adjustment remover,
It is preferable to add volatile ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate.

The halogenated photosensitive material H of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. For internal ridges, it is preferred to use one sinker of each color developing agent.

The silver halide photosensitive material of the present invention may contain various l-phenyl-3-pyrazolidones, if necessary, for the purpose of promoting color development.

Typical compounds thereof are disclosed in JP-A No. 33P,
j7-/μat≠7, j7-col//μ7, ll-10132, ll-10536, 1t-
No.jOjJJ, No.ll-10132, Mj I-
10! J No. 3 and the same re-//j≠Jlr No., etc.

Although various processing solutions in the present invention are used in io oc-zoac, it is preferable to develop at a temperature of 33°C to Jr'C. Second, West German Patent No. 770 or U.S. II% Patent No. 3, 4 for the purpose of light-sensitive materials
A treatment using cobalt reinforcement or peroxide bulk reinforcement as described in No. 7 Hiro, Kotata may be performed.

Each stretching bath may be provided with a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc., as necessary.

Example 1 A sample of the coupler of the present invention was prepared by coating the following emulsion layer and protection 1- on a cellulose triacetate transparent film support. J-t with tricresyl phosphate f:/! ? and ethyl acetate-0rrtl were added and dissolved by heating with Ao'C, and this solution was added to gelatin io
t:j? and sodium dodecylbenzenesulfonate I
F was mixed with an aqueous solution of gold chloride (looαB) and stirred at high speed using a low-speed stirring technique to obtain an emulsified dispersion.With respect to the total amount of this coupler dispersion, the composition of silver chloride and silver bromide and the batting average were J.
With Omol- and 70mol steamed rice, the particle size is 0. Silver chlorobromide tQ, /mol and gelatin 67,j at daytime tμ
A silver halide emulsion containing y / j OIf was added and mixed to form a coating solution containing λ-hydroxyl, sodium t-dichloro-6-triazate, and the amount of silver coated was coated on the support. Make sure to coat the sample with the preservation layer so that the concentration is 0.00 μmol/yys.
- Samples prepared by replacing equimolar amounts of J with B%
It was set as C. Furthermore, the following comparative couplers X-/, X-2,
Using X-J and X-μ, X-r, X-6, equimolar to the coupler rvL-/! A sample made by replacing it? υ, 9% F and 0% 11, respectively.

Sample A~IQ optical wet? After exposure to white light through the lens, the following processing steps are performed to perform centometric measurements. These results are shown in Table 1.

ko))) glance ``l'l'-1't'1shihe o □ o G(>c>(:bo θt'
〜 〜
ゝ ゝ ゝπ <Ro■c5￥−〇nee1≦ In Table 1, sensitivity is the relative value of the reciprocal of the exposure amount necessary to give a concentrated gold equivalent to Turnip IJ + /, 0, and gamma is It shows a 1-shield pattern connecting two points corresponding to dark q/, 0 and /, 7. The sensitivity was set at 100 for sample A.

Samples A, B, and C of the present invention all have higher sensitivity and harder gradation than other samples, and exhibit good color development.

Furthermore, among the samples of the present invention, sample B5 is found to have higher sensitivity and gamma than sample A, and sample C has higher sensitivity and gamma than sample B.

X-/ e8) 117(t) X −jc8”!? (1 -r X-A Treatment process (33°C) The ingredients for each treatment step are as follows.

Developer diethylenetriamine J vinegar 9 /, Of be/zyl alcohol /jrd diethylene glycol 10go Na2SO3x, op KBr O,jf hydroxylamine sulfate J, Of≠-amino-
3-Methyl-N-ethyl-[β-(methanesulfonamido)ethyl]-p-phenylenediamine sulfate! , O? N a 2
CU 3 (/water salt) toy fluorescent whitening agent (μ, μ'-diaminostilbene type) i, add OP water to make 1 liter (pFi/0, /) bleaching constant ammonium thiosulfate (yowt ( 4) / j
0yrtl〜a 2 S (J a
/ j j'N H4(k' e (ED
'L A "l) j j fEDTA
-JNa 1 Add water to make 1 liter (pi-t+,?) Example 2 Lime-treated gelatin 30? and sodium chloride! , rf
Dissolve in 1000cc of distilled water and keep at jzoc, add 1 silver nitrate! ? Distilled water/! 00r: cVC dissolved liquid and potassium bromide♂, l? and sodium chloride JrJf
Add a solution dissolved in 400cc of distilled water and f71 minutes.
mixed. After desalting and washing with water, this emulsion was chemically sensitized with sodium thiosulfate to obtain an emulsion a1000fft6. Similarly, lime-treated gelatin 3θ? and sodium chloride!
, jff Dissolve in 1000cc of distilled water and keep at tz OC, nitric acid @ Noko! t dissolved in 1 roocc of distilled water, potassium bromide 4ti, ry and sodium chloride 2/
, 4? Tomo 7 dissolved in fAOOcc distilled water! Add and mix within minutes. After desalting and washing with water, the emulsion was chemically sensitized with sodium thiosulfate to obtain an emulsion biooot.

Similarly, 30t of lime-processed gelatin and sodium chloride! ,! Dissolve f in 1000 cc of distilled water and maintain it at 7z'c, silver nitrate/2! F was dissolved in distilled water/10QCC, and a solution of potassium bromide 7r, rfb and sodium chloride It, 411% dissolved in distilled water with 0QCC, was added and mixed for 7j minutes. After desalting and washing with water, this emulsion was chemically sensitized with IJium (thiosulfate) and emulsion C10
00? Don't get it.

Coupler of the present invention M-ta/l, JP with tricresyl 7
Male 7 eight! /j? Add 20 d of ethyl acetate and heat to dissolve at 6o"C, and mix this solution with gelatin IO?
%- and sodium dobuflubenzenesulfonate/f'
100 pnl of the aqueous solution containing fz was mixed with VC and stirred using a high-speed stirrer to obtain an emulsified dispersion (a).

Furthermore, as a comparative coupler, the following X-7, ! The emulsified dispersion prepared by changing the procedure was designated as (b) and e→.

^
\No
Toichi
〇X
73 each for b and c! Mix in combination with t,
Furthermore, sodium co-hydroxybutyro-dichloro-3-triazate was added and coated together with a protective layer on a cellulose triacetate transparent film support so that the coated silver amount was 0.00 μm/m 2 . These samples %-J
- After exposing sample J to white light through an optical wedge,
A development process similar to that of Example 1 was carried out to obtain a second thorn panicle metal.

J a(ri 0 mol%) (()ii←P)K
b(IO) //(tt)L c
(10>//(ge)hi a(90) (
b)(X-7)N b(to)//(〃)
(J c(#) )//(//)P
a(Po) →(x-r)Q b(J
O) ge(〃) jjshi C(//) ) ノZ(
q) Gamma fog for the second thorny note! r J, jj O00! Present invention 7/
j, 4t0 0. OJ //100
J, 20 0.02
//μbu 2. ≠! 0.07 Comparative example!
Ta 2. Wo 0.03 //1
7 J, 02 0,02 //Hiroshi?
2. tl O,t)t/142
3.10 ri, θ3 〃5'/3.
01' 0.02 //The sense and how to take gamma are the same as in Example/, and /! 8 Stable is sample Ly<10
o.

In comparison couplers X-7 and X-r, the gamma decrease was large in emulsions a and b, which had a high silver chloride content, whereas in the coupler M-ta of the present invention, the gamma did not decrease and the emulsions containing silver chloride It shows a gamma equal to or higher than that of Emulsion C, which has a low ratio. It can be seen that the couplers of the present invention tend to exhibit particularly excellent performance for emulsions with a high silver chloride content.

Example 3 A color photosensitive material was prepared by coating the following photosensitive layers from layer 1 to layer 71 on a paper support whose both sides were fully coated with polyethylene. The polyethylene on the side coated with the first IfI contains titanium dioxide and a trace amount of the group'! l11
'Contains gold.

(Structure of Photosensitive Layer) The numbers corresponding to each component indicate all coatings in f/m2, and silver halide indicates coating 1 in terms of silver.

1st layer (tIf sensitive layer) Silver chlorobromide emulsion (silver bromide 10 mol%) ・・・・・・・・・@0. JO Yellow coupler (buttock 1) ・・・・・・・・・・・・
・0.70 Same as above solvent (TNP) ・・・・・・
......0. /! gelatin
・・・・・・・・・・・・／, 20vJkoJ# (middle layer) Gelatin ・・・・・・・・・・・・
Q, RiO-t-octylhydroquinone ......eO,O
r Same as above solvent (DBP) ・・・・・・・・・・・・
...0.10 Third layer (green-sensitive layer) Silver chlorobromide emulsion Emulsion of Example 1 ......Silver 0.10
22 Magenta wig (M-/bu)・・・・・・・・・
0. ≠3 Same as above solvent (TOP) ・・・・・・・・・
... Q, ≠ 3 anti-fading agent (tatami 2) ...
・・・・・・・・・0. Co-O gelatin
・・・－・・・・・・・・・i, o.

14th (Ultraviolet absorbing intermediate layer) Ultraviolet absorber (Kan 3/Ui 4/Fuki 5) ......0,0t10,2310. Ko! Solvent (TN)') -・・・・・・・・・・・・
・O, cox gelatin ・・・=・・・
・・・・・・／、! No.! Layer (red sensitive layer) Silver chlorobromide emulsion (70 moles of silver bromide) ・・・・・・・・・Sacrificial O, CoQ 7 uncoupler (+S/tatami 7) ・・・・・・・・・・・・・・・・O, KO10, J coupler solvent (TNk'/DBP) ・・・・・・・・・・・・0, / 010, KO
Gelatin ・・・・・・・・・・・・
Oliri 6th pane (UV absorbing intermediate layer) UV absorber (U3/忰47 5) ・・・・・・・・・・・・0.0AI0.2!10.2
Evening solvent (L) UP) ・・・・・・・・・
・・・O0λO gelatin ・・・・・・
・・・・・・・・・1. ! 7th Woman (protective layer) Gelatin ・・・・・・・・・・・・
・1. ! Here, DBPId diptylphthalate)e, T
UP is tri(n-octyl)phosphate 1TN)')')(n-nonyl)phosphate-)f Table f.

(Side 2) (Tatami 3) U)l (Tatami 4) OH U)i　UHe(J(JC,H□7 (side dish) e, 4) 1. (t) (Yellow 6) The following dyes were used as spectral sensitizers in each emulsion.

Blue-sensitive emulsion layer; (Addition of 2×10 mol per mol of silver halide.)
Green-sensitive emulsion layer; (halogenation @ J per mole, j'1./0
Mole addition. ) (Silver halide/mo, le hit,!
×10 molar feed port. ) The following dyes were used as anti-irradiation dyes in each emulsion layer.

Green-sensitive emulsion layer; Red-sensitive emulsion layer; This coated sample was designated as S. A sample prepared by replacing magenta coupler 7M-/O in the third layer of sample S with M-/7 and M-/r in equimolar amounts was designated as T2C. Furthermore, samples t-V, W, and X were prepared by replacing the comparative Cobras-X-2, X-10, and X-//.

These samples were exposed to green light through an optical wedge and developed in the same manner as in Example fl/, yielding the results shown in Table 3.

ko 5ssss pattern shi01, 'q(b o O(>
(：Ki ri mo 1 respect be 1λ
N6'=o'''1 ヰ Ikamachi 呵0 ) Takashi 4-1 臥 )o Oo
6o &, l (k ゝ \ \ 1 %-o ト &o 翫 5 \I \ \ \ \ \h, (1) = z > 2X Sensitivity and gamma were obtained by the same measurement as in Example/ Sensitivity was taken as a relative value with Sample S as 100.

Samples S and T% U of the present invention are both comparative samples V and W.
It can be seen that it shows superior performance with higher sensitivity and higher gamma than %X.

Furthermore, among the samples of the present invention, T shows better performance than S, and U shows better performance than T. Comparison sample with similar tendency■
, W, and X. However, S and Xt-
Even when compared, comparative sample X is not as good as sample S of the present invention.

(Effects of the Invention) As is clear from the results shown in Tables 7 and 2, the present invention makes it possible to obtain high-sensitivity, high-gamma color photographs without increasing fog.

X-// Procedural amendment (Showa! 7th/Month 3rd, 1939, Commissioner of the Patent Office, Mr. \゛-') 1, Indication of the case, 1932 Patent Application No. 23
16λ Ri No. 2, Name of the invention Silver halide color photographic light-sensitive material 3, Relationship with the person making the amendment Patent applicant Address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture (Date of shipment) & Subject of amendment Description & Amendment I will submit a complete statement of contents (no changes to the contents).

Procedural amendments 1985 μI [1 1, Director General of the Agency for Procedural Affairs, Inc. 16, 1985 Patent Application No. 23-24λ
No. 2, Name of the invention Silver halide power 2 - Photographic light-sensitive material 3, Relationship with the case of the person making the amendment Patent applicant Location 210 Nakanuma-ton, Minamiashigara City, Kanagawa Prefecture Subject of amendment Detailed description of the invention in the specification ”, the statement in the “Detailed Description of the Invention” section of the Description of Contents of the Amendment is amended as follows.

/) Joy of happiness? row "Any effect" “Any effect.” and correct it.

K) The 7th line of R. ``If there is no sutra, I will make it'' “I have to go through it.” and correct it.

3) The first page/line "Amylphenoxy-acetyl group" [Amylphenoxyacetyl group] and correct it.

li, page 22, line "Amylphenoxy-acetyl group" "Amylphenoxyacetyl group" and correct it.

The structural formula of page 32 M-/A is " ”? [ ” and correct it.

6) Structural formula of 33rd Sada M-/r ”? and correct it.

[haj Insert.

? )Page 62 H3 ” and correct it.

ri) No. 6! Sadait row “Hotomo” “With Kei.” and correct it.

IO) Page 76 "In the compound structural formula of green-sensitive emulsion No." 1” and correct it.

//) Page 76 Structural formula of the compound in the red emulsion layer 1
Correct ``1'' to 1 or more l/month in 1986? Hiroshima Prefecture Office Director-General's Palace 1, Incident Display 1985 Request No.-23-21
No. 2 No. 2, Name of the invention Silver halide color photographic light-sensitive material 3, Relationship with the person making the amendment Patent applicant Location 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Subject of amendment Scope of request for ¥fIFFrR in the specification '', column 5 of ``Detailed Description of the Invention,'' and ``Scope of Claims'' of the description of the contents of the amendment are amended as shown in the attached document.

The statement in the "Detailed Description of the Invention" section of the specification is amended as follows.

l) M-/! on page 31 Correct the chemical structural formula as shown in Appendix I.

e) After the chemical structural formula of M-λl on page 3≠, the attached sheet M of λ
-2λ~M Insert the chemical structural formula of -22.

3) Correct the 72nd to r/te as shown in Attachment 3.

The above was obtained from Attachment 1; Works Town\ = Q Σ Attachment 3 Sensitivity/Gamma Vi Actual Example 1 and measurements by colleagues. l Sensitivity was calculated relative to sample S as 100.

Samples S and T1U of the present invention both have a relative g sample V.

It can be seen that it exhibits superior performance with higher sensitivity and higher gamma than W and X.

Makoto, A: Among the invention samples, T shows better performance than S, and U shows better performance than T. Colleagues' tendencies are comparison sample V
, W, and X. However, even when comparing S and Xft, comparative sample X is not as good as sample S of the present invention.

-y N=夷C□3 X-// :H3 Example μ
A multilayer color photographic paper having the configuration shown in the table was produced. The coating solution was prepared by rA as follows.

Maki single-layer coating liquid preparation yellow coupler (a)/li, /f and color stabilizer (
bl Hiro, Hiro 1 with ethyl acetate 27, 2CI:: and solvent (c) 7. Add and dissolve CC, and add this solution 1i10%
Sodium dodecylbenzenesulfonate tcc kineimu 1
The emulsified fraction was made into 0% gelatin solution/lJ-tan. On the other hand, silver chlorobromide emulsion (JA silver oxide/, 0 molt, Ag 7 o
(containing t/'-9) and the evening-sensitizing dye fc shown below.
Add 1 mol of anchor and 0 mol of OX/0 mol to prepare a molten liquid. The above emulsified dispersion and this emulsion are mixed and dissolved, and the first layer is a thin liquid so as to have the composition shown in Table 1.
Made by A. The coating solutions for the second to seventh layer phases were also prepared in the same manner as the first layer@thin solution.

The gelatin hardening agent for each layer is /-oxy-3°! −
Dichloro5-) lyazine sodium sik was used.

The following spectral sensitizing dyes were used in each layer.

'a, 1 mol of silver halide emulsion (as, oxio-' mol) green-sensitive emulsion layer 5O3HN(C2H5)a (μ per 7 mol of silver halide, 0x10-' mol) and SOaI- IN(C2Hs) a (halo'y'F per mole of silver heptide)7.0x10-5 mol) red-sensitive emulsion layer ("ROKEN4fJkOl per mole xio-'
mol) For the red-sensitive emulsion layer, the following compound was added in ls×10 mol per mol of silver halide.

a, 4C'-bis(J, j-di(,2-naph
-thoxy)pyrimidin-IAyI-ami
no) stilbene-2,2'-d 1-sul
For the fonic acid-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, /-(j-methylureidophenyl)-!-mercaptotetrazole was added to each halogen (t[/-1-l]). r, jXiθ mol, 7°7X/θ-4 mol, J, jx/0-' mol additive.

The following dye P+ was added to emulsion JQ3 for isification lyi positive.

The structural formulas of the couplers and other compounds used in this example are as follows.

(a) Yellow coupler (b) Color stabilizer (C) Solvent (d) Color mixing inhibitor H Ce) Magenta coupler CsHx7 (tl) (f) Color image stabilizer (g) Solvent (Cs H170frP=0 and /Lv mixture (I amount ratio) (hl ultraviolet absorber and (i) color mixture inhibitor H (j) solvent (isoc9HxsO±TP=0 (k) cyan coupler (1) color image stabilizer and / :J:J mixture (molar ratio) A sample of the obtained color photographic paper was exposed to light through an optical wedge and carefully developed in the lower d-vi processing step.

Treatment process Time Temperature Color development
≠j seconds 3z0c Rinhakusei i
lAtsho 3!0C Rinse 1 minute 30 seconds 300C (μ tank cascade) Inuisho JOsho Toot: The composition of the treatment liquid used is as follows.

Color development IX' liquid water
Sodium sulfate 0.2 IN, N-
Diethylhydroxylamine Hiroshi, 2? Potassium bromide 0.0/? sodium chloride
/,! t-triethanolamine? ,oy potassium carbonate
30? N-ethyl-N-(,#-methanesulfonamidoethyl)-3 monomethyl-≠-aminoaniline sulfate Hiroshi, ta? Hiroshi, 4
L'-diaminostilbene type fluorescent whitening agent (Sumitomo Kaji 1 stock Whitex 411 2,
Add OS' water and bleach p) ilo, 2 with 1000 mKOH
≠oocx::Thioproammonium (70%)
troCc sodium imate
l♂2ethylenediami/tetraacetic acid (1 fl) Ammonium 36? Ethylenediaminetetraacetic acid j? add water
1oooCcp H4, 7jf Rinse solution/-Hydroxyethylidene/, /-Disulfonic acid (Aθ%)/, Off nitrilotriacetic acid /, Off Ethylenediaminetetraacetic acid re O, V Ethylenediamine-N, N.

N',N'-tetramethinephosphonic acid i,ot bismuth chloride (≠Q%) o,rymagnesium sulfate O1λ2ja acid zinc
0.32 ammonium light bread
o, jyj-chloro-2-methyl-≠ 1 inch azoline-3-off
30 ■ 2-Methyl-Hiro-isothiazolin-3-one ioηλ-octyl-Hiro-isothiazolin-3-one 10 ■ Ethylene glycol i, zy sulfanilamide o, iy/ , 2.3-benzotriazole 7.02 submv ammonium (4t
o%) 1. ot ammonia water (high)
2.6CX:.

Polyvinylpyrrolidone /, Of≠,
Hiro'-Diaminostilbe / Fluorescent white agent /, Of water sword Ω
10OOccK OH
An emulsion prepared as follows was used as a silver chloride emulsion of pH 7/Q No. 31.

Lime-treated gelatin JOff was added to 10OOcc of distilled water and dissolved at ψ0'C, then sodium chloride 6,! 2 to gravity σ and temperature! The temperature was raised to 0C. 6g silver A2. j? Solution dissolved in 730 total distilled water and sodium chloride 2/,! ? With a solution of 600 marks of distilled water! λ
,, While maintaining t'C, it was added to the previous solution and mixed for ≠θ minutes. In addition, 6 pieces of silver nitrate! T? Sodium chloride dissolved in distilled water roocc! /, j? i Distilled water 300cc
VC#I with the dissolved liquid j, r 20 while keeping 0C2
Add and mix for a minute. At the end of the addition, add the jη-sensitive dyes for the green-sensitive emulsion layer for each previous d, pour demineralized water into bales divided into lj, and add chemically using ls × 10' mol/Ag 1 mol of sodium thiosulfate. Sensitized.

The 4 fabric samples in Table ≠ were designated as Y. For sample Y, J j
Jga magenta coupler (e) 't19Il shown magenta coupler M-/! An equimolar amount of the sample was prepared as sample 2.

The results obtained for samples Y and Z are shown in Table 5 below.

Table 5 Sample Coupler Sensitivity Gamma Fog Remarks Y
(e) 192. Hirota 0.01 Comparative example ZM-/j100 Co, yr o, ot Coupler M-/! Sample Z using F1 has a higher sensitivity than coupler (e) which shows relatively good sensitivity F1.
, is a murky comma and is understood to be better.

Patent Applicant: Fuji Photo Film Co., Ltd. Attachment 2, Claims - ff M on all the silver halide emulsion layers containing the pyrazoloazole coupler represented by formula [I] on the support ¥ff! 1. A silver halide color photographic light-sensitive material.

Monofunctional Formula [1] In the general formula (1), 111 represents a hydrogen atom or a substituent, or can be separated by a coupling reaction with a hydrogen atom or an oxidized product of an aromatic primary amine developing agent. I wear S. Zake methine, substituted methine, =N- or -N
H-represents gold. zb and Zc are also methine, substituted methine, =
N-strapping-NH-'l&: represents, but at least one of Zb-Zc is included. When zb is the above-mentioned poet methine, one of Za and Zc is -NH-, and the other is methine, okikune mechi/, =N-. Z
When c is the above-mentioned okiki methine, Zalma-Nrl-
, Zb ke mechi/, okiki metin ゛゛゛ももも or =N-. R2 represents either an alkyl atom, l or a halogen atom. R3 and R4 are halogen atoms, alkyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy groups, carbamoyloxy groups, silyloxy groups,
Sulfonyloxy group, acylamino group, anilino group, amino structure, ureido group, imide moiety, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio-pole, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group group, sulfonamide group, carboxyl group, carbamoyl group, acyl group,
Sulfamoyl group, sulfonyl group, sulfinyl group, alkoxycarbonyl group, oryloxycarbonyl group.

2) The above pyrazoloazole coupler is one type [13
In that case, Zc! Silver halide according to claim 1, characterized in that R1 is not a tertiary alkyl group such as 7 when it is a methine group with a tertiary alkyl group as an It substituent. Color photographic material.

3) @Special feature 1, characterized in that the silver halide is silver chloride, silver chloride, or silver bromide, which does not substantially include silver iodide? !
+-A silver halide color photographic material according to claim 1.

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material comprising, on a support, a silver halide emulsion layer containing a pyrazoloazole coupler represented by the general formula [I]. ] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the general formula [I], R_1 represents a hydrogen atom or a substituent, and Represents the group to be obtained. Za is methine, substituted methine, =N- or -N
Represents H-. Zb and Zc are also methine, substituted methine, =
It represents N- or -NH-, and at least one of Zb and Zc is a substituted methine having ▲Numerical formula, chemical formula, table, etc. as a substituent▼. When Zb is the above-mentioned substituted methine, either Za or Zc is -NH-
and the other is either methine, substituted methine, or =N-. When Zc is the above substituted methine, Za is -N
H- and Zb is methine, substituted methine or =N-. R_2 represents either an alkyl group or a halogen atom. R_3 and R_4 are halogen atoms, alkyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy groups, carbamoyloxy groups, silyloxy groups, sulfonyloxy groups, acylamino group, anilino group, amino group, ureido group, imide group, sulfamoylamino group, carbamoylamino group, alkylthio group,
Arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, carboxyl group, carbamoyl group, acyl group, sulfamoyl group, sulfonyl group, sulfinyl group, alkoxycarbonyl group, aryloxycarbonyl group represent.