JPH02282252A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To increase the rate of color development of a sensitive material and max. color density and to reduce stains by using a prescribed pyrazoloazole type coupler and a specified compd. in combination. CONSTITUTION:This sensitive material contains a pyrazoloazole type coupler having one or more carboxyl groups (salts), e.g., a compd. represented by formula I and a compd. represented by formula II, III or IV and acting as a scavenger for a color developing agent. In the formulae Ii-IV, each of R1, R2 and R is an aliphat. or arom. group, etc., X is a group which is released by a reaction with the color developing agent, A is a group forming a chemical bond by a reaction with the agent, n is 1 or 0, B is H, and aliphat, group, etc., Y is a group accelerating the addition of the agent to the compd. represented by the formula III and Z is a nucleophilic group or a group releasing the nucleophilic group. A compd. represented by formula V is a concrete example of the compd. represented by the formula II, III or IV.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic photosensitive +A material, and more specifically, it relates to a silver halide color photographic photosensitive +A material, and more specifically, it contains a coupler that has a high maximum color density and a fast color development rate, and that is The present invention relates to a silver halide color photographic light-sensitive material that generates less.

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

Among these, in order to form a magenta color image, 5-
Pyrazolone, cyanoacetophenone, indasilone, pyrazolobenzimidazole, and pyrazolotriazole couplers are used.

Hitherto, most of the 5-pyrazolones have been widely put into practical use and researched as magenta color image-forming couplers. However, it has been known that dyes formed from 5-pyrazolone couplers have unnecessary absorption with a yellow component near 430 nm, causing color turbidity.

A birazolohenzimidazole skeleton is described in British Patent No. 1.047,612 as a magenta image forming skeleton that reduces this yellow component, and US Pat. No. 3,770,4
47, and the pyrazolo (5
, 1-c) 1.2.4-triazole skeleton has been proposed.

However, the magenta couplers described in these patents, when dispersed in hydrophilic protective colloids such as gelatin, give unsatisfactory color images or have high boiling points when mixed into silver halide emulsions. They are unsatisfactory because they have low solubility in organic solvents, are difficult to synthesize, and have relatively low coupling activity in common developing solutions. As a method to improve this problem, the imidazpyrazole skeleton shown in JP-A-59-162548 and the IH structure shown in JP-A-59-171956
-Pyrazolo(L5-b)-1,24-triazole skeleton, a pyrazolotetrazole skeleton shown in JP-A-60-33552 is disclosed. Also, Unexamined Japanese Patent Publication No. 1
Pyrazolo (5,1-c) shown in No.-98438
Couplers in which specific substituents are introduced into 1,2,4-triazole to improve color development are also known.

On the other hand, recently, various proposals have been made for using these pyrazoloazole couplers as cyan image-forming couplers by adjusting the substituents in various ways.

These are JP-A-63-145281 and JP-A-632647.
No. 53, Japanese Patent Application Publication No. 87-11506, Japanese Patent Application Publication No. 64-552, No. 64-554, No. 64-555, No. 64-556, No. 64-553, No. 64-55
No. 7, No. 63-199352, No. 63-250649
No. 63-250650, No. 63-280247, No. 6:9-281161.

In addition, recently, West German Patent Publication No. 3 636.364 and JP-A No. 61-231 describe a pyrazoloazole coupler having a carboxyl group as a part of the ballast group.
No. 452 was disclosed. Although the couplers described in these documents show improvements in color development speed and maximum density, the presence of a carboxyl group increases the amount of color developing agent incorporated into the photosensitive material, and the color developing agent remains sensitized even after development. It was found that colored stains remained in the wood and formed over time after treatment.

(Problems to be Solved by the Invention) An object of the present invention is to increase the color density of magenta dye by using a pyrazoloazole coupler having a carboxyl group and a fast color development rate and a compound that acts as a scavenger for a color developing agent. It is an object of the present invention to provide a silver halide color photographic light-sensitive material which is high in color and produces little colored stain.

(Means for Solving the Problems) The above-mentioned object of the present invention is to provide a pyrazoloazole coupler having at least one carboxyl group or a salt thereof and the following general formula (I), (II) or (III). This was achieved by a silver halide color photographic light-sensitive material containing at least one of the compounds shown above.

-Noshiro (1) %Formula% General formula (II) R2-C=Y In the formula, R, , , R2 are respectively an aliphatic group, an aromatic group,
Or represents a heterocyclic group. X represents a group that reacts with an aromatic amine developer and leaves the group, and A represents a group that reacts with an aromatic amine developer to form a chemical bond. n represents 1 or 0. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y represents a group that promotes addition of an aromatic amine developer to the compound of general formula (1). represents.

Here, Ro and X, Y and R2 or B may be bonded to each other to form a cyclic structure.

General formula (Iff) -Z In the formula, R represents an aliphatic group, an aromatic group or a heterocyclic group. Z represents a nucleophilic group or a group that decomposes in the photosensitive material to release a nucleophilic group.

The compounds represented by general formulas (I), (II) and (I[l) will be explained in more detail.

- For the compounds represented by Noshiro (1) and (II), the second-order reaction rate constant with P-anisidine measured by the method described in JP-A-63-158545 is 2 (80°C) 1
．． 0 f/mol -sec ~ I XI CV
Compounds in the range of 51/mol·sec are preferred. On the other hand, in the compound represented by -Noshiro (I), Z is Pearson's nucleophilic 'CH31 value (R, G, Pea
rson et al9. J.

A, m, Chem, Soc,, 9 standing, 319 (196
8)) is preferably a group derived from a nucleophilic functional group of 5 or more.

Among the compounds of -Noshiro (1) to (III) above, formula (
It is preferable to use the compound of formula (1) or (II) in combination with the compound of formula (Ill).

Each group of the compounds represented by general formulas (1), (II) and (III) will be explained in more detail.

The aliphatic group referred to in R, , R, , B and R represents a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group, which may be further substituted with a substituent. The aromatic group referred to in R,, R,, B and R is either a carbocyclic aromatic group (e.g. phenyl, naphthyl) or a heterocyclic aromatic group (e.g. furyl, thienyl, pyrazolyl, pyridyl, indolyl). It may be a monocyclic system or a condensed ring system (for example, henzofuryl, phenanthridinyl).Furthermore, these aromatic rings may have a substituent.

The heterocyclic group referred to in R,, R,, B, and R is preferably a group having a 3- to 10-membered ring structure composed of carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, or hydrogen atoms; The ring itself may be a saturated ring or an unsaturated ring, and may be further substituted with a substituent (eg, chromanyl, pyrrolidyl, pyrrolinyl, morpholinyl).

represents a group bonded to A via an oxygen atom, sulfur atom or nitrogen atom (e.g. 2-pyridyloxy, 2-pyrimidyloxy, 4-pyrimidyloxy, 2-(1,2
,3-)riazine)oxy,2-penzimidazolyl,
2-imidazolyl, 2-thiazolyl, 2-benzthiazolyl, 2-furyloxy, 2-thiopheyloxy, 4
-pyridyloxy, 3-isoxacylyloxy, 3-
Pyrazolidinyloxy 23-oxo-2-pyrazolonyl, 2-oxo-1-pyridinyl, 4-year-old xo-1-pyridinyl, 1-benzimidazolyl, 3-virazolyloxy, 3H-1,2,4-oxadiazoline- 5nioxy, aryloxy, afrecoxy, alkylthio, a.
Preferred are lylthio, substituted N-oxy) or halogen atoms.

- Formula CI) represents a group that reacts with an aromatic amine developer to form a chemical bond, and represents a group containing an atom of low electron density, for example, through an oxygen atom, a sulfur atom or a nitrogen atom. A group that binds to A (e.g. 2-pyridyloxy, 2-pyrimidyloxy, 4-pyrimidyloxy, 2-(1,2
, 3-triazine)oxy, 2-benzimidazolyl,
2-imidazolyl, 2-thiazolyl, 2-benzthiazolyl, 2-furyloxy, 2-thiopheyloxy, 4
-pyridyloxy, 3-isoxacylyloxy, 3-
and lazolidinyloxy, 3-year-old xo-2-pyrazolonyl, 2-year-old xo-1-pyridinyl, 4-oxo-1-pyridinyl, 1-benzimidazolyl, 3-pyrazolyloxy, 3H-1,2,4-oxadiazoline -5-oxy, aryloxy, alkoxy, alkylthio, arylox-oxy) or a halogen atom is preferred.

- Formula CI) represents a group that reacts with an aromatic amine developer to form a chemical bond, and includes a group with a low electron density, such as //X/ Y' /2 -L-8i - Contains. When X is a halogen atom, n represents all θ. Here, L single bond, alkylene group, -Q-, -8--N- 几''' zyl, naphthyl), heterocycle (e.g. piperidinyl,
pyranyl, furanyl, chromanyl), acyl groups (eg acetyl, benzoyl) and sulfonyl groups (eg methanesulfonyl, benzenesulfonyl).

L', L" and L"' include 10-5-3- and (e.g. carbonyl group, sulfonyl group, sulfinyl group, oxycarbonyl group, phosphonyl group, thiocarmenyl group, aminocarbonyl group, silyloxy group) .

Y ke general formula (II, has the same meaning as Y in l) Y' is Y
It has the same meaning as

R' and R" may be the same or different, and each -
L/// represents R. R″′ is preferably a hydrogen atom, an aliphatic group (eg, methyl, isobutyl, t-butyl, vinyl, benzyl, octadecyl, cyclohexyl), or an aromatic group (eg, phenyl, a divalent group represented by bily-alkylene-C-).

Among the compounds represented by general formula (I), more preferable compounds are general formula (I-a), -(r-, b), (I-
c) or (need d), and the second-order reaction rate constant with p-anisidine is 2 (80°C).
/l1oisec ~lXl0-5 sentences/mol・sec
It is a compound that reacts within the range of .

(1-+1)]I R1-Link -C-0-Ar (1-b) Chest (I-C) In the formula, R1 represents the same meaning as R1 in general formula (I),
Link represents a single bond and 10-, Ar represents R1,
Represents an aromatic group with the same meaning as defined for R2 and B, except that those released as a result of reaction with an aromatic amine developer are groups useful as photographic reducing agents, such as hydroquinone derivatives and catechol-packed conductors. It is never. R
a, Rb and Rc may be the same or different and each represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group with the same meaning as defined for R1, R2 and B,
Ra, Rb and Rc further represent an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group, an alkylamino group, an acyl group, an amide group, a sulfonamido group, a sulfonyl group, It represents an alkoxycarbonyl group, a sulfo group, a carboxyl group, a hydroxy group, an acyloxy group, a ureido group, a urethane group, a carbamoyl group, and a sulfamoyl group. Here, Ra and Rb or Rb or Rc may be combined with each other to form a 5- to 7-membered heterocycle, and this peterocycle may be further substituted with a substituent or form a spiro ring, bicyclo ring, etc. or may be fused with an aromatic ring. Z
l and Z2 represent a non-gold E and M group necessary to form a 5- to 7-membered heterocycle, and this petero ring may be further substituted with a substituent or form a spiro ring, bicyclo ring, etc. Alternatively, it may be fused with an aromatic ring.

- Especially among formulas (1-a) to (1-d) - formula (1-
The second-order reaction rate constant k with p-anisidine in a)
z (80' C) 1x10 bow IV, /mo 1.
s e c ~ I X 10-5ffi/mo I
, sec range, when Ar is a carbocyclic aromatic group, it can be adjusted by substituents. At this time, although it depends on the type of group of R1, the sum of Hammet's σ values of each substituent is 0.
．． 2 or more is preferable, 0.4 or more is more preferable, 0
．． It is even more preferable that it is 6 or more.

- When the compounds represented by formulas (1-a) to (1-d) are added at the time of producing a light-sensitive material, the total carbon number of the compounds themselves is preferably 13 or more. From the viewpoint of achieving the object of the present invention, the compound of the present invention is not preferably one that decomposes during development.

- Y in formula (11) is an oxygen atom, a sulfur atom, where R
4, R5 and R6 are hydrogen atoms, aliphatic groups (e.g. methyl, isopropyl, t-methyl, vinyl, hensyl,
octadecyl, cyclohexyl), aromatic groups (e.g. phenyl, pyridyl, naphthyl), heterocyclic groups (e.g. piperidyl, pyranyl, furanyl, chromanyl), acyl groups (e.g. acetyl, benzoyl), sulfonyl groups (e.g. methanesulfonyl, henzenesulfonyl). ), and R5 and R6 may be bonded to each other to form a cyclic structure.

Among the compounds represented by general formulas (T) and (II), a particularly preferred compound is general formula (r).

Among these, more preferred compounds are those represented by the general formula (Ia) or (1-c), and particularly preferred are the compounds represented by the formula (1-a).

Z in the general formula (III) represents a nucleophilic group or a group that decomposes in the light-sensitive material to release a nucleophilic group.

For example, a nucleophilic group in which the atom that directly chemically bonds with the oxidized product of an aromatic amine developer is an oxygen atom, a sulfur atom, or a nitrogen atom (e.g., an amine compound, an azils compound, a hydrazine compound, a mercapto compound, a sulfide compound, Sulfinic acid compounds, cyano compounds, thiocyano compounds, thiosulfate compounds, seleno compounds, halide compounds, carboxy compounds, hydroxamic acid compounds, active methylene compounds, phenol compounds, nitrogen heterocyclic compounds, etc.) are known.

A more preferable compound among the compounds of general formula (III) can be represented by the following formula (III-a).

- Formula (lla) where M is inorganic (e.g. Li, 'Na, K,
Ca.

Mg, etc.) or an atom or atomic group forming an organic salt (e.g. triethylamine, methylamine, ammonia, etc.), where 几 and R□6 may be the same or different,
Each represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group.几1. and R16 may be bonded to each other to form a j to 7-membered ring. R□7,/2 R18% R2O and R21 may be the same or different, and each represents n hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, sulfonyl group, ureido and urethane groups. However, R1
At least one of 7 and R1, and at least one of '20 and 几21 are hydrogen atoms.几1
．． - and R2□ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. 9 further includes an alkylamino group, an arylamino group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. Here “17%
"18%" At least the first group of □9 may be bonded to each other to form a 3- to 7-membered ring, and R20
At least λ groups of % R21 and 2□ may be bonded to each other to form a 3- to 7-membered ring. R23 represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, R24 represents a hydrogen atom, an aliphatic group, an aromatic group, a halogen atom, an acyloxy group or a sulfonyl group. R25 represents a λO hydrogen atom or a hydrolyzable group.

R5゜, R++, R+□, R1, and RI4 may be the same or different, and each represents a hydrogen atom, an aliphatic group (for example, methyl, isopropyl, t-butyl, vinyl, benzyl, octadecyl, cyclohexyl), an aromatic group ( (e.g. phenyl, pyridyl, naphthyl), hete[1 ring group (e.g. piperidyl, pyranyl, furanyl, chromanyl),
Halogen K atom (e.g. chlorine atom, bromine atom), 5
R26, 0R26, N R26, acyl group (e.g. acedel, henzyl), alkoxycarbonyl group (e.g. methoxycarbonyl, butoxycarbonyl, cyclohexylcarbonyl, octyloxycarbonyl), aryloxycarbonyl group (e.g. phenyloxycarbonyl, naphthyloxycarbonyl), sulfonyl groups (e.g. methanesulfonyl, benzenesulfonyl), sulfonamide groups (e.g. methanesulfonamide, henzenesulfonamide)
, sulfamoyl group, ureido group, urethane group, carhamoyl group, sulfo group, carboxyl group, nitro group, cyano group, alkoxy group (e.g. methoxalyl, isobutoxalyl, octyloxalyl, hendiyloxalyl), aryloxalyl group (e.g. phenoxalyl) ,
(naphthoxalyl), sulfonyloxy group (e.g. methanesulfonyl), two examples of these compounds are shown below,
This does not limit the compounds that may be used in the present invention.

represent. R26 and R27 may be the same or different, and each represents a hydrogen atom, an aliphatic group, an aromatic group, an acyl group, and a sulfonyl group, R211 and Rz
q may be the same or different and each represents a hydrogen atom, an aliphatic group, an aromatic group, an alkoxy group, or an aryloxy group.

Among these, for the -302M group, Ha of the benzene substituent
In terms of the effects of the present invention, it is preferable that the sum of the σ values of mmetL is 0.5 or more.

σ−4〕 chic (1-s) (r-7) IJ4) ”)cl 8’371 (II) 018 Ha’ 7 Br σ−S) α-lI+) (Ding-10) to 2 λ7 α q〉25ノ (,;-26) U21'i5 6 (r-27) (Ding-282 (■- and 9) CO□C2H5 (knee 3s (1-%) engraving of statement (r　-41) OCOf;+H+s(rono Rizuri (N-371 CO2C2H5 engraving of statement engraving of statement (■ ciV.

(I (■ C2H,,0 C,n-/ ) (II-,2) (II-J) C)I2-CH-810゜Q ) ((II) (II-4') (II,t) Pair 3 / g (tl3 da specification engraving (■ (I[-22) specification engraving 26) (I-23) >-271 H (II-24) (III-25) (4 )-?g, 1 H38C(CH3)4 [Yes]-2L1) H〇-mon (■OC!2H25 (m-3o1 NaN:+
-115855, 63-115866, 63-
It can be synthesized by the method described in No. 158545, European Patent Publication No. 2557.22, or a method analogous thereto.

Preferred compounds of the present invention include the above-mentioned patents and JP-A-62-
It also includes compounds specifically exemplified in the specifications of No. 283338 and No. 62-229145.

Compounds represented by general formulas (+), (11) and (III), such as those with low molecular weight and those that are easily soluble in water, are added to the processing solution, and the photosensitive materials are added to the processing solution during the development process. You can also take it inside. Preferably, it is added to a hydrophilic colloid layer in a photosensitive material at the stage of manufacturing the photosensitive material.

The latter method is usually performed by dissolving a high-boiling point solvent (oil) with a boiling point of +70°C or higher at atmospheric pressure alone, a low-boiling point solvent alone, or a mixed solvent of the above-mentioned oil and a low-boiling point solvent, and then adding gelatin or the like to this solution. It is prepared by emulsifying and dispersing it in an aqueous hydrophilic colloid solution.

In the present invention, the compounds represented by the general formulas (1), (H) and (■) are preferably those that can be dissolved in a high boiling point organic solvent. There is no particular restriction on the particle size of the emulsified dispersion particles, but it is preferably from 0.05μ to 0.5μ/l, particularly from 0.1μ to 0.05/l.
0.3μ is preferred. In particular, in terms of the effects of the present invention, the general formula (
+), (IT) and (III) is from 1X10-2 to 10 moles, preferably from 3X10-" to 5 moles per mole of coupler. If it is less than this, the effects of the present invention will be impaired. There is a tendency for it to become difficult to play, and if too much is used, the color reaction may be inhibited.

The pyrazoloazole skeleton of the pyrazoloazole coupler used in the present invention is represented by the following formula (III).

General formula (III) In the formula, RZ4 represents a hydrogen atom or a substituent, and Z21
Table 2S represents a hydrogen atom or a group that can be separated in reaction with an oxidized product of an aromatic primary amine color developing agent.
= or -NH-, one of the zza223 bond and the Zz+Zz□ bond is a double bond, and the other is a single bond. The case where ZZ322□ is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. However, R2
4. At least one of RZS and Z2+ represents a substituent containing a carboxyl group.

- In formula (I), RZ4 and R25 are hydrogen atoms,
halogen atom, alkyl group, aryl group, heterocyclic group,
cyano group, alkotso group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group,
Silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imido group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group , sulfonamide group, carbamoyl group, acyl group, sulfamoyl group, sulfonyl group, sulfinyl group, alkoxycarbonyl group, and aryloxycarbonyl group.

To explain these substituents in more detail, R44 and RAS are hydrogen atoms, halogen atoms (e.g. chlorine atom, bromine atom), alkyl groups (e.g. methyl, propyl, isopropyl, L-butyl, trifluoromethyl, l
・Lyzosyl, 3-(2,4-di-L-amylphenoxy)
Propyl, allyl, 2-todecyloxyethyl, 3-phenoxypropylene, 2-hexylsulfonyl-ethyl, 3-(2-butoxy-5-t-hexylphenylsulfonyl)propyl, cyclopentyl, benzyl), aryl group (e.g. phenyl, 4-t-butylphenyl, 2,4-di-amylphenyl, 4-tetradecanamidophenyl)
, heterocyclic groups (e.g., 2-furyl, 2-thienyl, 2
-pyrimidinyl, 2-hendithiazolyl), cyan group,
Alkoxy groups (e.g. methoxy, ethoxy, 2-methoxyethoxy, 2-dodecyloxyethoxy, 2-phenoxyethoxy, 2-methanesulfonylethoxy), aryloxy groups (e.g. phenoxy, 2-methylphenoxy, 2-methoxyphenoxy, 4-t-butylphenoxy), heterocyclic oxy groups (e.g., 2-henzimidazuryloxy), acyloxy groups (e.g., acetoxy, hexadecanoyloxy), carbamoyloxy groups (e.g., N-phenylcarbamoyloxy, N-ethylcarbamoyloxy), silyloxy groups (e.g. trimethylsilyloxy), it sulfonyloxy groups (e.g. dodecylsulfonyloxy), acylamino groups (e.g. acetamide, benzamide, tetradecanamide, α(2,4-di-L-amyl) phenoxy)butyramide, r-(3-t-butyl-4-hydroxyphenoxy)butyramide, α-[4
-(4-hydroxyphenylsulfonyl)phenoxy)
decanamide), anilino groups (e.g. phenylamino, 2-chloroanilino, 2-chloro-5-tetradecanamideanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-
5-(α-(3-L-butyl4-hydroxyphenoxy)dodecanamido)anilino), ureido group (e.g.
phenylureido, methylureido, N,N-dibutylureido), imide groups (e.g., N-succinimide,
3-henzylhydantoinyl, 4-(2-ethylhexanoylamino)phthalimide), sulfamoylamino groups (e.g., N,N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino) ), alkylthio groups (e.g. methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3-(4-t-butylphenoxy)propylthio), arylthio groups (e.g. phenylthio, 2-butoxy -5-1-octylphenylthio,
3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio), peterocyclic thio group (e.g., 2henzothiazolylthio), alkoxycarbonylamino group (e.g., methoxycarbonylamino, tetradecyloxycarbonyl) amino), aryloxycarbonylamino groups (e.g., phenoxycarbonylamino, 2,4-di-tert-butylphenoquinecarbonylamino), sulfonamide groups (e.g., methanesulfonamide, hexadecanesulfonamide, henzenesulfonamide, p- Toluenesulfonamide, octadecanesulfonamide, 2-methyloxy-
5-t-butylhenzensulfonamide), carbamoyl groups (e.g., N-ethylcarbamoyl, N,N-dibutylcarbamoyl, N-(2-dodecyloxyethyl)
Carbamoyl, N-methyl-N-dodecylcarbamoyl, N-(3-(2,4-di-tert-amylphenoxy)propyl)carbamoyl, acyl group (e.g. acetyl, (2,4-di-tert-amylphenoxy)acetyl), hendiyl), sulfamoyl groups (e.g., N-ethylsulfamoyl, NN-dipropylsulfamoyl, N-(2-dodecyloxyethyl)sulfamoyl,
N-ethyl-N-dodecylsulfamoyl, N,N-diethylsulfamoyl), sulfonyl groups (e.g. methanesulfonyl, octanesulfonyl, hensensulfonyl, toluenesulfonyl, 2-butoxy-5-tert)
-octylphenylsulfonyl), sulfinyl groups (e.g. octanesulfinyl, dodecylsulfinyl,
phenylsulfinyl), alkoxycarbonyl groups (e.g. methoxycarbonyl, butyloxycarbonyl,
dodecylcarbonyl, octadecylcarbonyl), aryloxycarbonyl group (e.g.
phenyloxycarbonyl, 3-bentatecyloxycarbonyl).

- In the formula (III), + represents a hydrogen atom or a group capable of leaving in reaction with an oxidized product of an aromatic primary amine color developing agent. In detail, the 22+ leaveable groups include halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom), alkoxy groups (e.g. dodecyloxy, dodecyloxycarbonylmethoxy, methoxycarbamoylmethoxy, carboxypropyloxy, methanesulfonyloxy) ), oryloxy (e.g., 4-methylphenoxy group, 4-tert-butylphenoxy,
4-methquinphenoxy, 4-methanesulfonylphenoxy, 4-(4-penzyloxyphenylsulfonyl)
phenoxy), acyloxy groups (e.g., acetoxy, tetrazokayloxy, hendiyloxy), sulfonyloxy groups (e.g., methanesulfonyloxy,
toluenesulfonyloxy), amide groups (e.g. cycloa, cetyl amino, methanesulfonylamine, trifonylphosphonamide), alkoxycarbonyloxy groups (e.g. ethoxycarbonyloxy, henzyloxycarbonyloxydicarbonyloxy groups (e.g. phenoxycarbonyl) 25
-di-octyloxyphenylthio, 2-(2-ethoxyethoxy)5-term-octylphenylthio, teI lazolylthio), imido groups (e.g. succinimide, hydantoinl, 2,4-dioxoxazolidin-3-yl) , 3-hensyl-4-ethoxyhydantoin-1-yl), N-heterocycle (e.g. 1-pyrazolyl,
Examples include 1-hensitriazolyl, 5chloro-1.2.4-triazol-1-yl), aromatic azo groups (eg, phenylazo group), and the like. These leaving groups may include photographically active groups.

At least one of the substituents represented by R44, R45 or Z41 represents a group substituted with a carboxyl group.

Further, R64 or Z□ of -formula (TV) may form a dimer or more multimers.

-Among the compounds represented by formula (IV), particularly preferred compounds are represented by general formula (V) or (VT).

General formula (V) They may be the same or different.

-Among formulas (V) and (Vl), -formula (Vl) is particularly preferred.

Examples of the magenta coupler compound represented by the general formula (V) or -numerical formula (VT) are illustrated below, but the invention is not limited thereto.

- Formula (V[) In the formula, R44, R6 and 241 represent the same meanings as stated in general formula (IV). The groups R44 and Ras are Engraving (M (M Engraving of the specification (M 100 U (M These couplers are described in U.S. Pat.
It can be synthesized according to the synthesis methods described in Japanese Patent Application Laid-open No. 171956, Japanese Patent Application Laid-Open No. 6098438, West German Patent Publication No. 3,636°364, and Japanese Patent Application Laid-Open No. 63-231452.

The coupler of general formula (III) used in the present invention is contained in the silver halide emulsion layer constituting the photosensitive layer, usually from 0.01 to 1.0 mol, preferably from 0.05 to 0.5 mol, per 1 mol of halogen. Collaboratively produced.

In the present invention, various known techniques can be applied to add the coupler of formula (I[l) to the photosensitive layer. Usually, it can be added by the oil-in-water dispersion method known as the oil protection method, and after being dissolved in a solvent, it is emulsified and dispersed in an aqueous gelatin solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water droplet dispersion with phase inversion. In addition, alkali-soluble couplers are
It can also be dispersed by the so-called Fisher dispersion method. The low-boiling organic solvent may be removed from the coupler dispersion by distillation, noodle washing, ultrafiltration, or the like, and then mixed with the photographic emulsion.

As a dispersion medium for such couplers, the dielectric constant (25°C
) 2 to 20 and a refractive index (25° C.) of 1° to 1.7, it is preferable to use a high boiling point organic solvent and/or a water-insoluble polymer compound.

The high boiling point organic solvent that can be used in the present invention will be explained in detail later.

The light-sensitive material of the present invention only needs to have at least one layer of a red-sensitive layer, a green-sensitive layer, and a silver halide emulsion layer of the red-sensitive layer on the support. There are no particular limitations on the number and order of the silver emulsion layer and the non-photosensitive layer. A typical example is a silver halide photographic material having on a support at least one photosensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. The photosensitive layer is a unit photosensitive layer that is sensitive to blue light, green light, or red light. The color layers are arranged in this order from the support side: a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. However, depending on the purpose, the two installation orders may be reversed, or the installation order may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
1343〆r No. 8, No. 59-1.1344'O, No. 61-2003
Coupler, DIR compound, etc. as described in No. 7, No. 61-20038, etc. may be included, and a color mixing inhibitor as commonly used may be included.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in German Patent No. 1,121,470 or British Patent No. 923.045. A two-layer configuration can be preferably used.

Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also, JP-A-57-
No. 112751, No. 62200350, No. 62-20
As described in No. 6541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support: low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (811) / high sensitivity green sensitive layer (Gl+) / low sensitivity green sensitive layer (GL) /High-sensitivity red-sensitive layer (R1+)/Low-sensitivity red-sensitive layer (RL)
or B H/B l, /GL/Gll/R1
1/RL order, also B II / B L / G
They can be installed in the order of II/Gl, /RL/RH, etc.

Further, as described in Japanese Patent Publication No. 55-34932, the blue-sensitive layer/G H/
They can also be arranged in the order of RH/GL/It L. Also, JP-A-56-25738 and JP-A No. 62-63
As described in No. 936, from the side farthest from the support, the blue-sensitive layer/GL/RL/G
They can also be arranged in the order of H/R11.

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low density is disposed and the photosensitivity gradually decreases toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same window color layer, the medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-sensitivity 7L layer may be arranged in this order from the side remote from the support.

In addition, high-sensitivity emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer,
Or low sensitivity? They may be arranged in the following order: L agent layer/medium temperature emulsion layer/high sensitivity emulsion layer.

Furthermore, even in the case of four or more layers, the arrangement may be changed as shown in ``2''.

2, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

When the photographic light-sensitive material of the present invention is a color 7 film or a color reversal film, the preferred material contained in the photographic emulsion layer contains about 30 mol% or less of silver iodide. Silver iodobromide, silver iodochloride, or silver iodochlorobromide. Particularly preferred is about 2 mol % to about 25 mol %.
Silver iodobromide or silver iodochlorobromide containing up to mol% silver iodide.

When the photographic light-sensitive material of the present invention is color stamp 11w1 paper, the silver halide contained in the photographic emulsion layer is composed of silver chlorobromide or silver chloride that does not substantially contain silver iodide. can be preferably used. Here, "substantially free of silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less.

Regarding the halogen composition of the silver chlorobromide emulsion, any silver bromide/silver chloride composition can be used. Although this ratio can vary over a wide range, it is preferable to use a material with a silver chloride ratio of 2 mol% or more.For light-sensitive materials suitable for rapid processing, so-called so-called materials with a high silver chloride content can be used. High silver chloride emulsions are preferably used.The silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more, and 90 mol% or more.
More preferably 5 mol% or more. For the purpose of reducing the amount of replenishment of the processing solution, an emulsion of almost pure silver chloride having a silver chloride content of 98 to 100 mol % is also preferably used.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsion that can be used in the present invention
(December 1978), 22-23, “■ Emulsion preparation and
1. ypes)”- and same No. 18716
(November 1979), 648 pages, "Physics and Chemistry of Photography" by Graf 4-de, published by Paul Monternet (P., G.
lafkides, Chemie el Pl
+1siqoe yen+aLo+: rapl+1que
, Paul MonLel, 1967) "True Emulsion Chemistry" by Duffin, published by Tsumekarubushi Sune (G.
, F, iiuffinPhotographic E
Mulsion Chemistry (Focai
(4S Sl, 966)), Zelikman et al., "Photograph 7 [, Preparation and Application of Agent σ1", Focalb 1]
．． Nune t1(1(ν, 14. Zplii+n[all
et a! , + MakinI! and C:
+atinp, 111t) ↑ag+:ipl c F
+++u, 1sion, Focal Press+
196d:';j, c:'::6m description sy"r't
It can be prepared using one method; -・8, U.S. Patent No. t) + +174 , (+ 2 b "j, bj
tl, 655, ,)9 r'j issue Jyi,,
(, and British Patent No. 1.
(,・1.,-:lL' put it :”:::,tl
+U'I (An emulsion is also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic
Science and EBincring),
Volume 14, pp. 248-257 (], 9970, U.S. Patent No. 4.434.226, U.S. Patent No. 4,414.310,
No. 4,433,048, 1. ．． 139,520 and British Patent No. 2.11.2,157.

The crystalline structure may be similar to that of silver halide, the inside and outside may have different halogen compositions, or may have a layered structure. For example, rodan silver, lead oxide, etc. may be bonded.
) may be bonded to a compound.

Also the crystal form of the gods i2') Ladle, 4-? R compounds may also be used.

3W 'i'L, agent is usually physical ψi
Use the one that has been chemically synthesized, chemically synthesized, and spectrally sensitized. Additives used in such processes are Research Disclosure+-No. 17643 and Research Disclosure+-No.
18716, 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 Linerci Disk 1 cordiers mentioned above, and the relevant descriptions are shown in the table below.

Motion 11 Non-RD176'13 RD187161 Chemical sensitizer page 23 Page 648 right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, 23-2
Page 4 Page 648 Right column ~ Super sensitizer 64
Page 9, right column 4 Brighteners Page 24 5 Antifogging agents Pages 24-25 Page 649 right column ~ and stabilizers 6 Light absorbers, pages 25-26 Page 649 right column ~ Filter dyes, Page 650 left column Ultraviolet absorption Agent 7 Anti-stain agent Page 25 right column 6, page 50 left to right column 8 Dye image stabilizer page 25 9 Hardener page 26 page 651 left column 10
Binder page 26 Same as above 11 Plasticizer 11, lubricant page 27 Page 650 right column 12 Coating aid, pages 26-27 Page 650 right column Surfactant 13 Statink Page 27 Same soil cutting agent Also, photographic performance with formaldehyde gas In order to prevent deterioration of U.S. Pat. No. 4,41. L987 and the same No. 1
Compounds that can be immobilized by reacting with formaldehyde as described in No. 1.435.503 can be added to photosensitive materials, and specific examples thereof can be found in the aforementioned Research Disclosure (
RD) No. 17643, ■-C-C.

Yellow couplers include, for example, U.S. Patent Section 3.93.
No. 3,501, No. 4.022.620, No. 4.3
No. 26.024, No. 4.401.752, No. 4.
248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425.020, British Patent No. 1,476.760, United States Patent Section 3.973.968, British Patent No. 4.314,
No. 023, same No. 1,511. ．． Preferred are those described in European Patent No. 649, European Patent No. 2.19,473Δ, and the like.

As magenta couplers, 5-pyraduron and birazoroadurone compounds are preferred, and U.S. Patent Section 4,31
No. 0,619, No. 4.35, No. 897, European Patent No. 73,636, U.S. Patent Section 3. OGl, No. 432, No. 3725.067, Research Disc 1 Codger No. 2.1220 (June 1984), JP-A-60-33552, Linarch Disclosure N
O, 24230 (June 1,984), JP-A-60-4
No. 3659, 61. -72238, same (io-35
No. 730-, No. 55-11.8034, No. 60-1.
Particularly preferred are those described in US Patent No. 85951, US Patent No. 4500.630, US Pat.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Patent Section 4,052.212.
No. 4. ],, No. 46,396, No. 4,228,
No. 233, No. I, No. 296.200, No. 2.3 [
i9.929, same No. 2. ) No. 301.171, No. 2
, 772.162, 2.895.826, 3,772,002, 3.75Ei, 308,
4,334.011, 4,327,173, West German Patent Publication No. 3329.729, European Patent No. 12
No. 13658, No. 249453A, U.S. Patent Section 3,
No. 446.622, No. 4,333.999, No. 4
．． 775.616, 4.451.559, 4,427,767, 4,690,889, 4, 254212, 4,296.1.99, Preferred are those described in JP-A-61-42658 and the like.

Research Disclosure N is a colored coupler for correcting unnecessary absorption of coloring dyes.

Section 17643-G, U.S. Patent Section 4.163,670
No. 57-39413, U.S. Patent Section 4.00,
Preferred are those described in No. 1,929, No. 4,138,258, and British Patent No. L 146.368. Also,
Couplers that correct unwanted absorption of chromogenic dyes by means of fluorescent dyes released upon coupling as described in U.S. Pat. It is also preferable to use a coupler having as a leaving group a dye precursor group capable of forming a dye.

Couplers whose coloring dyes have appropriate diffusivity are disclosed in U.S. Patent Section 4. ．． 366.237, British Patent No. 2,12
5,570, European Patent No. 96.570, West German Patent (
The one described in Japanese Publication No. 3,234,533 is preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4,367.282, No. 4. ．． 409.3
No. 20, No. C576910, British Patent No. 2.102.
It is described in No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors include the aforementioned RD 17643.
, Patents described in sections ■ to F, Japanese Patent Application Laid-Open No. 57-15194
No. 4, No. 57-15423.1, No. 60-1.842
No. 48, No. 63-37346, U.S. Patent/1.248
．． Those described in No. 962 and No. 4782.012 are preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2.097,140;
No. 2.1.31,188, JP 59-15763
No. 8, No. 59-170840 ζ Those described here are preferred.

Other couplers that can be used in the light-sensitive material of the present invention include the competitive couplers described in U.S. Pat. ．． No. 172, No. 4,338.393, No. 172, No. 4,338.393, No. 4,338. , , 3 +
, 0, 618, DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds or DTR redox releasing couplers described in JP-A-60-185950, JP-A-6224252, etc. Redox compounds, couplers that release dyes that fade after separation as described in European Patent No. 173302A, R, D, No. 11449, 242. II, bleach accelerator releasing coupler described in JP-A No. 61-201247, etc., U.S. Patent No. 4,553,47
Gantt release coupler described in No. 7, etc., JP-A-63-7
Examples include couplers that release leuco dyes as described in US Pat. No. 5,747, and couplers that release fluorescent dyes as described in US Pat.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling solvents used in oil-in-water dispersion methods are described in, for example, US Pat. No. 2.322.027.

The boiling point at normal pressure used in the oil-in-water dispersion method is 175°C.
Specific examples of the above-mentioned high-boiling organic solvents include phthalic acid esters (dibutyl phthalate, cyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-diamylphenyl) phthalate, , bis(2,4-diamyl phenyl) isotucrate, his(1,1-noethylbrobyl) phthalate, etc.), esters of phosphoric or phosphonic acids If (
+・Riphenylphosphate, tricresylbosphate, 2-ethylhexyldiphenylphosphate, tricyclohexylphosphate-I・, I-so-2-ethylhexylphosphate-1・, tridodecylbosphate-1・,
Tributoxyethyl phosphate sulfate, di-2-ethyl-1-silphenylphosphonate-1, etc.), benzoic acid esters (2-ethylhexylhenzoate-1-, todecylhenzoate, 2-ethylhexyl) -p-hydroxyhenzuate, etc.), amides (N,N-diethyltodecanamide, Δ,N-
Diethyl laurylamide, N-tetradecylpyrroli [
), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis(
2-ethylhexyl) sebacate, dioctyl azele
1., glycerol I, dibutyl-1., isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N,N-dibutyl-2-butoxy-5-Le
r t-octylaniline, etc.), hydrocarbons (paraffin, 1-decylbenzene, diisoprobylnafculene, etc.), and the like. In addition, as an auxiliary solvent, the boiling point is about 30°C or higher, preferably 50°C or higher and about 160°C.
Organic solvents of C or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

The process and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat.
It is described in West German Patent Application (OLS) No. 2,54L274 and OLS No. 2541, 230.

Alternatively, these couplers can be impregnated into a loadable latentx polymer (e.g., U.S. Pat. No. 4,203,716) in the presence or absence of the above-mentioned high-boiling point a solvent.
Alternatively, a water-insoluble polymer can be dissolved in a solvent-soluble polymer and emulsified and dispersed in an aqueous hydrophilic colloid solution.

Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. 8B100723 are used. In particular, the use of acrylamide-based polymers is preferred from the viewpoint of color image stabilization.

The color photosensitive +Δ material of the present invention includes JP-A-63-257
No. 747, No. 62-272248, and JP-A-1-
1,2-benzisothiapurine described in No. 80941
3-one, Kanobutyl p-hydroxyhensoate, phenol, 4-chloro-3,5-dimethylphenol, 2
- It is preferable to add various preservatives or antifungal agents such as phenoxyethanol and 2-(4-thiazolyl)benzimidazole.

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 paper.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, No. 17643, page 28, and the same No.
It is described from the right column on page 647 to the left column on page 648 of 1871.6.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, and even more preferably 20 μm or less. Further, the membrane swelling rate T1/2 is preferably 30 seconds or less, more preferably 20 seconds or less.

The film thickness means the film thickness measured at 25° C. and 55% relative humidity (2 days), and the film swelling rate TI/□ can be measured according to a method known in the art.

For example, Photographic Science Ant Engineering (Photogr, Sci, Eng.), 1 by Green et al.
9, No. 2, 124-129. By using a swellometer (swelling; i'I) of the type further described, the TI/.

The saturated film thickness is defined as 90% of the maximum swollen film thickness reached when treated with a color developing solution at 30°C for 13 minutes and 15 seconds, and this T, /
This is defined as the time required to reach the film thickness of 2.

The membrane swelling rate T, /2 can be adjusted by adding a hardening agent to gelatin as a binder, or by changing the aging conditions after coating. Further, the swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the conditions described above, using the formula: (maximum swollen film I
g-film thickness)/film thickness.

The color photographic material according to the present invention includes the above-mentioned RD,
No. 17643, pages 28-29, and No.
Development processing can be carried out by the usual method described in 615 left column to right column of No. 18716.

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. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N, 11-diethylaniline, 3-methyl-4- Amino-N-ethyl-N-β
-Hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-Nβ-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and their sulfates, hydrochloric acid Examples include salts and p-toluenesulfonates. Among these, 3-methyl-4-amino-■-ethyl-N
β-hydroxyethylaniline sulfate is preferred. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain p)lii buffering agents such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts, iodide salts, hendimidazoles, hendithiazoles or mercapto. It is common to include development inhibitors or antifoggants such as compounds. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, ethylene molar solvents such as glycols, diethylene glycol, development accelerators such as hensyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, Auxiliary developing agents, viscosity-imparting agents, various chelating agents such as aminopolycarboxylic acids, aminoborifospo〉' acids, alkylphosphonic acids, and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, and diethylenetriamine. Pentaacetic acid, cyclohe4-zandiaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,
1-diphosphonic acid, nitrilo-N,N,N-trimedylenephosphonic acid, ethylenediamine-N,N,N,N-tetramethylenebosphonic acid, ethylenediaminedi(0-hyl
Typical examples include XOxyphenylroic acid) and salts thereof.

In addition, when reversal processing is performed, color development is usually performed after bleaching processing. This black-and-white developer contains dihydroquinone such as hydroquinone, 1-phenyl-3
Known black and white developing agents such as 3-pyrazolidones such as -pyrazolidone or amicif-1-nols such as N-methyl p-aminophenol can be used alone or in combination.

These color developing solutions and black and white developing solutions generally have a pu of 9 to I2. Although the amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, it is generally below 3°C per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenishing solution,
It can also be less than mff1. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank.

The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below.

That is, the aperture ratio in ``2'' is preferably 0.1 or less,
More preferably, it is 0.001 to 0.05. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing solution in the processing tank, there is also a method described in Japanese Patent Application Laid-Open No.
The method using a movable lid described in Japanese Patent Application Laid-Open No. 63-21.6050.

The following development processing methods can be mentioned. Reducing the aperture ratio can be applied not only to both color development and black-and-white development processes, but also to all subsequent processes, such as bleaching, bleach-fixing, fixing, washing, and stabilization. preferable. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using high temperature and high p++ and using a high concentration of color developing agent.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment in two continuous bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. As the bleaching agent, for example, compounds of polyvalent metals such as iron (I[l), peracids, quinones, nitro compounds, etc. are used. Typical bleaching agents include organic complex salts of iron (III), such as aminopolymer salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol ether diaminetetraacetic acid. Carboxylic acids or complex salts of citric acid, tartaric acid, malic acid, etc. can be used. Among these, aminopolycarboxylic acid iron(III) complex salts, including ethylenediaminetetraacetic acid iron(1) complex salt and 1,3-diaminopropanetetraacetic acid iron(III) complex salt, are preferable from the viewpoint of rapid processing and prevention of environmental pollution. . In addition, iron aminopolycarboxylate (IT
1, ) complex salts are particularly useful in both bleach and bleach-fix solutions. These iron aminopolycarboxylic acids (
II) The pH of the bleaching solution or bleach-fixing solution using complex salts is usually 4.0 to 8, but it is also possible to process at a much lower pH for speeding up the processing.

A bleach accelerator can be used in the bleach solution, bleach-fix solution, and their 111 baths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893.85E1, West Germany 1,
No. 1,290,812, No. 2,059,988,
JP-A No. 53-32736-1 No. 53-57'831, No. 53-3711.8, No. 53-72623, No. 53-95630, No. 53-95631, No. 53-
No. 104232, No. 53-124424, No. 53-
1i1. ．． No. 623, 53. ．． No. 28426, Research Disc 1. J-Jar No., T, 7], 29”
Compounds having a mercap I group or a disulfide group as described in JP-A-1989-1 (July 1978) and others;
Thiazolidine derivatives described in No. 401.29, Tokkosho/
l5-8506 male, JP-A No. 52-20832, No. 53
-32735, thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent Section 1. , ], 227.
Iodide salts described in No. 71.5, JP-A-58-1.6,235; West German Patent Sections 966.41.0 and 2.148.
Polyoxyethylene compounds described in No. 430; Tokkosho/15-. No. 8836 i'1llll! Other polyamine compounds described in JP-A Nos. 49-42,434 and 49-5
No. 9.644, No. 53-9.1,927, No. 54-3
No. 5,727, No. 55-26,506, No. 58-16
Compounds described in No. 3.940; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect, and are particularly preferred in US Pat. No. 3,893,858, West German Patent Section 1.290,
Compounds described in No. 81.2 and JP-A No. 53-95.630 are preferred. Furthermore, compounds described in US Pat. No. 4,552,834 are also preferred. These bleach accelerators may be added during the cleaning period. These bleach accelerators are particularly effective when bleaching and fixing color photosensitive +4 materials for photography.

In addition to the above-mentioned compounds, the bleaching solution and bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach staining. Particularly preferred organic acids have an acid dissociation constant (pKa>2).
-5, specifically acetic acid, propionic acid, etc. are preferred.

Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used. Among them, ammonium thiosulfate is the most widely used. Further, combinations of thiosulfates, thiocyanates, 1,000-onythyl compounds, thiourea, etc. are also preferred. Preservatives for fixing solutions and bleach-fixing solutions include sulfites, bisulfites, and carbonyl bisulfites (1+
Preferred are the sulfinic acid compounds described in European Patent No. 29.1769Δ. Furthermore, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixing solution and bleach-fixing solution for the purpose of stabilizing the solution.

The total time of the desilvering process is preferably as short as possible without causing desilvering defects. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. In addition, the processing temperature is 25°C ~
50°C, preferably 35°C to 45'C. In a preferred temperature range, the degreasing speed increases and the occurrence of staining after treatment is effectively prevented.

In the desilvering step, it is preferable that stirring is possible and J strength is enhanced. Specific methods for strengthening stirring are described in JP-A-62-183460 and JP-A-62-18346.
The method of impinging a jet of processing liquid on the emulsion surface of the photosensitive 4A material described in No. 1, the 1-Gero method using a rotating means as described in JP-A No. 183461/1980, and the method of creating LJ in the liquid.
A method of improving the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with the wiper blade, which creates turbulence on the emulsion surface, increases the circulation flow rate of the entire processing solution. There are several methods. Such stirring direction means is effective for any of the bleaching solution, bleach-fixing solution, and fixing solution. It is believed that the direction of stirring speeds up the supply of the bleaching agent and fixing agent into the emulsion film, thereby increasing the desilvering rate. Furthermore, the agitation improvement means described above are more effective when a bleach accelerator is used, and the accelerating effect can be significantly increased and the fixing inhibiting effect caused by the bleach accelerator can be eliminated.

The automatic developing machine used for the photosensitive material of the present invention is
(No. 1-191257, No. 60-191258, No. 6
0-191. ．． It is preferable to have the photosensitive material valve feeding means described in No. 2.2.9. The above-mentioned Japanese Patent Application Publication No. 60-19
As described in No. 1.257, such a conveying means can significantly reduce the amount of processing liquid brought into the post bath from the front bath, and is highly effective in preventing deterioration of the performance of the processing liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is 1.1
o u r na l of the S'ociet
y of Motion r'1ture and
Te1evision Engineers Volume 64,
It can be determined by the method described in p. 248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of color photosensitive materials of the present invention, as a solution to these problems,
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288.838 can be used very effectively. Also, JP-A-57-8.542
Chlorine-based disinfectants such as isothiazolone compounds, thiahendazole, chlorinated sodium isocyanurate, and other benzo-1-lyazoles described in the issue, Hiroshi Horiguchi, "Chemistry of antibacterial and fungicidal agents J (1986), Sankyo Publishing. , Society of Hygiene Technology, Tai, "Microbial Sterilization, Disinfection, and Anti-Mildew Technology J (1982), Japan Society of Industrial Engineers, Japan Antibacterial and Antifungal Society, "Encyclopedia of Antibacterial and Antifungal Agents"
(1986) may also be used.

The pl+ of the washing water in the processing of the photosensitive material of the present invention is 4
-9, preferably 5-8. The washing water temperature and washing time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc.
Generally, a range of 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C is selected.

Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water.

In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-854
No. 3, No. 58-1.4834, No. 60-220345
All known methods described in this issue can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out; an example of this is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath for color photosensitive materials for photography. be able to. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite additives.

Various cleaning agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid from water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process.

In a process using an automatic processor or the like, when each of the above-mentioned processing liquids becomes monocondensed due to evaporation, it is preferable to add water to correct the concentration.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure 14, 85
0 and 15,159, aldol compounds described in 13,924, metal salt complexes described in U.S. Pat. No. 3,719,492, and JP-A-1983
-1.35628 can be mentioned.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-
Pyrazolidones may also be incorporated.

Typical compounds are JP-A-56-64339 and JP-A No. 57-
No. 144547 and No. 58-115438.

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, a temperature of 33°C to 38°C is standard, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. can be achieved.

In addition, West German Patent No. 2,226,7 was developed to save silver on photosensitive materials.
70 or U.S. Pat. No. 3,674,499 using Co/Nle I intensification or hydrogen peroxide intensification.

Further, the silver halide photosensitive material of the present invention is disclosed in U.S. Patent No. 4,
No. 500,626, JP-A-60-133449, No. 5
It can also be applied to heat-developable photosensitive materials such as those described in European Patent No. 9-218443, European Patent No. 61-238056, and European Patent No. 210,660 to No. 2.

(Left below) Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color brightening material, was prepared by applying layers having the compositions shown below.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/%, and for silver halide, the coating amount is expressed in terms of silver. However, for aggravating dyes, the coating amount is expressed in moles per mole of silver halide in the same layer.

(Sample 101) 1st layer (antihalation N) Black colloidal silver Silver 0.18 Gelatin 0.40 2nd layer (intermediate layer) 2.5-di-t-pentadecylhydroquinone 0.18E
-10,07 Eχ-30,02 1b /σ/ Enhanced dye■ Enhanced dye■ X-2 X-3 Sensitizing dye■ Sensitizing dye Eχ-3 Eχ-4 Eχ-2 B5-1 B5-2 Gelatin 6th layer (intermediate layer) Eχ-5 1,4X10-5 2.3X10-' 0.050 0.015 0 .060 1.30 Silver 1.60 5.4X10-' 1.4X10-s 2,, i X 10-' 0.010 0.080 0.097 0.22 0.10 1.63 0.0.10 B5-1 Gelatin 7th layer (first green emulsion N) Emulsion A Emulsion B Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ X-6 X-1 X-7 X-8 B5-1 HB S -3 Gelatin 8th layer (second green emulsion layer) Emulsion C Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ 0.020 0.80 0.15 Silver 0.15 3.0X10-5 1, OXl, O-'3.8X1.0-' 0.282 0.021 0.030 0.025 0.100 0.010 0.63 Silver 0.45 2, lX1O-5 7,0X10-5 2.6X10-' EX-6 EX-8 EX-7 B5-1 B5-3 Gelatin No. 9 Jii (third green-sensitive emulsion layer) Emulsion E Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ EX-13 EX-11 EX-1 B5 -1 B5-2 Gelatin 10th layer (yellow filter layer) Yellow colloidal silver EX, -5 0,102 0,018 0,026 0,,160 0,008 0,50 Silver 1.2 3.5X10-' 8 , OX] 0-5 3, OX 10-' 0.015 0.025 0.25 0, It') l, 54 Silver 0, O5 0,08 B5-1 Gelatin 11th layer (first blue-sensitive emulsion layer ) Emulsion A Emulsion B Emulsion F Enhanced dye ■ EX-9 EX-8 B5-1 Gelatin 12N (second blue-sensitive emulsion N) Emulsion G Enhanced dye ■ EX-9 EX-10 HB S -1 Gelatin 13th layer ( 3rd blue-sensitive emulsion layer) Emulsion H 0.03 0.95 Silver 0.08 Silver 0.07 Silver 0.07 3.5X10-' 0.721 0.042 0.28 1.10 1 0.45 2 , lXl0-' 0.154 0.007 0.05 0.78 0.77 /ρφ Sensitizing dye ■ EX-9 B5-1 Gelatin 14th layer (1 protection N) Emulsion I Silver HBS-] Gelatin 15th Layer (Second Capture N) Polymethylacryle -1-particles (diameter approximately 1.5 μm) Gelatin In addition to the above ingredients, -Giu H-1 and a surfactant were added to each gelatin layer.

2? ×10−′ 0.07 0.69 0.5 0.11 0.17 1.00 0.54 0.20 1.20 Chin hardening side 765″ EX-1 EX-2 EX-3 EX-7 EX EX-9 /θ8 I EX-4 EX-5 EX EX EX 1-4 (←) /θ7 //// Eχ Sensitizing dye■ Sensitizing dye■ Exacerbating pigment■ χ:y 30 (lft%) V B.S. to licresyl phosphate Di-n-butyl phthalate //3 Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Exacerbating pigment■ Comparison coupler (1) Month Cl(.

C)1. =[;l-1-SOx UHz LU
Table 1 shows samples in which EX-6 couplers in the 7th and 8th layers of Sample 101 were combined with various additives of the present invention, and samples in which EX-6 couplers were replaced with other couplers, similar to N-Zuki-L112. Created as follows.

These samples were exposed to wedge light according to a conventional method and processed according to the processing method shown below, and the photographic properties and occurrence of staining over time were evaluated and shown in Table 1.

Processing method processing time 2 minutes 30 seconds 3 minutes 00 seconds 20 seconds 20 seconds 20 seconds 50 seconds Processing temperature 40”C 40’C 56C 35″0 35″C 65’C Processing process color development bleach fixing Washing with water (1) Washing with water (2) stability drying ／〆Otsu Next, the composition of the treatment liquid will be described.

(Color developer) Diethylenetriaminepentaacetic acid 1-hydroxyethylidene 1.1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-(N-ethyl-N-β hydroxyethylamino) 2-Methylaniline Add sulfate solution H (bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate Ethylenediaminetetrahydric acid diodium salt (unit: g) 2.0 3.0 4.0 30.0 1.4 1.5 mg 2.4 4.5 1.0 °C 10.05 (Unit: g) 90.0 //7 Sodium sulfite ammonium thiosulfate water soluble? l (70%) Acetic acid (98%) Bleach accelerator 12.0 260.0 m! 5.0m9゜Add 0.01 mol water 1.0! P
H6,0 (Washing solution and tap water were mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B, manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-400, manufactured by Rohm and Haas).
Water was passed through a mixed-bed column packed with water to reduce the concentration of calcium and magnesium ions to 3 mg/l or less, and then 20 mg/ffi of sodium incyasulate dichloride and 0.15 g/l of sodium sulfate were added.

The pH of this liquid was in the range of 6.5 to 7.5.

(Stabilizer) (Unit: g) Formalin (37%) 2.0 m!
Polyoxyethylene-p -0,3 Monononylphenylethyl (average degree of polymerization 10) Ethylenediaminetetraacetic acid dis 0.05 Add thorium salt water 1, O! p
H5,0-8,0 As shown in Table 1, the magenta coupler of the present invention is an excellent coupler in that high color density can be obtained, but magentastin was generated in unexposed areas after development. However, when the additive of the present invention was added, the occurrence of magentastin could be significantly suppressed.

Further, even when the processing method was changed to the following method, the photographic behavior, the occurrence of magentastin, and the suppressing behavior thereof were almost the same.

Processing method Processing time Processing temperature 3 minutes 15 seconds 3800 6 minutes 30 seconds 3B’C 2 minutes 10 seconds 35°C Processing process color development bleached white Water washing Arrival: 4 minutes 20 seconds Washing with water (+) 1 minute 05 seconds Washing with water (2) 1 minute OO seconds Stable 1 minute 05 seconds Drying 4 minutes 20 seconds Next, the composition of the treatment liquid will be described.

(color developer) diethylenetriaminepentaacetic acid 1-hydroxyedylidene 1.1-diphosphonic acid 1-lium sulfite potassium carbonate potassium bromide potassium iodide Hydroxylamine sulfate 1 salt 4-(N-ethyl-N-β hydroxyethylamino) 2-Methylaniline sulfate salt add water 38°C 35”C 35°C 38°C 55°C (g) 1.0 3.0 30.0 1.4 1.5 mg 2.4 4.5 1.0! /2. Z /23 T) + ( (Bleach Y Night) Endyenediamine tetrahedral acid iron sodium trihydrate Ethylenediaminetetraacetic acid dibasic acid thorium salt ammonium bromide ammonium nitrate Ammonium water (27%) add water H (Fixed &,) Endylenediamine tetrahedral acid nina thorium salt 1-lium sulfite sodium bisulfite Ammonyl thiosulfate 1, water Solution (70%) add water 9cho 1 (g) ], 00.0 10.0 140.0 30.0 6.5mj! 1.0! 6.0 (g) 0.5 7.0 5.0 ], 70.0 mE 1-, ON.

(Washing liquid) Tap water is passed through a hot bed column filled with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite JR-400 manufactured by Rohm and Haas). and calcium and magnesium ion concentration to 3mg/I! , followed by treatment with sodium isocyanurate dichloride 20/1. and 1.5g/I of sulfuric acid and lithium! , was added.

The pH of this liquid was in the range of 6.5 to 7.5.

(Stable 1) (g) Formalin (37%) 2. Omp.

Polyoxyethylene-p -0,3 Monononylphenyl ethyl (average degree of polymerization 10) Ethylenediaminetetraacetic acid 0.05 Add distrium salt water 1.0 /! p
)I
5.0-8.0 Example 2 Each layer having the composition shown below was coated on a subbed cellulose triacetate film support to prepare a multilayer color light-sensitive material.

(Photosensitive layer composition) The numbers for each component indicate the coating amount in g/rd units, and for silver halide (emulsion), the coating amount in terms of silver. However, for sensitizing dyes, rlg /
Expressed in rtT units and for high boiling organic solvents (HBS) in cc/rrT units.

(Gonshikiryo 201) 1st layer (antihalation layer) Black colloidal silver 0.25
Gelatin N containing U-10,04 U-20,10 IJ-30,10 HBS-10,10 (dry film thickness 2 μm) Second layer (middle N) H-10,05 Containing HBS-20,05 Gelatin layer (dry thickness 1 μm) 3rd layer (first red-sensitive emulsion layer) Emulsion A 0.50 (
Monodisperse silver iodobromide emulsion, iodine content 4 mol%, cubic,
Average particle size 0.3 μm, s/r=0.15) Sensitizing dye S-11,40 Sensitizing dye S-20,06 C-10,20 /21 x7 C-20,05 H-10,01 HBS Gelatin layer containing -20,12 (dry film thickness 1 μm) 4th layer (second red-sensitive emulsion layer) Emulsion B O,80
(Monodisperse silver iodobromide emulsion, iodine content 2.5 mol%, 1
Tetrahedral, average particle size 0.55 μm, s/r =0.
15) Sensitizing dye S-11,60 Sensitizing dye S-2 0.06C-
10,55 C-20,14 HBS Gelatin N containing S-20,33 (dry film thickness 2.5 μm) 5th layer (intermediate layer) H-10,10 Gelatin layer containing HBS-20,10 (dry film y'11 μm) 6th layer (1st
Green-sensitive emulsion layer) Emulsion CO,70 (Silver iodobromide emulsion, iodine content 3 mol%, average grain size 0.3 μm) Sensitizing dye S-33,30 Sensitizing dye S-41,50 C-30, Gelatin layer containing π 1 (-10,01 HB S -20,26 (dry film thickness 1 μm) 7th layer (second green-sensitive emulsion layer) Emulsion D 0.70 (
Tabular silver iodobromide emulsion, iodine content 2.5 mol%, grains with a diameter/thickness ratio of 5 or more account for 50% of the projected area of all grains.
, average particle size O,]8 μm sensitizing dye S-31,3
0 Sensitizing dye S-40,50 C-40,25 1 (Gelatin layer containing B S -20,05 (dry film thickness 2.5 μm) 8th layer (intermediate layer) H-10,05 HB S-20 , 10 gelatin layer (dry film thickness 1 μm) 9th layer (yellow filter N) Yellow colloidal silver 0.10H-
Gelatin layer containing 10,02 1(-20,03 HB S-20,f)4 (dry film thickness μm) 1st O layer (1st blue emulsion N) Emulsion E O,60(
Silver iodobromide emulsion, iodine content 2.5 mol%, average grain size 0.7 μm) Gelatin N containing sensitizing dye S-51,00 C-50,50 14BS-20,10 (dry film W 1.5 μm) ) 11th layer (second blue emulsion layer) Emulsion F 1.10 (
Tabular silver iodobromide emulsion, iodine content 2.5 mol%, grains with a diameter/thickness ratio of 5 or more account for 50% of the projected area of all grains.
, average particle thickness 0.13 μm) Gelatin layer containing sensitizing dye S-51,70 C-51,20 HBS-20,23 (dry film thickness 3 μm) 12th layer (first protective layer) U-10,02 U-20,03 U-30,03 0-40,29 1 (Gelatin N containing BS-10,28 (dry film thickness 2 μm) 13th layer (second protection N) Emulsion G O,10
(Fine-grain silver iodobromide emulsion with a fogged surface, iodine content 1 mol%, average grain size 0.06 μm) Polymethyl acrylate-1 grains (diameter approx. 1.5 μm) 0.5
In addition to the above components, gelatin hardening agent 1-13 and a surfactant were added to each gelatin layer (dry thickness: 0.8 μm) containing 413θ /31 .

H H /33 L ONH /3tI- H D] Cl]++=C11SOzC)lzcf)↑l1lCI
I□CHz4HSOzCHzCONIICNz / 3rd evening BS ■ BS /37 (C112) as(h ''' 3g Similarly, the 6N C-3 coupler of sample 201 was changed or the additives of the present invention were used in various combinations. Samples 202 to 215 were prepared as shown in Table 2.

Each sample prepared as described above was exposed to light according to a conventional method, and then subjected to the reversal process described below to evaluate its photographic properties. The evaluation results are shown in Table 2.

Processing method - Development 6 minutes 38°C First washing 45 seconds 38 Inversion 45 38 I1 color development 6 minutes 38 Bleach 2 38 Bleach-fixing 4 38 t3 Second washing (1) Second Washing (2) The composition of each treatment solution was as follows.

Nitrilo-N N N-1-Rimethylenephosphonic acid pentasodium salt Sodium sulfite Hydroquinone Potassium monosulfonate Potassium carbonate 1-phenyl-4-methyl-4 Hydroxymethyl-3-pyrazolidone Potassium bromide Potassium thiocyanate Potassium iodide 2.0 g 0 g 0 g 3 g 2.0 g 2.5 g 1.2 g 2.0 mg 1000 ml pH 9.60 The pH was adjusted with hydrochloric acid or potassium hydroxide.

2.0 g of ethylenediaminetetramethylene 5.0 g of disodium phosphonate phosphate
Ete 1000se p H7,
00 pH was adjusted with hydrochloric acid or sodium hydroxide.

Inversion number nitrilo-N, NN-1-rimethyl without pH adjustment 3. Phosphonic acid, 5-1-lium salt, stannous chloride, dihydrate, p-aminophenol, 1.0 grams, 1 g, sodium hydroxide, and glacial acetic acid. 8g 15mj! 1000 Se 6,00 I calmed down with thorium.

Nitrilo-N,N,N-trimethylenephosphonic acid, pentasodium salt, sodium sulfite, trisodium phosphate, dodecahydrate, potassium bromide, potassium iodide, sodium hydroxide, N-ethyl citrazate, N-(β-methanesulfonamide). ethyl)-3-methyl-4-aminoaniline sulfate 2.0 g 7.0 g 6 g 1.0 g 0 mg 3.0 g 1.5 g 1 g lψnlψ3 3.6-cythiaoctane-1.8 - Add 1.0g diol and adjust pH to 1000
1,80 pn was prepared with hydrochloric acid or potassium hydroxide.

Ethylenediaminetetraacetic acid 2 sl-10.0g Lium salt dihydrate Ethylenediaminetetraacetic acid F e , (Iff) 1
20 g ammonium dichloroammonium bromide 100 g ammonium nitrate 10. g Bleach accelerator o, oos Molar pH 6.30 p■4 was adjusted with hydrochloric acid or aqueous ammonia.

Returned ethylenediaminetetraacetic acid/Fe() 50g/ammonium/dihydrate ethylenediaminetetraacetic acid/2 sodium 5. Add Oglium dihydrate ammonium thiosulfate 80 g and sodium sulfite 12.0 g to 1000 mlp H6,
60 pH was adjusted with hydrochloric acid or aqueous ammonia.

1; 1 JL of water Tap water was poured into a mixed bed column filled with I (strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and an OH anion exchange resin (Amberlite TR-400)). Water was passed through the solution to reduce the concentration of calcium and magnesium ions to 3 mg/42 or below, and then 20 mg/f of sodium dichloride isocyanurate and 1.5 g/f of sodium sulfate were added.The pH of this solution
is in the range of 65 to 7.5.

Yellow formalin (37%) Polyoxyethylene-P-monononyl ether (average degree of polymerization 10) H5.0 0.5 ml 1000 ml! As shown in Table 2, even in reversal development processing, by using the coupler of the present invention and the anti-fading agent of the present invention, macentastin can be significantly reduced while maintaining a sharp color density. I can see that the numbers are decreasing.

Example 3 A multilayer color photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows. This was designated as sample 301.

19.1 g of yellow coupler (Ex Y), 4.4 g of color image stabilizer (Cpd-1) and color image stabilizer (C
27.2 cc of ethyl acetate and 8.2 g of solvent (Solv-1) were added to 0.7 g of pd-7) and dissolved. Add 8 cc of 10% sodium dodecylhenzenesulfonate to the solution.
The mixture was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution. On the other hand, silver chlorobromide emulsion (cubic, average grain size 0.8
8μ, coefficient of variation of grain size distribution 0.08, and the grain surface contains 0.2 mol% of silver bromide as a proportion of the whole grain), and the following blue-sensitive sensitizing dyes were added to the grains at 2.0 μm per mol of silver, respectively.
A sulfur sensitized version was prepared after adding 0x10-' moles. Mixing and dissolving the emulsified dispersion and this emulsion,
A first layer coating solution was prepared to have the composition shown below.

Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. As the gelatin thickening agent for each layer, 1oxy-3,5-dichloro-s-triazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer. l tall Ta.

Blue-sensitive emulsion layer Green-sensitive emulsion layer (halogen ([4. OXl0-' mol per 1 mol) and (cnzL (CI(2): 1 So3+1.N(Czlls) (2. OX 104 each per mol of silver halide) mole) 0z SO3H' N(Cztls), l (7.0X10-5 mole per mole of halogenated compound)
/! ;t Red-sensitive emulsion layer (1 mole of halogenated compound: 0.9
2.6 x 10-3 mole per mole of silver genide and repellency u
LJko.

In addition, the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-light emulsion layer [for each layer, 1-(5-methylureidophenyl)5-mercabutotetradules were added at 8% per mole of silver chloride, 5X10-s mol, 7.7X10-' mol, 2,
5 x 10-' moles were added.

Further, ixto-' mol and 2X10-' mol of 4hydroxy-6-methyl-L3.3aT tetrazaindene were added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer, respectively, per 5.1 mol of halogenation.

The following dyes were added to the emulsion layer to prevent irradiation.

and Burn/13 (Layer composition) The composition of each layer is shown below. The numbers represent the coating amount (g/M). The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the i-4 side contains white face j4 (TiO□) and bluish dye ¥4 (ulmarine blue)] -th layer (blue-sensitive layer) The above-mentioned silver chlorobromide emulsion 0.30 Gelachi 7+,,86 Yellow Kabra (ExY) 0.82
Color image stabilizer (CP d, -1,,) 0
．． 19 solvent (S o 1. v-1)
0.35 color image stabilizer (cpa-de)
0.06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (
SoI v-1) 0.16 Solvent (SoRa 4) 0.08 Third layer (green sensitive layer) Silver chlorobromide emulsion (cubic, average grain size 0.55μ and 039μ 1: 3 (Ag molar ratio), the coefficient of variation of particle size distribution is 0.10 and 0.08, respectively.
, each # contains 0.8 mol% of AgBr localized on the particle surface as a percentage of the entire particle) 0.12 gelatin
1.24 magenta coupler (
ExM) 0.27 color image stabilizer (CPd-
3) O, 1, 5? Container (Sol
v-2)
0.54 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.4.1 Color mixture prevention agent (Cpd-5) 0.05? container
(Sol v-5,)
0.24 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic, average grain size of 0.58μ and 0.45μ mixed in a ratio of 1:4 (Ag molar ratio),
The coefficient of variation of particle size distribution is 0.09 and 0.1, respectively.
1. Each A g B r 0.6 as a proportion of the whole particle
0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer CCpd-6) 0.17 Color image stabilizer (Cpd4) 0.04 Color image Stabilizer (
Cpd-7) 0.40? Container (S
oIv-6)
0.15 Sixth layer (ultraviolet absorption layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (S
o I v-5) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic of polyvinyl alcohol 0.1 Fully modified copolymer (degree of modification 17%) Liquid paraffin-0.03 Engraving of specification (EXY ) Yellow coupler (ExM) Magenta coupler (ExC) Cyan coupler (Cpd 3) Color image stabilizer R=CJs C,lI.

(Cpd 5) Color mixing prevention agent (Cpd ■) Color image stabilizer l building /Bo (Cp, d 6) Color image stabilizer CI! .

2:4 4 mixture (weight ratio) (Cpd 7) Color image stabilizer (C) 12-C) I)-4 CONHC4) 1q(t) Average molecular weight 60,000 /60 (Solv-1) Solvent (Solv 2) Solvent (Solv-3) Solvent (Solv-4) Solvent/l (Cpd H (UV 1) 4-4 mixture (weight ratio) of ultraviolet absorber (weight ratio)/〆1 (So, lv 5) ?Volume C00C++Lt ( cHz)a COOC8H17/43 Sample 1 in which the additive of the present invention was added to the green sensitive layer of Sample 301 in combination with magenta coupler (ExM), and samples in which the magenta coupler was changed were prepared as shown in Table 3.

The name plate tq prepared as described above was exposed to wedge light according to a conventional method and processed by the processing method shown in F (chemical formula 1-1 liquid is a tank liquid), and the photographic properties thereof were evaluated and shown in Table 3.

Processing method ILIJ i Branch Time reading - Sleeve - Light amount Tough volume, amount Color development 38'C55 seconds 65mQ
6ff bleach fixing 30-36'C45 seconds 161
．． me 8P rinse ■ 30-37°C 20 seconds
-41゜Rinse■ 30~37"C20 seconds
-4! Rinse ■ 30~37°C 20 seconds -4i
Rinse ■ 30-37'C 30 seconds 20 (jrnff
41-Drying at 70-80°C for 60 seconds per 1rrf of photosensitive material (4-tank countercurrent method from rinsing ■ to ■) The composition of each processing solution is as follows.

)-Rani developer water ethylenediamine-N N NN-tetramethylenephosphonic acid triethylenediamine (1 4-diazapinoclo[2] potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4 aminoaniline sulfuric acid Salt diethylhydroxylamine optical brightener (4,4'-diaminostilhen pH (25'C) by adding water .0 g 6.0g +000mff1 ]0000m N10 (1510,85 1tl- 71g 1 liquid (tank liquid and refill liquid are the same) Water
400 mρ1000 ammonium sulfate (70%) ioomQ sodium sulfite 1'1G ethylenediaminetetraacetate iron (Ill) ammonium
5Eig ethylenediaminetetraacetic acid diss[-lium 5g ammonium bromide 40g -1--wood vinegar 1. '−'−,−,−1−9 Add water
], 000 mρpH (25”C)
' 5.40 IJ-y base - (tank liquid and replenisher are the same) ion-exchanged water (calcium-magnesiva) 1, each b 3 ppm or less) As shown in Table 3, the magenta coupler of the present invention has the highest color density. Although it is an excellent coupler in that it has a high chromatography, magenta staining occurs in unexposed areas after processing, which is a fatal defect in color photographs, especially color photographic paper, but it is not suitable for books. By adding the additive of the invention, it was possible to greatly suppress the occurrence of magentastin. What is interesting is that under the forced conditions of 80°C and 70'' ARH, the compound represented by formula (■) is slightly less effective than the compound represented by general formula (1), but when aged at room temperature, on the contrary, it is more effective. It is a visible point.-Formula (1
) and the compound of general formula (III) are most effective when used together.

The comparative coupler is inferior to the combination of the inventive coupler and the inventive additive in not only lower color density but also slightly less effect of the inventive additive.

(Effects of the Invention) Color light-sensitive materials using the coupler of the present invention in combination with the additive of the present invention are excellent in providing fast color density and high maximum color density, and at the same time, magenta which often occurs due to rapid processing, This photosensitive material has an unprecedented feature in that it can also suppress staining.

Claims (1)

[Claims] A pyrazoloazole coupler having at least one carboxyl group or a salt thereof, and the following general formula (I):
A silver halide color photographic material containing at least one compound represented by , (II) or (III). General formula (I) R_1-(A)_n-X General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 and R_2 are aliphatic groups, aromatic groups,
Or represents a heterocyclic group. X represents a group that reacts with an aromatic amine developer and leaves the group, and A represents a group that reacts with an aromatic amine developer to form a chemical bond. n represents 1 or 0. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y represents a group that promotes addition of an aromatic amine developer to the compound of general formula (II). represents. Here, R_1 and X, Y and R_2, or B may be combined with each other to form a cyclic structure. General formula (III) R-Z In the formula, R represents an aliphatic group, an aromatic group or a heterocyclic group. Z represents a nucleophilic group or a group that decomposes in the photosensitive material to release a nucleophilic group.