JPH05281677A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide color photographic sensitive material superior in color development and reproduction performances and storage stability of the photosensitive material and high in sensitivity and improved in desilverability CONSTITUTION:The silver halide color photographic sensitive material contains a compound to be allowed to release a bleach promoter by reaction with the Oxidation product of an aromatic primary amine color developing agent and a coupler represented by formula in which R<1> is H or a substituent; R<2> is a substituent; X is H or a group to be released by coupling; and Z<1> is a nonmetallic atomic group necessary to form an N-containing 6-membered heterocyclic ring having at least one dissociable group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material having high sensitivity and good color reproducibility and desilvering property.

[0002]

2. Description of the Related Art The exposed aromatic silver halide as an oxidant reacts with the oxidized aromatic primary amine type color developing agent and the coupler to give indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine. It is well known that a color image is formed by forming a dye and a dye similar thereto. In such a photographic system, a subtractive color method is used, and a color image is formed by yellow, magenta and cyan dyes.

Of these, phenol or naphthol couplers are generally used for forming a cyan dye image. However, since these couplers have an unfavorable absorption in the green region, they have a serious problem of significantly reducing color reproducibility, and it is desired to solve these problems.
As a means for solving this problem, US Pat. No. 4,8
73,183, pyrazoloazoles, EP24
Cyan couplers such as 2,4-diphenylimidazoles described in 9,453A2 have been proposed. The dyes formed from these couplers have less unfavorable absorption on the short-wave side than the conventional dyes, which is preferable for color reproduction. However, these couplers cannot be said to have sufficient color reproducibility, have low coupling activity, and have extremely low fastness to heat and light,
Further, when a developing treatment is carried out using a processing solution having a weak oxidative bleaching ability or a processing solution having a tired bleaching ability (a bleaching solution or a bleach-fixing solution), a decrease in color density occurs. The above problem remains. In addition, pyrazoloimidazoles are proposed in US Pat. No. 4,728,598. These couplers had improved coupling activity, but were insufficient in terms of hue.

Further, EP-0456226A1 proposes pyrrolopyrazoles. These couplers have some improvement in the fastness to heat and light of the dye formed, but further improvement in color reproducibility is desired. Further, since these couplers themselves do not have sufficient stability, there is room for improvement in terms of reduction in color density due to long-term storage of the light-sensitive material.

Further, these couplers have a problem that they cause a decrease in sensitivity. On the other hand, a silver halide color photographic light-sensitive material is basically processed by a color development step and a desilvering step. In the color developing step, the silver halide exposed by the color developing agent is reduced to produce silver, and the oxidized color developing agent reacts with the color developing agent (coupler) to give a dye image. The silver formed here is oxidized by a bleaching agent in the subsequent desilvering step, and further converted to a soluble silver complex by the action of a fixing agent and dissolved and removed.

In recent years, in the industry, speeding up of processing,
That is, there is a strong demand for shortening the processing time, and in particular, shortening the desilvering process, which occupies nearly half of the processing time, is a major issue.

As a means for shortening the desilvering process, a method of adding a bleaching accelerating compound to a light-sensitive material, a color developing bath, a bleaching bath or a bleach-fixing bath has been known for a long time. Representative bleach accelerators are, for example, US Pat.
No. 893,858, British Patent No. 1138842, various mercapto compounds as described in JP-A-53-141623, JP-A-53-956.
No. 30, a compound having a disulfide bond, a thiazolidine derivative as described in JP-B-53-9854, JP-A-53-94927.
Isothiourea derivatives as described in JP-B No. 45-8506, and thiourea derivatives as described in JP-B-49-26586, JP-A-49-
No. 42349, a thioamide compound as described in JP-A-55-26506, U.S. Pat. No. 4,552,834.
And arylene diamine compounds as described in the specification.

However, these methods have the drawbacks that the photographic performance is affected (for example, fog and desensitization), and the bleaching accelerator is easily deactivated. Another way to increase bleaching power is Research Disclosure Item No. 24241.
No. 1114949 and JP-A No. 61-201247 describe a bleach accelerating compound-releasing coupler. The use of a silver halide color photographic light-sensitive material containing such a bleach accelerating compound-releasing coupler can remove the bleach-accelerating compound-releasing coupler. It is known that the silver property is improved, and even if the bleaching process is performed for a short time, the occurrence of color turbidity can be suppressed to some extent.

[0009]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a silver halide color photographic light-sensitive material which is excellent in color developability, color reproducibility, storability of a light-sensitive material, high sensitivity and improved desilvering property. To provide.

[0010]

The objects of the present invention have been achieved by the following silver halide color photographic light-sensitive materials.

That is, in a silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, it reacts with an oxidant of an aromatic primary amine developing agent to accelerate bleaching. At least 1 releasing agent
Silver halide color photographic light-sensitive material, containing at least one coupler and at least one coupler represented by the following general formula (I). General formula (I)

[0012]

[Chemical 2]

In the general formula (I), R ¹ represents a hydrogen atom or a substituent, R ² represents a substituent, and X represents
A hydrogen atom or a group capable of splitting off in the coupling reaction with an oxidized product of a color developing agent is represented, and Z ¹ is a non-metal atom group necessary for forming a nitrogen-containing 6-membered heterocycle. However, the heterocycle has at least one dissociative group. Hereinafter, the compound which releases a bleaching agent by reacting with an oxidized product of the aromatic primary amine developing agent of the present invention will be described.

The bleach accelerator releasing compound used in the present invention is
Preferably, it can be represented by the following general formula (B).

The general formula (B) A- (L ₁ ) _k -Z A represents a group which cleaves (L ₁ ) _k -Z by reacting with an oxidized product of a developing agent, and L ₁ is a bond with A. Represents a group that cleaves Z, then k represents 0 or 1 and Z represents a bleaching accelerator.

Next, the general formula (B) will be described.

In the general formula (B), A specifically represents a coupler residue or a redox group.

Examples of the coupler residue represented by A include yellow coupler residues (eg, open-chain ketomethylene type coupler residues such as acylacetanilide and malondianilide), magenta coupler residues (eg 5-pyrazolone type, pyrazolotriazole). Type or an imidazopyrazole type coupler residue), a cyan coupler residue (for example, phenol type, naphthol type, imidazole type or the same type as described in European Patent Publication 249,453).
No. 4,001, such as a pyrazolopyrimidine type coupler residue) and a colorless coupler residue (for example, an indanone type or acetophenone type coupler residue). Also, U.S. Pat. Nos. 4,315,070, 4,183,752, 4,174,969, 3,961,959, 4,171,223 or JP-A-52-82423. It may be a heterocyclic coupler residue described in No.

When A represents a redox group, the redox group is a group which can be cross-oxidized by an oxidized product of a developing agent, and examples thereof include hydroquinones, catechols, pyrogallols, 1,4-naphthohydroquinones, 1 , 2-naphthohydroquinones, sulfonamide phenols,
Examples include hydrazides or sulfonamide naphthols. These groups are specifically described in, for example, JP-A-61-2.
30135, 62-251746, 61-27.
8852, 62-260153, and JP-A-2-93.
454, U.S. Pat. Nos. 3,364,022 and 3,3.
79,529, 3,639,417, 4,68
4,604 or J.Org.Chem., 29,588 (19
64).

In the general formula (B), L ₁ is preferably the following. (1) Group utilizing cleavage reaction of hemiacetal For example, US Pat. No. 4,146,396, JP-A-60-
No. 249148 and No. 60-249149, which are groups represented by the following general formula. Here, the * mark represents the position of bonding with A of the compound represented by the general formula (B), and the ** mark represents the position of bonding with Z. Formula (T-1) * - ( W-CR 11 (R 12)) t - ** In formula, W is an oxygen atom, a sulfur atom or -NR ₁₃ - represents a group, R ₁₁ and R ₁₂ are a hydrogen atom Or a substituent, R ₁₃ represents a substituent, and t represents 1 or 2.
When t is 2, two -W-CR ₁₁ (R ₁₂ ) represent the same or different. When R ₁₁ and R ₁₂ represent a substituent and typical examples of R ₁₃ are R ₁₅ group and R ₁₃ respectively.
Examples thereof include a ₁₅ CO- group, an R ₁₅ SO ₂ -group, an R ₁₅ (R ₁₆ ) NCO- group and an R ₁₅ (R ₁₆ ) NSO ₂ -group. Here, R ₁₅ represents an aliphatic group, an aromatic group or a heterocyclic group, and R _15
16 represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. The case where each of R ₁₁ , R ₁₂ and R ₁₃ represents a divalent group and is linked to form a cyclic structure is also included. Specific examples of the group represented by formula (T-1) include groups represented by the following "Chemical Formula 3" to "Chemical Formula 5".

[0021]

[Chemical 3]

[0022]

[Chemical 4]

[0023]

[Chemical 5]

(2) Group that causes cleavage reaction by utilizing intramolecular nucleophilic substitution reaction For example, a timing group described in US Pat. No. 4,248,292 can be mentioned. It can be represented by the following general formula. General formula (T-2) * -Nu-Link-E-** In the formula, * and ** have the same meanings as described for general formula (T-1), and Nu represents a nucleophilic group. Represents an example of a nucleophilic species such as an oxygen atom or a sulfur atom, E represents an electrophilic group, and is a group capable of undergoing a nucleophilic attack from Nu to cleave the bond with the ** mark, and Link represents that Nu and E are Represents a linking group that is sterically related so that it can undergo an intramolecular nucleophilic substitution reaction. Specific examples of the group represented by formula (T-2) include those represented by the following "Chemical formula 6" and "Chemical formula 7".

[0025]

[Chemical 6]

[0026]

[Chemical 7]

(3) A group which causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system, for example, US Pat. Nos. 4,409,323 and 4,42.
1,845, JP-A-57-188035, 58-
98728, 58-209736, 58-20.
9737, 58-209738, etc.,
It is a group represented by the general formula (T-3) represented by the following "Chemical Formula 8".

[0028]

[Chemical 8]

In the formula, *, **, W, R ₁₁ , R ₁₂ and t have the same meanings as described for (T-1). However, R ₁₁ and R ₁₂ may bond to each other to form a benzene ring or a heterocyclic ring. Further, R ₁₁ or R ₁₂ and W may combine with each other to form a benzene ring or a heterocycle. Z ₁ and Z ₂ each independently represent a carbon atom or a nitrogen atom, and x and y represent 0 or 1. When Z ₁ is a carbon atom, x is 1, and when Z ₁ is a nitrogen atom, x is 0. The relationship between Z ₂ and y is the same as the relationship between Z ₁ and x. Also, t represents 1 or 2,
t is two in the case of 2 - _{[Z 1 (R 11) x =} Z 2 (R 12) y ]
The-may be the same or different. The -CH ₂ adjacent to the mark ** - group may be substituted with an alkyl group or a phenyl group having 1 to 6 carbon atoms.

[Chemical formula 9] to [Chemical formula 12] below (T-
Specific examples of 3) will be given.

[0031]

[Chemical 9]

[0032]

[Chemical 10]

[0033]

[Chemical 11]

[0034]

[Chemical 12]

(4) Group Utilizing Cleavage Reaction by Hydrolysis of Ester For example, the following groups are the connecting groups described in West German Laid-Open Patent No. 2,626,315. In the formula, asterisks and asterisks have the same meanings as described for the general formula (T-1). General Formula (T-4) * -OCO-** General Formula (T-5) * -SCS-** (5) Group Utilizing Cleavage Reaction of Iminoketal For example, described in U.S. Pat. No. 4,546,073. It is a certain linking group, and is represented by the general formula (T-
It is a group represented by 6).

[0036]

[Chemical 13]

In the formula, *, ** and W are general formulas (T
-1) has the same meaning as described above, and R ₁₄ is R
It has the same meaning as ₁₃ . Specific examples of the group represented by formula (T-6) include groups represented by the following "Chemical Formula 14".

[0038]

[Chemical 14]

(6) A compound that becomes a coupler residue or a redox group after being cleaved from A. For example, JP-A-63-21
No. 4752 represented by B in the general formula (I), more preferably a redox group. In the general formula (B), L ₁ is preferably (T-1) to (T-5).
And particularly preferably (T-1) (T
-3) and (T-4).

The group represented by Z in the general formula (B) includes, in detail, a known bleaching accelerator group. For example, U.S. Pat. No. 3,893,858, British Patent No. 1138842, JP-A-53-141623.
Various mercapto compounds as described in Japanese Patent Publication No.
Compounds having a disulfide bond as described in JP-A-53-95630, JP-B-53-9854
Thiazolidine derivatives as described in JP-B No. 53-94927, isothiourea derivatives as described in JP-A-53-94927, JP-B-45-8506, and JP-B-4.
9-26586, a thiourea derivative as described in JP-A-49-42349, a thioamide compound as described in JP-A-55-26506, and a dithiocarbamate salt as described in JP-A-55-26506. An arylenediamine compound as described in US Pat. No. 4,552,834. These compounds have a substitutable heteroatom contained in the molecule,
It is a preferred example to bond with A- (L ₁ ) _k- in the general formula (B).

The group represented by Z is preferably a group represented by the following general formula (V), (VI) or (VII).

[0042]

[Chemical 15]

In the formula, the * mark represents the position at which it bonds with A- (L ₁ ) _k- , R ₃₁ represents a divalent aliphatic group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, and R ₃₂ represents R _32. A group having the same meaning as R ₃₁ ,
Represents a divalent aromatic group having 6 to 10 carbon atoms or a divalent heterocyclic group having a 3- to 8-membered ring, preferably a 5- or 6-membered ring, and X ₁ represents -O-, -S-,-. COO-, -SO _{2
-, - NR 33 -, -} NR 33 -CO -, - NR 33 -SO 2
-, -S-CO-, -CO-, -NR ₃₃ -COO-,-
_{N = CR 33 -, - NR} 33 CO-NR 34 -, or -NR
₃₃ SO ₂ NR ₃₄ — group, X ₂ represents an aromatic group having 6 to 10 carbon atoms, X ₃ is a 3-membered to 8-membered ring having at least one carbon atom bonded to S in the ring. And preferably represents a 5- or 6-membered heterocyclic group, Y ₁ is a carboxyl group or a salt thereof, a sulfo group or a salt thereof,
A hydroxyl group, a phosphonic acid group or a salt thereof, an amino group (which may be substituted with an aliphatic group having 1 to 4 carbon atoms),-
NHSO ₂ —R ₃₅ or —SO ₂ NH—R ₃₅ group (salt means sodium salt, potassium salt, ammonium salt or the like), and Y ₂ has the same meaning as described for Y _1. Alternatively, it represents a hydrogen atom, r represents 0 or 1, i represents an integer of 0 to 4, j represents an integer of 1 to 4, and k represents an integer of 0 to 4. However, j Y ₁ is R ₃₁ − {(X ₁ ) _r −R ₃₂ } _i
And X ₂ -{(X ₁ ) _r −R ₃₂ } _i are bonded at substitutable positions, and k Y ₁ are X ₃ − {(X ₁ ) _r −R ₃₂ }.
_When bonded to a substitutable position of _i , when k and j are plural, k and j Y ₁ 's each represent the same or different, and when i is plural, i (X ₁ ) _r- R ₃₂ Represents the same or different. Where R ₃₃ and R ₃₄
And R ₃₅ each represents a hydrogen atom or an aliphatic group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms. When R ₃₁ to R ₃₅ represent an aliphatic group, they may be linear or cyclic, linear or branched, saturated or unsaturated, substituted or unsubstituted. Although it is preferably unsubstituted, examples of the substituent include a halogen atom, an alkoxy group (eg, methoxy, ethoxy), and an alkylthio group (eg, methylthio, ethylthio).

The aromatic group represented by X ₂ and the aromatic group when R ₃₂ represents an aromatic group may have a substituent. Examples of the substituent include those enumerated as the aliphatic group substituents.

The heterocyclic group represented by X ₃ and the heterocyclic group when R ₃₂ represents a heterocyclic group are a saturated or unsaturated, substituted or unsubstituted heterocyclic group having an oxygen atom, a sulfur atom or a nitrogen atom as a hetero atom. It is a cyclic group. For example, pyridine, imidazole, piperidine, oxirane,
Mention may be made of sulfolane, imidazolidine, thiazepine or pyrazole. Examples of the substituent include those enumerated above as the aliphatic group substituents.

Specific examples of the group represented by the general formula (V) include the following.

[0047]

[Chemical 16]

[0048]

[Chemical 17]

Specific examples of the group represented by the general formula (VI) include the followings.

[0050]

[Chemical 18]

Specific examples of the group represented by the general formula (VII) include the followings.

[0052]

[Chemical 19]

[0053]

[Chemical 20]

Next, specific examples of the bleaching accelerator-releasing compound preferably used in the present invention will be given, but the present invention is not limited thereto.

[0055]

[Chemical 21]

[0056]

[Chemical formula 22]

[0057]

[Chemical formula 23]

[0058]

[Chemical formula 24]

[0059]

[Chemical 25]

[0060]

[Chemical formula 26]

[0061]

[Chemical 27]

[0062]

[Chemical 28]

[0063]

[Chemical 29]

[0064]

[Chemical 30]

[0065]

[Chemical 31]

[0066]

[Chemical 32]

[0067]

[Chemical 33]

[0068]

[Chemical 34]

Others, Research Disclosure I
tem Nos. 24241 and 11449, JP-A-61-
201247, 63-106749, 63-121843, 63-121844, 63-1474752 and 2-93.
The compounds described in Japanese Patent No. 454 are also used in the same manner.

The bleaching accelerator releasing compound used in the present invention can be easily synthesized based on the description in the above patent specifications.

The amount of the compound of the general formula (B) added varies depending on the structure of the compound, but is preferably 1 × 10 ⁻⁵ to 1 mol, and particularly preferably 1 × 10 ⁵ per 1 mol of silver present in the same layer or an adjacent layer. ^-4 to 0.5 mol.

The general formula (I) will be described in detail below. R ¹ represents a hydrogen atom or a substituent, and R ² represents a substituent. The substituents of R ¹ and R ² include aryl group, alkyl group, cyano group, acyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, formylamino group, acylamino group, alkoxycarbonylamino group, aryloxycarbonyl group. Amino group, sulfonamide group, ureido group, sulfamoylamino group, alkylamino group, arylamino group, alkoxy group, aryloxy group, heteryloxy group, alkylthio group, arylthio group, heterylthio group, heterocyclic group, halogen atom, Examples thereof include a hydroxy group, a nitro group, a sulfamoyl group, a sulfonyl group, an acyloxy group, a carbamoyloxy group, an imide group, a sulfinyl group, a phosphoryl group, a carboxyl group, a phosphono group and an unsubstituted amino group. Among these groups, a group which can further have a substituent may be substituted with the above-mentioned substituent. R
^As the substituents of ¹ and R ² , specifically, an aryl group (preferably having 6 to 30 carbon atoms, for example, phenyl, m-acetylaminophenyl, p-methoxyphenyl), an alkyl group (preferably having 1 to 30 carbon atoms, For example, methyl, trifluoromethyl, ethyl, isopropyl, heptafluoropropyl, t-butyl, n-octyl, n-dodecyl), cyano group, acyl group (preferably having 1 to 3 carbon atoms).
0, for example, acetyl, pivaloyl, benzoyl, furoyl, 2-pyridylcarbonyl), carbamoyl group (preferably having 1 to 30 carbon atoms, for example, methylcarbamoyl, ethylcarbamoyl, dimethylcarbamoyl, n-octylcarbamoyl), alkoxycarbonyl group (preferably C2-C30, such as methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl), an aryloxycarbonyl group (preferably C7-C, such as phenoxycarbonyl, p-methoxyphenoxycarbonyl, m-chlorophenoxycarbonyl, o-methoxy. Phenoxycarbonyl), formylamino group, acylamino group [preferably alkylcarbonylamino group having 2 to 30 carbon atoms (for example, acetylamino, propionylamino, cyanoamino). Chiruamino), preferably having a carbon number of 7
To 30 arylcarbonylamino groups (eg, henzoylamino, p-toluylamino, pentafluorobenzoylamino, m-methoxybenzoylamino), preferably C4 to C30 heterylcarbonylamino groups (eg, 2-pyridyl). Carbonylamino, 3-pyridylcarbonylamino, furoylamino)], an alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, methoxyethoxycarbonylamino), an aryloxycarbonylamino group (preferably carbon). Number 7-30,
For example, phenoxycarbonylamino, p-methoxyphenoxycarbonylamino, p-methylphenoxycarbonylamino, m-chlorophenoxycarbonylamino), sulfonamide group (preferably having 1 to 30 carbon atoms,
For example, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide), ureido group (preferably having 1 to 30 carbon atoms, for example, methylureido, dimethylureido, p-cyanophenylureido), sulfamoylamino group (preferably carbon). Number 1 to 30, such as methylaminosulfonylamino, ethylaminosulfonylamino, anilinosulfonylamino), alkylamino group (preferably having 1 to 30 carbon atoms, such as methylamino,
Dimethylamino, ethylamino, diethylamino, n-
Butylamino), an arylamino group (preferably having 6 to 30 carbon atoms such as anilino), an alkoxy group (preferably having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, n-butoxy, methoxyethoxy, n-dodecyloxy). ), An aryloxy group (preferably having 6 carbon atoms)
~ 30, for example phenoxy, m-chlorophenoxy, p
-Methoxyphenoxy, o-methoxyphenoxy), a heteryloxy group (preferably having 3 to 30 carbon atoms, for example, tetrahydropyranyloxy, 3-pyridyloxy, 2-
(1,3-benzimidazolyl) oxy), an alkylthio group (preferably having a carbon number of 1 to 30, such as methylthio,
Ethylthio, n-butylthio, t-butylthio), arylthio group (preferably having 6 to 30 carbon atoms, for example, phenylthio), heterylthio group (preferably having 3 to 3 carbon atoms).
0, for example 2-pyridylthio, 2- (1,3-benzoxazolyl) thio, 1-hexadecyl-1,2,3,4
-Tetrazolyl-5-thio, 1- (3-N-octadecylcarbamoyl) phenyl-1,2,3,4-tetrazolyl-5-thio), a heterocyclic group (preferably having a carbon number of 3 to 3)
30, for example, 2-benzoxazolyl, 2-benzothiazolyl, 1-phenyl-2-benzimidazolyl, 5-
Chloro-1-tetrazolyl, 1-pyrrolyl, 2-furanyl, 2-pyridyl, 3-pyridyl), halogen atom (fluorine, chlorine, bromine), hydroxy group, nitro group, sulfamoyl group (preferably having 0 to 30 carbon atoms, For example, methylsulfamoyl, dimethylsulfamoyl), sulfonyl group (preferably having 1 to 30 carbon atoms, for example, methanesulfonyl, benzenesulfonyl, toluenesulfonyl), acyloxy group (preferably having 1 to 30 carbon atoms, such as formyloxy, acetyl). Oxy, benzoyloxy), carbamoyloxy group (preferably having 1 to 30 carbon atoms, for example, methylcarbamoyloxy, diethylcarbamoyloxy), imide group (preferably having 4 to 30 carbon atoms, such as succinimide, phthalimido), sulfinyl group (Preferably carbon number 30, for example diethylamino sulfinyl), a phosphoryl group (preferably 0-3 carbon atoms
0, eg dimethoxyphosphoryl), a carboxyl group,
It is a phosphono group or an unsubstituted amino group.

[0073] Preferably, at least one of R ^1, R ² is the value of the substituent constant sigma _p of Hammett is 0.35 or more electron-withdrawing group, more preferably at least one of R ^1, R ² One of them is an electron-withdrawing group having a value of σ _p of 0.60 or more, and particularly preferably, at least one of R ¹ and R ² is a cyano group.

Here, the Hammett's substituent constant used in the present specification will be briefly described. Hammett's rule is an empirical rule proposed by LP Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives, which is widely accepted today. There are σ _p and σ _m values for the substituent constants obtained by Hammett's rule, and these values can be found in many general textbooks. For example, see JADean, “La.
nge's Handbook of Chemistry ", 12th Edition, 1979 (McGraw-Hill) and" The Area of Chemistry "Special Issue, No. 122, 9
See pages 6-103, 1979 (Nankodo) for details. In addition,
In the present invention, each substituent is limited or explained by Hammett's substituent constant σ _p, but this is found in the above-mentioned book, in the sense that it is limited only to certain substituents with known values in the literature. Needless to say, even if the value is unknown in the literature, it also includes a substituent that may be included in the range when measured based on Hammett's rule.

As the electron-withdrawing group having a σ _p value of 0.35 or more, a cyano group (σ _p value of 0.66) and a nitro group (0.7 _p
8), carboxyl group (0.45), perfluoroalkyl group (for example, trifluoromethyl (0.54), perfluorobutyl), acyl group (for example, acetyl (0.50), benzoyl (0.43)) ), A formyl group (0.42), a sulfonyl group (eg, trifluoromethanesulfonyl (0.92), methanesulfonyl (0.
72), benzenesulfonyl (0.70)), a sulfinyl group (for example, methanesulfinyl (0.49)),
A carbamoyl group (for example, carbamoyl (0.36),
Methylcarbamoyl (0.36), phenylcarbamoyl, 2-chloro-phenylcarbamoyl), an alkoxycarbonyl group (for example, methoxycarbonyl (0.4
5), ethoxycarbonyl, diphenylmethylcarbonyl), a heterocyclic residue (for example, pyrazolyl (0.37),
1-tetrazolyl (0.50)), an alkylsulfonyloxy group (for example, methanesulfonyloxy (0.3
6), a phosphoryl group (for example, dimethoxyphosphoryl (0.60), diphenylphosphoryl), a sulfamoyl group (0.57), a ventachlorophenyl group, a pentafluorophenyl group or a sulfonyl group-substituted aromatic group (for example, 2,4- Preferable examples include dimethanesulfonylphenyl).

Preferred examples of the electron-withdrawing group having a value of σ _p of 0.60 or more include a cyano group, a nitro group and a sulfonyl group.

X represents a hydrogen atom or a group which can be eliminated by a coupling reaction with a color developing agent, for example, an oxidation product of an aromatic primary amine developing agent (hereinafter referred to as a coupling-off group).

Specific examples of the coupling-off group will be given below.
Halogen atom (eg fluorine, chlorine, bromine), alkoxy group (eg ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy,
Methylsulfonylethoxy), aryloxy groups (eg 4-chlorophenoxy, 4-methoxyphenoxy, 4
-Carboxyphenoxy), acyloxy group (eg acetoxy, tetradecanoyloxy, benzoyloxy, sulfonyloxy group (eg methanesulfonyloxy, toluenesulfonyloxy), acylamino group (eg dichloroacetylamino, heptafluorobutyrylamino), sulfonamide Group (eg methanesulfonamide, p-toluenesulfonamide), alkoxycarbonyloxy group (eg ethoxycarbonyloxy, benzyloxycarbonyloxy), aryloxycarbonyloxy group (eg phenoxycarbonyloxy), alkylthio group (eg carboxymethylthio), An arylthio group (eg 2-butoxy-5-tert.
-Octylphenylthio), a heterocyclic thio group (e.g. tetrazolylthio), a carbamoylamino group (e.g. N-methylcarbamoylamino, N-phenylcarbamoylamino), a 5- or 6-membered nitrogen-containing heterocyclic group (e.g. imidazolyl, pyrazolyl, Triazolyl, tetrazolyl, 1,2-dihydro-2-oxo-1-pyridyl),
An imide group (eg, succinimide, hydantoinyl),
Aromatic azo group (eg phenylazo), sulfinyl group (eg 2-butoxy-5-tert-octylphenylsulfinyl), sulfonyl group (eg 2-butoxy-5)
-Tert-octylphenylsulfonyl) and the like, and these groups may be further substituted with a group which is allowed as a substituent for R ¹ .

Further, as a leaving group bonded via a carbon atom, there is a bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or a ketone. The leaving group of the present invention may contain a photographically useful group such as a development inhibitor and a development accelerator.

Z ¹ represents a nonmetallic atom group necessary for forming a nitrogen-containing 6-membered heterocycle, and has at least one dissociative group. The four divalent linking groups for constituting the nitrogen-containing 6-membered heterocycle include -NH-, -N (R)-, and -N.
=, -CH (R)-, -CH =, -C (R) =, -CO
-, - S -, - SO -, - SO 2 - , and the like.
(R represents a substituent, and examples thereof include the substituents mentioned for R ^1. ) Examples of the dissociative group include those having an acidic proton such as —NH— and —CH (R) —, and preferably pKa in water is It has a value of 3 to 12.

The dye-forming coupler represented by the general formula (I) can be preferably represented by the general formula (II) to the general formula (XIX).

[0082]

[Chemical 35]

[0083]

[Chemical 36]

[0084]

[Chemical 37]

(In the formula, R ¹ , R ² and X have the same meanings as in formula (I). R ³ , R ⁵ , R ⁶ ,
R ⁷ and R ⁸ represent a hydrogen atom or a substituent, and R ⁴
Represents a substituent. EWG is Hammett's substituent constant σ
_It represents an electron-withdrawing group having a _p value of 0.35 or more. )

Examples of the substituents of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same as those described for R ¹ .

The coupler represented by the general formula (I) has R ¹
To R ⁸ may have a coupler residue represented by the general formula (I) in the group to form a dimer or higher multimer, and the groups R ^{1 to} R ⁸ may be polymer chains. And may form a homopolymer or a copolymer. The homopolymer or copolymer bound to the polymer chain is typically a homopolymer or copolymer of an addition polymer ethylenically unsaturated compound having a coupler residue represented by formula (I). in this case,
One or more kinds of color-forming repeating units having a coupler residue represented by the general formula (I) may be contained in the polymer, and as a copolymerization component such as acrylic acid ester, methacrylic acid ester and maleic acid ester. It may be a copolymer containing one or more non-color-forming ethylene type monomers.

Next, examples of typical compounds of the coupler used in the present invention will be shown, but the present invention is not limited thereto. The substituents used in the compound examples are described below in numerical order.

[0089]

[Chemical 38]

[0090]

[Chemical Formula 39]

[0091]

[Chemical 40]

[0092]

[Chemical 41]

[0093]

[Chemical 42]

[0094]

[Chemical 43]

[0095]

[Chemical 44]

Typical examples of the compound of the coupler of the present invention are shown below, but the present invention is not limited thereto.

[0097]

[Table 1]

[0098]

[Table 2]

[0099]

[Table 3]

[0100]

[Table 4]

[0101]

[Table 5]

[0102]

[Table 6]

Next, synthesis examples of typical couplers of the present invention will be shown.

(Synthesis Example 1) Synthesis of coupler (III) -1

[0105]

[Chemical 45]

2-Amino-3-cyano-4-phenylpyrrole (Compound a) (18.3 g), which is easily obtained by condensing 2-aminoacetophenone hydrochloride and malononitrile in the presence of alkali, and diethyl ethoxyethylidenemalonate (25. Disperse 3 g in 300 ml of ethanol,
28% methanol solution of sodium methylate 2
2.0 ml was added and the mixture was heated under reflux for 5 hours. After cooling, ethyl acetate was added, the mixture was washed with water, the organic solvent was concentrated, and the precipitated crystals were collected by filtration to obtain 11.6 g of compound b. Then, 50 ml of fine oxochol 1600 and 2.0 g of titanium isopropoxide (Ti (Oi-Pr) ₄ ) were added thereto, and the mixture was heated at an oil bath temperature of 130 to 140 ° C. for 6 hours. After cooling
Purified by silica gel chromatography (hexane / ethyl acetate = 1/1) to give coupler (III) -1 14.
7 g was obtained as a pale yellow oil.

(Synthesis Example 2) Synthesis of coupler (III) -3

[0108]

[Chemical 46]

2-Amino-3-cyano-4-phenylpyrrole (Compound a) (18.3 g) and diethyl ethoxymethylenemalonate (24.0 g) were dispersed in ethanol (400 ml), and sodium methylate 28% methanol solution (22.0 ml) was dispersed therein. Was added and the mixture was heated under reflux for 1 hour. After cooling, the precipitated crystals were collected by filtration to obtain 28.0 g of compound c. Next, fine oxo call 1600 is added to this 150m
l, Ti (Oi-Pr) ₄ 4.0 g was added, and the oil bath temperature 130-
Heated at 140 ° C. for 2 hours. After cooling, the resulting product was purified by silica gel chromatography to obtain coupler (III) -33.
Obtained 6.2 g.

(Synthesis Example 3) Synthesis of coupler (II) -1

[0111]

[Chemical 47]

2-Amino-3-cyano-4-phenylpyrrole (Compound a) (18.3 g) and ethyl p-octadecyloxybenzoyl acetate (46.0 g) were dispersed in 300 ml of acetic acid, and the mixture was heated under reflux for 8 hours. After cooling, 1 liter of ethyl acetate and 1 liter of water were added, and the precipitated crystals were collected by filtration to obtain 29.0 g of coupler (II) -1. Other compounds can be synthesized by the same method.

The compound represented by the general formula (I) of the present invention is 1.0 to 1.0 × 10 ⁻³ per mol of silver halide.
It can be used in the molar range. Preferably 5.0
It is in the range of x10 ^{-1 to} 2.0 x 10 ^-2 mol, and more preferably 4.0 x 10 ^{-1 to} 5.0 x 10 ^-2 mol.

In the present invention, when the compound represented by the general formula (I) is used as the main coupler, it is preferably added to the red-sensitive silver halide emulsion layer or the non-photosensitive layer adjacent thereto. When the coupler releases a photographically useful group, it is added to the silver halide photosensitive layer or the non-photosensitive layer according to the purpose.

In the present invention, the compound represented by the general formula (I) may be used in combination of two or more kinds, or may be used in combination with other known couplers.

In the present invention, the compound represented by the general formula (I) can be introduced into the color light-sensitive material by various known dispersion methods described below.

In the present invention, the compound represented by the general formula (I) can be dispersed by using a high boiling point organic solvent. As a high boiling point organic solvent, the boiling point at atmospheric pressure is 175 ° C.
The above is preferable, and the amount thereof is 5.0 cc or less per 1 g of the compound of the general formula (I), preferably 0.
˜2.0 cc, more preferably 0˜1.0 cc.

The light-sensitive material of the present invention may have at least one of a blue-sensitive layer, a green-sensitive layer and a red-sensitive silver halide emulsion layer provided on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light, and in a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red-color-sensitive layer and green. The color sensitive layer and the blue color sensitive layer are installed in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. A non-photosensitive layer such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer includes JP-A Nos. 61-43748 and 59-113.
No. 438, No. 59-113440, No. 61-20037, No. 61-20038 may contain a coupler, a DIR compound, and the like, and a color mixing inhibitor may be used as is usually used. May be included. The plural silver halide emulsion layers constituting each unit light-sensitive layer preferably use a two-layer constitution of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. be able to. Usually, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. In addition,
57-112751, 62-200350, 62-206541, 62-2
As described in No. 06543, a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support. As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / High sensitivity blue photosensitive layer (BH) / High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) / High sensitivity red photosensitive layer (RH) / Low sensitivity red photosensitive layer (RL) order, or BH / BL / GL / GH / RH / RL order, or BH / BL / GH /
It can be installed in the order of GL / RL / RH. In addition,
As described in JP-A-55-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. Also, JP-A-56-25738 and 62-63936
It is also possible to arrange the layers in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support, as described in the specification. Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side distant from the support in the same color-sensitive layer. The layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer. In addition, they may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in the case of four layers or more, the arrangement may be changed as described above. In order to improve color reproducibility, U.S. Pat.Nos. 4,663,271 and 4,70
5,744, 4,707,436, JP-A-62-160448, 6
3- It is preferable to dispose the donor layer (CL) having a multi-layer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL and RL described in the specification of 89850 adjacent to or in proximity to the main photosensitive layer. . As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention contains silver iodobromide, silver iodochloride, or iodochlorobromide containing about 30 mol% or less of silver iodide. It is silver. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide is about
It may be fine particles of 0.2 μm or less or large-sized grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) N.
o.17643 (December 1978), pp. 22-23, "I. Emulsion production (Emu
lsion preparation and types) ”, and the same No.18716
(Nov. 1979), p. 648, ibid. No. 307105 (Nov. 1989), 863.
-865, and Graphide, Physics and Chemistry of Photography, published by Paul Montel (P.Glafkides, Chemie et P
hisique Photographique, PaulMontel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF D
uffin, Photographic Emulsion Chemistry (Focal Pres
s, 1966)), "Production and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (VL Zelikman et al.,
Making and Coating Photographic Emulsion, Focal Pr
ess, 1964) and the like.

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutoff, PhotographicScience by Gatov.
and Engineering), Vol. 14, pp. 248-257 (1970);
U.S. Pat.Nos. 4,434,226, 4,414,310, 4,433,0
It can be easily prepared by the methods described in 48, 4,439,520 and British Patent 2,112,157. The crystal structure may be uniform, may have a different halogen composition between the inside and the outside, may have a layered structure, and may have a different composition by epitaxial bonding. Alternatively, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used. The above emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which forms a latent image inside the grain or a type which has a latent image both on the surface and inside, but a negative type emulsion. It is necessary to be. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. The method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are described in Research Disclosure No. 17643, No. 18716 and No. 307105, and the corresponding portions are summarized in the table below. The light-sensitive material of the present invention comprises two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the light-sensitive silver halide emulsion.
It can be mixed and used in the same layer. US Patent No.
No. 4,082,553, the surface of which is covered with a silver halide grain, U.S. Pat. No. 4,626,498, JP-A-59-214852, the inside of which is covered with a silver halide grain, and a colloidal silver is a photosensitive halogenated photosensitive grain. It can be preferably used for a silver emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain that enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. .. A method for preparing a silver halide grain whose inside or surface is fogged is described in U.S. Pat.
It is described in No. 9-214852. The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged inside may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. There is no particular limitation on the grain size of these fogged silver halide grains, but as the average grain size,
0.01 to 0.75 μm, particularly 0.05 to 0.6 μm is preferable. Also,
The grain shape is not particularly limited and may be regular grains or polydisperse emulsion, but monodisperse (at least 95% of the weight or number of silver halide grains is within ± 40% of the average grain size) It is preferable that the particles have a particle size of

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that the fog is not fogged in advance. .. The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average diameter of circles in the projected area)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. The fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be chemically sensitized nor spectral sensitization. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be preferably contained in the layer containing the fine grain silver halide grains. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

Known photographic additives that can be used in the present invention are also described in the above-mentioned three Research Disclosures, and the related portions are shown in the following table. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer, page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, page 23 to 24, page 648, right column 866 to 868 Color sensitizer ~ page 649 right column 4.whitening agent page 24 647 page right column 868 page 5.fogging prevention page 24 ~ 25 page 649 page right column 868 ~ 870 agent, stabilizer 6.light absorber, 25 ~ Page 26 Page 649 Right column Page 873 Filter ~ Page 650 Left column Dye, UV absorber 7. Stain 25 Page Right column 650 Page Left column 872 Inhibitor ~ Right column 8. Dye image Page 25 650 Page Left column 872 Stabilizer 9. Hardener 26 pages 651 left column 874 to 875 10. Binder 26 pages 651 page left columns 873 to 874 11. Plasticizer, page 27 650 pages right column 876 Lubricants 12. Coating aids , Pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. static, page 27, page 650, right column, pages 876 to 877, inhibitor 14. matting agent, pages 878 to 879

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is preferable to add a compound capable of reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503 to a light-sensitive material. . In the light-sensitive material of the present invention, US Pat.
No. 4,788,132, JP-A-62-18539, JP-A 1-28
It is preferable to contain the mercapto compound described in No. 3551. A compound which, in the light-sensitive material of the present invention, releases a fog agent, a development accelerator, a silver halide solvent or a precursor thereof as described in JP-A 1-106052, irrespective of the amount of developed silver produced by development processing. Is preferably contained. In the light-sensitive material of the present invention, a dye dispersed by the method described in International Publication WO88 / 04794 or JP-A-1-502912 or
EP 317,308A, U.S. Pat.No. 4,420,555, JP 1-2593
It is preferable to include the dye described in No. 58. Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure No. 1764 mentioned above.
3, VII-CG, and No. 307105, VII-CG
Are described in the patents listed in. Yellow couplers include, for example, U.S. Patents 3,933,501 and 4,02.
No. 2,620, No. 4,326,024, No. 4,401,752, No.
4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,
No. 020, No. 1,476,760, U.S. Patent No. 3,973,968,
No. 4,314,023, No. 4,511,649, European Patent No. 24
Those described in Nos. 9,473A and 447,969A are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619, 4,351,897, and European Patent 73,63 are preferred.
6, U.S. Pat.Nos. 3,061,432, 3,725,067,
Research Disclosure No. 24220 (June 1984
Mon), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-71.
No. 2238, No. 60-35730, No. 55-118034, No. 60-185951
U.S. Pat.Nos. 4,500,630, 4,540,654, and
Those described in 4,556,630 and WO88 / 04795 are particularly preferable. Examples of cyan couplers that can be used in combination include phenol-based and naphthol-based couplers, and U.S. Pat. Nos. 4,052,212, 4,146,396, and
4,228,233, 4,296,200, 2,369,929,
No. 2,801,171, No. 2,772,162, No. 2,895,826
No. 3, No. 3,772,002, No. 3,758,308, No. 4,33
4,011, 4,327,173, West German Patent Publication 3,329,729
U.S. Patent Nos. 121,365A, 249,453A, U.S. Patents 3,446,622, 4,333,999, 4,775,6
No. 16, No. 4,451,559, No. 4,427,767, No. 4,6
Those described in 90,889, 4,254,212, 4,296,199, JP-A-61-42658 and the like are preferable. further,
Pyrazoloazole couplers described in JP-A-64-553, 64-554, 64-555 and 64-556, and U.S. Pat.
The imidazole couplers described in No. 8,672 can also be used. Typical examples of polymerized dye-forming couplers are U.S. Pat.Nos. 3,451,820, 4,080,211, 4,367,282, 4,409,320 and 4,576,910.
No. 2,102,137, European Patent No. 341,188A, and the like.

Examples of couplers in which the color forming dye has a suitable diffusibility include US Pat. No. 4,366,237 and British Patent 2,12.
5,570, European Patent 96,570, West German Patent (Publication)
Those described in 3,234,533 are preferable. Colored couplers for correcting unwanted absorption of color forming dyes are described in Research Disclosure No. 17643, Item VII-G, No. 307.
105 VII-G, U.S. Pat. No. 4,163,670, Japanese Examined Patent Publication No. 57
-39413, U.S. Pat.Nos. 4,004,929, 4,138,258
No., British Patent No. 1,146,368, JP-A-1-319744, 3-1.
Those described in 77836, 3-177837 and European Patent No. 423727 are preferable. Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in US Pat. No. 4,774,181, and US Pat.
It is also preferable to use a coupler having a dye precursor group as a leaving group capable of reacting with a developing agent to form a dye as described in No. 77,120. Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention. The DIR coupler releasing a development inhibitor is disclosed in the above-mentioned RD 17643, VII-F and the patents described in Nos. 307105 and VII-F, JP-A-57-151944 and 57-154234.
No. 60-184248, No. 63-37346, No. 63-37350, U.S. Pat.Nos. 4,248,962, 4,782,012, European Patent No. 4
Those described in No. 47920 are preferred. RDNo.11449,
The bleaching accelerator releasing coupler described in JP-A No. 24241 and JP-A No. 61-201247 is effective for shortening the processing time having a bleaching ability, and in particular, the tabular silver halide grains described above are used. The effect is great when it is added to a light-sensitive material. As a coupler that releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,097,140,
No. 2,131,188, JP-A Nos. 59-157638 and 59-170840.
Those described in No. 10 are preferable. In addition, JP-A-60-107029
No. 60-252340, JP-A-1-44940, and JP-A 1-45687, releasing a fog agent, a development accelerator, a silver halide solvent, etc. by a redox reaction with an oxidant of a developing agent. Also preferred are compounds.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,472 and 4,3.
38,393, 4,310,618 and the like, multi-equivalent couplers, DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds described in JP-A-60-185950 and JP-A-62-24252. Alternatively, DIR redox-releasing redox compounds, couplers releasing dyes that undergo color restoration after withdrawal described in European Patents 173,302A and 313,308A, ligand-releasing couplers described in U.S. Pat. -75747 couplers releasing leuco dyes, U.S. Pat.
Examples thereof include couplers that release the fluorescent dye described in No. 181.

The coupler used in the present invention can be introduced into the photographic material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Specific examples of the high-boiling organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bisyl phthalate). (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl)
Isophthalate, bis (1,1-diethylpropyl) phthalate, etc., phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di
-2-Ethylhexylphenylphosphonate, etc., Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), Amides (N, N-diethyldodecaneamide, N, N-diethyllauryl) Amides, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azetase Rate, glycerol tributyrate, isostearyl lactate,
Trioctyl citrate, etc., aniline derivatives (N, N-
Dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C.
Organic solvents with temperatures above 160 ° C can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate,
Examples thereof include methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like. The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-272248,
And 1,2-benzisothiazolin-3-one described in JP-A-1-80941, n-butyl p-hydroxybenzoate,
It is preferable to add various preservatives or antifungal agents such as phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole. The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.
Suitable supports that can be used in the present invention are, for example, the above-mentioned R
D. No.17643, page 28, No.18716, page 647 From right column 648
It is described on the left column of the page and on page 879 of the same No. 307105. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, particularly preferably 16 μm or less. Also, the film swelling speed T
_1/2 is preferably 30 seconds or less, more preferably 20 seconds or less.
The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, Photographic Science and Engineering (Photog
r.Sci.Eng.), No. 2, No. 2, pages 124 to 129 can be measured using a swellometer (swelling meter), and T _1/2 is 30 ° C. in a color developer. , 90% of the maximum swollen film thickness reached after 3 minutes and 15 seconds of treatment is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness. Membrane swelling speed T
_1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness-film thickness) / film thickness. The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer.
In this back layer, the above-mentioned light absorber, filter dye,
It is preferable to contain an ultraviolet absorber, an antistatic agent, a hardener, a binder, a plasticizer, a lubricant, a coating aid, a surface active agent and the like. The swelling ratio of this back layer is 150-500
% Is preferred.

The color photographic light-sensitive material according to the present invention has the RD. No.17643, pages 28 to 29, No. 18716, 651 left column to right column, and No. 307105, pages 880 to 881 can be developed by a usual method. The color developing solution used in the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As this color developing agent,
Aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N diethylaniline and 3-methyl-4-amino-N-. Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N
-Ethyl-β-methoxyethylaniline, 4-amino-3-
Methyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl- N-
(2-hydroxypropyl) aniline, 4-amino-3-ethyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-
Amino-3-methyl-N-propyl-N- (3-hydroxypropyl) aniline, 4-amino-3-propyl-N-methyl-N- (3-
Hydroxypropyl) aniline, 4-amino-3-methyl-N
-Methyl-N- (4-hydroxybutyl) aniline, 4-amino
-3-Methyl-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N-propyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethyl-N -Ethyl -N-
(3-hydroxy-2-methylpropyl) aniline, 4-amino-3-methyl-N, N-bis (4-hydroxybutyl) aniline, 4-amino-3-methyl-N, N-bis (5-hydroxy Pentyl) aniline, 4-amino-3-methyl-N- (5-hydroxypentyl) -N- (4-hydroxybutyl) aniline, 4-amino-3-methoxy-N-ethyl-N- (4-hydroxybutyl ) Aniline, 4-amino-3-ethoxy-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-propyl-N- (4-hydroxybutyl) aniline, and their sulfates and hydrochlorides Alternatively, p-toluenesulfonate may be used.
Among these, especially 3-methyl-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 4-amino-3-methyl-
N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline, and their hydrochlorides, p-toluenesulfonate or sulfuric acid Salt is preferred. Two or more kinds of these compounds can be used in combination depending on the purpose. Color developers include alkali metal carbonates, borates or phosphates.
It is common to include a pH buffer, a chloride salt, a bromide salt, an iodide salt, a development inhibitor such as a benzimidazole, a benzothiazole or a mercapto compound, or an antifoggant. Also, if necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catechol sulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Agent, aminopolycarboxylic acid,
Aminopolyphosphonic acid, alkylphosphonic acid, various chelating agents represented by phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1- Hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and them Can be mentioned as a representative example.

When the reversal process is carried out, black and white development is usually carried out and then color development is carried out. In this black-and-white developer, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination. The pH of these color developing solution and black-and-white developing solution is generally 9-12. The replenishment amount of these developers depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the light-sensitive material, and is 500 ml or less by reducing the bromide ion concentration in the replenisher. You can also When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area with the air in the processing tank. The contact area between the photographic processing liquid and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably 0.001 to 0.05. Is. As a method for reducing the aperture ratio in this way, in addition to providing a cover such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033 is disclosed. The slit development processing method described in 63-216050 can be mentioned. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps such as bleaching, bleach-fixing,
It is preferably applied in all steps such as fixing, washing with water, and stabilization. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution. The color development processing time is usually set to 2 to 5 minutes, but the processing time can be further shortened by setting the temperature and high pH and using the color developing agent at a high concentration.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process (bleach-fixing process) or separately. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents include organic complex salts of iron (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol etherdiaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Of these, aminopolycarboxylic acid iron (III) complex salts such as ethylenediaminetetraacetic acid iron (III) complex salt and 1,3-diaminopropanetetraacetic acid iron (III) complex salt are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. .. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleach accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patent 1,290,812.
No. 2,059,988, JP-A No. 53-32736, No. 53-57831
No. 53, No. 53-37418, No. 53-72623, No. 53-95630, No. 53
-95631, 53-104232, 53-124424, 53-141
623, 53-28426, Research Disclosure
No. 17129 (July 1978), etc., a compound having a mercapto group or a disulfide group; JP-A-50-140129
Thiazolidine derivatives described in JP-B-45-8506, JP-A-52-20832, JP-A-53-32735, and US Pat. No. 3,706,561.
Thiourea derivative described in Japanese Patent No. 1,127,715,
Iodide salt described in JP-A-58-16,235; West German Patent No. 966,
Polyoxyethylene compounds described in JP-A Nos. 410 and 2,748,430; polyamine compounds described in JP-B-45-8836; Other JP-A-49-40,943, 49-59,644, 53-94,92
No. 7, No. 54-35,727, No. 55-26,506, No. 58-163,940
Compounds described in No. 1; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of having a large accelerating effect, and in particular, US Pat.
3,858, West German Patent 1,290,812, JP-A-53-95,630
Compounds described in US Pat. Further, U.S. Pat.
The compounds described in No. 834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photographing. In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. Particularly preferred organic acid has an acid dissociation constant (pKa) of 2
A compound of -5, specifically acetic acid, propionic acid,
Hydroxyacetic acid and the like are preferred. Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts, but thiosulfates are generally used. In particular, ammonium thiosulfate can be used most widely. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. Preservatives for fixers and bleach-fixers include sulfites, bisulfites, carbonyl bisulfite adducts or European Patent No. 294
The sulfinic acid compounds described in No. 769A are preferable. Furthermore,
It is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution. In the present invention, the fixing solution or the bleach-fixing solution has a pH of
For adjustment, a compound having a pKa of 6.0 to 9.0, preferably an imidazole such as imidazole, 1-methylimidazole, 1-ethylimidazole, and 2-methylimidazole.
It is preferable to add 1 to 10 mol / l.

The total time for the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The treatment temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferable temperature range, the desilvering rate is improved and the stain generation after the processing is effectively prevented. In the desilvering process, it is preferable that the stirring is strengthened as much as possible.
As a specific method for strengthening stirring, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461 is used. Method of improving the effect, further moving the photosensitive material while the emulsion surface is in contact with the wiper blade provided in the solution to make the emulsion surface turbulent to further improve the stirring effect, circulation of the entire processing solution There is a method of increasing the flow rate. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film and, as a result, increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting effect of the bleaching accelerator. The automatic processor used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257.
No. 60-191258 and No. 60-191259. The above-mentioned JP-A-6
As described in No. 0-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment 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 washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment system such as countercurrent, forward flow, and other various conditions. It can be set in a wide range.
Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is as follows.
nd Tele-vision Engineers Volume 64, P. 248 ~ 253 (195
May, May issue). According to the multi-stage counter-current method described in the above literature, the amount of washing water can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problems arise. In the processing of the color light-sensitive material of the present invention, as a solution to this problem, the method of reducing calcium and magnesium ions described in JP-A-62-288,838 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986)
Sankyo Publishing, Sanitary Technology Society, "Microbial sterilization, sterilization, antifungal technology" (1982) Industrial Technology Association, Japan Antibacterial and Antifungal Society edited by "The Antibacterial and Antifungal Encyclopedia" (1986) Can also be used. PH of washing water in the processing of the light-sensitive material of the present invention
Is 4-9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the light-sensitive material, application, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes, preferably
A range of 30 seconds to 5 minutes at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, all known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used. Further, there is a case where further stabilization treatment is carried out after the water washing treatment, and an example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. be able to. As a dye stabilizer,
Aldehydes such as formalin and glutaraldehyde,
Examples thereof include N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.
Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the washing with water and / or the replenishment of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
It is preferable to correct the concentration by adding water. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline-based compounds described in U.S. Pat. Metal salt complexes described, JP-A-53-135
Urethane compounds described in No. 628 can be mentioned.
The silver halide color light-sensitive material of the present invention contains various types of 1-phenyl-3-methyl-3-phenyl-3-(-3-phenyl) -3-phenyl-3- (phenyl-3-phenyl) -3- (phenyl) -3-phenyl-3-(-3-phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3-phenyl-3-(-3-phenyl) -3- (phenyl) -3-phenyl-3-(-3-phenyl-3-phenyl-3-phenyl-3- (phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-fluoro-3-bromo-3-chloro-3-bromo-3-bromo-3-amino-3-bromo-3-amino-3-bromo-3-amino-3-bromo-3-amino-3-phenyl-3-phenyl-3-bromo-3-octyl-3-bromo-3-bromo-3-bromo-3-octyl-3-bromo-3-bromo-3-octyl-3-bromo-3-bromo-3-bromo-3-octyl-3-phenyl-3-bromo-3-bromo-3-bromo-3-bromo-3-octyl-3-phenyl-3-chloro-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo 3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3- did lead;
You may incorporate pyrazolidones. Typical compounds are described in JP-A-56-64339, JP-A-57-144547, and JP-A-58-115438. Various treatment liquids in the present invention are 10 ℃
Used at ~ 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to.

The silver halide color photographic light-sensitive material of the present invention is more likely to exhibit effects when applied to a lens-fitted film unit described in JP-B-2-32615, JP-B-3-39784 and the like. It is valid.

[0138]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. Example 1 (Preparation of Sample 101) Onto an undercoated cellulose triacetate film support, each layer having the composition as shown below was multilayer-coated to prepare Sample 101 which is a multilayer color light-sensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 HBS-1 0.20

Second Layer (Intermediate Layer) Emulsion G Silver 0.065 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-1 0.10 HBS-2 0.020 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Emulsion A Silver 0.25 Emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 Comparative coupler (1 ) 0.18 ExC-3 0.030 ExC-4 0.05 ExC-5 0.020 ExC-7 0.0050 ExC-8 0.010 Cpd-2 0.025 HBS-1 0.20 Gelatin 0.83

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion D Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 Comparative Coupler (1) 0.09 ExC- 2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.025 ExC-7 0.0010 ExC-8 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion E Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 Comparative coupler (1) 0.080 ExC- 3 0.069 ExC-8 0.025 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20

Sixth Layer (Intermediate Layer) Cpd-1 0.10 HBS-1 0.50 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion C Silver 0.35 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Emulsion D Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExM-2 0.13 ExM-3 0.030 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.90

Ninth Layer (High-Sensitivity Green Sensitive Emulsion Layer) Emulsion E Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.030 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.040 HBS-1 0.25 HBS-2 0.10 Gelatin 1.44

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.030 Cpd-1 0.16 HBS-1 0.60 Gelatin 0.60

Eleventh Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Emulsion C Silver 0.18 ExS-7 8.6 × 10 ^-4 ExY-1 0.020 ExY-2 0.022 ExY-3 0.050 ExY-4 0.020 HBS-1 0.28 Gelatin 1.10

12th layer (medium-speed blue-sensitive emulsion layer) Emulsion D Silver 0.40 ExS-7 7.4 × 10 ^-4 ExC-7 7.0 × 10 ^-3 ExY-2 0.050 ExY-3 0.10 HBS-1 0.050 Gelatin 0.78

13th layer (high-sensitivity blue-sensitive emulsion layer) Emulsion F Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 HBS-1 0.070 Gelatin 0.86

14th layer (first protective layer) Emulsion G Silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 1.00

Fifteenth layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- may be used. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains iridium salt and rhodium salt.

[0155]

[Table 7]

In Table 1, (1) Emulsions A to F were prepared according to the examples of JP-A-2-91938.
It was reduction sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to F were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 have been observed in tabular grains and normal crystal grains having a grain structure using a high voltage electron microscope.

[0157]

[Chemical 48]

[0158]

[Chemical 49]

[0159]

[Chemical 50]

[0160]

[Chemical 51]

[0161]

[Chemical 52]

[0162]

[Chemical 53]

[0163]

[Chemical 54]

[0164]

[Chemical 55]

[0165]

[Chemical 56]

[0166]

[Chemical 57]

[0167]

[Chemical 58]

[0168]

[Chemical 59]

[0169]

[Chemical 60]

[0170]

[Chemical formula 61]

[0171]

[Chemical formula 62]

[0172]

[Chemical 63]

(Preparation of Sample 102) Sample 101 is the same as Sample 101 except that the comparative coupler (1) of the third, fourth and fifth layers is replaced with the exemplary coupler (II-1) of the present invention in an equimolar amount. A sample 102 was prepared in the same manner as above. (Preparation of Sample 103) In Sample 101, the coating amount of the cyan coupler ExC-3 of the fifth layer was changed to 0.045 g / m ² ,
In addition, the compound B-32 of the present invention was added to the fifth layer in an amount of 0.020 g /
Sample 103 was prepared in the same manner as in Sample 101, except that the addition amount was changed to m ² . (Preparation of Sample 104) In Sample 102, the coating amount of the cyan coupler ExC-3 of the fifth layer was changed to 0.045 g / m ² ,
In addition, the compound B-32 of the present invention was added to the fifth layer in an amount of 0.020 g /
Sample 104 was prepared in the same manner as Sample 102, except that it was added so as to have m ² .

(Production of Samples 105 and 106) Sample 104
In, the exemplary couplers of the third, fourth and fifth layers (II-1)
Was prepared in the same manner as in Sample 104, except that the coupler was replaced with the coupler shown in Table 8 in an equimolar amount. (Preparation of Samples 107 and 108) Sample 104 was prepared in the same manner as in Sample 106, except that Exemplified Compound B-32 in the fifth layer was replaced with a compound shown in [Table 8] in an equimolar amount.

(Preparation of Sample 109) In Sample 105, Exemplified Compound B-32 in the fifth layer was mixed with B-in an equimolar amount.
A sample was prepared in the same manner as the sample 105 except that it was replaced with 16. (Preparation of Sample 110) In Sample 106, the Exemplified Compound B-32 of the fifth layer was removed, and the coating amount of the cyan coupler ExC-3 was changed to 0.045 g / m ² , and the compound Cpd of the sixth layer was further changed. -1 was changed to 0.03 g / m ² and the sixth compound of Example Compound B-28 was applied to the sixth layer in an amount of 0.08 g / m ^2.
A sample was prepared in the same manner as the sample 106 except that it was added so as to be m ² . (Preparation of Sample 111) Sample 110 was prepared in the same manner as in Sample 111, except that Exemplified Compound B-28 in the sixth layer was replaced with 3-fold molar amount of Exemplified Compound B-26. (Preparation of Sample 112) In Sample 110, the cyan coupler ExC-3 in the fifth layer was replaced with the equimolar exemplary coupler (III-
A sample was prepared in the same manner as the sample 110 except that it was replaced with 2).

Samples 101 to 112 produced as described above
The following evaluations were performed using. (Evaluation of color forming property) These samples were exposed to wedge light with white light, and development processing was carried out by a processing step 1 described below.
The density was measured. In the obtained characteristic curve, sample 1
The color development was evaluated by the cyan density of each sample at the exposure amount at which the cyan density of 01 was 1.8. (Evaluation of Sensitivity) In the characteristic curve obtained when (Evaluation of color forming property) was performed, the cyan density is represented by the logarithm of the reciprocal of the exposure amount giving the cyan fog density + 0.1. (Based on sample 101) (Evaluation of color turbidity) These samples were subjected to wedge exposure with red light, and then uniformly exposed to blue, and subjected to development processing in processing step 1 described below to measure density. I went. In the obtained characteristic curve, the value obtained by subtracting the cyan fog density from the yellow density at a cyan density of 1.8 was taken as the color turbidity. (Evaluation of storability of sensitive material) These samples were tested at 50 ° C and 80%.
The sample was allowed to stand for 3 days under the condition of RH and a time-lapse test was conducted. Exposure similar to (evaluation of color development) for samples before and after aging test,
Development processing and density measurement were performed. The storability of the light-sensitive material was evaluated by the cyan density of each sample after the aging test with an exposure amount such that the cyan density before the aging test was 1.8.

(Evaluation of desilvering property by short-time bleaching) These samples were subjected to wedge exposure with white light, and then the bleaching process was performed for 1 minute 45 seconds and 30 minutes in the following processing step 1.
Development processing is performed in the same manner as processing step 1 except that
The density was measured. The desilvering property was evaluated by the value obtained by subtracting the magenta density of 20 minutes for bleaching time from the magenta density of 1 minute and 45 seconds for bleaching time. (Evaluation of color turbidity by short-time bleaching) In the above (Evaluation of color turbidity), the same test and evaluation were performed except that the bleaching time was changed to 1 minute 45 seconds. These results are summarized in [Table 8].

[0178]

[Table 8]

As is apparent from [Table 8], the sample of the present invention has high color developability, little color turbidity, greatly improves the storability of the light-sensitive material, and can be desilvered even in a short-time bleaching step. You can see that it is excellent and there is little color turbidity. Further, it can be seen that the combined use of the cyan coupler of the present invention and the desilvering accelerator releasing compound increases the sensitivity. Processing step 1

Using an automatic processor and the method described below,
It was processed (until the cumulative replenishment amount of the developer became three times its tank volume). (Processing method) Process processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38 ° C 22 ml 20 liters Bleaching 3 minutes 00 seconds 38 ° C 25 ml 40 liters Water washing 30 seconds 24 ° C 1200 ml 20 liters Fixed 3 Minute 00 seconds 38 ℃ 25ml 30liters Washing with water (1) 30 seconds 24 ℃ 10liters from (2) to (1) Countercurrent piping system Washing with water (2) 30 seconds 24 ℃ 1200ml 10liters Stability 30 seconds 38 ℃ 25 ml 10 liter Dry 4 minutes 20 seconds 55 ° C Replenishment amount is 35 mm width 1 m per length

Next, the composition of the processing liquid will be described. (Color developer) Tank solution (g) Replenisher solution (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.3 Potassium iodide 1.5 mg-hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-hydroxyethylamino] -2-methylaniline sulfate 4.5 6.2 Add water 1.0 liter 1.0 liter pH 10.05 10.15

(Bleaching solution) Tank solution (g) Replenishing solution (g) Ethylenediaminetetraacetic acid sodium ferric trihydrate 100.0 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 11.0 3-Mercapto-1,2,4-triazole 0.08 0.09 Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35.0 Ammonia water (27%) 6.5 ml 4.0 ml Add water 1.0 liter 1.0 liter pH 6.0 5.7

(Fixer) Tank solution (g) Replenisher (g) Ethylenediaminetetraacetic acid disodium salt 0.5 0.7 Ammonium sulfite 20.0 22.0 Ammonium thiosulfate aqueous solution (700 g / liter) 290.0 ml 320.0 ml 1.0 liter 1.0 liter pH by adding water 6.7 7.0

(Stabilizing Solution) Tank Solution / Replenishing Solution Common (g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl 0.2 ether (Average degree of polymerization 10) Ethylenediaminetetraacetic acid disodium salt 0.05 1,2 , 4-Triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5

Example 2 In the sample 9 of Example 3 of JP-A-2-93641,
The cyan coupler ExC-1 in the third and fourth layers was replaced with a 0.6-fold mole of the exemplary coupler (II-1) of the present invention, and the cyan coupler ExC-4 in the fourth layer was replaced with a 0.7-fold mole of the exemplary coupler (II).
-2), and further, the coating amount of the additive Cpd-1 for the fifth layer was reduced to 1/3, and B-28 in the same mole as the reduced Cpd-1 was added.

The sample prepared in this manner was used as sample 20.
1 and the sample 9 of Example 3 of JP-A-2-93641,
The same evaluation as in Example 1 was performed. As a result, sample 20
Sample No. 1 was superior in color developability to the sample 9 and had less color stains, and was also excellent in desilvering property in bleaching for a short time.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, which reacts with an oxidant of an aromatic primary amine developing agent to accelerate bleaching. A silver halide color photographic light-sensitive material comprising a compound that releases an agent and a coupler represented by the following general formula (I). General formula (I): In the general formula (I), R ¹ represents a hydrogen atom or a substituent, R ² represents a substituent, X represents a hydrogen atom or a leaving group in a coupling reaction with an oxidant of a color developing agent. Represents a possible group, and Z ¹ represents a non-metal atom group necessary for forming a nitrogen-containing 6-membered heterocycle. However, the heterocycle has at least one dissociative group.