JPH0527381A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance sharpness and desilverability by incorporating a specified compound in one of layers for composing the photosensitive material and a specified yellow dye-forming coupler in a blue-sensitive silver halide emulsion layer. CONSTITUTION:At least one of the layers for composing the photosensitive material contains at least one of the compounds represented by formulae I and II, and at least one of the blue-sensitive silver halide emulsion layers contains at least one of the yellow dye-forming couplers of formula III. In formulae I and II, R<11> is R<14>OCONR<15>- or the like; R<14> is alkyl, alkenyl, or the like; R<15> is H, alkyl, or the like; each of R<12> and R<13> is H or a substituent having a Hammett's substituent constant sigmap of <=0.3; B is a group releasing X after being released from the oxidation product of the hydroquinone; X is a development inhibitor residue; k is an integer; each of A and A' is H or a group removable by alkali: Q1 is an atomic group necessary to form >=5 membered hetero ring; and R<21> is a substituent on the hydroquinone ring.

Description

Detailed Description of the Invention

[0001]

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 excellent in sharpness and desilvering property.

[0002]

2. Description of the Related Art In recent years, the demand for higher sensitivity and higher image quality of silver halide color photographic light-sensitive materials has been increasing, and technological development for this has become the most important issue in this industry. ..

Of these, the use of DIR compounds for improving the sharpness, particularly the edge effect, is currently generally practiced. Commonly used for this purpose are DIR couplers which release a development inhibitor imagewise by a coupling reaction with an oxidation product of a color developing agent to form a color forming dye.

However, when a DIR coupler is used, if the hue of the dye formed by the coupling reaction is different from that of the dye obtained from the main coupler, color turbidity occurs, which is not preferable for color reproduction. In order to prevent this, it is necessary to use a DIR coupler having a hue similar to that of the yellow, magenta and cyan main couplers. However, in this case, it is necessary to develop three types of compounds having the optimum reactivity, and the burden of development and synthesis costs increases, so that a colorless DIR compound has been demanded.

Colorless DIR compounds are classified into two types, a coupling type and a redox type, according to the reaction mode with an oxidant of a color developing agent. Of these, the coupling type is disclosed in Japanese Examined Patent Publications No. 51-16141 and No. 51-1.
6142, U.S. Pat. Nos. 4,171,223 and 42,269.
Nos. 43 and the like are known, and redox compounds are described in US Pat. Nos. 3,379,529 and 3,639,417.
JP-A-49-129536 and 64-546.
DIR hydroquinone compounds described in Japanese Patent Application No. 2-21127 or the like, or JP-A-61-213847 and 6
The DIR hydrazide compounds described in 4-88451 and U.S. Pat. No. 4,684,604 are known. The processing steps are black and white development (first development), color development (second development).
When applied to a color reversal light-sensitive material consisting of the above, it is preferable to release the inhibitor from the DIR compound in the first developing stage for the following reason. That is, since the second development aims to rapidly develop all the silver halide that has not been developed in the first development, the silver development speed is extremely high. For this reason, silver development is delayed when an imagewise effect of suppressing development is exerted in the second development. As a result, instability of processing in color development is introduced, which is not preferable.

Therefore, it is preferable to react the DIR compound in the first development, but in this case, it is necessary to use a redox DIR compound which can also react with an oxidant of a black and white developing agent.

On the other hand, as the yellow coupler among the image forming couplers, acylacetamide couplers represented by benzoylacetanilide couplers and pivaloylacetanilide couplers have been generally used conventionally. The former is generally high in coupling activity with an oxidized aromatic primary amine developer at the time of development, and has a large absorption coefficient of a yellow dye to be produced, so that a color light-sensitive material for photographing which requires high sensitivity, particularly Mainly used for color negative film. On the other hand, the latter is mainly used for color papers and color reversal films because it has excellent spectral absorption characteristics and fastness of yellow dye.

[0008]

However, when the redox DIR compound is used in combination with these conventionally used yellow couplers, the sharpness can be improved while the desilvering property is deteriorated. It was

Therefore, the object of the present invention is to provide excellent sharpness,
Another object of the present invention is to provide a color light-sensitive material having excellent desilvering property.

[0010]

The objects of the present invention have been achieved by the following means. That is, the present invention relates to a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, and at least one layer constituting the light-sensitive material has the following formula (I) and / or formula (II)
Containing at least one compound represented by, and
A silver halide color photographic light-sensitive material characterized in that at least one of blue-sensitive silver halide emulsion layers contains at least one yellow dye-forming coupler represented by the following formula (III).

[0011]

[Chemical 4] In the formula, R ¹¹ is R ¹⁴ —N (R ¹⁶ ) CON (R ¹⁵ ) —, R ^{14
OCON (R 15) -, R} 14 SO 2 N (R 15) -, R 14 -
_{^{N (R 16) SO 2 N}} (R 15) - or represents a R ¹⁷ CONH-. Here, R ¹⁴ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ^14
15 and R ¹⁶ represent a hydrogen atom, an alkyl group or an aryl group, and R ¹⁷ represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group having 2 or more carbon atoms in which a carbon atom adjacent to the carbonyl group is not substituted with a hetero atom. Alternatively, it represents a heterocyclic group. R ¹² and R ¹³ represent a hydrogen atom or a substituent having a Hammett's substituent constant σ _p of 0.3 or less, B represents a group which releases X after leaving from the hydroquinone mother nucleic acid product, and X represents a development inhibitor. Represents a residue, k represents an integer, and A and A ′ represent a hydrogen atom or a group capable of being removed with an alkali.

[0012]

[Chemical 5] In the formula, Q ¹ represents at least one heteroatom and represents an atomic group necessary for forming a 5-membered or more heterocyclic ring with a carbon atom to be bonded, and R ²¹ represents a group capable of substituting for a hydroquinone nucleus. Where B, X, k, A and A'have the same meanings as described in formula (I).

[0013]

[Chemical 6] In the formula, R ₁ represents a tertiary alkyl group, R ₂ represents a fluorine atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a dialkylamino group, an alkylthio group or an arylthio group, and R ₃ represents a benzene ring. Represents a substitutable group, X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidation product of an aromatic primary amine developing agent, and k represents an integer of 0 to 4. Where k
Is plural, plural R _{3 s} may be the same or different.

First, the compound of formula (I) in the present invention will be explained in more detail. R ¹¹ is R ¹⁴ -N (R
^{16) CON (R 15) -} , R 14 OCON (R 15) -, R 14
^{_{SO 2 N (R 15) -}} , R 14 -N (R 16) SO 2 N
(R ¹⁵⁾ - or represents a R ¹⁷ CONH-. Where R ¹⁴
Is a substituted or unsubstituted alkyl group (having 1 to 30 carbon atoms,
For example, methyl, ethyl, isopropyl, decyl, hexadecyl, t-butyl, cyclohexyl, benzyl), a substituted or unsubstituted alkenyl group (having 2 to 30 carbon atoms, for example, 1-butenyl, 1-octadecenyl), a substituted or unsubstituted alkynyl A group (having 2 to 30 carbon atoms, for example, ethynyl, 1-octynyl), a substituted or unsubstituted aryl group (having 6 to 30 carbon atoms, for example, phenyl, naphthyl, 3
-Dodecaneamidophenyl, 3-hexadecanesulfonamidophenyl, 4-dodecyloxyphenyl), or a heterocyclic group (5-membered to 20-membered ring containing at least one hetero atom of N, O, S, Se) , For example, 4-pyridyl, 2-furyl, pyrrolo, 2-thiazolyl,
2-oxazolyl, 2-imidazolyl, triazolyl,
Tetrazolyl, benzotriazolyl, morpholinyl). Examples of the substituent which R ¹⁴ has include an alkyl group, an arule group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a carboxylic acid amide group,
Sulfonamide group, alkoxycarbonylamino group, ureido group, carbamoyl group, alkoxycarbonyl group, sulfamoyl group, sulfonyl group, cyano group, halogen atom, acyl group, hydroxyl group, carboxyl group, sulfo group, nitro group or heterocyclic group can give.

R ¹⁵ and R ¹⁶ may be the same or different, and examples thereof include a hydrogen atom and R ¹⁴ .

Preferred as R ¹⁵ is a hydrogen atom.

R ¹⁷ is a substituted or unsubstituted alkyl group having 2 or more carbon atoms (preferably having 2 to 3 carbon atoms), in which a carbon atom adjacent to the carbonyl group is not substituted with a hetero atom.
0, for example, ethyl, nonyl, pentadecyl, isopropyl, t-butyl, 1-hexylnonyl, 3- (2,5-
Di-t-pentylphenoxy) propyl, cyclohexyl, benzyl), a substituted or unsubstituted alkenyl group (having 2 to 30 carbon atoms, such as vinyl, 1-octenyl, 2
-Phenylvinyl), a substituted or unsubstituted alkynyl group (having 2 to 30 carbon atoms, for example, ethynyl, phenylethynyl), a substituted or unsubstituted aryl group (having 6 to 3 carbon atoms).
0, for example phenyl, naphthyl, 3,5-bis (octadecaneamido) phenyl, 2-hexadecanesulfonamidophenyl, 4-dodecyloxyphenyl), or at least one of the heterocyclic groups (N, O, S, Se heteroatoms). 5-membered to 20-membered rings, including 3
-Pyridyl, 2-furyl, 3-thiazolyl, benzotriazolyl, benzimidazolyl).

Examples of the substituent of R ¹⁷ include those mentioned as the substituent of R ¹⁴ .

R ¹² and R ^{13 in the} formula (I) represent a hydrogen atom or a substituent having a Hammett's substituent constant σ _p of 0.3 or less. Examples thereof include alkyl groups (having 1 to 30 carbon atoms, such as methyl, ethyl, isopropyl, t
-Butyl, decyl, hexadecyl, cyclohexyl, benzyl, t-octyl), aryl group (having 6 to 3 carbon atoms)
0, for example, phenyl, naphthyl), an alkoxy group (having 1 to 30 carbon atoms, for example, methoxy, hexyloxy, hexadecyloxy, 2-dodecyloxy, benzyloxy), an aryloxy group (having 6 to 30 carbon atoms, for example, phenoxy, naphthoxy). ), An alkylthio group (having 1 to 3 carbon atoms)
0, for example methylthio, hexylthio, dodecylthio,
Benzylthio), an arylthio group (having 6 to 30 carbon atoms, for example, phenylthio, naphthylthio, 2-butyloxy-
5-t-octylphenyl), amide group (having 1 to 3 carbon atoms)
0, for example, acetamide, butanamide, hexadecanamide, benzamide), sulfonamide group (having 1 carbon atom)
To 30, for example, methanesulfonamide, octanesulfonamide, hexadecanesulfonamide, benzenesulfonamide), ureido group (having 1 to 30 carbon atoms, for example 3)
-Methylureido, 3-dodecylureido, 3-phenylureido), urethane group (having 2 to 30 carbon atoms, for example, methoxycarbonylamino, decyloxycarbonylamino, phenoxycarbonylamino), sulfamoylamino group (having 30 or less carbon atoms, Examples thereof include 3-methylsulfamoylamino, 3-phenylsulfamoylamino), a halogen atom (eg, chlorine, bromine, fluorine), a hydroxy group or-(B) _k- X.

R ¹² and R ¹³ may have a substituent,
Examples of those substituents include those mentioned as the substituents possessed by R ¹⁴ .

Next, the compound of formula (II) will be described in detail.

Q ^{1 in} formula (II) is a divalent group containing at least one heteroatom. Examples thereof include amide bond, divalent amino group, ether bond, thioether bond, imino bond, sulfonyl bond, carbonyl group,
Examples thereof include an alkylene group and an alkenylene group, and a group obtained by combining a plurality of these may be used, and these may further have a substituent. However, when Q ¹ contains an ether bond, it is not a 5-membered ring.

Examples of the heterocycle completed with Q ¹ are as follows.

[0024]

[Chemical 7]

[0025]

[Chemical 8] R ²¹ is a group capable of substituting for the hydroquinone nucleus, and specifically, in addition to the group described for R ¹³ in the formula (I), a substituted or unsubstituted acyl group (preferably having a carbon number of 1 to 30) And, for example, acetyl, octanoyl, benzoyl, chloroacetyl, 3-carboxypropionyl, octadecanoyl), a substituted or unsubstituted alkoxycarbonyl group (preferably having 2 to 30 carbon atoms, for example, methoxycarbonyl, octylcarbonyl, phenoxy). Carbonyl, octadecyloxycarbonyl, methoxyethoxycarbonyl), a substituted or unsubstituted carbamoyl group (preferably having 1 to 30 carbon atoms, for example, carbamoyl,
N-propylcarbamoyl, N-hexadecylcarbamoyl, N- {3- (2,4-di-tert-pentylphenoxy) propyl}, N-phenylcarbamoyl, N
-(3-dodecyloxybutyl), pyrrolidinocarbonyl), a substituted or unsubstituted sulfamoyl group (preferably having 0 to 30 carbon atoms, for example, sulfamoyl, dibutylsulfamoyl), a substituted or unsubstituted sulfonyl group (preferably Has 1 to 30 carbon atoms, and is, for example, methanesulfonyl, benzenesulfonyl, p-dodecylbenzenesulfonyl) or a heterocyclic group (N, O, S, Se).
A 5-membered to 20-membered ring containing at least one of 5-tetrazolyl, 2-benzoxazolyl, 2-thiazolyl, 2-imidazolyl, 2-pyridyl and morpholino.

A, A'in the formulas (I) and (II),
B and X will be described in detail.

In the formulas (I) and (II), when A and A'represent a group which can be removed by an alkali (hereinafter referred to as a precursor group), preferred examples thereof include the following: an acyl group. , An alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an imidoyl group, an oxalyl group, a sulfonyl group, and the like, which can be hydrolyzed; a group of the type utilizing the reverse Michael reaction described in US Pat. No. 4,009,029. Precursor group; Precursor group of the type described in U.S. Pat. No. 4,310,612 which utilizes an anion generated after the ring opening reaction as an intramolecular nucleophilic group; U.S. Pat. No. 3,674,47.
No. 8, No. 3,932,480 or No. 3,993.
No. 661, a precursor group which causes a cleavage reaction by electron transfer of an anion through a conjugated system;
A precursor group described in U.S. Pat. No. 4,335,200, which causes a cleavage reaction by electron transfer of an anion reacted after ring cleavage; or U.S. Pat. No. 4,363,86.
It is a precursor group utilizing the imidomethyl group described in No. 5 and No. 4,410,618.

In the formulas (I) and (II), the group represented by B is-(B) _k after the hydroquinone mother nucleus becomes a quinone form oxidized by the developing agent oxidant during development.
It represents a divalent group capable of releasing -X and further releasing X, and may have a function of adjusting its release timing. Further, it may be a group serving as a coupler which reacts with another molecule of an oxidized product of a developing agent to release X, or a redox group. Here, when k is 0, it means that X is directly bonded to the hydroquinone mother nucleus, and when k is 2 or more, two or more combinations of the same or different B are represented.

Examples of groups in which B has a timing adjusting function include, for example, US Pat. Nos. 4,248,962 and 4,4.
409,323, British Patent 2,096,783,
U.S. Pat. No. 4,146,396, JP-A-51-14
No. 6,828, and those described in JP-A-57-56,837. The Time (timing control group) may be a combination of two or more selected from those described in these.

Preferred examples of the timing control group include:
The following are listed.

(1) Group Utilizing Cleavage Reaction of Hemiacetal For example, US Pat. No. 4,146,396, JP-A-60.
No. 249148 and No. 60-249149 are mentioned.

(2) Group that causes cleavage reaction by utilizing intramolecular nucleophilic substitution reaction For example, the timing group described in US Pat. No. 4,248,962 can be mentioned.

(3) A group which causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system.

For example, those described in US Pat. Nos. 4,409,323 and 4,421,845 can be mentioned.

(4) A group which utilizes a cleavage reaction by hydrolysis of an ester.

For example, West German Published Patent No. 2,626,31
The linking group described in No. 5 is mentioned.

(5) A group which utilizes a cleavage reaction of an imino ketal.

Examples thereof include the linking groups described in US Pat. No. 4,546,073.

Examples of the group represented by B being a coupler or a redox group include the following.

The coupler, for example, in the case of a phenol type coupler, is one that binds to the hydroquinone nucleus at the oxygen atom excluding the hydrogen atom of the hydroxyl group. Also, 5
In the case of a pyrazolone-type coupler, it is bonded to a hydroquinone nucleus at an oxygen atom obtained by removing a hydrogen atom from a hydroxy group of a tautomerism of 5-hydroxypyrazole.

Each of these functions as a coupler only after leaving the hydroquinone nucleus, reacts with the oxidized form of the developing agent, and releases X bonded to their coupling positions.

Preferred examples when B is a coupler include the following formulas (C-1) to (C-4).

[0043]

[Chemical 9] In the formula, V ₁ and V ₂ represent a substituent, and V ₃ , V ₄ ,
V ₅ and V ₆ represent a nitrogen atom or a substituted or unsubstituted methine group, V ₇ represents a substituent, and x represents an integer of 0 to 4. When x is an integer of 2 or more, V _7's represent the same or different, and two V _7's may be linked to each other to form a cyclic structure. V ₈ is a -CO- group,-
A SO ₂ — group, an oxygen atom or a substituted imino group,
₉ to 5-membered not ring with -V ₈ -N-C = C- represents a nonmetallic atom group for forming an 8-membered ring, V ₁₀ represents a hydrogen atom or a substituent. Here, * means the bond to the hydroquinone nucleus, and ** means the bond to X.

In the formulas (I) and (II), when the group represented by B is a redox group, the redox group is preferably represented by the following formula (R-1).

[0045]

[Chemical 10] In the formula, P and Q each independently represent an oxygen atom or a substituted or unsubstituted imino group, at least one of n X and Y represents a methine group having -X as a substituent, and other X And Y represent a substituted or unsubstituted methine group or a nitrogen atom, n represents an integer of 1 to 3 (n Xs, n Ys represent the same or different), A represents a hydrogen atom or It represents a group that can be removed by an alkali and has the same meaning as A in formula (I). In addition, the case where any two substituents of P, X, Y, Q and A are linked as a divalent group to form a cyclic structure is also included. For example, (X = Y) _n forms a benzene ring, a pyridine ring, or the like.

Among the groups represented by the formula (R-1), particularly preferred groups are those represented by the following formula (R-2) or (R-3).

[0047]

[Chemical 11] In the formula, the * mark represents the position of bonding to the hydroquinone mother nucleus, and the ** mark represents the position of bonding to X.

R ₆₄ represents a substituent, and q represents an integer of 0, 1 or 3. When q is 2 or more, two or more R ₆₄
May be the same or different. Further, when two R ₆₄ are substituents on adjacent carbons, the case where they are each a divalent group and linked to each other to represent a cyclic structure is also included.

Examples of R ⁶⁴ include those mentioned for R ²¹ in the formula (II).

X means a development inhibitor residue. Preferred examples of X include a compound residue having a mercapto group bonded to the heterocycle represented by the formula (X-1) or a heterocyclic compound residue capable of forming an iminosilver represented by the formula (X-2). can give.

[0051]

[Chemical 12] In the formula, Z ₁ represents a group of non-metal atoms necessary for forming a monocyclic ring or a condensed ring heterocycle, and Z ₂ together with N forms a group of nonmetallic atoms necessary for forming a monocycle or a condensed ring heterocycle. Represents These heterocycles may have a substituent, and * represents a position bonded to B. The hetero ring formed by Z ₁ and Z ₂ is more preferably a 5-membered to 8-membered hetero ring containing at least one of nitrogen, oxygen, sulfur and selenium as a hetero atom, and most preferably 5 It is a membered ring or a 6-membered heterocycle.

Examples of the heterocycle represented by Z ₁ include azoles (eg, tetrazole, 1,2,4-triazole, 1,2,3-triazole, 1,3,4-thiadiazole, 1,3,4). -Oxadiazole, 1,3-thiazole, 1,3-oxazole, imidazole, benzothiazole, benzoxazole, benzimidazole, pyrrole, pyrazole, indazole), azaindenes (e.g., tetrazaindene, pentazaindene,
Triazaindene) and azines (eg pyrimidine, triazine, pyrazine, pyridazine).

Examples of the heterocycle represented by Z ₂ are triazoles (eg 1,2,4-triazole, benzotriazole, 1,2,3-triazole), indazole, benzimidazole, azaindenes (eg tetrazine). Den, pentazaindene), and tetrazole.

The preferred substituents contained in the development inhibitors represented by formulas (X-1) and (X-2) are as follows.

That is, R ₇₇ group, R ₇₈ O- group, R ₇₇ S-
Group, R ₇₇ OCO— group, R ₇₇ OSO ₂ — group, halogen atom, cyano group, nitro group, R ₇₇ SO ₂ — group, R ₇₈ CO—
Group, R ₇₇ COO-group, R ₇₇ SO ₂ N (R ₇₈ ) -group, R ₇₈
N (R ₇₉ ) SO ₂ — group, R ₇₈ N (R ₇₉ ) CO— group, R ₇₇
C (R ₇₈ ) = N-group, R ₇₇ N (R ₇₈ ) -group, R ₇₈ CON
(R ₇₉ ) -group, R ₇₇ OCON (R ₇₈ ) -group, R ₇₈ N (R
₇₉₎ CON (R ₈₀₎ - group, or include R ₇₇ SO ₂ O- group. Here, R ₇₇ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ₇₈ , R ₇₉ and R ₈₀ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. When two or more R ₇₇ , R ₇₈ , R ₇₉ and R ₈₀ are present in one molecule, they may be linked to form a ring (for example, a benzene ring).

Examples of the compound represented by the formula (X-1) include substituted or unsubstituted mercaptoazoles (eg 1-phenyl-5-mercaptotetrazole, 1-propyl-5-mercaptotetrazole, 1-butyl-). 5
-Mercaptotetrazole, 2-methylthio-5-mercapto-1,3,4-thiadiazole, 3-methyl-4
-Phenyl-5-mercapto-1,2,4-triazole, 1- (4-ethylcarbamoylphenyl) -2-mercaptoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2- Mercaptobenzoxazole, 2-phenyl-5-mercapto-1,3,4-oxadiazole, 1- {3- (3-methylureido) phenyl} -5-mercaptotetrazole, 1- (4-nitrophenyl)- 5-mercaptotetrazole, 5-
(2-Ethylhexanoylamino) -2-mercaptobenzimidazole), a substituted or unsubstituted mercaptoazaindene (for example, 6-methyl-4-mercapto-1,3,3a, 7-tetraazaindene, 4, 6-dimethyl-2-mercapto-1,3,3a, 7-tetraazaindene) and substituted or unsubstituted mercaptopyrimidines (eg, 2-mercaptopyrimidine, 2-mercapto-4-methyl-6-hydroxypyrimidine) Can be mentioned.

Examples of the heterocyclic compound capable of forming imino silver include substituted or unsubstituted toluazoles (eg 1,2,4-triazole, benzotriazole, 5
-Methylbenzotriazole, 5-nitrobenzotriazole, 5-bromobenzotriazole, 5-n-butylbenzotriazole, 5,6-dimethylbenzotriazole), substituted or unsubstituted indazoles (for example, indazole, 5-nitroindazole, 3-nitroindazole, 3-chloro-5-nitroindazole), and substituted or unsubstituted benzimidazoles (for example, 5-nitrobenzimidazole, 5,6-dichlorobenzimidazole).

Further, X is separated from B in the formulas (I) and (II) to become a compound having a development inhibitory property, and then it undergoes a certain chemical reaction with a developer component to substantially form a compound. It may be a compound that does not have development inhibitory property or is significantly reduced. Examples of the functional group that undergoes such a chemical reaction include an ester group, a carbonyl group, an imino group, an immonium group, a Michael addition accepting group, and an imide group.

Examples of such a deactivating type development inhibitor include, for example, US Pat. No. 4,477,563 and JP-A-60-2.
18644, No. 60-221750, No. 60-233.
No. 650, or the development inhibitor residues described in No. 61-11743.

Of these, those having an ester group are particularly preferable. Specifically, for example, 1- (3-phenoxycarbonylphenyl) -5-mercaptotetrazole, 1- (4-phenoxycarbonylphenyl) -5.
-Mercaptotetrazole, 1- (3-maleimidophenyl) -5-mercaptotetrazole, 5-phenoxycarbonylbenzotriazole, 5- (4-cyanophenoxycarbonyl) benzotriazole, 2-phenoxycarbonylmethylthio-5-mercapto-1,
3,4-thiadiazole, 5-nitro-3-phenoxycarbonylimidazole, 5- (2,3-dichloropropyloxycarbonyl) benzotriazole, 1- (4
-Benzoyloxyphenyl) -5-mercaptotetrazole, 5- (2-methanesulfonylethoxycarbonyl) -2-mercaptobenzothiazole, 5-cinnamoylaminobenzotriazole, 1- (3-vinylcarbonylphenyl) -5-mercaptotetrazole , 5-
Succinimidomethylbenzotriazole, 2- {4-
Succinimidophenyl} -5-mercapto-1,3,3
4-oxadiazole, 6-phenoxycarbonyl-2
-Mercaptobenzoxazole, 2- (1-methoxycarbonylethylthio) -5-mercapto-1,3,4
-Thiadiazole, 2-butoxycarbonylmethoxycarbonylmethylthio-5-mercapto-1,3,4-thiadiazole, 2- (N-hexylcarbamoylmethoxycarbonylmethylthio) -5-mercapto-1,3
Examples thereof include 4-thiadiazole and 5-butoxycarbonylmethoxycarbonylbenzotriazole.

Preferred as X are mercaptoazoles and benzotriazoles. Among the mercaptoazoles, mercaptotetrazoles and 5-mercapto-1,3,4-thiadiazoles and 5-mercapto-1,3,4-oxadiazoles are more preferable.

Most preferred as X are 5-mercapto-1,3,4-thiadiazoles.

In the formulas (I) and (II), k is preferably 0, 1 or 2.

Among the compounds represented by the formula (I), preferred compounds are the compounds represented by the formula (IA).

[0065]

[Chemical 13] In formula (IA), R ¹¹ , B, X, A, A ′ and k
Has the same meaning as defined in formula (I).

In formula (IA), preferred R ¹¹ is R ^{14
-N (R 16) CON (R} 15) - and R ¹⁴ OCON (R
¹⁵ )-, and R ¹⁴ , R ¹⁵ and R ¹⁶ have the same meanings as described above. Further, in the formula (IA), preferable k
Is 0 or 1.

In the formulas (I) and (II), A and A'are preferably hydrogen atoms.

In formula (II), Q ¹ is preferably --N.
^{(R 28) -CO-Q 2} - is represented by. Examples of Q ² are a divalent amino group, an ether bond, a thioether bond,
Examples thereof include an alkylene group, an ethylene bond, an imino bond, a sulfonyl bond, a carbonyl group, an arylene group, a divalent heterocyclic group, and a group obtained by combining a plurality of these.

R ²⁸ is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and may have a substituent. Preferred as R ²⁸ is a hydrogen atom.

R ²¹ is preferably a hydrogen atom or a substituent having a Hammett's substituent constant σ _p of 0 or more.

The number of ring members of the heterocycle containing Q ¹ is preferably a 5- to 7-membered ring, and among them, a compound represented by the following formula (IIA) is more preferable.

[0072]

[Chemical 14] In the formula (IIA), Q ² has the same meaning as described above and R 2
²¹ , A, A ', B, X and k have the same meaning as in formula (II).

When R ^{11 in the} formula (IA) is R ¹⁷ CONH—, the following formulas (IB) and (IC) are preferred.

[0074]

[Chemical 15]

[0075]

[Chemical 16] In the formula, R ³⁴ and R ³⁵ each represent a substituent, n ′ represents an integer of 2 or more, m represents an integer of 1 to 5, and when m is 2 or more,
R ³⁵ may be the same or different.
A, A ', B, X and k have the same meaning as in formula (I).

Examples of R ³⁴ and R ³⁵ include compounds represented by the formula (I)
Those mentioned as the substituent which R ¹⁴ has.
Further, these substituents may be further substituted. In formula (IB), R ³⁴ preferably has 5 to 3 carbon atoms.
It is a substituted ring of 0, and n ′ is preferably 2 to 5. In formula (IC), R ³⁵ has 5 to 3 carbon atoms.
It is preferably 0.

The compounds represented by the formulas (I) and (II) may be added to any of the emulsion layers and / or the photolabile layers. The addition amount is preferably 0.001
-0.2 mmol / m < ² >, more preferably 0.01-0.1
It is in the mmol / m ² range.

In order to more specifically arrange the contents of the present invention, specific examples of the compounds represented by the formulas (I) and (II) are shown below, but the compounds usable in the present invention are not limited thereto. is not.

[0079]

[Chemical 17]

[0080]

[Chemical 18]

[0081]

[Chemical 19]

[0082]

[Chemical 20]

[0083]

[Chemical 21]

[0084]

[Chemical formula 22]

[0085]

[Chemical formula 23]

[0086]

[Chemical formula 24]

[0087]

[Chemical 25]

[0088]

[Chemical formula 26]

[0089]

[Chemical 27]

[0090]

[Chemical 28]

[0091]

[Chemical 29]

[0092]

[Chemical 30]

[0093]

[Chemical 31]

[0094]

[Chemical 32]

[0095]

[Chemical 33]

[0096]

[Chemical 34]

[0097]

[Chemical 35]

[0098]

[Chemical 36]

[0099]

[Chemical 37]

[0100]

[Chemical 38]

[0101]

[Chemical Formula 39]

[0102]

[Chemical 40]

[0103]

[Chemical 41]

[0104]

[Chemical 42]

[0105]

[Chemical 43]

[0106]

[Chemical 44]

[0107]

[Chemical 45]

[0108]

[Chemical 46]

[0109]

[Chemical 47]

[0110]

[Chemical 48]

[0111]

[Chemical 49]

[0112]

[Chemical 50]

[0113]

[Chemical 51]

[0114]

[Chemical 52] Next, the compound represented by the formula (III) will be described in detail below.

In the formula (III), R ₁ has 4 to 2 carbon atoms.
4 tertiary alkyl groups (eg t-butyl, t-pentyl, t-hexyl, 1,1,3,3-tetramethylbutyl, 1-adamantyl, 1,1-dimethyl-2-chloroethyl, 2-phenoxy- 2-propyl, bicyclo [2,2,2] octan-1-yl).

In the formula (III), R ₂ is preferably a fluorine atom or an alkyl group having 1 to 24 carbon atoms (eg methyl, ethyl, isopropyl, t-butyl, cyclopentyl, n-octyl, n-hexadecyl, benzyl). ,
An aryl group having 6 to 24 carbon atoms (eg, phenyl, p
-Tolyl, o-tolyl, 4-methoxyphenyl), an alkoxy group having 1 to 24 carbon atoms (for example, methoxy, ethoxy, butoxy, n-octyloxy, n-tetradecyloxy, benzyloxy, methoxyethoxy), carbon atom. An aryloxy group having 6 to 24 carbon atoms (for example, phenoxy, p-tolyloxy, o-tolyloxy, p-methoxyphenoxy, p-dimethylaminophenoxy, m-pentadecylphenoxy), a dialkylamino group having 2 to 24 carbon atoms (for example, Dimethylamino, diethylamino, pyrrolidino, piperidino, morpholino), alkylthio groups having 1 to 24 carbon atoms (eg methylthio, butylthio, n-octylthio, n-hexadecylthio) or arylthio groups having 6 to 24 carbon atoms (eg phenylthio, 4 -Metoki Phenylthio represents 4-t-butylphenyl thio, 4-dodecyl phenyl thio).

In the formula (III), R ₃ is preferably a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) or an alkyl group having 1 to 24 carbon atoms (eg methyl, t-butyl, n-dodecyl). ), Carbon atoms 6-24
Aryl groups (eg, phenyl, p-tolyl, p-dodecyloxyphenyl), alkoxy groups having 1 to 24 carbon atoms (eg, methoxy, n-butoxy, n-octyloxy, n-tetradecyloxy, benzyloxy, methoxy). Ethoxy), aryloxy groups having 6 to 24 carbon atoms (eg phenoxy, pt-butylphenoxy, 4
-Butoxyphenoxy), an alkoxycarbonyl group having 2 to 24 carbon atoms (for example, ethoxycarbonyl, dodecyloxycarbonyl, 1- (dodecyloxycarbonyl) ethoxycarbonyl), an aryloxycarbonyl group having 7 to 24 carbon atoms (for example, phenoxycarbonyl). , 4-t-octylphenoxycarbonyl, 2,4-
Di-t-pentylphenoxycarbonyl), a carbonamide group having 1 to 24 carbon atoms (for example, acetamide, pivaloylamino, benzamide, 2-ethylhexanamide, tetradecanamide, 1- (2,4-di-t-pentylphenoxy)) Butanamide, 3- (2,4-di-
t-pentylphenoxy) 3-dodecylsulfonyl-2
-Methylpropanamide), a sulfonamide group having 1 to 24 carbon atoms (for example, methanesulfonamide, p-toluenesulfonamide, hexadecanesulfonamide),
A carbamoyl group having 1 to 24 carbon atoms (for example, N-methylcarbamoyl, N-tetradecylcarbamoyl, N,
N-dihexylcarbamoyl, 1-octadecyl-N-
Methylcarbamoyl, N-phenylcarbamoyl), a sulfamoyl group having 0 to 24 carbon atoms (for example, N-methylsulfamoyl, N-phenylsulfamoyl, N-).
Acetylsulfamoyl, N-propanoylsulfamoyl, N-hexadecylsulfamoyl, N, N-dioctylsulfamoyl), an alkylsulfonyl group having 1 to 24 carbon atoms (for example, methylsulfonyl, benzylsulfonyl, hexa). Decylsulfonyl), having 6 to 6 carbon atoms
24 arylsulfonyl groups (eg phenylsulfonyl, p-tolylsulfonyl, p-dodecylsulfonyl,
p-methoxysulfonyl), an ureido group having 1 to 24 carbon atoms (for example, 3-methylureido, 3-phenylureido, 3,3-dimethylureido, 3-tetradecylureido), a sulfa having 0 to 24 carbon atoms. A moylamino group (for example, N, N-dimethylsulfamoylamino),
Alkoxycarbonylamino group having 2 to 24 carbon atoms (eg, methoxycarbonylamino, isobutoxycarbonylamino, dodecyloxycarbonylamino), nitro group, heterocyclic group having 1 to 24 carbon atoms (eg, 4-pyridyl, 2-phenyl). , Phthalimide, octadecylsuccinimide), a cyano group, an acyl group having 1 to 24 carbon atoms (eg, acetyl, benzoyl, dodecanoyl),
An acyloxy group having 1 to 24 carbon atoms (eg acetoxy, benzoyloxy, dodecanoyloxy), an alkylsulfonyloxy group having 1 to 24 carbon atoms (eg methylsulfonyloxy, hexadecylsulfonyloxy) or 6 to 24 carbon atoms Is an arylsulfonyloxy group (for example, p-toluenesulfonyloxy, p-dodecylphenylsulfonyloxy).

In the formula (III), k is preferably an integer of 1 or 2.

In the formula (III), X is preferably a group capable of splitting off by a coupling reaction with an oxidation product of an aromatic primary amine developing agent (referred to as splitting group), specifically, a halogen atom (fluorine group). Atom, chlorine atom, bromine atom, iodine atom), a heterocyclic group bonded to the coupling active position with a nitrogen atom having 1 to 24 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, and 6 to 24 carbon atoms An arylthio group of (for example, phenylthio, pt-butylphenylthio,
p-chlorophenylthio, p-carboxyphenylthio), an acyloxy group having 1 to 24 carbon atoms (for example, acetoxy, benzoyloxy, dodecanoyloxy),
An alkylsulfonyloxy group having 1 to 24 carbon atoms (for example, methylsulfonyloxy, butylsulfonyloxy, dodecylsulfonyloxy), 6 to 24 carbon atoms
Arylsulfonyloxy group (for example, benzenesulfonyloxy, p-chlorophenylsulfonyloxy) or a heterocyclic oxy group having 1 to 24 carbon atoms (for example, 3-
Pyridyloxy, 1-phenyl-1,2,3,4-tetrazol-5-yloxy), and more preferably a heterocyclic group or an aryloxy group bonded to the coupling active position with a nitrogen atom.

When X represents a heterocyclic group bonded to the coupling active position at a nitrogen atom, X represents, in addition to the nitrogen atom, an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom, a selenium atom or a tellurium atom. It is a 5- to 7-membered, optionally substituted monocyclic or condensed-ring heterocycle which may contain a selected heteroatom. Examples thereof include succinimide, maleimide, phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4.
-Triazole, tetrazole, indole, indazole, benzimidazole, benzotriazole, imidazolidine-2,4-dione, oxazolidine-2,4
-Dione, thiazolidine-2,4-dione, imidazolidin-2-one, oxazoline-2-one, thiazolin-2-one, benzimidazolin-2-one, benzoxazoline-2-one, benzothiazolin-2-one ,
2-pyrrolin-5-one, 2-imidazolin-5-one, indoline-2,3-dione, 2,6-dioxypurine, parabanic acid, 1,2,4-triazolidine-3,
There are 5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone, 6-pyridazone, 2-pyrazone and the like, and these heterocyclic groups may be substituted. Examples of the substituent include a hydroxyl group, a carboxyl group, a sulfo group, an amino group (for example, amino, N-methylamino, N, N-dimethylamino, N, N-diethylamino, anilino, pyrrolidino, piperidino, morpholino), There are the substituents given as examples of R ₃ above.

When X represents an aryloxy group, X is an aryloxy group having 6 to 24 carbon atoms, and is substituted with a group selected from the above-mentioned substituent group mentioned when X is a heterocyclic group. May be. As the substituent, a carboxyl group, a sulfo group, a cyano group, a nitro group, an alkoxycarbonyl group, a halogen atom, a carbonamido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkyl group, an alkylsulfonyl group, an arylsulfonyl group or an acyl group. Is preferred.

Next, the above-mentioned substituents R ₁ , R ₂ , R ₃
With respect to each of X and X, examples of substituents particularly preferably used in the present invention will be described.

In the formula (III), R ₁ is particularly preferably a t-butyl group.

In the formula (III), R ₂ is particularly preferably a methyl group, an ethyl group, an alkoxy group, an aryloxy group or a dialkylamino group, and a methyl group, an ethyl group, an alkoxy group, an aryloxy group or a dimethylamino group. Is most preferred.

In the formula (III), R ₃ is particularly preferably an alkoxy group, a carbonamido group or a sulfonamide group.

In the formula (III), X is particularly preferably a heterocyclic group or an aryloxy group bonded to the coupling active position with a nitrogen atom.

When X represents the above-mentioned heterocyclic group, X is preferably represented by the following formula (IIIA).

[0128]

[Chemical 53] In the formula (III A), Z is —O—CR ₄ (R ₅ ) —,
_{-S-CR 4 (R 5)} -, - NR 6 -CR 4 (R 5)
_{-, - NR 6 -NR 7 -} , - NR 6 -CO -, - CR 4
(R ₅ ) -CR ₈ (R ₉ )-, or -CR 10 = CR ₁₁
Represents-. Here, R ₄ , R ₅ , R ₈ and R ₉ represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group or an amino group, R ₆ and R ₇ represent a hydrogen atom, an alkyl group, an aryl group, an alkylsulfonyl group, an arylsulfonyl group or an alkoxycarbonyl group, and R ₁₀ and R ₁₁ represent a hydrogen atom, an alkyl group or an aryl group. R ₁₀ and R ₁₁ may combine with each other to form a benzene ring. R ₄ and R ₅ , R ₅ and R ₆ , R ₆ and R ₇ , or R ₄ and R ₈ are bonded to each other to form a ring (for example, cyclobutane,
Cyclohexane, cycloheptane, cyclohexene, pyrrolidine, piperidine) may be formed.

Among the heterocyclic groups represented by the formula (IIIA), a particularly preferable one is Z in the formula (IIIA).
_{O-CR 4 (R 5)} -, - NR 6 -CR 4 (R 6) - or -NR ₆ -NR ₇ - is a heterocyclic group which is.

The total number of carbon atoms in the heterocyclic group represented by the formula (IIIA) is 2 to 24, preferably 4 to 20 and more preferably 5 to 16. Examples of the heterocyclic group represented by the formula (IIIA) include succinimido group, maleinimido group, phthalimido group, 1-methylimidazolidine-2,
4dione-3-yl group, 1-benzylimidazolidine-
2,4-dione-3-yl group, 5,5-dimethyloxazolidin-2,4-dione-3-yl group, 5-methyl-
5-propyloxazolidin-2,4-dione-3-yl group, 5,5-dimethylthiazolidin-2,4-dione-3-yl group, 5,5-dimethylimidazolidine-2,
4-dione-3-yl group, 3-methylimidazolidintrion-1-yl group, 1,2,4-triazolidine-
3,5-dione-4-yl group, 1-methyl-2-phenyl-1,2,4-triazolidine-3,5-dione-4
-Yl group, 1-benzyl-2-phenyl-1,2,4-
Triazolidine-3,5-dione-4-yl, 5-hexyloxy-1-methylimidazolidin-2,4-dione-3-yl group, 1-benzyl-5-ethoxyimidazolidin-2,4-dione- 3-yl group, 1-benzyl-
5-dodecyloxyimidazolidine-2,4-dione-
A 3-yl group can be mentioned.

Among the above heterocyclic groups, imidazolidine-
The 2,4-dione-3-yl group (eg 1-benzyl-imidazolidin-2,4-dione-3-yl) is the most preferred group.

When X represents an aryloxy group, 4-
Carboxyphenoxy, 4-methylsulfonylphenoxy, 4- (4-benzyloxyphenylsulfonyl) phenoxy, 4- (4-hydroxyphenylsulfonyl)
Phenoxy, 2-chloro-4- (3-chloro-4-hydroxyphenylsulfonyl) phenoxy, 4-methoxycarbonylphenoxy, 2-chloro-4-methoxycarbonylphenoxy, 2-acetamido-4-methoxycarbonylphenoxy, 4-iso. Propoxycarbonylphenoxy, 4-cyanophenoxy, 2- [N- (2-hydroxyethyl) carbamoyl] phenoxy, 4-nitrophenoxy, 2,5-dichlorophenoxy, 2,3,3.
5-trichlorophenoxy, 4-methoxycarbonyl-
2-Methoxyphenoxy and 4- (3-carboxypropanamide) phenoxy are the most preferred examples.

The coupler represented by the formula (III) is a dimer which is bonded to each other through a divalent or divalent or more divalent group in a benzene ring substituted by the substituents R ₁ , X or R ₂ , (R ₃ ) _k. It may also form a body or higher multimers.
In this case, the number of carbon atoms shown in each of the above substituents may be out of the specified range.

When the coupler represented by the formula (III) forms a multimer, an addition polymer having a yellow dye-forming coupler residue, a homopolymer or copolymer of an ethylenically unsaturated compound (yellow color-forming monomer) is typical. Here is an example.
In this case, the multimer contains a repeating unit represented by the following formula (III B), and one or more kinds of yellow color-forming repeating units represented by the formula (III B) may be contained in the multimer. It may be a copolymer containing one or more non-color-forming ethylene type monomers.

[0135]

[Chemical 54] In the formula, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom, A represents -CONH-, -COO-, or a substituted or unsubstituted phenylene group, and B represents a substituted or unsubstituted group. Represents an alkylene group, a phenylene group or an aralkylene group, wherein L is -CONH-, -NHCO
NH-, -NHCOO-, -NHCO-, -OCONH
-, -NH-, -COO-, -OCO-, -CO-,-
O -, - S -, - SO 2 -, - NHSO 2 - or -S
Representing the O ₂ NH-. a, b, and c represent 0 or 1.
Q is R ₁ , X or R of the compound represented by formula (III)
₂ represents a yellow coupler residue in which a hydrogen atom has been removed from the substituted benzene ring of (R ₃ ) _k .

As the multimer, a copolymer of a yellow color-forming monomer represented by the formula (III B) coupler unit and a non-color-forming ethylene-like monomer shown below is preferable.

The non-color forming ethylene type monomer which is not coupled with the oxidation product of the aromatic primary amine developing agent is:
Acrylic acid, α-chloroacrylic acid, α-alkylacrylic acid (for example, methacrylic acid) An amide or ester derived from these acrylic acids (for example, acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, dimethacrylate). Acetone acrylamide, methyl acrylate, ethyl acrylate,
n-propyl acrylate, n-butyl acrylate,
t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), vinyl esters (eg vinyl acetate, vinyl propio). And vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg styrene and its derivatives such as vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene),
Itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (eg vinyl ethyl ether), maleic acid ester, N-vinyl-2-
Pyrrolidone, N-vinyl pyridine and 2- and -4
-Such as vinyl pyridine.

Particularly, acrylic acid ester, methacrylic acid ester and maleic acid ester are preferable. Two or more kinds of the non-color forming ethylene type monomer used here can be used together. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene,
Butyl methacrylate and methacrylic acid, methyl acrylate and diacetone acrylamide can be used.

As is well known in the field of polymer couplers, the ethylenically unsaturated monomer for copolymerization with the vinyl monomer corresponding to the above formula (IIIB) has a physical property of the copolymer to be formed. And / or chemical properties such as solubility, compatibility of the photographic colloid composition with the binder (eg gelatin), its flexibility, thermal stability can be selected to be favorably influenced.

The yellow polymer coupler used in the present invention is prepared by dissolving a lipophilic polymer coupler obtained by polymerization of a vinyl-type monomer which gives a coupler unit represented by the above formula (IIIB) in an organic solvent and gelatinizing it. It may be emulsified and dispersed in the form of a latex in an aqueous solution, or may be directly emulsified by an emulsion polymerization method.

A method for emulsion-dispersing a lipophilic polymer coupler in the form of a latex in an aqueous gelatin solution is described in US Pat. No. 3,451,820, and an emulsion polymerization is described in US Pat. Nos. 4,080,211 and 3,370. The method described in No. 952 can be used.

Specific examples of X and R ₃ of the yellow dye-forming coupler represented by the formula (III) are shown below, but the invention is not limited thereto.

[0143]

[Chemical 55]

[0144]

[Chemical 56]

[0145]

[Chemical 57]

[0146]

[Chemical 58]

[0147]

[Chemical 59]

[0148]

[Chemical 60]

[0149]

[Chemical formula 61] Next, specific examples of the yellow dye-forming coupler represented by the formula (III) are shown in Tables 1 and 2, but the present invention is not limited thereto.

[0150]

[Table 1]

[0151]

[Table 2] In the table, the numbers in parentheses represent the numbers given to the specific examples of X and R ₃ , and the numbers in [] represent the substitution position on the anilide group.

The couplers of the present invention may be used alone or in combination of two or more. It may also be used as a mixture with a known yellow dye-forming coupler.

The coupler of the present invention can be used in any layer of the light-sensitive material, but it is preferably used in the light-sensitive silver halide emulsion layer or its adjacent layer, and more preferably in the light-sensitive silver halide emulsion layer. Most preferred.

The coupler of the present invention can be synthesized by a conventionally known synthesis method. Specific examples thereof include the synthesis method described in JP-A-63-123047.

The amount of the coupler of the present invention used in the light-sensitive material is 1 × 10 ^-5 mol to 10 ^-2 mol per m ² .
It is preferably 1 × 10 ⁻⁴ mol to 5 × 10 ⁻³ mol, more preferably 2 × 10 ⁻⁴ mol to 10 ⁻³ mol.

The light-sensitive material of the present invention may have at least one silver halide emulsion layer of a blue color-sensitive layer, a green color-sensitive layer and a red color-sensitive 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. Is. In that case, the photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, it is generally a unit photosensitive layer. The arrangement is such that the red color-sensitive layer, the green color-sensitive layer and the blue color-sensitive layer are arranged in this order from the support side. 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.

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

For the intermediate layer, JP-A-61-43748 is used.
No. 59-113438, No. 59-113440
Nos. 61-20037 and 61-20038, the couplers, the DIR compounds, etc. may be contained, and a color mixing inhibitor may be contained as is usually used.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are 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. A two-layer structure of emulsion layers can be preferably used. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also,
JP-A-57-112751, JP-A-62-200350
No. 62-206541, No. 62-206543, etc., 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.

Explaining based on a specific example, from the farthest side from the support, a 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), also BH / BL / GL / G
H / RH / RL order or BH / BL / GH / GL /
It can be installed in the order of RL / RH.

Further, as described in JP-B-55-34932, blue-sensitive layers / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. Further, JP-A-56-25738 and JP-A-62-63.
As described in Japanese Patent No. 936, a blue-sensitive layer / GL / RL / GH / RH may be arranged in this order from the side farthest from the support.

As another specific example, Japanese Examined Patent Publication (Kokoku) No. 49-1549.
As described in Japanese Patent Publication No. 5, a silver halide emulsion layer having the highest photosensitivity as an upper layer, a silver halide emulsion layer having a lower photosensitivity as an intermediate layer, and a halogen having a photosensitivity lower than that of an intermediate layer as a lower layer. An example is an arrangement in which silver halide emulsion layers are 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, in the same color-sensitive layer, the medium sensitivity from the side distant from the support is obtained. The layers may be arranged in the order of emulsion layer / high-speed emulsion layer / low-speed emulsion layer.

In addition, the layers 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, 4
In the case of more than one layer, the arrangement may be changed as described above.

In order to improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, 4,707,436 and JP-A-62-160448 are used.
No. 63-89850, and BL, G described in the specification.
It is preferable to dispose a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as L and RL, adjacent to or in proximity to the main photosensitive layer.

As described above, various layer structures and arrangements can be selected according to the purpose of each photosensitive material.
The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. .. Particularly preferred is from about 2 mol% to about 10
Silver iodobromide or silver iodochlorobromide containing up to mol% silver iodide.

The silver halide grains in a photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, and irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof.

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

The silver halide photographic emulsion which can be used in the present invention is described in, for example, Research Disclosure (RD) No.
17643 (December 1978), pp. 22-23,
"I. Emulsion preparation
ion and types) ”, and ibid. 187
16 (November 1979), p. 648, ibid. 3071
05 (November 1989), pages 863-865, and Graphide, "Physics and Chemistry of Photography," published by Paul Montel, P. Glafkides, Chemie et P.
hisque Photographie, Pa
ul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (G.F. Duffi).
n, Photographic Emulsion C
chemistry (Focal Press, 196)
6)), "Production and coating of photographic emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al. , Making and Coating P
photographic Emulsion, Foca
l Press, 1964) and the like.

US Pat. Nos. 3,574,628 and 3,
655,394 and British Patent No. 1,413,748.
The monodisperse emulsions described in JP-A No. 1994-1999 are also preferable.

Also, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering (Gutoff, Photograph).
ic Science and Engineererli
ng), Vol. 14, pp. 248-257 (1970);
U.S. Pat. Nos. 4,434,226 and 4,414,31
0, 4,433,048, 4,439,520
No. 2,112,157 and the like, and can be easily prepared.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining,
Further, it may be bonded with 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-mentioned emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which is formed inside the grain, or a type which has a latent image both on the surface and inside. It must be a negative emulsion. In the case of the internal latent image type, the core / shell type internal latent image type emulsion described in JP-A-63-264740 may be used. The preparation method of this core / shell type internal latent image type emulsion is described in JP-A-5-52.
9-133542. The thickness of the shell of this emulsion is 3 to 40 nm, although it depends on the development process.
Is preferred, and 5-20 nm is particularly preferred.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process are Research Disclosure No. 17643, ibid. 18716 and ibid.
No. 307105, the relevant parts are summarized in the table below.

The light-sensitive material of the present invention comprises a photosensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more kinds of emulsions having at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer.

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The prepared silver halide grains and colloidal silver can be preferably used in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer.
The fogged silver halide grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed portion and exposed portion of the light-sensitive material. .. A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,498 and JP-A-59-214852.

The silver halide forming the inner core of a core / shell type silver halide grain having a fogged grain 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. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.7.
It is preferably 5 μm, particularly preferably 0.05 to 0.6 μm. Also,
The particle shape is not particularly limited and may be regular particles. Although it may be a polydisperse emulsion, it is preferably monodisperse (in which at least 95% of the weight or number of silver halide grains has a grain size within ± 40% of the average grain size).

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 if necessary, silver chloride and / or
Alternatively, it may contain silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average diameter of circles corresponding to the projected area) of 0.01 to 50 μm, more preferably 0.02 to 0.2 μm.

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 optically sensitized and spectral sensitization is not required. 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.

The coated silver amount of the light-sensitive material of the present invention is 6.0 g /
m ² or less is preferable, and 4.5 g / m ² or less is most preferable.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table.

Types of additives RD17643 RD18716 RD307105 1 Chemical sensitizer page 23 648 page right column 866 2 Sensitivity enhancer page 648 right column 3 Spectral sensitizer, page 23-24 page 648 right column 866-868 page strong Color sensitizer: page 649, right column, 4 whitening agent, page 24, 647 page, right column, 868 page, 5 fog prevention, 24 to 25 pages, 649 page, right column, 868-870 pages, stabilizer, 6 light absorber, 25-26 pages, 649 Page right column page 873 filter dye, ~ page 650 left column UV absorber 7 anti-stain agent page 25 right column page 650 left column ~ right column 872 page 8 dye image stabilizer page 25 650 page left column page 872 9 hardener Page 26 Page 651 Left column 874 to 875 10 Binder Page 26 Page 651 Left column 873 to 874 Page 11 Plasticizers and lubricants Page 27 650 Right column 876 Page 12 Coating aid, Page 26 to 27 650 Right column 875 Page 876 Surface active agent 13 Static page 27 page 650 Right column page 876 to 877 Anti-static agent 14 matting agent page 876 to 879 To prevent performance degradation, by reacting with formaldehyde as described in U.S. Patent 4,411,987 No. and Nos 4,435,503, it is preferable to add a compound capable of immobilizing the photosensitive material.

The light-sensitive material of the present invention can be prepared according to US Pat.
0,456, 4,788,132, JP-A-62.
It is preferable to incorporate the mercapto compounds described in JP-A-18539 and JP-A-1-283551.

The light-sensitive material of the present invention can be incorporated into Japanese Patent Application Laid-Open No. 1-1060.
It is preferable to contain a compound which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof, as described in No. 52, regardless of the amount of developed silver produced by the development processing.

In the light-sensitive material of the present invention, the international publication W088 /
No. 04794, dyes dispersed by the method described in JP-A-1-502912 or EP317,308A,
U.S. Pat. No. 4,420,555, Japanese Patent Laid-Open No. 1-25935.
It is preferable that the dye described in No. 8 is contained.

Various color couplers can be used in the light-sensitive material of the present invention, specific examples of which are described in Research Disclosure No. 17643, VII-C to G,
And the same No. 307105, VII-C to G.

Examples of the yellow coupler which can be used in combination with the yellow coupler of the present invention include US Pat.
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4,401,752, No. 4,
No. 248,961, Japanese Patent Publication No. 58-10739, British Patent Nos. 1,425,020 and 1,476,760.
U.S. Pat. Nos. 3,973,968 and 4,31
Those described in 4,023, 4,511,649, European Patent 249,473A and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984)
Mon), JP-A-60-33552, Research Disclosure NO. 24230 (June 1984), JP-A Nos. 60-43659, 61-72238, and 60-.
No. 35730, No. 55-118034, No. 60-18.
Those described in US Pat. No. 5951, US Pat. No. 4,500,630, US Pat. No. 4,540,654, US Pat. No. 4,556,630, and International Publication W088 / 04795 are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
52,212, 4,146,396, and 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, 249,453A, U.S. Patents 3,446,622, 4,333,999.
No. 4,775,616, No. 4,451,55
9, No. 4,427,767, No. 4,690,8
89, 4,254,212 and 4,296,4
Those described in JP-A No. 199, JP-A-61-42658 and the like are preferable. Further, JP-A 64-553 and 64-5.
54, 64-555 and 64-556, and pyrazoloazole couplers described in US Pat. No. 4,818,
The imidazole couplers described in No. 672 can also be used.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,084.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, U.S. Pat. No. 2,102,137, European Patent 341,188A and the like.

As couplers in which the color forming dye has an appropriate diffusibility, US Pat. No. 4,366,237, US Pat. No. 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 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, ibid. VII of 307105-
Section G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-
39413, US Pat. Nos. 4,004,929, 4,138,258, and US Pat. No. 1,146,368.
Those described in No. 10 are preferable. Also, US Pat.
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in 4,181,
It is also preferable to use a coupler described in U.S. Pat. No. 4,777,120 having a dye precursor group capable of reacting with a developing agent to form a dye as a leaving group.

R. D. No. 11449, 24241,
The bleaching accelerator releasing coupler described in JP-A No. 61-201247 is effective for shortening the processing time having a bleaching ability, and is particularly useful for a light-sensitive material using the tabular silver halide grains described above. When added, the effect is great. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent 2,097,140.
No. 2,131,188, JP-A-59-1576.
Nos. 38 and 59-170840 are preferable. Also, JP-A-60-107029 and JP-A-60-25
2340, JP-A-1-44940, and 1-4568.
Compounds capable of releasing a fogging agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized product of a developing agent described in No. 7 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
Couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
No. 618 and the like, multiequivalent couplers, JP-A-60-18.
5950, DI described in JP-A-62-24252, etc.
R redox compound-releasing coupler, DIR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that recolors after separation described in European Patent Nos. 173,302A and 313,308A , A ligand releasing coupler described in U.S. Pat. No. 4,555,477, a coupler releasing a leuco dye described in JP-A-63-75747, and a fluorescent dye described in U.S. Pat. No. 4,774,181. Examples thereof include releasing couplers.

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 point 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 (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate). , Bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), phosphoric acid or phosphonic acid Esters (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-
Ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate), benzoic acid esters (for example, 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amide (Eg, N, N-diethyldodecane amide, N, N-
Diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (eg isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (eg bis (2-ethylhexyl) sebacate, Dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (eg N, N-dibutyl-2-butoxy-5-ter).
t-octylaniline) and hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene). As the auxiliary solvent, for example, the boiling point is about 3
Organic solvents above 0 ° C, preferably above 50 ° C and below about 160 ° C can be used. Typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in, for example, US Pat. No. 4,19.
No. 9,363, West German Patent Application (OLS) No. 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-62-257747 are used.
No. 272248, and 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol described in JP-A No. 1-80941. It is preferable to add various preservatives or antifungal agents such as-(4-thiazolyl) benzimidazole.

Suitable supports which can be used in the present invention are, for example, the above-mentioned DR. No. 17643, page 28, ibid. 18
716, right column, page 647 to left column, page 648, and ibid.
307105, page 879.

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, and 18 μm or less.
m or less is more preferable, and 16 μm or less is particularly preferable.
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 55% relative humidity (2 days). Membrane swelling speed T
_1/2 can be measured according to a method known in the art. For example, A Green (A. Gr
een, et al., Photographic Science and Engineering (Photogr. Sci. E)
ng), Vol. 19, No. 2, pp. 124-129. Further, T _1/2 is a color developing solution at 30 ° C. for 3 minutes 1
90% of the maximum swollen film thickness that arrives after the treatment for 5 seconds is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling speed T _1/2 can be adjusted by adding a film-hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (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 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. The back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is 150.
~ 500% is preferred.

The color developing solution used for 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. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used. As typical examples thereof, 3-methyl-4-amino-N, N diethylaniline, 3-methyl-4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-
Mention may be made of N-ethyl-β-methoxyethylaniline and their sulphates, hydrochlorides or p-toluenesulphonates. Of these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferable. Two or more kinds of these compounds can be used in combination depending on the purpose.

The color developing solution includes a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. It is common to include a development inhibitor or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic 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 Various chelating agents such as agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids may be used in combination. Among these, typical examples of the chelating agent include, 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,
Mention may be made of N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.

Next, processing solutions and processing steps for the color reversal light-sensitive material of the present invention other than the color developing solution will be described.

Among the processing steps of the color reversal light-sensitive material of the present invention, the steps from black development to color development are as follows.

1) Black-white development-water washing-reversal-color development 2) Black-white development-water washing-light reversal-color development 3) Black-white development-water washing-color development Steps 1) to 3) are all US patents. 4,8
In place of the rinse process described in No. 04,616, it is possible to simplify the process and reduce waste liquid.

Next, the steps after color development will be described.

4) Color development-adjustment-bleach-fixing-washing-stable 5) Color development-washing-bleaching-fixing-washing-stable 6) Color development-adjusting-bleaching-washing-fixing-washing-stable 7) Color development Development-washing-bleaching-washing-fixing-washing-stable 8) Color development-bleaching-fixing-washing-stable 9) Color development-bleaching-bleaching fixing-washing-stable 10) Color development-bleaching-bleaching fixing-fixing- Washing-stable 11) Color development-bleaching-washing-fixing-washing-stable 12) Color development-adjusting-bleach-fixing-washing-stable 13) Coloring development-washing-bleach-fixing-washing-stable 14) Color development-bleach-fixing -Washing-Stable 15) Color development-Fixing-Bleach-fixing-Water washing-Stable In the processing steps 4) to 15), the washing step immediately before the stabilizing step may be omitted. On the contrary, the stabilizing process of the final process may not be performed. Any one of the above steps 1) to 3) and any one of steps 4) to 15) are connected to form a color reversal step.

Next, the processing liquid in the color reversal processing step of the present invention will be described.

Known developing agents can be used in the black and white developing solution used in the present invention. As a developing agent,
Dihydroxybenzenes (eg hydroquinone),
3-Pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-p-aminophenol), 1-phenyl-3-pyrazolines, ascorbic acid and U.S. Pat. No. 4,067,8.
The heterocyclic compounds such as 1,2,3,4-tetrahydroquinoline ring and indrene ring described in No. 72 can be used alone or in combination.

In the black-and-white developing solution used in the present invention, other preservatives (eg, sulfite, bisulfite, etc.), buffers (eg, carbonate, boric acid, borate, alkanolamine) may be added, if necessary. Alkaline agents (eg hydroxide, carbonate), dissolving tablets (eg polyethylene glycols,
These esters), pH adjusters (eg organic acids such as acetic acid), sensitizers (eg quaternary ammonium salts), development accelerators, surfactants, defoamers, film hardeners, viscosity imparting agents, etc. Can be included.

The black-and-white developing solution used in the present invention needs to contain a compound which acts as a silver halide solvent, and a sulfite salt which is usually added as a preservative serves the function thereof. Specific examples of the sulfite and other silver halide solvents that can be used include KSCN and Na.
SCN, K ₂ SO ₃ , Na ₂ SO ₃ , K ₂ S ₂ O ₅ , N
It can be mentioned _{a 2 S 2 O 5, K} 2 S 2 O 3, Na 2 S 2 O 3.

The pH value of the developer thus adjusted is selected to an extent sufficient to give the desired density and contrast, but is in the range of about 8.5 to 11.5.

In order to carry out the sensitizing process using such a black-and-white developing solution, it is usually necessary to extend the time up to about 3 times the standard process. At this time, if the processing temperature is increased, the extension time for the sensitization processing can be shortened.

PH of these color developing solution and black and white developing solution
Is generally 9 to 12. Further, the replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material. However, the concentration of bromide ion in the replenisher can be reduced to 500 mL or less. 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 inoculated area of the photographic processing liquid and the air in the processing tank can be represented by the opening 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, more preferably Is 0.001 to 0.05. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank, JP-A-1-820 can be used.
Method using a movable lid described in JP-A No. 33-63, JP-A-63-
The slit development processing method described in No. 21650 can be mentioned. Reducing the aperture ratio is preferably applied not only in both the color developing step and the black and white developing step but also in the subsequent steps, for example, all the steps such as bleaching, bleach-fixing, fixing, washing and stabilizing. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution.

The reversal bath used after black and white development may contain a known fogging agent. That is, for example, stannous ion-organic phosphoric acid complex salt (US Pat.
No. 7,282), stannous ion organic phosphonocarboxylic acid complex salt (Japanese Patent Publication No. 56-32616), No. 1
Stannous ion complex salts such as tin ion-aminopolycarboxylic acid complex salts (US Pat. No. 1,209,050), borohydride compounds (US Pat. No. 2,984,5)
67), heterocyclic amine borane compounds (British Patent No. 1,011,000), and the like. The fogging bath (reversal bath) has a wide pH range from the acidic side to the alkaline side, and has a pH of 2 to 12, preferably 2.5 to 10, and particularly preferably 3 to 9. Instead of the reversal bath, a light reversal treatment by re-exposure may be performed, and the reversal step may be omitted by adding the fogging agent to the color developing solution.

The silver halide color photographic light-sensitive material of the present invention is bleached or bleach-fixed after color development. These treatments may be carried out immediately after color development without passing through other treatment steps. Alternatively, in order to prevent unnecessary post-development, air fogging, and to reduce the carry-in of the color developing solution into the desilvering process, the sensitizing material such as a sensitizing dye or dye contained in the photographic light-sensitive material and the photographic light-sensitive material In order to wash out and detoxify the color developing agent impregnated in the material, a bleaching treatment or a bleach-fixing treatment may be performed after a processing step such as stopping, adjusting and washing with water after the color developing treatment.

The photographic emulsion layer of the color developer 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 after bleaching 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 iron (III) organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, and the like. A complex salt of aminopolycarboxylic acids and iron (III), or a complex salt of citric acid, tartaric acid, malic acid and iron (III) can be used. Of these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are used for rapid treatment and prevention of environmental pollution. Is preferred. Furthermore, the aminopolycarboxylic acid iron (III) complex salt is
It is also particularly useful in a bleach-fix solution. The pH of a bleaching solution or a bleach-fixing solution using these iron (III) aminopolycarboxylic acid 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 prebath.
Specific examples of useful bleaching accelerators are described in the following specifications: for example U.S. Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988,
JP-A Nos. 53-32736, 53-57831, 53-37418, 53-72623, 53-
No. 95630, No. 53-95631, No. 53-104
No. 232, No. 53-124424, No. 53-1416
No. 23, No. 53-28426, Research Disclosure No. 17129 (July 1978), a compound having a mercapto group or a disulfide group; a thiazolidine derivative described in JP-A-50-140129; JP-B-45-8506, JP-A-52-20832.
No. 53-32735, U.S. Pat. No. 3,706,5
Thiourea derivatives described in No. 61; West German Patent No. 1,12
7,715, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966,410 and 2,748,
No. 430, polyoxyethylene compounds; Japanese Patent Publication No. 45-8836, polyamine compounds; Others, JP-A-49-40,943, 49-59,644, 53-94,927 54-35, 727, 5
Compounds described in Nos. 5-26,506 and 58-163,940; bromide ions can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, US Pat. No. 3,893,
858, West German Patent 1,290,812, JP-A-5
The compounds described in 3-95,630 are preferred. Furthermore,
The compounds described in US Pat. No. 4,552,834 are also preferred. 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 photography.

The bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain, in addition to the above compounds. Particularly preferable organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, and specifically, for example, acetic acid, propionic acid and hydroxyacetic acid are preferable.

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. It is commonly used, especially ammonium thiosulfate being the most widely used. Also,
Thiosulfates and thiocyanates, thioether compounds,
A combined use of thiourea and the like is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent 294769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

The total time of 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 processing 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 step, it is preferable that the stirring is strengthened as much as possible. As a concrete method for strengthening stirring, for example, a method in which a jet of a processing solution is made to collide with an emulsion surface of a light-sensitive material described in JP-A-62-183460,
A method of improving the stirring effect by using the rotating means of JP-A-62-183461, and further, moving the light-sensitive material while contacting the emulsion surface with a wiper blade provided in the liquid to make the emulsion surface turbulent. Depending on the method, a method of further improving the stirring effect and a method of increasing the circulation flow rate of the entire processing liquid can be mentioned. 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 inhibitory effect of the bleaching accelerator.

The automatic developing machine used in the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19125.
It is preferable to have the photosensitive material conveying means described in No. 8 and No. 60-191259. JP-A-60-1
As described in No. 91257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, so that it 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 replenishment amount of the processing liquid.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to a washing and / or stabilizing step after desilvering. 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 method such as counterflow or forward flow, and various other conditions. It can be set in a wide range. Of these, the relationship between the number of washing tanks and the water amount in the multi-stage countercurrent system is described in the Journal of the Soc.
yety of Motion Picture an
d Television Engineers No. 6
Volume 4, P. 248 to 253 (May 1955 issue). According to the multi-stage countercurrent method described in the above literature, the amount of washing water can be significantly reduced, but bacteria are propagated due to the increase in the retention time of water in the tank, and the produced suspended matter adheres to the photosensitive material. The problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, JP-A-62-288,8 has been proposed.
The method of reducing calcium ion and magnesium ion described in No. 38 can be used very effectively.
Further, isothiazolone compounds described in JP-A-57-8542, chlorine-based bactericides such as siabendazoles and chlorinated sodium isocyanurate, and other benzotriazoles are described in Hiroshi Horiguchi, "Antibacterial and Antifungal". Chemistry of agents "(1
986) Sankyo Publishing, Sanitary Technology Society, "Microbial sterilization, sterilization, antifungal technology" (1982) Industrial Technology Association, Japan Society for Antibacterial and Antifungal, "Antibacterial and Antifungal Encyclopedia" (1986) It is also possible to use the bactericide of.

Rinsing water in processing the light-sensitive material of the present invention
The pH is 4-9, preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but are generally in the range of 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C. for 30 seconds to 5 minutes. To be 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 stabilizing treatment, JP-A-57-8543 and 58-58 are used.
All known methods described in Nos. 14834 and 60-220345 can be used.

Further, after the water washing treatment, there is also a case where further stabilization treatment is performed. An example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as the final bath of a color light-sensitive material for photographing. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, 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 or the like, when each processing solution described above is concentrated by evaporation, it is preferable to add water to correct the concentration.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in US Pat. No. 3,342,597,
No. 3,342,599, Research Disclosure No. 14,850 and No. Schiff base type compounds described in No. 15,159, aldol compounds described in No. 13,924, metal salt complexes described in US Pat. No. 3,719,492, urethane compounds described in JP-A-53-135628. Can be mentioned.

The silver halide color light-sensitive material of the present invention comprises
In order to accelerate color development, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are disclosed in JP-A-56-64339 and JP-A-57-1.
No. 44547 and No. 58-115438.

Various processing solutions used in the present invention are 10 ° C. to 5 ° C.
Used at 0 ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to.

[0237]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

Example 1 Preparation of Sample 101 Sample 101 was prepared by preparing a multilayer color light-sensitive material having the following composition on a cellulose triacetate film support having a thickness of 127 μ and having an undercoat. The number is m ²
Indicates the amount added per unit. Moreover, the effect of the added compound is not limited to the described use.

First layer: antihalation layer Black colloidal silver 0.20 g Gelatin 1.9 g UV absorber U-1 0.04 g UV absorber U-2 0.1 g UV absorber U-3 0.1 g Ultraviolet absorber U-4 0.1 g Ultraviolet absorber U-6 0.1 g High boiling point organic solvent Oil-1 0.1 g Microcrystalline solid dispersion of dye E-1 0.1 g Second layer: intermediate Layer Gelatin 0.40 g High boiling point organic solvent Oil-3 0.1 g Dye D-4 0.4 mg Third layer: Intermediate layer Surface and internal fogged fine grain silver iodobromide emulsion (average grain size 0.06 μm , Variation coefficient 18%, AgI content 1 mol%) Silver amount 0.05 g Gelatin 0.4 g Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A Silver amount 0.1 g Emulsion B Silver amount 0.4 g Gelatin 0 0.8 g Coupler-C-1 0.15 g Coupler-C-2 0.0 g Coupler-C-3 0.05 g High-boiling-point organic solvent Oil-2 0.1 g Fifth layer: Medium-speed red-sensitive emulsion layer Emulsion B Silver amount 0.2 g Emulsion C Silver amount 0.3 g Gelatin 0.8 g Coupler-C-1 0.2 g Coupler-C-2 0.05 g Coupler-C-3 0.2 g High boiling point organic solvent Oil-2 0.1 g Sixth layer: high-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.4 g Gelatin 1.1 g Coupler-C-1 0.15 g Coupler-C-2 0.15 g Coupler-C-3 0.7 g Additive P-1 0.1 g Seventh layer: Intermediate Layer Gelatin 0.6 g Additive M-1 0.3 g Color mixing inhibitor Cpd-J 2.6 mg UV absorber U-1 0.1 g UV absorber U-6 0.1 g Dye D-10 .02 g Eighth layer: intermediate layer Silver iodobromide emulsion with surface and inside fogged (average grain size 0.06 μm, coefficient of variation 16) , AgI content 0.3 mol%) Silver amount 0.02 g Gelatin 1.0 g Additive P-1 0.2 g Color-mixing inhibitor Cpd-I 0.1 mg Color-mixing inhibitor Cpd-A 0.1 mg No. 9 Layer: low-sensitivity green-sensitive emulsion layer Emulsion E Silver amount 0.1 g Emulsion F Silver amount 0.2 g Emulsion G Silver amount 0.2 g Gelatin 0.5 g Coupler-C-7 0.05 g Coupler-C-8 0.2 g Compound Cpd-B 0.03 g Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g High boiling point organic solvent Oil-1 0.1 g High boiling organic solvent Oil-2 0.1 g 10th layer: Medium-speed green sensitive emulsion layer Emulsion G Silver amount 0.3 g Emulsion H Silver amount 0.1 g Gelatin 0.6 g Coupler-C-7 0.2 g Coupler-C-8 0.1 g Compound Cpd-B 0.03 g Compound Cpd-D 0.02g Compound Cpd-E 0.02g Compound Cpd-F 0.05g Compound Cpd-G 0.05g High boiling organic solvent Oil-2 0.01g Layer 11: High sensitivity green sensitive emulsion layer Emulsion I Silver amount 0.5 g Gelatin 1.0 g Coupler-C-4 0.3 g Coupler-C-8 0.1 g Compound Cpd-B 0.08 g Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g High boiling point organic solvent Oil-1 0.02 g High boiling point organic solvent Oil-2 0.02 g 12th layer: Intermediate layer Gelatin 0.6 g Dye D-10 .1 g Dye D-2 0.05 g Dye D-3 0.07 g 13th layer: yellow filter layer Yellow colloidal silver 0.07 g gelatin 1.1 g Gelatin mixture inhibitor Cpd-A 0 01 g High-boiling-point organic solvent Oil-1 0.01 g Microcrystalline solid dispersion of dye E-2 0.05 g 14th layer: intermediate layer gelatin 0.6 g 15th layer: low-sensitivity blue-sensitive emulsion layer Emulsion J Silver amount 0 .2 g Emulsion K Silver amount 0.3 g Emulsion L Silver amount 0.1 g Gelatin 0.8 g Coupler-C-5 0.3 g Coupler-C-6 0.3 g 16th layer: Medium sensitivity blue sensitivity. Emulsion layer Emulsion L Silver amount 0.1 g Emulsion M Silver amount 0.4 g Gelatin 0.9 g Coupler-C-5 0.2 g Coupler-C-6 0.2 g Coupler-C-9 0.1 g 17th layer: High-sensitivity blue-sensitive emulsion layer Emulsion N Silver amount 0.4 g Gelatin 1.2 g Coupler-C-5 0.2 g Coupler-C-6 0.2 g Coupler-C-9 0.4 g Eighteenth layer: First protective layer Gelatin 0.7 g UV absorber U-1 0.04 g UV absorber U-2 0.0 g UV absorber U-3 0.03 g UV absorber U-4 0.03 g UV absorber U-5 0.05 g UV absorber U-6 0.05 g High boiling organic solvent Oil-1 0.02 g Formalin scavenger Cpd -C 0.2 g Cpd-H 0.4 g Dye D-3 0.05 g Color mixing inhibitor Cpd-A 0.02 g 19th layer: 2nd protective layer Colloidal silver Silver amount 0.1 mg Fine grain silver iodobromide Emulsion (average particle size 0.06 μm, AgI content 1 mol%) Silver amount 0.1 g Gelatin 0.4 g 20th layer: third protective layer Gelatin 0.4 g Polymethyl methacrylate (average particle size 1.5 μ) 0.1 g Methyl methacrylate and acrylic acid 0.1 g 4: 6 copolymer (average particle size 1.5 μ) Silicone oil 0.03 g Surfactant W-1 3.0 mg Also, all emulsion layers Above In addition to the Narubutsu, additives F
-1 to F-8 were added. In addition to the above composition, gelatin hardener H-1 and surfactants W-2, W-3, W-4 and W-5 for coating and emulsifying were added to each layer.

Further, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol and phenethyl alcohol were added as antiseptic and antifungal agents.

The compounds used in Sample 101 are shown below.

[0242]

[Chemical formula 62]

[0243]

[Chemical 63]

[0244]

[Chemical 64]

[0245]

[Chemical 65]

[0246]

[Chemical 66]

[0247]

[Chemical 67]

[0248]

[Chemical 68]

[0249]

[Chemical 69]

[0250]

[Chemical 70]

[0251]

[Chemical 71]

[0252]

[Chemical 72]

[0253]

[Chemical formula 73]

[0254]

[Chemical 74]

[0255]

[Chemical 75]

[0256]

[Chemical 76] The silver iodobromide emulsion used for Sample 101 is as follows.

Emulsion name Average particle size Variation coefficient AgI content (μm) (%) (%) A Monodisperse tetradecahedral grains 0.25 15 4 B Monodisperse cubic internal latent image type grains 0.30 10 4 C Monodisperse tetrahedral grains 0.30 14 3 D polydispersed twin particles 0.60 25 2 E monodispersed cubic particles 0.17 13 4 F monodispersed cubic particles 0.20 15 4 G monodispersed cubic internal latent image type particles 0.25 11 4 H monodispersed cubic internal latent image type particles 0.30 9 3 I polydisperse tabular grains 0.80 28 2 average aspect ratio 4.0 J monodisperse tetrahedral grains 0.31 15 4 K monodisperse tetrahedral grains 0.36 15 4 L monodisperse cubic internal latent image grains 0.46 13 3 M polydisperse cubes Grain 0.53 25 3 N Polydisperse tabular grain 1.00 28 2 Average aspect ratio 7.0.

Spectral sensitization of Emulsions A to N Emulsion name Added sensitizing dye A S-1 S-2 B S-1 S-2 C S-1 S-2 D S-1 S-2 S-7 E S-3 S-4 F S-3 S-4 G S-3 S-4 H S-3 S-4 I S-3 S-4 S-8 J S-6 S-5 K S-6 S- 5 L S-6 S-5 M S-6 S-5 N S-6 S-5 The sensitizing dye was added in an amount of 0.01 to 0.25 g per mol of silver halide in the emulsion. .

Next, the couplers C-5, C-6 and C-9 of the fifteenth to seventeenth layers of Sample 101 were replaced with yellow couplers as shown in Table 3, and the fourteenth layer was used in the present invention. Samples 102 to 111 were prepared by adding such a compound.

[0260]

[Table 3] The samples 101 to 111 thus obtained were measured with a sensitometer whose color temperature was adjusted to 4800 ° K.
After exposing through a wedge for measuring TF and performing the following development processing, the MTF value was obtained. Value at 10 cycles / mm as low frequency area, 30 cycle / m as high frequency area
The values in m are shown in Table 3.

Fluorescence X was obtained for those obtained by exposing through a normal continuous wedge and applying the same processing as above.
The amount of residual silver was measured by the line. The amount of residual silver was constant regardless of the amount of exposure. The results are also shown in Table 3.

Treatment process Treatment process time Temperature Tank capacity Replenishment amount Black and white development 6 minutes 38 ° C 12L 2.21L / m ² First water washing 2 minutes 38 ° C 4L 7.5 L / m ² Inversion 2 minutes 38 ° C 4L 1.1 L / m ² color development 6 minutes 38 ℃ 12L 2.2 L / m ² adjustment 2 minutes 38 ℃ 4L 1.1 L / m ² bleaching 6 minutes 38 ℃ 12L 0.22L / m ² fixed 4 minutes 38 ℃ 8L 1.11L / m ² Second wash 4 minutes 38 ℃ 8L 7.5 L / m ² stable 1 minute 25 ℃ 2L 1.1 L / m ² .

The composition of each treatment liquid was as follows. Black-and-white developer Mother liquor Replenisher Nitrilo-N, N, N-trimethylenephosphone 2.0 g 2.0 g Acid-5 sodium salt sodium sulfite 30 g 30 g Hydroquinone potassium monosulfonate 20 g 20 g Potassium carbonate 33 g 33 g 1- Phenyl-4-methyl-4-hydroxy 2.0 g 2.0 g Methyl-3-pyrazolidone Potassium bromide 2.5 g 1.4 g Potassium thiocyanate 1.2 g 1.2 g Potassium iodide 2.0 mg-Add water 1000 mL 1000 mL pH 9.60 9.60 pH Was adjusted with hydrochloric acid or potassium hydroxide. Reversal solution Mother liquor Replenisher Nitrilo-N, N, N-trimethylenephosphone 3.0 g Acid, 5 sodium salt same as mother liquor Stannous chloride dihydrate 1.0 g p-Aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 1000 mL pH 6.00 pH was adjusted with hydrochloric acid or sodium hydroxide. Color developer Mother liquor Replenisher Nitrilo-N, N, N-trimethylenephosphone 2.0 g 2.0 g Acid-5 sodium salt Sodium sulfite 7.0 g 7.0 g Trisodium phosphate dodecahydrate 36 g 36 g Potassium bromide 1.0 g- Potassium iodide 90 mg-sodium hydroxide 3.0 g 3.0 g citrazinic acid 1.5 g 1.5 g N-ethyl- (β-methanesulfonamide 11 g 11 g ethyl) -3-methyl-4-aminoaniline sulfate 3,6- Dithia-1,8-octanediol 1.0 g 1.0 g Water was added to 1000 mL 1000 mL pH 11.80 12.00 pH was adjusted with hydrochloric acid or potassium hydroxide. Preparation liquid Mother liquor Replenishing liquid Ethylenediaminetetraacetic acid ・ 2 sodium salt ・ 8.0 g Dihydrate same as sodium bisulfite 12 g 1-Thioglycerin sorbitan ・ ester 0.1 g Water was added 1000 mL pH 6.20 pH was hydrochloric acid or sodium hydroxide I adjusted it with. Bleaching solution Mother liquor Replenishing solution Ethylenediaminetetraacetic acid ・ disodium salt ・ 2.0 g 4.0 g Dihydrate Ethylenediaminetetraacetic acid ・ Fe (III) ・ An 120 g 240 g Monium ・ dihydrate Potassium bromide 100 g 200 g Ammonium nitrate 10 g 20 g Water was added to 1000 mL 1000 mL pH 5.70 5.50 pH was adjusted with hydrochloric acid or sodium hydroxide. Fixer Mother liquor Replenisher Ammonium thiosulfate 8.0 g Sodium sulfite 5.0 g The same sodium bisulfite 5.0 g Water was added to mother liquor 1000 mL pH 6.60 pH was adjusted with hydrochloric acid or ammonium water. Stabilizer Mother liquor Replenisher Formalin (37%) 5.0 mL Polyoxyethylene-p-monononylphenyl 0.5 mL The same ether (average degree of polymerization 10) Water was added to the mother liquor 1000 mL Without pH adjustment From Table 3, from the present invention It is clear that the samples 104 to 111 are excellent in sharpness and desilvering property.

Example 2 Example 1 was repeated except that the developing process in Example 1 was changed to the following developing process, and the same result as in Example 1 was obtained.

Processing Step Time Temperature First development 6 minutes 38 ° C. First water wash 45 seconds 38 ° C. Reversal 45 seconds 38 ° C. Color development 6 minutes 38 degrees Bleach 1 minute 38 degrees Bleach fixing 4 minutes 38 degrees Second water wash (1 ) 1 minute 38 ° C Second washing (2) 1 minute 38 ° C Stability 1 minute 25 ° C The composition of each treatment solution was as follows. First developer Nitrilo-N, N, N-trimethylenephosphone 2.0 g Acid-5 sodium salt Sodium sulfite 30 g Hydroquinone potassium monosulfonate 20 g Potassium carbonate 33 g 1-Phenyl-4-methyl-4-hydroxy 2.0 g Methyl-3-pyrazolidone Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide 2.0 mg Water was added to 1000 mL pH 9.60 pH was adjusted with hydrochloric acid or potassium hydroxide. First water washing solution Ethylenediaminetetramethylene 2.0 g Phosphonic acid disodium phosphate 5.0 g Water was added to 1000 mL pH 7.00 pH was adjusted with hydrochloric acid or sodium hydroxide. Inversion solution Nitrilo-N, N, N-trimethylenephosphone 3.0 g Acid-5 sodium salt Stannous chloride dihydrate 1.0 g p-Aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 mL Water added 1000 mL pH 6.00 pH was adjusted with hydrochloric acid or sodium hydroxide. Color developer Nitrilo-N, N, N-trimethylenephosphone 2.0 g Acid-5 sodium salt sulfite 7.0 g Trisodium phosphate dodecahydrate 36 g Potassium bromide 1.0 g Potassium iodide 90 mg Sodium hydroxide 3.0 g Citrazine acid 1.5 g N-ethyl-N- (β-methanesulfonamide 11 g ethyl) -3-methyl-4-aminoaniline sulfate 3,6-dithiaoctane-1,8-diol 1.0 g Water was added to 1000 mL. pH 11.80 pH was adjusted with hydrochloric acid or potassium hydroxide. Bleaching solution Ethylenediaminetetraacetic acid ・ disodium salt ・ 10.0 g dihydrate Ethylenediaminetetraacetic acid ・ Fe (III) ・ Ann 120 g Monium ・ dihydrate Ammonium bromide 100 g Ammonium nitrate 10 g Bleaching accelerator 0.005 mol

[0266]

[Chemical 77] Water was added and 1000 mL pH 6.30 pH was adjusted with hydrochloric acid or ammonia water. Bleach-fixing solution Ethylenediaminetetraacetic acid ・ Fe (III) ・ Ann 50 g Monium ・ dihydrate Ethylenediaminetetraacetic acid ・ sodium ・ 5 g Dihydrate Ammonium thiosulfate 80 g Sodium sulfite 12.0 g Water 1000 mL pH 6.60 pH is It was adjusted with hydrochloric acid or aqueous ammonia. The same tap water as the second water washing liquid (1) and (2) was used as an H-type strongly acidic cation exchange resin (Amberlite IR- manufactured by Rohm and Haas Co.).
120B) and an OH type anion exchange resin (Amberlite IR-400) were passed through the column to treat calcium and magnesium ions at a concentration of 3 mg / L or less, followed by isocyanuric dichloride. Sodium 2
0 mg / L and 1.5 g / L sodium sulfate were added. The pH of this liquid is in the range of 6.5 to 7.5. Stabilizer Formalin (37%) 5.0 mL Polyoxyethylene-p-monononylphenyl 0.5 mL Ether (average degree of polymerization 10) Add water to 1000 mL Without pH adjustment

Claims (1)

Claims: 1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one layer constituting the light-sensitive material has the following formula (I) and Or or at least one compound represented by formula (II), and at least one yellow dye-forming coupler represented by formula (III) below in at least one of the blue-sensitive silver halide emulsion layers. A silver halide color photographic light-sensitive material characterized by: [Chemical 1] In the formula, R ¹¹ is R ¹⁴ —N (R ¹⁶ ) CON (R ¹⁵ ) —, R ^{14
OCON (R 15) -, R} 14 SO 2 N (R 15) -, R 14 -
_{^{N (R 16) SO 2 N}} (R 15) - or represents a R ¹⁷ CONH-. Here, R ¹⁴ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ^14
15 and R ¹⁶ represent a hydrogen atom, an alkyl group or an aryl group, and R ¹⁷ represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group having 2 or more carbon atoms in which a carbon atom adjacent to the carbonyl group is not substituted with a hetero atom. Alternatively, it represents a heterocyclic group. R ¹² and R ¹³ represent a hydrogen atom or a substituent having a Hammett's substituent constant σ _p of 0.3 or less, B represents a group which releases X after leaving from the hydroquinone mother nucleic acid product, and X represents a development inhibitor. Represents a residue, k represents an integer, and A and A ′ represent a hydrogen atom or a group capable of being removed with an alkali. [Chemical 2] In the formula, Q ¹ represents at least one heteroatom and represents an atomic group necessary for forming a 5-membered or more heterocyclic ring with a carbon atom to be bonded, and R ²¹ represents a group capable of substituting for a hydroquinone nucleus. Where B, X, k, A and A'have the same meanings as described in formula (I). [Chemical 3] In the formula, R ₁ represents a tertiary alkyl group, R ₂ represents a fluorine atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a dialkylamino group, an alkylthio group or an arylthio group, and R ₃ represents a benzene ring. Represents a substitutable group, X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidation product of an aromatic primary amine developing agent, and k represents an integer of 0 to 4. Where k
Is plural, plural R _{3 s} may be the same or different.