JPH0527385A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide color photographic sensitive material having excellent sharpness and aging stability. CONSTITUTION:This silver halide color photographic sensitive material contains a compd. represented by formula I or II in at least one of the silver halide emulsion layers and a cyan dye forming coupler represented by formula III, IV or V in at least one of the constituent layers.

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 stability over time.

[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 DIR compound is generally used at present to improve the sharpness, particularly the edge effect, but the one usually used is a cup with an oxidation product of a color developing agent. It is a DIR coupler that releases a development inhibitor imagewise by a ring reaction to form a color forming dye.

However, in the case of using a DIR coupler, if the dye formed by the coupling reaction has a hue 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.
Since it is necessary to develop three types of compounds having the optimum reactivity, and the burden of development and synthesis costs increases, there has been a demand for a color-free DIR compound.

Colorless DIR compounds are classified into two types, coupling type and redox type, depending on the reaction mode with the oxidant of the color developing agent. Of these, for the coupling type, Japanese Patent Publication Nos. 51-16141 and 51
-16142, U.S. Pat. Nos. 4,171,223, 4,226,943 and the like, and redox compounds are described in U.S. Pat. Nos. 3,379,529 and 3,3.
639, 417, JP-A-49-129536, and JP-A-6-129536.
DI described in 4-546, Japanese Patent Application No. 2-21127, etc.
R hydroquinone compound, or JP-A-61-213
No. 847, No. 64-88451, U.S. Pat. No. 4,684.
There are DIR hydrazide compounds described in 4,604.
Further, when the processing step is applied to a color reversal light-sensitive material comprising black and white development (first development) and color development (second development), it is preferable to release the inhibitor from the DIR compound in the first development. This is because the second development aims to develop all the silver halide that has not been developed in the first development promptly, so that the silver development speed is extremely fast, and therefore the second development is imagewise development inhibiting effect. This is because it is unfavorable because the development of silver would be delayed and the instability of processing in color development would be introduced.

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 the oxidant of the black and white developing agent.

On the other hand, as a cyan dye-forming coupler,
For example, 2-acylaminophenol couplers described in US Pat. Nos. 2,367,531 and 2,423,730, or US Pat. No. 3,772,002.
2-acylaminophenol cyan couplers described in JP-A Nos. 61-3142 and 61-9653, or U.S. Pat. No. 4,333,999 and JP-A-57.
-207593, 57-204544, 58-
Ureidophenol cyan couplers described in 11863 or JP-A-60-237448 and 61-15.
The 5-position substituted naphthol cyan couplers described in 3640 and 61-145557 have been conventionally used.

[0008]

However, when a redox DIR compound is used in combination with these cyan couplers, the sharpness is improved, but there is a problem that the photographic performance of the light-sensitive material changes greatly with the passage of time. .

Therefore, an object of the present invention is to provide a color light-sensitive material which is excellent in sharpness and stability over time.

[0010]

The objects of the present invention have been achieved by the following means. That is, in a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one layer constituting the light-sensitive material is a compound represented by the following formula (I) and / or formula (II) At least one of the following formula (II
It was achieved by using a silver halide color photographic light-sensitive material characterized by containing at least one cyan dye forming coupler represented by I). Formula (I)

[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 R ¹⁷ CONH-
(Here, R ¹⁴ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, R ¹⁵ and R ¹⁶ represent a hydrogen atom, an alkyl group or an aryl group, and R ¹⁷ is adjacent to a carbonyl group. . the alkyl group having 2 or more carbon atoms is a heteroatom to the carbon atom is not substituted, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group) a represents; R ¹² and R ¹³ are a hydrogen atom or a Hammett substituent The constant σ _p represents a substituent having a value of 0.3 or less; B represents a group that releases X after leaving the hydroquinone mother nucleic acid product; X represents a development inhibitor residue; k
Represents an integer; A and A'represent a hydrogen atom or a group capable of being removed with an alkali. Formula (II)

[0012]

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

[0013]

[Chemical 6] In the formula, R ₁ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ₂ represents a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, an acylamino group, an aliphatic oxy group or an aromatic oxy group. Represent

R ₁ and R ₂ may combine with each other to form a 5- to 7-membered ring. Z represents a hydrogen atom or a group or atom capable of splitting off upon reaction with an oxidized product of a developing agent.

Further, X ₁ and X ₂ represent a hydrogen atom or a halogen atom, and n represents an integer of 0-18.

The formula (I) of the present invention will be described 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 R ¹⁷ C
Represents ONH-. Here, 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 group (having 2 to 30 carbon atoms, for example, ethynyl, 1-octynyl), a substituted or unsubstituted aryl group (having 6 to 3 carbon atoms).
0, for example, phenyl, naphthyl, 3-dodecaneamidophenyl, 3-hexadecanesulfonamidophenyl, 4
-Dodecyloxyphenyl), or a heterocyclic group (N,
5- to 20-membered compounds containing at least one hetero atom of O, S and Se, for example, 4-pyridyl, 2-furyl, pyrrolo, 2-thiazolyl, 2-oxazolyl, 2
-Imidazolyl, triazolyl, tetrazolyl, benzotriazolyl, morpholinyl). The substituent which R ¹⁴ has is an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a carboxylic acid amide group, a sulfonic acid amide group, an alkoxycarbonylamino group, a ureido group, a carbamoyl group, an alkoxy Examples thereof include carbonyl group, sulfamoyl group, sulfonyl group, cyano group, halogen atom, acyl group, hydroxyl group, carboxyl group, sulfo group, nitro group and heterocyclic group.

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

R ¹⁵ is preferably a hydrogen atom.

R ¹⁷ is a substituted or unsubstituted alkyl group having 2 or more carbon atoms in which a carbon atom adjacent to the carbonyl group is not substituted with a hetero atom (preferably 2 to 30 carbon atoms,
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, such as ethynyl, phenylethynyl) ,
A substituted or unsubstituted aryl group (having 6 to 30 carbon atoms, such as phenyl, naphthyl, 3,5-bis (octadecaneamido) phenyl, 2-hexadecanesulfonamidophenyl, 4-dodecyloxyphenyl), or a heterocyclic group (N , 5-, 20-membered ones containing at least one hetero atom of O, S, Se, for example 3-pyridyl,
2-furyl, 3-thiazolyl, benzotriazolyl, benzimidazolyl).

Examples of the substituent of R ⁷¹ include those mentioned as the substituent of R ¹⁴ .

As R ¹² and R ^{13 in the} formula (I), a hydrogen atom or Hammett's substituent constant σ _p is 0.3.
The following substituents are represented, and examples thereof include an alkyl group (having 1 to 30 carbon atoms, for example, methyl, ethyl, isopropyl, t-butyl, decyl, hexadecyl, cyclohexyl, benzyl, t-octyl), an aryl group (having a carbon number of 6
To 30, for example, phenyl, naphthyl, an alkoxy group (having 1 to 30 carbon atoms, for example, methoxy, hexyloxy,
Hexadecyloxy, 2-dodecyloxy, benzyloxy), aryloxy groups (C6-30, such as phenoxy, naphthoxy), alkylthio groups (C1-C1).
30, for example, methylthio, hexylthio, dodecylthio, benzylthio), an arylthio group (having 6 to 3 carbon atoms).
0, for example, phenylthio, naphthylthio, 2-butyloxy-5-t-octylphenyl), amide group (having 1 to 30 carbon atoms, such as acetamide, butanamide, hexadecanamide, benzamide), sulfonamide group (having 1 to 30 carbon atoms, 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, such as methoxycarbonylamino, decyloxycarbonylamino, phenoxycarbonylamino), sulfamoylamino group (having 30 or less carbon atoms, such as 3-methylsulfamoylamino, 3- Phenylsulfamoylamino), a halogen atom (for example, 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 formula (II) will be described in detail.

Q ^{1 in} formula (II) is a divalent group containing at least one heteroatom, examples of which are:
Amide bond, divalent amino group, ether bond, thioether bond, imino bond, sulfonyl group, carbonyl group,
Examples thereof include an alkylene group and an alkenylene group. A group formed 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.

[0027]

[Chemical 7]

[0028]

[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) Yes, examples include acetyl, octanoyl, benzoyl, chloroacetyl, 3-carboxypropionyl, octadecanoyl), substituted and unsubstituted alkoxycarbonyl groups (preferably having 2 to 30 carbon atoms, and examples include methoxycarbonyl and octyl). Oxycarbonyl, phenoxycarbonyl, octadecyloxycarbonyl, methoxyethoxycarbonyl), a substituted or unsubstituted carbamoyl group (preferably having 1 to 30 carbon atoms, examples being carbamoyl,
N-propylcarbamoyl, N-hexadecylcarbamoyl, N- {3- (2,4-di-tert-pentylphenoxy) propyl}, N-phenylcarbamoyl, N
-(3-dodecyloxybutyl), pyrrolidinocarbonyl), substituted or unsubstituted sulfamoyl group (preferably having 0 to 30 carbon atoms, examples include sulfamoyl, dibutylsulfamoyl), substituted or unsubstituted sulfonyl group (Preferably having 1 to 30 carbon atoms, methanesulfonyl, benzenesulfonyl, p-dodecylbenzenesulfonyl) or a heterocyclic group (5 to 20-membered one containing at least one of N, O, S and Se, For example, 5-tetrazolyl, 2-benzoxazolyl, 2-thiazolyl, 2-imidazolyl, 2-pyridyl, morpholino) can be mentioned.

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

In 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), preferably an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group,
Hydrolyzable groups such as carbamoyl group, imidoyl group, oxalyl group and sulfonyl group, US Pat.
Precursor group of type utilizing reverse Michael reaction described in 9,029, Precursor group of type utilizing anion generated after ring cleavage reaction described in US Pat. No. 4,310,612 as an intramolecular nucleophilic group. , U.S. Pat. No. 3,67
No. 4,478, No. 3,932,480 or No. 3,
A precursor group in which the anion described in US Pat. No. 993,661 causes electron transfer through a conjugated system to thereby cause a cleavage reaction, and a cleavage by the electron transfer of the reacted anion after ring cleavage described in US Pat. No. 4,335,200. Precursor groups for reacting or US Pat. No. 4,363,865
No. 4,410,618, and precursor groups utilizing an imidomethyl group.

The groups represented by B in the formulas (I) and (II) are-(B) _k after the hydroquinone mother nucleus is oxidized by the oxidized form of the developing agent during development to form a quinone form.
-A coupler which emits X and represents a divalent group capable of releasing X thereafter, and which may have a timing adjusting function, and which releases X in response to another molecule of an oxidized developing agent. Or an oxidized ring-containing 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, the same or different combinations of two or more B's are represented.

When B is a group having a timing adjusting function, for example, US Pat. Nos. 4,248,962 and 4,409,323 and British Patent 2,096,783 are used.
U.S. Pat. No. 4,146,396, JP-A-51-
146,828, JP-A-57-56,837 and the like. The Time may be a combination of two or more selected from those described in these.

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

(1) Group utilizing cleavage reaction of hemiacetal: For example, it is described in US Pat. No. 4,146,396, JP-A-60-249148 and 60-249149.

(2) Group capable of causing a cleavage reaction by utilizing an intramolecular nucleophilic substitution reaction: For example, US Pat. No. 4,248,9.
Some of the timing groups described in No. 62 are mentioned.

(3) A group capable of causing a cleavage reaction by utilizing an electron transfer reaction along a conjugated system: for example, US Pat. No. 4,4.
09,323 or 4,421,845.

(4) Group utilizing cleavage reaction due to hydrolysis of ester: For example, West German Published Patent No. 2,626,31
It is a linking group described in No. 5.

(5) Group utilizing cleavage reaction of imino ketal: For example, a linking group 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.

As the coupler, for example, in the case of a phenol type coupler, the one bonded to the hydroquinone nucleus at the oxygen atom excluding the hydrogen atom of the hydroxyl group. In the case of a 5-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 hydroxypyrazole.

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

Preferred examples of B as 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, x represents an integer of 0 to 4, and when x is plural, V ₇ is 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, —SO ₂ —
Group, an oxygen atom or a substituted imino group, and V ₉ is -V
₈ -N-C = C-together represents a nonmetallic atom group for forming a 5- to 8-membered ring, V ₁₀ represents a hydrogen atom or a substituent. Where * is to the hydroquinone nucleus, and *
* Means to bond to X.

In the formulas (I) and (II), when the group represented by B is a redox group, it 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, and n X and Y
At least 1 represents a methine group having -X as a substituent, the other X and Y represent a substituted or unsubstituted methine group or a nitrogen atom, and n represents an integer of 1 to 3 (n X , N Y's represent the same or different), A represents a hydrogen atom or a group removable by an alkali, and has the same meaning as A in formula (I). Here, the case where any two substituents of P, X, Y, Q and A become a divalent group and are connected to each other 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 preferable 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 s} may be the same or different, and when two R _{64 s} are substituents on adjacent carbons, they are each a divalent group to form a ring structure. It also includes the case of representing.

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

X means a development inhibitor residue. As a preferable example of X, a compound having a mercapto group bonded to the heterocycle represented by the formula (X-1), or a compound represented by the formula (X
And the heterocyclic compound capable of forming imino silver represented by -2).

[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 or It is a 6-membered heterocycle.

Examples of the heterocycle represented by Z ₁ include, for example, azoles (tetrazole, 1,2,4-triazole, 1,2,3-triazole, 1,3,4-thiadiazole, 1,3,3). 4-oxadiazole, 1,3-
Thiazole, 1,3-oxazole, imidazole, benzothiazole, benzoxazole, benzimidazole, pyrrole, pyrazole, imidazole), azaindenes (tetrazaindene, pentazaindene, traazaindene), azines (pyrimidine, triazine,
Pyrazine, pyridazine) and the like.

Examples of the hetero ring represented by Z ₂ include, for example, traazoles (1,2,4-triazole, benzotriazole, 1,2,3-triazole), indazole, benzimidazole, azaindenes (tetrazaindene). , Pentazaindene), tetrazole and the like.

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. R in one molecule
When there are two or more of ₇₇ , R ₇₈ , R ₇₉ and R _80, these may be linked to form a ring (for example, a besisen ring).

Examples of the compound represented by the formula (X-1) include, for example, 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, etc., and substituted or unsubstituted mercaptoazaindenes (for example, 6-methyl-4)
-Mercapto-1,3,3a, 7-tetraazaindene, 4,6-dimethyl-2-mercapto-1,3,3
a, 7-Tetraazaindene and the like) substituted or unsubstituted mercaptopyrimidines (for example, 2-mercaptopyrimidine and 2-mercapto-4-methyl-6-hydroxypyrimidine).

Examples of the heterocyclic compound capable of forming imino silver include substituted or unsubstituted triazoles (eg, 1,2,4-triazole, benzotriazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, and the like). 5-bromobenzotriazole, 5-n
-Butylbenzotriazole, 5,6-dimethylbenzotriazole, etc.), substituted or unsubstituted indazoles (eg, indazole, 5-nitroindazole,
3-nitroindazole, 3-chloro-5-nitroindazole, etc.) and substituted or unsubstituted benzimidazoles (eg 5-nitrobenzimidazole, 5, 6
-Dichlorobenzimidazole) and the like.

Further, X is separated from B of 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 give a substantial effect. It may be a compound which 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.
0-218644, 60-221750, 60
The development inhibitor residues described in No. 233650, No. 61-11743 and the like are mentioned.

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
-Mecarptobenzoxazole, 2- (1-methoxycarbonylethylthio) -5-mercapto-1,3,4
-Thiadiazole, 2-butoxycarbonylmethoxy,
Carbonylmethylthio-5-mercapto-1,3,4-
Thiadiazole, 2- (N-hexylcarbamoylmethoxycarbonylmethylthio) -5-mercapto-1,
3,4-thiadiazole, 5-butoxycarbonylmethoxycarbonylbenzotriazole and the like can be mentioned.

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

Most preferably X is 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
Have the same meaning as those of 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. Moreover, in 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 divalent amino group examples of Q _2, an ether bond, a thioether bond,
Alkylene group, ethylene bond, imino bond, sulfonyl group, carbonyl group, arylene group, divalent heterocyclic group,
The group which combined these two or more is mentioned.

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

R ²⁸ is preferably 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, the compound represented by the following formula (IIA) is more preferable.

[0073]

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

It is preferable that R ^{11 in the} formula (IA) is R ¹⁷ CONH— and the following formulas (IB) and (IC) are given.

[0075]

[Chemical 15]

[0076]

[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 meanings as those in formula (I).

Examples of R ³⁴ and R ³⁵ include those represented by the formula (I)
Those mentioned as the substituent which R ¹⁴ has.

Further, these substituents may be further substituted.

In the formula (IB), preferred R ³⁴ is a substituent having 5 to 30 carbon atoms, and n ′ is preferably 2 to 5. In formula (IC), R ³⁵ preferably has 5 to 30 carbon atoms.

The compounds represented by formulas (I) and (II) may be added to any emulsion layer and / or any non-photosensitive layer. It may be added to both. The addition amount is preferably 0.001 to 0.2 mmol / m ² , and more preferably 0.01 to 0.1 mmol / m ² .

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.

[0082]

[Chemical 17]

[0083]

[Chemical 18]

[0084]

[Chemical 19]

[0085]

[Chemical 20]

[0086]

[Chemical 21]

[0087]

[Chemical formula 22]

[0088]

[Chemical formula 23]

[0089]

[Chemical formula 24]

[0090]

[Chemical 25]

[0091]

[Chemical formula 26]

[0092]

[Chemical 27]

[0093]

[Chemical 28]

[0094]

[Chemical 29]

[0095]

[Chemical 30]

[0096]

[Chemical 31]

[0097]

[Chemical 32]

[0098]

[Chemical 33]

[0099]

[Chemical 34]

[0100]

[Chemical 35]

[0101]

[Chemical 36]

[0102]

[Chemical 37]

[0103]

[Chemical 38]

[0104]

[Chemical Formula 39]

[0105]

[Chemical 40]

[0106]

[Chemical 41]

[0107]

[Chemical 42]

[0108]

[Chemical 43]

[0109]

[Chemical 44]

[0110]

[Chemical 45]

[0111]

[Chemical 46]

[0112]

[Chemical 47]

[0113]

[Chemical 48]

[0114]

[Chemical 49]

[0115]

[Chemical 50]

[0116]

[Chemical 51]

[0117]

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

In the formula (III), the "aliphatic group" means a linear, branched or cyclic aliphatic hydrocarbon group, and includes saturated and unsaturated groups such as alkyl, alkenyl and alkynyl groups. Is. Typical examples are methyl, ethyl, butyl, dodecyl, octadecyl, eicosenyl, iso-propyl, tert-butyl, t.
There are ert-octyl, tert-dodecyl, cyclohexyl, cyclopentyl, allyl, vinyl, 2-hexadecenyl, propargyl.

In the formula (III), R ₁ is preferably an aliphatic group having 1 to 36 carbon atoms, preferably 6 to 36 carbon atoms.
Represents an aromatic group or a heterocyclic group, which may further have other substituents.

In the formula (III), R ₂ is a hydrogen atom,
Halogen atom (eg fluorine, chlorine, bromine), aliphatic group, aromatic group, acylamino group (eg acetylamino, benzoylamino), aliphatic oxy group (eg methoxy, butoxy), aromatic oxy group (eg phenoxy) Of these, the substitutable group may further have another substituent.

In formula (III), Z represents a hydrogen atom or a coupling-off group, and examples thereof include a halogen atom (eg fluorine, chlorine, bromine), an alkoxy group (eg ethoxy, dodecyloxy, methoxyethylcarbamoyl). Methoxy, carboxypropyloxy, methylsulfonyl, ethoxy), aryloxy groups (eg 4-chlorophenoxy, 4-methoxyphenoxy, 4-
Carboxyphenoxy), acyloxy group (eg acetoxy, tetradecanoyloxy, benzoyloxy), sulfonyloxy group (eg methanesulfonyloxy, toluenesulfonyloxy), amide group (eg dichloroacetylamino, heptafluorobutyrylamino, methanesulfonylamino) , Toluenesulfonylamino), alkoxycarbonyloxy groups (eg ethoxycarbonyloxy, benzyloxycarbonyloxy), aryloxycarbonyloxy groups (eg phenoxycarbonyloxy), aliphatic or aromatic thio groups (eg ethylthio, phenylthio, tetrazolylthio), There are imide groups (eg succinimide, hydantoinyl), aromatic azo groups (eg phenylazo). These leaving groups may include photographically useful groups.

In formula (III), Z is preferably a hydrogen atom, a halogen atom, an alkyloxy group or an aryloxy group.

In formula (III), R ₁ and R ₂ may form a ring, in which case 5-membered and 6-membered rings are preferable, and 5-membered ring is most preferable.

In the formula (III), X ₁ and X ₂ represent a hydrogen atom or a halogen atom, and a fluorine atom is particularly preferable.

N represents an integer of 0 to 18, preferably 0 to 6, and most preferably 2 to 6.

Specific examples of the cyan coupler represented by the formula (III) are shown below, but the invention is not limited thereto.

[0127]

[Chemical 53]

[0128]

[Chemical 54]

[0129]

[Chemical 55]

[0130]

[Chemical 56]

[0131]

[Chemical 57]

[0132]

[Chemical 58]

[0133]

[Chemical 59]

[0134]

[Chemical 60]

[0135]

[Chemical formula 61]

[0136]

[Chemical formula 62] 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 of layers and the order of layers of the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. And the photosensitive layer is 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
No. 61-20037, No. 61-30038, and a DIR compound as described in JP-A-61-20037, and a DIR compound 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 light-sensitive 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.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
Can be installed in order.

Further, as described in JP-B-55-34932, layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Also, JP-A-56-25738 and 62-6393.
As described in No. 6, it is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest light sensitivity, the middle layer is a silver halide emulsion layer having a lower light sensitivity, and the lower layer is lower than the middle layer. Another example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. It may be arranged in the order of 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, BL, G
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 silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide.

The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, grains having 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, for example, Research Disclosure (RD) N.
o. 17643 (December 1978), pages 22-23,
"I. Emulsion preparation
ion and types) ”, and ibid.
716 (November 1979), page 648, ibid. Thirty
7105 (November 1989), pages 863-865, and Graphide, "Physics and Chemistry of Photography," published by Paul Montel, P. Glafkides, Chemieet.
Phisique Photographie, P
Aumontel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (G, F, Duffi).
n, Photographic Emulsion C
chemistry (Focal Press, 196)
6)) Zelikmann et al., "Manufacturing and Coating of Photographic Emulsions", published by Focal Press (VL Zelikmamm et.
al. , Making and Coating Ph
otographic Emulsion, Focal
It can be prepared using the method described in Press, 1964).

For example, US Pat. No. 3,574,628,
No. 3,655,394 and British Patent No. 1,413,
The monodisperse emulsion described in No. 748 is 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 Engineering
g), Vol. 14, pp. 248-257 (1970); U.S. Patent Nos. 4,434,226 and 4,414,310.
No. 4,433,048, No. 4,439,520 and British Patent No. 2,112,157.

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 emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which grains are formed, or a type having a latent image in both the surface and the inside. Must be a type of emulsion. Among the internal latent image types, the cores described in JP-A-63-264740 /
It may be a shell type internal latent image type emulsion. The preparation method of this core / shell type internal latent image type emulsion is described in JP-A-59-13.
3542. The shell thickness of this emulsion varies depending on the development process, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are Research Disclosure No. 17643, the same No. 18716 and No. 18716. 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 light-sensitive silver halide emulsion layer and / or the substantially light-insensitive 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,
It is described in JP-A-59-214852.

The silver halide forming the inner core of the fogged core / shell type silver halide grain 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 grain shape is not particularly limited and may be regular grains or polydisperse emulsion, but monodisperse grains (at least 95% of the weight or the number of silver halide grains are within ± 40% of the average grain size). It is preferable that the particles have a particle size of

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that the fog is not fogged in advance. ..

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and 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 0.5 μm, more preferably 0.02 to 0.2 μm.

The fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be optically sensitized,
Also, spectral sensitization is not necessary. 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 amount of silver coated on the light-sensitive material of the present invention was 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 page 648 page right column page 866 2. Sensitivity enhancer page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column, page 866 to 868, supersensitizer, page 649, right column, 4. Whitening agent Page 24 Page 647 Page right column Page 868 5. Fogging prevention page 24 to 25 page 649 right column 868 to 870 page agents and stabilizers 6. Light absorber, pages 25 to 26, page 649, right column, page 873, filter dye, page 650, left column, ultraviolet absorber 7. Stain page 25, right column, page 650, left column, page 872 Inhibitor to right column 8. Dye image stabilizer page 25 page 650 page left column page 872 9. Hardener 26 pages 651 pages left column 874-875 pages 10. Binder, page 26, page 651, left column, pages 873 to 874 11. Plasticizers and lubricants Page 27 Page 650 Page right column Page 876 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. Antistatic agent Page 27 Page 650 Page right column 876-877 Page 14. Matting agent pp. 878-879 Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, silver is fixed by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. It is preferable to add a compound capable of being converted into a light-sensitive material.

The light-sensitive material of the present invention can be prepared according to US Pat.
0,454, 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 prepared by the method described in JP-A-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.

The light-sensitive material of the present invention is the international publication WO88 /
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. 1-2593
It is preferable to include the dye described in No. 58.

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-
G, and the same No. 307105, VII-C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620.
Issue No. 4,326,024, No. 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107.
39, British Patent Nos. 1,425,020 and 1,4
76,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649,
Those described in EP 249,473A are preferred.

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-60-43659, 61-72238 and 60.
-35730, 55-118034, 60-1
Those described in US Pat. No. 8,5951, US Pat. No. 4,500,630, US Pat. No. 4,540,654, US Pat. No. 4,556,630 and International Publication WO88 / 04795 are particularly preferable.

With respect to the cyan coupler, phenol-type and naphthol-type couplers can be mentioned as cyan couplers that can be used in addition to the coupler of the present invention. For example, US Pat. Nos. 4,052,212 and 4,146,396 can be mentioned.
No. 4,228,233, 4,296,20
No. 0, No. 2,369,929, No. 2,801,1
No. 71, No. 2,772, 162, No. 2,895.
No. 826, No. 3,772,002, No. 3,75
No. 8,308, No. 4,334,011, No. 4,3
27,173, West German Patent Publication No. 3,329,729
No., European Patent Nos. 121,365A and 249,45
3A, US Pat. Nos. 3,446,622 and 4,3.
No. 33,999, No. 4,775,616, No. 4,
451,559, 4,427,767, 4,690,889, 4,254,212, 4,296,199, and JP-A-61-42658. Are preferred. Furthermore, JP-A-64-553
No. 64, No. 554, No. 64-555, No. 64-5
The pyrazoloazole-based couplers described in No. 56 and the imidazole-based couplers described in US Pat. No. 4,818,672 can also be used.

Typical examples of polymerized dye-forming couplers are, for example, US Pat. Nos. 3,451,820, 4,080,211, 4,367,282, and 4,409. No. 320, No. 4,576,910,
British Patent 2,102,137, European Patent 341,1
88A.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unnecessary absorption of color forming dyes are available from Research Disclosure N.
o. 17643, Item VII-G, ibid. 307105
VII-G, U.S. Pat. No. 4,163,670, JP-B-57-39413, U.S. Pat. No. 4,004,92.
No. 9, No. 4,138,258, and British Patent No. 1,14.
Those described in No. 6,368 are preferable. In addition, a coupler described in US Pat. No. 4,774,181 for correcting unnecessary absorption of a coloring dye by a fluorescent dye released upon coupling, and a developing agent described in US Pat. No. 4,777,120 are reacted. It is preferable to use a coupler having a dye precursor group capable of forming a dye as a leaving group.

R. D. No. 11449 and 2424
1, the bleaching accelerator releasing coupler described in JP-A-61-201247 is effective for shortening the processing time having a bleaching ability. In particular, the light-sensitive material using the tabular silver halide grains described above is used. The effect is great when it is added to the material. As a coupler which releases a nucleating agent or a development accelerator imagewise during development, British Patent 2,097,1
40, No. 2,131,188, JP-A-59-15.
Those described in 7638 and 59-170840 are preferable. In addition, JP-A-60-107029 and 60-
No. 152340, JP-A-1-44940, 1-45.
Compounds which release 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. 687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include, for example, US Pat.
Competitive couplers described in U.S. Pat.
No. 3,472, No. 4,338,393, No. 4,3
Multiequivalent couplers described in JP-A-10-618, JP-A-60-
No. 185950, JP-A No. 62-24252, DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent Nos. 173,302A, 313,308A. No. 4,551,477, etc., a ligand releasing coupler described in US Pat. No. 4,555,477, and a leuco dye releasing coupler described in JP-A-63-75747. Examples thereof include couplers that release the fluorescent dye described in Japanese Patent No. 4,774,181.

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

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. The boiling point at atmospheric pressure used in the oil-in-water dispersion method is 17
Specific examples of the high boiling point organic solvent having a temperature of 5 ° C. or higher 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 phosphone Acid esters (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl phenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate,
Tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate), benzoic acid esters (eg 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (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-dibutyrate) 2-butoxy--5-ter
t-octylaniline) and hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene). As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, and 2-ethoxy. Examples include ethyl acetate and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
63, West German Patent Application (OLS) No. 2,541,274
And No. 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.
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 2- (4-thiazoline) benzimidazole.

Suitable supports that can be used in the present invention are described in, for example, RD. No. 17643, page 28, ibid.
18716, page 647, right column to 648 left column, and ibid.
o. 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 rate T _2/1 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T
_1/2 can be measured according to a method known in the art. For example, A Green (A. Gr
een, et al., Photographic Science and Engineering (Photogr. Sci. E)
ng. ), Vol. 19, No. 2, pp. 124-129, can be measured by using a swellometer (swelling meter) of the type, and T _1/2 is treated with a color developer at 30 ° C. for 3 minutes 15 seconds. 90% of the maximum swollen film thickness reached at that time 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 photographic material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This 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 alkaline water-soluble, containing an aromatic primary amine type coloring dye main component as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and a typical example thereof is 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 contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole compound, a benzothiazole compound or a mercapto compound. It is common to include such development inhibitors or antifoggants. If necessary, hydroxylamine, diethylhydroxyamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acid, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers,
Auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, various chelating agents represented by aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, for example, ethylenediamine tetra Acetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1
-Diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof are representative examples. Can be mentioned.

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 below.

Among the processing steps of the color reversal photosensitive 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 wash-light reversal-color development 3) Black-white development-water wash-color development Steps 1) to 3) are all performed in the US patent. Fourth,
In place of the rinse process described in No. 804,616, it is possible to simplify the process and reduce waste liquid.

Next, the steps after color development will be described.

4) Color development-adjustment-bleaching-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-bleaching fixing-washing-stable 13) Coloring development-washing-bleaching fixing-washing-stable 14) Color development-bleaching fixing -Washing-Stable 15) Color development-Fixing-Bleach-fixing-Water washing-Stable In the processing steps from 4) to 15), the washing step immediately before the stabilizing step may be eliminated, or conversely, the stabilizing step of the final step may be omitted. It does not have to be done. The color reversal process is formed by connecting any one of the processes 1) to 3) and any one of the processes 4) to 15).

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. 4,067,872.
A heterocyclic compound such as 1,2,3,4-tetrahydroquinoline ring and an indole ring described in No.
They can be used alone or in combination.

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

The black-and-white developing solution used in the present invention must contain a compound acting as a silver halide solvent.
The sulfite, which is usually added as a preservative, plays the role. The sulfite and other silver halide solvents that can be used are specifically KSCN, NaSCN, K
₂ SO ₃ , Na ₂ SO ₃ , K ₂ S ₂ O ₅ , Na ₂ S ₂ O
₅ , K ₂ S ₂ O _{3 and the} like can be mentioned.

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

The sensitizing process using such a black-and-white developing solution is usually carried out by extending 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. The replenishing 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, and it is 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also do it. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area with the air in the processing tank.

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

That is, aperture ratio = [contact area between processing liquid and air (cm ² )] ÷
[Volume of Treatment Liquid (cm ³ )] The aperture ratio is preferably 0.1 or less, and more preferably 0.001 to 0.05. As a method of 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-1-82
No. 033, a method using a movable lid, JP-A-63-63
-216050 can be mentioned as a slit developing treatment method. To reduce the aperture ratio, not only the steps of color development and black and white development, but also the subsequent steps,
For example, it is preferably applied in all steps such as bleaching, bleach-fixing, fixing, washing with water, stabilization and the like. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The reversal bath used in the black and white developer may contain a known fogging agent. That is, stannous ion-organic phosphoric acid complex salt (US Pat. No. 3,617,282), stannous ion organic phosphonocarboxylic acid complex salt (Japanese Patent Publication No. 56-31626), stannous ion-
Aminopolycarboxylic acid complex salt (US Pat. No. 1,209,0
50), stannous ion complex salts, borohydride compounds (US Pat. No. 2,984,567),
Heterocyclic amine borane compounds (UK Patent No. 1,011,0
00 specification) and the like, 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 subjected to a bleaching treatment or a bleach-fixing treatment after a color forming dye. These treatments may be carried out immediately after the color development without passing through other processing steps, in order to prevent unnecessary post-development and air fog, and to reduce the carry-in of the color developing solution to the desilvering process. In addition, in order to wash out and detoxify the sensitizing dyes and dyes contained in the photographic light-sensitive material and the color-developing agent impregnated in the photographic light-sensitive material, a color-developing processing solution, stop, adjust, and wash with water. A bleaching treatment or a bleach-fixing treatment may be carried out after the treatment steps such as.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process (bleach-fixing process) or separately. Further, in order to accelerate the processing, a processing method of bleaching 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. As a typical bleaching agent, an organic complex salt of iron (III), for example, an amino acid such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol etherdiaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Of these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. .. Further, iron aminopolycarboxylate (II
The I) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. These iron aminopolycarboxylates (II
The pH of the bleaching solution or bleach-fixing solution containing the complex salt I) is usually 4.0 to 8, but it is also possible to process at a lower pH for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, JP No. 53-32736, No. 53-57831, No. 53
-37418, 53-72623, 53-95.
No. 630, No. 53-95631, No. 53-10423.
No. 2, No. 53-124424, No. 53-141623.
No. 53-28426, Research Disclosure No. Compounds having a mercapto group or a disulfide group described in 17129 (July 1978); thiazolidine derivatives described in JP-A No. 50-140129;
JP-B-45-8506, JP-A-52-20832,
53-32735, U.S. Pat. No. 3,706,561.
Derivatives described in Japanese Patent No. 1,127,7
No. 15, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966,410 and 2,748,43.
Polyoxyethylene compounds described in No. 0; JP-B-45
Polyamine compounds described in JP-A-8836;
9-40,943, 49-59,644, 53
-94,927, 54-35,727, 55-
26,506 and 58-163,940; bromide ions and the like can be used. Of these, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of having a large accelerating effect, and in particular, US Pat. No. 3,893,8
58, West German Patent 1,290,812, JP-A-53
The compounds described in -95,630 are preferred. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photographing.

In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. A particularly preferred organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, specifically, acetic acid,
Propionic acid, hydroxyacetic acid and the like are preferred.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. Use of thiosulfates Is most commonly used, with ammonium thiosulfate being the most widely used. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, 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 294,769A 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 in the range where desilvering failure does not occur. 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 the stirring, a method of causing a jet of a processing solution to collide with an emulsion surface of a light-sensitive material described in JP-A-62-183460, and stirring using a rotating means of JP-A-62-183461. A method to improve the effect, further a method to improve the stirring effect by moving the light-sensitive material while bringing the emulsion surface into contact with the wiper blade provided in the solution and making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such stirring improving means includes a bleaching solution, a bleach-fixing solution,
It is effective with any of the fixing solutions. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the stabilizer into the emulsion film and, as a result, increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting effect of the bleaching accelerator.

The automatic developing machine used for 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, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment system such as countercurrent, forward flow, and other various conditions. It can be set in a wide range.
Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in the Journal of the Society
y of Motion Picture and T
Evolution Engineers Volume 64,
P. 248 to 253 (May 1955 issue). According to the multi-stage counter-current method described in the above literature, the amount of washing water can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problems arise. In the processing of the color light-sensitive material of the present invention, as a solution to this problem, JP-A-62-288,838 is proposed
The method of reducing calcium ion and magnesium ion described in No. 10 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and benzotriazole are also described by Hiroshi Horiguchi in "Bacterial and Antifungal Agents". Chemistry "(1986)
Sankyo Publishing Co., Ltd., Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982), Industrial Technology Association, Japan Antibacterial and Antifungal Society, "Antibacterial and Antifungal Encyclopedia" (1986). Can also be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4-9, preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes,
A range of 30 seconds to 5 minutes at 25 to 40 ° C. is preferably 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, the washing treatment may be followed by a further stabilizing treatment. As an example of the stabilizing treatment, a stabilizing agent containing a dye stabilizer and a surfactant used as a final bath of a color light-sensitive material for photographing is used. You can mention the bath. 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 above washing with water and / or supplementation 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 photographic light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying the processing and speeding up 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,
Schiff base type compounds described in U.S. Pat. No. 3,342,599, Research Disclosures 14,850 and 15,159, aldol compounds described in U.S. Pat. No. 13,924, and U.S. Pat. No. 3,719,492. Examples thereof include metal salt complexes and urethane compounds described in JP-A No. 53-135628.

The silver halide color photographic light-sensitive material of the present invention may optionally contain various 1-phenyl-3-pyrazolidones for the purpose of promoting color development.
Typical compounds are JP-A Nos. 56-64339 and 57-57.
Nos. 144547 and 58-115438.

Various processing solutions used in the present invention are 10 ° C. to 50 ° C.
Used at ° 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.

[0217]

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 compositions on a cellulose triacetate film support having a thickness of 127 μ and having an undercoat. The numbers represent the amount added per m @ 2. 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 UV absorber U-4 0.1 g Ultraviolet absorber U-6 0.1 g High boiling organic solvent medium 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 organic solvent Oil-3 0.1 g Dye D -4 0.4 mg Third layer: intermediate layer Fine grained silver iodobromide emulsion (average grain size 0.06 µm, coefficient of variation 18%, AgI content 1 mol%) with fog on the surface and inside 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 0.8 g Coupler C-1 0.05 g Coupler C-2 0.10 g Coupler C-3 0.10 g High boiling point organic solvent Oil-2 0.1 g Fifth layer: Medium sensitivity red-sensitive emulsion layer Emulsion B Amount 0.2 g Emulsion C Silver amount 0.3 g Gelatin 0.8 g Coupler C-1 0.1 g Coupler C-2 0.2 g Coupler C-3 0.25 g High boiling 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 0.2 g coupler C-3 0.6 g additive P-1 0.1 g seventh layer: intermediate layer gelatin 0.6 g additive M-1 0.3 g mixed color Inhibitor Cpd-J 2.6 g Ultraviolet absorber U-1 0.1 g Ultraviolet absorber U-6 0.1 g Dye D-1 0.02 g Eighth layer: intermediate layer Silver iodobromide emulsion (average grain on the surface and inside) Diameter 0.06 μm, rolling coefficient 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 9th 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 point organic solvent Oil-2 0.1 g Tenth layer: intermediate 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 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.05 g Compound Cpd-G 0.05 g High boiling organic solvent Oil-2 0.01 g 11th layer: 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-1 0.1 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 Anti-color mixing agent Cpd-A 0.01 g High boiling point organic solvent Oil-1 0.01 g Microcrystalline solid of dye E-2 Dispersion 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 0.2 g Coupler C-9 0.4 g 16th layer: Medium speed blue sensitive emulsion layer Emulsion L Silver amount 0.1 g Emulsion M Silver amount 0.4 g Gelatin 0.9 g Coupler C-5 0.3 g Coupler C-6 0.1 g Coupler C-9 0.1 g Number 17 layers: High sensitivity blue feeling Emulsion layer Emulsion N Silver amount 0.4 g Gelatin 1.2 g Coupler C-6 0.1 g Coupler C-9 0.2 g Coupler C-10 0.6 g 18th layer: 1st protective layer gelatin 0.7 g UV absorber U-1 0.04 g UV ray Absorber U-2 0.01 g Ultraviolet absorber U-3 0.03 g Ultraviolet absorber U-4 0.03 g Ultraviolet absorber U-5 0.05 g Ultraviolet 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%) 0.1 g gelatin 0.4 g 20th layer: third protective layer gelatin 0.4 g polymethylmethacrylate (average particle size 1.5 μ) 0.1 g methylmethacrylate / acrylic acid 4: 6 copolymer (plain Grain size 1.5 μ) 0.1 g Silicone oil 0.03 g Surfactant W-1 0.03 g In addition to the above composition, all the emulsion layers have additive F-
1-F-8 were added. In addition to the above composition, gelatin hardener H-1 and coating and emulsifying surfactants W-2, W-3, W-4, W-5 and W-6 were added to each layer.

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

The compounds used in Sample 101 are shown below.

[0221]

[Chemical 63]

[0222]

[Chemical 64]

[0223]

[Chemical 65]

[0224]

[Chemical 66]

[0225]

[Chemical 67]

[0226]

[Chemical 68]

[0227]

[Chemical 69]

[0228]

[Chemical 70]

[0229]

[Chemical 71]

[0230]

[Chemical 72]

[0231]

[Chemical formula 73]

[0232]

[Chemical 74]

[0233]

[Chemical 75]

[0234]

[Chemical 76]

[0235]

[Chemical 77] The silver iodobromide emulsion used for Sample 101 is as follows. Emulsion name Average particle size (μm) Coefficient of variation (%) AgI content (%) A Monodisperse tetradecahedral grain 0.25 15 4 B Monodisperse cubic internal latent image type grain 0.30 10 4 C Monodisperse tetrahedral grain 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 Multi Dispersed tabular grains 0.80 28 2 Average aspect ratio 4.0 J Monodisperse tetrahedral grains 0.31 14 4 K Monodisperse tetrahedral grains 0.36 13 4 L L Monodisperse cubic internal latent image type grains 0.46 15 3 M Polydisperse cubic grains 0.53 25 3 N polydisperse tabular grains 1.00 28 2 tabular aspect ratio 7.0 The amount of sensitizing dye added was in the range of 0.01 to 0.25 g per mol of silver halide in the emulsion.

Next, the couplers C-1 to C-3 in the fourth to sixth layers of Sample 101 were replaced with cyan couplers as shown in Table 1, and the compound according to the present invention was added to the second layer. By doing so, Samples 102 to 115 were produced.

[0237]

[Table 1] The cyan couplers added to the fourth to sixth layers are shown below.

[0238]

[Chemical 78] The samples 101 to 115 thus obtained were measured with a sensitometer whose color temperature was adjusted to 4800 ° K.
After exposure through a TF measuring wedge and the following developing treatment, the MTF value was determined. Value at 10 cycle / mm as low frequency area, 30 cycle / mm as high frequency area
The values at are shown in Table 1.

Samples 101 to 115 were tested at 45 ° C. and 70%.
After being stored for 7 days under the condition of RH, the wafer was exposed to a wedge, and the same processing as above was performed together with the sample stored at room temperature to examine the change in photographic characteristics. Table 1 together with the results
Shown in.

Treatment process Treatment process time Temperature Tank capacity Replenishment amount Black and white development 6 minutes 38 ° C 12l 2.2 l / m ² First washing with water 2〃 38 ° C 4〃 7.5〃 Inversion 2〃 38 ℃ 4〃 1.1〃 Color development 6〃 38 ℃ 12〃 2.2〃 Adjust 2〃 38 ℃ 4〃 1.1〃 Bleach 6〃 38 ℃ 12〃 0.22〃 Fixed 4〃 38 ℃ 8〃 1.1〃 Second water wash 4〃 38 ℃ 8〃 7.5〃 1st 〃 25 ℃ 2 〃 1.1 〃 The composition of each processing solution was as follows. Black-and-white development 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-hydroxyme 2.0g 2.0g Cyl-3-pyrazolidone Potassium bromide 2.5g 1.4g Potassium thiocyanate 1.2g 1.2g Potassium iodide 2.0mg Add water 1000ml 1000ml pH 9.60 9.60 pH is hydrochloric acid Alternatively, it was adjusted with potassium hydroxide. Inversion solution Mother liquor Replenisher Nitrilo-N, N, N-trimethylenephosphone 3.0 g Same as mother liquor Acid 5 sodium salt Liquefied stannous dihydrate 1.0 g p-Aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 1000 ml pH 6.00 by adding ml water The 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 Iodine Potassium iodide 90 mg Sodium hydroxide 3.0 g 3.0 g Citrazinic acid 1.5 g 1.5 g N-ethyl- (β-methanesulfonamidoethyl 11 g 11 g) -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 11.8 12.00 pH was adjusted with hydrochloric acid or potassium hydroxide. Adjusting solution Mother liquor Replenishing solution Ethylenediaminetetraacetic acid disodium salt 8.0 g Same as mother dihydrate sodium bisulfite 12 g 1-thioglycerin sorbitan ester 0.1 g Add water 1000 ml pH 6.20 pH is 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) ・ 120 g 240 g Ammonium ・ 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 The pH was adjusted with hydrochloric acid or sodium hydroxide. Fixing solution Mother liquor Replenisher Ammonium thiosulfate 8.0 g Same sodium sulphite 5.0 g Sodium bisulfite 5.0 g Water was added to 1000 ml pH 6.60 pH was adjusted with hydrochloric acid or aqueous ammonia. Stabilizer Mother liquor Replenisher Formalin (37%) 5.0 ml Same as mother liquor Polyoxyethylene-p-monononyl 0.5 ml Phenyl ether (average degree of polymerization 10) 1000 ml without addition of water It is obvious that 108 to 115 are excellent in sharpness and have little change in photographic property with time. Example 2 Samples 205 to 215 were prepared in exactly the same manner except that the compound according to the present invention added to the second layer of Samples 105 to 115 prepared in Example 1 was changed to the compound shown in Table 2. When the same experiment as in Example 1 was repeated for Samples 101 to 104 and 205 to 215, the same results as in Example 1 were obtained.

[0241]

[Table 2]

Claims (1)

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 Alternatively, at least one of the compounds represented by formula (II) is contained, and at least one of the red-sensitive silver halide emulsion layers contains at least one of cyan dye-forming couplers represented by the following formula (III). Characteristic silver halide color photographic light-sensitive material. Formula (I): 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 R ¹⁷ CONH-
(Here, R ¹⁴ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, R ¹⁵ and R ¹⁶ represent a hydrogen atom, an alkyl group or an aryl group, and R ¹⁷ is adjacent to a carbonyl group. . the alkyl group having 2 or more carbon atoms is a heteroatom to the carbon atom is not substituted, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group) a represents; R ¹² and R ¹³ are a hydrogen atom or a Hammett substituent The constant σ _p represents a substituent having a value of 0.3 or less; B represents a group that releases X after leaving the hydroquinone mother nucleic acid product; X represents a development inhibitor residue; k
Represents an integer; A and A'represent a hydrogen atom or a group capable of being removed with an alkali. Formula (II): In the formula, Q ¹ represents at least one heteroatom and represents an atomic group necessary for forming a 5- or more-membered heterocyclic ring together with the carbon atom to be bonded, and R ²¹ represents a group capable of substituting on the hydroquinone nucleus. In the formula, B, X, k, A and A ′ have the same meanings as described in the formula (I). Formula (III): In the formula, R ₁ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ₂ represents a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, an acylamino group, an aliphatic oxy group or an aromatic oxy group. Represent R ₁ and R ₂ may combine with each other to form a 5- to 7-membered ring. Z represents a hydrogen atom or a group or atom capable of splitting off upon reaction with an oxidized product of a developing agent. Also, X ₁ , X
₂ represents a hydrogen atom or a halogen atom, and n is 0 to 18
Represents the integer.