JPH06194792A - Silver halide color photographic material - Google Patents

Abstract

PURPOSE:To provide a silver halide color photographic material capable of giving stable color processing property in which the fluctuation of photographic performance, including image qualities of sharpness and color reproductiveness is reduced. CONSTITUTION:A silver halide color photographic material has, on a support body, a red sensitive silver halide emulsion layer, a green sensitive silver halide emulsion layer, a blue sensitive silver halide emulsifier layer, and a non- photosensitive layer adjacent to the side closer to the support body of the green sensitive silver halide emulsion layer, and contains a development restrainer releasing compound represented by the formula, and a dye having a spectral absorption maximum wavelength in the wavelength area of 500-600nm in the film is further contained in the non-photosensitive layer. In the formula A-X, A represents a group which is reacted with a developing agent oxidized body to release X, and generates a soluble or color extinguishing compound in the processing solution, and X represents a development restrainer or its precursor residual group.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material. More specifically, the present invention relates to a silver halide color photographic light-sensitive material having improved color development processability and improved image quality.

[0002]

2. Description of the Related Art As one of means for improving image quality such as color reproducibility and sharpness, use of a compound releasing a development inhibitor or a precursor thereof has been proposed. One example is Research Disclosure (Resear
ch Disclosure, hereinafter abbreviated as RD) No. 1764
3 and No. 307105, each of which is described in the section VII-F. The development inhibitor releasing compound according to the present invention is described in, for example, JP-A-63-0.
No. 37350, Journal of the Photographic Society of Japan, Volume 52 (1989) 2
No. 150 to 155 (Kida) has one copy.

As one means for improving the sharpness, there has been proposed a method of preventing light scattering which occurs when light is transmitted through a film of a light-sensitive material when the light-sensitive material is photographed.
As one of the techniques, by coating an antihalation layer, the light transmitted through the silver halide emulsion layer becomes reflected light on the support surface, and the silver halide emulsion layer is exposed again to prevent blurring of the image. And, for example, JP-A-56-12
No. 639.

As an anti-irradiation method, as described in US Pat. No. 3,409,433, scattered light resulting from silver halide crystals in a photosensitive silver halide emulsion layer is added to the emulsion layer. However, naturally, there is a limit to the use of the dye in a light-sensitive material for photographing which requires high sensitivity.

Further, as a method for dyeing the non-photosensitive layer (intermediate layer), there is a method described in, for example, Japanese Patent Laid-Open No. 62-103641. The non-photosensitive layer on the exposure light source side is dyed with respect to the emulsion layer, which is completely different from the method of the present invention. Further, in the method described in JP-A-62-166330, the positional relationship between the photosensitive silver halide emulsion layer whose sharpness is desired to be improved and the non-photosensitive layer to be dyed is specified in particular. However, it is described that it is preferable to dye the non-photosensitive layer on the exposure light source side of the photosensitive silver halide emulsion layer, which is basically different from the present invention as described above.

Further, Japanese Patent Laid-Open No. 1-105947 and 1
No. 222222, a non-photosensitive layer is provided adjacent to a side of a green-sensitive silver halide emulsion layer near a support, and the non-photosensitive layer has a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm in the film. A light-sensitive material containing a non-diffusible dye and a development inhibitor-releasing compound in at least one of the silver halide light-sensitive layers is disclosed.

[0007]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
It is recognized that the methods described in Nos. 947 and 1-222257 can improve sharpness and color reproducibility without lowering the sensitivity of photographic properties, but the disclosed development inhibitor releasing compounds are disclosed. Reacts with an oxidized product of a developing agent to release a development inhibitor or its precursor and to form a non-diffusible dye. Therefore, unless the silver halide photosensitive layer to be used is selected according to the dye to be produced, there is a drawback that the color reproducibility is significantly impaired depending on the amount used. Some of them also describe non-diffusive colorless compounds that remain in the light-sensitive material after processing and often adversely affect storage stability such as fading and color change of color image. There is a drawback, and the usage amount is also limited. Further, the above-mentioned development inhibitor-releasing compounds have been unsatisfactory in order to provide a high quality image having excellent sharpness and color reproducibility as a color photographic material. Furthermore, in recent years, in the photographic industry, as one direction of environmental protection and resource saving, low replenishment and no discharge processing in color development processing have been earnestly pursued. However, the above-mentioned development inhibitor-releasing compound has a serious problem that, in such a color development processing, the photographic performance including the image quality largely varies, and stable performance cannot be obtained.

Accordingly, it is an object of the present invention to provide a silver halide color photographic light-sensitive material which provides stable color development processability with reduced fluctuations in photographic performance including image quality such as sharpness and color reproducibility.

[0009]

The above-mentioned object can be achieved by the silver halide color photographic light-sensitive material described below. That is, the support has a red-sensitive silver halide emulsion layer containing a cyan coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a blue-sensitive silver halide emulsion layer containing a yellow coupler, and the above green A silver halide color photographic light-sensitive material having a non-light-sensitive layer adjacent to the side of the light-sensitive silver halide emulsion layer close to the support, wherein a development inhibitor releasing compound represented by the following formula (I) is contained in the light-sensitive material. And a wavelength range of 500 in the non-photosensitive layer.
A silver halide color photographic light-sensitive material comprising a dye having a spectral absorption maximum wavelength in the range of to 600 nm.
Formula (I) A-X In the formula, A represents a group which reacts with an oxidized product of a developing agent to release X, and at the same time forms a compound soluble or decolorizable in a processing solution, X is a development inhibitor or a compound thereof. Represents a precursor residue.

Further, it can be achieved by the above-mentioned silver halide color photographic light-sensitive material containing a polymer coupler.

The present invention will be described in detail below.

First, the development inhibitor releasing compound represented by the formula (I) will be described. Specifically, the development inhibitor releasing compound represented by the formula (I) is represented by the following formulas (II) and (III)
It is represented by.

Formula (II) A- (TIME) _m -DI Formula (III) A- (TIME) _i -RED-DI In the formula, A is a coupling reaction with an oxidized product of an aromatic primary amine developing agent. Depending on (TIME) _m -DI or (T
IME) _i- RED-DI, which represents a coupler residue that produces a compound that is soluble or decolorizable in the treatment solution, and TIME represents a timing group that cleaves DI after it is released from A by a coupling reaction. In the formula, RED represents a group that cleaves DI by reacting with an oxidized product of a developing agent after leaving from A, DI represents a development inhibitor, m represents 1 or 2, and i represents 0 or 1. When m is 2, two TIMEs represent the same or different.

When A represents a yellow coupler residue, for example, pivaloyl acetanilide type, benzoyl acetanilide type, malon diester type, malon diamide type,
Dibenzoylmethane type, benzothiazolylacetamide type, malon ester monoamide type, benzoxazolylacetamide type, benzimidazolylacetamide type,
Examples thereof include quinazolin-4-one-2-ylacetanilide type or cycloalkanoylacetamide type coupler residues.

When A represents a magenta coupler residue, for example, 5-pyrazolone type, pyrazolo [1,5-a] benzimidazole type, pyrazolo [1,5-b] [1,2,
4] triazole type, pyrazolo [5,1-c] [1,
2,4] triazole type, imidazo [1,2-b] pyrazole type, pyrrolo [1,2-b] [1,2,4] triazole type, pyrazolo [1,5-b] pyrazole type or cyanoacetophenone type Coupler residue.

When A represents a cyan coupler residue, for example, phenol type, naphthol type, pyrrolo [1,2-b]
[1,2,4] triazole type, pyrrolo [2,1-c]
Examples include [1,2,4] triazole type and 2,4-diphenylimidazole type. Further, A may be a coupler residue that does not substantially leave a color image. Examples of this type of coupler residue include indanone type and acetophenone type coupler residues.

A preferred example of A is the following formula (Cp-1),
(Cp-2), (Cp-3), (Cp-4), (Cp-
5), (Cp-6), (Cp-7), (Cp-8),
It is a coupler residue represented by (Cp-9), (Cp-10), (Cp-11) or (Cp-12). These couplers are preferred because of their high coupling speed.

[0018]

[Chemical 1]

[0019]

[Chemical 2]

[0020]

[Chemical 3]

The free bond derived from the coupling position in the above formula represents the bonding position of the coupling leaving group. In the above formula, R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ ,
R ₅₆ , R ₅₇ , R ₅₈ , R ₅₉ , R ₆₀ , R ₆₁ , R ₆₂ , R ₆₃ , R
The carbon number of each of ₆₄ , R ₆₅ and R ₆₆ is preferably 10 or less. The coupler residue represented by A is an R ₇₁ OCO— group,
HOSO ₂ -group, HO-group, R ₇₂ NHCO-group or R
It is preferable to have at least one of the ₇₂ NHSO ₂ — groups as a substituent. That is, in the formula (Cp-1), R
_At least one of ₅₁ or R ₅₂ , at least one of R ₅₁ , R ₅₂ or R _{53 in} the formula (Cp-2), and at least one of R ₅₄ or R _{55 in} the formula (Cp-3);
Is R in the formulas (Cp-4) and (Cp-5).
_At least one of ₅₆ or R ₅₇ , and in the formula (Cp-6) at least one of R ₅₈ or R ₅₉ has the formula (Cp-
In 7), at least one of R ₅₉ or R ₆₀ is at least one of R ₆₁ or R _{62 in} the formula (Cp-8).
And in formulas (Cp-9) and (Cp-10) at least one R ₆₃ represents formulas (Cp-11) and (Cp-11).
In p-12), at least one of R ₆₄ , R ₆₅ or R ₆₆ is an R ₇₁ OCO— group, a HOSO ₂ — group, a HO— group,
It is preferable to have at least one R ₇₂ NHCO-group or R ₇₂ NHSO ₂ -group as a substituent. R ₇₁ represents a hydrogen atom, an alkyl group having 6 or less carbon atoms (for example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl) or a phenyl group, and R ₇₂ represents a group represented by R ₇₁ , R ₇₄
CO- _{group, R 74 N (R 75)} CO- group, R ₇₃ SO ₂ - group or a _{R 74 N (R 75) SO} 2 - represents a group, R ₇₃ is 6 carbon atoms
The following alkyl group (for example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl) or a phenyl group is represented, and R ₇₄ and R ₇₅ represent a group represented by R _71, which further has a substituent. You may have.

R _{51 to} R ₆₆ , a, b, d, e and f will be described in detail below. In the following, R ₄₁ is an alkyl group,
It represents an aryl group or a heterocyclic group, R ₄₂ represents an aryl group or a heterocyclic group, and R ₄₃ , R ₄₄ and R ₄₅ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R
₅₁ has the same meaning as R ₄₁ . a represents 0 or 1.
R ₅₂ and R ₅₃ have the same meanings as R ₄₃ . Formula (Cp
-2), when R ₅₂ is not a hydrogen atom, R ₅₂ and R ₅₁
May combine to form a 5- to 7-membered ring. b represents 0 or 1. R ₅₄ represents a group having the same meaning as R _41, R ₄₁ CON
(R ₄₃ ) -group, R ₄₁ SO ₂ N (R ₄₃ ) -group, R ₄₁ N (R
₄₃ ) -group, R ₄₁ S-group, R ₄₃ O-group or R ₄₅ N
_{(R 43) CON (R 44} ) - represents a group. R ₅₅ represents a group having the same meaning as R ₄₁ . R ₅₆ and R ₅₇ are each a group having the same meaning as the R ₄₃ group, R ₄₁ S- group, R ₄₃ O- group, R ₄₁ CON (R ₄₃ ).
-Group, R ₄₁ OCON (R ₄₃ ) -group or R ₄₁ SO ₂ N
Represents an (R ₄₃ ) -group. R ₅₈ represents a group having the same meaning as R ₄₃ . And R ₅₉ groups of the same meaning as _{R 41, R 41 CON (R} 43) -
Group, R ₄₁ OCON (R ₄₃ ) -group, R ₄₁ SO ₂ N (R ₄₃ ).
- _{group, R 43 N (R 44)} CON (R 45) - group, R ₄₁ O-
Group, R ₄₁ S- group, halogen atom or R ₄₁ N (R ₄₃ )-
Represents a group. d represents 0 to 3. When d is plural, plural R _59's represent the same substituent or different substituents. R
₆₀ represents a group having the same meaning as R ₄₃ . R ₆₁ represents a group having the same meaning as R _43, R ₄₃ OSO ₂ - _{group, R 43 N (R 44)} SO 2 - group,
R ₄₃ OCO- group, R ₄₃ N (R ₄₄ ) CO- group, cyano group,
_{R 41 SO 2 N (R 43} ) CO- _{group, R 43 CON (R 44)} C
O-group, R ₄₃ N (R ₄₄ ) SO ₂ N (R ₄₅ ) CO-group, R
_{43 N (R 44) CON (} R 45) CO- group, R ₄₃ N (R ₄₄₎
SO ₂ N (R ₄₅ ) SO ₂ − group, R ₄₃ N (R ₄₄ ) CON
It represents a (R ₄₅ ) SO ₂ — group. R ₆₂ is a group of the same meaning as R _41, R ₄₁ CONH- group, R ₄₁ OCONH- group, R ₄₁ SO
₂ NH- group, R ₄₃ N (R ₄₄ ) CONH- group, R ₄₃ N (R
₄₄ ) SO ₂ NH- group, R ₄₃ O- group, R ₄₁ S- group, halogen atom or R ₄₁ N (R ₄₃ )-group. Formula (Cp-
In 8), e represents an integer of 0 to 4, and when e is 2 or more, a plurality of R _62's are the same or different. R ₆₃ is a group having the same meaning as R ₄₁ , R ₄₃ CON (R
₄₄ ) -group, R ₄₃ N (R ₄₄ ) CO- group, R ₄₁ SO ₂ N (R
₄₃₎ - _{group, R 41 N (R 43)} SO 2 - group, R ₄₁ SO ₂ -
Represents a group, R ₄₃ OCO— group, R ₄₃ OSO ₂ — group, halogen atom, nitro group, cyano group or R ₄₃ CO— group.
In the formula (Cp-9), e represents an integer of 0 to 4,
When e is 2 or more, a plurality of R _62's are the same or different. In the formula (Cp-10), f is 0.
Represents an integer of 3 to 3, and when f is 2 or more, a plurality of R
Each ₆₃ represents the same or different. R ₆₄ , R
₆₅ and R ₆₆ are each a group having the same meaning as the R ₄₃ group, R ₄₁ S-
Group, R ₄₃ O— group, R ₄₁ CON (R ₄₃ ) — group, R ₄₁ SO ₂
N (R ₄₃ )-group, R ₄₁ OCO- group, R ₄₁ OSO ₂ -group,
R ₄₁ SO ₂ — group, R ₄₁ N (R ₄₃ ) CO— group, R ₄₁ N (R
₄₃ ) represents a SO ₂ — group, a nitro group or a cyano group.

In the above, R ₄₁ , R ₄₃ , R ₄₄ or R ₄₅
The alkyl group represented by has 1 to 10 carbon atoms, preferably 1
To 6 saturated or unsaturated, chain or cyclic, linear or branched, substituted or unsubstituted alkyl groups. Typical examples are methyl, cyclopropyl, isopropyl,
n-butyl, t-butyl, i-butyl, t-amyl, n
-Hexyl, cyclohexyl, 2-ethylhexyl, n
-Octyl, 1,1,3,3-tetramethylbutyl, n
-Decyl is mentioned. The aryl group represented by R ₄₁ , R ₄₂ , R ₄₃ , R ₄₄ or R ₄₅ is an aryl group having 6 to 10 carbon atoms, preferably substituted or unsubstituted phenyl, or substituted or unsubstituted naphthyl. . R ₄₁ ,
The heterocyclic group represented by R ₄₂ , R ₄₃ , R ₄₄ or R ₄₅ is a hetero atom having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, selected from a nitrogen atom, an oxygen atom or a sulfur atom, and preferably 3 It is a substituted or unsubstituted heterocyclic group having a 6- to 8-membered ring. Typical examples of the heterocyclic group are 2-pyridyl, 2-benzoxazolyl, 2-imidazolyl, 2-
Benzimidazolyl, 1-indolyl, 1,3,4-thiadiazol-2-yl, 1,2,4-triazole-
A 2-yl group or 1-indolinyl can be mentioned.

When the alkyl group, aryl group and heterocyclic group have a substituent, typical substituents are a halogen atom, R ₄₃ O- group, R ₄₁ S- group and R ₄₃ CON.
(R ₄₄₎ - _{group, R 43 N (R 44)} CO- group, R ₄₁ OCON
(R ₄₃ ) -group, R ₄₁ SO ₂ N (R ₄₃ ) -group, R ₄₃ N (R
₄₄₎ SO ₂ - radical, R ₄₁ SO ₂ - radical, R ₄₃ OCO- radical, R
₄₁ SO ₂ O— group, group having the same meaning as R ₄₁ , R ₄₃ N (R ₄₄ ).
Group, R ₄₁ CO ₂ — group, R ₄ OSO ₂ — group, cyano group or nitro group.

Next, R _{51 to} R ₆₃ , a, b, d, e and f
The preferable range of is described. R ₅₁ is preferably an alkyl group or an aryl group. Particularly preferably, a is 1. R
₅₂ and R ₅₅ are preferably aryl groups. R ₅₃ is preferably an aryl group when b is 1 and a heterocyclic group when b is 0. R
₅₄ is preferably an R ₄₁ CON (R ₄₃ ) -group or an R ₄₁ N (R ₄₃ ) -group. R ₅₆ and R ₅₇ are an alkyl group, an aryl group, R ₄₁ O-group, or R ₄₁ S- group. R ₅₈ is preferably an alkyl group or an aryl group. Formula (Cp-6)
Wherein R ₅₉ is a chlor atom, an alkyl group or R ₄₁ C
An ON (R ₄₃ )-group is preferred, and d is preferably 1 or 2. R ₆₀ is preferably an aryl group. In formula (Cp-7), R ₅₉ is preferably R ₄₁ CON (R ₄₃ ) — group, and d is 1
Is preferred. R ₆₁ is R ₄₃ OSO ₂ − group, R ₄₃ N (R ₄₄ ).
SO ₂ - group, R ₄₃ OCO- _{group, R 43 N (R 44)} CO-
Group, cyano group, R ₄₁ SO ₂ N (R ₄₃ ) CO— group, R ₄₃ C
ON (R ₄₄₎ CO- _{group, R 43 N (R 44)} SO 2 N
(R ₄₅ ) CO— group, R ₄₃ N (R ₄₄ ) CON (R ₄₅ ) CO
-Groups are preferred. In the formula (Cp-8), e is preferably 0 or 1, and R ₆₂ is R ₄₁ OCON (R ₄₃ )-
Group, R ₄₁ CON (R ₄₃ ) -group or R ₄₁ SO ₂ N
The (R ₄₃ )-group is preferable, and the substitution position thereof is preferably the 5-position of the naphthol ring. In formula (Cp-9), R ₆₃ is R ₄₁ CON (R ₄₃ ) — group, R ₄₁ SO ₂ N (R ₄₃ ).
-Group, R ₄₁ N (R ₄₃ ) SO ₂ -group, R ₄₁ SO ₂ -group, R
₄₁ N (R ₄₃ ) CO— groups, nitro groups or cyano groups are preferred. e is preferably 1 or 2. In formula (Cp-10), R ₆₃ is preferably R ₄₃ N (R ₄₄ ) CO— group, R ₄₃ OCO— group or R ₄₃ CO— group. f is preferably 1 or 2. In formulas (Cp-11) and (Cp-12), R ₆₄ and R ₆₅ are R ₄₁ OCO— groups and R ₄₁ OSO ₂ —.
Group, R ₄₁ SO ₂ — group, R ₄₄ N (R ₄₃ ) CO— group, R ₄₄ N
(R ₄₃ ) SO ₂ — group or cyano group is preferred, and R ₄₁ O
CO- _{group, R 44 N (R 43)} CO- group or a cyano group is particularly preferable. R ₆₆ is preferably a group having the same meaning as R ₄₁ . R
Each of _{51 to} R ₆₆ preferably has a total carbon number including the substituents of 18 or less, and more preferably 10 or less. In the present invention, A is preferably a group that produces a compound soluble in the treatment liquid.

Next, the development inhibitor represented by DI will be described. Examples of the development inhibitor represented by DI include Research Disclosure 76
Volume, No. 17643 (December 1978), US Pat. Nos. 4,477,563, 5,021,332, 5,026,628, 3,227,554, 3,384. 657, 3,615,506, 3,617,291, 3,733,201, 3,933,500, 3,958,993, 3,961,959. No. 4,149,886, No. 4,259,437, No. 4,095,984, No. 4,782,012, British Patent No. 1,450,479.
Or development inhibitors as described in US Pat. No. 5,034,311 and the like. Preferred is a heterocyclic thio group, a heterocyclic seleno group or a triazolyl group (monocyclic or condensed ring 1,2,3-triazolyl or 1,2,4-triazolyl), and particularly preferred is tetrazolylthio or tetrazolylseleno. 1, 3, 4
-Oxadiazolylthio, 1,3,4-thiadiazolylthio, 1- (or 2-) benzotriazolyl, 1,
2,4-triazol-1- (or 4-) yl, 1,
2,3-triazol-1-yl, 2-benzothiazolylthio, 2-benzoxazolylthio, 2-benzimidazolylthio and derivatives thereof are included. Preferred development inhibitors are represented by the following formulas DI-1 to DI-6.

[0027]

[Chemical 4]

In the formula, R ₃₁ is a halogen atom, R ₄₆ O-group,
R ₄₆ S- _{group, R 47 CON (R 48)} - group, R ₄₇ N (R ₄₈₎
CO- _{group, R 46 OCON (R 47)} - group, R ₄₆ SO ₂ N
(R ₄₇₎ - _{group, R 47 N (R 48)} SO 2 - group, R ₄₆ SO ₂
- group, R ₄₇ OCO- _{group, R 47 N (R 48)} CON (R 49)
- _{group, R 47 CON (R 48)} SO 2 - group, R ₄₇ N (R ₄₈₎
CON (R ₄₉ ) SO ₂ — group, a group having the same meaning as R ₄₆ , R ₄₇
N (R ₄₈₎ - group, R ₄₆ CO ₂ - group, R ₄₇ OSO ₂ - group,
A cyano group or a nitro group can be mentioned. R ₄₆ represents an alkyl group, an aryl group, or a heterocyclic group, and R ₄₇ , R ₄₈
And R ₄₉ each represents an alkyl group, an aryl group, a heterocyclic group or a hydrogen atom. The alkyl group represented by R ₄₆ , R ₄₇ , R ₄₈ or R ₄₉ has 1 to 32 carbon atoms, preferably 1 to 32 carbon atoms.
20 saturated or unsaturated, linear or cyclic, linear or branched, substituted or unsubstituted alkyl groups. Typical examples are methyl, cyclopropyl, isopropyl,
n-butyl, t-butyl, i-butyl, t-amyl, n
-Hexyl, cyclohexyl, 2-ethylhexyl, n
-Octyl, 1,1,3,3-tetramethylbutyl, n
-Decyl is mentioned. The aryl group represented by R ₄₆ , R ₄₇ , R ₄₈ or R ₄₉ is an aryl group having 6 to 32 carbon atoms, preferably substituted or unsubstituted phenyl, or substituted or unsubstituted naphthyl. R ₄₆ , R ₄₇ , R
_The heterocyclic group represented by ₄₈ or R ₄₉ has 1 to 32 carbon atoms,
As the 1 to 20 hetero atoms, a substituted or unsubstituted heterocyclic group having a 3- to 8-membered ring, which is selected from a nitrogen atom, an oxygen atom or a sulfur atom, is preferable. Typical examples of the heterocyclic group are 2-pyridyl, 2-benzoxazolyl, 2-imidazolyl, 2-benzimidazolyl, 1-indolyl, 1,3,4-thiadiazole-
2-yl, 1,2,4-triazol-2-yl group or 1-indolinyl can be mentioned. R ₃₂ represents a group having the same meaning as R ₄₆ . k is an integer of 1 to 4, g is 0 or 1, and h is 1 or 2. V represents an oxygen atom, a sulfur atom or -N ( _R46 )-. R ₃₁ and R ₃₂ may further have a substituent.

Next, the group represented by TIME will be described. The group represented by TIME may be any linking group capable of cleaving DI after cleaving from A during development processing. For example, U.S. Pat. No. 4,146,396
No. 4,652,516 or 4,698,29
A group utilizing the cleavage reaction of hemiacetal described in US Pat. Nos. 4,248,962 and 4,847,
185 or 4,857,440, a timing group for causing a cleavage reaction utilizing an intramolecular nucleophilic substitution reaction, as disclosed in US Pat. Nos. 4,409,323 and 4,421,845. A timing group that causes a cleavage reaction by using the described electron transfer reaction, a group that causes a cleavage reaction by using the hydrolysis reaction of iminoketal described in US Pat. No. 4,546,073, or published in West Germany Examples thereof include a group capable of causing a cleavage reaction by utilizing a hydrolysis reaction of an ester described in Japanese Patent No. 2626317. TIME is a hetero atom contained therein, preferably an oxygen atom, a sulfur atom or a nitrogen atom,
It binds to A in formula (II) or (III). Preferred TIME includes the following formulas (T-1), (T-2) or (T-3). Formula (T-1) * -W- ( X = Y) j -C (R 21) R 22 - ** Formula (T-2) * -W- CO - ** Formula (T-3) * -W -LINK-E-** In the formula, * represents a position bonded to A in the formula (II) or (III), ** represents a position bonded to DI or TIME (when m is plural), W Represents an oxygen atom, a sulfur atom or> N—R ₂₃ , X and Y each represent a methine or nitrogen atom, j represents 0, 1 or 2, R ₂₁ ,
R ₂₂ and R ₂₃ each represent a hydrogen atom or a substituent. Here, when X and Y represent a substituted methine, a substituent thereof,
Any two substituents of R ₂₁ , R ₂₂ and R ₂₃ may be linked to each other to form a cyclic structure (for example, a benzene ring or a pyrazole ring) or may not be formed. In formula (T-3), E represents an electrophilic group,
LINK represents a linking group that W and E are sterically related so that they can undergo an intramolecular nucleophilic substitution reaction. Formula (T-
Specific examples of TIME shown in 1) are as follows.

[0030]

[Chemical 5]

Specific examples of TIME represented by the formula (T-2) are as follows.

[0032]

[Chemical 6]

Specific examples of TIME represented by the formula (T-3) are as follows.

[0034]

[Chemical 7]

In the formula (II), when m is 2, (TIM
E) Specific examples of _m are as follows.

[0036]

[Chemical 8]

The group represented by RED in formula (III) will be described below. RED is a group that can be cleaved from A or TIME to become RED-DI and cross-oxidized by an oxidizing substance present during development, for example, an oxidized product of a developing agent. RED-DI may be any as long as it cleaves DI when oxidized. Examples of RED include hydroquinones, catechols, pyrogallols, 1,4
-Naphthohydroquinones, 1,2-naphthohydroquinones, sulfonamide phenols, hydrazides or sulfonamide naphthols. These groups are specifically described in, for example, JP-A-61-230135,
62-251746, 61-278852, U.S. Pat. Nos. 3,364,022 and 3,379,529.
Nos. 4,618,571 and 3,639,417
No. 4,684,604 or J.Org.Chem., 29.
Volume, page 588 (1964) is mentioned. Among the above, preferable RED is hydroquinone, 1,4-naphthohydroquinone, 2 (or 4) -sulfonamidophenol, pyrogallol or hydrazide. Among these, the redox group having a phenolic hydroxyl group is bonded to A or TIME at the oxygen atom of the phenol group.

Until the silver halide photographic light-sensitive material containing the compound represented by the formula (II) or (III) is developed, the photosensitivity of the compound represented by the formula (II) or (III) is added. For the purpose of fixing to a layer or a non-photosensitive layer,
The compound represented by the formula (II) or (III) preferably has a diffusion resistant group, and the diffusion resistant group is TIME or R
The case where it is contained in the ED is particularly preferable. In this case, the preferred diffusion resistant group has 8 to 40 carbon atoms, preferably 12 to
32 alkyl group or alkyl group (having 3 to 2 carbon atoms)
0), an alkoxy group (having 3 to 20 carbon atoms) or an aryl group (having 6 to 20 carbon atoms), and an aryl group having 8 to 40 carbon atoms, preferably 12 to 32 carbon atoms.

Regarding the method for synthesizing the compound represented by the formula (II) or (III), known patents or literatures cited for explaining TIME, RED and DI, JP-A Nos. 61-156127 and 58-58. No. 160954, 5
No. 8-162949, No. 61-249052, No. 63
-37350, U.S. Pat. No. 5,026,628, European Published Patent Nos. 443530A2 and 44.
No. 4501A2, etc.

Specific representative examples of the compound represented by formula (I) used in the present invention are shown below, but the present invention is not limited thereto.

[0041]

[Chemical 9]

[0042]

[Chemical 10]

[0043]

[Chemical 11]

[0044]

[Chemical 12]

[0045]

[Chemical 13]

[0046]

[Chemical 14]

[0047]

[Chemical 15]

[0048]

[Chemical 16]

[0049]

[Chemical 17]

[0050]

[Chemical 18]

The development inhibitor releasing compound represented by the above formula (I) of the present invention can be used in any layer in the light-sensitive material. That is, the photosensitive layer (blue sensitive emulsion layer,
Green-sensitive emulsion layer, red-sensitive emulsion layer, donor layer having a multi-layer effect having a spectral sensitivity distribution different from those of the main photosensitive layer) and non-photosensitive layer (for example, protective layer, yellow filter layer, intermediate layer, antihalation layer) It can be used for either layer. When the same color-sensitive layer is divided into two or more layers having different sensitivities, it may be added to any of the highest-sensitivity layer, the lowest-sensitivity layer and the intermediate-sensitivity layer, and to all layers. It can also be added. It is preferably used in the photosensitive layer and / or the non-photosensitive layer adjacent to the photosensitive layer.

The amount of the development inhibitor-releasing compound represented by the formula (I) used in the light-sensitive material is in the range of 5 × 10 ^{-4 to 2} g / m ² . The range is preferably 1 × 10 ^{−3 to} 1 g / m ² , and more preferably 5 × 10 ^{−3 to} 5 × 10 ⁻¹ g / m ^2.
It is in the range of m ² . Regarding the use of the development inhibitor-releasing compound represented by the formula (I) in the light-sensitive material, any known dispersion method can be used depending on the compound. For example, when it is alkali-soluble, it may be added as an alkaline aqueous solution or as a solution dissolved in an organic solvent miscible with water, or an oil-in-water dispersion method using a high-boiling organic solvent, or a solid dispersion method. You can

The development inhibitor releasing compound represented by the formula (I) may be used alone or in combination of two or more kinds. Also, the same compound can be used in two or more layers. Further, it may be used in combination with other known development inhibitor-releasing compounds or development inhibitor precursor-releasing compounds,
It can also be used in the presence of a coupler and other additives described below. These are appropriately selected according to the performance required of the photosensitive material.

The development inhibitor-releasing compound represented by the formula (I) of the present invention releases a development inhibitor by a coupling reaction with an oxidant of a developing agent, and at the same time, its mother nucleus (in the explanation of the above-mentioned formula (I)). A) forms a pigment. The formed dye is described in, for example, the Journal of the Photographic Society of Japan, Volume 52 (1989).
2) 150-155 (Kida et al) or 198
Proceedings of 9th Annual Meeting of the Photographic Society of Japan 2A0-22 (Kida)
As described in (1), the color solution is discharged during the color development process or the dye is bleached and erased. Therefore, the formed dye does not remain on the photosensitive material as a dye after color development processing. Therefore, the development inhibitor releasing compound represented by the formula (I) of the present invention is required for a light-sensitive material regardless of any layer constituting the light-sensitive material, for example, a red-sensitive emulsion layer, a green-sensitive emulsion layer or a blue-sensitive emulsion layer. There is an advantage in that the compound can be used depending on the performance performed. Furthermore, since the formed dye does not remain as a dye, it has an advantageous effect on color reproducibility. Further, the color image fastness may be improved in some cases. In addition, the development inhibitor-releasing compound represented by the formula (I) of the present invention is characterized in that it provides stable photographic performance and image quality in a low replenishment color development process when used in combination with a dye described below in a light-sensitive material. Have.

Next, a non-photosensitive layer is provided adjacent to the side of the green-sensitive silver halide emulsion layer of the present invention near the support,
The dye having a spectral absorption maximum wavelength in the wavelength range of 500 to 600 nm in the film in the non-photosensitive layer will be described. The dye used in the present invention is such that the dye added to the non-photosensitive layer during the production of the color light-sensitive material is substantially present in the non-photosensitive layer without diffusing into other layers and has a spectral absorption maximum wavelength of 500 to 600 nm. The object of the present invention is achieved as long as it has one.

The dye may be used in the non-photosensitive layer by directly dyeing gelatin, or by dispersing the dye in oil-in-water as described below, that is, by using a high-boiling organic solvent having a boiling point of 175 ° C. or higher at normal pressure. If necessary, the boiling point is 50 ° C or higher, 160
A method in which an organic solvent having a temperature of not more than 0 ° C. is also used for dissolution, and emulsion-dispersed one in an aqueous gelatin solution containing a surfactant is added, International Patent Publication WO88 / 4974, and Japanese Patent Publication No. 1-5.
No. 02912 and European Patent Publication No. 456,148, there is a method of adding a so-called solid dispersion, or a method of preventing diffusion of a dye through a typical polymer mordant shown in the following Chemical Formula 19 and the like. In the above, any of these methods can be used.

[0057]

[Chemical 19]

The light absorption property of the dye used in the present invention is substantially 500 to 600 nm in the non-photosensitive dry film containing the dye.
Any dye having a maximum spectral absorption wavelength may be used, and one kind or a combination of two or more kinds of dyes may be used.

The amount of the dye added is such that the average optical density in the 500 to 600 nm region in the dry film of the added non-photosensitive layer is 0.0.
It is 1 to 0.50, and preferably 0.03 to 0.30. In the present invention, a dye dispersed in the above-mentioned dispersion method in an amount capable of obtaining this average optical density may be added. The actual measuring method is to measure the density of 500 to 600 nm with a spectrophotometer on a sample obtained by coating a dye with gelatin on a transparent support and drying, and determine the average optical density at 500 to 600 nm from the integrated value.

The dye addition layer of the present invention is a non-photosensitive layer adjacent to the green-sensitive emulsion layer on the side opposite to the exposure side (support side),
Moreover, by localizing in the layer, the sharpness can be remarkably improved by the antihalation effect while keeping the sensitivity reduction of the green photosensitive layer to a minimum. In the layer-structured light-sensitive material in which at least one red-sensitive emulsion layer is present on the support side of the dye-insensitive layer according to the present invention, the dye-insensitive layer allows the red-sensitive emulsion layer to be on the short wavelength side (green sensitivity). By lowering the sensitivity of the (range), the change in hue due to the amount of exposure light is reduced, and more faithful color reproduction is possible.

The dyes listed below are known as dyes which satisfy these conditions when used in the present invention. For example, British Patent Nos. 506,385, 1,177,429, 1,311,884, 1,338,799, 1,385,371, 1,467,214, and 1,433,102, 1,553,516, JP-A-48-85,130, 49-114,420,
52-117,123, 55-161,233
No. 59-111, 640, and 61-7, 838.
No. 39/22, 069 / 43-13, 16
No. 8, 41-18,459, and U.S. Pat. No. 3,24.
No. 7,127, No. 3,469,958, No. 4,07
Oxonol dyes having a pyrazolone nucleus and a barbituric acid nucleus described in US Pat. No. 8,933, US Pat.
Other oxonol dyes described in 3,472, 3,379,533, British Patents 1,278,621, 1,538,943, British Patent 575, etc.
691, 680, 631, 599, 623,
No. 786,907, No. 907,125, No. 1,04
No. 5,609, U.S. Pat. No. 4,255,326, JP-A-59-211,043, JP-A-60-170,845 and the like, JP-A-50-100,116.
No. 54-118, 247, No. 60-32, 851
No. 60-186,567, British Patent No. 2,01
Azomethine dyes described in U.S. Pat. Nos. 4,598,750 and 031, anthraquinone dyes described in U.S. Pat. No. 2,865,752, U.S. Pat. No. 2,538,00.
No. 9, No. 2,688,541, No. 2,538,008
No., British Patent Nos. 584,609 and 1,210,25
No. 2, JP-A Nos. 50-40,625 and 51-3,62.
No. 3, No. 51-10, 927, No. 54-118, 24
No. 7, Japanese Patent Publication No. 48-3,286, No. 59-37, 30
Arylidene dyes described in No. 3 and the like, Japanese Patent Publication No. 28-
3,082, 44-16,594, 59-2
Styryl dyes described in US Pat. No. 8,898, British Patent Nos. 446,583, 1,335,422, and JP-A No.
9-228,250 and the like, triarylmethane dyes, British Patent Nos. 1,075,653 and 1,15.
No. 3,341, No. 1,284,730, No. 1,47
5,228, 1,542,807 and the like, merocyanine dyes, US Pat. No. 2,843,486,
Examples thereof include cyanine dyes described in JP-A-3,294,539.

Specific examples of more preferable dyes are not limited to the following, and any dyes are included in the scope of the present invention as long as they are used in accordance with the above-mentioned gist. Further, these dyes can be easily synthesized by the method described in the above-mentioned patent specification or a method similar thereto.

[0063]

[Chemical 20]

[0064]

[Chemical 21]

[0065]

[Chemical formula 22]

[0066]

[Chemical formula 23]

[0067]

[Chemical formula 24]

[0068]

[Chemical 25]

[0069]

[Chemical formula 26]

[0070]

[Chemical 27]

[0071]

[Chemical 28]

[0072]

[Chemical 29]

[0073]

[Chemical 30]

[0074]

[Chemical 31]

[0075]

[Chemical 32]

For the green-sensitive layer of the silver halide color photographic light-sensitive material of the present invention, it is preferable to use a polymer coupler obtained from a monomer represented by the following formula (PA) for its sharpness, processing dependence and after processing. Is more preferable in that the image storability is improved.

[0077]

[Chemical 33]

In the formula, R ₁₂₁ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or chlorine, and -D- represents -COO.
-, - CONR ₁₂₂ -, or a substituted or unsubstituted phenyl group, -E- represents a substituted or unsubstituted alkylene group, phenylene group or aralkylene group,
-F- is -CONR ₁₂₂ -, - NR ₁₂₂ CONR
_{122 -, - NR 122 COO -} , - NR 122 CO -, - O
_{CONR 122 -, - NR 122 -} , - COO -, - OCO
-, - CO -, - O -, - S -, - SO 2 -, - NR
₁₂₂ SO ₂ −, or —SO ₂ NR ₁₂₂ −. R
₁₂₂ represents a hydrogen atom or a substituted or unsubstituted aliphatic group or aryl group. When two or more R _122's are present in the same molecule, they may be the same or different. p, q, r
Represents 0 or 1. However, p, q, and r are 0 at the same time.
It never happens. T is a part of a coupler residue (Ar, Z ₅₁ , or R ₁₃₃ ) of a magenta coupler represented by the following formula (PB), and is-(D)-(E)-of formula (PA).
(Bonded to (F)-).

[0079]

[Chemical 34]

Ar ₅₁ is a substituent of the well-known type at the 1-position of the 2-pyrazolin-5-one coupler, such as an alkyl group, a substituted alkyl group (eg, haloalkyl such as fluoroalkyl, cyanoalkyl, benzylalkyl, etc.), a substituted group. Or, an unsubstituted heterocyclic group (for example, 4-pyridyl, 2-thiazoyl), a substituted or unsubstituted aryl group [as the heterocyclic group and the substituent of the aryl group, an alkyl group (for example, methyl, ethyl), an alkoxy group ( For example, methoxy, ethoxy), aryloxy group (for example, phenyloxy), alkoxycarbonyl group (for example, methoxycarbonyl), acylamino group (for example, acetylamino), carbamoyl group, alkylcarbamoyl group (for example, methylcarbamoyl, ethylcarbonyl), dialkylcarbamoyl group. For example, dimethylcarbamoyl), arylcarbamoyl group (for example, phenylcarbamoyl), alkylsulfonyl group (for example, methylsulfonyl), arylsulfonyl group (for example, phenylsulfonyl), alkylsulfonamide group (for example, methanesulfonamide), arylsulfonamide group (for example, phenyl). Sulfonamide), sulfamoyl group, alkylsulfamoyl group (eg ethylsulfamoyl), dialkylsulfamoyl group (eg dimethylsulfamoyl), alkylthio group (eg methylthio), arylthio group (eg phenylthio), cyano group, Nitro group,
Halogen atoms (for example, fluorine, chlorine, bromine, etc.) are mentioned, and when there are two or more substituents, they may be the same or different. Particularly preferred substituents include a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group and a cyano group. ]] Is represented.

R ₁₂₃ is an unsubstituted or substituted anilino group, an acylamino group (eg, alkylcarbonamide, phenylcarbonamide, alkoxycarbonamide, phenyloxycarbonamide), a ureido group (eg, alkylureido, phenylureido), a sulfonamide group,
Represents a halogen atom (eg, fluorine, chlorine, bromine, etc.), a linear or branched alkyl group (eg, methyl, t-butyl, octyl, tetradecyl), an alkoxy group (eg, methoxy, ethoxy). Two
-Ethylhexyloxy, tetradecyloxy), an acylamino group (for example, acetamide, benzamide, butanamide, octanamide, tetradecanamide, α)
-(2,4-di-tert-amylphenoxy) acetamide, α- (2,4-di-tert-amylphenoxy) butyramide, α- (3-pentadecylphenoxy) hexanamide, α- (4-hydroxy- 3-tert-butylphenoxy) tetradecanamide, 2-oxo-pyrrolidin-1-yl, 2-oxo-5-tetradecylpyrrolidin-1-yl, N-methyl-tetradecanamide), sulfonamide group (eg, methanesulfone) Amide, benzenesulfonamide, ethylsulfonamide, p-toluenesulfonamide, octanesulfonamide, p-dodecylbenzenesulfonamide, N-methyl-tetradecanesulfonamide), sulfamoyl group (for example, sulfamoyl, N-methylsulfamoyl, N-ethylsulfamoyl, N, N Dimethylsulfamoyl,
N, N-dihexylsulfamoyl, N-hexadecylsulfamoyl, N- [3- (dodecyloxy) -propyl] sulfamoyl, N- [4- (2,4-di-tert.
-Amylphenoxy) butyl] sulfamoyl, N-methyl-N-tetradecylsulfamoyl), carbamoyl group (for example, N-methylcarbamoyl, N-butylcarbamoyl, N-octadecylcarbamoyl, N- [4
-(2,4-di-tert-amylphenoxy) butyl] carbamoyl, N-methyl-N-tetradecylcarbamoyl), diacylamino group (N-succinimide, N-phthalimide, 2,5-dioxo-1-oxazolidinyl, 3-dodecyl-2,5-dioxo-1-hydantoinyl, 3- (N-acetyl-N-dodecylamino) succinimide), alkoxycarbonyl group (eg, methoxycarbonyl, tetradecyloxycarbonyl, benzyloxycarbonyl), alkoxysulfonyl Group (for example, methoxysulfonyl, butoxysulfonyl, octyloxysulfonyl, tetradecyloxysulfonyl), aryloxysulfonyl group (for example, phenoxysulfonyl, p-methylphenoxysulfonyl, 2,
4-di-tert-amylphenoxysulfonyl), alkanesulfonyl group (for example, methanesulfonyl, ethanesulfonyl, octanesulfonyl, 2-ethylhexylsulfonyl, hexadecanesulfonyl), arylsulfonyl group (for example, benzenesulfonyl, 4-nonylbenzenesulfonyl) , An alkylthio group (eg, methylthio, ethylthio, hexylthio, benzylthio, tetradecylthio, 2- (2,4-di-tert-amylphenoxy) ethylthio), an arylthio group (eg, phenylthio, p-tolylthio), alkyloxycarbonyl Amino group (eg, methoxycarbonylamino, ethyloxycarbonylamino, benzyloxycarbonylamino, hexadecyloxycarbonylamino), alkylureido group (eg, N- methylureido, N, N- dimethylureido, N- methyl -N- dodecyl ureido,
N-hexadecyl ureido, N, N-dioctadecyl ureido), an acyl group (for example, acetyl, benzoyl,
Octadecanoyl, p-dodecanamidobenzoyl),
Examples thereof include a nitro group, a carboxyl group, a sulfo group, a hydroxy group and a trichloromethyl group. However, among the above-mentioned substituents, those defined as an alkyl group have 1 to 36 carbon atoms, and those defined as an aryl group have 6 to 38 carbon atoms.

Z ₅₁ is a hydrogen atom or a halogen atom (for example,
Chlorine, bromine), a coupling-off group linked by an oxygen atom (for example, acetoxy, propanoyloxy, benzoyloxy, ethoxyoxaloyloxy, pyrvinyloxy, cinnamoyloxy, phenoxy, 4-cyanophenoxyl, 4-titanium sulfone). Amidophenoxy, α-
Naphthoxy, 4-cyanoxyl, 4-methanesulfonamide-phenoxy, α-naphthoxy, 3-pentadecylphenoxy, benzyloxycarbonyloxy, ethoxy, 2-cyanoethoxy, benzyloxy, 2-phenethyloxy, 2-phenoxy-ethoxy, 5-phenyltetrazolyloxy, 2-benzothiazolyloxy),
Those described in the coupling-off group linked by a nitrogen atom (for example, JP-A-59-99437), specifically, benzenesulfonamide, N-ethyltoluenesulfonamide, heptafluorobutanamide, 2,3,3. 4,
5,6-pentafluorobenzamide, octanesulfonamide, p-cyanophenylureido, N, N-diethylsulfamoylamino, 1-piperidyl, 5,5-
Dimethyl-2,4-dioxo-3-oxozolidinyl,
1-benzyl-5-ethoxy-3-hydantoinyl, 2
-Oxo-1,2-dihydro-1-pyridinyl, imidazolyl, pyrazolyl, 3,5-diethyl-1,2,4-
Triazol-1-yl, 5- or 6-bromo-benzotriazol-1-yl, 5-methyl-1,2,3
4-triazol-1-yl group, benzimidazolyl), coupling leaving group linked by sulfur atom (for example, phenylthio, 2-carboxyphenylthio, 2-methoxy-5-octylphenylthio, 4-methanesulfonylphenylthio, 4 -Octanesulfonamide phenylthio, benzylthio, 2-cyanoethylthio, 5-phenyl-2,3,4,5-tetrazolylthio, 2-benzothiazolyl). It is preferably a coupling-off group linked by a nitrogen atom, and particularly preferably a pyrazolyl group.

E represents an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, an aralkylene group, or a phenylene group, and the alkylene group may be linear or branched. Examples of the alkylene group include methylene, methylmethylene,
Examples of the dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decylmethylene and aralkylene groups include benzylidene,
Examples of the phenylene group include p-phenylene, m-phenylene and methylphenylene. Further, the substituent of the alkylene group, aralkylene group or phenylene group represented by E is an aryl group (eg phenyl) nitro group, a hydroxyl group, a cyano group, a sulfo group, an alkoxy group (eg methoxy), an aryloxy group (eg phenoxy), Acyloxy group (eg acetoxy), acylamino group (eg acetylamino), sulfonamide group (eg methanesulfonamide), sulfamoyl group (eg methylsulfamoyl), halogen atom (eg fluorine, chlorine, bromine), carboxy group, carbamoyl A group (for example, methylcarbamoyl), an alkoxycarbonyl group (for example, methoxycarbonyl), a sulfonyl group (for example, methylsulfonyl) and the like can be mentioned. When there are two or more substituents, they may be the same or different.

Next, as the non-color forming ethylene-like monomer which is not coupled with the oxidation product of the aromatic primary amine developing agent which is copolymerizable with the coupler monomer represented by the formula (PA), for example, acrylic acid can be used. Examples thereof include esters, methacrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, acrylamides, methacrylamides, vinyl ethers, and styrenes. Specific examples of these monomers will be given below. As acrylic acid esters, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-
Butyl acrylate, isobutyl acrylate, tert-
Examples thereof include butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, acetoxyethyl acrylate, phenyl acrylate, 2-methoxy acrylate, 2-ethoxy acrylate, and 2- (2-methoxyethoxy) ethyl acrylate. Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate and 2-ethoxyethyl methacrylate. Examples of crotonic acid esters include butyl crotonic acid and hexyl crotonic acid. Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate and the like. Examples of the maleic acid diester include diethyl maleate, dimethyl maleate, dibutyl maleate and the like. Examples of the fumarate diester include diethyl fumarate, dimethyl fumarate, dibutyl fumarate and the like. Examples of the itaconic acid diester include diethyl itaconic acid, dimethyl itaconic acid and dibutyl itaconic acid. Examples of acrylamides include acrylamide, methyl acrylamide, ethyl acrylamide, propyl acrylamide, n-butyl acrylamide, tert-butyl acrylamide, cyclohexyl acrylamide, 2-methoxyethyl acrylamide, dimethyl acrylamide, diethyl acrylamide and phenyl acrylamide. As methacrylamides, methyl methacrylamide, ethyl methacrylamide, n-butyl methacrylamide, tert-
Examples thereof include butyl methacrylamide, 2-methoxy methacrylamide, dimethyl methacrylamide, and diethyl methacrylamide. Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether and dimethylaminoethyl vinyl ether. As styrenes, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, chloromethylstyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromstyrene, vinyl benzoate. Examples thereof include acid methyl ester and 2-methylstyrene.

Examples of other monomers include allyl compounds (eg, allyl acetate), vinyl ketones (eg, methyl vinyl ketone), vinyl heterocyclic compounds (eg, vinyl pyridine), glycidyl esters (eg, glycidyl acrylate), unsaturated compounds. Nitriles (eg acrylonitrile), acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate (eg monomethyl itaconate), monoalkyl maleate (eg monomethyl maleate), citraconic acid, vinyl sulfonic acid, acryloyloxy Examples thereof include alkyl sulfonic acid (for example, acryloyloxymethyl sulfonic acid), acrylamido alkyl sulfonic acid (for example, 2-acrylamido-2-methylethane sulfone), and the like. These acids may be salts of alkali metals (eg Na, K) or ammonium ions. Among these monomers, comonomers preferably used include acrylic acid ester, methacrylic acid ester, styrenes, maleic acid ester,
Acrylamides and methacrylamides are included. Two or more kinds of these monomers may be used in combination. When two or more kinds are used in combination, examples thereof include n-butyl acrylate and styrene, n-butyl acrylate and butyl styrene, t-butyl methacrylamide and n-butyl acrylate.

The proportion of the color-forming portion corresponding to the formula (PB) in the magenta polymer coupler is usually 5 to 80% by weight. Is preferred. In this case, the equivalent molecular weight (the number of grams of the polymer containing 1 mol of the monomer coupler) is about 250 to 4,000, but is not limited thereto. The magenta polymer coupler is based on the coupler monomer, and when the same layer as silver halide is used, silver 1
0.005 to 0.5 mol per mol, preferably 0.0
It is preferable to add 3 to 0.25 mol. When the magenta polymer coupler is used in the non-photosensitive layer, the coating amount is
^{0.01g / m 2 ~1.0g / m 2} , preferably 0.1 g /
It is in the range of m ^{2 to} 0.5 g / m ² .

The polymer coupler used in the present invention is prepared by dissolving a lipophilic polymer coupler obtained by polymerization of a monomer coupler in an organic solvent as described above and emulsifying and dispersing in an aqueous gelatin solution in the form of a latex. Maybe,
Alternatively, it may be directly produced by an emulsion polymerization method. U.S. Pat. No. 3,451,820 for a method of emulsion-dispersing a lipophilic polymer coupler in the form of a latex in an aqueous gelatin solution, and U.S. Pat. No. 4,080,211 for emulsion polymerization.
No. 3,370,952 and European Patent No. 341,0.
The method described in No. 88A2 can be used. In the synthesis of the magenta polymer coupler, a polymerization initiator and a polymerization solvent are used in JP-A-56-5543 and JP-A-57.
-94752, JP-A-57-176038, JP-A-57.
-204038, JP-A-58-28745, and JP-A-58.
-10738, JP-A-58-42044, JP-A-58-58
It is carried out using the compound described in 145944. It is necessary to set the polymerization temperature in relation to the molecular weight of the polymer to be produced, the type of initiator, etc.
Although the above is possible, the polymerization is usually performed in the range of 30 ° C to 100 ° C. Next, specific examples of the magenta polymer coupler that can be used in the present invention will be given, but the present invention is not limited thereto. (The subscripts represent the molar ratio.)

[0088]

[Chemical 35]

[0089]

[Chemical 36]

[0090]

[Chemical 37]

[0091]

[Chemical 38]

[0092]

[Chemical Formula 39]

[0093]

[Chemical 40]

[0094]

[Chemical 41]

[0095]

[Chemical 42]

The light-sensitive material of the present invention may be provided with at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer 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 on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light. In a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red-color-sensitive layer and green. The color sensitive layer and the blue color sensitive layer are installed in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. Non-photosensitive layers such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer includes JP-A Nos. 61-43748 and 59-113.
No. 438, No. 59-113440, No. 61-20037, No. 61-20038 may contain a coupler, a DIR compound, and the like, and a color mixing inhibitor may be used as usual. May be included. The plural silver halide emulsion layers constituting each unit light-sensitive layer preferably have a two-layer constitution of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. be able to. 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. In addition,
57-112751, 62-200350, 62-206541, 62-2
As described in No. 06543, a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support. As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / High sensitivity blue photosensitive layer (BH) / High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) / High sensitivity red photosensitive layer (RH) / Low sensitivity red photosensitive layer (RL) order, or BH / BL / GL / GH / RH / RL order, or BH / BL / GH /
It can be installed in the order of GL / RL / RH. In addition,
As described in JP-A-55-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. In addition, JP-A-56-25738 and 62-63936
It is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support, as described in the specification. Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged, and the layer is composed of three layers having different sensitivities in which the sensitivities are gradually lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side distant from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order. In addition, they may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in the case of four or more layers, the arrangement may be changed as described above. In order to improve color reproducibility, U.S. Pat.Nos. 4,663,271 and 4,705,7
No. 44, No. 4,707,436, JP-A No. 62-160448, No. 63-
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 BL, GL and RL described in 89850, adjacent to or in proximity to the main photosensitive layer.
As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.

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

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

As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. Additives used in such a process are described in Research Disclosure No. 17643, No. 18716 and No. 307105, and the relevant portions are summarized in the table below. In the light-sensitive material of the present invention, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the light-sensitive silver halide emulsion,
It can be used by mixing in the same layer. US Patent No.
No. 4,082,553, the surface of which is covered with a silver halide grain, U.S. Pat. It can be preferably used for the silver emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface is a silver halide grain that enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. . A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat.
It is described in No. 9-214852. The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. There is no particular limitation on the grain size of these fogged silver halide grains, but as the average grain size,
0.01 to 0.75 μm, particularly 0.05 to 0.6 μm is preferable. Also,
The grain shape is not particularly limited, and may be regular grains or polydisperse emulsions, but monodisperse grains (at least 95% of the weight or number of silver halide grains are within ± 40% of the average grain size) (Having a particle size of 1).

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

Known photographic additives that can be used in the present invention are also described in the above 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, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, page 23 to 24, page 648, right column 866 to 868 Color sensitizer: page 649, right column 4. Whitening agent: page 24, page 647, right column 868, page 5, fogging prevention, page 24-25, page 649, right column, page 868-870, stabilizer, light absorber, 25- Page 26 Page 649 Right column Page 873 Filter ~ Page 650 Left column Dye, UV absorber 7. Stain 25 Page Right column 650 Page Left column 872 Inhibitor ~ Right column 8. Dye image Page 25 650 Page Left column 872 Stabilizer 9. Hardener 26 pages 651 left column 874 to 875 pages 10. Binder page 26 651 pages left column 873 to 874 pages 11. Plasticizer, page 27 650 pages right column 876 lubricants 12. Coating aids , Pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. static, page 27, page 650, right column, pages 876 to 877, inhibitors 14. matting agents, pages 878 to 879

In order to prevent deterioration of photographic performance due to formaldehyde gas, compounds which can be immobilized by reacting with formaldehyde described in US Pat. It is preferably added to the material. The light-sensitive material of the present invention preferably contains the mercapto compound described in U.S. Pat. A compound which, in the light-sensitive material of the present invention, releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof as described in JP-A 1-106052, irrespective of the amount of developed silver produced by development processing. Is preferably contained. Dyes or EP 317,308A, which are dispersed in the light-sensitive material of the present invention by the method described in International Publication WO88 / 04794 and JP-A-1-502912, US Patent
It is preferable to incorporate the dyes described in 4,420,555 and JP-A 1-259358. Various color couplers can be used in the present invention, specific examples of which are described in Research.
Disclosure No.17643, VII-CG, and the same
No. 307105, VII-C to G. Examples of yellow couplers include US Pat.
3,933,501, 4,022,620, 4,326,024,
No. 4,401,752, No. 4,248,961, Japanese Patent Publication No. 58-1073
9, British Patents 1,425,020, 1,476,760, U.S. Patents 3,973,968, 4,314,023, 4,511,
No. 649, No. 5,118,599, European Patent No. 249,473A,
Those described in No. 447,969A and No. 482,552A are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619, 4,351,897 and European Patent 73,63 are preferred.
6, U.S. Pat.Nos. 3,061,432 and 3,725,067,
Research Disclosure No. 24220 (June 1984
Month), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A 61-7.
No. 2238, No. 60-35730, No. 55-118034, No. 60-185951
U.S. Pat.Nos. 4,500,630, 4,540,654, and
Those described in 4,556,630 and International Publication WO88 / 04795 are particularly preferable. Examples of cyan couplers include phenol-based and naphthol-based couplers, and US Pat.
52,212, 4,146,396, 4,228,233, and
4,296,200, 2,369,929, 2,801,171,
No. 2,772,162, No. 2,895,826, No. 3,772,002
No. 3, No. 3,758,308, No. 4,334,011, No. 4,32
7,173, West German Patent Publication 3,329,729, European Patent 12
1,365A, 249,453A, U.S. Pat.No. 3,446,622
No. 4, No. 4,333,999, No. 4,775,616, No. 4,45
1,559, 4,427,767, 4,690,889, and
Those described in 4,254,212, 4,296,199 and JP-A-61-42658 are preferable. Furthermore, JP-A-64-553,
Pyrazoloazole couplers described in JP-A Nos. 64-554, 64-555 and 64-556 and imidazole couplers described in US Pat. No. 4,818,672 can also be used. Typical examples of polymerized dye-forming couplers are described in US Pat.
3,451,820, 4,080,211 and 4,367,282,
No. 4,409,320, No. 4,576,910, British patent 2,1
No. 02,137 and European Patent No. 341,188A.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237 and British Patent 2,12.
5,570, European Patent 96,570, West German Patent (Publication)
Those described in 3,234,533 are preferable. Colored couplers for correcting unnecessary absorption of color forming dyes are described in Research Disclosure No. 17643, Item VII-G, No. 307.
105 VII-G, U.S. Pat. No. 4,163,670, Japanese Examined Patent Publication No. 57
-39413, U.S. Pat.Nos. 4,004,929, 4,138,258
Nos. 1,146,368, JP-A No. 3-177837, and European Patent No. 423,727A are preferable. Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released upon coupling described in U.S. Pat.No. 4,774,181, and a dye capable of reacting with a developing agent described in U.S. Pat. It is also preferable to use a coupler having a precursor group as a leaving group. Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are described in RD 17643, Section VII-F and above.
No. 307105, Patents described in Section VII-F, JP-A-57-1
51944, 57-154234, 60-184248, 63-3734
6, 63-37350, U.S. Patents 4,248,962, 4,782,01
2, European Patent Nos. 464,612A, 482,552A and 49
Those described in No. 9,279A are preferable. RDNo.11449,
The bleaching accelerator releasing coupler described in JP-A No. 24241 and JP-A No. 61-201247 is effective for shortening the time of the processing step having a bleaching ability. In particular, the tabular silver halide grains described above are used. The effect is great when it is added to a light-sensitive material. As couplers that release a nucleating agent or a development accelerator imagewise during development, those described in British Patents 2,097,140 and 2,131,188 and JP-A-59-157638 and 59-170840 are preferable. Further, JP-A-60-107029,
Compounds that release a fogging agent, a development accelerator, a silver halide solvent, etc. by a redox reaction with an oxidant of a developing agent described in JP-A-60-252340, JP-A-1-44940, and JP-A 1-45687. Is also preferable.

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

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

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-272248,
And 1,2-benzisothiazolin-3-one described in JP-A-1-80941, n-butyl p-hydroxybenzoate,
It is preferable to add various preservatives or antifungal agents such as phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole. The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.
Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D. No.17643, page 28, No.18716, page 647 From right column 648
It is described on the left column of the page and on page 879 of the same No. 307105. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, particularly preferably 16 μm or less. Also, the film swelling speed T
_1/2 is preferably 30 seconds or less, more preferably 20 seconds or less.
The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, A. Green et al., Photographic Science and Engineering (Photog
r.Sci.Eng.), No. 19, No. 2, pages 124 to 129 can be measured by using a swellometer (swelling meter) of the type described, and T _1/2 is 30 ° C. in a color developer. , 90% of the maximum swollen film thickness reached after treatment for 3 minutes and 15 seconds is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness. Membrane swelling speed T
_1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness-film thickness) / film thickness. The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer.
In this back layer, the above-mentioned light absorber, filter dye,
It is preferable to contain an ultraviolet absorber, an antistatic agent, a hardener, a binder, a plasticizer, a lubricant, a coating aid, a surface active agent and the like. The swelling ratio of this back layer is 150-500
% Is preferred.

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

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

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

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

The total time for the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The treatment temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented. In the desilvering process, it is preferable that the stirring is strengthened as much as possible.
As a specific method for strengthening stirring, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461 Method to increase the effect, further moving the photosensitive material while the emulsion surface is in contact with the wiper blade provided in the solution to further improve the stirring effect by making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such a stirring improving means is effective in 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 consequently 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 action of the bleaching accelerator. The automatic processor used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257.
No. 60-191258 and No. 60-191259. The above-mentioned JP-A-6
As described in No. 0-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing step 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 countercurrent, 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 volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture a
nd Television Engineers Volume 64, P. 248-253 (1955)
May May issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly 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. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to this problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be very effectively used. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antibacterial and fungicide" (1986) Sankyo Publishing, Sanitary Technology Society, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society for Antibacterial and Antifungal, "Encyclopedia of Antibacterial and Antifungal Agents" (1986) The disinfectants described can also be used. PH of washing water in the processing of the light-sensitive material of the present invention
Is 4-9, preferably 5-8. The washing water temperature and the washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but in general, it is 20 seconds to 10 minutes at 15 to 45 ° C., preferably
A range of 30 seconds to 5 minutes at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, all known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used. In addition, there is a case where further stabilization treatment is carried out after the water washing treatment, and an example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. be able to. As a dye stabilizer,
Aldehydes such as formalin and glutaraldehyde,
Examples thereof include N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.
Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or replenishment of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
It is preferable to correct the concentration by adding water. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in U.S. Pat.No. 3,342,597, No. 3,342,599, Schiff base type compounds described in Research Disclosure Nos. 14,850 and No. 15,159, aldol compounds described in No. 13,924, U.S. Pat.No. 3,719,492. Metal salt complexes described, JP-A-53-135
The urethane compound described in No. 628 can be mentioned.
The silver halide color light-sensitive material of the present invention contains various 1-phenyl-3-methyl-3-phenyl-3-(-3-phenyl) -3-phenyl-3- (phenyl-3-phenyl) -3- (phenyl-3-phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3-(-3-phenyl-3-phenyl-3- (cyclohexyl) -3- (phenyl-3-phenyl-3-methyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3- (3-phenyl-3-phenyl-3- (3-phenyl-3- (phenyl-phenyl--3-one-
You may incorporate pyrazolidones. Typical compounds are described in JP-A-56-64339, JP-A-57-144547, JP-A-58-115438 and the like. Various treatment liquids in the present invention are 10 ℃
Used at ~ 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to.

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

[0116]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto.

EXAMPLE On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare Sample 101, which is a multilayer color light-sensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

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

[0119]

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Emulsion A Silver 0.25 Emulsion C Silver 0.25 ExS-1 4.5 × 10 ^-4 ExS-2 1.5 × 10 ^-5 ExS-3 4.5 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.0050 ExC-7 0.0050 ExC-8 0.020 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion D Silver 0.80 ExS-1 3.0 × 10 ^-4 ExS-2 1.2 × 10 ^-5 ExS-3 4.0 × 10 ^-4 ExC-1 0.12 ExC-2 0.060 ExC-4 0.080 ExC-7 0.0010 ExC-8 0.025 ExC-9 0.070 Cpd-2 0.023 HBS-4 0.10 Gelatin 0.75

Fifth Layer (High Sensitivity Red Sensitive Emulsion Layer) Emulsion E Silver 1.40 ExS-1 2.0 × 10 ^-4 ExS-2 1.0 × 10 ^-5 ExS-3 3.0 × 10 ^-4 ExC-1 0.095 ExC-3 0.040 ExC-6 0.020 ExC-8 0.007 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20

Sixth Layer (Intermediate Layer) Cpd-1 0.050 Cpd-4 0.050 HBS-1 0.30 HBS-4 0.15 Gelatin 0.80

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion A Silver 0.17 Emulsion B Silver 0.17 ExS-4 4.0 × 10 ^-5 ExS-5 1.8 × 10 ^-4 ExS-6 6.5 × 10 ^-4 ExM-1 0.010 ExM-2 0.11 ExM-3 0.086 P-7 0.25 Comparative coupler (1) 0.020 HBS-4 0.30 HBS-3 7.0 × 10 ^-3 Gelatin 0.73

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Emulsion D Silver 0.80 ExS-4 2.0 × 10 ^-5 ExS-5 1.4 × 10 ^-4 ExS-6 5.4 × 10 ^-4 ExM-2 0.055 ExM-3 0.045 P-7 0.12 Comparative coupler (1) 0.040 HBS-1 0.16 HBS-3 6.0 × 10 ^-3 gelatin 0.90

Ninth layer (high-sensitivity green-sensitive emulsion layer) Emulsion E Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 Comparative coupler (1) 0.015 ExM- 1 0.015 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.020 HBS-1 0.25 HBS-2 0.10 Gelatin 1.20

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.010 Cpd-1 0.10 Cpd-4 0.050 HBS-1 0.60 Gelatin 0.60

Eleventh Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Emulsion C Silver 0.25 Emulsion D Silver 0.40 ExS-7 8.0 × 10 ^-4 ExY-1 0.030 ExY-2 0.55 ExY-3 0.25 ExY-4 0.020 ExC-7 0.01 HBS-1 0.25 HBS-4 0.10 Gelatin 1.30

12th layer (high-sensitivity blue-sensitive emulsion layer) Emulsion F Silver 1.38 ExS-7 3.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.020 HBS-1 0.070 Gelatin 0.86

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

14th layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-4, B-4 to B- may be used. 6, F
-1 to F-18 and iron salt, lead salt, gold salt, platinum salt,
It contains iridium salt, palladium salt, and rhodium salt.

[0133]

[Table 1]

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

[0135]

[Chemical 43]

[0136]

[Chemical 44]

[0137]

[Chemical formula 45]

[0138]

[Chemical formula 46]

[0139]

[Chemical 47]

[0140]

[Chemical 48]

[0141]

[Chemical 49]

[0142]

[Chemical 50]

[0143]

[Chemical 51]

[0144]

[Chemical 52]

[0145]

[Chemical 53]

[0146]

[Chemical 54]

[0147]

[Chemical 55]

[0148]

[Chemical 56]

[0149]

[Chemical 57]

[0150]

[Chemical 58]

Then, the comparative coupler (1) used in the seventh to ninth layers of the sample 101 was replaced with the comparative coupler (2) shown in Chemical formula 59 in an equimolar amount to prepare a sample 102.

[0152]

[Chemical 59]

Subsequently, Samples 103 and 104 are Sample 1
Comparative coupler (1) used in the seventh to ninth layers of No. 01 was used as a development inhibitor releasing compound (2) represented by the formula (I) of the present invention.
Samples were prepared by replacing 4) and (11) with equimolar amounts. Samples 105 to 108 are the sixth of Samples 101 to 104.
Dye D-14 of the present invention was added to the layer (intermediate layer) at 5.0 × 10 ^−3.
A sample was prepared by adding with a 5% methanol solution of g / m ² . At this time, the spectral absorption maximum wavelength in the gelatin dry film was 565 nm, and the optical density at 550 nm was 0.07. Hereinafter, the samples 109 to 117 are the seventh sample of the sample 107.
Samples were prepared by substituting the compound (24) represented by the formula (I) of the present invention used in the layers to the ninth layer with another compound also represented by the formula (I) of the present invention as shown in Table 2. did. Samples 118 to 120 are the sixth of Samples 113 to 115.
The dye D-14 of the present invention used for the layer (intermediate layer) was replaced with D-
Samples were prepared by changing the coating amounts shown in Tables 32, D-15, and D-17. The addition was made as a methanol solution or an aqueous solution. Sample 121 was prepared by using D-14 of the present invention used in the sixth layer (intermediate layer) of Sample 113 and using the same amount of D-14 in the tenth layer (yellow filter layer).

[0154]

[Table 2]

The produced samples 101 to 121 were cut and processed, subjected to gradation exposure of white light (4800 ° K), and subjected to the color development processing shown below.

(Processing step) Process Processing time Processing temperature Color development 3 minutes 5 seconds 38.0 ° C Bleaching 50 seconds 38.0 ° C Bleaching fixing 50 seconds 38.0 ° C fixing 50 seconds 38.0 ° C Water washing 30 Seconds 38.0 ° C Stable (1) 20 seconds 38.0 ° C Stable (2) 20 seconds 38.0 ° C Dry 1 minute 60 ° C

The composition of the processing liquid is shown below. (Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 Sodium sulfite 3.9 Potassium carbonate 37.5 Potassium bromide 1.4 Potassium iodide 1.3 mg Hydroxylamine sulfate 2.4 2-Methyl-4 -[N-Ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 Add water to 1.0 liter pH (adjust with potassium hydroxide and sulfuric acid) 10.05

(Bleaching Solution) (Unit: g) 1,3-Diaminopropanetetraacetic acid Ammonium ferric acid monohydrate 130 Ammonium bromide 80 Ammonium nitrate 15 Hydroxyacetic acid 50 Acetic acid 40 Water is added to 1.0 liter pH [adjusted with ammonia water] ] 4.4

(Bleaching Fixing Solution) A 15:85 (volume ratio) mixture of the above bleaching solution and the following fixing solution. (PH 7.0)

(Fixer) (Unit: g) Ammonium sulfite 19 Ammonium thiosulfate aqueous solution (700 g / liter) 280 ml imidazole 15 Ethylenediaminetetraacetic acid 15 Water was added to 1.0 liter pH [adjusted with ammonia water and acetic acid] 7.4

(Washing water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and OH-type strongly basic anion exchange resin (Amberlite IR-400) were passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 mg.
/ Liter or less, followed by sodium diisocyanurate dichloride 20 mg / liter and sodium sulfate 150
mg / l was added. The pH of this liquid is 6.5 to 7.
It was in the range of 5.

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

The sample which has been color-developed is RG
-B density is measured to obtain respective characteristic curves, and from these characteristic curves of R and G densities, the logarithmic value of the reciprocal of the exposure amount giving the density of the minimum density +0.2 is obtained as sensitivity (S) Difference between samples 101 as a reference (ΔS)
Was calculated.

Next, each sample was subjected to imagewise exposure using an interference filter having a wavelength of 550 nm (half-value width of 5 nm), and the G and R densities of the samples obtained by carrying out the above treatment were measured. The ratio of the G density value obtained by subtracting the minimum density value at the exposure amount giving 0.0 to the R density value at the same exposure amount was determined, and this density ratio was compared as a scale of color reproducibility. The smaller the density ratio value, the smaller the color mixture of the R density (red) to the G density (green), which means that the color reproducibility is preferable. Further, using the sample obtained by finely adjusting the coating composition so that the gradation of the characteristic curve of the G concentration obtained by subjecting the samples 101 to 121 to gradation exposure of white light is the same, Exposure to white light through a conventional MTF pattern is performed, and after the above processing is performed, the magenta image M
The TF value (40 cycles / mm) was measured and the sharpness was compared. The results are summarized in Table 3.

[0165]

[Table 3]

From the results shown in Table 3, a dye having a spectral absorption maximum wavelength in the film in the range of 500 to 600 nm in the non-photosensitive layer adjacent to the side closer to the support of the green-sensitive emulsion layer having the constitution of the present invention. Samples 107-120 containing a dye and containing a development inhibitor releasing compound of the present invention contain dyes in comparison to the samples containing no dye of Comparative Samples 101-106 or using a development inhibitor releasing coupler of the present invention. Without deteriorating the photographic property (sensitivity) of the red-sensitive emulsion layer on the side closer to the support than the contained layer,
Further, it is clear that the green-sensitive emulsion layer on the side farther from the support than the layer containing the dye exhibits a high photographic property and is a color light-sensitive material excellent in color reproducibility and sharpness of a magenta color image. Further, the dye of the present invention may be added to a non-photosensitive layer adjacent to the side of the green-sensitive emulsion layer closer to the support. Samples 113 and 118 and Comparative Sample 1 are superior in image quality such as photographic property (sensitivity), color reproducibility and sharpness to those when added to the 10th layer, yellow filter layer).
It is clear when comparing with 21.

Example 2 Color developer composition used in the color development process used in Example 1,
The processing temperature and pH were changed as shown below, and the samples 101 to 121 produced in Example 1 were used, and the sensitivity, color reproducibility and sharpness of the magenta color image obtained in Example 1 were similarly measured. Examined.

The numerical values of the color developing solution composition shown below represent the number of grams per liter. (Color developer) Process B Process C Process D Potassium bromide 1.7 2.7 7.0 Hydroxylamine sulfate 2.4 3.5 4.5 2-Methyl-4- [N-ethyl-N- (β-hydroxylethyl) amino] aniline sulfate 4.7 6.0 10.0 pH 10.05 10.05 10.25 Development temperature 38.0 ° C. 40.0 ° C. 45.0 ° C. Incidentally, after bleaching, the treatment shown in Example 1 was carried out as it was.

The values of sensitivity, color reproducibility and sharpness of the magenta color image obtained by carrying out the above processing are based on the results obtained by carrying out in Example 1 (this is called processing A), The processability of color development was examined by obtaining the difference as a variation due to the processing between the same samples. Some of the results are shown in Table 4.

[0170]

[Table 4]

From the results shown in Table 4, it was found that when potassium bromide, hydroxylamine sulfate and the color developing agent were processed in a processing solution having a higher concentration than that of the color developing solution of Example 1, or the color developing processing temperature and pH were set. Samples 107 to 1 satisfying the constitutional requirements of the present invention when treated with a treatment liquid having a high
15, 118-120 are comparative samples 101, 103, 10
It can be seen that, compared with 5, the fluctuations in the photographic sensitivity, color reproducibility and sharpness of the magenta color image are small even if the color development processing factors are changed, and stable processing properties are provided.

Example 3 Based on the sample 107 prepared in Example 1, the magenta couplers P-7 and 9 used for the seventh and eighth layers were used.
ExM-4 used in the layer was converted to the comparative coupler (A) shown in Chemical formula 60 in an equimolar amount (in this case, one constitutional unit of the polymer coupler containing 1 mole of the monomer coupler of the coupler P-7 was converted to 1 mole). Sample 301 was prepared by replacing the above.

[0173]

[Chemical 60]

Then, as shown in Table 5, in Samples 302 to 107, the coupler P-7 of the seventh and eighth layers of the sample 107 and the coupler ExM-4 of the ninth layer were replaced by equimolar amounts.
305 was produced.

[0175]

[Table 5]

The produced samples 301 to 305 were cut and processed, and subjected to color development processing (processing A) according to the method described in the examples, and the photographic sensitivity, color reproducibility and sharpness were examined. Further, the treatment C and the treatment D of the second embodiment were carried out, and the difference between the treatment C and the treatment D was obtained with reference to the value of the treatment A as in the second embodiment. These results are summarized in Table 6 together with the results of Samples 101 and 107 of Example 1 and Example 2.

[0177]

[Table 6]

From Table 6, it can be seen that even in the constitution of the present invention, the magenta coupler used in the green-sensitive emulsion layer is a polymer coupler, which is excellent in photographic sensitivity, color reproducibility and sharpness. . Further, it is clear that even if the processing is carried out while changing the composition of the color developing solution, the processing temperature and the pH, the fluctuations of the above-mentioned various properties are small and the stable processing property is given.

Example 4 Samples 101 to 121 prepared in Example 1 and Example 3,
Nos. 301 to 305 were used to examine the sensitivity, color reproducibility and sharpness of a magenta color image in the same manner as in Example 1 using the following color development processing steps and processing solution compositions. The treatment was carried out by using an automatic developing machine, and the separately image-wise exposed sample was subjected to a running treatment until the amount became three times the tank capacity, and then the treatment of the sample for examining the above performance was carried out. The treatment process and the treatment liquid composition are shown below. This is referred to as process E.

(Processing step) Process Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 38.0 ° C 23 ml 1 liter Bleach 50 seconds 38.0 ° C 5 ml 2 liter Bleach fixing 50 seconds 38.0 ° C-2 liters 50 seconds 38.0 ° C 16 ml 2 liters Water wash 30 seconds 38.0 ° C 34 ml 2 liters Stable (1) 20 seconds 38.0 ° C-2 liters Stable (2) 20 seconds 38.0 ° C 20 ml 2 liters Dry 1 minute 30 seconds 60 ° C * Replenishment amount per 35 mm width of light-sensitive material 1.1 m (equivalent to 24 Ex. 1) The stabilizing solution was a countercurrent system from (2) to (1), and the overflow solution of washing water was all introduced into the fixing bath. When replenishing the bleach-fixing bath, a cutout is provided on the bleaching tank of the automatic processor and on the top of the fixing tank so that all of the overflow solution generated by supplying the replenishing solution to the bleaching tank and the fixing tank is added to the bleach-fixing bath. I was allowed to flow in. The amount of developing solution brought into the bleaching step, the amount of bleaching solution brought into the bleach-fixing step, the amount of bleach-fixing solution brought into the fixing step, and the amount of fixing solution brought into the water washing step were 1. 2.5 ml, 2.0 ml, and 2.
It was 0 ml and 2.0 ml. Also,
The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the processing liquid is shown below. (Color developer) Tank solution (g) Replenisher solution (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 3.9 5.1 Potassium carbonate 37.5 39.0 Potassium bromide 1.4 0.4 Potassium iodide 1.3 mg-hydroxylamine sulfate 2.4 3.3 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 6.0 Water was added to 1.0 liter 1.0 liter pH (to potassium hydroxide and sulfuric acid 10.05 10.15

(Bleaching solution) Tank solution (g) Replenisher solution (g) 1,3-Diaminopropanetetraacetic acid Ammonium ferric acid monohydrate 130 195 Ammonium bromide 70 105 Ammonium nitrate 14 21 Hydroxyacetic acid 50 75 Acetic acid 40 60 Water 1.0 liter 1.0 liter pH [adjusted with ammonia water] 4.4 4.4

(Bleaching Fixing Tank Liquid) A 15:85 (volume ratio) mixture of the above bleaching tank liquid and the following fixing tank liquid. (P
H7.0)

(Fixing liquid) Tank liquid (g) Replenishing liquid (g) Ammonium sulfite 19 57 Ammonium thiosulfate aqueous solution (700 g / l) 280 ml 840 ml Imidazole 15 45 Ethylenediaminetetraacetic acid 15 45 Water 1.0 liter 1.0 liter pH [Adjust with ammonia water and acetic acid] 7.4 7.45

(Washing Water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and OH-type strongly basic anion exchange resin (Amberlite IR-400) were passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 mg.
/ Liter or less, followed by sodium diisocyanurate dichloride 20 mg / liter and sodium sulfate 150
mg / l was added. The pH of this liquid is 6.5 to 7.
It was in the range of 5.

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

The photographic sensitivity, color reproducibility, and sharpness of the obtained magenta color image are shown in Table 3 as a result and Table 6 as Treatment A.
It was confirmed that the sample satisfying the constitution of the present invention was superior to the comparative sample. Subsequently, the composition of the color developing solution was changed as shown below. This is designated as process F.

(Color developer) Tank solution (g) Replenisher solution (g) Diethylenetriaminepentaacetic acid 2.0 4.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 3.9 6.5 Potassium carbonate 37.5 39.0 Potassium bromide 7.0 0.0 Iodine Potassium iodide 1.3 mg-hydroxylamine sulfate 4.5 7.0 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 10.0 22.3 Water was added to 1.0 liter 1.0 liter pH (potassium hydroxide 10.25 12.2 The processing temperature for color development was 45 ° C.

Using the above color developing solution, the same running process as above was carried out, and then the sensitivity, color reproducibility and sharpness of the magenta color image were examined in the same manner, and these characteristic values were the same as those in Example 2. Thus, the difference was obtained as the treatment (EF).

The results are similar to those of the treatments (A-D) shown in Tables 4 and 6, and the samples satisfying the constitutional requirements of the present invention were subjected to color development in which the treatment composition, pH and temperature were changed as compared with the comparative sample. However, it was confirmed that the above various performances were excellent.

Example 5 Developer of the color developer of processing E used in Example 4, 2-
Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate was added to 2-methyl-4- [N
-Ethyl-N- (δ-hydroxybutyl) amino] aniline sulfate was replaced with an equimolar amount, and the color development time was 2 minutes 3
The sensitivity, the color reproducibility, and the sharpness of the photographic property of a magenta color image were obtained by using Samples 101 to 121 of Example 1 and Samples 301 to 305 of Example 3 after adjusting the time to 0 seconds and making no other changes. It investigated in the same way as Example 1. Part of the results is shown in Table 7.

[0192]

[Table 7]

From Table 7, the developing agent is 2-methyl-4-
[N-ethyl-N- (δ-hydroxybutyl) amino]
Samples 107 to 11 satisfying the constitutional requirements of the present invention even if the processing is carried out with a color developing solution replaced with aniline sulfate.
5, 118 to 120 and 301 to 305 are clearly superior to the comparative sample in photographic sensitivity, color reproducibility and sharpness. Furthermore, by changing the developing agent, it is clear that the difference in photographic sensitivity and color reproducibility from the comparative sample is rather widened, and the sample having the constitution of the present invention is more superior.

When the developing agent in Process D described in Example 2 was replaced with the same developing agent as described above in an equimolar amount, a performance difference similar to that shown in Table 7 was observed. It was confirmed that there was no change in the excellent sample.

Example 6 22 ml of water, 5 wt% aqueous solution of sodium p-octylphenoxyethoxyethoxyethane sulfonate 3
10 ml of a 5 wt% aqueous solution of p-octylphenoxypolyoxyethylene ether (polymerization degree: 10) was placed in a 700 ml pot mill, 5.0 g of dye D-10 and zirconium oxide beads (diameter: 1) were added.
mm) 500 ml and the contents were dispersed for 2 hours using a BO type vibration ball mill (manufactured by Chuo Koki). After the dispersion, the content was taken out, 8 g of a 12.5 wt% gelatin aqueous solution was added, and the beads were filtered to obtain a gelatin dispersion of Dye D-10. This gelatin dispersion of Dye D-10 was replaced with Dye D-14 used in the sixth layer of Samples 107 to 115 of Example 1 and the amount was determined so that the optical density was 0.07. Was produced. The spectral absorption maximum wavelength in the gelatin dry film was about 565 nm.

The prepared samples 601 to 609 are the same as those in Example 1.
In the same manner as the sample 101 of Example 1, the photographic sensitivity (for R and G), color reproducibility, and sharpness were examined by the color development processing described in the same example as in Example 1.

As a result, the samples 601 to 609 can obtain the results corresponding to the samples 107 to 115 in Table 3, and the samples satisfying the constitution of the present invention have a red-sensitive property closer to the support than the dye-containing layer. It was confirmed that it is effective for improving the image quality of color reproducibility and sharpness without impairing the photographic sensitivity of the emulsion layer.

Example 7 Samples 101 and 111 prepared in Examples 1 and 3,
118-120, 302, 305 Japanese Patent Publication No.
A film unit with a lens was produced according to the method described in No. 15. These 7 types of film unit with lens are used to shoot various subjects under the same conditions,
-560 BAL (manufactured by Fuji Photo Film Co., Ltd.) was used for color development processing, and then Fuji Mini Lab Champion, printer processor FA-140 (manufactured by Fuji Photo Film Co., Ltd.) was used to print on Fuji Color Paper and Super FAV ( CP-45X was used for color development processing).

When the patterns obtained by printing these were compared and observed, Samples 111 and 11 satisfying the constitution of the present invention were obtained.
It was confirmed that each of Nos. 8 to 120, 302, and 305 was superior to the comparative sample 101 in delicate depiction of the subject and color saturation, and could provide a print with good image quality.

Example 8 PEN having a thickness of 85 μm, which was provided with an undercoat layer and was heat-treated.
[2,6-naphthalenedicarboxylic acid / ethylene glycol (100/100 weight ratio)] Using a support, samples 101, 112, 118 to 120 of Example 1 and Example 3 were used.
The same coating composition as in Samples 303 and 305 was applied to prepare a color light-sensitive material. These seven kinds thus prepared were subjected to the processing E and F of the running processing carried out in Example 4, and the photographic sensitivity, color reproducibility and sharpness of the magenta color image were examined in the same manner as in Example 1.

The obtained results show that the photographic sensitivity and color reproducibility are the same as those of Example 4, and the sharpness is slightly higher in the sample using the PEN support of this Example. (0.01 to 0.02), and good results could be obtained. Furthermore, using these samples,
When the treatment described in Example 5 was carried out, similarly, the difference in photographic sensitivity and color reproducibility from the comparative sample was enlarged, and obviously the sensitive material of the present invention was preferable, and the sharpness was as described above. Similarly, it was found that the light-sensitive material using the PEN support of the present invention showed a higher overall value, though it was slightly, and was preferable.

[0202]

INDUSTRIAL APPLICABILITY In the film, a non-photosensitive layer adjacent to the side of the green-sensitive silver halide emulsion layer containing the development inhibitor-releasing compound represented by the above formula (I) of the present invention is formed. 5
By using a dye having a spectral absorption maximum wavelength in the range of 00 to 600 nm, it is possible to provide a silver halide color photographic light-sensitive material having improved image quality and excellent color development processability.

Claims (2)

[Claims] 1. A red-sensitive silver halide emulsion layer containing a cyan coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a blue-sensitive silver halide emulsion layer containing a yellow coupler are provided on a support. A silver halide color photographic light-sensitive material having a non-light-sensitive layer adjacent to the side of the green-sensitive silver halide emulsion layer close to the support, the development represented by the following formula (I) in the light-sensitive material. A silver halide color photographic light-sensitive material containing an inhibitor-releasing compound, wherein the non-photosensitive layer contains a dye having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm in the film. Formula (I) A-X In the formula, A represents a group which reacts with an oxidized product of a developing agent to release X, and at the same time forms a compound soluble or decolorizable in a processing solution, X is a development inhibitor or a compound thereof. Represents a precursor residue. 2. The silver halide color photographic light-sensitive material according to claim 1, which contains a polymer coupler.