JPH09329878A - Silver halide color photographic sensitive material and color image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material and a color image forming method excellent in safety and easy rapid processing property, by which good color developing property and good hue can be obtd., production of stains after the treatment can be suppressed without requiring a bleach-fixing process. SOLUTION: This photosensitive material is produced by forming photographic layers comprising a photosensitive silver halide emulsion layer and a nonphotosensitive layer on a supporting body. In this case the photographic layer contains a reducing agent for color development expressed by formula, a diffusive dye forming coupler and a mordant. The nonphotosensitive layer has a releasing layer. (In formula, Cα is a carbon atom, Z is a carbamoyl group, acyl group, alkoxycarbonyl group or aryloxycarbonyl group, and Q represents atoms to form an unsatd. ring coupled with Cα.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color photographic technique, and in particular, it is excellent in environmental protection, safety and simple and quick processing property, has excellent color forming property and hue, and does not require a bleach-fixing step. The present invention relates to a silver halide color photographic light-sensitive material and a color image forming method capable of effectively suppressing the generation of stain after color development processing.

[0002]

2. Description of the Related Art Generally, a color image is formed using a silver halide color photographic light-sensitive material by exposing the silver halide color photographic light-sensitive material to color development and then reacting the oxidized p-phenylenediamine derivative with a coupler. It is carried out by In such color image formation,
A color reproduction method using a subtractive color method is used, and in order to reproduce blue, green, and red, color images of yellow, magenta, and cyan, which are in a complementary color relationship with each other, are formed. by the way,
The color development is carried out by exposing the exposed color photographic material.
It is carried out by immersing in an alkaline aqueous solution (color developing solution) in which a p-phenylenediamine derivative is dissolved.

However, the p-phenylenediamine derivative in the alkaline aqueous solution is unstable and easily deteriorates with time.
Therefore, there is a problem that the color developing solution must be replenished frequently in order to maintain stable developing performance. In addition, the used color developing solution containing the p-phenylenediamine derivative is complicated to dispose of, and
Since a large amount is discharged by the replenishment, how to dispose of this is a big problem. Therefore,
There is a strong demand for reducing the replenishment amount and the discharge amount of the color developing solution.

The silver contained in the silver halide color photographic light-sensitive material, after being developed, remains in the silver halide color photographic light-sensitive material as metallic silver unless special treatment is carried out. However, since this metallic silver exhibits a black color and deteriorates the purity of the dye image, it is preferably removed from the silver halide color photographic light-sensitive material. Therefore, conventionally, the unfixed metallic silver is undeveloped by bleaching this metallic silver to form silver ions and fixing this (hereinafter, such a processing step is referred to as "bleach-fixing step"). And the silver halide described above were removed from the light-sensitive material. However, since the bleach-fixing solution used in the bleach-fixing step contains a large amount of an inorganic salt such as iron, a chelating agent, etc., the bleach-fixing solution is disposed of similarly to the color developing solution. It's a big problem.

As one of the methods for eliminating the bleach-fixing step, the Journal of the Photographic Society of Japan, Vol. 51, No. 3, pp. 191 (1988).
Year), Japanese Patent Publication No. 61-48148, 63-203.
30 publication, 63-20332 publication, JP-A-3-1.
A method for performing intensification treatment with hydrogen peroxide as described in Japanese Patent No. 11844 and the like is known. In this method, the intensification treatment forms an amplified image on the developed silver, so that even if a silver halide color photographic light-sensitive material having a significantly reduced amount of silver is used, a high image density is obtained. Can be obtained. As a result, in this method, color contamination due to metallic silver is negligible, and the bleach-fixing step can be omitted. However,
In the case of the intensifying treatment, hydrogen peroxide and p-
Since it contains the phenylenediamine derivative, there is a problem that the stability of the development intensifying solution is not sufficient. In order to solve this problem, it is necessary to increase the exchange rate of the development intensifying liquid, and it becomes necessary to supply a large amount of fresh development intensifying liquid or to dispose of it.

As another method of eliminating the bleach-fixing step, a dye formed from a diffusible coupler and a p-phenylenediamine derivative described in JP-A-7-168335 is adsorbed on a mordant layer. There is known a method of removing the metallic silver produced during the color developing treatment and the residual silver halide by peeling the coated layer using a peeling layer after the color developing treatment. However, in this method, since the bleach-fixing step can be omitted, the problem of the bleach-fixing solution can be solved, but the problem of the color developing solution is still unsolved.

The following methods are known as methods for removing the p-phenylenediamine derivative from the color developing solution to reduce the replenishing amount and the discharging amount of the development intensifying solution. One is a method of incorporating an aromatic primary amine developing agent or a precursor thereof into a hydrophilic colloid layer as described in JP-A-7-168335. Examples of the aromatic primary amine developing agent or its precursor that can be used in this method include, for example, US Pat. Nos. 2,507,114, 3,764,328, 4,060,418, and JP-A-56-6235. , Ibid. 58-1920
The compounds described in Japanese Patent No. 31 and the like are mentioned. However, in the case of this method, since the aromatic primary amine developing agent and its precursor are unstable, a stain is generated when the unprocessed silver halide color photographic light-sensitive material is stored for a long period of time or during color development. There is a problem that it will end up.

The other one is European Patent 0545491A1.
No. 6,565,165 A1 and the like, a method of incorporating a sulfonylhydrazine type compound into the hydrophilic colloid layer. However, in the case of this method, even when a sulfonylhydrazine type compound is used, a sufficient color density is not obtained at the time of color development, and the sulfonylhydrazine type compound scarcely develops color even when used in a 2-equivalent coupler. There is a problem that is not applicable to. The 2-equivalent coupler has advantages that it can reduce stain derived from the coupler as compared with the 4-equivalent coupler, and that it can be a mordant type as described in JP-A-7-168335. Therefore, it is desired to develop a technique applicable to a two-equivalent coupler.

On the other hand, the dye obtained from the hydrazine compound and the dye-forming coupler is a dissociative dye and shows color when dissociated. Therefore, when image formation is carried out using this dissociative dye, color development processing is carried out. Then, the dissociative dye is immersed in an alkaline solution to dissociate the dye, so that a color image cannot be obtained. However, in the case of such image formation, under the condition that the dissociative dye dissociates, the remaining hydrazine compound itself also dissociates, and it becomes easy to react with the coupler. When stored, there is a problem that stains frequently occur on the image-formed product.

[0010]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems in the prior art, is extremely excellent in color developability and hue, is excellent in environmental protection, safety, and quick and easy processability. Is unnecessary, the replenishment amount and the discharge amount of the development intensifying solution can be reduced, and the stain generation can be effectively suppressed even if stored for a long time after color development processing. An object is to provide a light-sensitive material and a color image forming method.

[0011]

Means for solving the above problems are as follows. (1) In a silver halide color photographic light-sensitive material comprising a support and a photographic constituent layer having at least one photosensitive silver halide emulsion layer and at least one non-photosensitive layer, the photographic constituent layer is At least one color-forming reducing agent represented by the following general formula (I), a diffusible dye-forming coupler and a mordant are contained, and one layer of the non-photosensitive layer is a release layer. It is a silver halide color photographic light-sensitive material. General formula (I)

Embedded image In the formula, Cα represents a carbon atom. Z represents a carbamoyl group, an acyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. Q represents an atomic group forming an unsaturated ring by combining with Cα.

(2) The silver halide color photographic light-sensitive material according to (1), wherein in the general formula (I), Z is a carbamoyl group having at least one hydrogen atom on the nitrogen atom. (3) The silver halide color photographic light-sensitive material as described in (1) or (2), wherein in the general formula (I), the unsaturated ring is a heterocycle. (4) In the general formula (I), the unsaturated ring is a benzene ring having at least one substituent, and the Hammett substituent constant σ value of the substituent (1, 2 with respect to Cα is 1 or 2).
Or a σp value is used for a substituent on a carbon atom having a relationship of 1,4, and a σm value is used for a substituent on a carbon atom having a relationship of 1,3 with respect to Cα). The silver halide color photographic light-sensitive material as described in (1) or (2), which is 0.8. (5) The photosensitive silver halide emulsion layer is composed of three types of silver halide emulsion layers having different sensitivities, and the total coated silver amount is 0.003 to 12 g / m ² (1) to (4) )
Which is a silver halide color photographic light-sensitive material. (6) The silver halide color photograph as described in any one of (1) to (5), wherein the photosensitive silver halide emulsion layer contains at least one color-forming reducing agent represented by the general formula (I). Photosensitive material. (7) The silver halide color photographic light-sensitive material according to any one of (1) to (6), wherein the non-photosensitive layer contains at least one mordant. (8) The silver halide color photographic light-sensitive material according to (7), wherein the photographic constituent layer has a release layer between the silver halide emulsion layer and the layer containing a mordant. (9) The photographic constituent layer further has a barrier layer (1)
The silver halide color photographic light-sensitive material described in any one of (8) to (8). (10) The total coated silver amount is 0.003 to 0.3 g / m ^2.
Which is the silver halide color photographic light-sensitive material described in (5).

(11) After exposing the silver halide color photographic light-sensitive material according to any one of claims 1 to 10,
It is a color image forming method characterized in that development processing is carried out using an alkaline solution containing substantially no developing agent. (12) The exposure time is 10 ^-8 to 1 per pixel
The color image forming method according to (11), which is 0 to ⁴ seconds, and is scanning exposure in which adjacent rasters overlap each other.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The color-forming reducing agent represented by the general formula (I) in the present invention is a compound that is oxidized by exposed silver halide in an alkaline solution, or is oxidized by a redox reaction with an oxidized auxiliary developing agent. A compound of which the oxidant is further capable of reacting with a dye forming coupler to form a dye.

In the color-forming reducing agent represented by the general formula (I), Z, Cα and Q are as follows. Z is
It represents a carbamoyl group, an acyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. Among these, a carbamoyl group is preferable, and a hydrogen atom on the nitrogen atom is 1
A carbamoyl group having one or more groups is particularly preferable. As the carbamoyl group, a carbamoyl group having 1 to 50 carbon atoms is preferable, and a carbamoyl group having 1 to 40 carbon atoms is more preferable. Specific examples thereof include a carbamoyl group, a methylcarbamoyl group, an ethylcarbamoyl group, an n-propylcarbamoyl group, a sec-butylcarbamoyl group,
n-octylcarbamoyl group, cyclohexylcarbamoyl group, tert-butylcarbamoyl group, dodecylcarbamoyl group, 3-dodecyloxypropylcarbamoyl group, octadecylcarbamoyl group, 3- (2,4-t
ert-pentylphenoxy) propylcarbamoyl group, 2-hexyldecylcarbamoyl group, phenylcarbamoyl group, 4-dodecyloxyphenylcarbamoyl group, 2-chloro-5-dodecyloxycarbonylphenylcarbamoyl group, naphthylcarbamoyl group, 3-pyridylcarbamoyl group. , 3,5-bis-octyloxycarbonylphenylcarbamoyl group, 3,5-bis-tetradecyloxyphenylcarbamoyl group, benzyloxycarbamoyl group, 2,5-dioxo-1-pyrrolidinylcarbamoyl group and the like.

The acyl group is preferably an acyl group having 1 to 50 carbon atoms, and more preferably an acyl group having 1 to 40 carbon atoms. Specific examples thereof include formyl group, acetyl group, 2-methylpropanoyl group, cyclohexylcarbonyl group, n-octanoyl group, 2-hexyldecanoyl group, dodecanoyl group, chloroacetyl group, trifluoroacetyl group, benzoyl group. , 4-dodecyloxybenzoyl group, 2-hydroxymethylbenzoyl group, 3-
(N-hydroxy-N-methylaminocarbonyl) propanoyl group.

As the alkoxycarbonyl group and aryloxycarbonyl group, an alkoxycarbonyl group having 2 to 50 carbon atoms and an aryloxycarbonyl group are preferable, and an alkoxycarbonyl group having 2 to 40 carbon atoms and an aryloxycarbonyl group are more preferable. Specific examples thereof include methoxycarbonyl group, ethoxycarbonyl group, isobutyloxycarbonyl group, cyclohexyloxycarbonyl group, dodecyloxycarbonyl group, benzyloxycarbonyl group, phenoxycarbonyl group,
Examples thereof include a 4-octyloxyphenoxycarbonyl group, a 2-hydroxymethylphenoxycarbonyl group, and a 4-dodecyloxyphenoxycarbonyl group.

Q represents an atomic group forming an unsaturated ring by combining with Cα, and the unsaturated ring is preferably a 3- to 8-membered ring, more preferably a 5- or 6-membered ring. Examples of these unsaturated rings include benzene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, 1,
2,4-triazine ring, 1,3,5-triazine ring, pyrrole ring, imidazole ring, pyrazole ring, 1,2,3
-Triazole ring, 1,2,4-triazole ring, tetrazole ring, 1,3,4-thiadiazole ring, 1,2,2
4-thiadiazole ring, 1,2,5-thiadiazole ring, 1,3,4-oxadiazole ring, 1,2,4-oxadiazole ring, 1,2,5-oxadiazole ring,
Heterocycles such as a thiazole ring, an oxazole ring, an isothiazole ring, an isoxazole ring, and a thiophene ring are preferable. These unsaturated rings may be condensed rings formed by condensing each other.

The unsaturated ring may further have a substituent. The substituent preferably has 50 or less carbon atoms, and more preferably 42 or less carbon atoms. Specific examples of the substituent include a linear or branched chain or cyclic alkyl group having 1 to 50 carbon atoms (eg, trifluoromethyl group, methyl group, ethyl group, propyl group, heptafluoropropyl). Group, isopropyl group, butyl group, t-
A butyl group, a t-pentyl group, a cyclopentyl group, a cyclohexyl group, an octyl group, a 2-ethylhexyl group, a dodecyl group), a linear or branched chain or cyclic alkenyl group having 2 to 50 carbon atoms (for example, , Vinyl group, 1
-Methylvinyl group, cyclohexen-1-yl group, etc.),
An alkynyl group having 2 to 50 carbon atoms (for example, an ethynyl group,
1-propynyl group, etc.), aryl group having 6 to 50 carbon atoms (eg, phenyl group, naphthyl group, anthryl group, etc.), acyloxy group having 1 to 50 carbon atoms (eg, acetoxy group, tetradecanoyloxy group, benzoyl) An oxy group), a carbamoyloxy group having 1 to 50 carbon atoms (eg, N, N-dimethylcarbamoyloxy group, etc.), a carbonamido group having 1 to 50 carbon atoms (eg, formamide group, N-methylacetamide group, acetamide) Base, N
-Methylformamide group, benzamide group, etc.), C1-C50 sulfonamide group (for example, methanesulfonamide group, dodecanesulfonamide group, benzenesulfonamide group, p-trienesulfonamide group, etc.), carbon number 1 To 50 carbamoyl groups (for example, N-methylcarbamoyl group, N, N-diethylcarbamoyl group, N-mesylcarbamoyl group and the like), sulfamoyl groups having 0 to 50 carbon atoms (for example, N-butylsulfamoyl group, N , N
-Diethylsulfamoyl group, N-methyl-N- (4-
Methoxyphenyl) sulfamoyl group, etc.), 1 to 1 carbon atoms
50 alkoxy groups (eg, methoxy group, propoxy group, isopropoxy group, octyloxy group, t-octyloxy group, dodecyloxy group, 2- (2,4-di-t)
-Pentylphenoxy) ethoxy group, etc.), C6-5
0 aryloxy group (eg, phenoxy group, 4-methoxyphenoxy group, naphthoxy group, etc.), C7-5
0 aryloxycarbonyl group (eg, phenoxycarbonyl group, naphthoxycarbonyl group, etc.), carbon number 2
To 50 alkoxycarbonyl groups (eg, methoxycarbonyl group, t-butoxycarbonyl group, etc.), carbon number 1
To 50 N-acylsulfamoyl groups (eg, N-tetradecanoylsulfamoyl group, N-benzoylsulfamoyl group, etc.), alkylsulfonyl groups having 1 to 50 carbon atoms (eg, methanesulfonyl group, octyl group) Sulfonyl group, 2-methoxyethylsulfonyl group, 2-hexyldecylsulfonyl group, etc.), arylsulfonyl group having 6 to 50 carbon atoms (for example, benzenesulfonyl group, p-toluenesulfonyl group, 4-phenylsulfonylphenylsulfonyl group, etc.) , An alkoxycarbonylamino group having 2 to 50 carbon atoms (eg, ethoxycarbonylamino group, etc.), an aryloxycarbonylamino group having 7 to 50 carbon atoms (eg, phenoxycarbonylamino group, naphthoxycarbonylamino group, etc.), carbon number 0-50 amino groups (eg, amino groups Methylamino group, a diethylamino group, diisopropylamino group, an anilino group, morpholino group, etc.), a cyano group, a nitro group, a carboxyl group, hydroxy group, sulfo group, a mercapto group, 1 to 50 carbon atoms
Alkylsulfinyl group (for example, methanesulfinyl group, octansulfinyl group, etc.), arylsulfinyl group having 6 to 50 carbon atoms (for example, benzenesulfinyl group, 4-chlorophenylsulfinyl group, p-toluenesulfinyl group, etc.), carbon number 1 To 50 alkylthio groups (eg, methylthio group, octylthio group, cyclohexylthio group, etc.), arylthio groups having 6 to 50 carbon atoms (eg, phenylthio group, naphthylthio group, etc.), ureido groups having 1 to 50 carbon atoms (eg, 3-Methylureido group, 3,3-dimethylureido group, 1,3-diphenylureido group, etc., and a heterocyclic group having 2 to 50 carbon atoms (hetero atoms contained in the heterocyclic group include, for example, nitrogen and oxygen). , Sulfur, etc., and the heterocyclic group contains fewer heteroatoms. Also comprise one or more, 3 to 12
It is a monocyclic or condensed ring having a member ring. Specific examples of the heterocyclic group include 2-furyl group, 2-pyranyl group, 2-pyridyl group, 2-thienyl group, 2-imidazolyl group, morpholino group, 2-quinolyl group, 2-benzimidazolyl group, 2
-Benzothiazolyl group, 2-benzoxazolyl group, etc.), acyl group having 1 to 50 carbon atoms (for example, acetyl group, benzoyl group, trifluoroacetyl group, etc.), sulfamoylamino group having 0 to 50 carbon atoms ( For example, N-butylsulfamoylamino group, N-phenylsulfamoylamino group, etc.), silyl group having 3 to 50 carbon atoms (eg, trimethylsilyl group, dimethyl-t-butylsilyl group, triphenylsilyl group, etc.), A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) can be mentioned. These substituents may further have a substituent, and examples of such a substituent include the substituents listed here.

The total number of carbon atoms in the unsaturated ring is preferably 30 or less, including the number of carbon atoms of the substituent when the unsaturated ring has the substituent, 2
4 or less is more preferable, and 18 or less is particularly preferable. When the unsaturated ring is formed by only carbon atoms (eg, benzene ring, naphthalene ring, anthracene ring, etc.), the substituents on the unsaturated ring are Hammett's substituents on all the substituents. Basic constant σ value (1,
When there is a relationship of 2, 1, 4, ...
When there is a relationship of 1,3,1,5, ... to "σm"
Are used respectively. The total sum of () is preferably 0.8 or more, more preferably 1.2 or more, and particularly preferably 1.5 or more. The upper limit of the Hammett's substituent constant σ value is not particularly limited, but is preferably 3.8 or less from the viewpoint of availability of the compound.

Regarding the Hammett's substituent constants "σp" and "σm", see, for example, Naoki Inamoto, "Hammet's Rule-Structure and Reactivity-" (Maruzen), "New Experimental Chemistry Course 14.
"Synthesis and Reaction of Organic Compounds V" 2605 (Chemical Society of Japan, Maruzen), Tadao Nakaya "Commentary on Theoretical Organic Chemistry" 217 (Tokyo Kagaku Dojin), Chemical Review (Vol. 91), 1
It is explained in detail in books such as pages 65 to 195 (1991).

Specific examples of the color-forming reducing agent represented by the general formula (I) are shown below. The present invention is not limited to these specific examples.

[0023]

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[0024]

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[0025]

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[0026]

[Chemical 6]

[0027]

[Chemical 7]

[0028]

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[0029]

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[0030]

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[0031]

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[0032]

[Chemical 12]

[0033]

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[0034]

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[0035]

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The color-forming reducing agent represented by the general formula (I) in the present invention may be contained in the photosensitive silver halide emulsion layer or in the non-photosensitive layer in the photographic constituent layers. However, the former is preferable. The color-forming reducing agent represented by the general formula (I) in the present invention is used together with a compound which forms a diffusible dye by an oxidative coupling reaction (hereinafter sometimes referred to as “diffusible dye-forming coupler”). . As the coupler, a 2-equivalent coupler is preferable. An example of the coupler is theory
Of the photographic process (4th.E
d. , T. H. Edited by James, Macmillan,
1977) 291 to 334 and 354 to 361.
Page, JP-A-58-12353, JP-A-58-1490.
46, 58-149047, 59-1.
1114, 59-124399, 59.
No. 174835, No. 59-231539,
It is described in detail in JP-A-59-231540, JP-A-60-2951, JP-A-60-14242, JP-A-60-23474, JP-A-60-66249 and the like.

As the diffusible dye forming coupler,
There is no particular limitation as long as the diffusible dye formed by coupling with the oxidized product of the color-forming reducing agent can reach the mordant, but the diffusible dye preferably has the following modes.

The diffusible dye preferably has at least one dissociative group having a pKa of 12 or less, more preferably at least one dissociating group having a pKa of 8 or less, and particularly preferably a dissociative group having a pKa of 6 or less. Further, from the viewpoint of imparting diffusibility, the molecular weight of the diffusible dye is 20
0 to 2000 is preferred. Furthermore, the ratio of the molecular weight of the diffusible dye to the number of dissociative groups having a pKa of 12 or less (molecular weight of the diffusible dye / the number of dissociating groups having a pKa of 12 or less) is 10
0-2000 are preferable and 100-1000 are more preferable. The value of pKa is the value measured using a solvent of dimethylformamide: water = 1: 1.

The solubility of the diffusible dye is 25 ° C.
Therefore, it is preferably dissolved in the alcal liquid having a pH of 1 × 10 ⁻⁶ mol / liter or more, more preferably 1 × 10 ⁻⁵ mol / liter or more, and particularly preferably 1 × 10 ⁻⁴ mol / liter or more. The diffusion constant of the diffusible dye is 25 ° C. in an alkaline solution of pH 11,
1 × 10 when dissolved at a concentration of 10 ⁻⁴ mol / liter
^-8 m ² · s ^-1 or more, preferably 1 × 10 ^-7 m ²
· More preferably s ⁻¹ or more, 1 × 10 ⁻⁶ m ² ·
It is particularly preferably s ^-1 or more.

Examples of the diffusible dye forming coupler include
Preferable examples are compounds represented by the following general formulas (1) to (12). These compounds are generally known as active methylene, pyrazolone, pyrazoloazole, phenol, naphthol, and pyrrolotriazole, respectively, and are known in the art.

[0041]

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[0042]

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[0043]

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Of these, the compounds represented by the general formulas (1) to (4) are diffusible dye-forming couplers called active methylene couplers. General formula (1)-
In (4), R ¹⁴ is an optionally substituted acyl group, cyano group, nitro group, aryl group, heterocyclic residue,
It represents an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group or an arylsulfonyl group. In formulas (1) to (3), R ¹⁵ represents an alkyl group, an aryl group or a heterocyclic residue which may have a substituent. In the general formula (4), R ¹⁶ represents an aryl group which may have a substituent or a heterocyclic residue. Examples of the substituent that R ¹⁴ , R ¹⁵ or R ¹⁶ may have include those exemplified as the substituent of the unsaturated ring.

In the general formulas (1) to (4), Y is a group capable of imparting diffusion resistance to the diffusible dye-forming coupler, and is removed by the coupling reaction with the oxidant of the color-forming reducing agent. It is a group that can be released. Specific examples of Y include a heterocyclic group (as the heteroatom contained in the heterocyclic group, nitrogen, oxygen, sulfur, etc. are included, and the heterocyclic group contains at least one of these heteroatoms and is saturated or It is an unsaturated 5- to 7-membered monocyclic or condensed ring, for example, a succinimide group, a maleinimide group, a phthalimide group, a diglycolimide group, a pyrrole group, a pyrazole group, an imidazole group, 1,2,4-triazole. Group, tetrazole group, indole group, benzopyrazole group, benzimidazole group, benzotriazole group, imidazoline-2,4-dione group, oxazolidine-2,4-dione group, thiazolidine-2,4-dione group, imidazolidine- 2-one group, oxazoline-2-one group, thiazolin-2-one group, benzimidazoline-2 One group,
Benzoxazoline-2-one group, benzothiazoline-
2-one group, 2-pyrrolin-5-one group, 2-imidazolin-5-one group, indoline-2,3-dione group,
2,6-dioxypurine group, parabanic acid group, 1,2,4
-Triazolidine-3,5-dione group, 2-pyridone group, 4-pyridone group, 2-pyrimidone group, 6-pyridazone group, 2-pyrazone group, 2-amino-1,3,4-thiazolidine group, 2- Imino-1,3,4-thiazolidin-4-one group etc.), aryloxy group (eg phenoxy group, 1-naphthoxy group etc.), heterocyclic oxy group (eg pyridyloxy group, pyrazolyloxy group etc.), Acyloxy group (eg, benzoyloxy group), alkoxy group (eg, dodecyloxy group), carbamoyloxy group (eg, morpholinocarbonyloxy group), aryloxycarbonyloxy group (eg, phenoxycarbonyloxy group), Alkoxycarbonyloxy group (for example, n-dodecyloxycarbonyloxy group, n-hexadeoxy) Oxy carbonyloxy group,
2-hexyldecyloxycarbonyloxy group, 2-octyldodecyloxycarbonyloxy group, 2- (2
4-t-pentylphenoxy) ethoxycarbonyloxy group etc.), an arylthio group (for example, a phenylthio group,
Naphthylthio group, etc.), heterocyclic thio group (eg, tetrazolylthio group, 1,3,4-thiadiazolylthio group,
1,3,4-oxadiazolylthio group, benzimidazolylthio group, etc.), alkylthio group (eg, octylthio group, hexadecylthio group, etc.), alkylsulfonyloxy group (eg, n-hexylsulfonyloxy group, n
-Dodecylsulfonyloxy group, 3- (2,4-t-pentylphenoxy) propylsulfonyloxy group, n-
Hexadecylsulfonyloxy group, etc.), arylsulfonyloxy group (eg, benzenesulfonyloxy group,
Toluenesulfonyloxy, etc.), carbonamide group (for example, 2-ethylhexanoylamino group, 2-hexyldecanoylamino group, 2- (2,4-t-pentylphenoxy) butanoylamino group, 3-penatadecyl Benzoylamino group), sulfonamide group (eg, benzenesulfonamide), alkylsulfonyl group (eg, n-hexylsulfonyl group, 2-ethylhexylsulfonyl group, 2-hexyldecylsulfonyl group, 3-dodecyloxypropylsulfonyl group) , N-hexadecylsulfonyl group etc.), arylsulfonyl group (eg benzenesulfonyl etc.), alkylsulfinyl group (eg n-hexylsulfinyl group, 2-ethylhexylsulfinyl group, 2-hexyldecylsulfinyl group,
n-hexadecylsulfinyl group, 4-hexadecyloxybenzylsulfinyl group etc.), arylsulfinyl group (eg benzenesulfinyl etc.), arylazo group (eg phenylazo, naphthylazo etc.), carbamoylamino group (eg N-2- Ethylhexylcarbamoylamino etc.) and the like.

The above Y may be substituted with a substituent, and examples of the substituent include those exemplified as the substituent of the unsaturated ring. The total number of carbon atoms contained in Y is preferably 6 to 50, more preferably 8 to 40, and particularly preferably 10 to 30. Among the above-mentioned examples, Y is preferably an aryloxy group, a heterocyclic oxy group, an acyloxy group, an aryloxycarbonyloxy group, an alkoxycarbonyloxy group, or a carbamoyloxy group. In addition, general formula (1)-
In (4), and R ¹⁴ and R ¹⁵ can alternatively and R ¹⁴ R
¹⁶ may combine with each other to form a ring.

The compound represented by the general formula (5) is a diffusible dye-forming coupler called a 5-pyrazolone type coupler. In the general formula (5), R ¹⁷ represents an alkyl group, an aryl group, an acyl group or a carbamoyl group.
Among these, an aryl group or an acyl group is preferable,
Specifically, phenyl group, 2-chlorophenyl group, 2-
Methoxyphenyl group, 2-chloro-5-tetradecanamidophenyl group, 2-chloro-5- (3-octadecenyl-1-succinimido) phenyl group, 2-chloro-5
-Aryl group such as octadecyl sulfonamide phenyl group or 2-chloro-5- [2- (4-hydroxy-3-t-butylphenoxy) tetradecanamide] phenyl group or acetyl group, 2- (2,4-di- t-pentylphenoxy) butanoyl group, benzoyl group, 3- (2,4)
An acyl group such as -di-t-amylphenoxyacetamido) benzoyl group is preferable. These groups may further have a substituent and the like, and as the substituent and the like,
Examples thereof include an organic substituent linked with a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom, or a halogen atom. In the general formula (5), Y has the same meaning as described above.

R ¹⁸ represents a phenyl group or a phenyl group substituted with one or more halogen atoms, alkyl groups, cyano groups, alkoxy groups, alkoxycarbonyl groups or acylamino groups. Among these, a phenyl group substituted with one or more halogen atoms is preferable, and specifically, a 2,4,6-trichlorophenyl group and a 2,5-
Substituted phenyl groups such as dichlorophenyl group and 2-chlorophenyl group are preferable.

The compound represented by the general formula (6) is a diffusible dye forming coupler called a pyrazoloazole coupler. In the general formula (6), R ¹⁹ represents a hydrogen atom or a substituent. Q ³ represents a group of non-metal atoms necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring has a substituent (including a condensed ring). Good. Among the pyrazoloazole-based couplers represented by the general formula (6), the imidazo [1,2-b] pyrazoles described in U.S. Pat. No. 4,500,630, in terms of the spectral absorption characteristics of the coloring dye, U.S. Pat. No. 4,500,
No. 654, pyrazolo [1,5-b] -1,2,4
-Triazoles and pyrazolo [5,1-c] -1,2,4-triazoles described in U.S. Pat. No. 3,725,067 are preferable.

Details of the substituent of the azole ring represented by R ¹⁹ or Q ³ are described in, for example, US Pat.
No. 0,654, column 2, line 41 to column 8, line 27. Preferred specific examples of the pyrazoloazole-based coupler represented by the general formula (6) include a branched alkyl group described in JP-A No. 61-65245, which is directly bonded to the 2, 3 or 6-position of the pyrazolotriazole group. Pyrazoloazole coupler, JP-A-61-65
Pyrazoloazole couplers containing a sulfonamide group in the molecule described in JP-A No. 245/1987.
Pyrazoloazole couplers having an alkoxyphenyl sulfonamide ballast group described in Japanese Patent No. 254,254, and Japanese Patent Application Laid-Open No. 62-209457 or 63-30745.
Pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position described in Japanese Patent Publication No. 3 and the pyrazolotriazole couplers having a carbonamide group in the molecule described in Japanese Patent Application No. 1-222279, etc. Can be mentioned. In the general formula (6), Y has the same meaning as described above.

The compounds represented by the general formulas (7) and (8) are diffusible dye-forming couplers called phenol couplers and naphthol couplers, respectively. In the general formulas (7) and (8), R ²⁰ is a hydrogen atom or-
CONR ²² R ²³ , -SO ₂ NR ²² R ²³ , -NHCO
R ^22, -NHCONR ²² R ²³ and -NHSO ₂ NR ²² R
Represents a group selected from ²³ ; Here, R ²² and R ²³ represent a hydrogen atom or a substituent. In formulas (7) and (8), R ²¹ represents a substituent. 1 represents an integer selected from 0 to 2. m represents an integer selected from 0 to 4.
When l and m are 2 or more, R ²¹ may be different from each other. Examples of R ²¹ , R ^{22 and} R ²³ include those enumerated as the substituents of the unsaturated ring. Note that Y is
It is synonymous with the above.

Specific examples of the phenolic coupler represented by the general formula (7) include US Pat. No. 2,369,929.
No. 2,801,171, No. 2,
2-Acylamino-5-alkylphenol couplers described in U.S. Pat. No. 2,772,162, U.S. Pat. No. 2,895,826, U.S. Pat. No. 2,772. , 162, ibid., 3,
758,308, 4,126,396, 4,334,011, and 4,32.
No. 7,173, West German Patent Publication No. 3,329,72
No. 9, 2,5-diacylaminophenol couplers described in JP-A-59-166956 and the like, US Pat. Nos. 3,446,622 and 4,4.
Preferable examples thereof include 2-phenylureido-5-acylaminophenol couplers described in 333,999, 4,451,559, 4,427,767 and the like. To be Note that Y has the same meaning as described above.

Specific examples of the naphthol coupler represented by the general formula (8) include US Pat. Nos. 2,474,293, 4,052,212 and 4,1.
46,396, 4,282,233, 4,296,200, etc.
-Carbamoyl-1-naphthol type couplers and 2-as described in U.S. Pat. No. 4,690,889 and the like.
Suitable examples include carbamoyl-5-amido-1-naphthol couplers and the like. Note that Y has the same meaning as described above.

The compounds represented by the general formulas (9) to (12) are diffusible dye-forming couplers called pyrrolotriazole. R ³² , R ³³ or R ³⁴ represents a hydrogen atom or a substituent. Y has the same meaning as described above. R ³² ,
Examples of the substituent of R ³³ or R ³⁴ include those listed as examples of the substituent capable of substituting on the unsaturated ring. Specific examples of the pyrrolotriazole-based couplers represented by the general formulas (9) to (12) include European Patent 488,248A.
No. 1, 491, 197A1, No. 5
Examples thereof include couplers in which at least one of R ³² and R ³³ described in Japanese Patent No. 45,300 and the like is an electron-withdrawing group. Note that Y has the same meaning as described above.

In addition to the above diffusible dye forming couplers, the diffusible dye forming couplers usable in the present invention include condensed ring phenol type couplers, imidazole type couplers, pyrrole type couplers, 3-hydroxypyridine type couplers and active compounds. Examples thereof include methylene type couplers, activated methine type couplers, 5,5-condensed heterocyclic ring type couplers, and 5,6-condensed heterocyclic ring type couplers. Examples of the condensed phenol type couplers include US Pat. Nos. 4,327,173, 4,564,586 and 4,9.
Examples thereof include couplers described in the specification of No. 04,575. Examples of the imidazole-based coupler include US Pat. Nos. 4,818,672 and 5,051,34.
Examples thereof include couplers described in No. 7 specification. As the 3-hydroxypyridine-based coupler, there is disclosed in Japanese Patent Laid-Open No.
Examples thereof include couplers described in No. 315736. Examples of the active methylene-based couplers and active methine-based couplers include the couplers described in US Pat. Nos. 5,104,783 and 5,162,196.

As the 5,5-condensed heterocyclic type coupler, a pyrrolopyrazole type coupler described in US Pat. No. 5,164,289, JP-A-4-17442 can be used.
Examples thereof include pyrroloimidazole-based couplers described in JP-A-9. Examples of the 5,6-condensed heterocyclic couplers include pyrazolopyrimidine couplers described in U.S. Pat. No. 4,950,585, and JP-A-4-204.
Examples thereof include a pyrrolotriazine-based coupler described in Japanese Patent No. 730, and a coupler described in European Patent No. 556,700.

In the present invention, further, West German Patent No. 3,819,051A and No. 3,823,04.
9, U.S. Pat. No. 4,840,883,
No. 5,024,930, No. 5,051,3
No. 47, No. 4,481,268, European Patent No. 304,856A2, No. 329,03.
No. 6, No. 354,549 A2, No. 3
74,781A2, 379,110A2, 386,930A1 and JP-A-63.
-141055, 64-32260, 64-32261, JP-A-2-297547, 2-44340, 2-110555, 3-7938, 3 -160440, 3-172839, 4-172447, 4-179949, 4-182645.
No. 4-184437 and No. 4-18813.
8 gazette, the same 4-188139 gazette, the same 4-1948.
47 publication, 4-204532 publication, 4-204.
The couplers described in Japanese Patent No. 731, Japanese Patent No. 4-204732, etc. can be used.

The total number of carbon atoms in the portion excluding Y in the above-mentioned coupler for forming a diffusible dye used in the present invention is preferably 3 to 30, more preferably 3 to 24.
-18 are the most preferable. When the total number of carbon atoms is within the above-mentioned preferable range, it is advantageous in that the dye to be released tends to be diffusible. Specific examples of the diffusible dye forming coupler that can be used in the present invention are shown below. The present invention is not limited to these specific examples.

[0059]

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[0060]

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[0061]

[Chemical 21]

[0062]

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[0063]

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[0064]

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[0065]

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[0066]

[Chemical formula 26]

[0067]

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[0068]

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[0069]

[Chemical 29]

[0070]

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[0071]

[Chemical 31]

[0072]

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[0073]

[Chemical 33]

The amount of the color-forming reducing agent used is from 0.01 to 10 per layer from the viewpoint of obtaining a sufficient color density.
mmol / m ² is preferable, and 0.05 to 5 mmol / m
² is more preferable, and 0.1 to 1 mmol / m ² is particularly preferable. The amount of the diffusible dye forming coupler used in the layer in which the color-forming reducing agent is used is preferably 0.05 to 20 times, and preferably 0.1 to 10 times the molar amount of the color-forming reducing agent. Is more preferable, and 0.2 to 5 times is particularly preferable.

Next, the mordant which can be used in the present invention will be described. When the mordant is used, the dissociative dye is adsorbed to the mordant, which is advantageous in that the dissociation is facilitated. To prevent the occurrence of stain after the development process,
It is necessary not to dissociate the remaining color-forming reducing agent, but to dissociate only the dye that is produced. For that purpose, the color-forming reducing agent and the coupler are separated from the mordant, and only the produced dye is adsorbed to the mordant. (Hereinafter, may be referred to as "transfer-mordanting type"). in this case,
It is preferable that the color-forming reducing agent and the coupler have a leaving group having a ballast property that is released during coupling. When the color-forming reducing agent and the coupler have the leaving group, the color-forming reducing agent and the coupler can be retained in a layer other than the mordant layer, and only the dye produced by the development process can be diffused and adsorbed to the mordant. become. The color-forming reducing agent represented by the general formula (I) is suitable for the transfer-mordanting type because it exhibits a favorable color-forming reaction with a coupler having a leaving group at the coupling position.
The sulfonylhydrazine type compounds described in 91A1 specification and 565165A1 specification are not suitable for the transfer-mordanting type because they hardly react with the coupler having a leaving group at the coupling position.

In the present invention, the mordant may be added to any layer, but is preferably added to a layer other than the layer containing the color-forming reducing agent. in this case,
It is advantageous in that the stability of the color-forming reducing agent is not reduced. Further, the diffusible dye formed from the color-forming reducing agent and the diffusible dye-forming coupler diffuses in the swollen gelatin film during the color-developing process and is dyed with a mordant. Therefore, to obtain good sharpness,
It is preferable that the diffusion distance of the diffusible dye is short, and therefore, the mordant is preferably added to a layer adjacent to the layer containing the color-forming reducing agent.

Since the color-forming reducing agent and the diffusible dye are water-soluble dyes, they may flow out into the color-developing processing solution. Therefore, in order to prevent this, the layer to which the mordant is added is preferably located on the side opposite to the support with respect to the layer containing the color-forming reducing agent. However, JP-A-7-1683
As described in JP-A-35-35, when the barrier layer is provided on the side opposite to the support (the side far from the support) with respect to the layer to which the mordant is added, the reducing agent for color formation is contained. The layer to which the mordant is added may be located on the side of the support with respect to the existing layer.

The mordant may be added to a plurality of layers, and when there are a plurality of layers containing the color-forming reducing agent, they may be added to adjacent layers. The mordant may be any mordant which is commonly used in photographic light-sensitive materials and can fix the diffusible dye, and among these, a polymer mordant is particularly preferable.

Here, the polymer mordant means a polymer having a function as a mordant such as a polymer having a tertiary amino group, a polymer having a nitrogen-containing heterocyclic portion, and a polymer having a quaternary cation group. Examples of the polymer having a tertiary amino group include homopolymers or copolymers containing a vinyl monomer unit. As specific examples thereof, the following compounds P-1 to P-3 are preferably cited. In addition, the number in a monomer unit represents mol% (Hereinafter, it is the same also in compound P-4 to 28).

[0080]

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Examples of the polymer having a nitrogen-containing heterocyclic moiety include homopolymers and copolymers containing a vinyl monomer unit having a tertiary imidazole group. Specific examples of these include US Pat.
No. 305, No. 4,115,124, No. 3,148,061, and JP-A-60-1188.
No. 34, No. 60-122941, No. 62-2.
In addition to the mordants described in JP-A-44043 and JP-A-64-244036, the following compounds P-4 to 1
7 is preferable.

[0082]

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[0083]

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[0084]

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Examples of the polymer having a quaternary cation group include a homopolymer or a copolymer containing a vinyl monomer unit having a quaternary imidazolium salt and a homopolymer or a copolymer having a vinyl monomer unit having a quaternary ammonium salt. . Specific examples of the former include British Patent No. 2,056,101 and No. 2,056,101.
No. 093,041, No. 1,594,961, No. 4,124,386, No. 4,115,124, No. 4,450,224.
In addition to the mordants described in JP-A No. 48-28325 and the like, the following compounds P-18 to 21 are preferably mentioned.

[0086]

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As a concrete example of the latter, US Pat.
09,690, 3,898,088, 3,958,995, JP-A-60-5.
7836, 60-60643, 6
Suitable compounds include the mordants described in 0-122940, 60-122942, 60-235134 and the like, and the following compounds P-22 to 28.

[0088]

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[0089]

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In addition to the above mordants, the mordants usable in the present invention include US Pat. Nos. 2,548,564, 2,484,430 and 3,1.
48,161, 3,756,814 and other vinyl pyridine polymers and vinyl pyridinium cation polymers; US Pat.
694, 3,859,096, 4,128,538, British Patents 1,27.
Polymer mordants capable of cross-linking with gelatin and the like described in 7,453, etc .; US Pat. No. 3,958,995, 2,721,852, 2,79.
No. 8,063, JP-A Nos. 54-115228, 54-145529, and 54-26027.
Aqueous sol type mordants described in U.S. Pat. No. 3,898,088; water insoluble mordants described in U.S. Pat. No. 3,898,088; U.S. Pat. No. 4,168,976 (JP-A-54-137333). Reactive mordants capable of covalently bonding with dyes described in US Pat. No. 3,709,69.
No. 0, No. 3,788,855, No. 3,642,482, No. 3,488,706
No. 3,555,066, No. 3,557,066
271,147, JP-A-50-71332, 53-30328, and 52-155528.
Mordants described in JP-A Nos. 53-125, 53-1024, and US Pat. No. 2,675,316.
And the mordants described in JP-A-2,882,156.

The molecular weight of the polymer mordant is
1,000 to 1,000,000 is suitable, and 10,
000 to 200,000 is particularly preferable. The polymer mordant is usually used as a mixture with a hydrophilic colloid. Examples of the hydrophilic colloid include gelatin,
Examples thereof include highly hygroscopic synthetic polymers. These may be used alone or in combination. Among these,
Gelatin is the most representative. The mixing ratio of the polymer mordant and the hydrophilic colloid, and the coating amount of the polymer mordant, the amount of the diffusible dye to be mordant, the type and composition of the polymer mordant, various conditions in the image forming process, etc. The mixing ratio (mordanting agent / hydrophilic colloid) can be appropriately determined according to
20/80 to 80/20 (weight ratio) is preferable, and the coating amount is preferably 0.2 to 15 g / m ^{2 and} is 0.2.
It is more preferably 5 to 8 g / m ² .

Next, the release layer in the present invention will be described. When the mordant is contained in a layer other than the photosensitive silver halide emulsion layer for the purpose of peeling and removing metallic silver remaining after color development processing from the transferred dye image, the peeling layer is It is preferably located between the layer containing the mordant and the light sensitive silver halide emulsion layer.
In order to prevent stain after color development processing, it is also preferably located between the layer containing the color-forming reducing agent and / or the diffusible dye-forming coupler and the mordant-containing layer.

Examples of the peeling of the peeling layer include dry peeling performed in a dried state of the peeling layer and wet peeling performed by softening the peeling layer in a color development processing solution or a similar solution. In the case of the dry peeling, the material used for the peeling layer is, for example, US Pat. No. 4,459,34.
Suitable examples include the perfluorinated release agent described in No. 6 specification. In the case of the wet peeling, the material used for the peeling layer is, for example, US Pat. No. 2,759,8.
25. Gum arabic, cellulose acetate / phthalate, polyvinyl alcohol, hydroxyethyl cellulose, vitroxypropyl cellulose, hydroxypropylmethyl cellulose, methyl cellulose, ethyl cellulose, alginate cellulose, etc. described in US Pat. No. 4,459,346. Linear alkyl group perfluoroalkylate sulfonamide ester, polyethylene oxide perfluoroalkylate
Sulfonamide ester, etc .; JP-A-60-214357
Suitable examples include acrylic acid compounds, condensation compounds of dialkylbarbituric acid and formaldehyde, condensation compounds of dialkylhydantoin and formaldehyde, and the like described in Japanese Patent Laid-Open Publication No. 2003-242242. In the present invention, among these compounds, those soluble in an alkaline aqueous solution are preferable, and specifically, hydroxyalkyl cellulose such as hydroxyethyl cellulose, hydroxypropyl cellulose and hydroxypropylmethyl cellulose are preferable.

[0094] The used amount of the material used for the peeling layer is not particularly limited but is preferably ^{0.01~1.0g / m 2, 0.05~0.5g / m} 2 is more preferable.
As the thickness of the release layer, if too thick prevents the diffusible dye from diffusing into the mordant layer, and if it is too thin, the releasability deteriorates and uniform release becomes impossible, resulting in uneven release. In any case, it is not preferable.

In the present invention, a barrier layer (a layer having a function of preventing the diffusible dye formed from the color-forming reducing agent and the coupler from flowing out into the color-developing processing solution during color-developing processing) is provided. Is preferred. Particularly, with respect to the layer containing the color-forming reducing agent and the coupler, when the layer containing the mordant is on the support side, it is preferable to provide the barrier layer. In this case, the barrier layer is It is preferably located on the side opposite to the support with respect to the layer containing the color-forming reducing agent and the coupler. The barrier layer may be a film that is impermeable to the diffusible dye and allows only an alkali for development to pass through. As a material for such a barrier layer,
For example, the polymers described in JP-A No. 7-168335 are preferable.

The polymer used in the barrier layer (hereinafter sometimes referred to as "barrier polymer") has an ion-forming functional group (functional group) of about 1 × 10 ⁻⁵ to 4 × 10 ⁻ per 1 g of the polymer. ^It is preferably contained in an amount of ³ moles, more preferably about 5 × 10 ⁻⁵ to 2 × 10 ⁻³ moles per gram of polymer. Further, the barrier polymer does not contain a salt capable of effectively scavenging or mordanting the diffusible dye, for example, a secondary amine salt, a tertiary amine salt or a quaternary ammonium salt. The barrier polymer has a property that it is swellable in an aqueous solution or a color development processing solution while balancing hydrophobicity and hydrophilicity, but when it is applied, it is not completely dissolved in the aqueous solution or the development processing solution. Is preferred. Further, it is preferable that it has a function of allowing the development processing solution to pass therethrough, whether it is applied alone or in combination with gelatin. Furthermore, when prepared for coating, they preferably have the property of being dispersible or soluble in water. The molecular weight of the barrier polymer is 50,000 to 1,00 from the viewpoint that the polymer can be actually applied.
10,000 is preferable.

The barrier polymer may be used in a photographic element as long as the content of the ion-forming functional group is within the above range and the water swelling property in a color developing processing solution is appropriate. It may contain a repeating unit derived from the above monomer. Examples of the barrier polymer include water-dispersible polyesters, polyamides,
Examples thereof include polyethers, polysulfones, polyurethanes, polyphosphazenes, and chemically modified natural polymers (eg, proteins, polysaccharides and chitins). The monomers include, for example, vinyl monomers, especially acrylates, methacrylates, acrylamides and methacrylamides (including analogs of said monomers) and the like, which are very suitable for radical polymerization.

More preferable examples of the barrier polymer include polymers containing a repeating unit represented by the formula:-(A)-(B)-. In the above formula, A is
Represents a hydrophobic ethylenically unsaturated monomer. B represents an ionic hydrophilic ethylenically unsaturated monomer. Such a barrier polymer is a hydrophobic / hydrophilic mixture and is effective for the barrier property of the diffusible dye and the penetrability of the color development processing solution. A in the above formula is, for example, vinyl ketones, alkyl vinyl esters, ethers, styrenes, alkyl styrenes, halostyrenes, acrylonitriles, butadiene, isoprene, chloroprene, ethylene and alkyl-substituted ethylenes, alkyl-substituted alkylamides. , Alkyl-substituted methacrylamides, haloethylenes, and vinylidene halogen compounds. Other examples of the hydrophobic ethylenically unsaturated monomer are described in Research Disclosure, 19551, No. 3
Listed on page 01, July 1980.

Examples of B in the above formula include vinyl monomers containing the above-mentioned ion-forming functional group and capable of performing free radical polymerization. Examples thereof include itaconic acid, fumaric acid, vinyl ketones, N-vinyl amides and vinyl. Sulfonic acid, vinyl ethers, vinyl esters, vinyl ureylenes, vinyl urethanes, vinyl nitriles,
It is selected from vinyl anhydride, allylamine, maleic anhydride, maleimides, vinylimides, vinyl halides, vinyl aldehydes, substituted styrenes, and vinyl heterocyclic rings. Other examples of ionic hydrophilic ethylenically unsaturated monomers are described in Research Disclosure, 1955.
1, page 303, July 1980. A
And more preferred examples of B are acrylamides,
Methacrylamides and methacrylates are mentioned.

As the ion-forming functional group for B,
It may be an ionic group, an ion-forming functional group, or a group capable of performing a reaction capable of forming an ion-forming functional group, for example, by hydrolysis or pH-induced protonation, and the presence of the group Any ion-forming functional group may be used as long as it can increase the water swelling property of the polymer during color development processing. The ion-forming functional group may be cationic or anionic.
The barrier polymer having such an ion-forming functional group may be formed from a monomer having an opposite charge so that the polymer is amphoteric.

In the present invention, the above formula,-(A) m-
A polymer represented by (B) n- and containing a repeating unit derived from an ethylenically unsaturated monomer is particularly preferable. In the above formula, A represents a hydrophobic monomer unit represented by the following structural formula.

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In the formula, R represents a hydrogen atom or a methyl group. E represents -OR ² or -NR ³ R ^4. R ² represents a substituted or unsubstituted linear, branched or cyclic alkyl group or aryl group having about 1 to 10 carbon atoms. R ³
And R ⁴ each represent hydrogen or the same group as the group of R ² ,
It contains at least 3 carbon atoms in total. m is
It is 0-99.5 mol%. In the above formula, B represents a hydrophilic monomer unit represented by the following structural formula.

[0104]

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In the formula, R represents a hydrogen atom or a methyl group. W represents -OR ⁵ or -NR ⁶ R ^7. R ⁵ represents a linear, branched or cyclic alkylene group or arylene group having about 1 to 10 carbon atoms. R ⁶ represents a hydrogen atom or a linear, branched or cyclic alkyl group or aryl group having about 1 to 6 carbon atoms. R ⁷ represents a linear, branched or cyclic alkylene group having about 1 to 10 carbon atoms or an arylene group. n is 0.5 to 100 mol%
Represents Q is (a) -NH ₂ or its acid addition salt (-N
H ₂ : HX (X represents an acid anion), or
_{(B) -CO 2 M, -SO} 3 M, -OSO 3 M, -OPO 3
A functional group selected from M and -OM (M represents a cation).

With respect to A in the above formula, R ² , R ³ and R ⁴ are substituted with a nonionic functional group which does not impair the hydrophobicity of the monomer unit represented by A or does not interfere with the polymerization. Good. Examples of such a non-ion forming functional group include a halogen atom alkoxy group, an acryloxy group, a styryl group, a sulfooxyalkyl group, a sulfoalkyl group, a nitro group, a thio group, a keto group and a nitrile group. . The monomer unit represented by A is a reactive functional group capable of exhibiting other photographic useful functions common to the image forming layer, the protective layer provided thereon, and the intermediate layer provided between both layers. It may contain a group. In the formula, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ may be substituted with a group capable of forming a heterocyclic ring. Regarding A and B, the linear, branched or cyclic alkyl group may contain one or more unsaturated sites. The monomer unit represented by A preferably contains an unsaturated linear or branched alkyl group having 4 to 8 carbon atoms.
The monomer unit represented by B preferably contains a linear or branched alkyl group having 3 to 8 carbon atoms.

As the monomer units represented by A and B, acrylamides or methacrylamides in which the amide nitrogen is monosubstituted are particularly preferable. In the above formula, m
Represents about 0 to 99.5 mol%, and n represents about 0.5 to 1
It represents 0.00 mol%. Regarding the Q, the acid ion and the cation may be organic or inorganic. In addition, as a preferable anion, for example, C
l ⁻ , Br ⁻ , ClO 4 ⁻ , I ⁻ , F ⁻ , NO ⁻ , HS
O ₄ ⁻ , SO ₄ ²⁻ , HCO ₃ ⁻ and CO ₃ ²⁻ can be mentioned. The present invention is not limited to these. Of these, Cl ⁻ is particularly preferable. On the other hand, preferable cations include, for example, H ⁺ , alkali metal ions, ammonium ions and the like. The present invention is not limited to these. Of these, Na ⁺ and H ⁺ are the most preferable.

Where the barrier polymer is derived from the monomeric unit represented by A and the monomeric unit represented by B, both of which are acrylamide or methacrylamide wherein the amide nitrogen is monosubstituted, These polymers are based on Thermo Reversible Gellin
It becomes a group of polymers known as g (TRG) polymers. This TRG polymer is a preferable group of polymers in the present invention, and is described in Japanese Patent Application No. 4-506378 (EP 476117A1). Among the TRG polymers described in the above publication, those within the above-mentioned parameters can be used in the present invention. When the polymer used for the barrier layer is the TRG polymer, the m is about 4
0 to 99 mol% is preferable, and n is preferably about 1 to 60 mol%.

Preferred examples of the monomer unit represented by A include N-isopropylacrylamide and Nt.
-Butyl acrylamide, N-butyl acrylamide,
N-t-butylmethacrylamide, N- (1,1-dimethyl-3-oxobutyl) acrylamide, N-butylmethacrylate, 2-ethylhexylmethacrylate,
Benzyl methacrylate and the like. As a preferable example of the monomer unit represented by B, N- (3-
Aminopropyl) methacrylamide hydrochloride, aminoethylmethacrylate hydrochloride, sulfoethylmethacrylate sodium salt, N- (2-sulfo-1,1-dimethylethyl) acrylamide sodium salt, N-2-carboxyethylacrylamide and the like. To be

In order to increase the water swelling property and increase the penetrability into the color development processing solution, the barrier polymer contains at least 1 × 10 ⁻⁵ mol of the ionic functional group per 1 g of the polymer. , May contain a repeating unit derived from a hydrophilic nonionic monomer. Any hydrophilic monomer capable of free radical polymerization is preferred if they do not contain substituents such as secondary amines, tertiary amines or quaternary ammonium.

As the hydrophilic nonionic monomer,
Ethylenically unsaturated monomers are preferred, specifically N
-Vinylpyrrolidone, N-vinyl-ε-caprolactam, vinyloxazolidone, vinylmethyloxazolidone, maleimide, N-methylolmaleimide, maleic anhydride, N-vinylsuccinamide, acryloylurea, cyanomethyl-acrylate, 2-cyanoethylacrylate, glyceryl Acrylate, acryloyloxypolyglycerol, allyl alcohol, vinylbenzyl alcohol, p-methanesulfonamide styrene,
Examples include methyl vinyl ether, and the like, and block copolymers formed from polymethylene oxide, polypropylene oxide and polyurethanes, and acrylate or methacrylate end groups.

More preferable examples of the hydrophilic nonionic monomer include acrylate, methacrylate, acrylamide, methacrylamide, and monomers of analogs thereof. Representative examples of these monomers include N- (isobutoxymethyl) acrylamide, methyl-2-methoxyacetate, methyl-2-
Acrylamide-2-methoxyacetate, N-hydroxypropyl acrylamide, ethyl acrylamide acetate, N-acetanide acrylamide, N- (m
-Hydroxyphenyl) -acrylamide, 2-acrylamido-2-hydroxymethyl-1,3-propanediol and N- (3- or 5-hydroxymethyl-2-
Methyl-4-oxo-2-pentyl) acrylamide and the like can be mentioned.

Other preferable examples of the hydrophilic nonionic monomer are listed in Research Disclosure, 19551, No. 305, July 1980. Among these, acrylamide, methacrylamide, N, N-
Dimethyl acrylamide, hydroxyethyl acrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate,
Hydroxypropyl methacrylate, methylene-bis-
Acrylamide and the like are preferable. The content of the hydrophilic nonionic monomer in the barrier polymer is preferably about 0 to 70 mol%, and about 10 to 65 mol%.
Is more preferred.

The barrier layer must also have sufficient physical integrity to maintain the state before the color development processing even after the color development processing. However, most of the above-mentioned monomers are structurally structured. You can guarantee this performance. For example, a polymer containing N- (3-aminopropyl) -methacrylamide cation hydrochloride, which is a cationic hydrophilic monomer, is
It can be cross-linked by a gelatin hardener. Further, in order to strengthen the hardening by crosslinking, a monomer having a group capable of being crosslinked by a hardening agent can be introduced into the barrier polymer. Examples of the monomer having such a group include aldehydes, bis (vinylsulfonyl) compounds,
Epoxides, aziridines, isocyanates and carbodiimides are mentioned. However, the present invention is not limited to these monomers. Also,
Preferable examples include monomers containing an active methylene group such as 2-acetoacetoxy-ethylmethacrylate, ethylmethacroylacetoacetate and (N-2-acetoacetoxyethyl) acrylamide. Alternatively, di- or polyfunctional monomers such as methylene-bis-acrylamide or ethylene glycol-dimethacrylate can be used to prepare the water-swellable and water-dispersible crosslinked colloidal particle polymers.

In the present invention, the barrier polymer shown in Table 3 is composed of the monomers shown in Tables 1 and 2 below, in that it is easy to synthesize and is effective in reflecting the diffusible dye. Polymers are particularly preferred.

[0116]

[Table 1]

[0117]

[Table 2]

[0118]

[Table 3]

These barrier polymers can be synthesized by a well-known synthetic method, and may be applied by a usual method. The degree of permeability in the barrier layer can be adjusted by adding gelatin or another water-soluble polymer to the barrier layer. The amount of such a water-soluble polymer added to the barrier layer is preferably 80% or less, more preferably 50% or less, and particularly preferably 25% or less. This method is particularly effective in adjusting the permeability in barrier polymers containing a high proportion of hydrophobic monomers. The barrier layer having a desired degree of permeability can be obtained by appropriately changing the thickness of the polymer / gelatin layer.

On the other hand, the permeability of the barrier layer can also be adjusted by using a surfactant or a surfactant-like compound together with the polymer. The surfactant or the surfactant-like compound, for example, 2,5-dihydroxy-4- (1-methylheptadecyl) benzenesulfonic acid sodium-monopotassium salt is not added to the barrier layer, but is added to other layers. You may use. These surfactant compounds diffuse and combine with the polymer to affect the permeability of the polymer. All surfactants are
Surfactants or surfactant-like compounds that increase the hydrophobicity of the barrier polymer, but which have an opposite charge to the barrier polymer, are particularly effective in reducing the permeability of the polymer. The TRG polymers are a particularly preferred group of barrier polymers of the present invention. A solution of such a barrier polymer is effective in coating because it is thickened by heat or cooled when it is applied to a film, and the boundary between the barrier layer and another layer becomes clear. The manufacture of the TRG polymer is described in detail in EP 476117 A1.

The silver halide color photographic light-sensitive material of the present invention basically has a single-layer or multi-layer photographic constituent layer formed by coating a support with a hydrophilic colloid layer. Photosensitive silver halide, the diffusible dye-forming coupler, and the color-forming reducing agent are contained in the same or different layers of the photographic constituent layers. In the present invention, the diffusible dye-forming coupler and the color-forming reducing agent are most typically added to the same layer, but if they are in a reactive state, they are added to separate layers. May be. In the silver halide color photographic light-sensitive material, the dye-forming coupler and the color-forming reducing agent are preferably added to the light-sensitive silver halide emulsion layer or an adjacent layer thereof, and both are added to the light-sensitive silver halide emulsion layer. Is particularly preferred.

In the present invention, the auxiliary developing agent and its precursor are preferably used and added to the silver halide color photographic light-sensitive material. The auxiliary developing agent and its precursor will be described below. The auxiliary developing agent in the present invention is a compound having an action of promoting electron transfer from the color-forming reducing agent to silver halide in the process of developing silver halide grains, and preferably exposed silver halide grains And a oxidant capable of oxidizing the color-forming reducing agent (hereinafter sometimes referred to as “cross oxidation”). Preferable examples of the auxiliary developing agent include compounds such as pyrazolidones, dihydroxybenzenes, reductones and aminophenols. Among these, compounds of pyrazolidones are particularly preferable. The diffusibility of these compounds in the photographic constituent layer, that is, the hydrophilic colloid layer, is preferably low, for example, the solubility in water (25 ° C.) is preferably 0.1% or less,
0.05% or less is more preferable, and 0.01% or less is particularly preferable.

The precursor of the auxiliary developing agent in the present invention stably exists in the silver halide color photographic light-sensitive material, but once it is processed with the color developing processing solution, the auxiliary developing agent is rapidly released. It is a compound. The diffusivity of these compounds in the photographic constituent layer, that is, the hydrophilic colloid layer is preferably as low as in the case of the auxiliary developing agent. For example, the solubility in water (25 ° C.) is 0.
1% or less is preferable, 0.05% or less is more preferable,
0.01% or less is particularly preferable. The solubility of the auxiliary developing agent released from the precursor of the auxiliary developing agent is not particularly limited, but the solubility of the auxiliary developing agent itself is preferably low.

As the precursor of the auxiliary developing agent in the present invention, the compound represented by formula (A) is particularly preferable. In formula (A) A- (L) _n -PUG, A represents a blocking group in which the bond with (L) _n -PUG is cleaved during color development processing. L represents a linking group in which the bond between L and PUG in the general formula (A) is cleaved after the bond between L and A is cleaved. n represents an integer of 0 to 3. PUG stands for auxiliary developing agent. As the auxiliary developing agent, an electron-emitting compound according to the Kendal-Perts rule other than p-phenylenediamine compounds is used, and the pyrazolidone compounds are preferably used.

As the block group represented by A, the following publicly known ones can be applied. That is, US Pat.
Block groups such as acyl groups and sulfonyl groups described in JP-A-11-476, block groups utilizing reverse Michael reaction described in JP-A-59-105642, JP-A-2-280140. Block groups utilizing quinone methide or compounds similar to quinone methide by intramolecular electron transfer described in JP-A-63-31855.
A block group utilizing an intramolecular nucleophilic substitution reaction described in Japanese Patent Publication No. 5 (European Patent Publication No. 0295729), and the like,
Block groups utilizing the addition reaction of a nucleophile to a conjugated unsaturated bond described in JP-A-4-186344 and blocks utilizing the β-elimination reaction described in JP-A-62-163051. Group, a block group utilizing the nucleophilic substitution reaction of diarylmethanes described in JP-A-61-188540, a block group utilizing a Rossen rearrangement reaction described in JP-A-62-187850,
Block groups utilizing the reaction of an N-acyl derivative of thiazolidine-2-thione with an amine described in JP-A-62-147457, two electrophiles described in WO93 / 03419. Examples thereof include a blocking group having a group and reacting with a dinucleophile. The group represented by L is a linking group capable of cleaving (L) _n-1 PUG after leaving the group represented by A during color development processing, and having this function. Then there is no particular limitation.

The auxiliary developing agent or its precursor is specifically shown below. The present invention is not limited to these specific examples.

[0127]

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[0128]

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In the present invention, these compounds may be added to any of a light-sensitive silver halide emulsion layer or a non-light-sensitive layer such as an intermediate layer, an undercoat layer and a protective layer. When the layer contains an auxiliary developing agent, it is preferably used by adding it to the non-photosensitive layer. As a method of incorporating these compounds into a silver halide color photographic light-sensitive material, a method of dissolving them in a water-miscible organic solvent such as methanol and directly adding them to a hydrophilic colloid layer, coexisting with a surfactant, an aqueous solution or A method of adding it as a colloidal dispersion, a method of dissolving it in a solvent or an oil substantially immiscible with water and then adding it dispersed in water or a hydrophilic colloid, a method of charging in the state of solid fine particle dispersion, etc. Is mentioned. Conventional known methods can be applied alone or in combination. A method for preparing a solid fine particle dispersion is described in JP-A-2-
No. 235044, page 20. The amount of these compounds added to the silver halide color photographic light-sensitive material is usually 1 to 200 m with respect to the color-forming reducing agent.
ol%, preferably 5 to 100 mol%, 10 to
50 mol% is more preferable.

In the silver halide color photographic light-sensitive material of the present invention, conventionally known photographic materials such as photographic supports and additives can be used. Examples of the photographic support include known supports such as transmissive supports and reflective supports. Examples of the transmissive support include transparent films such as cellulose nitrate film and polyethylene arephthalate, polyesters of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG), and NDCA and terephthalic acid. Preferable examples include those in which an information recording layer such as a magnetic layer is provided on polyester of EG and the like. The reflective support is, for example, laminated with a plurality of polyethylene layers or polyester layers, and at least one layer of such a water-resistant resin layer (laminate layer) contains a white pigment such as titanium oxide, a fluorescent whitening agent, etc. There are things to do. Of these, the latter type of reflective support is preferred in the invention. In these photographic supports, a hydrophilic colloid layer containing a white pigment or the like may be coated on the surface thereof. Further, these photographic supports may have a specular reflective or second-class diffuse reflective metallic surface.

Suitable examples of the fluorescent whitening agent include benzoxazole-based, coumarin-based, and pyrazoline-based compounds. Among these, benzoxazolylnaphthalene-based and benzoxazolyl-stilbene-based compounds are preferred. More preferable. The amount of the fluorescent whitening agent used is not particularly limited, but is preferably 1 to 100 mg / m ² . When the fluorescent whitening agent is mixed with the waterproof resin, the mixing ratio is 0.0005 to 3 with respect to the waterproof resin.
Weight% is preferable, and 0.001 to 0.5 weight% is more preferable. In the present invention, the fluorescent whitening agent may be used by dispersing it in the hydrophilic colloid layer in the silver halide color photographic light-sensitive material.

The silver halide emulsion used in the light-sensitive silver halide emulsion layer in the silver halide color photographic light-sensitive material of the present invention has a silver chloride content of 95 mol% or more from the viewpoint of rapid processability. Alternatively, a silver chlorobromide emulsion is preferable, and a silver halide emulsion having a silver chloride content of 98 mol% or more is more preferable. Among these silver halide emulsions, those having a silver bromide localized phase on the surface of silver chloride grains are particularly preferable in terms of high sensitivity and stable photographic performance.

In the present invention, the above-mentioned reflection type support, silver halide emulsifier, different metal ion species doped in silver halide grains, storage stabilizer or antifoggant for silver halide emulsion, chemical sensitization method. (Chemical sensitizer), Spectral sensitization method (Spectral sensitizer), Emulsion dispersion method of coupler, Color image storability improving agent (Anti-staining agent, Anti-browning agent), Dye (Coloring layer), Gelatin species, Halogen Tables 4 and 5 show the layer structure of the silver halide color photographic light-sensitive material (hereinafter sometimes abbreviated as "sensitive material"), the coating film pH of the photosensitive material, the scanning exposure, the preservative in the developing solution and the like. Those described in 1. can be preferably applied.

[0134]

[Table 4]

[0135]

[Table 5]

Cyan, magenta and yellow couplers which can be used in the present invention are described in JP-A-62-215.
No. 272, page 91, upper right column, line 4 to page 121, upper left column 6
Line 3, JP-A-2-33144, page 3, upper right column, line 14 to page 18, upper left column, end line and page 30, upper right column, line 6 to 3
Page 5, lower right column, line 11, EP0355,660A2, page 4, lines 15 to 27, page 5, lines 30 to 28, last line, page 45, lines 29 to 31 and page 47 Line 23 ~
Suitable examples thereof include couplers described on page 63, line 50 and the like. Preferable examples of the antibacterial and antifungal agents that can be used in the present invention include those described in JP-A-63-271247.

The total amount of silver coated in the silver halide color photographic light-sensitive material of the present invention (hereinafter sometimes referred to as "total coated silver amount") is 0.003 to 12 in terms of silver.
g / m ² is preferred. For transparent material of the color negative film or the like, wherein the total amount of coated silver is preferably ^{1~12g / m 2, 3~10g / m} 2 is more preferable. In the case of a reflective material such as color paper, the total coating silver amount is 0.003 to 1 g / in terms of rapid processing and low replenishment.
m ² is preferable, and the total coated silver amount in each layer in this case is 0.00 per one photosensitive silver halide emulsion layer.
1 to 0.4 g / m ² is preferable. When the silver halide color photographic light-sensitive material of the present invention is subjected to intensification processing, the total coating amount of silver is preferably 0.003 to 0.3 g / m ² , and 0.01 to 0.1 g / m ^2. Is more preferable, and 0.
015 to 0.05 g / m ² is particularly preferable. in this case,
0.001 to 0. 0 per photosensitive silver halide emulsion layer.
1 g / m ² is preferable, and 0.003 to 0.03 g / m ²
Is more preferred. If the total coated silver amount in each light-sensitive silver halide emulsion layer is less than 0.001 g / m ² , dissolution of the silver salt may proceed and a sufficient color density may not be obtained. Further, in the case of performing the intensification treatment, if it exceeds 0.1 g / m ² , Dmin increases or bubbles are generated, and it becomes difficult to endure the viewing.

The total amount of gelatin in the silver halide color photographic light-sensitive material of the present invention is 1.0 to 30 g / m ^2.
Is suitable and 2.0 to 20 g / m ² is preferable. pH
Regarding the swelling of the silver halide color photographic light-sensitive material of the present invention when the alkaline solution of No. 12 is used, as the time to reach the swelling film thickness of 1/2 of the saturated swelling film thickness (90% of the maximum swelling film thickness) Is preferably 15 seconds or less, more preferably 10 seconds or less. Also, the swelling ratio [(maximum swollen film thickness-film thickness)
/ [Film thickness x 100] is preferably 50 to 300%, particularly preferably 100 to 200%.

The silver halide color photographic light-sensitive material of the present invention can be suitably used not only in a printing system using a general negative printer but also in a scanning exposure system using a cathode ray (CRT). Scanning exposure using a cathode ray (CRT) can be performed using a cathode ray tube exposure apparatus, but the cathode ray tube exposure apparatus is simpler and smaller in size and lower in cost than an apparatus using a laser. It is also advantageous in that it is easy to adjust the optical axis and color. For the cathode ray tube used for image exposure, various light-emitting bodies that emit light in the spectral region, phosphors that emit light in the infrared region, and the like are used as necessary. For example, any one kind or a mixture of two or more kinds of a red light emitting body, a green light emitting body, a blue light emitting body, and a phosphor emitting light in an infrared region is used. In particular, a cathode ray tube which emits white light by mixing these light emitters is often used.
The spectral region is not limited to red, green and blue,
Yellow, orange and purple are also used.

When the silver halide color photographic light-sensitive material has a plurality of light-sensitive silver halide emulsion layers having different spectral sensitivity distributions, and the cathode ray tube also has a phosphor that emits light in a plurality of spectral regions, a plurality of light-sensitive silver halide emulsion layers are used. Colors may be exposed at once, that is, image signals of a plurality of colors may be input to the cathode ray tube to cause the tube surface to emit light. In the present invention, a method of sequentially inputting image signals for each color to sequentially emit light of each color and exposing through a film for cutting colors other than that color (plane sequential exposure) can be adopted. In case of sequential exposure,
It is advantageous in that a high resolution cathode ray tube can be used and high image quality can be achieved.

The silver halide color photographic light-sensitive material of the present invention comprises a gas laser, a light emitting diode, a semiconductor laser,
Alternatively, it is preferably used in a digital scanning exposure method using monochromatic high-density light such as a second harmonic generation (SHG) light source in which a solid-state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal are combined. A device using an SHG light source that is a combination of a semiconductor laser or a solid-state laser and a nonlinear optical crystal is preferable in that it is compact and inexpensive, and a semiconductor laser and a nonlinear optical crystal are combined in that it has a long life and high stability. Devices using SHG light sources are preferred. When such a scanning exposure light source is used, the spectral sensitivity maximum wavelength of the silver halide color photographic light-sensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source used. In the SHG light source,
Since the laser oscillation wavelength can be halved, blue light and green light can be obtained. Therefore, the maximum spectral sensitivity of the silver halide color photographic light-sensitive material can be provided in the usual three wavelength regions of blue, green and red. The exposure time in such scanning exposure is preferably 10 ^-4 seconds or less, and more preferably 10 ^-6 seconds or less, defined as the time for exposing the pixel size when the pixel density is 400 dpi. The lower limit of the exposure time is not particularly limited, but is about 10 ⁻⁸ seconds. Suitable examples of the scanning exposure method applicable to the present invention are described in detail in the publications shown in Table 5. In the present invention, scanning exposure in which there is an overlap between adjacent rasters is preferable.

Next, the materials and methods for color development (hereinafter sometimes simply referred to as "development") processing that can be used in the present invention will be described in detail. In the present invention,
The silver halide color photographic light-sensitive material is subjected to development (silver development / cross oxidation of built-in reducing agent), desilvering, and washing with water or stabilization. In addition, after the washing or stabilizing treatment, a treatment for enhancing color development by applying an alkali may be performed. When the silver halide color photographic light-sensitive material of the present invention is subjected to development processing, from the viewpoint of suppressing processing fluctuation, development processing is carried out using an alkaline solution (hereinafter referred to as "activator solution") substantially containing no developing agent. Is preferred.
Here, the "developing agent" is a compound that is oxidized by silver halide and means a color developing agent and an auxiliary developing agent described later. The term "substantially free of" means
The amount of the developing agent in the processing liquid is 1.5 mmol / liter or less, preferably 0.5 mmol / liter or less. The "alkaline solution" is different from the one used for the alkaline treatment after bleach-fixing and water washing (rinsing) used in the examples described later. The alkali treatment after the washing with water is difficult to dissociate the dye formed from the color-forming reducing agent of the present invention and the conventional coupler in the neutral (or acidic) state, so that a dye having a desired hue is obtained. Since it does not develop color, it is performed to dissociate this dye and change it to a dye having a desired hue.

The activator solution has a function as a developing agent for silver halide, and / or
In some cases, a compound having a function of cross-oxidizing a reducing agent for color formation contained in a silver halide color photographic light-sensitive material is used as an oxidized product of a developing agent generated in silver development. For the activator solution, compounds such as pyrazolidones, dihydroxybenzenes, reductones and aminophenols are preferably used, and pyrazolidones are particularly preferably used.

Further, in order to develop the silver halide color photographic light-sensitive material of the present invention, for example, JP-A-2-207 can be used.
250, page 26, lower right column, line 1 to page 34, upper right column, line 9, and JP-A-4-97355, page 5, upper left column 17
The materials and methods for the development processing described in line 20 to page 18, lower right column, line 20 can be preferably used. Further, as the preservatives that can be used in the development processing solution, the compounds described in the publications shown in Table 5 are preferable.

According to the silver halide color photographic light-sensitive material and the method for forming a color image of the present invention, a fixing bleaching step is not required, and the metallic silver remaining after the development processing is peeled from the transferred dye image using a peeling layer. Can be removed. Further, the peeling makes it possible to remove the unreacted color-forming reducing agent and the coupler at the same time, and suppress the stain generated from the unreacted color-forming reducing agent and the coupler after the development processing.

[0146]

Embodiments of the present invention will be described below. The present invention is not limited by these examples.

Example 1 A surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and the first layer shown below was further provided. Coating liquid ~
A sample (100) of a silver halide color photographic light-sensitive material having a photographic constituent layer formed by applying a third layer coating solution was prepared. -First layer coating liquid-Coupler (ExY1) 32 g, color-forming reducing agent (56) 2
0 g and 80 g of the solvent (Solv-1) were dissolved in ethyl acetate, and this solution was emulsified and dispersed in a 16% gelatin solution containing 10% sodium dodecylbenzenesulfonate and citric acid to prepare an emulsified dispersion A. On the other hand, silver chlorobromide emulsion A (cubic; 3: 7 mixture of large size emulsion A with average grain size 0.88 μm and small size emulsion A with 0.70 μm (silver molar ratio); coefficient of variation of grain size distribution is , 0.08 and 0.10, respectively; 0.3 mol% of silver bromide was added to each size emulsion in a part of the surface of the grain based on silver chloride as a polar agent). In this silver chlorobromide emulsion, the following blue-sensitive sensitizing dyes A, B, and C were used as spectral sensitizing dyes per mol of silver, and 1.4 × for each large-sized emulsion A.
10 ⁻⁴ mol, and 1.7 × 10 ⁻⁴ mol was added to the small-sized emulsion A, respectively. The chemical ripening of this silver chlorobromide emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer.

[0148]

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The emulsified dispersion A and the silver chlorobromide emulsion A were mixed and dissolved to prepare a coating solution for the first layer having the following composition. The second layer coating liquid and the third layer coating liquid were prepared in the same manner as the first layer coating liquid. 1-oxy-3,5 as a gelatin hardener in the first to third layers
-Dichloro-s-triazine sodium salt was used. Cpd-2 and Cpd- are included in each of the first to third layers.
3, Cpd-4 and Cpd-5, the total amount of each is 1
^{5.0mg / m 2, 60.0mg / m} 2, 50.0mg
/ M ² and 10.0 mg / m ² were added.
Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to the first layer in an amount of 3.0 × 10 ⁻³ mol per mol of silver halide.

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The coating amount of silver halide emulsion represents the coating amount in terms of silver. - support - [polyethylene of the first layer side contains a white pigment and (TiO ₂₎ and bluish dye (ultramarine)] Polyethylene laminated paper - first layer - silver chlorobromide emulsion A 0.20 Gelatin 1.50 Yellow Coupler (ExY1) 0.32 Coloring reducing agent (56) 0.20 Solvent (Solv-1) 0.80-Second layer-Gelatin 3.17 Surfactant (Cpd-1) 0.01-Third layer (Protective layer) -Gelatin 1.01 Polyvinyl alcohol acrylic modified copolymer (modification rate 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-1) 0.01

Sample (100) was prepared by replacing the yellow coupler (ExY1) and the color-forming reducing agent contained in the coating liquid for the first layer with the yellow coupler and the color-forming reducing agent shown in Table 6 in equimolar amounts. Samples (101) to (105) were prepared in the same manner as the preparation of (100). In the sample (100), the yellow coupler and the color-forming reducing agent contained in the coating solution for the first layer were replaced with the yellow coupler shown in Table 6 in an equimolar amount, and gelatin was used in the sample (1).
Sample (20) was prepared in the same manner as Sample (100) except that the mordant shown in Table 6 was added to the second layer coating solution so that 3.21 g / m ^{2 of the} same amount as that of Sample (00) was applied.
0) to (208) were produced. However, sample (200)
In (-208), 1,2-bis (vinylsulfonylacetamido) ethane was used as a gelatin hardener and (Cpd-6) was used as a surfactant.

Using the emulsified dispersion A and the silver chlorobromide emulsion A used in the sample (100), a sample (30
0) was prepared. Cp is added to each layer in the same way as the sample (100)
The total amount of d-2, Cpd-3, Cpd-4 and Cpd-5 was 15.0 mg / m ² and 60.0 mg / m ² , respectively.
m ² , 50.0 mg / m ² and 10.0 mg / m ² were added to give 1- (5-methylureidophenyl).
-5-Mercaptotetrazole was added in an amount of 3.0 × 10 ^-3 mol per mol of silver halide.

-Support-Polyethylene laminated paper [Polyethylene on the first layer side contains a white pigment (TiO ₂ ) and a bluish dye (ultraviolet)]-First layer (mordanting layer) -Gelatin 3.17 Mordanting agent (P -27) 3.21 Surfactant (Cpd-6) 0.01-Second Layer (Release Layer) -Release Polymer (Cpd-7) 0.05 Release Agent (Cpd-8) 0.03-Third Layer (Photosensitive layer) -Silver chlorobromide emulsion A 0.20 Gelatin 1.50 Yellow coupler (C-14) 0.32 Coloring reducing agent (56) 0.20 Solvent (Solv-1) 0.80-Fourth Layer (Barrier Layer) -Gelatin 0.107 Barrier Polymer (Cpd-9) 0.996 Surfactant (Cpd-6) 0.01

In the sample (300), the yellow coupler and the color-forming reducing agent contained in the coating solution for the third layer were replaced with the yellow coupler and the color-forming reducing agent shown in Tables 6 and 7 in equimolar amounts. , Same as sample (300),
Samples (301) to (308) were prepared. Sample (10
0), the silver chlorobromide emulsion A contained in the first layer coating solution
Was replaced with the silver chlorobromide emulsion B shown below in an equimolar amount, and the yellow coupler, the color-forming reducing agent and the mordant were replaced with the magenta coupler and the color-forming reducing agent shown in Table 8 in an equimolar amount. Outside, in the same manner as the preparation of the sample (100),
Samples (400) to (407) were prepared. Sample (10
0), the silver chlorobromide emulsion A in the coating solution for the first layer was replaced with the silver chlorobromide emulsion B shown below in an equal silver amount, and the yellow coupler and the color-forming reducing agent are shown in Table 8. The magenta coupler and the color-forming reducing agent are replaced with equimolar amounts, and the mordants shown in Tables 8 and 9 contained in the second layer coating solution are added.
Sample (50) was prepared in the same manner as in the preparation of sample (100) except that 3.21 g was added per 1 m ^2.
0) to (510) were produced. However, sample (500)
In (-510), 1,2-bis (vinylsulfonylacetamido) ethane was used as a gelatin hardener and (Cpd-6) was used as a surfactant.

Silver chlorobromide emulsion B (cubic; 1: 3 mixture of large size emulsion B having an average grain size of 0.55 μm and small size emulsion B having a grain size of 0.39 μm (Ag molar ratio); variation of grain size distribution) Coefficients were 0.10 and 0.08, respectively. In each size emulsion, 0.8 mol% of AgBr was contained in a part of the surface of the grain based on silver chloride. The following sensitizing dyes D, E and F were added to the silver chlorobromide emulsion B as spectral sensitizing dyes. Sensitizing dye D
Is 3.0 × 10 ⁻⁴ mol for large size emulsion and 3.6 for small size emulsion per mol of silver halide.
^{X10 -4} mol, sensitizing dye E is 4.0 × 10 ^-5 mol for large size emulsion and 7.0 × 10 ^-5 mol for small size emulsion per mol of silver halide , Sensitizing dye F
Is 2.0 × 10 ⁻⁴ mol for large size emulsion and 2.8 for small size emulsion per mol of silver halide.
× 10 ⁻⁴ mol was added.

[0156]

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In sample (300), silver chlorobromide emulsion A contained in the coating solution for the third layer was replaced with silver chlorobromide emulsion B in the same silver amount, and a yellow coupler, a color-forming reducing agent and a mordant were used. Was replaced with the magenta coupler and the color-forming reducing agent shown in Tables 8 and 9 in equimolar amounts.
Samples (600) to (610) in the same manner as in (0).
Was produced. In Sample (100), silver chlorobromide emulsion A contained in the coating liquid for the first layer was replaced with silver chlorobromide emulsion C shown below in an equal silver amount, and the yellow coupler and the reducing agent for color formation are shown in Table 10. Samples (700) to (705) were prepared in the same manner as the preparation of the sample (100) except that the cyan coupler and the color-forming reducing agent shown were replaced with equimolar amounts.

In Sample (100), the silver chlorobromide emulsion A contained in the coating solution for the first layer was replaced by the silver chlorobromide emulsion C shown below.
To the cyan coupler and the color-forming reducing agent shown in Table 10 in an equimolar amount, and the second layer is applied so that 3.21 g can be applied per 1 m ^2. Samples (800) to (808) were produced in the same manner as the sample (100) except that the mordant shown in Table 10 was added to the liquid. However, the sample (8
In (00) to (808), 1,2-bis (vinylsulfonylacetamido) ethane was used as a gelatin hardener and (Cpd-6) was used as a surfactant.

Silver chlorobromide emulsion C (cubic; 1: 4 mixture of large size emulsion C having an average grain size of 0.5 μm and small size emulsion having a grain size of 0.41 μm (Ag molar ratio); coefficient of variation of grain size distribution) 0.09 and 0.11; AgBr 0.8 mol% was added to each size emulsion to a portion of the surface of the grain based on silver chloride. To the silver chlorobromide emulsion C, the following spectral sensitizing dyes G and H are added as spectral sensitizing dyes. Spectral sensitizing dyes G, H
^Were added to the large-sized emulsion at 5.0 × 10 ⁻⁵ mol and the small-sized emulsion at 8.0 × 10 ⁻⁵ mol, respectively, per mol of silver halide.

[0160]

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In Sample (300), the silver chlorobromide emulsion A contained in the coating solution for the third layer was replaced with the silver chlorobromide emulsion C in the same silver amount, and the yellow coupler and the color-forming reducing agent were added in Table 10. And a sample (300) except that the cyan coupler, the color-forming reducing agent and the mordant shown in Table 11 were replaced by equimolar amounts.
Samples (900) to (908) were produced in the same manner as in.

[0162]

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[0163]

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[0164]

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[0165]

[Chemical 51]

[0166]

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[0167]

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Fuji Film Co .: FWH type sensitometer (color temperature of light source: 3200 ° K) was used to prepare a sample (10
0)-(105), (200)-(208) and (30)
Samples (400) to (407), (50) for (0) to (308) using a blue filter for sensitometry.
For 0) to (510) and (600) to (610), the sample (70
0) to (705), (800) to (808) and (90)
0) to (908) were each subjected to gradation exposure with a red filter for sensitometry. Samples (100) to (105), (200) to (208) after exposure,
With respect to (400) to (407), (700) to (705) and (800) to (808), the treatments 1 and 2 were performed using the following treatment liquids.

--Processing step 1-- Processing step temperature Time development 40 ° C. 30 seconds Bleach fixing 40 ° C. 45 seconds Rinse room temperature 45 seconds Alkaline treatment room temperature 30 seconds --- Processing step 2 --- Processing step temperature time development 40 ° C. 30 seconds Bleach-fixing 40 ℃ 45 seconds Rinse room temperature 45 seconds

Samples (300) to (308), (600)
About (610) and (900) to (908), after performing the treatments according to the following treatment steps 3 and 4, peeling is performed by the peeling layer according to the method described in US Pat. No. 5,164,280. went. --- Processing step 3-- Processing step temperature Time development 40 ° C. 30 seconds Rinse room temperature 45 seconds Alkaline processing room temperature 30 seconds Drying 80 ° C. 10 seconds --- Processing step 4 --- Processing step temperature time development 40 ° C. 30 seconds Rinse room temperature 45 seconds Drying 80 ℃ 10 seconds

<Development processing solution> Water 600 ml Potassium phosphate 40 g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 10 g KC1 5 g Hydroxyethylidene-1,1-diphosphonic acid (30%) 4 ml 1-phenyl- 4-Methyl-4-hydroxymethyl-3-pyrazolidone 2 g Water was added to 1000 ml pH (at 25 ° C./potassium hydroxide) 12 <bleach-fixing solution> Water 600 ml Ammonium thiosulfate (700 g / liter) 93 ml Ammonium sulfite 40 ml Ethylenediamine tetra Iron (III) acetate 55 g Ethylenediaminetetraacetic acid 2 g Nitric acid (67%) 30 g Water was added to 1000 ml pH (25 ° C./acetic acid and ammonia water) 5.8 <Rinse solution> Sodium chlorinated isocyanurate 2g deionized water (conductivity 5 [mu] S / cm or less) 1000ml pH 6.5 1000ml pH 10 by addition of <alkaline processing liquid> water 800ml potassium carbonate 30g water

The maximum color density portion of each sample after the development processing is determined by the samples (100) to (105) and (200) to (2).
08) and blue light for (300) to (308),
Samples (400) to (407), (500) to (510)
And (600) to (610) with green light, and samples (700) to (705), (800) to (808) and (900) to (908) with red light. did. The concentration of the sample processed in the processing steps 1 and 3 was set to “Da (max)”, and the concentration of the sample processed in the processing steps 2 and 4 was set to “Dn (max)”. The results are shown in Tables 6 to 7, Tables 8 to 9 and Tables 10 to 11, respectively. Samples (300) to (308), (60
For 0) to (610) and (900) to (908), the concentration on the peeled support side was measured.

In addition, unexposed and untreated samples (100) to
(105), (200)-(208), (400)-
(407), (500)-(510), (700)-
Two sheets each of (705) and (800) to (808) were prepared and desilvered in the above bleach-fixing step. Of these, samples (300) to (308), (600) to (61)
For 0) and (900) to (908), peeling was performed with the peeling layer. Further, with respect to these samples, one sample was subjected to alkali treatment with the above-mentioned alkali treatment solution, and the other sample was not subjected to alkali treatment.
A forced thermostat was conducted for 4 weeks at a temperature of 70 ° C and a humidity of 70%.
After the thermo test, the samples (100) to (10) for both the alkali-treated sample and the non-alkali-treated sample were tested.
5), (200) to (208) and (300) to (30)
8) blue light, samples (400) to (407),
Green light and blue light for (500) to (510) and (600) to (610), and samples (700) to (70).
5), (800) to (808) and (900) to (90)
For 8), it was measured with red light and blue light. The concentration of the alkali-treated sample was “Da (min)”, and the concentration of the sample not alkali-treated was “Dn (min)”. The results are shown in Tables 6-7, 8-9, and 10-11.

[0174]

[Table 6]

[0175]

[Table 7]

[0176]

[Table 8]

[0177]

[Table 9]

[0178]

[Table 10]

[0179]

[Table 11]

In the case of the silver halide color photographic light-sensitive material of the present invention, as the results of the above examples show, the metallic silver remaining after the development treatment on the silver halide color photographic light-sensitive material due to the peeling of the peeling layer. Can be removed.
Therefore, it is not necessary to perform the bleach-fixing step, it is not necessary to use the bleach-fixing solution, and it is not necessary to perform a complicated waste liquid treatment. Further, as is clear from the results of Tables 6 to 11, a sample using a reducing agent for color formation and a coupler for comparison and not using a mordant shows only a slight color unless the alkali treatment is carried out, but the alkali treatment is carried out. And the density of the unexposed area increases due to storage under heat and humidity conditions. On the other hand, in the case of a sample of a silver halide color photographic light-sensitive material using a color-forming reducing agent, a diffusible dye-forming coupler and a mordant in the present invention, a sufficient color-forming density can be obtained without alkali treatment, and It is clear that the color development of the unexposed area is suppressed under the condition that the treatment is not performed. However,
A slight amount of coloration is observed, and an increase in yellow stain is also observed. On the other hand, in the case of a sample of a silver halide color photographic light-sensitive material coated with a release layer, the reducing agent for color formation and the coupler for forming diffusible dye have not been removed after the release layer was released. It can be seen that the stain in the exposed area is extremely small, including the yellow stain. The stain of the unexposed portion simulates the stain of the light-sensitive material after the bleach-fixing process or after the peeling process, and the wet heat treatment.

Example 2 The surface of a paper support laminated on both sides with polyethylene was subjected to corona discharge treatment, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and the following first layer A sample (1100) of a silver halide color photographic light-sensitive material having a photographic constituent layer formed by coating a fourth layer was prepared. The coating liquid for the second layer was prepared in the same manner as the coating liquid for the first layer in Example 1. The first layer coating solution, the third layer coating solution and the fourth layer coating solution were also prepared in the same manner as the second layer coating solution. As the gelatin hardener in each of the first to fourth layers, 1-
Oxy-3,5-dichloro-s-triazine sodium salt was used. In addition, Cpd-2 and Cpd- are included in each layer.
3, Cpd-4 and Cpd-5, the total amount of each is 1
^{5.0mg / m 2, 60.0mg / m} 2, 50.0mg
/ M ² and 10.0 mg / m ² were added.
The blue sensitizing dyes A, B and C used in Example 1 were used for the silver chlorobromide emulsion contained in the coating solution for the second layer. Moreover, 1- (5-methylureidophenyl)-
5-Mercaptotetrazole was added in an amount of 3.0 × 10 ⁻³ mol per mol of silver halide.

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The coating amount of silver halide emulsion represents the coating amount in terms of silver. - support - [containing a white pigment in a polyethylene of the first layer side (TiO ₂₎ and bluish dye (ultramarine)] Polyethylene laminated paper - first layer - Gelatin 1.12 1,5-diphenyl-3-pyrazolidone 0 .02 (Solid dispersion of fine particles) -Second layer-Silver chlorobromide emulsion A 0.20 Gelatin 1.50 Yellow coupler (ExY1) 0.32 Color reducing agent (56) 0.20 Solvent (Solv-1) 0 80-Third layer-Gelatin 3.17 Surfactant (Cpd-1) 0.01-Fourth layer-Gelatin 1.01 Acrylic modified copolymer of polyvinyl alcohol (Degree of modification 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-1) 0.01

In the sample (1100), the yellow coupler and the color-forming reducing agent contained in the coating solution for the first layer are shown in Table 12.
Samples (1101) to (1105) were prepared in the same manner as the sample (1100) except that the yellow coupler and the color-forming reducing agent shown in (4) were replaced with equimolar amounts. Sample (110
In 0), the yellow coupler and the color-forming reducing agent contained in the coating solution for the first layer were replaced with the yellow coupler and the color-forming reducing agent shown in Table 12 in equimolar amounts, and 3.21 g was applied per 1 m ² . Samples (1200) to (1208) were prepared in the same manner as sample (1100) except that the mordant shown in Table 12 was added to the two-layer coating liquid. However, in Samples (1200) to (1208), 1,2-bis (vinylsulfonylacetamide) ethane was used as a gelatin hardener.

Using the emulsified dispersion A and the silver chlorobromide emulsion A used in the sample (1100), a sample (1300) having the following layer structure was prepared. In this sample (1300), as in the sample (1100), Cpd-
2, Cpd-3, Cpd-4 and Cpd-5, respectively, in a total amount of 15.0 mg / m ² , 60.0 mg / m ² , 5
0.0 mg / m ² and 10.0 mg / m ² so that 1- (5-methylureidophenyl) -5 was added.
-Mercaptotetrazole was added in an amount of 3.0 × 10 ^-3 mol per mol of silver halide.

(Layer constitution) -Support-Polyethylene laminated paper [Polyethylene on the first layer side contains a white pigment (TiO ₂ ) and a bluish dye (ultraviolet)]-First layer (mordanting layer) -Gelatin 3. 17 Mordant (P-27) 3.21 Surfactant (Cpd-6) 0.01-Second Layer (Release Layer) -Release Polymer (Cpd-7) 0.05 Release Agent (Cpd-8) 0.03 -Third layer-Silver chlorobromide emulsion A 0.20 Gelatin 1.50 Yellow coupler (ExY1) 0.32 Coloring reducing agent (56) 0.20 Solvent (Solv-1) 0.80-Fourth layer- Gelatin 1.12 1,5-Diphenyl-3-pyrazolidone 0.02-Fifth layer (barrier layer) -Gelatin 0.107 Barrier polymer (Cpd-9) 0.996 Surfactant (Cpd-6) 0.01

In the sample (1300), the yellow coupler and the color-forming reducing agent contained in the third layer coating solution are shown in Table 12.
Samples (1301) to (1308) were prepared in the same manner as sample (1300), except that the yellow coupler and the reducing agent for color development shown in Table 13 were replaced with equimolar amounts. In Sample (1100), silver chlorobromide emulsion A contained in the coating liquid for the first layer was replaced with silver chlorobromide emulsion B in an equal silver amount, and the coupler and the color-forming reducing agent were a magenta coupler shown in Table 14 and Samples (1400) to (14) were prepared in the same manner as sample (1100), except that the reducing agent for color formation was replaced with equimolar amount.
07) was prepared. In the sample (1100), the silver chlorobromide emulsion A contained in the coating solution for the first layer was replaced with the silver chlorobromide emulsion B.
By replacing the yellow coupler and the color-forming reducing agent by equimolar amounts with the magenta coupler and the color-forming reducing agent shown in Table 14, and the mordant shown in Table 14 so that 3.21 g can be applied per 1 m ^2. Sample (1500) was prepared in the same manner as sample (1100) except that it was added to the second layer coating solution.
(1510) were produced. However, sample (1500)
In (1510), as a gelatin hardener,
1,2-bis (vinylsulfonylacetamide) ethane was used and (Cpd-6) was used as the surfactant.

In Sample (1300), silver chlorobromide emulsion A contained in the coating solution for the third layer was replaced with silver chlorobromide emulsion B in the same silver amount, and couplers and color-forming reducing agents were used in Tables 14 and 15. Samples (1600) to (1610) were prepared in the same manner as the sample (1300) except that the magenta coupler, the color-forming reducing agent and the mordant shown in were replaced by equimolar amounts. In Sample (1100), the silver chlorobromide emulsion A contained in the coating solution for the first layer was replaced with the silver chlorobromide emulsion C in the same silver amount, and the coupler and the color-forming reducing agent were changed to cyan couplers shown in Table 16 and The sample (1
Samples (1700) to (170) in the same manner as 100).
5) was produced.

In Sample (1100), silver chlorobromide emulsion A contained in the coating solution for the first layer was replaced with silver chlorobromide emulsion C in the same silver amount, and the yellow coupler and the color-forming reducing agent are shown in Table 16. The same procedure as in Sample (1100) was carried out except that the cyan coupler and the color-forming reducing agent shown were replaced with equimolar amounts and the mordant shown in Table 16 was added to the second layer coating solution so that 3.21 g per m ² could be applied. , Samples (1800) to (18
08) was produced. However, samples (1800) to (18
For 08), 1,2-bis (vinylsulfonylacetamido) ethane was used as a gelatin hardening agent, and (Cpd-6) was used as a surfactant. In Sample (1300), silver chlorobromide emulsion A contained in the coating solution for the third layer was replaced with silver chlorobromide emulsion C in the same silver amount, and couplers, color-forming reducing agents and mordants were added in Tables 16 and 17. Sample (13) except that the cyan coupler and the reducing agent for color development shown in
00), samples (1900) to (1908)
Was produced.

Fuji Film Co., Ltd .: An FWH type sensitometer (color temperature of light source: 3200 ° K) was used to prepare a sample (11
00) to (1105), (1200) to (1208), and (1300) to (1308), using a blue filter for sensitometry, samples (1400) to (14).
07), (1500) to (1510) and (1600)
~ (1610) with a green filter for sensitometry, samples (1700) to (1705), (18
00) to (1808) and (1900) to (1908)
Was subjected to gradation exposure with a red filter for sensitometry. Sample after exposure (1100)
(1105), (1200) to (1208), (140
0) to (1407), (1500) to (1510),
(1700) to (1705) and (1800) to (18
For No. 08), treatments according to treatment steps 5 and 6 were performed using the following treatment liquids.

--- Processing step 5 --- Processing step temperature Time development 40 ° C. 30 seconds Bleach fixing 40 ° C. 45 seconds Rinse room temperature 45 seconds Alkaline treatment Room temperature 30 seconds --- Processing step 6 --Processing step temperature time development 40 ° C. 30 seconds Bleach-fixing 40 ℃ 45 seconds Rinse room temperature 45 seconds

Samples (1300) to (1308), (16
00) to (1610) and (1900) to (1908)
With respect to (1), after performing the following treatment steps 7 and 8, the peeling layer was used for peeling according to the method described in US Pat. No. 5,164,280. - process 7-- process Temperature Time development 40 ° C. 30 seconds Rinse room temperature 45 seconds alkali treatment at room temperature for 30 seconds Drying 80 ° C. 10 seconds - process 8-- process Temperature Time development 40 ° C. 30 seconds Rinse room temperature 45 seconds Drying 80 ℃ 10 seconds

<Development Processing Solution> Water 600 ml Potassium phosphate 40 g KC1 5 g Hydroxyethylidene-1,1-diphosphonic acid (30%) 4 ml Water was added to 1000 ml pH (at 25 ° C./potassium hydroxide) 12 Bleach-fixing solution For rinsing liquid and alkaline treatment liquid,
The same as used in Example 1 was used.

The color density portion of the sample after the development treatment was
Samples (1100) to (1105), (1200) to (1
208) and (1300) to (1308) with blue light, samples (1400) to (1407), (150).
0) to (1508) and (1600) to (1610) with green light, samples (1700) to (170).
5), (1800) to (1808) and (1900) to
(1908) was measured with red light. The concentration of the sample processed in the processing steps 5 and 7 was set to "Da (max)", and the concentration of the sample processed in the processing steps 6 and 8 was set to "Dn (max)". The results are shown in Tables 12 to 13, Tables 14 to 15, and Tables 16 to 1, respectively.
7 shows. Samples (1300) to (1308), (16
00) to (1610) and (1900) to (1908)
For, the concentration on the side of the peeled support was measured.

Moreover, unexposed and untreated sample (1100)
~ (1105), (1200) to (1208), (14
00) to (1407), (1500) to (1510),
(1700) to (1705) and (1800) to (18
No. 08) two samples each were prepared and desilvered in the bleach-fixing step. In addition, samples (1300) to (130
8), (1600) to (1610) and (1900) to
For (1908), peeling was performed using a peeling layer.
For each sample, one sheet was alkali-treated with the above-mentioned alkali treatment solution, and the other was not alkali-treated.
A weekly forced thermo test was conducted. After the thermo test, samples (1100) to (1105), (1200) for both alkali-treated and non-alkali-treated samples
~ (1208) and (1300) to (1308) with blue light, samples (1400) to (1407),
(1500) to (1510) and (1600) to (16)
For 10), the sample (170
0) to (1705), (1800) to (1808) and (1900) to (1908) were measured with red light and blue light, respectively. The concentration of the alkali-treated sample was “Da (min)”, and the concentration of the sample not alkali-treated was “Dn (min)”. The results are shown in Tables 12 to 13, Tables 14 to 15 and Tables 16 to 17.

[0195]

[Table 12]

[0196]

[Table 13]

[0197]

[Table 14]

[0198]

[Table 15]

[0199]

[Table 16]

[0200]

[Table 17]

From these results, 1,5-diphenyl-
It is clear that, when 3-pyrazolidone is contained in the sample, almost the same results as in Example 1 are obtained except that the coloring property is improved.

Example 3 Sample of Example 2 (1100)
~ (1105), (1200) to (1208), (13
00) to (1308), (1400) to (1407),
(1500) to (1510), (1600) to (161
0), (1700) to (1705), (1800) to
Silver silver chlorobromide emulsions A, B and C contained in the silver halide emulsion layers in (1808) and (1900) to (1908) were replaced with silver chlorobromide emulsions E, F and G shown below to form coated silver. 0.01 g and 0.01 g per 1 m ² respectively
And 0.015 g, but in the same manner as in Example 2,
A sample was prepared.

Silver chlorobromide emulsion D (cubic; 3: 7 mixture of large size emulsion D having p-uniform grain size 0.10 μm and small size emulsion D having 0.08 μm (Ag molar ratio); Coefficients of variation were 0.08 and 0.10, respectively. In each size emulsion, AgBr 0.3 mol% was contained in a part of the grain surface based on silver chloride). The chemical ripening of this silver chlorobromide emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer. The silver chlorobromide emulsion D contains
Blue-sensitive sensitizing dyes A, B and C used in Example 1
^Were added to the large-sized emulsion D in an amount of 7.0 × 10 ⁻⁴ mol and the small-sized emulsion D in an amount of 8.5 × 10 ⁻⁴ mol, respectively, per mol of silver halide.

Silver chlorobromide emulsion E (cubic; 1: 3 mixture of large size emulsion B having an average grain size of 0.10 μm and small size emulsion B having a grain size of 0.08 μm (Ag molar ratio); variation of grain size distribution) Coefficients were 0.10 and 0.08, respectively. In each size emulsion, 0.8 mol% of AgBr was contained in a part of the grain surface based on silver chloride). In the silver chlorobromide emulsion E, the green sensitizing dye D used in Example 1 was used in an amount of 1.5 × 10 ⁻³ mol for a large-sized emulsion, and a small-sized emulsion for a large-sized emulsion. For 1.
8 × 10 ^-3 mol, and green sensitizing dye E as silver halide 1
2.0 × 10 ⁻⁴ mol for a large-sized emulsion, 3.5 × 10 ⁻⁴ mol for a small-sized emulsion, and green sensitizing dye F per mol of a large amount of silver halide per mol. 1.0 × 10 ^-3 mol was added to the size emulsion and 1.4 × 10 ^-3 mol was added to the small size emulsion.

Silver chlorobromide emulsion F (cubic; 1: 4 mixture of large size emulsion C having an average grain size of 0.10 μm and small size emulsion of 0.08 μm (Ag molar ratio); coefficient of variation of grain size distribution Of 0.09 and 0.11, and AgBr 0.8 mol% was added to each size emulsion in a part of the surface of the grain based on silver chloride. For the silver chlorobromide emulsion F, the red sensitizing dyes G and H used in Example 1 were used.
^Were added to the large-sized emulsion in an amount of 2.5 × 10 ⁻⁴ mol and the small-sized emulsion in an amount of 4.0 × 10 ⁻⁴ mol, per mol of silver halide.

Using these samples, the pH obtained by adding hydrogen peroxide to the developing solution used in Example 2 was used as the developing solution.
Test and evaluation were conducted in the same manner as in Example 2 except that treatment was carried out using a 12.0 hydrogen peroxide 0.3% aqueous solution as an intensifying liquid, and the silver halide color was significantly reduced. Even when the photographic light-sensitive material was used, an image having a high maximum density was obtained as in Example 2. Further, in the silver halide color photographic light-sensitive material of the present invention, the increase in stain was significantly suppressed even under the forced thermostatting condition carried out in Example 3. It has been found that the silver halide color photographic light-sensitive material of the present invention is also suitable for amplified image formation by intensifying the silver halide color photographic light-sensitive material having a significantly reduced silver content.

Example 4 Using the sample of Example 2, the same treatment and evaluation as in Example 2 were carried out except that the following exposure was carried out. (Exposure) Semiconductor laser GaA1As (oscillation wavelength:
473 nm semiconductor laser GaA1As obtained by converting the wavelength of a YAG solid-state laser (oscillation wavelength: 946 nm) using 808.5 nm as an excitation light source by the KNb03 SHG crystal.
YVO ₄ with (oscillation wavelength: 808.7 nm) as excitation light source
A solid laser (oscillation wavelength: 1064 nm) was wavelength-converted by KTP SHG crystal and extracted at 532 nm, AlGaInP
(Oscillation wavelength: about 670 nm, Toshiba Corp .: Type No.TOL
D9211) was used. The laser light is an apparatus capable of sequentially performing scanning exposure on a silver halide color photographic light-sensitive material that moves in the direction perpendicular to the scanning direction by each rotating polyhedron. Using this apparatus, the amount of light was changed to determine the relationship D-logE between the density (D) and the amount of light (E) of the silver halide color photographic light-sensitive material. At this time, the laser light of three wavelengths was modulated in light quantity using an external modulator to control the exposure quantity. This scanning exposure is performed at 400 dpi, and the average exposure time per pixel at this time is about 5 × 1.
^0-8 seconds. The temperature of the semiconductor laser was kept constant by using a Peltier element in order to suppress fluctuations in light quantity due to temperature.

According to Example 4, an image having a high maximum density was obtained even in an image formed by high-illuminance digital exposure. In the silver halide color photographic light-sensitive material of the present invention, the increase in stain was significantly suppressed even under the forced thermostatic condition of Example 4. From the results of this Example 4,
It is clear that the silver halide color photographic light-sensitive material of the present invention is suitable for image formation by digital exposure with high illuminance.

[0209]

According to the present invention, the above-mentioned conventional problems can be solved. According to the present invention,
Excellent color development and hue, environmental protection, safety,
It is excellent in terms of simple and quick processing, does not require a bleach-fixing process, and can reduce the amount of development intensifying solution replenishment and discharge, and even when it is stored for a long time after color development processing, stains do not occur. It is possible to provide a silver halide color photographic light-sensitive material and a color image forming method which can be effectively suppressed.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location G03C 5/08 G03C 5/08 7/00 510 7/00 510 520 520 7/32 7/32 7 / 396 7/396 7/407 7/407

Claims (12)

[Claims] 1. A silver halide color photographic light-sensitive material comprising a support having thereon a photographic constituent layer having at least one photosensitive silver halide emulsion layer and at least one non-photosensitive layer. At least one color-forming reducing agent represented by the following general formula (I), a diffusible dye-forming coupler and a mordant are contained, and one layer of the non-photosensitive layer is a release layer. Silver halide color photographic light-sensitive material. General formula (I) In the formula, Cα represents a carbon atom. Z represents a carbamoyl group, an acyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. Q represents an atomic group forming an unsaturated ring by combining with Cα. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein Z in the general formula (I) is a carbamoyl group having at least one hydrogen atom on the nitrogen atom. 3. The silver halide color photographic light-sensitive material according to claim 1, wherein in the general formula (I), the unsaturated ring is a heterocycle. 4. In the general formula (I), the unsaturated ring is a benzene ring having at least one substituent, and the Hammett substituent constant σ value of the substituent (1,2 with respect to Cα is 1,2). Or a σp value is used for a substituent on a carbon atom having a relationship of 1,4, and a σm value is used for a substituent on a carbon atom having a relationship of 1,3 with respect to Cα). The silver halide color photographic light-sensitive material according to claim 1 or 2, which is 0.8. 5. The photosensitive silver halide emulsion layer is composed of three types of silver halide emulsion layers having different sensitivities, and the total coated silver amount is 0.003 to 12 g / m ^2. 4. A silver halide color photographic light-sensitive material according to any one of 4 above. 6. The silver halide color photograph according to claim 1, wherein the light-sensitive silver halide emulsion layer contains at least one reducing agent for color formation represented by formula (I). Photosensitive material. 7. The silver halide color photographic light-sensitive material according to claim 1, wherein the non-photosensitive layer contains at least one mordant. 8. The silver halide color photographic light-sensitive material according to claim 7, wherein the photographic constituent layer has a release layer between the silver halide emulsion layer and the layer containing a mordant. 9. The silver halide color photographic light-sensitive material according to claim 1, wherein the photographic constituent layer further has a barrier layer. 10. The total amount of coated silver is 0.003 to 0.3 g.
6. The silver halide color photographic light-sensitive material according to claim 5, which is / m ² . 11. A color characterized by exposing the silver halide color photographic light-sensitive material according to any one of claims 1 to 10 and then developing it with an alkali solution containing substantially no developing agent. Image forming method. 12. The exposure time is 10 pixels per pixel.
The color image forming method according to claim 11, wherein scanning exposure is performed for ^-8 to 10 ^-4 seconds and there is an overlap between adjacent rasters.