JPH11282140A - Method for forming color image by using silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color image forming method by using the silver halide color photographic sensitive material capable of matching simple and rapid and hue- improving processing not needing a desilvering process, and capable of developing color uniformly on the total faces of the photosensitive material by discharging a small amount of waste solution. SOLUTION: The silver halide color photographic sensitive material having at least one photographic constituent layer on a support is subjected to color development processing with an alkaline processing solution containing no color developing agent, and one of the constituent layers contains at leans one kind of dye forming coupler and a compound to be allowed to form a dye having absorption in the visible light wavelength region by coupling with an the oxidation product of a kind of coupler oxidized by a kind of silver halide or the precursor of the coupler. The total coated amount of silver of all the coating layers of the photosensitive material is 0.003-0.3, g/m<2> , and after the alkaline developing solution has been fed, a peroxide containing solution is supplied to the photosensitive material through plural nozzles by jetting droplets. The surface tension of the peroxide containing solution is rendered not higher by 10 dyne/cm<2> than that of the alkaline processing solution.

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 relates to a silver halide color photographic light-sensitive material which has good color development, storage stability, color image fastness and hue, can be processed quickly and can be processed without desilvering. A color image forming method that enables both “low waste liquid amount” and “reduction in processing fluctuation” by processing using a processing liquid application method that can apply a small amount of processing liquid uniformly and stably. .

[0002]

2. Description of the Related Art Generally, a color photographic light-sensitive material undergoes color development after exposure, whereby an oxidized p-phenylenediamine derivative and a coupler react to form an image. In this method, a color reproduction method based on a subtractive color method is used, and in order to reproduce blue, green, and red, yellow, magenta, and cyan color images having respective complementary colors are formed.

[0003] Color development is achieved by immersing the exposed color photographic light-sensitive material in an aqueous alkaline solution (color developer) containing a p-phenylenediamine derivative.

[0004] Oxidation of the p-phenylenediamine derivative is carried out by silver halide in the light-sensitive material, but silver in the light-sensitive material remains in the light-sensitive material as metallic silver after being developed. Metallic silver shows black color and lowers the purity of the dye image, so it is preferable to remove it from the photosensitive material. Conventionally, metallic silver has been bleached into silver ions, and fixed together with the undeveloped silver halide to remove from the photosensitive material. Since the bleach-fix solution for performing such bleach-fix contains a large amount of an inorganic salt such as iron, a chelating agent, and the like, disposal of the bleach-fix solution is a major problem. Also, in the case of a minilab or the like that performs dispersion processing, the apparatus is preferably small, but in order to perform this bleach-fixing step, a processing tank, a tank for storing the bleach-fix solution, and the like are required. It is one of the factors that hinders the development of the technology. As one of methods for eliminating such a bleach-fixing step, Journal of the Photographic Society of Japan, Vol. 51, No. 3, p. 191 (198)
8 years) and JP-B-61-48148, 63-20
No. 330, 63-20332, JP-A-3-1118
No. 44, etc., for example, a method of performing intensification treatment with hydrogen peroxide. Since the intensified processing forms an amplified image on the developed silver, the required image density can be obtained even when a photosensitive material whose silver content is significantly reduced is used. Therefore, the color contamination due to the metallic silver can be made negligible, and the need for bleach-fixing is eliminated.

When such an intensifying process is carried out, a p-phenylenediamine derivative which is oxidized by silver halide in a color developing solution and then coupled with a coupler to form a dye, and an intensifier for intensifying silver. An alkali which accelerates the reaction by dissociating a peroxide such as hydrogen oxide, a coupler or a p-phenylenediamine derivative is essential. However, when a p-phenylenediamine derivative and a peroxide such as hydrogen peroxide coexist, there is a problem that a peroxide such as hydrogen peroxide decomposes the p-phenylenediamine derivative. In addition, in an alkaline state, a problem arises in that peroxide such as hydrogen peroxide is easily decomposed itself.

In order to stabilize such an intensifying color developing solution, it is conceivable to remove the p-phenylenediamine derivative from the color developing solution.

[0007] When the p-phenylenediamine derivative is removed from the color developer, no color development occurs. As a method of solving such a problem, a method of incorporating a p-phenylenediamine derivative or a compound having a similar function into the light-sensitive material can be considered. p-
If a phenylenediamine derivative or a compound having a similar function is incorporated in the photosensitive material, it is not necessary to include the p-phenylenediamine derivative in the processing solution. As a method of incorporating a p-phenylenediamine derivative or a compound having a similar function into a photosensitive material, for example, there is a method of incorporating an aromatic primary amine or a precursor thereof into the photosensitive material. US Pat. Nos. 2,507,114, 3,763,328, and 406 as group-III primary amine developing agents or precursors thereof.
0418, JP-A-56-6235 and JP-A-58-192.
031, Japanese Patent Application No. 9-266793, and 9-2655
No. 68 and No. 9-265569, and the like. Among them, Japanese Patent Application Nos. 9-266793 and 9-2
Compounds that release an aromatic primary amine using a peroxide rearrangement reaction described in, for example, Nos. 65568 and 9-265569 are excellent in terms of achieving both storage stability and color development. Another effective means is disclosed in, for example, European Patent Nos. 0545491A1, 565165A1, JP-A-8-286340, JP-A-8-292529 and JP-A-8-292529.
-297354, 8-320542, 8-29
Hydrazine compounds described in U.S. Pat.
No.021240, Research Disclosure 1510
8 (November 1976) and the like, in which a stable color-forming reducing agent such as a sulfonamidophenol compound is incorporated in a hydrophilic colloid layer. These color-forming reducing agents are characterized by being excellent in storage stability and having high color-forming properties.

[0008] Even if the p-phenylenediamine derivative is removed from the intensifying color developing solution, an alkali and a peroxide such as hydrogen peroxide coexist in the intensifying color developing solution. The stability of peroxides such as hydrogen cannot be maintained. In order to solve this problem, it is conceivable to separately supply alkali and hydrogen peroxide into the photosensitive material. When supplying an alkali solution and a peroxide-containing solution in a normal tank treatment, there is a problem that the alkali solution supplied first is gradually brought into the peroxide-containing solution and the stability of the peroxide-containing solution is deteriorated. Occurs. Therefore, the latter peroxide-containing liquid which has come into contact with the photosensitive material cannot be used for a long time. Therefore, it is necessary to use up the peroxide-containing liquid, but there is a problem that a large amount of waste liquid is generated in the tank treatment.

[0009] To reduce the amount of liquid, see JP-A-63-235.
Nos. 940 and 64-26855 and JP-A-2-1186.
No. 33, No. 2-137784 and the like. If this method is used, it is possible to use up even a small amount of liquid.However, in order to make it equivalent to the case where replenishment processing is performed using a tank, the slit width must be several tens of microns, and the photosensitive material must be used. It is very difficult to pass between the slits. In contrast to these methods, a treatment in which a small amount of a processing solution is evenly applied to the surface of the photosensitive material is conceivable. Patent 26
No. 12205, etc., a method of applying with roller coat, felt cloth, sponge coat, etc.
No. 324455 and No. 9-17927. There is a method of spraying from a thin nozzle and spraying a processing liquid. Even when the processing liquid is applied to the surface of the photosensitive material, when the coating part of the coating device comes into contact with the photosensitive material, the coating part is gradually contaminated with alkali, peroxide is decomposed at the coating part, and the coating liquid is formed by bubbles. This causes problems such as uneven coating. Therefore, in order to apply the peroxide-containing liquid on the surface of the photosensitive material, it is necessary to use a method of applying the liquid on the photosensitive material in a non-contact manner.
The method of applying a treatment liquid using the treatment liquid application device described in No. 2 is effective.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to use a silver halide color photographic light-sensitive material which is good in color development, storage stability, color image fastness and hue, and which can be processed quickly and easily without desilvering. The present invention relates to a color image forming method capable of achieving both “low waste liquid amount” and “reduction in processing fluctuation” by performing processing using a processing liquid application method capable of applying a small amount of processing liquid uniformly and stably. An object of the present invention is to process a silver halide color photographic light-sensitive material with a small amount of a processing solution, and to form a color evenly to the edge of the light-sensitive material coated with the processing solution. It is an object of the present invention to provide a color image forming method which enables uniform color development to be exhibited over the entire surface of the image.

[0011]

SUMMARY OF THE INVENTION It has been found that the object of the present invention is achieved by the following method. (1) In a color image forming method, a silver halide color photographic light-sensitive material having at least one photographic constituent layer on a support is subjected to color development processing using an alkaline processing solution containing substantially no color developing agent. The silver halide photosensitive material is oxidized to at least one of the photographic constituent layers by at least one dye-forming coupler and at least one silver halide, and the oxidized product forms a dye having absorption in the visible region by coupling with the coupler. And the precursor thereof, and the total amount of silver in all coating layers of the light-sensitive material is 0.003 to 0.003 in terms of silver.
0.3 g / m ² , and after supplying the alkaline processing liquid onto the photosensitive material, the peroxide-containing liquid is supplied onto the photosensitive material by droplet ejection from a plurality of nozzle holes. The three droplets ejected from the nozzle holes and adhered to the photosensitive material adjacent to each other and attached to the photosensitive material in a state where there is no gap between the droplets. A color image forming method, wherein the surface tension of the peroxide-containing liquid is not more than 10 dyn / cm as compared with the surface tension of the alkaline processing liquid. (2) A compound which is oxidized by the silver halide and forms a dye having an absorption in the visible region by coupling the oxidized product with a coupler is represented by the following general formula (I) or (II). A color image forming method according to the above mode (1).

[0012]

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[0013]

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In the formula, R _{1 to} R ₄ represent a hydrogen atom or a substituent. A ₁ and A ₂ represent a hydroxyl group or a substituted amino group. X is -CO -, - SO -, - SO 2 -, it represents a divalent or higher linking group selected from -PO <. Y _1K and Z _1K represent a nitrogen atom or —CR ₅ ＝
(R ₅ is a hydrogen atom or a substituent). k
Represents an integer of 0 or more. P represents a proton-dissociable group or a group that can be a cation, and an oxidant generated by a redox reaction between the present compound and exposed silver halide is coupled with a coupler, and then the electron transfer from P is triggered. Has the function of forming a dye by cleavage of the NX bond and elimination of the substituent bonded to the coupling site of the coupler. Y represents a divalent linking group. Z is a nucleophilic group and represents a group capable of attacking X when the present compound is oxidized. n is 1 or 2 when X is -PO <, and 1 when X is another group. Two or more atoms or substituents arbitrarily selected from R ₁ and R ₂ , R ₃ and R _4, and Y _1K , Z _1K and P may be independently bonded to each other to form a ring. (3) A compound which is oxidized by the silver halide and forms a dye having an absorption in the visible region by coupling the oxidized product with a coupler is represented by the following general formula (III) ( The color image forming method according to the above item 1).

[0015]

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In the formula, R ¹¹ is an aryl group or a heterocyclic group which may have a substituent, and R ¹² is an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a hetero group which may have a substituent. It is a ring group. X ⁰ is -SO ₂ -, - C
O-, -COCO-, -CO-O-, -CONH
(R ¹³ )-, -COCO-O-, -COCO-N
(R ¹³ ) — or —SO ₂ —NH (R ¹³ ) —. Here, R ¹³ is a hydrogen atom or a group described for R ¹² . (4) The color image forming method according to item (3), wherein the compound represented by formula (III) is represented by formula (IV) or (V).

[0017]

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Wherein Z ¹ is an acyl group, a carbamoyl group,
Represents an alkoxycarbonyl group or an aryloxycarbonyl group, Z ² represents a carbamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group,
X ¹ , X ² , X ³ , X ⁴ and X ⁵ represent a hydrogen atom or a substituent. However, the sum of the Hammett's substituent constant σp value of X ¹ , X ³ and X ^{5 and} the Hammett's substituent constant σm value of X ² and X ⁴ is 0.08 or more and 3.80 or less. R ^3a represents a heterocyclic group. (5) The color image forming method as described in (4), wherein the compounds represented by the general formulas (IV) and (V) are represented by the general formulas (VI) and (VII), respectively.

[0019]

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In the formula, R ^1a and R ^2a represent a hydrogen atom or a substituent, and X ¹ , X ² , X ³ , X ⁴ and X ⁵ represent a hydrogen atom or a substituent. However, the sum of the Hammett's substituent constant σp value of X ¹ , X ³ and X ^{5 and} the Hammett's substituent constant σm of X ² and X ⁴ is 0.80 or more and 3.80 or less. R ^3a represents a heterocyclic group. (6) The color image forming method as described in (5), wherein the compounds represented by formulas (VI) and (VII) are represented by formulas (VIII) and (IX), respectively.

[0021]

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In the formula, R ^4a and R ^5a represent a hydrogen atom or a substituent, and one of R ^4a and R ^5a is a hydrogen atom;
X ⁶ , X ⁷ , X ⁸ , X ⁹ , and X ¹⁰ represent a hydrogen atom, a cyano group,
Represents a sulfonyl group, a sulfinyl group, a sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a trifluoromethyl group, a halogen atom, an acyloxy group, an acylthio group, or a heterocyclic group. However, the sum of the Hammett's substituent constant σp value of X ⁶ , X ⁸ and X ^{10 and} the Hammett's substituent constant σm value of X ⁷ and X ⁹ is 1.20 or more and 3.80 or less. Q ¹
Represents a non-metallic atomic group necessary for forming a nitrogen-containing 5- to 8-membered heterocyclic ring together with C. (7) A precursor of a compound which is oxidized by the silver halide and forms a dye having an absorption in the visible region when the oxidized product is coupled with a coupler is represented by the following general formula (X). (1) The color image forming method according to the above (1).

[0023]

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In the formula, Ar represents an aryl group or a heterocyclic group; X represents a methylene group in which a formyl group has been substituted at a position capable of releasing a color developing agent under an oxidizing action;
Represents a linking group, m represents an integer of 0 to 3, and PPD represents a color developing agent. (8) The color image forming method as described in (7), wherein the compound represented by the general formula (X) is represented by the general formula (XI).

[0025]

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In the formula, R represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an acyloxy group, an acylamino group, a sulfonylamino group,
Or, it represents another amino group, and in some cases, Rs may be connected to each other to form a ring. —CH ₂ — represents a methylene group located ortho or para to the formyl group, L represents a linking group, PPD represents a color developing agent, 1 represents an integer, and n represents an integer of 1 to 4. . (9) The method for forming a color image according to item (8), wherein the compound represented by formula (XI) is represented by formula (XII).

[0027]

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In the formula, R ¹ represents a hydrogen atom, an alkyl group, an aryl group, or an acyl group, and R has the same meaning as in formula (XI). —CH ₂ — represents a methylene group located ortho or para to the formyl group, PPD represents a color developing agent, and r represents an integer of 0 to 3.

(10) (1), (2), (3), (4), and (5), wherein the method of supplying the alkaline processing solution onto the photosensitive material is a method of applying by coating. ,
(6), (7), (8) or (9). (11) The method of supplying the alkaline processing liquid onto the photosensitive material is such that droplets are ejected from a plurality of nozzle holes, and three liquids ejected from these nozzle holes and attached to the photosensitive material are adjacent to each other. (10) The color image forming method according to the above (10), wherein the droplets are adhered to the photosensitive material while being in contact with each other without any gaps between the droplets. (12) The surface tension of the alkaline treatment liquid is 60 dyn /
cm or less, the color image forming method according to item (11). (13) (1), (2), (3), wherein the total amount of the alkaline processing solution and the peroxide-containing solution applied in the photosensitive material is 100 ml / m ² or less. (4),
(5), (6), (7), (8), (9), (10),
(11) The color image forming method according to the above (12). (14) (1), (2), (3), and (4), wherein the time from application of the alkaline treatment liquid to application of the peroxide-containing liquid is 10 seconds or less. , (5),
(6), (7), (8), (9), (10), (1)
The color image forming method according to the above (1), (12) or (13). (15) The peroxide-containing liquid is an aqueous hydrogen peroxide solution, (1), (2), (3), (4),
(5), (6), (7), (8), (9), (10),
The color image forming method according to (11), (12), (13) or (14). (16) An exposure time per pixel of 10 ^-8 to 10 ^-4 seconds, and exposure is performed by a scanning exposure having an overlap between adjacent rasters (1), (2), (3),
(4), (5), (6), (7), (8), (9),
(10), (11), (12), (13), (14),
(15) The color image forming method according to the above (16).

[0030]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention realizes an intensifying process which does not require bleaching. First time according to the present invention A system that does not require bleaching can be constructed. 2. The processing machine can be reduced in size. 3. Processing can be performed with a processing liquid that has little effect on the environment. 4. The amount of waste liquid is small. 5. A uniform image without unevenness can be formed. Image forming method can be provided.

In the present invention, "a compound or a precursor thereof which is oxidized by silver halide and forms a dye having an absorption in the visible region by coupling an oxidized form thereof to a coupler" (hereinafter referred to as a color developing compound) ) May be used as long as it has the function, and any compound including a known compound may be used. However, the following reducing agent for sulfonamide phenol type coloring, reducing agent for hydrazine type coloring, hydrogen peroxide A color developing agent precursor that releases an aromatic primary by a rearrangement reaction is preferred in that both storage stability and color forming properties are compatible.

Hereinafter, the present invention will be described in detail. The compounds represented by formulas (I) and (II) will be described in detail. An alkyl group (alkyl residue), an aryl group (aryl residue), an amino group (amino residue), and the like described below are used in the present specification to include those in which a substituent is further substituted. . The compounds represented by the general formulas (I) and (II) represent developing agents classified as aminophenol derivatives and phenylenediamine derivatives. In the formula, R _{1 to} R ₄ represent a hydrogen atom or a substituent, and examples of the substituent include a halogen atom (for example, a chloro group, a bromo group) and an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group). , N-butyl group, t-butyl group), aryl group (for example, phenyl group, tolyl group, xylyl group), carbonamide group (for example, acetylamino group, propionylamino group, butyroylamino group, benzoylamino group), sulfone Amido group (for example, methanesulfonylamino group, ethanesulfonylamino group, benzenesulfonylamino group, toluenesulfonylamino group), alkoxy group (for example, methoxy group,
An ethoxy group), an aryloxy group (eg, a phenoxy group), an alkylthio group (eg, a methylthio group, an ethylthio group, a butylthio group), an arylthio group (eg, a phenylthio group, a tolylthio group), a carbamoyl group (eg, a methylcarbamoyl group, a dimethylcarbamoyl group, Ethylcarbamoyl group, diethylcarbamoyl group, dibutylcarbamoyl group, piperidinocarbamoyl group, morpholinocarbamoyl group, phenylcarbamoyl group, methylphenylcarbamoyl group, ethylphenylcarbamoyl group,
Benzylphenylcarbamoyl group), sulfamoyl group (eg, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, dibutylsulfamoyl group, piperidinosulfamoyl group, morpholinosulfa Moyl group, phenylsulfamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group), cyano group, sulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group, phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbo group) Le group), an acyl group (e.g. acetyl group, propionyl group, butyloyl group, a benzoyl group, an alkyl benzoyl group), a ureido group (e.g., methylamino carbonamido group, a diethylamino carbonamido group), a urethane group (e.g., methoxy carbonamido group,
A butoxycarbonamide group) or an acyloxy group (eg, an acetyloxy group, a propionyloxy group, a butyroyloxy group). Among R _{1 to} R ₄ , R ₂
And / or R ₄ is preferably a hydrogen atom. When A ₁ or A ₂ is a hydroxyl group, the sum of Hammett constant σp values of R _{1 to} R ₄ is preferably 0 or more,
When A ₁ or A ₂ is a substituted amino group, the sum of Hammett constant σp values of R _{1 to} R ₄ is preferably 0 or less.

A ₁ and A ₂ represent a hydroxyl group or a substituted amino group (for example, dimethylamino group, diethylamino group, ethylhydroxyethylamino group), and A ₂ is preferably a hydroxyl group. X is -CO -, - SO -, - SO 2 -, - represents a bivalent or more linking group selected from the PO <. Y _1k and Z _1k represent a nitrogen atom or —CR ₅
= Represents a group represented by (R ₅ is a hydrogen atom or a substituent).
Here, as examples of R _5, mention may be made similarly like those exemplified as the substituents of R ₁ to R _4. P represents a proton-dissociable group or a group that can be a cation, and an oxidant generated by a redox reaction between the present compound and exposed silver halide is coupled with a coupler, and then the electron transfer from P is triggered. Has the function of forming a dye by cleavage of the NX bond and elimination of the substituent bonded to the coupling site of the coupler. Specifically, after the coupling reaction, electron transfer occurs from an unshared electron pair of an atom that can be a proton-dissociated anion or cation on P toward the coupling site, and the electron transfer between X and Y _1k (where k = 0) In some cases, a double bond is generated between X and P) to cause cleavage of the NX bond, and furthermore, a double bond is generated between the coupling site of the coupler and the N atom, and at the same time, substitution on the coupler side is performed. The group leaves as an anion. This series of electron transfer mechanisms results in the formation of a dye and the elimination of a substituent. Examples of the atom having such a function in P include an oxygen atom, a sulfur atom, a selenium atom, and a nitrogen atom or a carbon atom substituted by an electron-withdrawing group as the proton-dissociating atom. In addition, examples of atoms that can be cations include a nitrogen atom and a sulfur atom.

P is a group of substituents bonded to the above atom. Examples of the substituent bonded to this atom include an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, an n-butyl group, t-butyl group), aryl group (for example, phenyl group, tolyl group, xylyl group), carbonamido group (for example, acetylamino group, propionylamino group, butyroylamino group, benzoylamino group), sulfonamide group (for example, methanesulfonyl group) Amino group, ethanesulfonylamino group, benzenesulfonylamino group, toluenesulfonylamino group), alkoxy group (eg, methoxy group, ethoxy group), aryloxy group (eg, phenoxy group), alkylthio group (eg, methylthio group, ethylthio group, butylthio group) Group), an arylthio group (for example, phenylthio) Group, tolylthio group), carbamoyl group (for example, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, diethylcarbamoyl group, dibutylcarbamoyl group, piperidylcarbamoyl group, morpholylcarbamoyl group, phenylcarbamoyl group, methylphenylcarbamoyl group, ethylphenyl Carbamoyl group, benzylphenylcarbamoyl group), sulfamoyl group (for example, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, dibutylsulfamoyl group, piperidylsulfamoyl group, mol Holylsulfamoyl, phenylsulfamoyl, methylphenylsulfamoyl, ethylphenylsulfamoyl, benzylphenylsulfamoyl), shea Group, a sulfonyl group (e.g., methanesulfonyl group, ethanesulfonyl group,
Phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group), acyl group (for example, Acetyl group, propionyl group, butyroyl group,
Represents a benzoyl group, an alkylbenzoyl group), an acyloxy group (eg, an acetyloxy group, a propionyloxy group, a butyroyloxy group), a ureido group, a urethane group, or the like. Among them, preferred are an alkyl group, an aryl group and a heterocyclic group.

Z represents a nucleophilic group. After the present compound reduces the exposed silver halide, the resulting oxidized product is coupled with a coupler, and the nucleophilic group is converted to a carbon atom of X; A group having a function of forming a dye by nucleophilic attack on a sulfur atom or a phosphorus atom. In this nucleophilic group, nucleophilicity is expressed by an atom having an unshared electron pair (eg, a nitrogen atom, a phosphorus atom, an oxygen atom, a sulfur atom, a selenium atom), as is common in the field of organic chemistry. etc)
And anionic species (eg, nitrogen anion, oxygen anion, carbon anion, sulfur anion). Examples of the nucleophilic group include a group having a partial structure or a dissociated form thereof described in the following specific examples.

[0036]

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Specific examples of Z include those in which a hydrogen atom or a substituent described above as a substituent of P is bonded to one end of the above group. Y represents a divalent linking group. The term "linking group" refers to a group that links Z to a position that allows convenient nucleophilic attack on X via Y. In practice, it is preferable that the atoms are linked so that the transition state when the nucleophilic group makes a nucleophilic attack on X can constitute a 5- or 6-membered ring by the number of atoms. Preferred as such a linking group Y are, for example, a 1,2- or 1,3-alkylene group, a 1,2-cycloalkylene group, a 2-vinylene group, a 1,2-arylene group, a 1,8-naphthylene group And the like. k is preferably an integer of 0 to 5, and more preferably an integer of 0 to 2. R ₁ and R ₂ ,
R ₃ and R ₄ and 2 arbitrarily selected from Y _1k , Z _1k and P
One or more atoms or substituents may be independently bonded to each other to form a ring.

Next, specific examples of the compounds represented by the general formulas (I) and (II) are shown, but the compounds of the present invention are not limited thereto.

[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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The structure of the color-forming reducing agent represented by the general formula (III) will be described in detail below.

In the general formula (III), R ¹¹ represents an aryl group or a heterocyclic group which may have a substituent. The aryl group of R ^11, preferably that of 6 to 14 carbon atoms include, for example, phenyl or naphthyl. R ¹¹
As the heterocyclic group, preferably, nitrogen, oxygen, sulfur,
It is a saturated or unsaturated 5-, 6- or 7-membered ring containing at least one of selenium. These may be condensed with a benzene ring or a hetero ring. R
Examples of ¹¹ heterocycles are furanyl, thienyl, oxazolyl, thiazolyl, imidazolyl, triazolyl,
Pyrrolidinyl, benzoxazolyl, benzothiazolyl, pyridyl, pyridazyl, pyrimidinyl, pyrazinyl, triazinyl, quinolinyl, isoquinolinyl, phthalazinyl, quinoxalinyl, quinazolinyl, purinyl,
Pteridinyl, azepinyl, benzoxepinyl and the like.

Examples of the substituent of R ¹¹ include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group and a heterocyclic thio group. , Acyloxy group, acylthio group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, amino group, alkylamino group, arylamino group, amide group, alkoxycarbonylamino group An aryloxycarbonylamino group, a ureido group, a sulfonamide group, a sulfamoylamino group,
Acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, acylcarbamoyl group,
Carbamoylcarbamoyl group, sulfonylcarbamoyl group, sulfamoylcarbamoyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, alkoxysulfonyl group, aryloxysulfonyl group, sulfamoyl group,
Examples include acylsulfamoyl, carbamoylsulfamoyl, halogen, nitro, cyano, carboxyl, sulfo, phosphono, hydroxyl, mercapto, imide, and azo groups. R ¹² represents an optionally substituted alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group.

The alkyl group for R ¹² is preferably a linear, branched or cyclic C 1-16 alkyl group such as methyl, ethyl, hexyl, dodecyl, 2-octyl, t-butyl, cyclopentyl, cyclooctyl. And the like. The alkenyl group for R ¹² is preferably a chain or cyclic group having 2 to 16 carbon atoms, and includes, for example, vinyl, 1-octenyl and cyclohexenyl.

The alkynyl group for R ¹² preferably has 2 to 16 carbon atoms, such as 1-butynyl and phenylethynyl. As the aryl group and heterocyclic group for R ¹² , those described for R ¹¹ can be mentioned.
Examples of the substituent of R ¹² include those described for the substituent of R ¹¹ . X ⁰ is -SO _2- , -CO-,-
COCO -, - CO-O - , - CON (R 13) -, - C
OCO-O -, - COCO- N (R 13) - or -SO
₂ -N (R ¹³⁾ - and the like. Here, R ¹³ is a hydrogen atom or a group described for R ¹² . Of these groups, -CO
—, —CON (R ¹³ ) — and —CO—O— are preferable, and —CON (R ¹³ ) — is particularly preferable in that color developing properties are particularly excellent. Among the compounds represented by the general formula (III), the compounds represented by the general formulas (IV) and (V) are preferable, and the compounds represented by the general formulas (VI) and (VII) are more preferable. Compounds represented by (IX) are more preferred. The following formulas (IV) to (IX)
The compound represented by is described in detail.

In the general formulas (IV) and (V, Z
¹ represents an acyl group, a carbamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group, and Z ² represents a carbamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. The acyl group is preferably an acyl group having 1 to 50 carbon atoms, and more preferably 2 to 40 carbon atoms. Specific examples include acetyl, 2-methylpropanoyl, cyclohexylcarbonyl, n-octanoyl, 2-hexyldecanoyl, dodecanoyl, chloroacetyl, trifluoroacetyl, benzoyl, Dodecyloxybenzoyl group, 2-hydroxymethylbenzoyl group, 3
-(N-hydroxy-N-methylaminocarbonyl) propanoyl group. The case where Z ¹ and Z ² are carbamoyl groups will be described in detail by the general formulas (VIII) to (IX).

The alkoxycarbonyl group and the aryloxycarbonyl group are preferably an alkoxycarbonyl group and an aryloxycarbonyl group having 2 to 50 carbon atoms, more preferably 2 to 40 carbon atoms. Specific examples include a methoxycarbonyl group, an ethoxycarbonyl group,
Isobutyloxycarbonyl group, cyclohexyloxycarbonyl group, dodecyloxycarbonyl group, benzyloxycarbonyl group, phenoxycarbonyl group, 4-octyloxyphenoxycarbonyl group, 2-hydroxymethylphenoxycarbonyl group, 2-dodecyloxyphenoxycarbonyl group, and the like. Can be

X ¹ , X ² , X ³ , X ⁴ and X ⁵ represent a hydrogen atom or a substituent. Here, examples of the substituent include a linear or branched, chain or cyclic alkyl group having 1 to 50 carbon atoms (for example, trifluoromethyl, methyl, ethyl,
Propyl, heptafluoropropyl, isopropyl, butyl, t-butyl, t-pentyl, cyclopentyl, cyclohexyl, octyl, 2-ethylhexyl, dodecyl, etc.), linear or branched, chain or cyclic alkenyl group having 2 to 50 carbon atoms (Eg, vinyl, 1-methylvinyl, cyclohexen-1-yl, etc.), having 2 to 50 carbon atoms in total.
Alkynyl group (e.g., ethynyl, 1-propynyl, etc.), an aryl group having 6 to 50 carbon atoms (e.g., phenyl, naphthyl, anthryl, etc.), an acyloxy group having 1 to 50 carbon atoms (e.g.,

Acetoxy, tetradecanoyloxy, benzoyloxy, etc.), a carbamoyloxy group having 1 to 50 carbon atoms (eg, N, N-dimethylcarbamoyloxy), a carbonamide group having 1 to 50 carbon atoms (eg, formamide) , N-methylacetamide, acetamide,
N-methylformamide, benzamide, etc.), having 1 carbon atom
~ 50 sulfonamide groups (e.g., methanesulfonamide, dodecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, etc.);
Carbamoyl group (for example, N-methylcarbamoyl,
N, N-diethylcarbamoyl, N-mesylcarbamoyl, etc.), a sulfamoyl group having 0 to 50 carbon atoms (for example,
N-butylsulfamoyl, N, N-diethylsulfamoyl, N-methyl-N- (4-methoxyphenyl) sulfamoyl and the like, an alkoxy group having 1 to 50 carbon atoms (for example, methoxy, propoxy, isopropoxy, Octyloxy, t-octyloxy, dodecyloxy, 2-
(2,4-di-t-pentylphenoxy) ethoxy and the like), an aryloxy group having 6 to 50 carbon atoms (for example, phenoxy, 4-methoxyphenoxy, naphthoxy and the like),
An aryloxycarbonyl group having 7 to 50 carbon atoms (for example, phenoxycarbonyl, naphthoxycarbonyl, etc.),

An alkoxycarbonyl group having 2 to 50 carbon atoms (eg, methoxycarbonyl, t-butoxycarbonyl, etc.), an N-acylsulfamoyl group having 1 to 50 carbon atoms (eg, N-tetradecanoylsulfamoyl, N-
Benzoylsulfamoyl, etc.), an alkylsulfonyl group having 1 to 50 carbon atoms (eg, methanesulfonyl, octylsulfonyl, 2-methoxyethylsulfonyl, 2-hexyldecylsulfonyl, etc.), and an arylsulfonyl group having 6 to 50 carbon atoms (eg, Benzenesulfonyl, p-toluenesulfonyl, 4-phenylsulfonylphenylsulfonyl, etc.), an alkoxycarbonylamino group having 2 to 50 carbon atoms (eg, ethoxycarbonylamino, etc.), and an aryloxycarbonylamino group having 7 to 50 carbon atoms (eg, Phenoxycarbonylamino, naphthoxycarbonylamino, etc.), an amino group having 0 to 50 carbon atoms (eg, amino, methylamino, diethylamino, diisopropylamino, anilino, morpholino, etc.), cyano group, nitro group, carboxyl , A hydroxy group, a sulfo group, a mercapto group, etc.), an alkylsulfinyl group having 1 to 50 carbon atoms (eg, methanesulfinyl, octanesulfinyl, etc.), an arylsulfinyl group having 6 to 50 carbon atoms (eg, benzenesulfinyl, 4-chlorophenyl) Sulfinyl, p-toluenesulfinyl, etc.), having 1 to 5 carbon atoms
An alkylthio group of 0 (eg,

Methylthio, octylthio, cyclohexylthio, etc.), an arylthio group having 6 to 50 carbon atoms (eg, phenylthio, naphthylthio, etc.), 1 to 50 carbon atoms
Ureido group (eg, 3-methylureido, 3,3-
Dimethylureide, 1,3-diphenylureide, etc.),
A heterocyclic group having 2 to 50 carbon atoms (as a hetero atom, for example, a 3- to 12-membered monocyclic or condensed ring containing at least one or more of nitrogen, oxygen, sulfur and the like;
Furyl, 2-pyranyl, 2-pyridyl, 2-thienyl,
2-imidazolyl, morpholino, 2-quinolyl, 2-benzimidazolyl, 2-benzothiazolyl, 2-benzoxazolyl, etc.), an acyl group having 1 to 50 carbon atoms (eg, acetyl, benzoyl, trifluoroacetyl, etc.), carbon Sulfamoylamino groups of numbers 0 to 50 (e.g., N-butylsulfamoylamino, N-phenylsulfamoylamino, etc.), silyl groups of 3 to 50 carbon atoms (e.g., trimethylsilyl, dimethyl-t-butylsilyl, Triphenylsilyl and the like, and a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom and the like). The above substituents may further have a substituent,
Examples of the substituent include the substituents mentioned here. X ¹ , X ² , X ³ , X ⁴ and X ⁵ may be bonded to each other to form a condensed ring. The condensed ring is preferably a 5- to 7-membered ring, more preferably a 5- to 6-membered ring.

The number of carbon atoms of the substituent is preferably 50 or less, more preferably 42 or less, and most preferably 34 or less. Also, one or more is preferable.

In the general formula (IV), X ¹ , X ² , X ³ ,
Regarding X ⁴ and X ⁵ , the sum of Hammett's substituent constant σp value of X ¹ , X ³ and X ⁵ and Hammett's substituent constant σm value of X ² and X ⁴ is 0.80 or more and 3.80 or less. It is. X ⁶ , X ⁷ , X ⁸ , X ⁹ , and X ⁶ in the general formula (VIII)
X ¹⁰ is a hydrogen atom, a cyano group, a sulfonyl group, a sulfinyl group, a sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a trifluoromethyl group, a halogen atom, an acyloxy group, an acylthio group or a heterocyclic group Which may further have a substituent and may be bonded to each other to form a condensed ring. X ¹ ,
This is the same as that described for X ² , X ³ , X ⁴ , and X ⁵ . However, in the general formula (VIII), the sum of the Hammett's substituent constant σp value of X ⁶ , X ⁸ and X ^{10 and} the Hammett's substituent constant σm value of X ⁷ and X ⁹ is 1.20 or more and 3.80. Or less, preferably 1.50 or more and 3.80 or less, more preferably 1.70 or more and 3.80 or less. Where σ
If the sum of the p value and the σm value is less than 0.80, there is a problem such as insufficient color development. On the contrary, if it exceeds 3.80, it becomes difficult to synthesize and obtain the compound itself.

The Hammett's substituent constants σp and σm are described, for example, by Naoki Inamoto, “Hammet Rule—Structure and Reactivity—” (Maruzen), “New Experimental Chemistry Course 14, Synthesis and Reaction of Organic Compounds V” 2605. Page (Chemical Society of Japan, Maruzen), Tadao Nakaya, "Explanation of Theoretical Organic Chemistry", 217 pages (Tokyo Kagaku Dojin), Chemical Review (91), 165-195.
The book is described in detail in pages (1991).

R ¹ and R in the general formulas (VI) and (VII)
R ^4a and R ^5a in ² , (VIII) and (IX) represent a hydrogen atom or a substituent, and specific examples of the substituent include X ¹ and X
² , X ³ , X ⁴ and X ⁵ have the same meaning as described above, but are preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted alkyl group having 6 to 50 carbon atoms. And a substituted or unsubstituted heterocyclic group having 1 to 50 carbon atoms, more preferably R
^At least one of ^1a and R ^2a and at least one of R ^4a and R ^5a are a hydrogen atom.

In formulas (V) and (VII), R ^3a represents a heterocyclic group. The preferred heterocyclic group here has 1 to 1 carbon atoms.
50 heterocyclic groups, and the hetero atom is, for example,
It is a saturated or unsaturated 3- to 12-membered (preferably 3- to 8-membered) monocyclic or condensed ring containing at least one or more nitrogen, oxygen and sulfur atoms. , Pyran, pyridine, thiophene, imidazole, quinoline, benzimidazole, benzothiazole, benzoxazole, pyrimidine, pyrazine, 1,2,4-thiadiazole, pyrrole, oxazole, thiazole, quinazoline, isothiazole,
Pyridazine, indole, pyrazole, triazole,
Quinoxaline and the like. These heterocyclic groups may have a substituent, and preferably have at least one electron-withdrawing group. Here, the electron-withdrawing group means a group having a positive Hammett σp value. When the color-forming reducing agent of the present invention is incorporated in a light-sensitive material, it is preferable that at least one of Z ¹ , Z ² , R ^{1a to} R ^5a , and X ^{1 to} X ¹⁰ has a ballast group. .
Examples of the heterocycle completed by Q ₁ are specific compound examples I-
16-I-74.

Next, the color-forming reducing agent represented by the general formula (III) will be specifically described, but the scope of the present invention is not limited to these specific examples.

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In the present invention, the compound represented by the general formula (I) or (II)
And the compound represented by formula (III) can be used in the same photosensitive material. In this case, they may be added separately to different layers of the light-sensitive material,
It may be added to the same layer. The ratio of each compound used may be any ratio.

Next, the compound represented by formula (X) will be described in detail. In the general formula (X), Ar is a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. The aryl group preferably has 6 to 30 carbon atoms, and specific examples include a phenyl group and a naphthyl group. Further, the heterocyclic group is preferably a 3- to 8-membered ring having at least one oxygen atom, nitrogen atom or sulfur atom as a hetero atom in a ring-constituting atom, and condensed with another aromatic ring. And specific examples thereof include a 2-pyridyl group, a 2-furyl group, a 2-benzoxazolyl group, and a 2-thienyl group.
Particularly preferred as Ar is a phenyl group.

As the substituent for Ar, a hydroxyl group, a cyano group, a carboxyl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), preferably a linear or branched one having 1 to 60 carbon atoms. Alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, 2-ethylhexyl group, nonyl group,
Undecyl group, pentadecyl group, n-hexadecyl group,
3-decanamidopropyl group), preferably having 3 carbon atoms
~ 60 cycloalkyl groups (e.g., cyclopropyl groups,
1-ethylcyclopropyl group, cyclopentyl group, cyclohexyl group, etc.), preferably an aryl group having 6 to 30 carbon atoms (eg, phenyl group, naphthyl group, etc.), preferably a heterocyclic group having 2 to 60 carbon atoms (hetero atom Is a compound having at least one oxygen atom, nitrogen atom or sulfur atom, and is a 3- to 8-membered monocyclic or condensed ring,
2-pyridyl group, 2-furyl group, 2-benzoxazolyl group, 2-thienyl group, etc.), preferably having 1 to 60 carbon atoms
(E.g., methoxy, ethoxy, butoxy, n-octyloxy, hexadecyloxy, 2-methoxyethoxy, etc.), preferably 6 carbon atoms
To 60 aryloxy groups (for example, phenoxy group, 2,
4-t-amylphenoxy group, 4-t-butylphenoxy group, naphthoxy group and the like, preferably an acyloxy group having 6 to 60 carbon atoms (for example, benzoyloxy group, octanoyloxy group, 2-hexadecanoyloxy group) , 2-
(2 ′, 4′-di-t-amylphenoxy) butanoyloxy group and the like), preferably an acylamino group having 2 to 60 carbon atoms {for example, acetylamino group, n-butanoylamino group, octanoylamino group, 2-hexadecanoylamino group, 2- (2 ', 4'-di-t-amylphenoxy) butanoylamino group, benzoylamino group, nicotinoylamino group, etc., preferably sulfonylamino having 1 to 60 carbon atoms Group (for example, methanesulfonylamino group,
Phenylsulfonylamino group), preferably having no carbon
~ 60 other amino groups (e.g., unsubstituted amino groups,
Monoalkylamino group, dialkylamino group, arylamino group, alkylarylamino group, specifically, an unsubstituted amino group, diethylamino group, n-octylamino group, 3- (2 ′, 4′-di-t-amyl) Phenoxy) propylamino group, morpholino group and the like, preferably an alkylthio group having 1 to 60 carbon atoms (eg, methylthio group, ethylthio group, butylthio group, hexadecylthio group and the like),
Preferably an arylthio group having 6 to 60 carbon atoms (for example,
Phenylthio group, 4-dodecyloxyphenylthio group, etc.), preferably an acyl group having 1 to 60 carbon atoms (for example,
Acetyl group, benzoyl group, butanoyl group, dodecanoyl group, etc., preferably a sulfonyl group having 1 to 60 carbon atoms (for example, methanesulfonyl group, butanesulfonyl group,
Such as a toluenesulfonyl group), preferably having 2 to 60 carbon atoms.
An alkoxycarbonyl group (e.g., ethoxycarbonyl group, hexyloxycarbonyl group, dodecyloxycarbonyl group, etc.), preferably an aryloxycarbonyl group having 7 to 30 carbon atoms (e.g., phenoxycarbonyl group, naphthyloxycarbonyl group, etc.), A carbamoyl group having preferably 1 to 60 carbon atoms (for example, N, N-dicyclohexylcarbamoyl group and the like),
60 sulfamoyl groups (for example, N, N-dimethylsulfamoyl group and the like).

Among these substituents, a hydroxyl group, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group and a sulfonylamino group are preferred, and a hydroxyl group, an alkoxy group and a sulfonylamino group are particularly preferred. .

If possible, these substituents may be linked to each other to form a ring. These substituents may further have a substituent, if possible. As the substituent, the substituents listed as the substituents on the Ar group can be applied. Preferably, an alkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfonyl group, a sulfamoyl group, a cyano group,
It is a carboxyl group or a hydroxyl group, particularly preferably an alkyl group, an alkoxy group or an alkoxycarbonyl group.

At least one of the substituents on the Ar group preferably incorporates a ballast group commonly used in immobile photographic additives such as couplers. A ballast group is a group that is inert to photographic properties,
For example, an alkyl group having 8 or more carbon atoms, an alkoxy group, an aryl group, an aryloxy group, and
These groups can be selected from amide groups, ureido groups, sulfonamide groups, ester groups, sulfonyl groups, acyl groups and the like, and combinations of these groups with each other and with a hydroxyl group.

In the general formula (X), X is a substituted or unsubstituted methylene group, and examples of the substituent include the above-described substituents on the Ar group. When the Ar group is an aryl ring, the bonding position of X in Ar is ortho or para to the formyl group;
When the group is a heterocyclic ring, when the formyl group is at the 1-position, the formyl group is at the 2- or 4-position, and after the formyl group is converted into a hydroxyl group, the color developing agent (PPD) can be released by electron transfer. There is a positional relationship on the Ar group.

L represents a linking group and includes a known time adjusting group (timing group). For example, DE-A-28031
Described in No. 45

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A group is mentioned. In this group, (-
O) The atom is bonded to the releasing compound (OHC-Ar-X-), and the carbon atom is bonded to the hetero atom in the color developing agent (PPD) to link the emitting compound and the color developing agent. Further, as described in DE-A-2855697, a group which undergoes an intramolecular nucleophilic reaction when released from a color developing agent precursor of the general formula (X) to release the color developing agent, After the release from the color developing agent precursor of general formula (X), as described in DE-A-3105 026, electron transfer takes place along the conjugated system, leading to the release of the color developing agent. And the like. Also, L
Participates in a coupling reaction or a redox reaction by itself when released from the compound of the general formula (X),
A group capable of imagewise releasing PPD by a coupling reaction with a nucleophile imagewise released as a result of the reaction or an imagewise redox reaction with silver halide.

M represents an integer of 0 to 3, preferably 1 or 2.

PPD represents a color developing agent. As the color developing agent, a p-phenylenediamine derivative is preferable.
A preferable example is described in Japanese Patent Application Laid-Open No. 4-249244.
Page 23, left column, line 23 to right column, line 16;
No. 43, p. 4, right lower column, line 7 to page 6, line 20; p-phenylenediamine derivatives; preferred specific examples are N, N-diethyl-p-phenylenediamine, 4-
Amino-N, N-diethyl-3-methylaniline, 4-
Amino-N- (β-hydroxyethyl) -N-methylaniline, 4-amino-N-ethyl-N- (β-hydroxyethyl) aniline, 4-amino-N-ethyl-N-
(Β-hydroxyethyl) -3-methylaniline, 4-
Amino-N-ethyl-N- (3-hydroxypropyl)
-3-methylaniline, 4-amino-N-ethyl-N-
(4-hydroxybutyl) -1-methylaniline, 4-
Amino-N-ethyl-N- (β-methanesulfonamidoethyl) -3-methylaniline, 4-amino-N, N-
Diethyl-3- (β-hydroxyethyl) aniline, 4
-Amino-N-ethyl-N- (β-methoxyethyl)-
3-methylaniline, 4-amino-N- (β-ethoxyethyl) -N-ethyl-3-methylaniline, 4-amino-N- (3-carbamoylpropyl) -NN-propyl-3-methylaniline, 4-amino-N- (3-carbamoylbutyl) -NN-propyl-3-methylaniline, N- (4-amino-3-methylphenyl) -3
-Hydroxypyrrolidine, N- (4-amino-3-methylphenyl) -3- (hydroxymethyl) pyrrolidine,
N- (4-amino-3-methylphenyl) -3-pyrrolidinecarboxamide, and among the above p-phenylenediamine derivatives, preferably 4-amino-N-ethyl-N
-(Β-methanesulfonamidoethyl) -aniline, 4
-Amino-N-ethyl-N (β-hydroxyethyl)-
3-methylaniline, 4-amino-N-ethyl-N-
(3-hydroxypropyl) -3-methylaniline, and 4-amino-N-ethyl-N- (4-hydroxybutyl) -3-methylaniline.

A preferred compound among the compounds represented by the general formula (X) is represented by the general formula (XI). In the general formula (XI), L and PPD have the same meanings as in the general formula (X). As the group represented by R, the substituents listed for the substituent of the general formula (X) can be applied, and preferably, R is a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acylamino group. , Sulfonylamino group, other amino groups, particularly preferred groups are hydroxyl group, alkyl group, alkoxy group,
Acylamino group and other amino groups. -CH ₂ -
Represents a methylene group located at the ortho or para position of the formyl group, l represents an integer, and 0 or 1 is preferable. n represents an integer of 1 to 4, and 1 or 2 is preferable.

Preferred compounds among the compounds represented by formula (XI) are represented by formula (XII). In the general formula (XII), R ¹ represents an alkyl group, an aryl group, or an acyl group, R and PPD have the same meanings as in the general formula (XI),
Represents an integer of 0 to 2. —CH ₂ — represents a methylene group located at the ortho or para position of the formyl group.

Specific examples of the compound included in the general formula (X) of the present invention are shown below, but the present invention is not limited thereto.

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As couplers preferably used in the present invention, there are compounds having structures represented by the following general formulas (1) to (12). These are compounds generally referred to as active methylene, pyrazolone, pyrazoloazole, phenol, naphthol, and pyrrolotriazole, respectively, and are compounds known in the art.

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Formulas (1) to (4) represent couplers referred to as active methylene couplers, wherein R ¹⁴ represents an optionally substituted acyl group, cyano group, nitro group, aryl group, A heterocyclic residue, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, and an arylsulfonyl group.

In the general formulas (1) to (3), R ¹⁵ is an optionally substituted alkyl group, aryl group or heterocyclic residue. In the general formula (4), R ¹⁶ is an aryl group or a heterocyclic residue which may have a substituent. R
^14, as the R ^15, the substituent that may be R ¹⁶ has, include those mentioned as examples of X ¹ to X ⁵ as described above.

In the general formulas (1) to (4), Y is a hydrogen atom or a group which can be eliminated by a coupling reaction with an oxidized form of a color-forming reducing agent. Examples of Y include a heterocyclic group (a heterocyclic atom is a saturated or unsaturated monocyclic or condensed 5- to 7-membered ring containing at least one nitrogen, oxygen, sulfur or the like, and examples thereof include succinimide and maleic Imide, phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, benzopyrazole, benzimidazole, benzotriazole, imidazoline-2,4-dione, oxazolidin-2,4-dione , Thiazolidine-2,4-dione, imidazolidine-2-one, oxazolin-2-one, thiazoline-2
-One, benzimidazolin-2-one, benzoxazolin-2-one, benzothiazolin-2-one, 2-
Pyrrolin-5-one, 2-imidazolin-5-one, indoline-2,3-dione, 2,6-dioxypurine,
Parabanic acid, 1,2,4-triazolidine-3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone,
6-pyridazone, 2-pyrazone, 2-amino-1,3,
4-thiazolidine, 2-imino-1,3,4-thiazolidine-4-one, etc.), halogen atom (eg, chlorine atom, bromine atom, etc.), aryloxy group (eg, phenoxy, 1-naphthoxy, etc.), hetero A ring oxy group (eg, pyridyloxy, pyrazolyloxy, etc.), an acyloxy group (eg, acetoxy, benzoyloxy, etc.),
Alkoxy group (eg, methoxy, dodecyloxy, etc.), carbamoyloxy group (eg, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, etc.), aryloxycarbonyloxy group (eg, phenoxycarbonyloxy, etc.), alkoxycarbonyloxy group (Eg, methoxycarbonyloxy, ethoxycarbonyloxy, etc.), arylthio groups (eg, phenylthio, naphthylthio, etc.), heterocyclic thio groups (eg, tetrazolylthio, 1,3,4-thiadiazolylthio, 1,3,4- Oxadiazolylthio, benzimidazolylthio, etc.), alkylthio group (eg, methylthio, octylthio, hexadecylthio, etc.), alkylsulfonyloxy group (eg, methanesulfonyloxy, etc.), arylsulfonyloxy Groups (eg, benzenesulfonyloxy, toluenesulfonyloxy, etc.), carbonamide groups (eg, acetamide, trifluoroacetamide, etc.), sulfonamide groups (eg, methanesulfonamide, benzenesulfonamide, etc.), alkylsulfonyl groups (eg, , Methanesulfonyl, etc.), an arylsulfonyl group (eg, benzenesulfonyl, etc.), an alkylsulfinyl group (eg, methanesulfinyl, etc.), an arylsulfinyl group (eg, benzenesulfinyl, etc.), an arylazo group (eg, phenylazo, naphthylazo, etc.), A carbamoylamino group (for example, N-methylcarbamoylamino and the like);

Y may be substituted by a substituent,
Examples of the substituent for substituting Y include those described for X ^{1 to} X ⁵ . Y is preferably a halogen atom, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an aryloxycarbonyloxy group, an alkoxycarbonyloxy group, or a carbamoyloxy group. General formula (1)
In (4), R ¹⁴ and R ¹⁵ , and R ¹⁴ and R ¹⁶ may be bonded to each other to form a ring. Formula (5) represents a coupler called a 5-pyrazolone-based coupler, wherein R ¹⁷ represents an alkyl group, an aryl group, an acyl group, or a carbamoyl group. 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.

In the 5-pyrazolone coupler represented by the general formula (5), R ¹⁷ is an aryl group or an acyl group,
A phenyl group in which ¹⁸ is substituted with one or more halogen atoms is preferred. To describe these preferred groups in detail, R ¹⁷ is a phenyl group, a 2-chlorophenyl group, a 2-
Methoxyphenyl group, 2-chloro-5-tetradecanamidophenyl group, 2-chloro-5- (3-octadecenyl-1-succinimido) phenyl group, 2-chloro-5
An aryl group such as -octadecylsulfonamidophenyl group or 2-chloro-5- [2- (4-hydroxy-3-t-butylphenoxy) tetradecanamido] phenyl group or an acetyl group, 2- (2,4-di- t-pentylphenoxy) butanoyl group, benzoyl group, 3-
(2,4-di-t-amylphenoxyacetamido) is an acyl group such as a benzoyl group, and these groups may further have a substituent, and these groups may be a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. It is a connecting organic substituent or a halogen atom. Y has the same meaning as described above.

R ¹⁸ is preferably a substituted phenyl group such as a 2,4,6-trichlorophenyl group, a 2,5-dichlorophenyl group and a 2-chlorophenyl group. The general formula (6) represents a coupler called a pyrazoloazole coupler, wherein R ¹⁹ represents a hydrogen atom or a substituent. Q ³ represents a group of nonmetallic atoms necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). Among the pyrazoloazole couplers represented by the general formula (6), imidazo [1,2-b] pyrazoles described in U.S. Pat. U.S. Patent No. 4,
No. 500,654, pyrazolo [1,5-b]-
1,2,4-triazoles, U.S. Pat.
No. 067, pyrazolo [5,1-c] -1,2,4
-Triazoles are preferred.

For details of the azole ring substituents represented by the substituents R ¹⁹ and Q ³ , see, for example, US Pat.
No. 0,654, column 2, line 41 to column 8, line 27. Preferably, JP-A-61-
No. 65245, a pyrazoloazole coupler having a branched alkyl group directly bonded to the 2, 3 or 6-position of the pyrazolotriazole group, and a sulfonamide group in the molecule described in JP-A-61-65245. A pyrazoloazole coupler having an alkoxyphenylsulfonamide ballast group described in JP-A-61-147254;
Pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position described in JP-A-209457 or JP-A-63-307453;
No. 201443 is a pyrazolotriazole coupler having a carboxamide group in the molecule. Y has the same meaning as described above.

The general formulas (7) and (8) are couplers called phenol couplers and naphthol couplers, respectively, wherein R ²⁰ is a hydrogen atom or —CONR ²² R
_{^{23, -SO 2 NR 22 R 23}} , -NHCOR 22, -NHCO
NR ²² R ^23, represents a group selected from -NHSO ₂ NR ²² R ^23. R ²² and R ²³ represent a hydrogen atom or a substituent. In the general formulas (7) and (8), R ²¹ represents a substituent, 1 represents an integer selected from 0 to 2, and 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 the substituent of R ^{21 to} R ²³ include those described as examples of X ^{1 to} X ^{5 in} the general formulas (II) and (IV). Y has the same meaning as described above.

Preferred examples of the phenolic coupler represented by the general formula (7) include US Pat. No. 2,369,9.
No. 29, No. 2,801,171, No. 2,772
No. 162, No. 2,895,826, No. 3,77
2,002 and the like, 2-acylamino-5-alkylphenols, U.S. Pat. Nos. 2,772,162, 3,758,308, 4,126,396;
Nos. 4,334,011, 4,327,173
No. 3,329,729, West German Patent Publication No.
2,166-9656, 2,5-diacylaminophenol, U.S. Pat. Nos. 3,446,622, 4,333,999, 4,451,559, and 4,427, No. 767, etc., and 2-phenylureido-5-acylaminophenols. Y is the same as described above.

The naphthol coupler represented by the general formula (8)
Preferable examples of US Pat. No. 2,474,29
No. 3, 4,052, 212 and 4,146, 3
No. 96, No. 4,282,233, No. 4,296,
2-carbamoyl-1-naphthol described in No. 200, etc.
And 2 described in U.S. Pat. No. 4,690,889.
-Carbamoyl-5-amido-1-naphthols and the like.
I can do it. Y is the same as above
is there. General formulas (9) to (12) represent pyrrolotriazole
Is a coupler called R ³², R³³, R³⁴Is a hydrogen atom
Or a substituent. Y is as described above.
You. R³², R³³, R³⁴Is a substituent of the aforementioned X¹ ~ X
^Five Are mentioned as examples. General formula (9)
Preferred are pyrrolotriazole couplers represented by (12).
A good example is EP 488,248 A1,
No. 491,197A1 and No. 545,300
R³², R³³At least one is an electron-withdrawing group
Couplers. Same as above for Y
The same. In addition, fused phenol, imidazole,
Roll, 3-hydroxypyridine, other active methyl
Ren, active methine, 5,5-fused heterocycle, 5,6-fused ring
A coupler having a structure such as a heterocyclic ring can be used.

Examples of the fused phenol couplers include US Pat. Nos. 4,327,173 and 4,564,586.
And the couplers described in JP-A Nos. 4,904,575 and the like can be used. As the imidazole coupler, couplers described in U.S. Pat. Nos. 4,818,672 and 5,051,347 can be used. As the 3-hydroxypyridine-based coupler, couplers described in JP-A-1-315736 and the like can be used.

As active methylene and active methine couplers, US Pat. Nos. 5,104,783 and 5,16
The couplers described in 2,196 and the like can be used. 5,5
-As a fused heterocyclic coupler, US Pat.
Pyrrolopyrazole couplers described in JP-A-4,289, and pyrroleimidazole couplers described in JP-A-4-174429 can be used. Examples of 5,6-fused heterocyclic couplers include pyrazolopyrimidine couplers described in U.S. Pat. No. 4,950,585 and JP-A-4-20473.
No. 0, pyrrolotriazine couplers described in EP-A-556700, and the like can be used.

In the present invention, in addition to the couplers described above, West German Patent Nos. 3,819,051A and 3,823,049.
No. 4,840,883, US Pat.
No. 4,930, No. 5,051,347, No. 4,4
No. 81,268, European Patent Nos. 304,856A2, 329,036, 354,549A2, 374,781A2, 379,110A2, 386,930A1, 63-141055
Nos. 64-32260, 64-32261, JP-A-2-29747, JP-A-2-44340, and 2-
No. 110555, No. 3-7938, No. 3-16044
No. 0, No. 3-172839, No. 4-17247,
4-179949, 4-182645, 4-
Nos. 184437, 4-188138, 4-188
No. 139, No. 4-194847, No. 4-204532
And the couplers described in JP-A Nos. 4-207473 and 4-204732 can also be used. Specific examples of the coupler that can be used in the present invention are shown below, but the present invention is of course not limited thereto.

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The color developing compound used in the present invention is used in an amount of 0.01 to 0.01% per color forming layer in order to obtain a sufficient color forming density.
It is preferred to use 10 mmol / m ² . A more preferred amount is 0.05 to 5 mmol / m ² , and a particularly preferred amount is 0.1 to 1 mmol / m ² . This range is preferred in that a sufficient color density can be obtained. The amount of the coupler in the color-forming layer in which the color-developing compound used in the present invention is used is preferably 0.05 to 0.05 mol in terms of mol with respect to the color-developing compound.
It is 20 times, more preferably 0.1 to 10 times, particularly preferably 0.2 to 5 times. This range is preferred in that a sufficient color density can be obtained.

The color light-sensitive material used in the present invention is basically formed by coating a support with a photographic constituent layer composed of at least one hydrophilic colloid layer. Contains silver, a coupler for forming a dye, and a color developing compound. The most typical embodiment is to add the dye-forming coupler and the color developing compound to the same layer, but they can be separately added to another layer if they can react. These components are preferably added to a silver halide emulsion layer or a layer adjacent to the silver halide emulsion layer in the light-sensitive material, and particularly preferably added to a silver halide emulsion layer. The total coated silver amount of the sum of the amount of silver in the coating layer of the silver halide color photographic material to be processed in the present invention is in terms of silver, a 0.003~0.3g / m ^2, each of the layers of silver coated The amount is 0.001 per photosensitive layer
0.1 g is preferred. The total coated silver amount is preferably 0.01
0.1 g / m ² , more preferably 0.015 to 0.0
5 g / m ² . In the present invention, in order to reduce color contamination and the like of a color image as much as possible because bleach-fixing does not need to be performed, the smaller the coated silver amount, the better,
The amount of silver applied to each photosensitive layer is 0.001 / m ²
If the amount is less than 0.1 g, the dissolution of the silver salt proceeds, and it becomes difficult to obtain a sufficient color density, and if the intensification exceeds 0.1 g, the processing stain increases and bubbles are easily generated.

The color developing compound and coupler of the present invention can be introduced into a light-sensitive material by various known dispersion methods, dissolved in a high-boiling organic solvent (optionally using a low-boiling organic solvent in combination), and emulsified and dispersed in an aqueous gelatin solution. The oil-in-water dispersion method in which the silver halide emulsion is added to a silver halide emulsion is preferred. The high boiling organic solvent that can be used in the present invention has a melting point of 100 ° C. or less and a boiling point of 140 ° C.
Any compound that is immiscible with water at a temperature of not less than ° C and is a good solvent for the color developing compound and coupler can be used. The melting point of the high boiling organic solvent is preferably 80 ° C. or lower. The boiling point of the high boiling organic solvent is preferably 160 ° C. or higher, more preferably 170 ° C. or higher. Details of these high-boiling organic solvents are described in JP-A-62-215272, page 137, lower right column to page 144, upper right column. The high boiling organic solvent used in the present invention has an electron donating parameter ΔV of 80 as described in JP-A-8-320542 in that a dye formed from a color developing compound and a coupler can be dissociated from a low pH. It is preferable to use the above-mentioned high boiling point organic solvent. In the present invention,
When the high boiling organic solvent is used, the amount of the high boiling organic solvent may be any amount, but preferably, the ratio of the high boiling organic solvent / color developing compound to the color developing compound by weight is 20 or less. Is preferable, 0.02 to 5 is more preferable, and 0.2 to 4 is particularly preferable. In the present invention, a known polymer dispersion method may be used. The steps and effects of the latex dispersion method as one of the polymer dispersion methods and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) 2,541,274, and US Pat. No. 2,541,230, Japanese Patent Publication No. 53-41091, European Patent Publication No. 029104, and the like. Also, a dispersion method using a water-insoluble and organic solvent-soluble polymer is described in PCT International Publication No. WO88 / 00723. It is described in.

The average particle size of the lipophilic fine particles containing the color-developing compound of the present invention is not particularly limited, but is preferably from 0.05 to 0.3 μm from the viewpoint of color-forming properties. Further, the thickness is more preferably 0.05 μm to 0.2 μm.

In general, in order to reduce the average particle size of the lipophilic fine particles, it is necessary to select the type of surfactant, increase the amount of the surfactant used, increase the viscosity of the hydrophilic colloid solution, This can be achieved by lowering the viscosity of the organic layer by using a low-boiling organic solvent in combination, increasing the shearing force such as increasing the rotation of the stirring blades of the emulsifier, or increasing the emulsification time. The particle size of the lipophilic fine particles can be measured by, for example, a device such as Nanosizer manufactured by Coulter, UK.

In the present invention, when the dye formed from the color developing compound and the dye-forming coupler is a diffusible dye, it is preferable to add a mordant to the light-sensitive material. When the present invention is applied to such a form, it is not necessary to immerse in an alkali to form a color, and therefore, the image stability after the processing is remarkably improved. The mordant may be used in any layer, but when added to the layer containing the color developing compound of the present invention, the stability of the color developing compound is deteriorated. Is preferably used. Further, the dye formed from the color developing compound and the coupler diffuses in the swollen gelatin film during processing and dyes it with a mordant. Therefore, it is preferable that the diffusion distance is short in order to obtain good sharpness. Therefore, the layer to which the mordant is added is preferably added to the layer adjacent to the layer containing the color developing compound. Also, since the color developing compound of the present invention and the dye formed from the coupler of the present invention are water-soluble dyes,
It may flow out into the processing solution. Therefore, the layer to which the mordant is added to prevent this is preferably on the side opposite to the support with respect to the layer containing the color developing compound. However, when a barrier layer as described in JP-A-7-168335 is provided on the side opposite to the support with respect to the layer to which the mordant is added, the layer to which the mordant is added contains a color developing compound. It is also preferred that it is on the same side of the support as the layer.

The mordant of the present invention may be added to a plurality of layers. In particular, when there are a plurality of layers containing a color developing compound, the mordant may be added to each adjacent layer. preferable. The coupler forming the diffusible dye may be any coupler as long as the diffusible dye formed by coupling with the color developing compound of the present invention reaches the mordant.
It preferably has one or more dissociating groups having a Ka (acid dissociation constant) of 12 or less, more preferably has one or more dissociating groups having a pKa of 8 or less, and particularly preferably has a dissociating group having a pKa of 6 or less. The molecular weight of the diffusible dye formed is 200
It is preferably at least 2,000. Further, (the molecular weight of the dye to be formed / the number of dissociating groups having a pKa of 12 or less) is preferably from 100 to 2,000, and more preferably from 100 to 1,000. Here, as the value of pKa, a value measured using dimethylformamide: water = 1: 1 as a solvent is used.

The coupler for forming the diffusible dye is 1 × 1 in an alkaline solution having a pH of 11 until the solubility of the diffusible dye formed by coupling with the color developing compound of the present invention is 25 ° C.
It is preferable to dissolve 0 ^-6 mol / l or more, 1 × 1
More preferably soluble 0 ^-5 mol / l or more, 1
It is particularly preferable to dissolve at least × 10 ⁻⁴ mol / l. The coupler forming the diffusible dye was dissolved in an alkaline solution having a diffusion constant of 25 ° C. and a pH of 11 at a concentration of 10 ⁻⁴ mol / l in an alkaline solution having a diffusible dye formed by coupling with the color developing compound of the present invention. Sometimes 1 × 10 ^-8 m ² / s
It is preferably at least ^−1, more preferably at least 1 × 10 ⁻⁷ m ² / s ⁻¹ , particularly preferably at least 1 × 10 ⁻⁶ m ² / s ⁻¹ .

The mordant which can be used in the present invention can be arbitrarily selected from mordants usually used.
Among them, a polymer mordant is particularly preferable. Here, the polymer mordant is a polymer having a tertiary amino group,
Examples of the polymer include a polymer having a nitrogen-containing heterocyclic moiety, and a polymer including a quaternary cation group.

Specific examples of homopolymers and copolymers containing a vinyl monomer unit having a tertiary imidazole group include US Pat. Nos. 4,282,305 and 4,11.
No. 5,124, No. 3,148,061, JP-A-60
No. 118834, No. 60-122941, No. 62-
The following may be mentioned, including the mordant layers described in Nos. 240443 and 62-244036.

Preferred specific examples of homopolymers and copolymers containing a vinyl monomer unit having a quaternary imidazolium salt include British Patent Nos. 2,056,101, 2,093,041, and 1,594. U.S. Pat. Nos. 4,124,386 and 4,115,12.
4, No. 4,450,224, JP-A-48-283.
The following may be mentioned, including the mordants described in No. 25 and the like.

Other preferred specific examples of homopolymers and copolymers having a vinyl monomer unit having a quaternary ammonium salt include US Pat. No. 3,709,690.
No. 3,898,088, No. 3,958,99
No. 5, JP-A-60-57836 and JP-A-60-60643.
No. 60-122940, No. 60-122942
And mordants described in JP-A-60-235134 and the like.

In addition, US Pat. No. 2,548,564
No. 2,484,430 and 3,148,16
No. 3,756,814 and the like, vinylpyridine polymer and vinylpyridinium cationic polymer; US Pat. No. 3,625,694
No. 3,859,096, No. 4,128,53
No. 8, No. 1,277,453 and the like, polymer mordants crosslinkable with gelatin and the like; US Pat. Nos. 3,958,995 and 2,721,852
No. 2,798,063, JP-A-54-1152.
No. 28, No. 54-145529, No. 54-26027
Aqueous sol-type mordant disclosed in the specification of US Pat. No. 3,898,088; water-insoluble mordant disclosed in the specification of US Pat. No. 3,898,088; US Pat. No. 3,709,690, 3,788,855, and 3,642,482; reactive mordants capable of forming a covalent bond with the dyes disclosed in the specification and the like; No. 3,488,706,
No. 3,557,066, No. 3,271,147
No., JP-A-50-71332 and JP-A-53-30328.
Nos. 52-155528, 53-125, 5
Examples include mordants disclosed in the specification of JP-A-3-1024. Other US Pat. No. 2,675,316
And the mordants described in JP-A-2,882,156.

The polymer mordant of the present invention has a molecular weight of 1,0.
100 to 1,000,000 is suitable, and especially 10,000
00 to 200,000 is preferred. The above-mentioned polymer mordant is usually used by being mixed with a hydrophilic colloid. As the hydrophilic colloid, a hydrophilic colloid, a highly hygroscopic polymer or both of them can be used, and gelatin is most typical. The mixing ratio of the polymer mordant and the hydrophilic colloid, and the amount of the polymer mordant to be applied are easily determined by those skilled in the art according to the amount of the dye to be mordant, the type and composition of the polymer mordant, and the image forming process to be used. But the mordant / hydrophilic colloid ratio is 20/80
~ 80/20 (weight ratio), mordant applied amount is 0.2 ~ 15
g / m ² is suitable, preferably for use in the 0.5 to 8 g / m ^2. In the present invention, it is preferable to use an auxiliary developing agent and its precursor in the light-sensitive material, and these compounds will be described below. The auxiliary developing agent used in the present invention is a compound having an action of promoting electron transfer from a color developing compound to silver halide in the course of developing silver halide grains, and preferably exposed silver halide grains. And a compound whose oxidized form can oxidize a color developing compound (hereinafter referred to as cross-oxidation). As the auxiliary developing agent used in the present invention, pyrazolidones, dihydroxybenzenes, reductones or aminophenols are preferably used, and pyrazolidones are particularly preferably used. The diffusivity of these compounds in the hydrophilic colloid layer is preferably low. For example, the solubility in water (25 ° C.) is preferably 0.1% or less, more preferably 0.05% or less, and particularly preferably 0% or less. 0.01% or less. The precursor of the auxiliary developing agent used in the present invention is a compound which is stably present in the light-sensitive material, but which releases the above-mentioned auxiliary developing agent quickly once it is processed with a processing solution. In this case, it is preferable that the diffusivity in the hydrophilic colloid layer is low.
For example, the solubility in water (25 ° C.) is preferably 0.1% or less, more preferably 0.05% or less, and particularly preferably 0.01% or less. The solubility of the auxiliary developing agent released from the precursor is not particularly limited, but the auxiliary developing agent itself preferably has low solubility. The auxiliary developing agent precursor of the present invention is preferably represented by the general formula (A).

Formula (A) A- (L) _n -PUG A represents a block group in which the bond to (L) _n -PUG is cleaved during development processing, and L represents L and A in formula (A). Represents a linking group in which the bond between L and PUG is cleaved after the bond is cleaved, n represents an integer of 0 to 3, and PUG represents an auxiliary developing agent. As the auxiliary developing agent, an electron-emitting compound according to the Kendall-Peltz rule other than the p-phenylenediamine compounds is used, and the above-mentioned pyrazolidones are preferably used. As the blocking group represented by A, the following known ones can be applied. That is, a blocking group such as an acyl group or a sulfonyl group described in U.S. Pat. No. 3,311,476, a blocking group utilizing a reverse Michael reaction described in JP-A-59-105542 or the like;
No. 280140, a blocking group utilizing quinone methide or a compound similar to quinone methide by intramolecular electron transfer, JP-A-63-318555 (European Patent Publication 0)
No. 295729), a blocking group utilizing an intramolecular nucleophilic substitution reaction, a blocking group utilizing an addition reaction of a nucleophile to a conjugated unsaturated bond described in JP-A-4-186344, and the like. 62-163051, a blocking group utilizing a β-elimination reaction, JP-A-61-188540, a blocking group utilizing a nucleophilic substitution reaction of diarylmethanes, and JP-A-62-187850. Group utilizing the Rossen rearrangement reaction of
No. 7457, a blocking group utilizing the reaction of an N-acyl compound of thiazolidine-2-thione with an amine, and a dithiolidine having two electrophilic groups described in WO 93/03419. Blocking groups that react with a nucleating agent can be exemplified. The group represented by L is a linking group capable of cleaving (L) _n-1 -PUG after leaving from the group represented by A during development processing. Absent. Specific examples of the auxiliary developing agent or its precursor are shown below, but the compounds used in the present invention are not limited to these specific examples.

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These compounds may be added to any of the photosensitive layer, the intermediate layer, the undercoat layer and the protective layer. When the compound contains an auxiliary developing agent, it is preferably added to the non-photosensitive layer. As a method of incorporating these compounds into the photosensitive material, a method of dissolving in a water-miscible organic solvent such as methanol and directly adding the compound to the hydrophilic colloid layer, and coexisting with a surfactant to form an aqueous solution or a colloidal dispersion. The method of addition, after dissolving in a solvent or oil that is substantially immiscible with water,
A method of adding a substance dispersed in water or a hydrophilic colloid, a method of adding a dispersion in the form of a solid fine particle dispersion, and the like can be used, and a conventionally known method can be applied alone or in combination. The method for preparing the solid fine particle dispersion is described in detail in page 20 of JP-A-2-23544. The amount added to the photosensitive material is 1 mole% based on the color developing compound.
~ 200 mole%, preferably 5 mole% to 100 mole%,
More preferably, it is 10 mol% to 50 mol%.

The support used in the present invention includes glass,
Any support such as paper and plastic film which can be coated with a photographic emulsion layer can be used as long as it is a transmission or reflection support. As the plastic film used in the present invention, a polyester film such as polyethylene terephthalate, polyethylene naphthalate, cellulose triacetate or cellulose nitrate, a polyamide film, a polycarbonate film, a polystyrene film and the like can be used. The "reflective support" that can be used in the present invention refers to a support that enhances reflectivity to sharpen a dye image formed in a silver halide emulsion layer. A substrate coated with a hydrophobic resin containing a light-reflective substance such as titanium oxide, zinc oxide, calcium oxide, or calcium sulfate, or a hydrophobic resin itself containing a light-reflective substance dispersed therein was used as a support. Things included. For example, polyethylene-coated paper, polyester-coated paper, polypropylene-based synthetic paper, supports provided with a reflective layer or combined with a reflective substance, for example, glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide films , Polycarbonate film, polystyrene film, and vinyl chloride resin. As the polyester-coated paper, a polyester-coated paper containing polyethylene terephthalate as a main component described in European Patent EP 0,507,489 is particularly preferably used.

The reflective support used in the present invention is preferably a paper support coated on both sides with a waterproof resin layer, wherein at least one of the waterproof resins contains fine white pigment particles. The white pigment particles are preferably contained at a density of 12% by weight or more, more preferably 14% by weight or more. As the light-reflective white pigment, it is preferable to sufficiently knead the white pigment in the presence of a surfactant, and it is preferable that the surface of the pigment particles is treated with a divalent to tetravalent alcohol. In the present invention, a support having a second type diffuse reflection surface can be preferably used. With the second kind diffuse reflection,
Diffuse reflectivity obtained by dividing a surface having a mirror surface into mirror surfaces oriented in minutely different directions by giving irregularities to a surface having a mirror surface. The unevenness of the surface of the second type diffuse reflection has a three-dimensional average roughness of 0.1 to 2 μm, preferably 0.1 to 1.2 μm with respect to the center plane.
m. Details of such a support are described in JP-A-2-239244.

In order to obtain a wide range of colors on the chromaticity diagram using the three primary colors of yellow, magenta and cyan, at least three silver halide emulsion layers having photosensitivity in different spectral regions are used in combination. Can be For example, three layers of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and three layers of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer are coated on the support in combination. Each photosensitive layer can adopt various arrangement orders known for ordinary color photosensitive materials. Each of these photosensitive layers may be divided into two or more layers as necessary. In the photosensitive material, the photosensitive layer and the protective layer, an undercoat layer, an intermediate layer,
A photographic component layer composed of various non-photosensitive layers such as an antihalation layer and a back layer can be provided. Further, various filter dyes can be added to the photographic component layer in order to improve color separation.

As the binder or protective colloid that can be used in the light-sensitive material according to the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin. The calcium content of the gelatin is preferably 800 ppm or less,
The content of iron is preferably not more than 5 ppm, more preferably not more than 3 ppm, more preferably not more than 200 ppm. In order to prevent various fungi and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image, it is preferable to add a fungicide as described in JP-A-63-271247.

The total amount of gelatin in the light-sensitive material of the present invention is 1 m ²
1.0 to 30 g, preferably 2.0 to 20 g
g. In the swelling of the present photosensitive material using an alkaline solution having a pH of 12, the saturated swelling film thickness (90% of the maximum swelling film thickness) is obtained.
%) Is preferably 15 seconds or less, more preferably 10 seconds or less. The swelling ratio [(maximum swollen film thickness−film thickness) / film thickness × 100] is 50 to
300% is preferable, and especially 100-200% is preferable.

When the photosensitive material of the present invention is exposed to a printer, it is preferable to use a band stop filter described in US Pat. No. 4,880,726. As a result, light color mixing is removed, and color reproducibility is significantly improved. The light-sensitive material of the present invention is suitable for a scanning exposure method using a cathode ray (CRT) in addition to being used for a printing system using a normal negative printer. A cathode ray tube exposure apparatus is simpler, more compact, and lower in cost than an apparatus using a laser. Further, adjustment of the optical axis and color is also easy. Various light emitters that emit light in a spectral region are used as necessary for a cathode ray tube used for image exposure. For example, any one of a red light emitter, a green light emitter, and a blue light emitter, or a mixture of two or more thereof is used.
The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in a yellow, orange, purple, or infrared region is also used. In particular, a cathode ray tube which emits white light by mixing these light emitters is often used.

When the photosensitive material has a plurality of photosensitive 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 colors are exposed at a time, that is, the cathode ray tube is exposed. The image signal of a plurality of colors may be input to the display unit to emit light from the display screen. A method of sequentially inputting image signals for each color, sequentially emitting light of each color, and exposing through a film that cuts a color other than that color (plane sequential exposure)
However, in general, field-sequential exposure is preferable for improving image quality because a cathode ray tube with high resolution can be used. The photosensitive material of the present invention is a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a second harmonic generation light source (S
HG), etc., for digital scanning exposure using monochromatic high-density light. In order to make the system compact and inexpensive, it is preferable to use a semiconductor laser, or a second harmonic generation light source (SHG) combining a semiconductor laser or a solid-state laser with a nonlinear optical crystal. Particularly, in order to design a device that is compact, inexpensive, and has a long life and high stability, it is preferable to use a semiconductor laser.
It is desirable to use a semiconductor laser as at least one of the exposure light sources.

When such a scanning exposure light source is used,
The maximum spectral sensitivity of the light-sensitive material of the present invention can be arbitrarily set depending on the wavelength of the scanning exposure light source used. Solid-state laser using a semiconductor laser as an excitation light source or SHG obtained by combining a semiconductor laser with a nonlinear optical crystal
In the light source, the laser oscillation wavelength can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be provided in the usual three regions of blue, green and red. In order to use a semiconductor laser as a light source in order to make the device inexpensive, highly stable and compact, it is preferable that at least two layers have a spectral sensitivity maximum at 670 nm or more. This is because the currently available, inexpensive and stable III-V based semiconductor laser has an emission wavelength range only in the red to infrared region. However, at the laboratory level, oscillations of II-VI group semiconductor lasers in the green and blue regions have been confirmed, and if semiconductor laser manufacturing technology develops, these semiconductor lasers can be used stably at low cost. It is fully anticipated.
In such a case, the necessity for at least two layers to have a spectral sensitivity maximum at 670 nm or more is reduced.

In such scanning exposure, the time during which the silver halide in the photosensitive material is exposed is the time required for exposing a small area. As the minute area, a minimum unit for controlling the amount of light from each digital data is generally used and is called a pixel. Therefore, the exposure time per pixel changes depending on the size of the pixel. The size of this pixel depends on the pixel density, and a practical range is 50 to 2000 dpi. The exposure time is preferably defined as ^10-4 seconds or less, and more preferably ^10-6 seconds or less, when the pixel density is defined as 400 dpi and the pixel size is defined as the exposure time.

The silver halide grains used in the present invention include silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide,
It is silver chloroiodobromide. Other silver salts, such as rodin silver,
Silver sulfide, silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as a part of silver halide grains. When rapid development and desilvering (bleaching, fixing and bleach-fixing) steps are desired, so-called high silver chloride grains having a silver chloride content of 90 mol% or more are desirable. In order to appropriately suppress development, it is preferable to contain silver iodide. The preferred silver iodide content depends on the intended light-sensitive material. The high silver chloride emulsion used in the present invention preferably has a structure having a silver bromide localized phase in a layered or non-layered form inside and / or on the surface of silver halide grains. The halogen composition of the localized phase is preferably at least 10 mol% in terms of silver bromide content.
More than mol% is more preferred. The silver bromide content of the silver bromide localized layer is determined by an X-ray diffraction method (for example, “The Chemical Society of Japan,
New Experimental Chemistry Course 6, Structural Analysis "Maruzen. ) And the like. These localized phases can be inside the grains, at the edges, corners, or planes of the grain surfaces. One preferred example is a phase epitaxially grown at the corners of the grains. It is also effective to further increase the silver chloride content of the silver halide emulsion in order to reduce the replenishment amount of the developing solution. In such a case, a substantially pure silver chloride emulsion having a silver chloride content of 98 to 100 mol% is also preferably used.

The value obtained by dividing the circle equivalent diameter of the projected area by the grain thickness is called an aspect ratio, and defines the shape of tabular grains. Tabular grains having an aspect ratio greater than 1 can be used in the present invention. The average aspect ratio of 80% or more of the total projected area of the grains is desirably 1 or more and less than 100. It is more preferably 2 or more and less than 20 and particularly preferably 3 or more and less than 10. The shape of the tabular grains can be selected from triangles, hexagons, and circles. US Patent 4,79
A regular hexagon having substantially equal lengths of six sides as described in US Pat. No. 7,354 is a preferred form.

The emulsion used in the present invention may be a polydisperse emulsion having a wide grain size distribution, or a monodisperse emulsion having a narrow size distribution. As a scale representing the size distribution, a variation coefficient of a circle equivalent diameter of a projected area of a particle or a sphere equivalent diameter of a volume may be used. When a monodispersed emulsion is used, the coefficient of variation is 25% or less,
It is more preferable to use an emulsion having a size distribution of 20% or less, more preferably 15% or less. In the photosensitive material used in the present invention, the various additives described above are used.
In addition, various additives can be used according to the purpose. These additives are described in more detail in Research Disclosure Item 17643 (December 1978), It
em 18716 (November 1979) and Item 307105
(11/1989), and the relevant locations are summarized in the table below.

[0167]

[Table 1]

In the present invention, the processing liquid is applied to the surface of the photosensitive material by the coating apparatus of the present invention. Therefore, the photosensitive material must be easily wetted by the processing solution. In the present invention, in order to improve the wettability of the surface of the light-sensitive material, it is preferable to coat a surfactant on the layer farthest from the support in the hydrophilic colloid layer of the light-sensitive material. Among the surfactants, betaine-based surfactants, surfactants containing a fluorine atom, and the like are preferable. It is also preferable that a layer farthest from the support in the hydrophilic colloid layer of the photosensitive material contains a hydrophilic polymer or the like from the viewpoint of improving the wettability by facilitating the penetration of the processing solution into the photosensitive material. As the hydrophilic polymer, an acrylic acid-based polymer, polyvinyl alcohol, a copolymer of acrylic acid and vinyl alcohol, and the like are preferable.

The processing method of the present invention will be described below. In the present invention, the processing step comprises an application step of an alkaline processing liquid, a coating step of a peroxide-containing liquid, a development intensification step, a washing step, and, in some cases, a stabilization step. Hereinafter, each step will be described in detail.

The alkaline treatment liquid used in the alkaline treatment liquid application step will be described. The alkaline processing liquid used in the present invention is characterized in that it does not substantially contain a color developing compound, and may contain other components (alkali, halogen, chelating agent, etc.). In some cases, it is preferable that a reducing agent is not contained in order to maintain processing stability. In this case, it is preferable that an auxiliary developing agent, hydroxyamines, sulfites, and the like are not substantially contained.
(Here, “substantially not contained” means preferably 0.5 mmol / liter or less, more preferably 0.1 mmol / liter or less.
mmol / liter or less. In particular, it is preferable not to contain at all. The pH of the treatment liquid used in the present invention is preferably 9 to 14, and particularly preferably 10 to 14.

In the present invention, any method may be used to supply the alkaline processing solution onto the photosensitive material. As a method of immersing the photosensitive material in an alkaline processing solution,
Tank processing method using ordinary tank, Patent 261220
No. 5, a method of passing through a thin slit, dip coating, and the like. As a method of supplying the photosensitive material by bringing the coated portion of the coating apparatus of an alkaline processing solution into contact with the coating material, Yuji Harazaki, "Coating Science" (especially, P253 to 255), Asakura Shoten (Showa 46), Paper Industry Times Hen "Paper Processing Handbook" P129-138 (Showa 48
And a method of applying a liquid contained in a material that absorbs an alkaline processing liquid such as a roller coater, a rod coater, a squeeze coater, a felt cloth or a sponge coat, and the like. JP-A-6-32 discloses a method for supplying a photosensitive material and an alkaline processing solution in a non-contact manner.
No. 4,455, JP-A-9-179272, a method of spraying from a fine nozzle and spraying a processing liquid.

[0172] From the viewpoint of reducing the size of the processing apparatus and the amount of waste liquid when used up processing is performed, it is preferable to perform the application processing.
From the viewpoint of prevention of contamination of the applied portion by the effluent from the photosensitive material of the applied portion, non-contact application processing is preferable,
From the viewpoint of uniformly applying a small liquid amount, a coating method using a processing liquid coating apparatus described in JP-A-9-17927, which will be described later, is more preferable. Further, in the present invention, a method of repeatedly applying the developer many times can be used. Also,
By squeezing the applied treatment liquid, it is also possible to remove the alkaline treatment liquid having a swelling amount or more.

In the present invention, the alkaline processing liquid is applied to the surface of the light-sensitive material. In this case, the applied alkaline processing solution must spread sufficiently on the surface of the photosensitive material, and in order to sufficiently spread on the surface of the photosensitive material, the surface tension is preferably 60 dyn / cm or less, and 45 dyn / cm or less.
The following are more preferred.

As a method for lowering the surface tension of the alkaline processing liquid, any method may be used. As a method of reducing the surface tension, a method of adding a surfactant can be considered. In addition, a method of adding a water-soluble alcohol-based organic solvent such as methanol, ethanol, isopropyl alcohol, and glycol is usually considered. However,
When the former is used, the pressurizing and depressurizing are repeated in the coating apparatus, so that bubbles are easily formed, bubbles are generated, and there is a portion where the alkaline processing liquid cannot be ejected from the nozzle due to the bubbles adhering to the nozzle surface. However, it is not preferable in that a white spot occurs in the processed photosensitive material. Also, when adding a water-soluble alcohol-based organic solvent, a large amount of alcohol-based organic solvent must be added to lower the surface tension. It is not preferable because the rate of penetration into the photosensitive material is reduced, and the progress of development is delayed.

The water-soluble stilbene compound is preferable to the above compounds in that foaming is small and the surface tension can be reduced by adding a small amount of the compound. Among the stilbene compounds, diaminostilbene represented by the general formula (X) is effective as a compound whose surface tension can be reduced by adding a small amount.
The diaminostilbene compound represented by the general formula (X) is also preferable in that the addition of the diaminostilbene compound to the treatment liquid has a small degree of lowering the contact angle with the metal.

[0176]

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In the general formula (X), L ¹ and L ² may be the same or different, and are represented by —OR ¹ or —NR ² (R ³ )
And four substituents L ¹ in the general formula (X)
And L ² have a total of two or more substituents in the general formula (XI) group. Here, R ¹ and R ² each represent a hydrogen atom, an alkyl group, an aryl group, or an alkyl group having a substituent in the following general formula (XI) group or an aryl group, and R ³ represents an alkyl group or an aryl group. Alternatively, it represents an alkyl group having a substituent or an aryl group in the following general formula (XI) group. General formula (XI)

[0178]

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(In the general formula (XI), X represents a halogen, R represents an alkyl group. In the general formulas (X) and (XI), M represents a hydrogen atom, an alkali metal, a tetraalkylammonium or a pyridinium. The diaminostilbene compound of the present invention is represented by the general formula (XI):
Is preferably a compound having a ₃ M group, L ¹ and L ² -N
—R ² (R ³ ), and R ² is more preferably a hydrogen atom. Further, it is more preferable that the number of —SO ₃ M groups is 4 or more. The preferable addition amount of the diaminostilbene compound of the present invention is 0.1 to 10 mmol / L.
And more preferably 0.5 to 6 mmol / L. If less than this, sufficient surface tension lowering ability cannot be shown,
On the other hand, if it is too large, precipitation and a decrease in the contact angle with the nozzle occur, which is not preferable. Table 2 shows preferred diaminostilbene compounds.
As shown in Table 4, the present invention is not limited by this.

[0180]

[Table 2]

[0181]

[Table 3]

[0182]

[Table 4]

Further, among the surfactants, a fluorine-based surfactant having a polyoxyalkylene group is preferably added for the purpose of the present invention in that the surface tension is reduced with a small amount of addition and foaming is small.

In the above general formula Rf- (A) mX, in the present invention, X is particularly preferably a substituted or unsubstituted polyoxyethylene group.
0 is preferred. Rf is preferably a fluoro, alkyl, alkenyl or aryl group having 4 or more carbon atoms, and more preferably a perfluoro, alkyl, alkenyl or aryl group having 6 to 14 carbon atoms. A is preferably an alkylene group (including those having a substituent, such as an ethylene group, a trimethylene group, and an oxyalkylene group), and an arylene group (including those having a substituent).
For example, a phenylene group, an oxyphenylene group, or the like, an alkylarylene group (including a group having a substituent, such as a propylphenylene group), or an arylalkylene group (including a group having a substituent, such as a phenylethylene group or phenyl) Oxyethylene group), and these groups include an oxygen atom, an ester group, an amide group, a sulfonamide group, a sulfonyl group, a divalent linking group interrupted by a different atom such as a sulfur atom, or a divalent linking group Is also included. m is more preferably 0, and when m = 1, A is preferably an alkylene group. The addition amount of the fluorine-based surfactant having a polyoxyalkylene group preferably used in the present invention is 0.1 to 5 mmol / L, more preferably 0.5 to 1 mmol / L. If the amount is smaller than this, sufficient surface tension lowering ability cannot be exhibited, and if it is larger, precipitation and a decrease in the contact angle with the nozzle undesirably occur.

In order to prevent a decrease in the contact angle with the nozzle, it is preferable to coat the nozzle surface with a fluororesin.

Specific examples of the fluorine-based surfactant having a polyoxyalkylene group preferably used in the present invention are shown below, but the present invention is not limited thereto.

[0187]

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[0188]

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As described above, an alkali solution and a peroxide-containing solution are separately supplied to a photosensitive material containing a color developing compound.
In addition, the peroxide-containing liquid is supplied by a coating method using a processing liquid coating apparatus described in JP-A-9-179272, whereby the stability of the processing liquid used for intensification processing can be maintained. In addition, it is possible to perform processing with a small amount of processing liquid. However, when the coating is performed using a processing liquid coating apparatus described in Japanese Patent Application Laid-Open No. HEI 9-179272 where the alkaline liquid is applied, particularly, the color is sufficiently developed at the end portion where the liquid is applied. There is a problem that no problem occurs. The present invention solves this problem. Next, the peroxide-containing liquid application step used in the present invention will be described.
First, the peroxide-containing liquid of the present invention will be described. The peroxide-containing liquid of the present invention has a surface tension difference of 10 d, particularly from the viewpoint of improving the color developing property up to the end portion where the liquid is applied.
yn / cm or less. Preferably,
8 dyn / cm or less, and more preferably 5 dyn / cm or less. Since the alkaline treatment liquid is preferably 60 dyn / cm or less, the peroxide-containing liquid is preferably 70 dyn / cm or less, and the alkaline treatment liquid is more preferably 45 dyn / cm or less, and therefore more preferably 55 dyn / cm or less, and 53 dyn / cm or less. Is particularly preferred, and 50 dy
Most preferably n / cm or less. Naturally, the same phenomenon occurs when the surface tension of the peroxide-containing liquid is lower than that of the alkaline processing liquid.
Even when it is smaller than 0 dyn / cm, the color density at the edge of the liquid is reduced. In order to keep the surface tension within the range of the present invention, it is preferable to add a water-soluble stilbene compound and a fluorine-based surfactant having a polyoxyalkylene group, which are preferably used for adjusting the surface tension of the alkaline treatment liquid. Further, it is preferable to adjust the liquid composition with the alkaline processing liquid to increase the color developing property to the end of the liquid applied, and the alkaline processing liquid contains, for example, a cation, an anion, It is also a preferred embodiment to combine a surface tension reducing agent, an antifoggant, a chelating agent, and the like, adjust the pH with an acid such as sulfuric acid or nitric acid, and add hydrogen peroxide. In the present invention, in order to maintain the stability of the developing intensifying solution, a compound or a precursor thereof which is oxidized by silver halide and forms a dye having an absorption in the visible region by coupling the oxidized product with a coupler is exposed to light. The photosensitive material and the developing intensifying solution are brought into contact with each other by a method in which the alkaline processing solution and the peroxide-containing solution are divided and mixed on the photosensitive material.
Therefore, it is necessary that the peroxide-containing liquid contains substantially no color developing agent. Further, from the viewpoint of the stability of the peroxide, the pH of the peroxide-containing liquid needs to be 9 or less, preferably 8 or less, particularly preferably 7 or less. Further, since the development intensification proceeds in a state where the alkaline processing solution and the peroxide-containing solution are mixed, a pH of 9 or more is required for the intensification reaction to proceed.
The pH of the peroxide-containing liquid is required to be 2 or more so that the pH does not drop too much, preferably 3 or more, more preferably 4 or more, particularly preferably 5 or more. As the peroxide contained in the peroxide-containing liquid to be used for the intensification treatment, hydrogen peroxide and a compound that releases hydrogen peroxide are preferable. As the compound that releases hydrogen peroxide, perboric acid and percarbonate are preferable. Of these, hydrogen peroxide is particularly preferred. The addition amount of these compounds is preferably from 0.005 mol / L to 2 mol / L, more preferably from 0.01 mol / L to 1.0 mol / L, and more preferably from 0.02 mol / L to 0.5 mol / L. Per liter is more preferred.

In the present invention, when a color developing agent precursor which releases an aromatic primary amine by a rearrangement reaction with a peroxide represented by the general formula (X) is used, the peroxide is also used for releasing. A contained solution is used. As the peroxide used for releasing, it is preferable to use hydrogen peroxide and a peroxide represented by the following general formula.

ROOH RCOOOH In the formula, R is a hydrogen atom, a substituted or unsubstituted alkyl group,
An aryl group.

Specific examples of the compound represented by the above general formula and examples of other peroxides preferable for generating a color developing agent from a color developing agent precursor are shown below.

[0193]

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In order to generate a color developing agent from a color developing agent precursor, the amount of peroxide added is 0.1 mm
1 / liter to 1 mol / liter is preferred, and more preferably 0.2 mmol / liter to 0.5 mol.
/ Liter.

In the present invention, two or more kinds of peroxides may be used in combination. For example, it is suitable for generating a color developing agent from a peroxide suitable for the intensifying process and a color developing agent precursor. It is also a preferred embodiment to use a mixture of peroxides.

In order to apply the peroxide-containing liquid of the present invention onto a light-sensitive material by the method of the present invention, it is preferable to use a processing liquid coating apparatus described in JP-A-9-179272.

The coating device will be described in detail.

FIG. 1 is a schematic overall configuration diagram of a processing liquid coating apparatus used for carrying out the present invention. The apparatus used in the present invention has a coating apparatus as shown for a peroxide-containing liquid and, if necessary, for an alkaline processing liquid. As shown in FIG. 1, an injection tank 312 that constitutes a part of the coating device 310 is disposed at a position of the processing liquid coating unit 50 that faces the transport path A of the photosensitive material 16. Reference numeral 32 denotes a transport roller for the photosensitive material 16, and reference numeral 34 denotes a take-up roller for the processed photosensitive material.

As shown in FIG. 1, this injection tank 312
A processing liquid bottle 332 that stores a processing liquid to be supplied to the injection tank 312 is disposed at the lower left of the processing tank.
A filter 334 for filtering the processing liquid is disposed above the processing liquid bottle 332. A water supply pipe 342 in which a pump 336 is disposed on the way connects the processing liquid bottle 332 and the filter 334. Further, on the right side of the injection tank 312, a processing liquid bottle 33 is provided.
A sub-tank 338 for storing the processing liquid sent from 2 is arranged, and a water supply pipe 344 extends from the filter 334 to the sub-tank 338.

Accordingly, when the pump 336 is operated, the processing liquid is sent from the processing liquid bottle 332 to the filter 334 side, and the water filtered through the filter 334 is sent to the sub tank 338, and the processing liquid is sent to the sub tank 338. Will be stored once. Also, the sub tank 338
The water supply pipe 346 connecting between the water and the injection tank 312 is
The processing liquid, which is disposed between them, is sent from the processing liquid bottle 332 by the pump 336 via the filter 334, the sub-tank 338, the water supply pipe 346, and the like, so that the injection tank 312 is filled.

In the lower part of the injection tank 312, a tray 34 connected to a processing liquid bottle 332 by a circulation pipe 348 is provided.
The tray 340 collects the processing liquid water overflowing from the injection tank 312 and returns the processing liquid water to the processing liquid bottle 332 via the circulation pipe 348. The circulation pipe 348 is connected to the sub-tank 338 so as to protrude and extend into the sub-tank 338, and returns excess water accumulated in the sub-tank 338 to the processing liquid bottle 332. . Further, after the injection tank of FIG. 1, there are usually steps of heat retention, desilvering, washing and drying on a heat panel, but these steps are omitted in the figure. The heat panel is installed from just before the transport roller (the left end in the diagram of FIG. 1) to before the desilvering process, and usually a photosensitive material is placed on this panel and moved.

Next, the structure and operation of the injection tank 312 will be described in detail with reference to FIGS. 2 is an enlarged perspective view of the injection tank, FIG. 3 is a bottom view of the injection tank showing a state where the photosensitive material is conveyed below, FIG. 4 is an enlarged view of a main part of FIG. 3, and FIG. FIG. 3 is a plan view of the photosensitive material in a state where droplets are ejected and applied. As shown in FIG. 3, a nozzle plate 32 formed by bending an elastically deformable rectangular thin plate is provided on a part of the wall surface of the injection tank 312 and opposed to the transport path A of the photosensitive material 16.
2 are installed.

As shown in FIGS. 2 to 4, the nozzle plate 322 has a plurality of nozzle holes 324 (for example, several tens μm in diameter) for injecting the processing liquid filled in the injection tank 312. At least two rows are arranged in a staggered manner over the entire width direction of the photosensitive material 16 while being linearly arranged along a direction intersecting the transport direction A of the photosensitive material 16 at a constant interval. Therefore, these nozzle holes 32
4, the processing liquid in the injection tank 312 can be discharged to the photosensitive material 16 side. A feature of the present invention resides in that a processing liquid is simultaneously applied from a plurality of injection nozzles to the entire width of a photosensitive material. As shown in FIG. 4, the respective nozzle holes 324 are formed in a circular shape having the same inner diameter d, so that substantially the same volume of water droplets L can be ejected from the respective nozzle holes 324. Further, three nozzle holes 324 adjacent to each other are arranged on the nozzle plate 322 such that the centers S of the nozzle holes 324 become the vertices of an equilateral triangle. On the other hand, as shown in FIGS. 1 and 2,
An exhaust pipe 330 extends from the upper part of the injection tank 312, and the exhaust pipe 330 enables communication between the inside and the outside of the injection tank 312. A valve (not shown) for opening and closing the exhaust pipe 330 is provided in the middle of the exhaust pipe 330, and the opening and closing movement of the valve causes the injection tank 312 to open and close.
The inside can be communicated with outside air and closed.

As shown in FIG. 5, in the present invention, three droplets L ejected from the nozzle hole 324 and adhered to the photosensitive material 16 adjacent to each other have a gap between each other. In this state, the photosensitive material 16 is attached to the photosensitive material 16 without contact. The pitch, which is the distance between the centers S1 of the droplets L, is the same as the pitch P, which is the distance between the centers S of the adjacent nozzle holes 324 (see FIG. 4). As a result, three droplets L are attached to the photosensitive material 16 in contact with each other without any gap between them.

[0205]

(Equation 1)

When the volume of one droplet of the processing liquid ejected from the nozzle hole is V, and the contact angle when the processing liquid is deposited on the photosensitive material is θ, the alkalinity of one droplet deposited on the photosensitive material is The diameter D of the treatment liquid is represented by the following equation.

[0207]

(Equation 2)

By repeatedly ejecting the droplet L at an appropriate timing according to the transport speed of the photosensitive material 16, the lines connecting the centers S1 form an equilateral triangle as shown in FIG. A droplet L is formed on the surface of the photosensitive material 16.
Will adhere. However, in practice, when the droplets L after atomization and adhesion are in contact with each other on the surface of the photosensitive material 16 and interfere with each other, the droplets L tend to aggregate to reduce the surface energy. L immediately agglomerates and becomes integral as a whole.

[0209] The center S1 of the droplet L thus attached forms the vertex of an equilateral triangle, and the center of gravity of the equilateral triangle is completely covered by the three droplets L on the photosensitive material 16. , All liquid droplets can be aggregated with the least amount of liquid. As described above, it is possible to form a uniform coating film on the photosensitive material 16 without causing the processing liquid to become dirty and causing deterioration of the image recording apparatus itself and deterioration of image quality.

[0210] The coating amount of the alkaline processing solution is preferably 95 ml / m ² from 5 ml / m ² as a liquid amount of the coating liquid, the coating amount of the peroxide-containing solution from 5ml / m ² 95ml / m
² is preferred. More preferably, the amount of the coating solution for both the alkaline treatment liquid and the peroxide-containing liquid is 10 ml / m ² to 50 ml / m ² . The total amount of the coating solution of the alkaline processing solution and the peroxide-containing solution is from 10 ml / m ² to 100
It is preferably ml / m ² . PH when alkaline processing liquid and liquid containing hydrogen peroxide are mixed on photosensitive material
Is preferably 9 or more and 13 or less, more preferably 10 or more and 12.5 or less. The time from application of the alkaline coating solution to application of the hydrogen peroxide-containing solution is preferably 10 seconds or less, more preferably 5 seconds or less, and particularly preferably 1 second or less.

Next, the developing intensifying step will be described. The development intensification step is a step of performing development intensification using the applied alkaline processing liquid and peroxide-containing liquid. In the present invention, a mixed solution of an alkaline processing solution for performing development intensification and a peroxide-containing solution is used in a state of being applied on a photosensitive material. Therefore, it must remain on the photosensitive material during processing,
It is preferable that the photosensitive material is placed horizontally during the development intensification. Also, a mixture of an alkaline processing liquid and a peroxide-containing liquid is placed on the photosensitive material so that this step is completed during the transfer from the peroxide-containing liquid application step to the next step such as a washing step or a stabilization step. It is also a preferable embodiment to carry the sheet while keeping it horizontal while it is placed on it. In the present invention, it is also preferable to keep the temperature constant in order to eliminate variations due to processing. A preferred treatment temperature is from 20 ° C to 80 ° C, more preferably from 25 ° C to 60 ° C, even more preferably from 30 ° C to 60 ° C.
C. to 50C. In order to maintain this temperature, the photosensitive material must be brought into close contact with the heat panel and transported, or the process must be completed in a constant temperature / humidity room maintained at a constant temperature or humidity. Is also preferred. In order to keep the preferred temperature of the present invention constant from the beginning to the end of processing, it is also preferable to keep the alkaline processing solution, the peroxide-containing solution and the photosensitive material in advance. The time for the development intensification step is preferably 5 seconds or more and 60 seconds or less, and
The time is preferably from 40 seconds to 40 seconds, more preferably from 10 seconds to 30 seconds.

The washing step and the stabilizing step of the present invention can be performed by using known methods. For the water washing step, a method described in JP-A-9-152693 or the like is preferably used. However, in the present invention, since there is little that must be washed out from the processed photosensitive material, a small amount such as shower water washing is used. A simple washing method such as disposable use of a washing amount of the washing solution is also preferable. The stabilization treatment is preferably performed using a stabilizing solution described in JP-B-63-20330, JP-B-63-20332, etc. In this case as well, the treatment can be performed by a coating treatment without tank treatment. preferable.

In the present invention, a bleaching process, a fixing process, or a bleach-fixing process can be performed after the process.
Examples of the bleaching agent include compounds of polyvalent metals such as iron (III), cobalt (III), chromium (IV) and copper (II), peracids,
Examples include quinones and nitro compounds. Among these, iron (III) aminopolycarboxylate such as iron (III) complex salt of ethylenediaminetetraacetate; iron (III) complex salt of 1,3-diaminopropanetetraacetate, hydrogen peroxide, persulfate, etc. are rapidly treated and polluted by the environment. It is preferable from the viewpoint of prevention. Examples of the fixing agent include thiosulfates, thiocyanates, thioureas, a large amount of iodide, nitrogen-containing heterocyclic compounds having a sulfide group described in JP-A-4-365037 and JP-A-5-66540, and mesoionic compounds. And thioether compounds. The bleaching step, the fixing step, and the bleach-fixing step are described in detail in JP-A-9-152693, and these methods are preferably used. In these steps, it is also preferable to perform a coating process in order to eliminate the processing tank.

Various additives are used in the treatment applied to the present invention, and are described in more detail in Research Disclosure Item 36544 (September, 1994). Was. Processing agent type Page Antifoggant 537 Chelating agent 537 Right column Buffering agent 537 Right column Surfactant 538 Left column and 539 Left column Bleach 538 Bleaching accelerator 538 Right column to 539 Left column Bleaching chelating agent 539 Left column Rehalogen Agent 539 Left column Fixing agent 539 Right column Fixing agent preservative 539 Right column Fixing chelating agent 540 Left column Stabilizing surfactant 540 Left Stabilizing scum inhibitor 540 Right Stabilizing chelating agent 540 Right Bactericidal Detergent 540 right color image stabilizer 540 right

[0215]

Next, the present invention will be described in more detail with reference to examples. Example 1 (Preparation of photosensitive material) A corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further applied. A multilayer color printing paper (100) having the following layer configuration was produced. The coating solution was prepared as follows. First layer coating solution 23 g of coupler (C-21), color developing compound (I-3)
2) 16 g and a solvent (Solv-1) 80 g were dissolved in ethyl acetate, and this solution was added to a 16% gelatin solution 4 containing 10% sodium dodecylbenzenesulfonate and citric acid.
The resulting mixture was emulsified and dispersed in 00 g to prepare an emulsified dispersion A. On the other hand, silver chlorobromide emulsion A (cubic, average grain size 0.20
μm large size emulsion A and 0.10 μm small size emulsion A
3: 7 mixture (silver molar ratio). The coefficient of variation of the grain size distribution was 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride in each size emulsion). did. In this emulsion, the following blue-sensitive sensitizing dyes A, B and C were contained in an amount of 7.0 × 10 ^-4 mol per mol of silver per mol of silver.
For small size emulsion A, 8.5 × 10
^-4 mol is added. The emulsion was chemically ripened by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion A and the silver chlorobromide emulsion A were mixed and dissolved to prepare a first layer coating solution having the following composition. The emulsion coating amount indicates a silver equivalent coating amount.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Cpd-12, Cpd
-13, Cpd-14 and Cpd-15 the total amount each ^{15.0mg / m 2, 60.0mg / m} 2, 5.0mg
/ M ² and 10.0 mg / m ² . The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer. Blue-sensitive emulsion layer

[0219]

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(Per mol of silver halide, 7.0 × 10 ^-4 mol was added to the large-size emulsion and 8.5 × 10 ^-4 mol was added to the small-size emulsion, respectively.) Emulsion layer

[0219]

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(The sensitizing dye D was used in an amount of 1.5 × 10 ^-3 mol for a large-sized emulsion, 1.8 × 10 ^-3 mol for a small-sized emulsion, and Sensitizing dye E was used in an amount of 2.0 × 10 ^-4 mol per mol of silver halide, and 3.10 mol per mol of silver halide.
5 × 10 ^-4 mol, and the sensitizing dye F a per mol of silver halide, 1.0 × 10 ^-3 mol to the large size emulsion, 1.4 × 10 to the small size emulsion ^{- 3} mol was added. )

[0221]

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[0222] (per mol of silver halide, respectively 2.5 × 10 ^-4 mol to the large size emulsion and each 4.0 × 10 ^-4 mol per mol for the small grain size emulsion.) Furthermore, The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

[0223]

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Also, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer in an amount of 3.3 × per mole of silver halide. 10 ^-4 mol, 1.0 × 1
0 ^-3 mol and 5.9 × 10 ^-4 mol were added. Further, the second layer, the fourth layer, the sixth layer, and the seventh layer each have a .0 layer.
2 mg / m ² , 0.2 mg / m ² , 0.6 mg / m ² ,
It was added to a concentration of 0.1 mg / m ² .

Further, 4-hydroxy-6-methyl-1,3,3a, 4-hydroxy-6-methyl-1,3,3a,
7-tetrazaindene was added in an amount of 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol per mol of silver halide. To prevent irradiation, the following dyes were added to the emulsion layer (the amount in parentheses indicates the coating amount).

[0226]

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(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene Laminated Paper [Polyethylene on the first layer side contains the following optical brightener (I), white pigment (TiO ₂ , 15 wt%) and bluish dye (ultramarine)]

First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A 0.015 Gelatin 1.50 Yellow coupler (C-21) 0.23 Color developing compound (I-16) 0.16 Solvent ( Solv-1) 0.80

Second layer (color mixture preventing layer) Gelatin 1.09 Color mixture inhibitor (Cpd-7) 0.11 Solvent (Solv-2) 0.19 Solvent (Solv-3) 0.07 Solvent (Solv-4) 0.25 Solvent (Solv-5) 0.09 1,5-diphenyl-3-pyrazolidone 0.03 (fine particle solid dispersion state)

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion B: cubic, 1: 3 mixture of large-size emulsion B having an average grain size of 0.1 μm and small-size emulsion B having an average grain size of 0.08 μm (Ag Molar ratio). The variation coefficients of the grain size distribution were 0.10 and 0.08, respectively, and 0.8 mol% of AgBr was locally contained in a part of the grain surface having silver chloride as a base in each size emulsion. 0.01 Gelatin 1.50 Magenta coupler (C-56) 0.24 Color developing compound (I-32) 0.16 Solvent (Solv-1) 0.80

Fourth layer (color mixture preventing layer) Gelatin 0.77 Color mixture inhibitor (Cpd-7) 0.08 Solvent (Solv-2) 0.14 Solvent (Solv-3) 0.05 Solvent (Solv-4) 0.14 Solvent (Solv-5) 0.06 1,5-diphenyl-3-pyrazolidone 0.02 (fine particle solid dispersion state)

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion C: cubic, 1: 4 mixture of large-sized emulsion C having an average grain size of 0.1 μm and small-sized emulsion C of 0.08 μm (Ag mole ratio). The coefficient of variation of the grain size distribution was 0.09 and 0.11, and in each size emulsion, 0.8 mol% of AgBr was locally contained on a part of the grain surface composed of silver chloride as a substrate. 0.01 Gelatin 0.15 Cyan coupler (C-43) 0.21 Color developing compound (I-16) 0.20 Solvent (Solv-1) 0.80

Sixth layer (ultraviolet absorbing layer) Gelatin 0.64 Ultraviolet absorbing agent (UV-1) 0.39 Color image stabilizer (Cpd-7) 0.05 Solvent (Solv-6) 0.05

Seventh layer (protective 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 Improvement of wettability Agent (Cpd-8) 0.09 Wetting agent (Cpd-9) 0.03 Wetting agent (Cpd-10) 0.03

[0236]

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[0237]

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[0238]

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[0239]

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[0240]

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[0241]

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Sample (101) was prepared in exactly the same manner as Sample (100) except that the coupler and the color developing compound were replaced with the coupler and the color developing compound shown in Table 5 in an equimolar amount. To (108).

[0243]

[Table 5]

(Preparation of Processing Liquid) The following developing intensifying liquid was prepared.

Developing intensifying solution Water 800 ml 5 Sodium sulfosalicylate 25 g KCl 1.25 g Benzotriazole 0.01 g Hydroxyethylidene-1,1-diphosphonic acid (30% aqueous solution) 2 ml Surface tension reducing agent (Stil- 1) 2.5 g Hydrogen peroxide (30% aqueous solution) 15 ml Add water 1000 ml pH 12

[0246]

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The following alkaline processing liquid a-1 was prepared.

Alkaline treatment liquid a-1 Water 800 ml 5 Sodium sulfosalicylate 50 g KC1 2.5 g Benzotriazole 0.02 g Hydroxyethylidene-1,1-diphosphonic acid (30% aqueous solution) 4 ml Add water and 1000 ml Table 13 shows the surface tension reducing agents shown in Table 6 with respect to pH 13 treatment solution a-1.
The processing liquids a-2 to a-10 added in the amounts shown in the following were prepared.

[0249]

[Table 6]

The following hydrogen peroxide-containing solution b-1 was prepared.

Hydrogen peroxide-containing liquid Water 800 ml 5 Sodium sulfosalicylate 50 g KCl 2.5 g Benzotriazole 0.02 g Hydroxyethylidene-1,1-diphosphonic acid (30% aqueous solution) 4 ml Hydrogen peroxide 30 ml Add water 1000 ml pH 7 Table 7 shows the surface tension reducing agents shown in Table 7 for the treatment liquid b-1.
The processing solutions b-2 to b-10 to which the amounts shown in (1) and (2) were added were prepared.

[0252]

[Table 7]

Stabilizing solution Potassium carbonate 15 g 2-Mercaptobenzimidazole-5-sodium sulfonate 1 g Hydroxyethylidene-1,1-diphosphonic acid (30% aqueous solution) 1 ml 5-Chloro-2-methyl-4-isothiazolin-3-one 0.02g Add water and 1000ml pH 7

Rinse solution 0.02 g of chlorinated sodium isocyanurate Deionized water (conductivity 5 μS / cm or less) 1000 ml pH 6.5

[0255]

Treatment Method 2 Treatment Step Temperature Time Alkaline Treatment Liquid Coating 40 ° C .— (Applying Treatment Method by Methods Described in Tables 8, 9 and 10: 40 cc / m ^{2 of} Treatment Liquid) Hydrogen Peroxide-Containing Liquid Smearing 40 ° C-(Smearing treatment according to the method described in Tables 8, 9 and 10 The amount of treatment liquid applied is 40 cc / m ² ) Leave on a heat panel 40 ° C for 30 seconds Stabilizing treatment 40 ° C for 45 seconds 30 ° C 90 seconds Drying 70 ° C 60 seconds

An FWH type photometer manufactured by FUJIFILM Corporation (color temperature of light source: 3200.K) was used for all the prepared samples.
Was used to give a gradation exposure of a three-color separation filter for sensitometry.

Tables 8, 9 and 10 for each sample after exposure
The processing was performed according to the processing method shown in FIG.

For each sample after the treatment, blue light, green light,
The concentration was measured with red light. Tables 8, 9 and 10 show the densities measured for each color.

An unexposed and untreated sample was 5 cm × 10
cm and the whole was exposed to white light. The exposed samples were processed according to the processing methods and processing conditions shown in Tables 8, 9 and 10. When the treatment liquid was applied, the application was performed such that the side of 10 cm was horizontal to the application direction.

The concentration of the sample after the treatment was measured at a portion 0.3 cm inside the outer edge of the long side of 10 cm and 3 cm inside the short side of 5 cm, and the concentration was measured 4 cm from the inside. The average of the measured concentrations is De.
And In addition, a portion (center portion) 5 cm inside the outer edge of the long side of 10 cm was measured 4 cm from 3 cm inside the short side of 5 cm. The average value of the measured densities is defined as Dc.

[0262]

[Table 8]

[0263]

[Table 9]

[0264]

[Table 10]

Coating method 1 The photosensitive material is immersed in a tank containing an alkaline processing solution or a hydrogen peroxide-containing solution. Coating method 2 An alkaline processing solution or a hydrogen peroxide-containing solution is inserted into a thin slit and the photosensitive material is passed through. Coating method 3 Using a known roller coat (width 5.5 cm, coating length 12 cm) Coating method 4 Using a treatment liquid coating apparatus described in JP-A-9-179272 (nozzle width 5.5 cm, coating) Attached length is 12c
m). At this time, droplets are ejected from the nozzle holes, and three droplets ejected from these nozzle holes and adhered to the photosensitive material adjacent to each other come into contact with each other in a state where there is no gap between each other, and the photosensitive material is exposed. To be deposited on the material.

As apparent from Tables 8, 9 and 10, the treatment No. When tank processing is performed using a developing intensifying liquid as in processing method 1 as in 1 or the like, color development occurs, but bubbles are generated due to decomposition of hydrogen peroxide during processing, and the processing liquid deteriorates. . In addition, unevenness is observed in the processed sample. On the other hand, when the alkaline treatment liquid and the peroxide-containing liquid were separately supplied as in the treatment method 2, no unevenness of the treated sample due to generation of bubbles was observed. However, processing N
o. The surface tension of the peroxide-containing liquid, such as 3 to 6, 10, 14, etc., is 10 dyn higher than the surface tension of the alkaline treatment liquid.
If it is larger than / cm, the value of De is extremely small, and it can be seen that poor application of the hydrogen peroxide-containing solution has occurred around the photosensitive material. On the other hand, processing No.
The surface tension of the peroxide-containing liquid, such as 2, 7, 11, 13 or 15, is 10 dy with respect to the surface tension of the alkaline treatment liquid.
When it is not larger than n / cm, De shows almost the same value as Dc, and it can be seen that the peroxide-containing liquid is sufficiently applied to the periphery of the photosensitive material.

Example 2 Using the samples (100) to (108) of Example 1 and the alkaline treatment liquids a-1 to a-10 and b-1 to b-10, the gradation of three-color separation was obtained by the following method. Exposure was performed and processing was performed according to Example 1. The color density of the processed photosensitive material and the state of color development by uniform application were examined. (Exposure) A YAG solid-state laser (oscillation wavelength, 946 nm) using a semiconductor laser GaAlAs (oscillation wavelength, 808.5 nm) as an excitation light source as a light source is SHG of KNbO ₃ .
A YVO ₄ solid-state laser (oscillation wavelength, 108.7 nm) using a semiconductor laser GaAlAs (oscillation wavelength, 808.7 nm) as an excitation light source, having a wavelength of 473 nm, which has been taken out by wavelength conversion by a crystal.
532 nm, AlGaInP (oscillation wavelength, about 6 nm)
70 nm: Toshiba type No. TOLD9211) was used. Each of the laser beams is a device capable of sequentially scanning and exposing a color photographic paper moving in a direction perpendicular to a scanning direction by a rotating polyhedron. Using this apparatus, the relationship between the density (D) of the photosensitive material and the light amount (E) D-logE was obtained by changing the light amount. At this time, the laser light of three wavelengths modulates the light amount using an external modulator,
Exposure was controlled. This scanning exposure is performed at 400 dpi, and the average exposure time per pixel at this time is about 5 × 10 ⁻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.

As a result, even when an image formed by digital exposure with high illuminance is processed by the image forming method of the present invention, a high color density is exhibited as in the case of Example 1, and the end of the photosensitive material is obtained. It turned out that the color was developed evenly.

[0269]

According to the present invention, it is possible to easily and rapidly form a color photographic image which is excellent in color development, storage stability, color image fastness and hue, and realizes both low waste liquid amount and reduced processing fluctuation. it can. ADVANTAGE OF THE INVENTION According to the color image forming method of the present invention, it is possible to uniformly develop the color evenly to the edge portion of the photosensitive material coated with the processing liquid and apply the uniform coloring property over the entire surface of the processed photosensitive material. It has an excellent effect.

[Brief description of the drawings]

FIG. 1 is a schematic overall configuration diagram of a coating apparatus used for carrying out the present invention.

FIG. 2 is an enlarged perspective view of an injection tank used for implementing the present invention.

FIG. 3 is a bottom view showing a state in which a photosensitive material is conveyed below an injection tank used for carrying out the present invention.

FIG. 4 is an enlarged view of a main part of FIG. 3;

FIG. 5 is a plan view showing a photosensitive material in a state where droplets of a processing liquid are ejected and applied from nozzle holes of an ejection tank in the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03D 5/04 G03D 5/04 Z

Claims (16)

[Claims] 1. A color image forming method for performing color development processing on a silver halide color photographic light-sensitive material having at least one photographic constituent layer on a support using an alkaline processing solution substantially free of a color developing agent. The silver halide photographic material is oxidized to at least one of the photographic constituent layers by at least one dye-forming coupler and at least one silver halide, and the oxidized product is coupled with the coupler to have a dye having absorption in the visible region. And a precursor thereof, and the total amount of silver in all the coating layers of the light-sensitive material is 0.
003 to 0.3 g / m ² , and after the alkaline processing liquid is supplied onto the photosensitive material, the peroxide-containing liquid is supplied onto the photosensitive material by droplet ejection from a plurality of nozzle holes. A method in which three droplets ejected from these nozzle holes and adhered to the photosensitive material adjacent to each other are attached to the photosensitive material in a state where there is no gap between them. A color image forming method, wherein the surface tension of the peroxide-containing liquid is not more than 10 dyn / cm as compared with the surface tension of the alkaline processing liquid. 2. A compound which is oxidized by the silver halide and forms a dye having an absorption in the visible region by coupling the oxidized product with a coupler is represented by the following general formula (I) or (II). 2. The color image forming method according to claim 1, wherein: Embedded image Embedded image In the formula, R _{1 to} R ₄ represent a hydrogen atom or a substituent.
A ₁ and A ₂ represent a hydroxyl group or a substituted amino group. X is -C
O -, - SO -, - SO 2 -, it represents a divalent or higher linking group selected from -PO <. Y _1K and Z _1K represent a nitrogen atom or a group represented by —CR ₅ （(R ₅ is a hydrogen atom or a substituent). k represents an integer of 0 or more. P represents a proton-dissociable group or a group capable of becoming a cation, and an oxidant generated by a redox reaction between the present compound and exposed silver halide is coupled with a coupler, and then the electron transfer from P is triggered. NX
It has a function of forming a dye by breaking a bond and removing a substituent bonded to a coupling site of a coupler. Y
Represents a divalent linking group. Z is a nucleophilic group and represents a group capable of attacking X when the present compound is oxidized. n is X
Is 1 or 2 when —PO <, and 1 when X is another group. R ₁ and R ₂ , R ₃ and R ₄ and Y _1K , Z
Two or more atoms or substituents arbitrarily selected from _1K and P may be independently bonded to each other to form a ring. 3. A compound which is oxidized by the silver halide and forms a dye having an absorption in the visible region by coupling of the oxidized product with a coupler is represented by the following general formula (II):
2. The color image forming method according to claim 1, wherein: Embedded image In the formula, R ¹¹ is an aryl group or a heterocyclic group which may have a substituent, and R ¹² is an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group which may have a substituent. is there. X ⁰ is _{-SO 2 -, - CO -,} - CO
CO -, - CO-O - , - CONH (R 13) -, - CO
CO-O -, - COCO- N (R 13) - or -SO ₂
—NH (R ¹³ ) —. Here, R ¹³ is a hydrogen atom or a group described for R ¹² . 4. The color image forming method according to claim 3, wherein the compound represented by the general formula (III) is represented by the general formula (IV) or (V). Embedded image In the formula, Z ¹ represents an acyl group, a carbamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group, and Z ² represents a carbamoyl group, an alkoxycarbonyl group,
Or an aryloxycarbonyl group, X ¹ ,
X ² , X ³ , X ⁴ and X ⁵ represent a hydrogen atom or a substituent. Here, Hammett's substituent constant σ of X ¹ , X ³ and X ⁵
The sum of the p value and the Hammett's substituent constant σm value of X ² and X ⁴ is 0.08 or more and 3.80 or less. R ^3a represents a heterocyclic group. 5. The color image forming method according to claim 4, wherein the compounds represented by formulas (IV) and (V) are represented by formulas (VI) and (VII), respectively. Embedded image In the formula, R ^1a and R ^2a represent a hydrogen atom or a substituent,
X ¹ , X ² , X ³ , X ⁴ and X ⁵ represent a hydrogen atom or a substituent. However, the sum of the Hammett's substituent constant σp value of X ¹ , X ³ and X ^{5 and} the Hammett's substituent constant σm of X ² and X ⁴ is 0.80 or more and 3.80 or less. R ^3a represents a heterocyclic group. 6. The method according to claim 5, wherein the compounds represented by formulas (VI) and (VII) are represented by formulas (VIII) and (IX), respectively. Embedded image In the formula, R ^4a and R ^5a represent a hydrogen atom or a substituent,
One of R ^4a and R ^5a is a hydrogen atom, and X ⁶ , X
⁷ , X ⁸ , X ⁹ , and X ¹⁰ represent a hydrogen atom, a cyano group, a sulfonyl group, a sulfinyl group, a sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a trifluoromethyl group, a halogen atom, an acyloxy group. Represents a group, an acylthio group, or a heterocyclic group. However, the sum of the Hammett's substituent constant σp value of X ⁶ , X ⁸ and X ^{10 and} the Hammett's substituent constant σm value of X ⁷ and X ⁹ is 1.20 or more and 3.80 or less. Q ¹ represents a group of nonmetallic atoms necessary for forming a nitrogen-containing 5- to 8-membered heterocyclic ring together with C. 7. A precursor of a compound which is oxidized by the silver halide and forms a dye having an absorption in a visible region by coupling the oxidized product with a coupler is represented by the following general formula (X): 2. The color image forming method according to claim 1, wherein: Embedded image In the formula, Ar represents an aryl group or a heterocyclic group, X represents a methylene group in which a formyl group has been oxidized and substituted at a position capable of releasing a color developing agent, L represents a linking group, and m represents a linking group. Represents an integer of 0 to 3, and PPD represents a color developing agent. 8. The color image forming method according to claim 7, wherein the compound represented by the general formula (X) is represented by the general formula (XI). Embedded image In the formula, R is a hydrogen atom, a hydroxyl group, a halogen atom,
Represents an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an acyloxy group, an acylamino group, a sulfonylamino group, or another amino group. May be formed. —CH ₂ — represents a methylene group located ortho or para to the formyl group, L represents a linking group, PPD represents a color developing agent, 1 represents an integer, and n represents an integer of 1 to 4. . 9. The color image forming method according to claim 8, wherein the compound represented by the general formula (XI) is represented by the general formula (XII). Embedded image In the formula, R ¹ represents a hydrogen atom, an alkyl group, an aryl group, or an acyl group, and R has the same meaning as that in formula (XI). −
CH ₂ — represents a methylene group located ortho or para to the formyl group; PPD represents a color developing agent;
Represents an integer of 0 to 3. 10. The method according to claim 1, wherein the supply method of the alkaline processing liquid onto the photosensitive material is a supply method by coating. The color image forming method as described above. 11. A method of supplying said alkaline processing liquid onto a photosensitive material, wherein droplets are ejected from a plurality of nozzle holes and ejected from these nozzle holes and adhered to said photosensitive material adjacent to each other. 11. The color image forming method according to claim 10, wherein the method is performed by a method in which two liquid droplets are brought into contact with each other with no gap therebetween and adhered to the photosensitive material. 12. The alkaline processing liquid having a surface tension of 60.
The color image forming method according to claim 11, wherein dyn / cm or less. 13. The total amount of the alkaline processing liquid and the peroxide-containing liquid applied to the light-sensitive material is 100 ml / m ^2.
Claims 1, 2, 3, 4,
The method for forming a color image according to 5, 6, 7, 8, 9, 10, 11 or 12. 14. The method according to claim 1, wherein the time from application of said alkaline treatment liquid to application of said peroxide-containing liquid is 10 seconds or less. ,
The color image forming method according to 7, 8, 9, 10, 11, 12, or 13. 15. The method according to claim 1, wherein the peroxide-containing liquid is an aqueous solution of hydrogen peroxide.
The color image forming method according to 6, 7, 8, 9, 10, 11, 12, 13, or 14. 16. An exposure time per pixel of 10 ^-8 to 1
The exposure is performed by a scanning exposure in which ^0-4 seconds and overlap between adjacent rasters is performed.
5, 6, 7, 8, 9, 10, 11, 12, 13, 14,
17. The color image forming method according to 15 or 16.