JP2000284434A - Color image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming method for a silver halide color photographic sensitive material by which processing stability is considerably enhanced. SOLUTION: When a silver halide photosensitive material with photographic constituent layers containing a photosensitive silver halide emulsion on the substrate is subjected to image amplification processing after exposure to form a color image, an amplifying solution of pH 3-8 not containing halogen ions and a color developing agent but containing hydrogen peroxide or a compound which supplies hydrogen peroxide is applied as a thin layer to the surface of the silver halide photosensitive material containing a dye forming coupler and a reducing agent for color development represented by the formula in any of the photographic constituent layers to form the objective developed color image. In the formula, R11 is aryl which may have a substituent or a heterocyclic group, R12 is alkyl which may have a substituent, alkenyl, alkynyl or aryl, X is-SO2-, -CO-, -COCO-, -CO-O-, -CONH(R13)-, -COCO-O- or -SO2-NH(R13)- and R13 is H or the same meaning as R12.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for forming a color image of a silver halide photographic material. Further, the present invention relates to a method for forming a color image of a silver halide photographic light-sensitive material which is excellent in processing stability and suitable for simple and rapid processing.
A color image forming method by amplifying silver halide photographic light-sensitive material, which can process a small amount of processing solution with just one use and is suitable for obtaining a uniform and clear image even when using a light-sensitive material with greatly reduced silver. About.

[0002]

2. Description of the Related Art In general, a silver halide color photographic material is formed into an image through a color developing step and a silver removing step.
In the color development step, the exposed silver halide grains are developed (reduced) by an aromatic primary amine developing agent, and a color reaction image is obtained by the subsequent reaction of the oxidized product with the coupler. For example, in color paper processing, 4-amino-N-ethyl-N- (β
-Methanesulfonamidoethyl) -aniline sulfate.

[0003] When the above-mentioned color developing agent or the like is converted to an alkaline liquid, it is oxidized by air and deteriorates remarkably. Therefore, a large amount of preservative and a large amount of replenisher are used, and the liquid composition and photographic performance are maintained. In recent years, in the technical field of photographic processing services, it has been desired to reduce the environmental load and the amount of waste and to reuse the same, and the processing chemicals of the color developer and the replenishment thereof have been actively promoted. However,
In order to maintain both photographic performance in continuous processing and light processing, and to reduce the amount of replenishment, it is necessary to further concentrate the processing chemicals in the replenisher, and the processing chemicals have not yet been reduced significantly. It is. Further, when the replenishment is promoted, there is a problem that the fluctuation of the stain and the photographic performance due to the accumulated components is remarkably increased.

[0004] As an effective solution for reducing and reducing replenishment of processing chemicals, it is conceivable to incorporate a color developing agent or a precursor thereof into a light-sensitive material and process it with an alkaline solution containing no developing agent. 2nd, 507, 11
No. 4, No. 3,764,328 and No. 4,060,418. However, these aromatic primary amine developing agents and their precursors are unstable, and have a drawback that stain occurs during long-term storage or color development of unprocessed photosensitive materials.

[0005] Other than the color development method described so far, for example, European Patent Nos. 0545491A1 and 0
A method is known in which a sulfonylhydrazine type compound described in 565 165 A1 and the like and a coupler are incorporated in a photosensitive layer to form a coupling image during development. For example, a 2-equivalent coupler has advantages over a 4-equivalent coupler in that the stain during storage of the coupler itself can be reduced and various functions can be imparted to the leaving group. When an equivalent coupler was used, there was a disadvantage that almost no color was formed.
For example, carbamoylhydrazine compounds as hydrazine compounds which exhibit sufficient color development even when a 2-equivalent coupler is used are disclosed in JP-A-8-234388 and JP-A-8-32054.
No. 2. JP-A-8-297354 describes that a simple and rapid processing system can be obtained by subjecting a low-silver amount photosensitive material containing these hydrazine compounds to an amplification treatment using an aqueous hydrogen peroxide solution. When a low silver content photosensitive material containing a hydrazine compound for color development and a coupler as described above is continuously processed with an amplification solution containing hydrogen peroxide or a compound for supplying hydrogen peroxide and not containing a color developing agent, a conventional method is used. Continuous processing stability is greatly improved as compared with processing with an amplification developer containing a color developing agent and hydrogen peroxide. However, it has been found that the deterioration of the image due to the generation of microbubbles inside the image, the fluctuation of the sensitivity and the gradation still occur, and the uneven processing due to the fluctuation of the stirring also occurs.

[0006]

Thus, a color photographic light-sensitive material using a color-forming reducing agent in a light-sensitive material contains hydrogen peroxide or a hydrogen peroxide-supplying compound substantially free of a color developing agent. In the case of processing using an amplifying solution, it is necessary to further suppress the deterioration of the image and the fluctuation of the photographic properties. An object of the present invention is to provide a method for forming an image of a silver halide color photographic light-sensitive material capable of performing simple and quick processing with an amplification solution using hydrogen peroxide and obtaining a clear image with a light-sensitive material having a significantly reduced silver content. To provide. Another object of the present invention is to provide a method for forming an image of a silver halide color photographic light-sensitive material, in which the above-mentioned amplification solution is applied to a small-volume light-sensitive material and the processing stability is further improved.

[0007]

In view of such a problem,
As a result of intensive studies, the present inventors have found that the above object can be achieved by the following means. That is, the present invention can be achieved by the following method. (1) A method for forming a color image by exposing a silver halide light-sensitive material having at least one photographic constituent layer containing a photosensitive silver halide emulsion on a support to form a color image after exposure, The surface of a silver halide photosensitive material containing at least one dye-forming coupler and a color-forming reducing agent represented by the general formula (I) is substantially free of halogen ions and a color-developing agent. PH 3 to 3 including compounds that supply hydrogen oxide or hydrogen peroxide
8. A method for forming a color image, comprising forming a color image by applying the amplifying solution of No. 8 in a thin layer. General formula (I)

[0008]

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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 is -SO ₂ -, - CO
-, - 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 . (2) The color image forming method according to item (1), wherein an alkaline processing solution containing no color developing agent is applied before or after the application of the amplification solution according to item (1). (3) An auxiliary developing agent is contained in any of the photographic layers described in (1), (1) or (2).
Item. (4) (1), (2), or (2), wherein the total silver content of all coating layers contains silver halide of 0.003 to 0.3 g / m ^{2 in} terms of silver. (3) The color image forming method according to the above (1). (5) (1), (2), (3) or (1) wherein the concentration of hydrogen peroxide or a compound supplying hydrogen peroxide is 0.1% or more and 3% or less in terms of hydrogen peroxide. 4) The color image forming method according to the item. (6) The supply amount of the amplification solution applied in the form of a thin layer is 5 ml or more and 50 ml or less per 1 m ² , wherein (1), (2), (3), (4) or (5) is provided. Color image forming method. (7) The exposure is performed by scanning exposure of 10 ^-8 to 10 ^-4 seconds per pixel (1), (2),
The color image forming method according to the above mode (3), (4), (5) or (6). (8) In the method of applying the processing liquid to the surface of the photosensitive material in a thin layer, a plurality of nozzle holes for jetting the processing liquid are provided, and adjacent droplets ejected from these nozzles have a gap therebetween. (1), (2), (3), (4),
(5) The color image forming method according to (6) or (7).

[0010] In the present invention, image amplification processing refers to reduction for color formation using a latent image of silver halide grains or developed silver as a catalyst and an oxidizing agent (intensifier) such as hydrogen peroxide in the presence of the catalyst. Oxidizing agent or developing agent for color formation, or cause the oxidation reaction in parallel with the development, to form a color image by the color development reaction of the oxidized product and the coupler for dye formation, to form a dye image (referred to as image intensification) This is a processing method for amplification. For example, there is a case where amplification is performed after development, a case where development and amplification are performed in parallel after development, and a case where development and amplification proceed simultaneously. The amplification rate refers to the amplified dye concentration (the concentration in the amplification process) / the dye concentration corresponding to the silver development amount (the concentration in the processing of a processing solution without an amplifying agent). In the present invention, the amplification solution refers to a solution containing an intensifier and no color developing agent, and the amplification developer refers to a solution containing both the intensifier and the color developing agent.

The silver halide light-sensitive material containing a color-forming reducing agent and a coupler used in the present invention is excellent in long-term storage stability. When the photosensitive material is subjected to ordinary tank processing with an alkaline processing solution containing hydrogen peroxide without containing a color developing agent, processing unevenness occurs due to agitation fluctuations, and continuous processing is performed while replenishing the amount of hydrogen peroxide consumed in the processing. Processing also causes fluctuations in photographic performance (maximum density, sensitivity, gradation, etc.). In addition, micro bubbles may be generated in the processed image. Furthermore, when the alkaline processing solution is applied in a thin layer and processed, the fluctuation of the photographic performance can be suppressed, but 1) fine bubbles in the image increase, and when the coating is applied from a nozzle described later, it is remarkable. 2) White spot unevenness different from the processing unevenness occurs, and 3) In the coating apparatus, particularly, the metal member to which the hydrogen peroxide-containing processing solution comes into contact easily deteriorates. Problems arise. The silver halide emulsion used in the present invention, a photosensitive material containing a color-forming reducing agent and a dye-forming coupler, after applying an alkaline processing solution containing no color-developing agent, containing no color-developing agent and halogen ions, When a processing solution having a pH of 3 to 8 containing hydrogen peroxide or a hydrogen peroxide supply compound is applied in the form of a thin layer and processed, a color image showing high color development in a short time, high color density and low minimum density is obtained. Is obtained.
In addition, there is no generation of bubbles, no fine bubbles even in the screen, and an image free of white spots and processing unevenness is obtained. Furthermore, the stability of the hydrogen peroxide treatment solution is good, the coating is stable even in the equipment used for coating, and the coating of a small amount of liquid is stable with little deterioration (for example, metal corrosion) of the equipment. It becomes possible.

In the present invention, it is preferable to apply an alkaline processing solution containing no color developing agent before or after applying the hydrogen peroxide-containing processing solution, and particularly to apply an alkaline processing solution before applying the hydrogen peroxide processing solution. Preferably, a liquid is applied. In particular, in the present invention, when a hydrogen peroxide-containing treatment liquid or an alkaline treatment liquid is applied in a thin layer, the treatment liquid is spray-coated from an apparatus having a plurality of nozzles, whereby the treatment liquid stability and the treatment uniformity are also good. Gives a favorable image.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a specific configuration of the present invention will be described in detail. Hereinafter, the structure of the color-forming reducing agent represented by the general formula (I) will be described in detail. General formula (I)
In the above, 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. The heterocyclic group represented by R ¹¹ is preferably a saturated or unsaturated 5-, 6- or 7-membered ring containing at least one of nitrogen, oxygen, sulfur and selenium. These may be condensed with a benzene ring or a hetero ring. Examples of the hetero ring of R ¹¹ include furanyl, thienyl, oxazolyl, thiazolyl,
Imidazolyl, triazolyl, pyrrolidinyl, benzoxazolyl, benzothiazolyl, pyridyl, pyridazyl, pyrimidinyl, pyrazinyl, triazinyl, quinolinyl, isoquinolinyl, phthalazinyl, quinoxalinyl, quinazolinyl, purinyl, pteridinyl, azepinyl, benzooxepinyl and the like; Of these heterocycles, thiadiazolyl is particularly preferred.

The substituent of R ¹¹ includes 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 represents -SO _2- , -CO-, -C
OCO -, - CO-O - , - CON (R 13) -, - CO
CO-O -, - COCO- N (R 13) - or -SO ₂
—N (R ¹³ ) —. 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 (I), the following compounds represented by the general formulas (II) and (III) are preferable, and the compounds represented by the general formulas (IV) and (V) are more preferable. Compounds represented by VI) and (VII) are more preferred.

[0017]

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[0018]

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[0019]

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The compounds represented by formulas (II) to (VII) will be described below in detail. In the general formulas (II) and (III), 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, A dodecyloxybenzoyl group, a 2-hydroxymethylbenzoyl group, and a 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 (VI) to (VII).

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 carbon atoms of 1
Up to 50 linear or branched, chain or cyclic alkyl groups (e.g., trifluoromethyl, methyl, ethyl, propyl, heptafluoropropyl, isopropyl, butyl, t-butyl, t-pentyl, cyclopentyl, cyclohexyl, octyl, 2-ethylhexyl, dodecyl, etc.), a linear or branched, chain or cyclic alkenyl group having 2 to 50 carbon atoms (eg, vinyl, 1-methylvinyl,
Cyclohexen-1-yl and the like), an alkynyl group having a total of 2 to 50 carbon atoms (eg, ethynyl, 1-propynyl and the like),
An aryl group having 6 to 50 carbon atoms (for example, phenyl, naphthyl, anthryl and the like), an acyloxy group having 1 to 50 carbon atoms (for example,

Acetoxy, tetradecanoyloxy, benzoyloxy and the like, a carbamoyloxy group having 1 to 50 carbon atoms (for example, N, N-dimethylcarbamoyloxy and the like), and a carbonamide group having 1 to 50 carbon atoms (for example, 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 and sulfur;
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. As for X ¹ , X ² , X ³ , X ⁴ and X ⁵ in the general formula (II), X
Hammett's substituent constant σp value of ¹ , X ³ and X ⁵ and X ² and X ⁴
Sum of the Hammett's substituent constant σm value of 0.80 or more,
3.80 or less. X ⁶ , X ⁷ , X ⁸ , X ⁹ and X ¹⁰ in the general formula (VI) 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, Represents 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,
It may combine with each other to form a condensed ring. These specific examples are the same as those described for X ¹ , X ² , X ³ , X ⁴ and X ⁵ . However, in the general formula (VI), X ⁶ , X ⁸ ,
The sum of the Hammett's substituent constant σp value of 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. And more preferably 1.70 or more and 3.80 or less. Here, if the sum of the σp value and the σm value is less than 0.80, there is a problem that the coloring properties are not sufficient, and conversely, 3.80.
If it exceeds the limit, 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 in the general formulas (IV) and (V)¹, R^Two,
R in (VI) and (VII)^4a, R^5aIs a hydrogen atom or
And a specific example of the substituent is X¹, X^Two, X^Three,
X^Four, X ^FiveHas the same meaning as described for
Or a hydrogen atom or a substituted or unsubstituted group having 1 to 50 carbon atoms.
Substituted alkyl group, substituted or absent having 6 to 50 carbon atoms
A substituted aryl group, substituted or unsubstituted having 1 to 50 carbon atoms
And more preferably R^1a, R^2aLittle
At least one and R^4a, R^5aAt least one is hydrogen
Is an atom.

In the general formulas (III) and (V), 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,
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, and a specific example of the heterocyclic ring is furan. , Pyran, pyridine, thiophene, imidazole, quinoline, benzimidazole, benzothiazole, benzoxazole, pyrimidine, pyrazine, 1,2,4-thiadiazole, pyrrole, oxazole, thiazole, quinazoline, isothiazole,
Pyridazine, indole, pyrazole, triazole,
Examples thereof include quinoxaline, and 1,2,4-thiadiazole is particularly preferable. 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 used in the present invention is incorporated in the photosensitive material, at least one of Z ¹ , Z ² , R ^{1a to} R ^5a , and X ^{1 to} X ¹⁰ has a ballast group. Is preferred. Q
Examples of the heterocycle completed in ₁ are specific compound examples I-1
6 to 1-74.

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

[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[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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[0044]

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The couplers for dye formation used in the present invention are described in paragraphs 0053 to 0083 of JP-A-9-152696 and paragraphs 0039 to 0083 of JP-A-9-152705.
Paragraph 0066 and Japanese Patent Application No. 9-281207, paragraph 006.
The general formulas and specific examples of the compounds are described in detail in paragraphs 2 to 0096 and the like, and other compounds are appropriately used depending on the application.
The light-sensitive material used in the present invention basically has a photographic component layer comprising at least one hydrophilic colloid layer on a support, and one of the photographic component layers contains a photosensitive silver halide and a dye. Contains a forming coupler and a color-forming reducing agent.

The color-developing reducing agent used in the present invention may be added to either the photosensitive layer or the non-photosensitive layer, but is preferably added to the photosensitive layer together with the dye-forming coupler. Further, it is preferably added after being emulsified with a coupler. The reducing agent for color development used in the present invention is used in an amount of 0.01 to 10 per color forming layer in order to obtain a sufficient color density.
It is preferred to use 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 . The amount of the coupler in the color-forming layer in which the color-forming reducing agent used in the present invention is used is preferably 0.05 to 20 times, more preferably 0.1 to 10 times, in terms of mol, based on the color-forming reducing agent.
Particularly preferably, it is 0.2 to 5 times.

The color-forming reducing agent and coupler used in the present invention can be introduced into a photographic material by various known dispersion methods.
High boiling organic solvent (use low boiling organic solvent if necessary)
In water, and then emulsified and dispersed in an aqueous gelatin solution and added to the silver halide emulsion. The high-boiling organic solvent that can be used in the present invention is a compound that is immiscible with water having a melting point of 100 ° C. or lower and a boiling point of 140 ° C. or higher and can be used as long as it is a good solvent for the color-forming reducing agent and the coupler. 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. In particular, it is preferable to use a high-boiling organic solvent having an electron donating parameter of 8 or more described in JP-A-7-149492. In the present invention, when the high boiling organic solvent is used, the amount of the high boiling organic solvent used may be any amount. Preferably, the high boiling organic solvent / color developing solvent is preferably used in a weight ratio to the color-forming reducing agent. The reducing agent ratio is preferably 20 or less.
02 to 5 are more preferable, and 0.2 to 4 are particularly preferable.
A tertiary amine such as trilaurylamine or a quaternary ammonium salt such as a tetraoctylammonium salt or a quaternary ammonium-based polymer or an imidazole-based polymer is contained in the high-boiling organic solvent containing the color-forming reducing agent. It is preferred to include. 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. 2,54
No. 1,230, JP-B-53-41091, and European Patent Publication No. 029104. As a more preferable method, a dispersion method using a water-insoluble and organic solvent-soluble polymer is described in PCT International Publication No. WO88.
/ 00723.

In the present invention, when the color-forming reducing agent is contained in the form of lipophilic fine particles, the average particle size is not particularly limited, but is preferably 0.05 to 0.3 μm from the viewpoint of color-forming properties. Further, the thickness is more preferably 0.05 to 0.2 μm. Generally, 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, and increase the lipophilic organic layer. This can be achieved by lowering the viscosity by using a low boiling point organic solvent in combination, or by increasing the shearing force such as increasing the rotation of the stirring blade of the emulsifying device, or by lengthening the emulsifying 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, 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 released color developing agent to silver halide in the course of developing silver halide grains, and is preferably an exposed halogen. It is a compound capable of developing silver halide particles and oxidizing the color developing agent from which the oxidized product has been released (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
%, More preferably 0.05% or less, 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 used in 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 Kender-Loupertz rule other than the p-phenylenediamine compound 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 blocking group 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, but are preferably used by adding 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. Addition methods include a method of dissolving in a solvent or oil that is substantially immiscible with water and then adding a substance dispersed in water or a hydrophilic colloid or a method of adding a solid fine particle dispersion. 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 light-sensitive material is from 1 mole% to 200 mole%, preferably from 5 mole% to 100 mole%, more preferably from 10 mole% to 50 mole%, based on the color developing agent precursor.

In the present invention, the silver halide light-sensitive material preferably contains a basic metal compound which is hardly soluble in water. For example, from page 3, column 31, line 31 of Japanese Patent Publication No. 2612205-
The compounds described on page 4, column 7, line 12 are used. In this case, the amplification solution contains page 17, column 17, 17 of Japanese Patent Publication No. 2612205.
A compound capable of forming a complex with a metal ion constituting the basic metal compound described in line 14 to column 14, line 48 is used. When both perform a complexing reaction during amplification development, a base (alkali) is generated in the film of the photosensitive material, whereby the pH in the film accompanying amplification development is compensated, and image formation is promoted.

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 water-resistant resin layer, wherein at least one of the water-resistant 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 is obtained by dividing a surface having a mirror surface into fine mirror surfaces oriented in different directions by giving irregularities. The unevenness on the surface of the second type diffuse reflection surface has a three-dimensional average roughness of 0.1 to 2 μm, preferably 0.1 to 1.2, with respect to the center plane.
μm. 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 a binder or protective colloid which 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, more preferably 200 ppm or less.
The content of heavy metals contained as impurities such as copper, zinc, and manganese is preferably 5 ppm or less, more preferably 3 ppm or less. Further, in order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image, Japanese Patent Application Laid-Open No.
It is preferable to add an antifungal agent as described in 271247.

As the silver halide light-sensitive material used in the present invention, other conventionally known photographic materials and additives can be used. For example, as described above, a transmissive support or a reflective support can be used as the photographic support. Examples of the support for permeation include a permeation film such as a cellulose triacetate film and polyethylene terephthalate, a polyester of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG), and NDCA
A material in which an information recording layer such as a magnetic layer is provided on polyester of terephthalic acid and EG and the like is preferably used. As the reflective support, a reflective support laminated with a plurality of polyethylene layers or polyester layers, and containing a white pigment such as titanium oxide in at least one of such water-resistant resin layers (laminated layers) is preferable.

Further, it is preferable that the water-resistant resin layer contains a fluorescent whitening agent. The fluorescent whitening agent may be dispersed in the hydrophilic colloid layer of the light-sensitive material. As the fluorescent whitening agent, preferably, benzoxazole type, coumarin type,
A pyrazoline-based fluorescent whitening agent can be used, and a benzoxazolylnaphthalene-based or benzooxazolylstilbene-based fluorescent whitening agent is more preferable. The amount used is not particularly limited, but is preferably 1 to 100 mg / m ² . The mixing ratio when mixed with the water-resistant resin is preferably 0.0005 to 3% by weight based on the resin, and more preferably 0.1 to 3% by weight.
001 to 0.5% by weight. As a reflective support,
A transmission type support or a reflection type support as described above provided with a hydrophilic colloid layer containing a white pigment may be used.

As the silver halide emulsion used in the present invention, silver iodochloride, silver iodobromide, silver bromide, silver chlorobromide, silver chloride and the like are used. From the viewpoint of rapid processing, the silver chloride content is 95%. A silver chloride or silver chlorobromide emulsion having a silver chloride content of 98 mol% or more is more preferable. Among such silver halide emulsions, those having a silver bromide localized phase on the surface of silver chloride grains or those doped with a gold salt can provide high sensitivity and stabilize photographic performance. Is particularly preferred.

The above-mentioned silver halide emulsions, furthermore, foreign metal ion species doped in silver halide grains, storage stabilizers or antifoggants for silver halide emulsions, chemical sensitization (sensitizers), spectroscopy Sensitization method (spectral sensitizer), emulsification dispersion method of cyan, magenta, yellow coupler, etc., color image preservability improver (anti-stain agent and anti-fading agent), dye (colored layer), gelatin type, photosensitive material With respect to the layer constitution and the coating pH of the photosensitive material, those described in the patents of Tables 1 and 2 can be preferably applied to the present invention.

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[Table 1]

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[Table 2]

In the present invention, in order to form a color image having a high amplification factor and granularity with a small amount of silver, it is effective that the silver halide grains are small, for example, 0.01 μm to 0.5 μm.
Is preferably, and more preferably, 0.03 μm to 0.3 μm.
It is. The total coated silver amount of the photosensitive material used in the present invention is:
The amount is preferably 0.003 to 1 g per m ^{2 in} terms of silver, in which case the amount of each layer added is 0.001 to 1 per photosensitive layer.
~ 0.4 g is preferred. In particular, when performing the amplification development processing in the present invention, the amount is preferably 0.003 g to 0.3 g,
It is more preferably 0.01 to 0.1 g, particularly preferably 0.015 to 0.05 g. In this case, the amount is preferably 0.001 to 0.1 g, more preferably 0.003 g to 0.03 g, for one photosensitive layer. In the present invention, if the coated silver amount of each photosensitive layer is less than 0.001 g per 1 m ² , the dissolution of the silver salt proceeds, and a sufficient color density cannot be obtained.
On the other hand, if it exceeds 0.1 g, Dmin increases and bubbles are generated, and it becomes difficult to endure viewing.

The total amount of gelatin in the light-sensitive material used in the present invention is from 1.0 to 30 g, preferably from 2.0 to 20 g, per m ² . In the swelling of the present light-sensitive material using an alkaline solution having a pH of 12, the time required to reach a swelling film thickness which is 1/2 of its saturated swelling film thickness (90% of the maximum swelling film thickness) is preferably 15 seconds or less, and more preferably 10 seconds Seconds or less are preferred. The swelling ratio ((maximum swelled film thickness-film thickness) / film thickness × 10
0) is preferably 50 to 300%, particularly 100 to 20%.
0% is preferred. When the photosensitive material used in the present invention is exposed to a printer, it is preferable to use a band stop filter described in U.S. Pat. No. 4,880,726. As a result, light color mixing is removed, and color reproducibility is significantly improved.

The photosensitive material used in the present invention may be used in a printing system using a normal negative printer, or may be a gas laser, a light emitting diode, a semiconductor laser, a solid state laser using a semiconductor laser or a semiconductor laser as an excitation light source. It is preferably used for digital scanning exposure using monochromatic high-density light such as a second harmonic generation light source (SHG) in which a non-linear optical crystal is combined. 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 which is compact, inexpensive, and has a long life and high stability, it is preferable to use a semiconductor laser, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

When such a scanning exposure light source is used,
The spectral sensitivity maximum of the photosensitive material used in the present invention can be arbitrarily set depending on the wavelength of the scanning exposure light source used. A solid-state laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser with a nonlinear optical crystal can halve the laser oscillation wavelength, 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 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, at least two layers are 67
The need to have a spectral sensitivity maximum above 0 nm is reduced.

In such scanning exposure, the exposure time of the silver halide in the photosensitive material 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 is a practical range of 50 to 2000 dpi. When the exposure time is defined as the time for exposing the pixel size when the pixel density is 400 dpi, a preferable exposure time is 10 ^-4 seconds or less, more preferably 10 ^-6 seconds or less, and further preferably 10 ^-8 to 10 ^-4 seconds. In particular, by exposing with a scanning exposure in which the exposure time per pixel is 10 ^-8 to 10 ^-4 seconds and there is overlap between adjacent rasters,
It is preferable in that reciprocity failure is improved. The preferred scanning exposure applied in the present invention is described in JP-A-7-1044.
No. 48, column 76, line 6 to column 77, line 41.

In addition, the photosensitive material used in the present invention is:
It is also suitable for a scanning exposure method using a cathode ray (CRT). A cathode ray tube exposure apparatus is simpler, more compact, and lower in cost than an apparatus using a laser.

For the cathode ray tube used for image exposure, various luminous bodies which emit light in a spectral region are used as necessary. 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 luminous body 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 luminous body which emits light in a plurality of spectral regions, a plurality of colors are exposed at a time, ie, the cathode ray tube is exposed. Image signals of a plurality of colors may be input to the device to emit light from the back. A method of sequentially inputting image signals for each color to sequentially emit light of each color, and exposing through a filter for cutting a color other than that color (plane sequential exposure) may be employed. However, since a high-resolution cathode ray tube can be used, it is preferable for high image quality.

In the present invention, the "amplifying solution" is characterized in that it does not substantially contain a p-phenylenediamine-based color developing agent and a halogen ion as conventionally used, and other components (buffer, A fluorescent whitening agent, a wetting agent or a chelating agent). Further, it is preferable that a reducing agent is not contained in order to maintain processing stability,
In such a case, it is preferable that an auxiliary developing agent, hydroxyamines, sulfites and the like are not substantially contained. Here, the term "substantially not contained" means that in the case of a color developing agent and other reducing agents, it is preferably 1 × 10 ⁻³ mol / L or less.
More preferably, it is 1 × 10 ⁻⁴ mol / liter or less.
In particular, it is preferable not to contain at all. The amount substantially not containing halogen ions such as chlorine ions and bromine ions is 5 × 10 ⁻³ mol / L or less, preferably 1 × 1 ⁻³ mol / L or less.
0 is ^-3 mol / l or less. 0.5 × iodine ion
It is at most 10 ^-4 mol / l, preferably at most 1 × 10 ^-5 mol / l. It is particularly preferred that no halogen ion is contained. The pH of the amplification solution is preferably 3
To 8, and particularly preferably 4 to 7. If the pH is less than 3, metal corrosion tends to occur, and if the pH exceeds 8, microbubbles are generated and the stability of hydrogen peroxide is deteriorated. The amount of hydrogen peroxide or the hydrogen peroxide supply compound contained in the amplification solution is preferably 0.1% to 3% in terms of hydrogen peroxide (weight).
%, More preferably 0.5% to 2%. 0.
If it is less than 1%, a long processing time is required to obtain a sufficient concentration, and if it exceeds 3%, the sensitivity and the amplification factor decrease. A photosensitive material for amplification development processing and its processing are described in, for example,
No. 234388, No. 8-297354, Japanese Patent Application No. 8-
Nos. 227381 and 8-229253 also apply.

The method for applying the treatment liquid (alkaline treatment liquid and amplification liquid) in the present invention will be described in detail. In the present invention, a method of applying an alkaline processing solution or an amplification solution in a thin layer on a light-sensitive material is disclosed in
No. 324455, Japanese Patent Application Laid-Open No. 9-179272, a method of spraying and spraying liquid from a thin nozzle, Japanese Patent Publication No. 261
The method of passing through a slit described in No. 2205 or a method of applying a thin layer on the surface of a photosensitive material by a coating method using a roller coat, a felt cloth, a sponge sheet, or the like is preferably used. In particular, the apparatus has a plurality of nozzle holes for ejecting an alkaline processing solution and an amplifying solution, and uses a device for causing adjacent droplets ejected from these nozzles to adhere to each other so as not to have a gap therebetween. A method of applying while spraying while keeping the material in a non-contact state is preferable. When the alkaline processing solution and the amplifying solution are applied in a thin layer on a light-sensitive material in the present invention, the total film thickness is preferably 500 μm or less, more preferably 3 μm to 200 μm, and still more preferably 5 μm to 50 μm. When the thickness is 5 μm or less, the liquid thickness unevenness easily occurs, and when the thickness is 50 μm or more, the image unevenness easily occurs. When the amplification solution used in the present invention is applied in a thin layer on a photosensitive material, the supply amount is 5 ml or more and 50 ml per 1 m ² of the photosensitive material.
The following is preferable, and more preferably 10 ml or more and 40 ml
Below, more preferably 15 ml or more and 30 ml or less. Generally, it is not necessary to increase the viscosity of the alkaline treatment liquid and the amplification liquid, but when the coating thickness greatly depends on the viscosity as in dip coating, a slight thickener may be added. The viscosity of the applied liquid is 10 centipoise or less at 20 ° C., preferably 1 to 5 centipoise. The surface tension of the alkaline treatment solution and the amplification solution is 60 dyn / cm or less, preferably 50 dyn / cm or less, and more preferably 15 to 45 dyn / cm. When using the liquid,
The contact angle on the photosensitive material film surface is preferably 50 ° or less, more preferably 30 ° or less.

The processing material and processing method used in the present invention will be described in detail. In the present invention, the photosensitive material is subjected to amplification development, desilvering, and washing or stabilizing with water. Preferably, a silver salt is fixed by a fixing agent such as thiosulfate or a silver salt is stabilized by a stabilizer such as a nitrogen-containing mercapto compound without using a bleach such as a ferric salt. More preferably, desilvering or stabilization such as bleach-fixing or fixing is not performed, and washing or stabilization is performed immediately after amplification development.

In addition, various chelating agents can be used in the treatment liquid as an agent for preventing precipitation of calcium or magnesium, or for improving the stability of the amplification liquid. The addition amount of these chelating agents may be an amount sufficient to mask the metal ions in the treatment liquid, and is, for example, about 0.1 g to 10 g per liter. In the present invention, an optional antifoggant can be added as needed. As the antifoggant, a nitrogen-containing heterocyclic compound such as a benzimidazole compound or a benzotriazole compound is used. The addition amount of the nitrogen-containing heterocyclic compound is 1 ×
10 ^-6 to 1 × 10 ^-4 mol / l, preferably 1 ×
It is 10 ^-5 to 1 × 10 ^-4 mol / l.

An optional development accelerator can be added to the amplification solution, if necessary. The amplification solution preferably contains a fluorescent whitening agent. In particular, it is preferable to use a 4,4'-diamino-2,2'-disulfostilbene compound. The processing temperature of the amplification solution applied to the present invention is 20 to 50 ° C, preferably 30 to 45 ° C. The processing time is 5 seconds to 2 minutes, preferably 10 seconds to 1 minute. When the desilvering process is performed after the amplification development, there are a case where a fixing process is performed and a case where a bleaching and a fixing process are performed. When performing the bleaching and fixing processes, the bleaching process and the fixing process may be performed separately or simultaneously (bleach-fixing process). Further, processing in two continuous bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. It is also preferable to carry out a stabilization treatment without performing a desilvering treatment after the development to stabilize a silver salt or a color image.

Examples of the bleaching agent used in the bleaching solution or the bleach-fixing solution include iron (III), cobalt (III), chromium (I
V), compounds of polyvalent metals such as copper (II), peracids, quinones and nitro compounds. Among them, iron (III) aminopolycarboxylate such as iron (III) complex salt of ethylenediaminetetraacetate and iron (III) complex of 1,3-diaminopropanetetraacetate, hydrogen peroxide, persulfate, etc. are rapidly treated and cause environmental pollution. It is preferable from the viewpoint of prevention. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is 3 to 8, preferably 5 to 7. The pH of the bleaching solution using persulfate or hydrogen peroxide is 4 to 11
And preferably 5 to 10. A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and the prebath thereof, if necessary.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioureas, large amounts of iodides, and JP-A-4-365037, pages 11 to 2.
Examples thereof include a nitrogen-containing heterocyclic compound having a sulfide group, a mesoionic compound, and a thioether compound described on page 1 and 5-66540, pages 1088 to 1092. As a preservative of the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct, or a sulfinic acid compound described in EP-A-294769A is preferable. The fixing solution or the bleach-fixing solution may further contain various fluorescent whitening agents; antifoaming agents; surfactants; polyvinylpyrrolidone;

The processing temperature in the desilvering step is 20 to 50 ° C., preferably 30 to 45 ° C. The processing time is 3 seconds to 1 minute, preferably 5 seconds to 30 seconds. Although the replenishment amount is preferably small, it is ^{3 to} 200 ml, preferably 5 to 100 ml, more preferably 10 to 50 ml per m ^{2 of} the photographic material. It is also preferable to perform the treatment without replenishment, to the extent that the evaporation amount is supplemented with water. The processing solution used for desilvering, stabilization, or washing with water is preferably applied to the surface of the photosensitive material after the amplification solution is applied.
It is applied in a thin layer at a liquid thickness of 100 μ, more preferably 10 to 50 μ.

The photosensitive material used in the present invention generally undergoes a washing step before drying. When the stabilization treatment is performed, the washing step may be omitted. In such a stabilization process, JP-A-57-8543 and 58-1
Nos. 4834 and 60-220345 and JP-A-58-127926 and 58-13837.
All known methods described in JP-A-58-140741 can be used. Further, a washing step and a stabilizing step in which a stabilizing bath containing a dye stabilizing agent and a surfactant represented by processing of a color light-sensitive material for photographing is used as a final bath may be performed. The washing and stabilizing solutions include sulfites; hard water softeners such as inorganic phosphoric acid, polyaminocarboxylic acid and organic aminophosphonic acid; metal salts such as Mg salts, Al salts and Bi salts; surfactants; Film agents; pH buffering agents; fluorescent whitening agents; silver salt-forming agents such as nitrogen-containing heterocyclic compounds can be used. As a dye stabilizer of the stabilizing solution,
Aldehydes such as formalin and glutaraldehyde,
Examples thereof include N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. The pH of the washing or stabilizing solution is 4 to 9, preferably 5 to 8. The processing temperature is generally from 15 to 45 ° C, preferably from 25 to 40 ° C. The processing time is generally from 5 seconds to 2 minutes, preferably from 10 seconds to 40 seconds. The overflow solution accompanying the washing and / or replenishment of the stabilizing solution can be reused in other steps such as a desilvering step.

The amount of the washing water and / or the stabilizing solution can be set in a wide range depending on various conditions, but the replenishing amount is preferably 3 to 200 ml per 1 m ² of the photographic material, and is preferably 10 to 50 ml.
l is more preferred. In order to reduce the amount of replenishment water, it is preferable to use a plurality of tanks and carry out the method in a multistage countercurrent system. Further, it is also preferable that the washing water or the stabilizing liquid is used up and used with a small amount by a shower method or the like. In the present invention, water obtained by treating an overflow liquid or a liquid in a tank with a reverse osmosis membrane for water saving can be used. For example, the treatment by reverse osmosis is preferably performed on water in the second and subsequent tanks for multi-stage countercurrent washing and / or stabilization.

In the present invention, it is preferable that the stirring is strengthened as much as possible. Specific methods of strengthening the stirring are described in JP-A-62-183460 and JP-A-62-1834.
No. 61, a method of impinging a jet jet of a processing liquid on an emulsion surface of a light-sensitive material, a method of increasing a stirring effect by using a rotating means of JP-A-62-183461, and a wiper blade provided in a liquid A method in which the photosensitive material is moved while bringing the emulsion surface into contact with the emulsion surface to make the emulsion surface turbulent, thereby improving the stirring effect, and a method of increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is useful in any of a bleaching solution, a fixing solution, a bleach-fixing solution, a stabilizing solution, and water washing, but is particularly useful in water washing and stabilizing. These methods are effective in that the supply of the effective component in the liquid into the photosensitive material and the diffusion of the unnecessary component of the photosensitive material are promoted.

In the present invention, when the treatment is performed in the tank after the amplification treatment and before the drying, the liquid opening ratio [air contact area (cm ² ) / liquid volume (cm ³ )] is excellent in any state. However, the liquid opening ratio is preferably ⁰ to 0.1 cm ^-1 from the viewpoint of the stability of the liquid component. In the continuous treatment, practically 0.001 cm ^{-1 to} 0.05 c
m ^-1 is preferred, and more preferably 0.002 to
0.03 cm ^-1 . In a processing apparatus using a plurality of tanks for the photosensitive material used in the present invention, it is preferable to shorten the crossover time (air time) in order to shorten the processing time.
4, 5 or 6, and Japanese Patent Laid-Open No. 5-66540.
It is preferable to use a method of transporting between the processes described in FIG. 4 or FIG. 5 via a blade having a shielding effect. In the case where each processing solution is concentrated by evaporation in the continuous processing, it is preferable to add water to correct the concentration.

The processing time of the step in the present invention means the time required from the start of processing of the photosensitive material in one step to the start of processing in the next step. The actual processing time in an automatic developing machine is usually determined by the linear velocity and the capacity of the processing bath.
000 mm / min. In particular, in the case of a small developing machine, it is preferably 500 to 2500 mm / min. All processing steps, that is, the processing time from the amplification development step to the drying step is 3
It is preferably 60 seconds or less, more preferably 120 seconds or less, and particularly preferably used for 60 to 15 seconds. Here, the processing time is the time from the start of amplification and development of the photosensitive material to the time when the photosensitive material leaves the processor drying section.

In the present invention, since an amplification solution having a pH of 3 to 8 is used, it is preferable to use an alkaline processing solution containing no color developing agent before and / or after the application of the amplification solution. The alkaline processing liquid includes an alkali agent such as potassium hydroxide or sodium hydroxide, a buffer such as phosphate, a fluorescent whitening agent such as a diaminostilbene compound, an alkali metal halide such as potassium chloride, or the like. Antifoggants for nitrogen-containing heterocyclic compounds, water softeners such as organic phosphonic acids and aminopolycarboxylic acids, surfactants that reduce surface tension such as alkyl sulfates and polyoxyethylene alkyl ethers, preservatives, hardeners A film agent and a development accelerator are used. The pH of the alkaline treatment liquid is preferably from 11 to 14, more preferably from 12.5 to 14. The temperature of the treatment solution is preferably from 20C to 50C, more preferably from 25C to 40C. The amount of the alkaline processing liquid applicable in the image forming method of the present invention is 1 m of the photosensitive material.
5 ml or more and 50 ml or less, preferably 10 ml or more and 40 ml or less, more preferably 15 ml or more per ² pieces.
It is not less than 30 ml and not less than 30 ml. In the present invention, it is preferable to apply the alkaline treatment liquid in a thin layer. The time from the application of the alkaline treatment solution to the application of the intensifying solution containing hydrogen peroxide is preferably 10 seconds or less, more preferably 5 seconds or less.

Various additives are used in the treatment applied to the present invention, and more specifically, Research Disclosure I
tem 36544 (September 1994), and the relevant locations are summarized below. 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 Bleach accelerator 538 Right column-539 Left column Bleaching chelating 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 antibacterial deodorant 540 right color image Stabilizer 540 right The water saving technology applied to the invention is described in detail in Research Disclosure Item 36544 (1994).
September, 540 page, right column to page 541, left column.

[0088]

The present invention will be described below in detail with reference to examples.
You. However, the present invention is limited to only these examples.
Not something. Example 1 (Preparation of photosensitive material) Double-sided lamination with polyethylene
After performing corona discharge treatment on the paper support surface, dodecyl
Undercoat of gelatin layer containing sodium benzenesulfonate
Layers, and further coated with various photographic constituent layers shown below.
A multilayer color photographic paper having a layer configuration was produced. This is the sample (1
00). The polyethylene has the following fluorescent whitening structure
The agents (I) and (II) were added at a weight ratio (II / I) of 20 /
80, content 15 mg / m ^TwoAgainst polyethylene
The proportion was contained at 0.05%.

[0089]

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The coating solution was prepared as follows. Preparation of First Layer Coating Solution (Preparation of Emulsion) Cyan Coupler (ExC-1) 16.
0 g, color-forming reducing agent (I-16) 13.6 g, Cpd-
4.3 g of A, 14.4 g of Cpd-B and 18 g of trioctylamine are dissolved in 39 g of a solvent (Solv-1) and 93 cc of ethyl acetate, and the solution is dissolved in 15% sodium 10% sodium dodecylbenzenesulfonate and citric acid.
Emulsion A was prepared by emulsifying and dispersing in 300 cc of an aqueous gelatin solution.

On the other hand, a silver chlorobromide emulsion A (cubic, average grain size 0.12 μm, silver bromide 25 mol%) was prepared.
This emulsion contains red-sensitive sensitizing dyes A-1 and A-2. The chemical ripening of this emulsion was optimally performed 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.

Preparation of Coating Solutions for Second to Seventh Layers Coating solutions for the second to seventh layers were prepared in the same manner as for the coating solution for the first layer. The coating solution for each of the above-mentioned layers was applied onto the support to prepare a sample (100) of a photosensitive material having the following layer constitution. 1-oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardener for each of the above layers. Further, the total amount each layer Cpd-4 and Cpd-5, respectively, was added such that 25.0 mg / m ² and 50 mg / m ^2. The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer.

[0093]

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[0094]

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Further, 1- (5-methylureidophenyl) was added to the red-sensitive emulsion layer, green-sensitive emulsion layer and blue-sensitive emulsion layer.
-5-mercaptotetrazole was added in an amount of 3.0 × 10 ^-4 mol, 2.0 × 10 ^-4 mol, and 8.0 × 10 ^-4 mol per mol of silver halide, respectively. With respect to the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 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, respectively. To prevent irradiation, the following dyes were added to the emulsion layer (the values in parentheses indicate the coating amount).

[0096]

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The following compounds (ExC-1) were used for the cyan coupler, (ExM-1) for the magenta coupler, and (ExY-1) for the yellow coupler.

[0098]

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(Layer Structure) The composition 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. In the table, TLA represents trilaurylamine _{(N (n-C 12 H} 25) 3).

[0100]

[Table 3]

[0101]

[Table 4]

[0102]

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[0103]

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[0104]

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[0105]

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An auxiliary developing agent (ETA-6) for the second and fourth intermediate layers was 46 mg / m 2 in solid dispersion.
^{2 were} added.

A sensitometer (manufactured by Fuji Photo Film Co., Ltd., type FW, color temperature of light source 3200 ° K) was used for each sample.
A gradation exposure of a three-color separation filter for sensitometry was provided. The exposed samples were processed using the following processing steps and processing solution compositions.

The alkali development and amplification are described in JP-A-9-17.
The processing liquid was sprayed from an apparatus having a plurality of nozzle holes similar to that described in the drawing on page 9 to 12 of No. 9272, and the adjacent liquid droplets were applied so that no gap was formed between them.

Processing Step Temperature Time Coating amount (per 1 m ² ) Alkaline development 40 ° C. 1 second 25 ml Amplification 40 ° C. 30 seconds 25 ml Fixing / stable 30 ° C. 5 seconds 25 ml Rinse 30 ° C. 5 seconds 25 ml * Preliminarily heated to 40 ° C. A predetermined amount of the alkali solution was sprayed onto the surface of the photosensitive material by a nozzle (heated from the back side of the paper support on an aluminum heating plate), and after 1 second, the amplification solution was sprayed by the nozzle. After fixing
A predetermined amount of the stabilizer and water was sprayed.

The following solutions were used as the alkaline solution, the amplifying solution and the fixing / stabilizing solution. "Alkaline solution" Water 800 ml Potassium hydroxide 40 g UVX (the following structure) 5 g Antifoggant F (the following structure) 4 mg Potassium chloride 5 g Surfactant W (the following structure) 0.5 g Hydroxyethylidene-1,1-diphosphonic acid 4 ml ( HEP) (60% solution) 1 liter with water

[0111]

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[Amplification solution] 1 2 3 4 Water 800 ml 水 〃 水 素 Hydrogen peroxide (30%) 15 ml 〃 〃 UVX 5 g 〃 〃 ベ ン ゾ Benzotriazole 4 mg 〃 〃 HEP (60%) 4 ml 〃 〃 Ｃｌ KCl-2 g -2 g 1 liter by adding water pH 12.0 〃 7.0 〃 “Fixation stabilizing solution” 800 ml of water 10 g of sodium sulfite 12 g of sodium bisulfite 10 g of sodium thiosulfate pentahydrate 10 g of UVZ (the following structure) 2 g

[0113]

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[Washing water] Tap water

The image densities of yellow, magenta, and cyan after treatment with the respective amplifying solutions were measured through B, G, and R filters corresponding to the respective dyes, and the minimum and maximum densities (Dmin) and (Dmax) were measured. ) Was measured.

The degree of generation of microbubbles inside each processed image was visually judged based on the following criteria. The spot non-uniformity of white spots (non-bubbles, but non-image density non-uniformity) occurring in the image was visually judged based on the same criteria. (Visual evaluation) Almost no observation. ○ It is observed in a part of the image. △ Observed in the entire image area. ×

Table 5 shows the obtained results.

[0118]

[Table 5]

As a result, when the sample (100) was applied with an alkaline solution and then applied with each amplification solution, a high Dmax was obtained.
It can be seen that an image having is obtained. Further, even in the repetitive processing, an image having little processing unevenness and little fluctuation in image density and gradation was obtained. However, when the processing was performed using the amplification solutions 1 and 2, generation of microbubbles and uneven white spots in the image were observed, which was not sufficient.
It can be seen that the generation of microbubbles can be suppressed by lowering the pH of the amplification solution to near neutrality, and that the white spot-like unevenness disappears when chlorine ions are removed.

Example 2 Processing was performed with the composition of the amplification solution shown in Table 6 (the pH, the concentration of hydrogen peroxide, and the presence or absence of halide ions were changed with respect to the amplification solution 3). Table 7 shows the results. In addition to the evaluation described in Example 1, the maximum concentration (Ds) of the resulting blue-sensitive layer and the maximum concentration (Df) of the new solution obtained when the amplification solution was left at 40 ° C. for 7 days and subjected to the same treatment. (ΔDmax) was calculated. ΔDmax = Ds−Df The measured value indicates a value measured through a G filter. Further, in order to evaluate the metal corrosiveness due to the amplification solution, a nickel plate having a thickness of 0.5 mm was immersed in the amplification solution for one day, and then the surface of the nickel plate was observed to determine whether pinholes were generated.

[0121]

[Table 6]

[0122]

[Table 7]

As a result, 1) When the pH is 3 or less and 8 or more, microbubbles are generated in the image, so that the S / N (maximum density / minimum density) of the image is inferior. It can be seen that when the pH is 8 or more, the stability over time of the amplification solution is inferior. 2) If the concentration of hydrogen peroxide is 0.1% or less, a sufficient image density cannot be obtained by a short-time amplification treatment.
%, The S / N decreases. Also, the sensitivity decreases. 3) It can be seen that any halide ions generate microbubbles in the image and increase metal corrosion. This indicates that the amplification solution preferably does not contain halide ions and has a pH of 3 to 8. Except for the amplification solutions 20 and 24, examples of the invention according to claim 1 and examples and comparative examples of the invention cited therein are shown. The tests of the amplification solutions 20 and 24 are out of the range of the hydrogen peroxide content defined in the fifth aspect of the present invention, but the results are not necessarily poor on the image.

Example 3 From the sample (100) of Example 1, the auxiliary developing agent (ETA)
A sample (101) was produced in exactly the same manner except that -6) was excluded. Using this sample, E was added to the alkaline solution of Example 1.
The treatment was carried out in exactly the same manner as in Example 1, except that a liquid containing 0.5 g / liter of TA-6 was used. As a result, an image having a low image density and a high S / N was not obtained, and some color mixing occurred during processing. For this reason, the sample preferably contains an auxiliary developing agent. Example 4 (Preparation of photosensitive material) A multilayer color photographic paper having the following layer constitution was prepared on the same support as in Example 1. This is designated as Sample (200).

A coating solution was prepared as follows. Preparation of First Layer Coating Solution 19.1 g of coupler for yellow coloring (ExY-2), 10.6 g of reducing agent for coloring (I-32), Cpd-A
3 g, 14.4 g of Cpd-B and 18 g of trioctylamine are dissolved in 52 g of a solvent (Solv-4) and 93 cc of an ethyl acetate solution, and the solution is dissolved in 15% sodium dodecylbenzenesulfonate and citric acid.
Emulsion D
Was prepared.

On the other hand, silver chlorobromide emulsion D (cubic, having an average grain size of 0.30 μm). The coefficient of variation of the particle size distribution was 0.10, and 0.3 mol% of silver bromide was locally contained in a part of the surface of the silver chloride-based substrate. This emulsion was added with the following blue-sensitive sensitizing dyes 1, 2 and 3 in an amount of 1.7 × 10 ^-4 mol per mol of silver. The chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion D and this silver chlorobromide emulsion D were mixed and dissolved to prepare a first layer coating solution.

[0127]

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The coating solutions for the third and fifth layers were prepared in the same manner as the coating solution for the first layer by the following method. That is, silver chlorobromide emulsion E for the third layer (cubic, average grain size 0.15 μm, variation coefficient of grain size distribution is 0.11, silver bromide 0.8 mol%, silver chloride as a base material) (Partially contained on a part of the particle surface). To this emulsion, the following green-sensitive sensitizing dye 1 was added in an amount of 3.6 × 10 ^-4 mol per mol of silver, and green-sensitive sensitizing dye 2 was added in an amount of 7.0 × 10 ^-5 mol per mol of silver. Have been. The green-sensitive sensitizing dye 3 was added in an amount of 2.8 × 10 ⁻⁴ mol per mol of silver per mol of silver. This silver chlorobromide emulsion E and an emulsion E containing a magenta coloring coupler (ExM-2) prepared in the same manner as the emulsion D were mixed and dissolved to prepare a third layer coating solution.

[0129]

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Fifth layer silver chlorobromide emulsion F (cubic, average grain size 0.12 μm, variation coefficient of grain size distribution:
0.11 and 0.8 mol% of silver bromide were locally contained on a part of the surface of the silver chloride-based grain). The emulsion per mol of silver a red-sensitive sensitizing dye-1 shown below in, 6.0 × 10 ^-5 mol, and per mol of silver a red-sensitive sensitizing dye -2, 6.0 × 10 ^-5 Mole is added.

[0131]

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Further, the same A-2 used in Example 1 was used.
The compound was added to the fifth layer in an amount of 2.6 × 10 ⁻³ mol per mol of silver. This silver chlorobromide emulsion F and an emulsion F containing a coupler for cyan coloring (ExC-2) prepared in the same manner as the emulsion D were mixed and dissolved to prepare a fifth layer coating solution.

The second layer, the sixth layer and the seventh layer were also prepared so as to have the following compositions. An auxiliary developing agent (ETA-6) was added to the intermediate layer of the second layer and the fourth layer in an amount of 53 mg per 1 m ^{2 in} a state of fine particle solid dispersion. solvent,
The same compounds as in Example 1 were used as a color image stabilizer, an ultraviolet absorber, a color mixing inhibitor, a surfactant and the like. As the gelatin hardener for each layer, 1-oxy-3,5-dichloro-s
-Triazine sodium salt was used. In addition, Cp is added to each layer.
The total amount of each of d-4 and Cpd-5 was 25 mg / m ^2.
And 50 mg / m ² .

The blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer were treated with 1- (5-methylureidophenyl)-
5-mercaptotetrazole was replaced by silver halide 1
8.5 × 10 ^-5 mol, 9.0 × 10 ^-4 mol per mol,
2.5 × 10 ^-4 mol was added. Further, 4-hydroxy-6-methyl-1, 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, respectively. The same dye as that of the sample (100) of Example 1 was added to the emulsion layer to prevent irradiation. ExC-2 for cyan coupler, E for magenta coupler
The following compounds of ExY-2 were used for xM-2 and yellow coupler.

[0135]

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(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). It represents the amount of silver halide emulsion and silver equivalent.

[0137]

[Table 8]

[0138]

[Table 9]

Using the (200) sample, the same processing and evaluation as in Example 1 were carried out except that the amplification solution 3 of Example 1 was used and 15 seconds were used. As a result, even in the short-time amplification process, as in Example 1, there was no generation of fine bubbles, no white spot-like unevenness or processing unevenness, and an image having a high Dmax and a good S / N was obtained. Use of high silver chloride emulsions is effective for rapid amplification.

Example 5 The procedure of Example 4 was repeated except that the trilaurylamine (TLA) of the green-sensitive layer (GL) of the sample (200) was removed and replaced with the following TOAW (0.8 g / m ² ). A sample (300) was prepared. The reducing agent for color development of the sample (300) was determined as (I-16), (I-31), (I-37), (I-
38), (I-50), (I-65) or (I-6)
Samples (301), (302), (303), and (30) corresponding to the respective samples were performed in exactly the same manner except that
4), (305), (306) and (307) were produced. The same processing and evaluation as in Example 4 were performed.

[0141]

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Table 10 shows the results.

[0143]

[Table 10]

As a result, when the color-forming reducing agent of the present invention was used similarly to the reducing agent of Example 4, it was found that even in a short time, there was no image unevenness and a high-quality image having a high Dmax could be obtained. . In particular, thiadiazolylcarbamoylhydrazine gives a high Dmax. It was also found that a color image with little color turbidity and high color purity was provided.

Example 6 The same processing and evaluation as in Example 4 were performed using the sample (304) of Example 5 except that the following exposure was performed. (Exposure) A YAG solid 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 KNb03.
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-log E was obtained by changing the light amount. At this time, the amount of the laser light of three wavelengths was modulated using an external modulator to control the exposure amount. 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 in the image formed by the digital exposure with high illuminance, a high S / N image was obtained in which no bubble was generated in the image and no image unevenness due to the processing was obtained.

[0147]

According to the color image forming method of the present invention,
Even when the processing is performed in a short time, there is an excellent effect that a high quality image having a high maximum density can be obtained without bubbles or image unevenness in the image. Further, the silver halide light-sensitive material containing a color-forming reducing agent and a coupler used in the present invention is excellent in long-term storage stability.

Claims (8)

[Claims] 1. A method for forming a color image by exposing a silver halide light-sensitive material having at least one photographic constituent layer containing a photosensitive silver halide emulsion on a support, followed by exposing the photographic constituent layer to a color image. Wherein the surface of a silver halide photosensitive material containing at least one dye-forming coupler and a color-forming reducing agent represented by formula (I),
A color image is formed by applying, in a thin layer, an amplification solution having a pH of 3 to 8 which is substantially free from halogen ions and a color developing agent and contains hydrogen peroxide or a compound supplying hydrogen peroxide. Color image forming method. General formula (I) 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 is _{-SO 2 -, - CO -,} - COC
O -, - CO-O - , - CONH (R 13) -, - COC
O-O -, - COCO- N (R 13) - or -SO ₂ -
NH (R ¹³⁾ - is. Where R ¹³ is a hydrogen atom or R
^This is the group described in ¹² . 2. The color image forming method according to claim 1, wherein an alkaline processing solution containing no color developing agent is applied before or after applying the amplification solution according to claim 1. 3. A color image forming method according to claim 1, wherein an auxiliary developing agent is contained in any of the photographic constituent layers according to claim 1. 4. The silver coating according to claim 1, wherein the total silver content of all coating layers contains 0.003 to 0.3 g / m ² of silver halide in terms of silver. 4. The color image forming method according to 3. 5. The method according to claim 1, wherein the concentration of hydrogen peroxide or the compound supplying hydrogen peroxide is 0.1% or more and 3% or less in terms of hydrogen peroxide. Color image forming method. 6. The supply amount of the amplification liquid applied in a thin layer is 1 m.
6. The color image forming method according to claim 1, wherein 5 to 50 ml is used per ² pieces. 7. An exposure time per pixel of 10 ^-8 to 10
7. The color image forming method according to claim 1, wherein the exposure is performed by scanning exposure for ^-4 seconds. 8. A method for applying a processing liquid in a thin layer on the surface of a photosensitive material, comprising a plurality of nozzle holes for jetting the processing liquid, and adjacent droplets jetted from these nozzles having a gap between each other. 5. The method according to claim 1, wherein the liquid is applied while being sprayed so as not to be attached.
The color image forming method according to 5, 6, or 7.