JPH11231456A - Color image forming method using silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance the color forming ability and shelf stability and to make adaptable to a simple rapid processing by incorporating a dye forming coupler and a specified reducing agent for color forming into a photographic constituent layer. SOLUTION: A silver halide color photographic sensitive material contg. one or more dye forming couplers and one or more reducing agents for color forming represented by formula I or II in a photographic constituent layer is coated with an alkaline processing soln. by spraying the soln. from plural nozzles so that adjacent three droplets are stuck to the sensitive material without leaving a gap. The surface tension of the alkaline processing soln. is 15-60 dyn/cm and the contact angle of the droplets of the soln. with the sensitive material is 10-30 deg.. In the formulae I and II, R1 -R4 are each H or a substituent, A1 and A2 are each hydroxyl or substd. amino, X is a di- or higher valent combining group selected from -CO-, -SO-, etc., Y1k and Z1k are each N or the like, P is a proton dissociable group or the like, Y is a divalent combining group and Z is a nucleophilic group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color photographic technique, and uses a silver halide color photographic light-sensitive material which has good color developability, storage stability, color image fastness and hue and can cope with simple and rapid processing. The present invention relates to a color image forming method that enables both a low waste liquid amount and a reduction in processing fluctuation by uniformly applying a liquid.

[0002]

2. Description of the Related Art Generally, a color photographic light-sensitive material undergoes color development after exposure, whereby an oxidized p-phenylenediamine derivative and a coupler react to form an image. In this method, a color reproduction method based on a subtractive color method is used, and in order to reproduce blue, green, and red, yellow, magenta, and cyan color images having respective complementary colors are formed. Color development is achieved by immersing the exposed color photographic light-sensitive material in a p-phenylenediamine derivative-containing alkaline aqueous solution (color developing solution). In general, such processing requires a tank for immersing the color photographic light-sensitive material in a color developing solution and a replenishing tank for storing a solution for replenishing the consumed color developing solution. I have to grow. In particular, in the case of a minilab or the like which performs a dispersion process, it is preferable that the size of the device is small. In order to reduce the size of the device, it is required to reduce the number of tanks as described above. In reducing the number of tanks, it is conceivable to first eliminate the processing tank. Japanese Patent No. 26122 discloses a method of eliminating a processing tank.
As described in No. 05, a method of applying the processing liquid to the surface of the photosensitive material without collecting the processing liquid in the tank can be considered. However, in such a method, if the p-phenylenediamine derivative required for color development is to be contained in the processing solution, a large amount of the processing solution must be applied or the concentration of the p-phenylenediamine derivative in the processing solution must be increased. Must.
In the former case, a large amount of the processing solution is used, and the size of the stock tank must be increased, and a large amount of processing waste liquid is generated. In the latter case, since the solubility of the p-phenylenediamine derivative in water is limited, there is a problem that a high concentration causes precipitation or the like. Also, JP-A-7-261353, 9-171
As described in JP-A-244, for example, it is conceivable to use an image forming method by transferring a dye instead of using an image forming method by coupling a coupler with a p-phenylenediamine derivative. According to the methods described in these patents, the dye is originally contained in the photosensitive material, and the base is also contained in the photosensitive material in the form of a base generator. Formation is possible. However, the methods described in these patents require an image receiving sheet for mordanting the transferred dye in addition to the photosensitive material, which causes problems such as waste material.

As one of the methods for solving the above problems, a method of incorporating p-phenylenediamine or a compound having a similar function into the light-sensitive material can be considered. If p-phenylenediamine or a compound having a similar function is incorporated in the light-sensitive material, it is not necessary to include p-phenylenediamine in the processing solution, and p-phenylenediamine or a compound having the same function can be obtained. No image receiving sheet is required to form a dye by coupling the compound with the coupler. As a method of incorporating p-phenylenediamine or a compound having a similar function into the photosensitive material, for example, there is a method of incorporating an aromatic primary amine or a precursor thereof into the photosensitive material. As the primary amine developing agent or its precursor, US Pat.
No. 07114, No. 3764328, No. 40604
No. 18, JP-A-56-6235 and JP-A-58-19203
No. 1 and the like. However, since these aromatic primary amines and precursors thereof are unstable, they have a drawback that stain is generated during long-term storage or color development of unprocessed photosensitive materials. Another effective means is described in, for example, European Patent Nos. 0545491A1, 565165A1, JP-A-8-286340, JP-A-8-292529, JP-A-8-297354, and 8-3.
Hydrazine compounds described in US Pat. A method of embedding in a layer is mentioned. These color-forming reducing agents are characterized by having excellent storage stability and high color-forming properties as compared with the above-mentioned aromatic primary amines and precursors thereof.

When a compound containing the above-described color-forming reducing agent in a light-sensitive material is colored, an alkali solution is required. As a method of supplying a small amount of an alkaline solution onto the surface of a photosensitive material, a method of passing through a slit described in Japanese Patent No. 2612205 can be considered first. However, in such a method, a large amount of alkaline solution must be used. On the other hand, if a method of applying an alkaline solution to the surface of the photosensitive material in a thin layer using a roller coat, a felt cloth, a sponge coat, or the like is used, the amount of the alkaline solution used can be greatly reduced. However, in these methods, the coated portion is gradually contaminated by the substance flowing out of the photosensitive material, which may cause a process variation or the like. Therefore, the coated portion of the coating apparatus and the photosensitive material need to be in non-contact. In addition, if unevenness occurs in the application, the coloration also becomes uneven. Therefore, when performing the application processing, it is necessary to apply the processing liquid uniformly. As a method of applying the processing solution uniformly on the photosensitive material surface without contact,
There is a method described in JP-A-9-17927 and JP-A-6-324455, in which a processing liquid is sprayed from a thin nozzle and sprayed. As a method of uniformly applying a processing solution without contacting the photosensitive material, it is particularly effective to apply a processing solution using a processing solution application apparatus described in JP-A-9-179272. However, when the processing liquid is applied using such a processing liquid application apparatus, the unevenness of the processing liquid after application, although it can be applied evenly, causes a problem that the color density particularly at the start of application decreases. Occurred.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to use a silver halide color photographic light-sensitive material which has good color developability, storage stability, color image fastness and hue and can cope with simple and rapid processing, and uses a small amount of processing solution. The purpose of the present invention is to provide a color image forming method that enables both a low waste liquid amount and a reduction in processing fluctuations by performing development processing with a processing liquid applied by a nozzle jetting method that can uniformly apply.

[0006]

It has been found that the object of the present invention is achieved by the following method. (1) A color image forming method in which a silver halide color photographic light-sensitive material having at least one photographic constituent layer on a support is subjected to color development processing using an alkaline processing solution substantially free of a color developing agent. Any of the constituent layers contains at least one kind of dye-forming coupler and at least one kind of a color-forming reducing agent represented by the following general formula (I) or (II), and the alkaline processing liquid is applied onto the photosensitive material. Supplies the alkaline processing liquid from a plurality of nozzle holes, and the three adjacent droplets attached to the photosensitive material are separated from each other in a state where there is no gap between them. And the surface tension of the alkaline treatment liquid is 15 dyn / cm or more and 60 dyn / cm or more.
cm or less, and a contact angle between the droplet of the alkaline processing liquid and the photosensitive material is 10 ° or more and 30 ° or less.

[0007]

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[0008]

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In the formula, R _{1 to} R ₄ represent a hydrogen atom or a substituent. A ₁ and A ₂ represent a hydroxyl group or a substituted amino group. X is -CO -, - SO -, - SO 2 -, it represents a divalent or higher linking group selected from -PO <. Y _1K and Z _1K represent a nitrogen atom or —CR ₅ ＝
(R ₅ is a hydrogen atom or a substituent). k
Represents an integer of 0 or more. P represents a proton-dissociable group or a group that can be a cation, and an oxidant generated by a redox reaction between the present compound and exposed silver halide is coupled with a coupler, and then the electron transfer from P is triggered. Has the function of forming a dye by cleavage of the NX bond and elimination of the substituent bonded to the coupling site of the coupler. Y represents a divalent linking group. Z is a nucleophilic group and represents a group capable of attacking X when the present compound is oxidized. n is 1 or 2 when X is -PO <, and 1 when X is another group. Two or more atoms or substituents arbitrarily selected from R ₁ and R ₂ , R ₃ and R _4, and Y _1K , Z _1K and P may be independently bonded to each other to form a ring. (2) In a color image forming method, a silver halide color photographic light-sensitive material having at least one photographic constituent layer on a support is subjected to color development processing using an alkaline processing solution substantially free of a color developing agent. Any of the constituent layers contains at least one dye-forming coupler and at least one color-forming reducing agent represented by the following general formula (III). The processing is performed by ejecting the processing liquid from a plurality of nozzle holes, and applying the alkaline processing liquid in a state where there are no gaps between the three mutually adjacent droplets attached to the photosensitive material. The surface tension of the alkaline processing liquid is 15 dyn / cm or more and 60 dyn / cm or less, and the contact angle between the droplet of the alkaline processing liquid and the photosensitive material is 10 ° or more and 30 ° or less. Color image forming method comprising and.

[0010]

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

[0012]

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

[0014]

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

[0016]

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In the formula, R ^4a and R ^5a represent a hydrogen atom or a substituent, and X ⁶ , X ⁷ , X ⁸ , X ⁹ and X ¹⁰ represent a hydrogen atom, a cyano group, a sulfonyl group, a sulfinyl group, a sulfamoyl group, Carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, trifluoromethyl group, halogen atom, acyloxy group, acylthio group,
Or a heterocyclic group. However, the sum of the Hammett's substituent constant σp value of X ⁶ , X ⁸ and X ^{10 and} the Hammett's substituent constant σm value of X ⁷ and X ⁹ is 1.20 or more and 3.80 or less. Q ¹ represents a group of nonmetallic atoms necessary for forming a nitrogen-containing 5- to 8-membered heterocyclic ring together with C. (6) To supply an alkaline processing solution to the photosensitive material,
The coating apparatus has a plurality of nozzle holes for spraying the alkaline processing liquid onto the photosensitive material by spraying the alkaline processing liquid, and the volume of one drop of the alkaline processing liquid ejected from these nozzle holes is defined as V, When the contact angle when is attached to the photosensitive material is θ,

[0018]

(Equation 2)

The pitch P between adjacent nozzle holes calculated on the basis of the diameter D of one drop of the alkaline processing liquid adhered on the photosensitive material represented by the following formula is set to a value of (√3) · D / 2 or less. (1) characterized in that a coating device is used.
(2), (3), (4) or (5). (7) The contact angle between the alkaline processing liquid and the nozzle surface of the coating device is 40 ° or more (1).
(2), (3), (4), (5) or (6). (8) The thickness of the liquid film of the alkaline processing liquid applied in the photosensitive material is 50 μm or less (1).
(2), (3), (4), (5), (6) or (7)
Item. (9) The light-sensitive material described in (1), (2), (3), (4), (5) or (6) is obtained by adding the silver amount of all the coating layers to the coated silver amount in terms of silver. (1) A photosensitive material containing 0.003 to 0.3 g / m < ² > of silver halide, wherein the alkaline processing solution containing substantially no color developing agent contains hydrogen peroxide. , (2), (3),
(4), (5), (6), (7) or (8). (10) Exposure is performed by scanning exposure in which an exposure time per pixel is 10 ^-8 to 10 ^-4 seconds and there is an overlap between adjacent rasters (1), (2), (3),
(4), (5), (6), (7), (8) or (9)
Item.

The present invention is based on the "deviation of the applied processing solution" which is peculiar to the use of a processing solution application apparatus which can apply a small amount of the solution uniformly on the surface of the photosensitive material in a non-contact manner. It is an object of the present invention to improve the decrease in the color density at the start of application. The object of the present invention cannot be achieved only by a small contact angle between the photosensitive material and the alkaline processing solution, and cannot be achieved only by a low surface tension of the processing solution. This can be effectively achieved when the contact angle between the photosensitive material and the alkaline processing solution is within the range of the present invention, and the surface tension of the processing solution is within the range of the present invention. First time according to the present invention The processing machine can be reduced in size. 2. Processing can be performed with a processing liquid that has little effect on the environment. 3. The amount of waste liquid is small. 4. A uniform image without unevenness can be formed. Image forming method can be provided.

[0021]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The compounds represented by formulas (I) and (II) will be described in detail. An alkyl group (alkyl residue), an aryl group (aryl residue), an amino group (amino residue), and the like described below are used in the present specification to include those in which a substituent is further substituted. . General formula (I)
And a compound represented by the general formula (II) represents a developing agent classified into an aminophenol derivative and a phenylenediamine derivative. In the formula, R _{1 to} R ₄ represent a hydrogen atom or a substituent, and examples of the substituent include, for example, a halogen atom (eg, a chloro group, a bromo group) and an alkyl group (eg, a methyl group, an ethyl group, an isopropyl group). , N-butyl group, t-butyl group), aryl group (for example, phenyl group, tolyl group, xylyl group), carbonamido group (for example, acetylamino group, propionylamino group, butyroylamino group, benzoylamino group), sulfone Amido group (eg, methanesulfonylamino group, ethanesulfonylamino group, benzenesulfonylamino group, toluenesulfonylamino group), alkoxy group (eg, methoxy group, ethoxy group), aryloxy group (eg, phenoxy group), alkylthio group (eg, methylthio group) Group, ethylthio group, butylthio group), arylthio group For example, phenylthio group, tolylthio group), carbamoyl group (eg, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, diethylcarbamoyl group, dibutylcarbamoyl group, piperidinocarbamoyl group, morpholinocarbamoyl group, phenylcarbamoyl group, methylphenylcarbamoyl group , Ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), sulfamoyl group (for example, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, dibutylsulfamoyl group, piperidinosulfa Moyl group, morpholinosulfamoyl group, phenylsulfamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfa Moyl group), cyano group, sulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group, phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-
Toluenesulfonyl group), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group), acyl group (for example, acetyl group, propionyl group, butyroyl group, benzoyl group, An alkylbenzoyl group), a ureido group (eg, a methylaminocarbonamide group, a diethylaminocarbonamide group), a urethane group (eg, a methoxycarbonamide group, a butoxycarbonamide group), or an acyloxy group (eg, an acetyloxy group, a propionyloxy group, a butyroyloxy group) Group) and the like. Among R _{1 to} R ₄ , R ₂ and / or R ₄ are preferably a hydrogen atom. When A ₁ or A ₂ is a hydroxyl group, the sum of Hammett constant σp values of R _{1 to} R ₄ is preferably 0 or more, and when A ₁ or A ₂ is a substituted amino group, R _{1 to} R 4 _Four
Is preferably 0 or less.

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

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

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

[0025]

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Specific examples of Z include those in which a hydrogen atom or a substituent described above for P is bonded to one end of the above group. Y represents a divalent linking group. The term "linking group" refers to a group that links Z to a position that allows convenient nucleophilic attack on X via Y. In practice, it is preferable that the atoms are linked so that the transition state when the nucleophilic group makes a nucleophilic attack on X can constitute a 5- or 6-membered ring by the number of atoms. Preferred as such a linking group Y are, for example, a 1,2- or 1,3-alkylene group, a 1,2-cycloalkylene group, a 2-vinylene group, a 1,2-arylene group, a 1,8-naphthylene group And the like. k is preferably an integer of 0 to 5, and more preferably an integer of 0 to 2. R ₁ and R ₂ ,
R ₃ and R ₄ and 2 arbitrarily selected from Y _1k , Z _1k and P
One or more atoms or substituents may be independently bonded to each other to form a ring. Next, specific examples of the compounds represented by the general formulas (1) and (2) are shown, but the compounds of the present invention are not limited thereto.

[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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Hereinafter, the structure of the color-forming reducing agent represented by the general formula (III) will be described in detail. In the general formula (III), R ¹¹ represents an aryl group or a heterocyclic group which may have a substituent. The aryl group of R ^11, preferably that of 6 to 14 carbon atoms include, for example, phenyl or naphthyl. 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, and quinazolinyl. , Purinyl, pteridinyl, azepinyl, benzoxepinyl and the like.

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

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

The alkynyl group for R ¹² preferably has 2 to 16 carbon atoms, such as 1-butynyl and phenylethynyl. As the aryl group and heterocyclic group for R ¹² , those described for R ¹¹ can be mentioned.
Examples of the substituent of R ¹² include those described for the substituent of R ¹¹ . X ⁰ is -SO _2- , -CO-,-
COCO -, - CO-O - , - CON (R 13) -, - C
OCO-O -, - COCO- N (R 13) - or -SO
₂ -N (R ¹³⁾ - and the like. Here, R ¹³ is a hydrogen atom or a group described for R ¹² . Of these groups, -CO
—, —CON (R ¹³ ) — and —CO—O— are preferable, and —CON (R ¹³ ) — is particularly preferable in that color developing properties are particularly excellent. Among the compounds represented by the general formula (III), the compounds represented by the general formulas (IV) and (V) are preferable, and the compounds represented by the general formulas (VI) and (VII) are more preferable. Compounds represented by (IX) are more preferred. The following formulas (IV) to (IX)
The compound represented by is described in detail. In the general formulas (IV) and (V, Z ¹ represents an acyl group, a carbamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group, and Z ² represents a carbamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. The acyl group is preferably an acyl group having 1 to 50 carbon atoms, more preferably 2 to 40 carbon atoms.
It is. Specific examples include acetyl, 2-methylpropanoyl, cyclohexylcarbonyl, n-octanoyl, 2-hexyldecanoyl, dodecanoyl, chloroacetyl, trifluoroacetyl, benzoyl, 4-benzoyl, Dodecyloxybenzoyl group, 2-hydroxymethylbenzoyl group, 3- (N-hydroxy-
(N-methylaminocarbonyl) propanoyl group. The case where Z ¹ and Z ² are carbamoyl groups will be described in detail by the general formulas (VIII) to (IX). The alkoxycarbonyl group and the aryloxycarbonyl group are preferably an alkoxycarbonyl group having 2 to 50 carbon atoms and an aryloxycarbonyl group, more preferably having 2 to 4 carbon atoms.
0. Specific examples include methoxycarbonyl, ethoxycarbonyl, isobutyloxycarbonyl, cyclohexyloxycarbonyl, dodecyloxycarbonyl, benzyloxycarbonyl, phenoxycarbonyl, 4-octyloxyphenoxycarbonyl, 2-hydroxy Examples include a methylphenoxycarbonyl group and a 2-dodecyloxyphenoxycarbonyl group.

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

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

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

Methylthio, octylthio, cyclohexylthio, etc.), an arylthio group having 6 to 50 carbon atoms (eg, phenylthio, naphthylthio, etc.), 1 to 50 carbon atoms
Ureido group (eg, 3-methylureido, 3,3-
Dimethylureide, 1,3-diphenylureide, etc.),
A heterocyclic group having 2 to 50 carbon atoms (as a hetero atom, for example, a 3- to 12-membered monocyclic or condensed ring containing at least one or more of nitrogen, oxygen, sulfur and the like;
Furyl, 2-pyranyl, 2-pyridyl, 2-thienyl,
2-imidazolyl, morpholino, 2-quinolyl, 2-benzimidazolyl, 2-benzothiazolyl, 2-benzoxazolyl, etc.), an acyl group having 1 to 50 carbon atoms (eg, acetyl, benzoyl, trifluoroacetyl, etc.), carbon A sulfamoylamino group having a number of 0 to 50 (for example, N-butylsulfamoylamino, N-phenylsulfamoylamino, etc.), a silyl group having 3 to 50 carbon atoms (for example, 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. Regarding X ¹ , X ² , X ³ , X ⁴ and X ⁵ in the general formula (IV), Hammett's substituent constant σp value of X ¹ , X ³ and X ⁵ and Hammett's substituent of X ² and X ⁴ The sum of the constant σm values is 0.8
It is 0 or more and 3.80 or less. X ⁶ , X ⁷ , X ⁸ , X ⁹ and X ¹⁰ in the general formula (VIII) 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 and may be bonded to each other to form a condensed ring. Examples of these are X ¹ , X ² , X ³ , X ⁴ , X ⁵
It is the same as that described above. However, in the general formula (VIII), the sum of Hammett's substituent constant σp value of X ⁶ , X ⁸ and X ¹⁰ and Hammett's substituent constant σm value of X ⁷ and X ⁹ is 1.
20 or more and 3.80 or less, 1.50 or more and 3.8
0 or less, more preferably 1.70 or more;
80 or less. Here, the sum of the σp value and the σm value is
If it is less than 0.80, there are problems such as insufficient coloring properties, and if it exceeds 3.80, it becomes difficult to synthesize and obtain the compound itself.

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

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

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

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

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In the present invention, the compound represented by the general formula (I) or (II)
And the compound represented by formula (III) can be used in the same photosensitive material. In this case, they may be added separately to different layers of the light-sensitive material,
It may be added to the same layer. The ratio of each compound used may be any ratio. The couplers preferably used in the present invention include the following general formulas (1) to (1)
There is a compound having a structure as described in 2). These are compounds generally referred to as active methylene, pyrazolone, pyrazoloazole, phenol, naphthol, and pyrrolotriazole, respectively, and are compounds known in the art.

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

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

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

Y may be substituted with a substituent,
Examples of the substituent for substituting Y include those described for X ^{1 to} X ⁵ . Y is preferably a halogen atom, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an aryloxycarbonyloxy group, an alkoxycarbonyloxy group, or a carbamoyloxy group. General formula (1)
In (4), R ¹⁴ and R ¹⁵ , and R ¹⁴ and R ¹⁶ may be bonded to each other to form a ring. Formula (5) represents a coupler called a 5-pyrazolone-based coupler, wherein R ¹⁷ represents an alkyl group, an aryl group, an acyl group, or a carbamoyl group. R ¹⁸ represents a phenyl group or a phenyl group substituted with one or more halogen atoms, alkyl groups, cyano groups, alkoxy groups, alkoxycarbonyl groups, or acylamino groups.

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

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

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

Formulas (7) and (8) are couplers called phenol couplers and naphthol couplers, respectively, wherein R ²⁰ is a hydrogen atom or —CONR ²² R
_{^{23, -SO 2 NR 22 R 23}} , -NHCOR 22, -NHCO
NR ²² R ^23, represents a group selected from -NHSO ₂ NR ²² R ^23. R ²² and R ²³ represent a hydrogen atom or a substituent. In the general formulas (7) and (8), R ²¹ represents a substituent, 1 represents an integer selected from 0 to 2, and m represents an integer selected from 0 to 4. When l and m are 2 or more, R ²¹ may be different from each other. Examples of the substituent of R ^{21 to} R ²³ include those described as examples of X ^{1 to} X ^{5 in} the general formulas (II) and (IV). Y has the same meaning as described above.

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

Preferred examples of the naphthol coupler represented by the general formula (8) include US Pat. No. 2,474,29.
No. 3, 4,052, 212 and 4,146, 3
No. 96, No. 4,282,233, No. 4,296,
No. 200, etc., and 2-carbamoyl-1-naphthols described in US Pat. No. 4,690,889 and the like.
-Carbamoyl-5-amido-1-naphthol type and the like. Y is the same as described above. Formula (9) to (12) are couplers called ^{pyrrolotriazoles, R 32, R 33, R} 34 represents a hydrogen atom or a substituent. Y is as described above. As the substituents for R ³² , R ³³ and R ³⁴ , X ^{1 to} X
Examples described in ⁵ are given. General formula (9)
Preferable examples of the pyrrolotriazole coupler represented by (12) include EP 488,248 A1,
Couplers in which at least one of R ³² and R ³³ described in JP-A-491,197A1 and JP-A-545,300 are electron-withdrawing groups are exemplified. Y is the same as described above. In addition, couplers having a structure such as fused phenol, imidazole, pyrrole, 3-hydroxypyridine, active methylene, active methine, 5,5-fused heterocycle, and 5,6-fused heterocycle other than those described above can be used.

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

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

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

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The color-forming reducing agent of the present invention is used in an amount of 0.01 to 10 mmol / m ² per color-forming layer in order to obtain a sufficient color-forming density.
It is preferred to use. A more preferred amount is 0.0
The amount is 5 to 5 mmol / m ² , and the particularly preferred amount is 0.1 to 1
mmol / m ² . This range is preferred in that a sufficient color density can be obtained. The amount of the coupler in the color-forming layer in which the color-forming reducing agent of the present invention is used is preferably 0.05 to 20 times, more preferably 0.1 to 10 times, particularly preferably 0.1 to 10 times the molar amount of the color-forming reducing agent. Is 0.2 to 5 times.
This range is preferred in that a sufficient color density can be obtained.

The color light-sensitive material used in the present invention is basically formed by coating a support with a photographic constituent layer comprising at least one hydrophilic colloid layer, and any of the photographic constituent layers is coated with a photosensitive halide. Contains silver, dye-forming coupler, and color-forming reducing agent. The most typical embodiment is to add the dye-forming coupler and the color-forming reducing agent to the same layer, but they can be added separately to separate layers if they can react. These components are preferably added to a silver halide emulsion layer or a layer adjacent thereto in a light-sensitive material,
In particular, it is preferable to add them together to the silver halide emulsion layer.

The color-forming reducing agent and coupler of the present invention can be introduced into a light-sensitive material by various known dispersion methods, and are dissolved in a high-boiling organic solvent (optionally using a low-boiling organic solvent in combination).
An oil-in-water dispersion method in which the emulsion is dispersed in an aqueous gelatin solution and added to the silver halide emulsion is preferred. 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 less and a boiling point of 140 ° C. or more, and can be used as long as it is a good solvent for a color-forming reducing agent and a 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. The high-boiling organic solvent used in the present invention has an electron-donating parameter ΔV described in JP-A-8-320542 in that a dye formed from a reducing agent for coloring and a coupler can be dissociated from a low pH. It is preferable to use an organic solvent having a high boiling point of 80 or more. In the present invention, when a high boiling organic solvent is used, the amount of the high boiling organic solvent used may be any amount, but preferably, the high boiling organic solvent / color developing solvent is preferably used in a weight ratio with respect to the color-forming reducing agent. The reducing agent ratio is preferably 20 or less, more preferably 0.02 to 5, and 0.2 to 5
4 is particularly preferred. 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. 2,541,2
No. 30, JP-B-53-41091 and European Patent Publication No. 029104, and a dispersion method using a water-insoluble and organic solvent-soluble polymer is described in PCT International Publication No. WO88 / 00723. I have.

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

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

In the present invention, the contact angle between the alkaline processing solution and the light-sensitive material of the present invention needs to be 30 ° or less. When the contact angle between the alkaline processing solution and the photosensitive material of the present invention is large, the processing solution applied on the photosensitive material shrinks before it sufficiently penetrates into the photosensitive material. This causes a phenomenon in which the density of the portion is lower than that of the other portions. The value of the contact angle between the alkaline processing solution of the present invention and the photosensitive material of the present invention is preferably 25 ° or less,
20 ° or less is more preferable. Further, in order to maintain the thickness of the applied liquid film and to secure the necessary amount of the alkaline processing liquid per unit area, the contact angle needs to be 10 ° or more, and preferably 15 ° or more. The contact angle mentioned here is a measured value measured by the droplet method described in p97, Experimental Chemistry, Vol. .

Any method can be used to adjust the contact angle between the alkaline processing solution of the present invention and the light-sensitive material of the present invention within the range of the present invention. The method of adding the compound which reduces the contact angle to the alkaline treatment liquid is preferable. As the compound which preferably reduces the contact angle when added to the uppermost layer of the light-sensitive material, a water-soluble polymer or a surfactant is preferable. Examples of the water-soluble polymer include a carboxylic acid group or a salt thereof, a sulfate group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphate group or a salt thereof, a dithiophosphate group or a salt thereof, a hydroxyl group,
At least one substituent selected from an amino group and an amide group
More preferred are hydrophilic polymers having different types. However, this water-soluble polymer is other than gelatin usually used as a binder. Examples of these water-soluble polymers include those described in JP-A-63-103240, page 2, lower right column to page 6, lower right column.
Specific examples of the water-soluble polymer that can be used in the present invention are shown below, but the present invention is not limited to these.

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The molecular weight of the water-soluble polymer is preferably as small as possible.
It is preferably about 0, particularly preferably about 10,000 to 800,000, and more preferably about 10,000 to 500,000.
The coating amount of the water-soluble polymer in the uppermost layer is 1
× 10 ^{-3 to 1} g / m ² is preferable, and 1 × 10 ^-2 to 1 g / m ² is more preferable.
5 × 10 ⁻¹ g / m ² is preferred.

As the surfactant, any surfactant can be used as a compound capable of lowering the contact angle. Among them, an amphoteric surfactant and a fluorine-based surfactant are more preferable. The amphoteric surfactant preferably used in the present invention will be described. Amphoteric surfactants are disclosed in
No. 08036, JP-A-8-62797, etc., but an interface having two different functional groups of anionic functional group, cationic functional group, and nonionic functional group in one molecule. It means an activator and is roughly classified into an anion / cation type, an anion / nonion type, and a cation / nonion type. Of these, anionic / cationic amphoteric surfactants are preferred. Examples of anionic / cationic amphoteric surfactants include carboxybetaine type (having a quaternary alkyl ammonium ion (or a salt thereof) in the cation portion and a carboxylate ion (or a salt thereof) in the anion portion), and sulfobetaine. Type (having a quaternary alkylammonium ion (or salt) in the cation portion and a sulfonate ion (or a salt thereof) in the anion portion), sulfate ester type (quaternary alkylammonium ion (or a salt thereof) in the cation portion) has, -OSO ₃ in the anion portion ^- having a group (or salt)), phosphoric acid ester type has the (quaternary alkyl ammonium ions in the cationic portion (or a salt thereof), -OPO ₃ to anion ^- group ( or with a salt thereof)), amino acid type (cation portion - ⁺ NH ₂ - (or has a salt thereof), anionic portion carboxylate ion (also With its salt)), amino acid type (cation portion - ⁺ NH
_2- (or a salt thereof) and a sulfonate ion (or a salt thereof) in the anion portion. Of these, carboxybetaine-type amphoteric surfactants are particularly preferred, and carboxybetaine-type amphoteric surfactants having a carboxylic acid amide linkage in the alkyl chain are most preferred.
Specific examples of the amphoteric surfactant which can be preferably used are shown below, but the present invention is not limited to these.

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Next, the fluorine-based surfactant preferably used in the present invention will be described. Fluorinated surfactants that can be preferably used in the present invention include, for example, British Patent Nos. 1 and 2
No. 93,189, No. 1,259,398, No. 1,
No. 330,356; U.S. Pat. No. 3,589,906;
Nos. 3,666,478 and 3,754,924
No. 3,775,236, No. 3,850,64
0, JP-A-54-48520 and JP-A-56-11494.
No. 4, No. 50-161236, No. 51-151127
No., No. 50-59025, No. 50-11221,
Nos. 50-99525, 53-84712, 54
No. 14224, No. 50-113221, No. 49-1
No. 0722, JP-B-48-43130, 57-65
No. 77, JP-A-2-33144, I & EC Product Research and Development (I & EC Product Research and Development)
d Development) 1 (3) (1962.
9), Oil Chemistry 12 (12) (1963) p653, etc., and is preferably represented by the following general formula.
Rf- (A) mX In the formula, Rf has an alkyl group or an alkoxy group having at least three fluorine atoms (including those having a substituent. For example, dodecafluorohexyl group, heptadecafluorooctyl group, dodeca group) Fluorohexyloxy group, tetradecafluorooctyl group, tetradecafluorooctyloxy group, etc., alkenyl group (including those having a substituent; for example, heptafluorobutylene group, etc.) or aryl group or aryloxy group (substituent For example, a trifluorophenyl group, a pentafluorophenyl group, a pentafluorophenyloxy group, etc.). A represents a divalent linking group, X represents a hydrophilic group, and m represents 0 or 1.

A is preferably an alkylene group (including those having a substituent, for example, an ethylene group, a trimethylene group, an oxyalkylene group, etc.) and an arylene group (including those having a substituent, for example, a phenylene group, an oxyphenylene. Group), an alkylarylene group (including those having a substituent, such as a propylphenylene group),
Or an arylalkylene group (including those having a substituent; for example, a phenylethylene group, a phenyloxyethylene group, and the like), and these groups include an oxygen atom, an ester group, an amide group, a sulfonamide group, a sulfonyl group, and a sulfur group. Also included are divalent linking groups interrupted by heterogeneous atoms such as atoms or heterogeneous groups.

X is a hydrophilic group, for example,-(BO)
-NR ₁ polyoxyalkylene group (where B is -CH
_{2 -CH 2 -, - CH 2} -CH 2 -CH 2 -, - CH 2
—CH (OH) —CH ₂ — and —CH ₂ —CH (CH
₃ ) represents an alkylene group such as-, and n represents an average degree of polymerization of the polyoxyalkylene group, and is an integer of 1 to 50.
R ₁ represents a hydrogen atom, an alkyl group including a substituent, or an aryl group including a substituent. )); For example,- ⁺ N (R ₂ )
(R ₃ ) —R ₄ —COO ⁻ and − ⁺ N (R ₂ ) (R ₃ )
—R ₄ —SO ₃ ^— (wherein, R ₄ represents an alkylene group having 1 to 5 carbon atoms, for example, methylene, ethylene, propylene, and butylene, and R ₂ and R ₃ represent a substituent having 1 to 8 carbon atoms. A hydrophilic betaine group represented by an alkyl group including those having a substituent, an aryl group also including a substituent having a substituent, for example, a methyl group, an ethyl group, a benzyl group, etc .;
_{^{+ N (R 2) (R}} 3) -R 5 · Y - ( wherein, R _2, R
₃ and R ₅ have the same meanings as R ₂ described above, and Y ⁻ represents an anion, for example, a hydroxy group, a halogen group, a sulfate group, a carbonate group, a perchlorate group, an organic carboxylic acid group, an organic sulfonic acid group, an organic Represents a sulfate group and the like. Hydrophilic cationic group represented by); for example _{-SO 3 M, -OSO 3 M,} -COOM, -O-P (=
O) (OM) ₂ , -OP (= O) (-OA-Rf)
-OM (wherein, M represents an inorganic or organic cation, and is preferably a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, an alkylamine having 1 to 3 carbon atoms, etc., and A and Rf are as defined above. And a hydrophilic anionic group represented by the formula:

Further, those in which X is a polyoxyalkylene group are more preferred. Particularly, a substituted or unsubstituted polyoxyethylene group is preferable, and 5 to 3
0 is preferred. Further, Rf is preferably a fluoro, alkyl, alkenyl or aryl group having 4 or more carbon atoms, and more preferably a perfluoro, alkyl, alkenyl or aryl group having 6 to 14 carbon atoms. A is preferably a group containing a sulfonamide group having an alkyl group, an alkylene group or an aryl group on a nitrogen atom.

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The amount of the surfactant preferably used in the present invention is preferably 1 × 10 ^{−3 to} 1 mmol / m ² ,
0 ^-2 ~0.5mmol / m ² is more preferable. It is also preferable to use the amphoteric surfactant of the present invention in combination with a fluorinated surfactant, and particularly preferable to use a carboxybetaine-type amphoteric surfactant and a fluorinated surfactant having a polyoxyalkylene group in combination.

Further, it is more preferable to use a water-soluble polymer and a surfactant in combination, and it is particularly preferable to use a water-soluble polymer, an amphoteric surfactant and a fluorine-containing surfactant in combination. It is particularly preferable to use a betaine-type amphoteric surfactant and a fluorine-based surfactant having a polyoxyalkylene group in combination. The molar ratio of the amphoteric surfactant and the fluorosurfactant used is 1
The ratio of the water-soluble polymer and the surfactant (the sum of the two surfactants when used in combination) is 1/10 to 10%.
A range of 10 times is preferred.

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

The mordant of the present invention may be added to a plurality of layers. In particular, when there are a plurality of layers containing a color-forming reducing agent, the mordant is added to each adjacent layer. Is also preferred. The coupler forming the diffusible dye may be any coupler as long as the diffusible dye formed by coupling with the color-forming reducing agent of the present invention reaches the mordant, but the diffusible dye formed is pKa
(Acid dissociation constant) It is preferable to have one or more dissociating groups of 12 or less, more preferably one or more dissociating groups of pKa 8 or less, and particularly preferably a dissociating group of pKa 6 or less. The molecular weight of the formed diffusible dye is preferably 200 or more and 2000 or less. Further, (the molecular weight of the formed dye / the number of dissociating groups having a pKa of 12 or less) is 100 to 20.
00 or less, more preferably 100 or more and 1000 or less. Here, as the value of pKa, a value measured using dimethylformamide: water = 1: 1 as a solvent is used.

The coupler which forms the diffusible dye is 1 × 10 5 in an alkaline solution having a pH of 11 until the solubility of the diffusible dye formed by coupling with the reducing agent for color formation of the present invention reaches 25 ° C.
^-6 mol / liter or more is preferable, and 1 × 10
^-5 mol / liter or more preferably 1 ×
It is particularly preferred that the dissolution is 10 ^-4 mol / l or more.
The coupler forming the diffusible dye is dissolved in an alkaline solution having a diffusion constant of 25 ° C. and a pH of 11 at a concentration of 10 ⁻⁴ mol / liter in an alkaline solution having a diffusible dye formed by coupling with the color-forming reducing agent of the present invention. In this case, it is preferably 1 × 10 ⁻⁸ m ² / s ⁻¹ or more, more preferably 1 × 10 ⁻⁷ m ² / s ⁻¹ or more, and 1 × 10 ⁻⁶ m ² / s ^−. It is particularly preferred that it is ¹ or more.

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

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

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

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

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

The polymer mordant of the present invention has a molecular weight of 1,0.
100 to 1,000,000 is suitable, and especially 10,000
00 to 200,000 is preferred. The above-mentioned polymer mordant is usually used by being mixed with a hydrophilic colloid. As the hydrophilic colloid, a hydrophilic colloid, a highly hygroscopic polymer or both of them can be used, and gelatin is most typical. The mixing ratio of the polymer mordant and the hydrophilic colloid, and the amount of the polymer mordant to be applied are easily determined by those skilled in the art according to the amount of the dye to be mordant, the type and composition of the polymer mordant, and the image forming process to be used. But the mordant / hydrophilic colloid ratio is 20/80
~ 80/20 (weight ratio), mordant applied amount is 0.2 ~ 15
g / m ² is suitable, preferably for use in the 0.5 to 8 g / m ^2.

In the present invention, it is preferable to use an auxiliary developing agent or a precursor thereof in the light-sensitive material, and these compounds will be described below. The auxiliary developing agent used in the present invention is a compound having an action of promoting electron transfer from a color-forming reducing agent to silver halide in the course of developing silver halide grains, and preferably, an exposed silver halide. It is a compound which develops particles and whose oxidized form can oxidize a color-forming reducing agent (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. .01%
It is as follows. The precursor of the auxiliary developing agent used in the present invention is a compound which is stably present in the light-sensitive material, but which releases the above-mentioned auxiliary developing agent quickly once it is processed with a processing solution. In this case, it is preferable that the diffusivity in the hydrophilic colloid layer is low. For example, the solubility in water (25 ° C.) is preferably 0.1% or less, more preferably 0.05% or less, and particularly preferably 0.01% or less. The solubility of the auxiliary developing agent released from the precursor is not particularly limited, but the auxiliary developing agent itself preferably has low solubility. The auxiliary developing agent precursor of the present invention is preferably represented by the general formula (A).

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

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

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 a paper support coated on both sides with a water-resistant resin layer, wherein at least one of the water-resistant resins contains white pigment fine particles, a fluorescent whitening agent and the like. preferable. 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.

Suitable examples of the above-mentioned fluorescent whitening agent include benzoxazole, coumarin and pyrazoline compounds, among which benzooxazolyl naphthalene and benzooxazolyl stilbene compounds. Is more preferred. The amount of the fluorescent whitening agent is not particularly limited, but is preferably 1 to 100 mg / m ² . When the fluorescent whitening agent is mixed with the water-resistant resin, the mixing ratio is preferably 0.0005 to 3% by weight, more preferably 0.001 to 0.5% by weight, based on the water-resistant resin. In the present invention, a fluorescent whitening agent may be used by dispersing it in a hydrophilic colloid layer in a silver halide color photographic light-sensitive material. In the present invention, a support having a second type diffuse reflection surface can be preferably used. The second type diffuse reflectivity refers to diffuse reflectivity obtained by imparting irregularities to a surface having a mirror surface and dividing the mirror surface into minute mirror surfaces facing different directions. The unevenness of 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 μm with respect to the center plane. Details of such a support are described in JP-A-2-239244.

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

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

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

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

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

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

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

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

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

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The total amount of silver applied to the light-sensitive material of the present invention is preferably 0.003 to 12 g per m ^{2 in} terms of silver. In the case of a transmission material such as a color negative film, the weight is preferably 1 to 12 g, more preferably 3 to 10 g.
0.003 to 1 g for reflective materials such as color paper
Is preferred in terms of rapid processing and low replenishment. In this case, the amount of each layer added is preferably 0.001 to 0.4 g per photosensitive layer. Particularly when the light-sensitive material of the present invention is subjected to intensification processing, the total coated silver amount is preferably 0.003 g to 0.3 g, more preferably 0.01 to 0.1 g, and particularly preferably 0.015 to 0.1 g. It is 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, 1 m ² per 0.00 silver coverage of the light-sensitive layer
If the amount is less than 1 g, the dissolution of the silver salt proceeds, and a sufficient color density cannot be obtained.
An increase in min and bubbles are generated, and it becomes difficult to endure appreciation.

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

The configuration and operation of the device used in the present invention will be described below. FIG. 1 is a schematic overall configuration diagram of a treatment liquid application apparatus used in the first embodiment of the present invention. As shown in FIG. 1, an injection tank 312 that constitutes a part of the coating device 310 is disposed at a position of the processing liquid coating unit 50 that faces the transport path A of the photosensitive material 16. Reference numeral 32 denotes a transport roller for the photosensitive material 16, and reference numeral 34 denotes a take-up roller for the processed photosensitive material. As shown in FIG. 1, a processing liquid bottle 332 for storing a processing liquid to be supplied to the injection tank 312 is disposed below and to the left of the injection tank 312. A filter 334 for filtering the liquid is provided. And the pump 336 on the way
Is disposed in the processing liquid bottle 3.
32 and the filter 334. Further, on the right side of the injection tank 312, a sub tank 338 for storing the processing liquid sent from the processing liquid bottle 332 is arranged, and a water supply pipe 344 extends from the filter 334 to the sub tank 338.

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

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

Next, the structure and operation of the injection tank 312 will be described in detail with reference to FIG. 2 is an enlarged perspective view of the ejection tank, FIG. 3 is a bottom view of the ejection tank showing a state where the photosensitive material is conveyed below, FIG. 4 is an enlarged view of a main part of FIG.
FIG. 5 is a sectional view of the injection tank. As shown in FIGS. 3 and 5, an elastically deformable rectangular thin plate is formed on a part of the wall surface of the injection tank 312 facing the transport path A of the photosensitive material 16. Nozzle plate 32
2 are installed.

As shown in FIGS. 2 to 4, the nozzle plate 322 has a plurality of nozzle holes 324 (for example, several tens μm in diameter) for injecting the processing liquid filled in the injection tank 312. At least two rows are arranged in a staggered manner over the entire width direction of the photosensitive material 16 while being linearly arranged along a direction intersecting the transport direction A of the photosensitive material 16 at a constant interval. Therefore, these nozzle holes 32
4, the processing liquid in the injection tank 312 can be discharged to the photosensitive material 16 side. A feature of the present invention resides in that an alkaline processing liquid is simultaneously applied from a plurality of injection nozzles to the entire width direction of a photosensitive material. As shown in FIG. 4, the respective nozzle holes 324 are formed in a circular shape having the same inner diameter d, so that substantially the same volume of water droplets L can be ejected from the respective nozzle holes 324. Further, the three nozzle holes 324 adjacent to each other are placed on the nozzle plate 3 so that the center S of the nozzle holes 324 becomes the vertex of the equilateral triangle.
22. On the other hand, as shown in FIG. 1 and FIG.
30 and the exhaust pipe 330 is connected to the injection tank 31.
The inside and outside of 2 can communicate. Also, this exhaust pipe 33
A valve (not shown) that opens and closes the exhaust pipe 330 is provided in the middle of 0, and the opening and closing movement of this valve allows the inside of the injection tank 312 to communicate with and close to outside air.

FIG. 6 is a sectional view showing a state in which the processing liquid is injected from the injection tank. As shown in the figure, both ends of the nozzle plate 322 which is an end of the nozzle plate 322 located in a direction orthogonal to the longitudinal direction of the plurality of nozzle holes 324 arranged linearly are respectively provided on a pair of lever plates 320. The nozzle plate 322 is connected by bonding with an adhesive or the like.
And the pair of lever plates 320 are connected. The pair of lever plates 320 are connected to the pair of side walls 31 of the injection tank 312.
Narrow support portions 312B respectively formed at the lower part of 2A
Are fixed to the pair of side walls 312A, respectively. On the other hand, a part of a pair of top walls 312C that contact each other to form the top surface of the injection tank 312 protrudes to the outside of the injection tank 312.
On the lower side of 12C, a plurality of piezoelectric elements 326 (three on each side in the present embodiment) serving as an actuator are bonded and arranged. The lower end of the piezoelectric element 326 is bonded to the outer end side of the lever plate 320 so that the piezoelectric element 32
6 and the lever plate 320 are connected.

Therefore, the piezoelectric element 326 and the lever plate 3
20 and the support portion 312B constitute a lever mechanism, and when the outer end side of the lever plate 320 is moved by the piezoelectric element 326, the lever plate 320 is moved in the opposite direction to this movement.
The inner end side of the will move. The piezoelectric element 326
Is formed of laminated piezoelectric ceramics, for example, and has a large displacement in the axial direction of the piezoelectric element 326. A power source (not shown) controls the timing of voltage application by a controller. It is connected. And the valve for opening and closing the exhaust pipe 330 described above also
It is connected to this controller, which also controls the opening and closing movement of the valve. On the other hand, the lever plate 320, the side wall 312A, the support portion 312B, and the top wall 312C form part of an integrally formed frame 314, and as shown in FIG. And a pair of lever plates 320, a pair of side walls 312A, a pair of top walls 312C, and a pair of support portions 3 by being screwed with bolts (not shown).
12B are arranged facing each other,
The outer frame of the injection tank 312 will be formed.

[0157] Further, the left and right ends of the nozzle plate 322, which are the ends of the nozzle plate 322 positioned in the longitudinal direction of the nozzle holes 324, and the ends of the pair of frames 314, are provided with thin sealing portions. A stop plate 328 (see FIG. 3) is disposed in a state of being bonded to the pair of frames 314. further,
Inside the sealing plate 328, the left and right ends of the nozzle plate 322 and the ends of the pair of frames 314 are provided.
In order to fill the gap between them and prevent water from leaking from between them, for example, an elastic adhesive which is a silicone rubber-based adhesive is filled. Therefore, the gap of the injection tank 312 is sealed by the elastic adhesive without obstructing the movement of the left and right ends of the nozzle plate 322. Note that the left and right ends of the injection tank 312 may be sealed with only the elastic adhesive without using the thin sealing plate 328. As described above, when power is supplied to the piezoelectric element 326 from the power supply, the piezoelectric element 326 is extended, as shown in FIG.
As the piezoelectric element 326 is rotated about 2B,
Displaces the nozzle plate 322 while deforming it so that the central part of the nozzle plate 322 rises in the direction of arrow B. Then, with the deformation of the nozzle plate 322, the pressure of the processing liquid in the injection tank 312 increases, and a small amount of the processing liquid droplets L are collectively linearly formed from the nozzle holes 324 arranged in two rows. It will be injected.

Further, by repeatedly supplying current to the piezoelectric element 326 and repeatedly extending the piezoelectric element 326, the droplet L can be continuously ejected from the nozzle hole 324. FIG. 7 shows a state in which droplets are ejected from the nozzle holes of the ejection tank and adhere to the photosensitive material. As shown in the figure, when the volume of one droplet L ejected from the nozzle hole 324 is defined as a volume V, and the contact angle when the processing liquid is deposited on the photosensitive material 16 is defined as a contact angle θ, The diameter D of one droplet L on the photosensitive material 16 is obtained by the above equation. The volume V of this one droplet L is equal to the volume of the piezoelectric element 32 of the nozzle plate 322.
6 can be obtained from the following Table 2 showing experimental results in which the condition of the variation width (nozzle amplitude h) at the location corresponding to the nozzle hole 324 at the time of displacement by 6 is changed. Here, the inner diameter d of the nozzle hole 324 is set to 30 μm,
The data of m is displayed as an example.

[0159]

[Table 2]

In the present invention, three droplets L ejected from the nozzle hole 324 and adhered to the photosensitive material 16 adjacent to each other come into contact with each other in a state where there is no gap between them. It is to be deposited on the material 16. The process of spraying droplets from the nozzle holes of the spray tank and applying the droplets to the photosensitive material will be described in more detail with reference to FIGS.
FIG. 8 is an explanatory view in which the position of the nozzle hole of the ejection tank is projected on the photosensitive material, FIG. 9 is a plan view showing the photosensitive material in a state where droplets are ejected from the nozzle hole of the ejection tank and applied, and FIG.
Reference numeral 0 is an enlarged conceptual diagram showing three droplets taken out from the photosensitive material in a state where the droplets are ejected from the nozzle holes of the ejection tank and applied. First, as shown in FIG. 10, the pitch, which is the distance between the centers S1 of the droplets L, is different from that of the adjacent nozzle holes
Pitch P, which is the distance between the centers S of the H.24 (see FIG. 4)
Therefore, if the pitch P is set to a value determined by the following equation, the three droplets L adhere to the photosensitive material 16 in contact with each other without any gap between them. Become.

[0161]

(Equation 3)

Further, appropriate timing in accordance with the transport speed of the photosensitive material 16, that is, the dotted line 324A in FIG.
After the processing liquid is sprayed at the moment when the nozzle hole 324 is positioned above the portion indicated by, the processing liquid is then sprayed at the moment when the nozzle hole 324 is positioned above the portion indicated by the solid line 324B in FIG. By repeatedly ejecting the droplet L at the timing, as shown in FIG.
The arrangement is such that the connecting lines form an equilateral triangle, and the droplet L adheres to the surface of the photosensitive material 16. However, in practice,
When the droplets L after being atomized and adhered touch each other on the surface of the photosensitive material 16 and interfere with each other, the droplets L tend to agglomerate in order to reduce the surface energy.
Immediately agglomerate and become integral as a whole. Photosensitive material 1
6 describes the operation and operation when the processing liquid is attached by injection from the injection tank 312 (for example, FIG.
5, 6, and 7). First, the valve of the exhaust pipe 330 is closed by the controller. In this state, when the processing liquid is sprayed from the nozzle plate 322 while being atomized, a voltage is applied to the piezoelectric elements 326 by energization from a power supply controlled by the controller, and the piezoelectric elements 326 are deformed so as to extend simultaneously. Let it.

When the piezoelectric element 326 is deformed in this way,
The displacement is transmitted to the nozzle plate 322 via the rotation of the pair of lever plates 320 around the support portion 312B, and the nozzle plate 32
2 is displaced so as to pressurize the processing liquid in the injection tank 312. As a result, as shown in FIG. 7, the processing liquid filled in the injection tank 312 can be ejected from the nozzle holes 324 while being atomized, and adhere to the photosensitive material 16 being conveyed. The processing liquid is applied over the entire surface of the photosensitive material 16 by spraying the processing liquid from the nozzle holes 324 many times at an arbitrary timing in combination with the transport speed of the photosensitive material 16. At this time, a plurality of nozzle holes 324 for injecting the processing liquid are arranged in two rows over the entire width direction of the photosensitive material 16 on a nozzle plate 322 provided in the ejection tank 312 as a part of the wall surface of the ejection tank 312. Then, as described above, the volume V of the droplet L ejected from these nozzle holes 324 is obtained from the inner diameter d of the nozzle holes 324 and the nozzle amplitude h.

As a result, if the pitch P between the nozzle holes 324 is set to a value within the range of the equation (3), three droplets L adhering to the photosensitive material 16 adjacent to each other will each have a diameter of Since these droplets have a size of D, these droplets L come into contact with each other and adhere to the photosensitive material 16 in a state where there is no gap between them. The coating apparatus described above has the following operational effects. This will be described below with reference to FIGS. From the relationship between the diameter D of one droplet L and the pitch P between adjacent nozzle holes 324, the nozzle holes 32
By ejecting the processing liquid from No. 4, the droplets L can be uniformly attached to the photosensitive material 16 without any gaps between them. For this reason, it is possible to form a uniform coating film on the photosensitive material 16 even with the spray tank 312 that is not in contact with the photosensitive material 16. That is, the nozzle holes 324 are arranged so that all the droplets are aggregated, and a uniform aggregated liquid film is formed on the photosensitive material 16 immediately after spraying and adhering the liquid, thereby eliminating coating unevenness. Can be.

Then, the center S1 of the droplet L thus attached forms a vertex of an equilateral triangle, and the center of gravity of the equilateral triangle is completely covered by the three droplets L on the photosensitive material 16. , All liquid droplets can be aggregated with the least amount of liquid. As described above, it is possible to form a uniform coating film on the photosensitive material 16 without causing the processing liquid to become dirty and causing deterioration of the image recording apparatus itself and deterioration of image quality. On the other hand, the injection tank 31
2 has a nozzle hole 324, and the processing liquid is ejected from the nozzle hole 324. Therefore, compared with a coating apparatus in which a photosensitive material or the like is immersed and applied in a tank in which the processing liquid is stored, a smaller amount of the processing liquid is used. The coating can be performed, and drying can be performed in a short time. In addition, since the ejection tank 312 has a plurality of nozzle holes 324 arranged over the entire width of the photosensitive material 16, the processing liquid is simultaneously ejected from these nozzle holes 324 by a single displacement by the piezoelectric element 326. The processing liquid can be applied over a wide area over the entire width of the photosensitive material 16 by one jet. Therefore, it is not necessary to scan the nozzle plate 322 on a two-dimensional plane, and it is possible to apply a large area in a short time.
The application time can be reduced.

Further, lever plates 320 are connected at both ends of the nozzle plate 322 in a direction orthogonal to the longitudinal direction of the nozzle holes 324, and the nozzle plate 322 and the piezoelectric element 326 are connected via the lever plate 320. Therefore, the nozzle holes 324 can be collectively and stably displaced along the longitudinal direction of the plurality of nozzle holes 324 arranged linearly with the same displacement amount, and the photosensitive material 16 can be more uniformly processed. The liquid can be applied. On the other hand, since it is only necessary to form a plurality of nozzle holes 324 in the nozzle plate 322, no integration technology is required, and the coating device 310 can be manufactured at low cost. Further, when the processing liquid is jetted from the nozzle holes 324 of the nozzle plate 322, although the processing liquid in the injection tank 312 sequentially decreases, the sub tank 338 supplies the processing liquid to keep the water level in the injection tank 312 constant. Since it has the function, the processing liquid is supplied from the sub tank 338 side, and the water pressure in the injection tank 312 during atomization can be maintained at a constant value, and continuous water injection is ensured.

Next, the position of the nozzle hole 324 of the injection tank 312 according to the second embodiment of the present invention is
The projection above is shown in FIG. 11 and will be described below.
The same members as those described in the first embodiment are denoted by the same reference numerals, and redundant description will be omitted.

As shown in FIG. 11, the nozzle plate 322 of the injection tank 312 according to the present embodiment is provided with a plurality of nozzle holes 324 for injecting the processing liquid at regular intervals.
A pattern in which two nozzle rows arranged in a straight line along a direction intersecting the transport direction A are arranged in a zigzag pattern is repeatedly formed. That is, four nozzle rows are used, and the dotted line 3
The ejection of the droplet L is repeated at the timing indicated by 24C and the solid line 324D. Thereby, the present embodiment also has the same operation as the first embodiment, but can further increase the redundancy of atomization accompanying the injection. That is, even if one of the nozzle holes 324 is clogged, the location is complemented by the other nozzle holes 324, so that the aggregation unevenness does not occur. In the first embodiment, two rows of nozzles are arranged at a position where the line connecting the centers S of the nozzle holes 324 becomes an equilateral triangle. However, a position where the line connecting the centers S of the nozzle holes 324 becomes an equilateral triangle. However, it is not always necessary to arrange two nozzle rows. For example, two nozzle rows may be arranged several rows apart. Further, the nozzle row is not limited to two rows,
The number of rows may be three or more. By increasing the number of nozzle rows, it is possible to reduce the number of times the actuator is driven.

Although the relationship between the pitch P and the diameter D of the droplet L has been described using the limit value, in practice, the flying direction is considered in consideration of the unevenness of the flying direction of the droplet L and the tolerance of the particle size of the droplet L. It is conceivable to arrange the nozzle holes at a higher density than in the above-described embodiment so that when the unevenness of the droplet L is the maximum and the droplet L has the minimum particle size, all the droplets are aggregated. On the other hand, the volume V of the applied droplet L is in the range of 0.00001 to 0.01 mm ³ , and the contact angle θ is 4
0 ° or less, the liquid film thickness formed on the photosensitive material 16 is 1 to 1
Within the range of 00 μm, 5 μm or more and 50 μm
The following is preferred. Further, in the first and second embodiments, the nozzle rows are arranged at right angles to the transport direction. However, the nozzle rows need not be limited to right angles, and may be arranged at an angle to the transport direction.

In the present invention, in order to use up the processing solution, the temperature of the processing solution may be higher than that in a normal tank treatment, preferably 20 ° C. to 80 ° C., more preferably 30 ° C. to 50 ° C. . In order to maintain this temperature during processing, it is preferable to control not only the temperature of the processing solution but also the temperature of the photosensitive material. The coating apparatus used in the present invention is combined with a photosensitive material magazine for storing photosensitive materials, an exposure section, a transport section, a temperature control section after applying a processing liquid, a bleach-fix section, a washing apparatus, a drying section, and the like to form one image forming apparatus. It is preferred that In addition, it is preferable that a combination of a squeezing device for wiping excess processing liquid, a nip roller for transporting the photosensitive material, a cutter for cutting the roll-shaped photosensitive material into a sheet, and the like are additionally provided in the apparatus.

The processing material and processing method used in the present invention will be described. In the present invention, the photosensitive material is subjected to desilvering, washing with water or stabilizing treatment after development (silver development / cross oxidation of a built-in reducing agent) depending on the processing. After the washing or stabilizing treatment, a treatment for enhancing color development such as alkali addition may be performed. The development processing of the present invention will be described. In the color developing process of the present invention, a color-forming reducing agent is incorporated in a light-sensitive material, and the color developing agent is processed with an alkaline processing solution containing substantially no color developing agent. The alkaline processing liquid used in the present invention is characterized in that it does not substantially contain a color developing agent, and may contain other components (alkali, halogen, chelating agent, etc.). In some cases, it is preferable that a reducing agent is not contained in order to maintain processing stability. In this case, it is preferable that an auxiliary developing agent, hydroxyamines, sulfites, and the like are not substantially contained.

Here, "substantially not contained" means preferably 0.5 mmol / liter or less, more preferably 0.1 mmol / liter or less. In particular, it is preferable not to contain at all. The pH of the alkaline treatment liquid used in the present invention is preferably from 9 to 14, and particularly preferably from 10 to 13. After development, an intensification treatment can be applied. As the compound that intensifies, hydrogen peroxide and a compound that releases hydrogen peroxide are preferable from the viewpoint of environmental protection. As the compound releasing hydrogen peroxide, perboric acid and percarbonate windows are preferable. Among them, hydrogen peroxide is particularly preferred. The addition amount of these compounds is preferably 0.005 to 1 mol / l, more preferably 0.01 to 0.5 mol / l, and particularly preferably 0.02 to 0.25 mol / l.

The alkaline processing liquid of the present invention has a surface tension of 6
It needs to be 0 dyn / cm or less. In the present invention, when the surface tension of the alkaline processing liquid is large, the part which has begun to be applied since the processing liquid applied on the photosensitive material contracts before sufficiently penetrating into the photosensitive material. A phenomenon occurs in which the density is not as high as in other parts. The alkaline treatment liquid of the present invention more preferably has a surface tension of 45 dyn / cm or less. The surface tension is 15 dyn / c in order for the alkaline processing liquid to form uniform droplets.
m is required. The surface tension mentioned here is experimental chemistry course 18
Volume “Interface and Colloid” (edited by The Chemical Society of Japan, 1977
20 Mar, issued by Maruzen Co., Ltd.)
It is a measured value measured by the lhelmy method. Also,
Usually, a metal such as nickel is used for the nozzle of the processing liquid application device, and the processing liquid used in the present invention preferably has a contact angle with the nozzle material of 40 ° or more. When the affinity with the nozzle surface is strong and the contact angle is low, the processing liquid is not discharged well from the nozzle hole, and it is not preferable because uniform coating is not performed.

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

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

[0176]

Embedded image

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

[0178]

Embedded image

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

[0180]

[Table 3]

[0181]

[Table 4]

[0182]

[Table 5]

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

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

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

After development, desilvering is generally performed. The desilvering process includes a fixing process and a bleaching and fixing process. 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. Conventionally known bleaching baths and fixing baths can be used. 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.

The processing temperature in the desilvering step is from 20 to 50 ° C., preferably from 30 to 45 ° C. The processing time is 5 seconds to 2 minutes, preferably 10 seconds to 1 minute. The replenishment amount is preferably small, but is preferably 15 to 600 ml, preferably 25 to 200 ml, more preferably 35 to 100 ml per m ^{2 of} the light-sensitive material.
ml. It is also preferable to perform the treatment without replenishment, to the extent that the evaporation amount is supplemented with water. The light-sensitive material of the present invention generally undergoes a washing step after desilvering. When the stabilization treatment is performed, the washing step may be omitted. The pH of the washing or stabilizing solution is 4 to 9, preferably 5 to 8. The processing temperature is 15 to 45 ° C, preferably 25 to 40 ° C.
It is. Processing time is 5 seconds to 2 minutes, preferably 10 seconds to 4 minutes.
0 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 washing water and / or stabilizing solution can be set in a wide range depending on various conditions. The replenishing amount is preferably 15 to 360 ml per 1 m ² of the photographic material, and is preferably 25 to 120 ml.
ml is more preferred.

The total processing step, that is, the processing time from the developing step to the drying step is preferably 360 seconds or less, more preferably 120 seconds or less, and particularly preferably 90 to 20 seconds. The processing time with the alkaline processing liquid is usually 60 seconds or less, preferably 10 to 45 seconds, and more preferably 15 to 40 seconds. Here, the processing time is the time from when the processing liquid is applied to the photosensitive material to when it comes out of the drying unit in the processing machine in all the processing steps. The processing time with the alkaline processing solution is a time period after the photosensitive material is coated with the alkaline processing solution and before the bleach-fixing step is started (on a heat panel in the embodiments described later).

Various additives are used in the treatment applied to the present invention, and they are described in more detail in Research Disclosure Item 36544 (September 1994), and the relevant portions 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 Bleaching accelerator 538 Right column to 539 Left column Bleaching chelating agent 539 Left column Rehalogen Agent 539 Left column Fixing agent 539 Right column Fixing agent preservative 539 Right column Fixing chelating agent 540 Left column Stabilizing surfactant 540 Left Stabilizing scum inhibitor 540 Right Stabilizing chelating agent 540 Right Bactericidal Detergent 540 right color image stabilizer 540 right

[0191]

Next, the present invention will be described in more detail with reference to examples. Example 1 (Preparation of photosensitive material) A corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further applied. A multilayer color printing paper (100) having the following layer configuration was produced. The coating solution was prepared as follows. First layer coating solution 23 g of coupler (C-21), color reducing agent (I-3)
2) 16 g and a solvent (Solv-1) 80 g were dissolved in ethyl acetate, and this solution was added to a 16% gelatin solution 4 containing 10% sodium dodecylbenzenesulfonate and citric acid.
The resulting mixture was emulsified and dispersed in 00 g to prepare an emulsified dispersion A. On the other hand, silver chlorobromide emulsion A (cubic, average grain size 0.88
μm large size emulsion A and 0.70 μm small size emulsion A
3: 7 mixture (silver molar ratio). The coefficient of variation of the grain size distribution was 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride in each size emulsion). did. This emulsion contains the following blue-sensitive sensitizing dyes A, B, and C in an amount of 1.4 × 10 ^-4 mol per mol of silver per mol of silver.
For the small size emulsion A, 1.7 × 10
^-4 mol is added. 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 are mixed and dissolved,
A coating solution for the first layer was prepared to have the composition shown below.
The emulsion coating amount indicates a silver equivalent coating amount.

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

[0193]

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(Per mol of silver halide, 1.4 × 10 ^-4 mol was added to the large-size emulsion and 1.7 × 10 ^-4 mol was added to the small-size emulsion, respectively.) Green sensitivity Emulsion layer

[0195]

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(The sensitizing dye D was used in an amount of 3.0 × 10 ^-4 mol for a large-size emulsion, 3.6 × 10 ^-4 mol for a small-size emulsion, and Sensitizing dye E was used in an amount of 4.0 × 10 ⁻⁵ mol for a large-size emulsion and 7.0 for a small-size emulsion per mol of silver halide.
0 × 10 ^-5 mol, and the sensitizing dye F a per mol of silver halide, 2.0 × 10 ^-4 mol to the large size emulsion, to the small size emulsion 2.8 × 10 ^{- 4} mol added)

[0197]

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(5.0 × 10 ⁻⁵ mol of large-size emulsion and 8.0 × 10 ⁻⁵ mol of small-size emulsion were added per mol of silver halide). The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

[0199]

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Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer in an amount of 3.3 × per mole of silver halide. 10 ^-4 mol, 1.0 × 1
0 ^-3 mol and 5.9 × 10 ^-4 mol were added. Further, the second layer, the fourth layer, the sixth layer, and the seventh layer each have a .0 layer.
2 mg / m ² , 0.2 mg / m ² , 0.6 mg / m ² ,
It was added to a concentration of 0.1 mg / m ² . Further, 4-hydroxy-6 was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
-Methyl-1,3,3a, 7-tetrazaindene was added in an amount of 1 × 10 ⁻⁴ mol, 2 mol
× 10 ^-4 mol was added. In order to prevent irradiation, the following dyes were added to the emulsion layer (the coating amount is shown in parentheses).

[0201]

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(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. Support Polyethylene laminated paper [The first layer of polyethylene contains the following optical brightener (I), a white pigment (TiO ₂ , 15 wt%) and a bluish dye (ultramarine)] First layer (blue-sensitive emulsion layer) The above-mentioned silver chlorobromide emulsion A 0.20 gelatin 1.50 yellow coupler (C-21) 0.23 color-forming reducing agent (I-16) 0.16 solvent (Solv-1) 0.80

Second layer (color mixture preventing layer) Gelatin 1.09 Color mixture inhibitor (Cpd-6) 0.11 Solvent (Solv-2) 0.19 Solvent (Solv-3) 0.07 Solvent (Solv-4) 0.25 Solvent (Solv-5) 0.09 1,5-diphenyl-3-pyrazolidone 0.03 (fine-particle solid dispersion state) Third layer (green-sensitive emulsion layer) Silver chlorobromide emulsion B: Cubic, average grain 1: 3 mixture of large emulsion B (0.55 μm) and small emulsion B (0.39 μm) (Ag molar ratio). The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively, and 0.8 mol% of AgBr was locally contained in a part of the grain surface containing silver chloride as a base in each size emulsion. 0.20 Gelatin 1.50 Magenta coupler (C-56) 0.24 Coloring reducing agent (I-32) 0.16 Solvent (Solv-1) 0.80

Fourth layer (color mixture preventing layer) Gelatin 0.77 Color mixture inhibitor (Cpd-6) 0.08 Solvent (Solv-2) 0.14 Solvent (Solv-3) 0.05 Solvent (Solv-4) 0.14 Solvent (Solv-5) 0.06 1,5-diphenyl-3-pyrazolidone 0.02 (fine particle solid dispersion state) Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion C: Cubic, average grain 1: 4 mixture of large size emulsion C of size 0.50 μm and small size emulsion of 0.41 μm (Ag molar ratio). The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively, and 0.8 mol% of AgBr was locally contained in a part of the grain surface having silver chloride as a base in each size emulsion. 0.20 Gelatin 0.15 Cyan coupler (C-43) 0.21 Color-forming reducing agent (I-16) 0.20 Solvent (Solv-1) 0.80

Sixth layer (ultraviolet absorbing layer) Gelatin 0.64 Ultraviolet absorbing agent (UV-1) 0.39 Color image stabilizer (Cpd-8) 0.05 Solvent (Solv-6) 0.05 Seventh layer (Protective layer) Gelatin 1.01 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-1) 0.01

[0206]

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[0207]

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[0208]

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[0209]

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[0210]

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[0211]

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Sample (101) to Sample (100) were prepared in exactly the same manner as in the preparation of Sample (100), except that the wettability improver shown in Table 6 was added to the seventh layer to Sample (100).
(117) was produced.

[0213]

[Table 6]

(Preparation of Processing Solution) The following developing solution (alkali activating solution) a-1 was prepared. Developing solution (alkali activating solution) (100) Water 600 ml KOH 14 g KCl 2.5 g Benzotriazole 0.02 g Hydroxyethylidene-1,1-diphosphonic acid (30%) 4 ml Add water 1000 ml pH 13.0 Processing solution a -1 and the surface tension reducing agents shown in Table 7 in Table 7
The processing liquids a-2 to a-13 added in the amounts shown in (1) and (2) were prepared.

[0215]

[Table 7]

All the prepared samples were cut into a size of 14 cm × 12 cm, and were all exposed to white light. The exposed sample was subjected to a coating treatment using the treatment liquid prepared above using the following treatment steps. (Processing Step 1) Processing Step Temperature Time Developer Coating 40 ° C. − (Coating using the coating apparatus of the present invention The coating amount of the processing liquid is 40 cc / m ² The pitch P between the nozzle holes is ( √3) · D / 2 or less = 150 μm The width of the nozzle is 5.5 cm (meaning the width from end to end of the plurality of nozzle hole groups of the injection tank (direction intersecting the moving direction of the photosensitive material)) The length is 12cm (The length when the photosensitive material is moved under the nozzle and the alkaline processing liquid is applied to a certain length.) The processing liquid is shown in Table 7.) Leave on the heat panel 40 ° C 30 seconds Bleaching and fixing 40 ° C 45 seconds Rinse 30 ° C 90 seconds Drying 70 ° C 60 seconds

The bleach-fixing solution and the washing solution include the following bleach-fixing solutions:
A rinsing solution was used. Bleaching-fixing solution Water 600 ml Ammonium thiosulfate (700 g / l) 93 ml Ammonium sulfite 40 g Ammonium iron (III) ethylenediaminetetraacetate 55 g Ethylenediaminetetraacetic acid 2 g Nitric acid (67%) 30 g Water is added 1000 ml pH (25 ° C./acetic acid and ammonia water) 5.8 Rinse solution Chlorinated sodium isocyanurate 0.02 g Deionized water (conductivity 5 μS / cm or less) 1000 ml pH 6.5 The center of the portion where the sample after treatment was applied with the treatment liquid (5.5 cm) Of the center of the sample, however, when there was a white spot, a portion without the spot was measured.) The density was measured in the coating direction (direction of 12 cm) with blue light, green light and red light. 4. The average from the beginning of application to 1 cm is Di, and
The average from 5 cm to 6.5 cm was defined as Dm. (The measured values of Dm of blue light, green light, and red light were 2.31, 2.48, and 1.56 at any level, respectively.) Di is shown in Tables 8 and 9. Tables 8 and 9 show the presence or absence of white spots.

[0218]

[Table 8]

[0219]

[Table 9]

The following can be understood from the above results. Comparing Processing Level 2 and Processing Level 7, etc., Processing Level 2 where the photosensitive material and the processing liquid have a contact angle of 30 ° or more has large white spots, and is also smeared due to unevenness of the applied processing liquid. A decrease in coloring at the beginning is observed. On the other hand, in the case of the processing level 7 in which the contact angle between the photosensitive material and the processing solution is 30 ° or less, no white spots are observed, and the color development at the beginning of application due to the unevenness of the applied processing solution. Is hardly observed (each is close to the value of Dm). Comparing the processing level 6 with the processing level 7, the surface tension of the processing solution is 60 dy even when the contact angle between the photosensitive material and the processing solution is 30 ° or less.
In the case of the processing level 6 of n / cm or more, the color development at the beginning of application is reduced due to the unevenness of the applied processing liquid, but in the case of the processing level 7 of 60 dyn / cm or less, the No reduction in color development at the beginning of application due to bias is observed. On the other hand, from the comparison between the processing levels 11 and 16, when the contact angle between the nozzle and the processing liquid is less than 40 °, fine white spots due to poor spraying of the processing liquid are observed, but the contact angle between the nozzle and the processing liquid is 40 °. In the above case, such white spots are not observed. Processing level 7, 19, 23, 2
From the comparison of 6, 32, 33, 34, etc., regarding the method of using the contact angle lowering agent which can be brought into the range of the contact angle intended for the present invention, the water-soluble polymer, amphoteric surfactant and fluorine-based surfactant are used alone. Also, it can be seen that when two types are used in combination, the color development at the start of application due to the unevenness of the applied processing liquid is less reduced, and when three types are used in combination, the reduction is further reduced.

Example 2 A sample (201) similar to the sample (100), except that the color-forming reducing agent and coupler of the sample (100) of Example 1 were replaced with the coloring-forming reducing agent and coupler shown in Table 10 in equimolar amounts. ) ~
(206) was produced. The sample of Example 1 (11
Sample (11) except that the color-forming reducing agent and coupler of 7) were replaced with the color-forming reducing agent and coupler shown in Table 11 in equimolar amounts.
Samples (301) to (306) similar to 7) were produced.
After exposing the produced sample in the same manner as in Example 1, the sample was treated with the developing solution shown in Table 7 produced in Example 1 in the same manner as in Example 1, and evaluated similarly.

[0222]

[Table 10]

[0223]

[Table 11]

[0224]

[Table 12]

[0225]

[Table 13]

Even if the color-forming reducing agent and the coupler are changed, only when the contact angle and the surface tension are within the range of the present invention, there is little reduction in the color development at the beginning of application due to the unevenness of the applied processing solution. I understand.

Example 3 The silver chlorobromide emulsions A, B and C of the first layer, the third layer and the fifth layer of the sample (100) of Example 1 are shown below as silver chlorobromide emulsions E, F and A sample (400) having exactly the same components as in Example G except that the amount of silver applied was changed to 0.01 g, 0.01 g, and 0.015 g per m ^{2 in place of} G. Silver chlorobromide emulsion D: cubic, average grain size 0.20 μm
3: 7 mixture of large emulsion D and 0.10 μm small emulsion D (Ag molar ratio). The variation coefficients of the grain size distribution were 0.08 and 0.10, respectively, and 0.3 mol% of AgBr was locally contained in a part of the grain surface containing silver chloride as a base in each size emulsion. Chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer. For the silver chlorobromide emulsion D, the following blue-sensitive sensitizing dyes A, B, and C used in Example 1 were used.

(Each of sensitizing dyes A, B and C per mol of silver halide was 7.0 × 10 ^-4 mol for large-size emulsion D, or 7.0 × 10 ^-4 mol for small-size emulsion D. 8.5 × 10 ^-4 mol of each was added.) Silver chlorobromide emulsion E: cubic, average grain size 0.10 μm
1: 3 mixture of a large-size emulsion B and a small-size emulsion B of 0.08 μm (Ag molar ratio). The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively, and 0.8 mol% of AgBr was locally contained in a part of the grain surface containing silver chloride as a base in each size emulsion. Green sensitizing dye D used in Example 1 was used for silver chlorobromide emulsion E,
E and F were used in the following amounts. (Sensitizing dye D was used in an amount of 1.5 × 1
0 ^-3 mol, per 1 mol of silver halide 1.8 × 10 ^-3 mol, and the sensitizing dye E to the small size emulsion, 2.0 × 10 ^-4 mol to the large size emulsion, 3.5 × 10 ^-4 mol for the small-sized emulsion, and 1.0 mol for the large-sized emulsion,
× 10 ^-3 mol, 1.4 × 10 ^-3 for small size emulsions
Mole added)

Silver chlorobromide emulsion F: cubic, 1: 4 mixture of large-sized emulsion C having an average grain size of 0.10 μm and small-sized emulsion of 0.08 μm (Ag molar ratio). The coefficient of variation of the grain size distribution was 0.09 and 0.11, and 0.8 mol% of AgBr was locally contained in a part of the grain surface having silver chloride as a base in each size emulsion. The silver chlorobromide emulsion F contains the red sensitizing dye G used in Example 2,
H was used in the amount shown below. (2.5 x 10 ^-4 moles per mole of silver halide for large size emulsions.)
4.0 × 10 ^-4 mol was added to the small size emulsion. The silver chlorobromide emulsions A, B and C of the first, third and fifth layers of the sample (117) of Example 1 were replaced with the silver chlorobromide emulsions E, F and G described above, Samples (417) of exactly the same components were made except that the amounts were 0.01 g, 0.01 g and 0.015 g per m ² , respectively. The following developing intensifier b-1 was prepared.

Development intensifying solution Water 800 ml Sodium 5-sulfosalicylate 50 g Benzotriazole 0.02 g KCl 2.5 g Hydroxyethylidene-1,1-diphosphonic acid (30% aqueous solution) 4 ml Hydrogen peroxide (30% aqueous solution) 30 ml Water In addition, Samples b-2 to b-5 were prepared by adding the following surface tension reducing agent to 1 liter pH 11.5 b-1. Surface tension lowering agent type Additive amount b-2 SR-13 4.5 mmol / l b-3 SR-32 4.5 mmol / l b-4 F-4 1 mmol / l b-5 F-4 6 mmol / l After the photosensitive material and the samples (400) and (417) were solid-exposed, the following processing was performed using the developing intensifiers b-1 to b-5.

(Processing Step 2) Processing Step Temperature Time Developing 40 ° C .— (Coating Processing Using Coating Apparatus of the Present Invention—The Coating Amount of Processing Solution is 50 cc / m ² ) Leave on Heat Panel 40 ℃ 30 seconds Washing 40 ° C 90 seconds Stabilization treatment 30 ° C 15 seconds Drying 70 ° C 60 seconds However, the following stabilizing solution was used.

Stabilizer Sodium bisulfite 23 g 2-Mercaptobenzimidazole-5-sodium sulfonate 1 g Hydroxyethylidene-1,1-diphosphonic acid (30% aqueous solution) 1 ml 5-chloro-2-methyl-4-isothiazoline-3- ON 0.02 g 1 liter by adding water pH 7.5 Even if desilvering is unnecessary by using a photosensitive material having a significantly reduced silver content, a photosensitive material having a contact angle and a surface tension within the range of the present invention can be used. Even when the developing intensifying solution was used, the color development at the beginning of application due to the unevenness of the applied processing solution as in Example 1 was not observed, and uniform color development was observed.

Example 4 The sample (117) of Example 1 was subjected to three-color separation gradation exposure for sensitometry. (Exposure) A YAG solid-state laser (oscillation wavelength, 946 nm) using a semiconductor laser GaAlAs (oscillation wavelength, 808.5 nm) as an excitation light source as a light source is SHG of KNbO ₃ .
A YVO ₄ solid-state laser (oscillation wavelength, 108.7 nm) using a semiconductor laser GaAlAs (oscillation wavelength, 808.7 nm) as an excitation light source, having a wavelength of 473 nm, which has been taken out by wavelength conversion by a crystal.
532 nm, AlGaInP (oscillation wavelength, about 6 nm)
70 nm: Toshiba type No. TOLD9211) was used. Each of the laser beams is a device capable of sequentially scanning and exposing a color photographic paper moving in a direction perpendicular to a scanning direction by a rotating polyhedron. Using this apparatus, the relationship between the density (D) of the photosensitive material and the light amount (E) D-logE was obtained by changing the light amount. At this time, the laser light of three wavelengths modulates the light amount using an external modulator,
Exposure was controlled. This scanning exposure is performed at 400 dpi, and the average exposure time per pixel at this time is about 5 × 10 ⁻⁸ seconds. The temperature of the semiconductor laser was kept constant by using a Peltier element in order to suppress fluctuations in light quantity due to temperature. The exposed sample (117) was treated in the same treatment step 1 as in Example 1 using the treatment liquid a-2. As a result, even in an image formed by high-illuminance digital exposure, even when the processing liquid of the present invention is applied to the coating apparatus, the reduction in color development at the start of application due to the unevenness of the applied processing liquid is reduced. An image which was not seen and had no uniform unevenness was obtained.

[0234]

According to the present invention, color development, storage stability,
A color photographic image having excellent color image fastness and hue can be easily and quickly formed, and both "low waste liquid amount" and "reduction in processing fluctuation" can be realized. Further, even when the processing liquid is applied by the coating apparatus, no reduction in the color density at the start of application due to the unevenness of the applied processing liquid is observed, and a uniform and uniform image can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic overall configuration diagram of a coating apparatus according to a first embodiment of the present invention.

FIG. 2 is an enlarged perspective view of the injection tank according to the first embodiment of the present invention.

FIG. 3 is a bottom view showing a state in which a photosensitive material is conveyed below an injection tank according to the first embodiment of the present invention.

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

FIG. 5 is a sectional view of an injection tank according to the first embodiment of the present invention.

FIG. 6 is a cross-sectional view illustrating a state in which the processing liquid is injected from the injection tank according to the first embodiment of the present invention.

FIG. 7 is a conceptual cross-sectional view showing a state in which droplets are ejected from the nozzle holes of the ejection tank and adhere to the photosensitive material according to the first embodiment of the present invention.

FIG. 8 is an explanatory diagram in which the positions of the nozzle holes of the injection tank according to the first embodiment of the present invention are projected on a photosensitive material.

FIG. 9 is a plan view showing the photosensitive material in a state where droplets are ejected from the nozzle holes of the ejection tank and applied according to the first embodiment of the present invention.

FIG. 10 is an enlarged conceptual diagram showing three droplets taken out of a photosensitive material in a state where droplets are ejected from a nozzle hole of an ejection tank and applied according to the first embodiment of the present invention.

FIG. 11 is an explanatory diagram in which the position of a nozzle hole of an injection tank according to a second embodiment of the present invention is projected on a photosensitive material.

[Explanation of symbols]

 Reference Signs List 16 photosensitive material (image recording material) 62 treatment liquid coating unit 310 coating device 312 injection tank 322 nozzle plate 324 nozzle hole 326 piezoelectric element

Claims (10)

[Claims] 1. A color image forming method for performing color development processing on a silver halide color photographic light-sensitive material having at least one photographic constituent layer on a support using an alkaline processing solution substantially free of a color developing agent. At least one dye-forming coupler and at least one of the following general formulas (I) or (II) in any of the photographic constituent layers
Wherein the supply of the alkaline processing solution onto the photosensitive material is performed by ejecting the alkaline processing solution from a plurality of nozzle holes to adjoin the photosensitive material adhering to the photosensitive material. The three droplets are applied by applying the alkaline processing liquid in a state where there is no gap between them, and the surface tension of the alkaline processing liquid is 15 dyn / cm or more, and
dyn / cm or less, and the contact angle between the droplet of the alkaline processing liquid and the photosensitive material is 10 ° or more and 30 ° or less. Embedded image Embedded image In the formula, R _{1 to} R ₄ represent a hydrogen atom or a substituent.
A ₁ and A ₂ represent a hydroxyl group or a substituted amino group. X is -C
O -, - SO -, - SO 2 -, it represents a divalent or higher linking group selected from -PO <. Y _1K and Z _1K represent a nitrogen atom or a group represented by —CR ₅ （(R ₅ is a hydrogen atom or a substituent). k represents an integer of 0 or more. P represents a proton-dissociable group or a group capable of becoming a cation, and an oxidant generated by a redox reaction between the present compound and exposed silver halide is coupled with a coupler, and then the electron transfer from P is triggered. NX
It has a function of forming a dye by breaking a bond and removing a substituent bonded to a coupling site of a coupler. Y
Represents a divalent linking group. Z is a nucleophilic group and represents a group capable of attacking X when the present compound is oxidized. n is X
Is 1 or 2 when —PO <, and 1 when X is another group. R ₁ and R ₂ , R ₃ and R ₄ and Y _1K , Z
Two or more atoms or substituents arbitrarily selected from _1K and P may be independently bonded to each other to form a ring. 2. A color image forming method for performing color development processing on a silver halide color photographic light-sensitive material having at least one photographic constituent layer on a support, using an alkaline processing solution containing substantially no color developing agent. Any of the photographic constituent layers contains at least one kind of dye-forming coupler and at least one kind of a color-forming reducing agent represented by the following general formula (III), and the supply of the alkaline processing solution onto the photosensitive material is The alkaline processing liquid is sprayed from a plurality of nozzle holes, and three mutually adjacent droplets attached to the photosensitive material are coated with the alkaline processing liquid in a state where there is no gap between each other. And the surface tension of the alkaline processing liquid is 15 dyn / cm or more and 60 dyn / cm or less, and the contact angle between the droplets of the alkaline processing liquid and the photosensitive material is 10 ° or more and 30 ° or less. Color image forming method characterized in that there. Embedded image In the formula, R ¹¹ is an aryl group or a heterocyclic group which may have a substituent, and R ¹² is an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group which may have a substituent. is there. X ⁰ is _{-SO 2 -, - CO -,} - CO
CO -, - CO-O - , - CONH (R 13) -, - CO
CO-O -, - COCO- N (R 13) - or -SO ₂
—NH (R ¹³ ) —. Here, R ¹³ is a hydrogen atom or a group described for R ¹² . 3. The method according to claim 2, wherein the compound represented by the general formula (III) is represented by the general formula (IV) or (V). Embedded image In the formula, Z ¹ represents an acyl group, a carbamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group, and Z ² represents a carbamoyl group, an alkoxycarbonyl group,
Or an aryloxycarbonyl group, X ¹ ,
X ² , X ³ , X ⁴ and X ⁵ represent a hydrogen atom or a substituent. Here, Hammett's substituent constant σ of X ¹ , X ³ and X ⁵
The sum of the p value and the Hammett's substituent constant σm value of X ² and X ⁴ is 0.08 or more and 3.80 or less. R ^3a represents a heterocyclic group. 4. The method according to claim 3, wherein the compounds represented by formulas (IV) and (V) are represented by formulas (VI) and (VII), respectively. Embedded image In the formula, R ^1a and R ^2a represent a hydrogen atom or a substituent,
X ¹ , X ² , X ³ , X ⁴ and X ⁵ represent a hydrogen atom or a substituent. However, the sum of the Hammett's substituent constant σp value of X ¹ , X ³ and X ^{5 and} the Hammett's substituent constant σm of X ² and X ⁴ is 0.80 or more and 3.80 or less. R ^3a represents a heterocyclic group. 5. The color image forming method according to claim 4, wherein the compounds represented by formulas (VI) and (VII) are represented by formulas (VIII) and (IX), respectively. Embedded image In the formula, R ^4a and R ^5a represent a hydrogen atom or a substituent,
X ⁶ , X ⁷ , X ⁸ , X ⁹ , and X ¹⁰ represent a hydrogen atom, a cyano group,
Represents a sulfonyl group, a sulfinyl group, a sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a trifluoromethyl group, a halogen atom, an acyloxy group, an acylthio group, or a heterocyclic group. However, the sum of the Hammett's substituent constant σp value of X ⁶ , X ⁸ and X ^{10 and} the Hammett's substituent constant σm value of X ⁷ and X ⁹ is 1.20 or more and 3.80 or less. Q ¹
Represents a non-metallic atomic group necessary for forming a nitrogen-containing 5- to 8-membered heterocyclic ring together with C. 6. A coating apparatus having a plurality of nozzle holes for spraying an alkaline processing liquid to apply the alkaline processing liquid to the photosensitive material in order to supply the alkaline processing liquid to the photosensitive material. Assuming that the volume of one droplet of the alkaline processing liquid to be ejected is V and the contact angle when the alkaline processing liquid is deposited on the photosensitive material is θ, A coating apparatus in which the pitch P between adjacent nozzle holes calculated on the basis of the diameter D of one drop of the alkaline processing liquid adhered on the photosensitive material expressed by the following formula, is a value of (√3) · D / 2 or less. 6. The color image forming method according to claim 1, wherein the method is used. 7. A color image forming apparatus according to claim 1, wherein a contact angle between said alkaline processing liquid and a nozzle member of said coating apparatus is 40 ° or more. Method. 8. The method according to claim 1, wherein the thickness of the liquid film of the alkaline processing liquid applied to the photosensitive material is 50 μm or less. Color image forming method. 9. The coated silver amount of the light-sensitive material according to claim 1, 2, 3, 4, 5, or 6, which is the total silver amount of all coated layers, is 0.003 to 0.3 g / m 2 in terms of silver. ^2. The photosensitive material containing silver halide of item 2, wherein the alkaline processing solution containing substantially no color developing agent contains hydrogen peroxide. 9. The color image forming method according to 6, 7, or 8. 10. An exposure time per pixel of 10 ^-8 to 1
The exposure is performed by a scanning exposure in which ^0-4 seconds and overlap between adjacent rasters is performed.
10. The method for forming a color image according to 5, 6, 7, 8 or 9.