JPH06337506A - Color photographic sensitive material and method for forming color image and color proof - Google Patents

Abstract

(57) [Abstract] [Purpose] A high maximum image density and a low minimum image density are obtained, and a white image is excellent (color reproducibility is good), and a yellow image with good image quality is provided, and storage stability and processing stability are provided. A color photographic light-sensitive material suitable for producing a good color proof. [Structure] At least one blue-sensitive layer, at least one green-sensitive layer and at least one non-photosensitive layer containing a silver halide grain and a color coupler are provided on a support, The color coupler of the blue-sensitive layer is an acetamide type yellow coupler represented by the following formula (Y), and a layer containing fine powder of the dye represented by the following formula (I) is used as the non-photosensitive layer. A color photographic light-sensitive material, characterized in that it is contained as a functional layer. An image forming method in which the photographic light-sensitive material is treated with a specific developing treatment liquid, and a color proof forming method. Dyes represented by the following formulas (II) to (V) are preferable. [Chemical 1]

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material. More specifically, the present invention relates to a silver halide color photographic light-sensitive material capable of obtaining an image quality with excellent whiteness, and particularly suitable for producing a color proof used for plate inspection and adjustment in color plate making and printing processes. .

[0002]

2. Description of the Related Art An operation process of a color printed matter includes a process of color-separating a color original document and converting the color original document into a halftone image to form a transmission halftone image. A printing plate is made from the obtained transmission type halftone dot image, and prior to this, there is a step of inspecting the state, characteristics, etc. of the final printed matter (actual printing) and performing necessary proofing (color proofing). As a color proofing method, conventionally, a method of making a printing plate and making a test print has been used. However, in recent years, various color proofs have been produced for the purpose of speeding up the calibration process and reducing costs. As a method for producing a color proof, a photopolymer, a diazo method, a surprint method using a photoadhesive polymer, an overlay method and the like are known (for example, US Pat. No. 3,582,327, JP-A-56-5).
01217 and 59-97140). However, all of these methods require superposition and transfer of images, and also require superposition and transfer of a plurality of figures, and the process is complicated and requires a lot of time and cost. . Japanese Patent Application Laid-Open No. 56-104335 discloses a method for producing a color proof using a color photographic light-sensitive material. This method has a great merit in that the process is simple and the cost is low, and the tone is good. It has features such as excellent reproducibility. The color proofing method using the above color photographic light-sensitive material uses a silver halide color photographic light-sensitive material of a coloring method having a continuous gradation, and a magenta (M) color, cyan (C) color, yellow ( Y)
This is a method of obtaining a color proof by sequentially exposing each color plate of black color and black (B) color to a color paper so as to print a color negative and then performing a designated color development processing. This method has the features that the steps are simple and easy to automate as compared with the various methods described above. There are several possible silver halide color photographic light-sensitive materials that can be used in such color proofs. Among them, the transmission type black and white halftone image used in the production process of the color printed matter described above is often a positive type especially in Japan and Europe, and therefore, as a silver halide color photographic light-sensitive material for color proofing. Posi-positive type photosensitive materials are often used. Among them, the direct positive type color photographic light-sensitive material, of which the practical application technology has been rapidly advanced in recent years, has been noted as being most suitable for use in color proof because of the ease of processing.

As a method for forming a positive image using a conventionally known direct positive color silver halide photographic light-sensitive material, there is a method using an internal latent image type silver halide emulsion which has not been fogged in advance. This method is a method of directly obtaining a positive color image by subjecting a photographic light-sensitive material to image development, surface-development after or after fogging treatment. The internal latent image type silver halide photographic emulsion which has not been previously fogged is a type of halogenated type in which a silver halide grain has a photosensitive nucleus mainly inside and a latent image is mainly formed inside the grain by exposure. A silver photographic light sensitive emulsion. Various techniques have been known so far in this field. For example, US Pat. No. 25
92250, 2466957, 2497875.
No. 2, 588,982, No. 3,317,322, No. 37.
61266, 3761276, 3796577
And British Patents 1151363, 115055
No. 3 and No. 1011062 are the main ones. The formation mechanism of the direct positive image is explained as follows. That is, when imagewise exposure is performed, a so-called internal latent image is formed on the silver halide, and a fog treatment is then performed to cause a surface desensitizing action due to the internal latent image (that is, the silver halide in the exposed portion is exposed). No development nuclei (fog nuclei) are generated on the surface of the), and development nuclei are selectively generated only on the surface of the silver halide in the unexposed area. An image (positive image) is formed. As the method of the fogging treatment, there are a so-called "light fogging method" for exposing the entire surface of the photosensitive layer and a "chemical fogging method" for using a nucleating agent.

As described above, with the diversification of applications of direct positive color photographic light-sensitive materials, the demand for the obtained image (image quality) becomes more and more strict, and the maximum image density is high and the minimum image density is low, that is, It is desired that the image has a large ratio between the maximum image density and the minimum image density. Particularly in the application of color proof, it is important to obtain a high color reproducibility by increasing the maximum image density and decreasing the minimum image density. A positive color image is formed by the formation of a coloring dye by a coupling reaction between an oxidized product of a developing agent and a color coupler. Conventionally, for yellow couplers, an acetamide type yellow coupler having a pivaloyl group as an acyl group has been preferably used (see JP-A-2-220049). However, the acetamide type yellow couplers having the above-mentioned pivaloyl group which have been conventionally used have a problem that the color density is low. Therefore, it has not always been sufficiently satisfactory in applications such as color copying and color proofing in which the above-mentioned image quality characteristics are required. Further, with the diversification and expansion of the applications of the above-mentioned light-sensitive materials, the maximum image density is lowered or the minimum image density is raised (whiteness is lowered) in many cases. For example, factors that increase the minimum image density include long-term storage (raw storage) of photosensitive materials under high temperature and high humidity, local pressure due to external mechanical action, or increase in frequency of use. Along with this, there is a change in the composition of the processing liquid during development processing (for example, when deterioration of the processing liquid due to continuous processing progresses). One of the other major factors is that the colloidal silver contained in the non-photosensitive layer (yellow filter layer, antihalation layer, etc.) provided in a normal light-sensitive material is not sufficiently desilvered even after processing. It may remain because of this. For this reason, it is also desired that the photosensitive material has a characteristic that it is relatively insensitive to the above factors. It is known to use various dyes in place of the colloidal silver contained in the non-photosensitive layer for the purpose of improving the desilvering property as described above (for example, JP-A-2-278257 and 3). -131844, 4-
No. 321028), further improvement is desired.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a yellow image having a high maximum image density and a low minimum image density, excellent whiteness (good color reproducibility) and good image quality. It is to provide a photographic light-sensitive material. It is also an object of the present invention to provide a color photographic light-sensitive material that has characteristics that are relatively unaffected even when the above-mentioned factors that deteriorate image quality occur, and that is suitable for producing a color proof. .

[0006]

DISCLOSURE OF THE INVENTION The present inventors have aimed to realize a yellow image in which the maximum density of the obtained yellow image is high and the minimum density is low, particularly the minimum density is low, and the whiteness is further improved. Diligently studied. As a result, the photographic light-sensitive material was processed by using the specific yellow coupler represented by the above formula in a system using a specific dye in place of the colloidal silver usually contained in the non-photosensitive layer. In doing so, it was found that the above objects can be achieved by selecting and using a specific developing agent, and completed the present invention.

According to the present invention, at least one blue-sensitive layer, at least one green-sensitive layer and at least one non-photosensitive layer containing silver halide grains and a color coupler are provided on a support. In the silver halide color photographic light-sensitive material having, the color coupler of the blue photosensitive layer is an acetamide type yellow coupler represented by the following formula (Y),

[0008]

[Chemical 4]

[In the formula (Y), R ^Y1 represents a substituent excluding a hydrogen atom, Q is a 3- to 5-membered hydrocarbon ring together with C, or at least selected from N, S, O and P.] Represents a group of non-metal atoms necessary to form a 3- to 5-membered heterocycle containing one heteroatom in the ring, R ^Y2 represents an alkyl group, an aryl group or a heterocyclic group, and X ^Y represents Represents a group capable of splitting off by a coupling reaction with a hydrogen atom or an oxidized product of a color developing agent. However, R ^Y1 may combine with Q to form a polycycloalkyl group which is a bicycloalkyl group or more. ] And a color photographic light-sensitive material comprising a layer in which fine powder of a dye represented by the following formula (I) is dispersed in a binder as the above non-photosensitive layer.

[0010]

[Chemical 5]

[In the formula (I), D represents a compound having a chromophore, and X represents a dissociative proton bonded to D directly or via a divalent linking group or a group having a dissociative proton. , Y represents an integer of 1 to 7. ]

According to the present invention, the above color photographic light-sensitive material is subjected to image exposure and then the following formula (D):

[0013]

[Chemical 6]

[In the formula, R ^D1 represents an alkyl group, and R ^D2
Represents an alkylene group, provided that R ^D1 and R ^D2 may ^combine with each other to form a ring. ] It is a color image forming method characterized by carrying out development processing using a developing agent.

The present invention further provides a cyan plate halftone dot image film, a magenta halftone dot image film, a yellow halftone dot image film, and a black halftone dot obtained by color separation and halftone image conversion of the above color photographic light-sensitive material. Using image film,
A method for producing a color proof is characterized in that color development processing is performed after sequential exposure with red light, green light and blue light.

Furthermore, the present invention is a color image forming method characterized in that the color photographic light-sensitive material is scanned and exposed for an exposure time of 10 ^-3 seconds or less per pixel, and then color development processing is performed.

The preferred embodiments of the present invention will be described below. (1) The fine powder dye is at least one compound selected from compounds represented by the following formulas (II), (III), (IV) and (V).

[0018]

[Chemical 7]

In the formula, A ¹ and A ² each represent an acidic nucleus. B ¹ represents a basic nucleus. Q represents an aryl group or a heterocyclic group, and L ¹ , L ² and L ³ each represent a methine group. m represents 0, 1, 2, n and p are 0,
Indicates 1, 2, and 3. However, the compounds of the formulas (II) to (V) are carboxylic acid groups, sulfonamide groups, arylsulfamoyl groups, sulfonylcarbamoyl groups,
It has at least one group selected from the group consisting of a carbonylsulfamoyl group, an enol group of an oxonol dye, and a phenolic hydroxyl group. (2) The non-photosensitive layer provided as an antihalation layer between the support and the red photosensitive layer is a layer containing fine powder of the dye represented by the formula (I). (3) The non-photosensitive layer provided as a yellow filter layer between the blue photosensitive layer and the green photosensitive layer comprises a layer containing fine powder of the dye represented by the formula (I). There is. (4) The non-photosensitive layer provided as a magenta filter layer between the green photosensitive layer and the red photosensitive layer is a layer containing fine powder of the dye represented by the formula (I). There is. (5) The color photographic light-sensitive material contains a nucleating agent in at least one of the photosensitive layer and the non-photosensitive layer.

[0020]

By using the color photographic light-sensitive material of the present invention and by selectively using a specific developing agent, the maximum density is high and the minimum density is low (high whiteness). A yellow image can be obtained. In particular, there is almost no effect on the minimum density (whiteness) of the obtained yellow image even when the above-mentioned light-sensitive material is stored under high temperature and high humidity for a long period of time or when the composition of the processing liquid changes. A yellow image with good image quality can be obtained. Therefore, the photographic light-sensitive material of the present invention is suitable as a material for producing a color proof. Also, the blue-sensitive layer,
When a color proof is prepared by using a light-sensitive material having a normal layer structure having a green light-sensitive layer and a red light-sensitive layer in this order, it is sequentially exposed to blue light, green light and red light. In this case, it is preferable that the obtained image density does not change due to the fluctuation of the exposure amount. The red-sensitive emulsion layer easily feels green light. Therefore, when the exposure amount of green light is higher than the reference amount, the maximum density of a cyan image may be reduced and the dot reproducibility may be reduced. . However, by providing a layer containing fine powder of the dye represented by the formula (I) as a magenta filter layer between the green photosensitive layer and the red photosensitive layer, it is possible to reduce the above-mentioned maximum density or to reduce the mesh. It is possible to suppress a decrease in point reproducibility.

[Detailed Description of the Invention] The color photographic light-sensitive material of the present invention will be described in detail below. The color photographic light-sensitive material of the present invention can be used as a color negative film, a color positive film (color reversal film, a film for color printing), a color reversal paper, a color auto positive film, a color auto positive paper, etc. As described above, the image has excellent image characteristics and a good hue, so that it is suitable as a material for making a color proof, a color auto positive paper (direct positive color photographic light-sensitive material).
It is preferable to use

In general, a silver halide color photographic light-sensitive material has a red light-sensitive layer containing a color coupler and silver halide grains, a green light-sensitive layer containing a color coupler and silver halide grains and a color coupler on a support. At least one blue-sensitive layer containing silver halide grains is provided, and at least one non-photosensitive layer is provided together with these photosensitive layers. The color photographic light-sensitive material of the present invention is as described above, wherein the blue light-sensitive layer contains the specific acetamide type yellow coupler represented by the formula (Y) and the non-light-sensitive layer has the above-mentioned formula. It is characterized by including a layer containing fine powder of the dye represented by (I).

First, the dye represented by the following formula (I) will be described.

[0024]

[Chemical 8]

In the formula, D represents a compound having a chromophore,
X represents a dissociative proton bonded to D directly or via a divalent linking group or a group having a dissociative proton, and y
Represents an integer of 1 to 7.

The compound having a chromophore represented by D can be selected from many known dye compounds. Examples of these compounds include oxonol dyes, merocyanine dyes, cyanine dyes, arylidene dyes, azomethine dyes, triphenylmethane dyes, azo dyes, anthraquinone dyes, and indoaniline dyes.

The group having a dissociative proton represented by X is non-dissociated when the compound represented by the formula (I) is added to the silver halide photographic light-sensitive material of the present invention.
It has the property of rendering the compound of formula (I) substantially water-insoluble, and has the property of dissociating to render the compound of formula (I) substantially water-soluble in the process of developing the same. Examples of these groups include a carboxylic acid group, a sulfonamide group, an arylsulfamoyl group, a sulfonylcarbamoyl group, a carbonylsulfamoyl group, an enol group of an oxonol dye, and a phenolic hydroxyl group. Among the compounds represented by formula (I), more preferred are the following formulas (II), (III), (IV) and (V)
Is a compound represented by.

[0028]

[Chemical 9]

In the formula, A ¹ and A ² each represent an acidic nucleus. B ¹ represents a basic nucleus. Q represents an aryl group or a heterocyclic group, and L ¹ , L ² and L ³ each represent a methine group. m represents 0, 1, 2, n and p are 0,
Indicates 1, 2, and 3. However, the compounds of the formulas (II) to (V) are carboxylic acid groups, sulfonamide groups, arylsulfamoyl groups, sulfonylcarbamoyl groups,
It has at least one group selected from the group consisting of a carbonylsulfamoyl group, an enol group of an oxonol dye, and a phenolic hydroxyl group, and has no other water-soluble group (for example, a sulfonic acid group or a phosphoric acid group).

The acidic nucleus represented by A ¹ and A ² is preferably a cyclic ketomethylene compound or a compound having a methine group sandwiched by electron withdrawing groups. Examples of cyclic ketomethylene compounds include 2-pyrazolin-5-one, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoxazolone, barbituric acid, thiobarbituric acid, indandione, dioxopyrazolo Pyridine, hydroxypyridone, pyrazolidinedione and 2,5-dihydrofuran can be mentioned.
These may have a substituent. A compound having a methylene group sandwiched between electron withdrawing groups is Z ¹ CH ₂
It can be represented as Z ² . Here, Z ¹ and Z ² are —CN, —SO ₂ R ¹ , —COR ¹ and —COOR, respectively.
_{^{2, -CONHR 2, -SO 2 NHR}} 2, -C [= C
(CN) ₂ ] R ¹ or -C [= C (CN) ₂ ] NHR
Represents ¹ . R ¹ represents an alkyl group, an aryl group, or a heterocyclic group, R ² represents a hydrogen atom, a group represented by R ¹ , and each of these may have a substituent.

Examples of the basic nucleus represented by B ¹ include pyridine, quinoline, indolenine, oxazole, imidazole, thiazole, benzoxazole, benzimidazole, benzothiazole, oxazoline, naphthoxazole and pyrrole. . Each of these may have a substituent.

Examples of the aryl group represented by Q include a phenyl group and a naphthyl group. Each of these may have a substituent. Examples of the heterocyclic group represented by Q include pyrrole, indole, furan, thiophene, imidazole, pyrazole, indolizine,
Mention may be made of quinoline, carbazole, phenothiazine, phenoxazine, indoline, thiazole, pyridine, pyridazine, thiadiazine, pyran, thiopyran, oxadiazole, benzoquinoline, thiadiazole, pyrrolothiazole, pyrrolopyridazine, tetrazole, oxazole, coumarin, and coumarone. it can.
Each of these has a substituent.

The methine group represented by L ¹ , L ² and L ³ may have a substituent, and the substituents are linked to each other to form a 5- or 6-membered ring (eg, cyctopentene, cyclohexene). It may be formed.

The substituent which each of the above groups may have is not particularly limited as long as it is a substituent which does not substantially dissolve the compounds of the formulas (I) to (V) in water of pH 5 to pH 7. Absent. For example, the following substituents can be mentioned. Carboxylic acid group, sulfonamide group having 1 to 10 carbon atoms (for example, methanesulfonamide, benzenesulfonamide,
Butanesulfonamide, n-octanesulfonamide), a sulfamoyl group having 0 to 10 carbon atoms (eg, unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl, butylsulfamoyl), carbon number 2
10 to 10 sulfonylcarbamoyl groups (for example, methanesulfonylcarbamoyl, propanesulfonylcarbamoyl, benzenesulfonylcarbamoyl), and 1 to 1 carbon atoms
0 acylsulfamoyl group (eg, acetylsulfamoyl, propionylsulfamoyl, pivaloylsulfamoyl, benzoylsulfamoyl), carbon number 1
~ 8 chain or cyclic alkyl group (for example, methyl, ethyl, isopropyl, butyl, hexyl, cyclopropyl, cyclopentyl, cyclohexyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxyethyl,
Benzyl, phenethyl, 4-carboxybenzyl, 2
-Diethylaminoethyl), an alkenyl group having 2 to 8 carbon atoms (for example, vinyl, allyl), an alkoxy group having 1 to 8 carbon atoms (for example, methoxy, ethoxy, butoxy), a halogen atom (for example, F, Cl, Br). , Carbon number 0 to 1
0 amino group (for example, unsubstituted amino, dimethylamino, diethylamino, carboxyethylamino), C 2-10 ester group (for example, methoxycarbonyl), C 1-10 amide group (for example, acetylamino) , Benzamide), a carbamoyl group having 1 to 10 carbon atoms (eg, unsubstituted carbamoyl, methylcarbamoyl, ethylcarbamoyl), an aryl group having 6 to 10 carbon atoms (eg, phenyl, naphthyl, 4-carboxyphenyl, 3-carboxy) Phenyl, 3,5-dicarboxyphenyl, 4-methanesulfonamidophenyl, 4-butanesulfonamidophenyl), an aryloxy group having 6 to 10 carbon atoms (eg, phenoxy, 4-carboxyphenoxy, 3-methylphenoxy, naphthoxy). , Alkyl having 1 to 8 carbon atoms Group (e.g., methylthio, ethylthio, octylthio), an arylthio group having 6 to 10 carbon atoms (e.g., phenylthio, naphthylthio), 1 carbon atoms
An acyl group having 10 to 10 (for example, acetyl, benzoyl, propanoyl), a sulfonyl group having 1 to 10 carbon atoms (for example, methanesulfonyl, benzenesulfonyl), an ureido group having 1 to 10 carbon atoms (for example, ureido, methylureido), Urethane group having 2 to 10 carbon atoms (eg, methoxycarbonylamino, ethoxycarbonylamino), cyano group, hydroxyl group, nitro group, heterocyclic group (eg, 5-carboxybenzoxazole ring), pyridine ring, sulfolane ring, pyrrole ring , Pyrrolidine ring, morpholine ring, piperazine ring, pyrimidine ring, furan ring).

The formulas (I) used in the present invention are described below.
Specific examples of the compound represented by (V) will be described.

[0036]

[Chemical 10]

[0037]

[Chemical 11]

[0038]

[Chemical 12]

[0039]

[Chemical 13]

[0040]

[Chemical 14]

[0041]

[Chemical 15]

[0042]

[Chemical 16]

[0043]

[Chemical 17]

[0044]

[Chemical 18]

[0045]

[Chemical 19]

[0046]

[Chemical 20]

[0047]

[Chemical 21]

[0048]

[Chemical formula 22]

The dye used in the present invention is represented by International Patent WO
88/04794, European Patent EP027472
3A1, 276566, 299435, JP-A-52-92716, 55-155350, 5
5-155351, 61-205934, 48
-68623, U.S. Pat. Nos. 2,527,583, 348.
No. 6897, No. 37465939, No. 3933798
No. 4130429, No. 4040841, No. 3-282244, No. 3-7931, and No. 3-167.
It can be synthesized according to the method described in the specification or publication such as No. 546 or according to the method.

The dye represented by the formula (1) is preferably used as a solid dispersion of fine powder (fine crystal particles). The fine (crystal) particle solid dispersion of the dye is used in the presence of a dispersant by using a suitable solvent (water, alcohol, etc.), if desired, by a known refining means (for example, ball mill, vibrating ball mill, planetary ball mill, sand mill, It can be prepared mechanically using a colloid mill, jet mill, roller mill). Further, the fine (crystal) particles of the dye can be prepared by dissolving the dye in a suitable solvent using a dispersing surfactant,
A method of adding fine dyes to a poor solvent for precipitating fine crystals, or p
By controlling H, the dye can be first dissolved, and then the pH can be changed to obtain microcrystals. The layer containing the fine powder of the dye is prepared as a solid dispersion of substantially uniform particles by dispersing the fine (crystal) particles of the dye thus obtained in a suitable binder. It can be provided by coating on a desired support. It can also be provided by using a method in which a dye in a dissociated state is applied in the form of a salt and then an acidic gelatin is overcoated to obtain dispersion fixation at the time of application. The binder is not particularly limited as long as it is a hydrophilic colloid that can be used in the light-sensitive emulsion layer and the non-light-sensitive layer, but gelatin or a synthetic polymer is usually used.

The fine particles of the dye in the solid dispersion have an average particle size of 0.005 μm to 10 μm, preferably 0.01 μm.
m to 1 μm, more preferably 0.01 μm to 0.5 μm
m, and particularly preferably 0.01 μm to 0.3 μm.

The solid dispersion of fine particles of the dye represented by formula (I) used in the present invention is contained in the non-photosensitive layer according to the hue of the dye, but a plurality of non-photosensitive layers are provided. In the light-sensitive material of the aspect described above, the light-sensitive material may be contained in these plural layers. In the present invention, an antihalation layer is provided between the support and the red photosensitive layer, a yellow filter layer is provided between the blue photosensitive layer and the green photosensitive layer, and a green photosensitive layer and the red photosensitive layer are provided. Magenta filter layers are preferably provided between the layers, but these layers are layers each containing fine powder of the dye represented by formula (I). Further, in the present invention, when the non-photosensitive layer is provided as the functional layer as described above, all the layers are layers containing fine powder of the dye represented by the formula (I). Is preferred.
The addition amount of the dye represented by the above formula (1) is preferably in the range of 5 × 10 ⁻² mol to 5 × 10 ⁻⁷ mol / m ² , and particularly 1
The range of x10 ^-3 mol to 5 x 10 ^-5 mol / m ² is preferable.

Next, the acetamide type yellow coupler represented by the following formula (Y) will be described in detail.

[0054]

[Chemical formula 23]

In the formula (Y), R ^Y1 represents a substituent excluding a hydrogen atom. Q is a non-metal necessary for forming a 3- to 5-membered hydrocarbon ring with a carbon atom or a 3- to 5-membered heterocycle containing a hetero atom selected from N, S, O and P in the ring. Represents a group of atoms. X ^Y represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized product of an aromatic primary amine developing agent (hereinafter, leaving group). R ^Y2 represents an alkyl group, an aryl group or a heterocyclic group. R ^Y1 may combine with Q to form a polycycloalkyl group having a bicycloalkyl group or more.

Hereinafter, R ^Y1 , Q, X ^Y and R ^Y2 in the formula (Y) will be described in detail. The substituent represented by R ^Y1 is a halogen atom, a cyano group, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or 1 to 30 carbon atoms.
Is preferably an alkylthio group having 6 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, or an arylthio group having 6 to 30 carbon atoms. These groups may have a substituent, and examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, a nitro group, an amino group, a carbonamido group, a sulfonamide group, and an acyl group. it can. R ^Y1 is particularly preferably an alkyl group (for example, ethyl, isobucityl, n-octyl, benzyl, hexadecyl, phenoxymethyl).

The ring formed by Q together with the carbon atom may contain an unsaturated bond in the ring, and may be substituted or unsubstituted. Q preferably represents a nonmetallic atom group necessary for forming a hydrocarbon ring having 3 to 30 carbon atoms or a heterocycle having 2 to 30 carbon atoms together with carbon atoms. Examples of the ring formed by Q together with the carbon atom include a cyclopropane ring,
Examples thereof include a cyclobutane ring, a cyclopentane ring, a cyclopropene ring, a cyclobutene ring, a cyclopentene ring, an oxetane ring, an oxolane ring, a 1,3-dioxolane ring, a thietane ring, a thiolane ring, and a pyrrolidine ring. Examples of the substituent include a halogen atom, a hydroxyl group, an alkyl group, an aryl group, an acyl group, an alkoxy group, an aryloxy group, a cyano group, an alkoxycarbonyl group, an alkylthio group, and an arylthio group.

Further, by combining Q with R ^Y1 ,
It is preferable that a polycycloalkyl group having a bicycloalkyl group or more is formed. Examples of such groups include:
Bicyclo [2.1.0] pentan-1-yl group, bicyclo [2.2.0] hexan-1-yl group, bicyclo [3.1.0] hexan-1-yl group, bicyclo [3.
2.0] heptan-1-yl group, bicyclo [3.3.
0] octane-1-yl group, bicyclo [4.1.0] heptan-1-yl group, bicyclo [4.2.0] octane-1-yl group, bicyclo [4.3.0] nonane-1. -Yl group, bicyclo [5.1.0] octane-1-yl group,
Bicyclo [5.2.0] nonan-1-yl group, bicyclo [1.1.1] heptan-1-yl group, bicyclo [2.
1.1] Hexan-1-yl group, bicyclo [2.2.
1] heptane-1yl group, bicyclo [2.2.2] octane-1-yl group, tricyclo [3.1.1.0 ^3,6 ].
Heptane-6-yl group, tricyclo [3.3.0.0 ^3,
7 ] Octane-1-yl group, and tricyclo [3.3.
^1.03,7 ] nonan-3-yl group can be mentioned. These groups may have a substituent. Examples of the substituent include a substituent capable of substituting the ring formed by Q together with the carbon atom. The substitution position of the substituent is preferably a position excluding the α-position (β-position for the carbonyl group to be bonded).

The ring formed with the carbon atom to which Q is bonded is preferably a 3-membered ring or a 4-membered ring, more preferably a 3-membered ring.
The ring formed by Q together with the carbon atom is preferably a hydrocarbon ring. The group formed with the carbon atom to which Q and R ^YI are bonded is
1-alkylcyclopropan-1-yl group, bicyclo [2.1.0] pentan-1-yl group, bicyclo [3.
1.0] Hexan-1-yl group, bicyclo [4.1.
0] heptane-1-yl group, bicyclo [2.2.0] hexan-1-yl group, bicyclo [1.1.1] heptane-
1-yl group, bicyclo [2.1.1] hexane-1yl group, and tricyclo [3.1.1.0 ^3,6 ] heptane-
A 6-yl group is particularly preferred.

Any of the alkyl group, aryl group or heterocyclic group represented by R ^Y2 may have a substituent.
The heterocyclic group represents a 5 to 7-membered optionally condensed heterocycle containing at least one hetero atom selected from N, S, O or P in the ring. The above R ^Y2 is preferably an aryl group, and more preferably a group represented by the following formula (Ya).

[0061]

[Chemical formula 24]

In the above formula (Ya), R ^Y3 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group or amino. R ^Y4 represents a substitutable group on the benzene ring. k represents an integer of 0 to 4. However,
When k is plural, plural R ^Y4 may be the same or different from each other.

R ^Y3 is a halogen atom, an optionally substituted alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or a carbon number. 0-30 amino groups are preferred. Examples of these substituents include a halogen atom, an alkyl group, an alkoxy group, and an aryloxy group. R ^Y3 is particularly preferably a halogen atom (among others, a chlorine atom) and an aryloxy group.

Preferred examples of the group represented by R ^Y4 which can be substituted on the benzene ring include a halogen atom, an optionally substituted alkyl group having 1 to 30 carbon atoms, and 6 to 30 carbon atoms. Aryl group, C1-C30 alkoxy group, C2-C30 alkoxycarbonyl group, C7-C30 aryloxycarbonyl group, C1-C30 carbonamido group, C1-C30 Sulfonamide group, carbamoyl group having 1 to 30 carbon atoms, sulfamoyl group having 0 to 30 carbon atoms, alkylsulfonyl group having 1 to 30 carbon atoms, arylsulfonyl group having 6 to 30 carbon atoms, ureido group having 1 to 30 carbon atoms , Carbon number 0-30
Sulfamoylamino group, C2-30 alkoxycarbonylamino group, C1-30 acyl group, C1-30 alkylsulfonyloxy group, C6
To 30 arylsulfonyloxy groups and 1 to 1 carbon atoms
Thirty heterocyclic groups can be mentioned.

Examples of the substituent include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group and an alkylsulfonyl group. , Arylsulfonyl group, acyl group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonylamino group, sulfamoylamino group, ureido group, cyano group, nitro group, acyloxy group, alkoxycarbonyl group, aryl An oxycarbonyl group, an alkylsulfonyloxy group, and an arylsulfonyloxy group can be mentioned. R above
^Y4 is preferably substituted at the meta or para position on the benzene ring with respect to the acetamide-bonding group (-CHCONH-).

The above k is preferably 1 or 2.

The group (or atom) (leaving group) capable of splitting off by the coupling reaction with the oxidation product of the aromatic primary amine developing agent represented by X ^Y is a halogen atom, an acyloxy group or an aryloxy group. Group, alkylthio group, arylthio group, heterocyclic thio group, heterocyclic oxy group,
Alternatively, a heterocyclic group bonded to the coupling active position with a nitrogen atom can be mentioned. The above X ^Y is preferably a heterocyclic group or an aryloxy group which is bonded to the coupling active position by a nitrogen atom.

When X ^Y represents a heterocyclic group, X ^Y is preferably an optionally substituted imidazolidine-2,
4-dione-3-yl group, oxazolidin-2,4-dione-3-yl group, 1,2,4-triazolidine-3,
It is a group selected from a 5-dione-4-yl group, a succinimide group, a 1-pyrazolyl group, or a 1-imidazolyl group. When ^XY represents an aryloxy group, at least one electron withdrawing group (eg, a halogen atom, a cyano group,
An aryloxy group substituted with a nitro group, a trifluoromethyl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group) is preferable. ^XY is particularly preferably a 5-membered heterocyclic group.

The yellow coupler represented by the formula (Y) is
The substituents R ^Y1 , Q, X ^Y and R ^Y2 may form a dimer or a multimer which is bonded to each other via a bonding group or a divalent or higher valent group. In this case, the number of carbon atoms shown in each of the above substituents may be out of the specified range. Specific examples of the yellow coupler represented by the formula (Y) are shown below.

[0070]

[Chemical 25]

[0071]

[Chemical formula 26]

[0072]

[Chemical 27]

[0073]

[Chemical 28]

[0074]

[Chemical 29]

[0075]

[Chemical 30]

The yellow coupler represented by the above formula (Y) may be used alone or in combination of two or more kinds. Further, these may be used as a mixture with other known yellow couplers.

The synthesis examples of the yellow coupler represented by the above formula (Y) are shown below. Synthesis Example 1 (Synthesis of Compound Y-1) Compound Y-1 can be synthesized by the following synthetic route.

[0078]

[Chemical 31]

Gotkis, D. et al, J. Am. Chem. Soc., 1
934, 56 2710, 25 g of 1-methylcyclopropanecarboxylic acid, 100 methylene chloride
ml, and N, N-dimethylformamide (1 ml) in a mixture of 38.1 g of oxalyl chloride at room temperature.
It dripped over minutes. After the dropwise addition, the mixture was reacted at room temperature for 2 hours, and methylene chloride and excess oxalyl chloride were removed under reduced pressure with an alpyrator to obtain an oily substance of 1-methylcyclopropanecarbonyl chloride. 1 g of methanol in a mixture of 6.0 g of magnesium and 2 ml of carbon tetrachloride.
00 ml was added dropwise at room temperature over 30 minutes, and the mixture was refluxed over time and then ethyl 3-oxobutanoate 32.6.
g is added dropwise with heating under reflux over 30 minutes. 2 more after dropping
The mixture is heated under reflux for a period of time, and methanol is completely distilled off under reduced pressure of an aspirator. Tetrahydrofuran 100 ml is added to the reaction product to disperse it, and 1-methylcyclopropanecarbonyl chloride obtained above is added dropwise at room temperature. After reacting for 30 minutes, the reaction solution was extracted with 300 ml of ethyl acetate and diluted sulfuric acid water, washed with water, the organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off to give ethyl 2- (1-methylcyclopropanecarbonyl) acetate. 55.3 g of oil (a) was obtained.

202 g of 2,4-dichlorobenzoic acid under cold water
Is dissolved in 500 ml of sulfuric acid, and 6 g of fuming nitric acid 70 g is added under water cooling.
It was dripped in 0 minutes. After stirring for another 30 minutes, the reaction solution was added to 2
The mixture was added to kg of ice and stirred. The precipitated crystals were filtered, washed with water and dried to obtain 242 g of 2,4-dichloro-5-nitrobenzoic acid. 242 g of 2,4-dichloro-5-nitrobenzoic acid, 220 g of tetradecanol,
5 g of p-toluenesulfonic acid and 500 ml of toluene
The mixture was heated and refluxed for 8 hours while distilling off water with a water separator. After toluene was distilled off with an evaporator, 1 liter of methanol was added for crystallization. The precipitated crystals were filtered, washed with methanol and dried to obtain 410 g of tetradecyl 2,4-dichloro-5-nitrobenzoate tetradecyl.

A mixture of 10 g of ammonium chloride, 240 ml of water and 2.4 liter of isopropanol was added with 390 g of iron powder under stirring with heating, and the mixture was further heated under reflux for 30 minutes.
Tetradecyl 4,2,4-dichloro-5-nitrobenzoate
10 g was added over 30 minutes, and the mixture was heated under reflux for 1.5 hours. After filtering the reaction solution, the filtrate was concentrated under reduced pressure, and 1.5 liter of methanol was added for crystallization. The deposited crystals were filtered and dried to obtain 296 g of crystals of tetradecyl 5-amino-2,4-dichlorobenzoate (b).

40.3 g of compound (a) and 5 (b)
1.3 g of the mixture was stirred under reduced pressure with an aspirator at 140 ° C. for 2 hours. Excess compound (a) was distilled off under reduced pressure with a vacuum pump, cooled to 80 ° C., and 1.5 liter of methanol was added for crystallization. The precipitated crystals were filtered and dried to obtain 55 g of compound (c) crystals. 49.9 g of compound (c) was dissolved in 200 ml of methylene chloride,
Under ice cooling, 13.6 g of sulfuryl chloride was added dropwise. After stirring for 30 minutes, the reaction solution was washed with water, separated, calcium chloride was added, and the mixture was dried. The methylene chloride solution was concentrated under reduced pressure and stirred at room temperature. 5-Ethoxy-1-benzylimidazolidine-
59 g of 2,4-dione and 50 ml of N, N-dimethylformamide were added. Triethylamine 35.3g in 1
The mixture was added dropwise over time, and the mixture was further stirred for 5 hours.

300 ml of ethyl acetate was added to the reaction solution, followed by washing with water, washing with a 5% aqueous sodium hydroxide solution and washing with water in that order to separate the layers and to dry them. The ethyl acetate solution was concentrated under reduced pressure, 600 ml of methanol was added, and crystallization was performed. The precipitated crystal was filtered, washed with methanol, and then dried to obtain 62.2 g of a crystal of Exemplified Compound (Y-1).
The melting point of this compound was 67 to 69 ° C., and the structure was confirmed by elemental analysis, ¹ H NMR spectrum and mass spectrum.

For introducing the yellow coupler represented by the above (Y) into the light-sensitive material, various known dispersion methods can be used. For example, an oil-in-water dispersion method (US Pat. No. 2,322,027) using a high-boiling organic solvent, a latex dispersion method (US Pat. No. 4,199,363, West German Patent (OLS) Nos. 2541274 and 2541230) and an organic solvent-soluble method. Polymer Dispersion Method (PCT Application No. JP87
/ 00492 specification).

Specific examples of the high-boiling organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate,
Decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), phosphoric acid or Esters of phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate,
Tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N- Diethyl dodecane amide, N, N-diethyl lauryl amide, N-tetradecyl pyrrolidone, etc.),
Alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate) , Trioctyl citrate, etc.), aniline derivatives (N, N
-Dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Examples include ethoxyethyl acetate and dimethylformamide.

[0086] Using amount of the light-sensitive material of the yellow coupler represented by the formula (Y), the photosensitive material 1 m ² per
The range of 0.0001 g to 2.0 g is general. However, when the leaving group X ^Y contains a photographically useful group component (for example, a development inhibitor, a development accelerator, a fogging agent, a bleaching accelerator, etc.), the amount used is 0.0005 to 0.5 g / m 2.
² is preferable, and more preferably 0.01 to 0.30 g.
/ M ² and the leaving group X ^Y does not contain the photographically useful group component as described above, the amount used is 0.001 to
1.5 g / m ² is preferable, and 0.01 is more preferable.
Is about 1.0 g / m ² .

The silver halide emulsion used in the color photographic light-sensitive material of the present invention is a so-called surface latent image type emulsion in which a latent image is mainly formed on the surface of silver halide grains, or a latent image is mainly silver halide grains. Any of the so-called internal latent image type emulsions formed inside may be used. However, as described above, a type (a direct positive color photographic light-sensitive material) of a type having an emulsion layer containing an internal latent image type silver halide grain which has not been fogged in advance can be preferably used as the silver halide emulsion layer. The internal latent image type silver halide grains not previously fogged will be described later.

The grains contained in the silver halide emulsion used in the present invention are preferably silver bromide, silver chlorobromide or silver chloride containing substantially no silver iodide. The term "substantially free of silver iodide" as used herein means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. Further, regarding the halogen composition distribution of silver halide grains, a so-called uniform structure grain having the same composition in any portion of the silver halide grain, a core inside the silver halide grain and a shell (shell) surrounding it. ) (A single layer or a plurality of layers) has a so-called laminated structure having a different halogen composition or a structure having a non-layered portion having a different halogen composition inside or on the surface (in the case of being on the surface of the particle, edges, corners of the particle or There are particles having a structure in which parts of different compositions are bonded on the surface), and these can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use either of the latter two rather than the particles having a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the structure as described above, the boundary between different portions in the halogen composition is an unclear boundary because a mixed crystal is formed due to the composition difference even if the boundary is clear. Alternatively, it may be one that positively has a continuous structural change. Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide /
A silver chloride ratio can be used. This ratio is
Wide range depending on the purpose, but the silver chloride ratio is 2%
The above is preferable.

A so-called high silver chloride emulsion having a high silver chloride content is preferably used for a light-sensitive material suitable for rapid processing. The silver chloride content of the high silver chloride emulsion is preferably 90 mol% or more,
95% or more is more preferable. In such a high silver chloride emulsion, a structure having a silver bromide localized layer in the inside and / or the surface of the silver halide grain in the form of layer or non-layer as described above is preferable. The halogen composition of the localized layer preferably has a silver bromide content of at least 10 mol%, more preferably more than 20 mol%, and these localized layers are formed inside the grain, at the edges of the grain surface, at the corners. Or it may be on the surface. As one preferable example, there may be mentioned one epitaxially grown at the corner portion of the grain. It is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the replenishment amount of the developing solution. In such a case, an almost pure silver chloride emulsion having a silver chloride content of 98 mol% to 100 mol% can also be preferably used.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of the circle equivalent to the projected area of the grain and the number average thereof is taken) is 0. The thickness is preferably 1 μm to 2 μm (more preferably 0.2 μm to 1.2 μm). Further, the particle size distribution thereof is preferably a so-called monodisperse coefficient of variation of 20% or less (standard deviation of particle size distribution divided by average particle size), preferably 15% or less. In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodispersed silver halide emulsions having different grain sizes or a plurality of emulsions having the same size but different sensitivities are used in the emulsion layers having substantially the same color sensitivity. The particles can be mixed in the same layer or multi-layered in different layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or laminated and used.

The silver halide grains contained in the photographic emulsion have a regular crystal form such as a cube, octahedron, dodecahedron or tetradecahedron, spherical,
It is possible to use a material having an irregular crystal shape such as a plate shape, or a material having a composite shape of these. It may also be a mixture of those having various crystal forms. In the present invention, among these, the particles having the above-mentioned regular crystal form are contained in an amount of 50% or more, preferably 70% or more, more preferably 90% or more. In addition to these, an emulsion in which tabular grains having an average aspect ratio (diameter in terms of circle / thickness) of 5 or more, preferably 8 or more exceeds 50% of the total grain as a projected area can also be preferably used.

The silver chlorobromide emulsion used in the present invention is described in P. Glaf
Chides "Chimie et Photograph-ique" (Paul Mon
tel, 1967), GF Duffin, "(Photog
raph-ic Emulsion Chemistry "(Focal Press, 1
966), V. L. Zelikman et al, "Making a
nd Coating Photographic Emulsion "(Focal Press, Inc., 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used, and as a method of reacting the soluble silver salt and the soluble halogen salt, any method such as a one-sided mixing method, a simultaneous mixing method, and a combination thereof may be used. You may use. It is also possible to use a method of forming particles in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

In the silver halide emulsion used in the present invention, various polyvalent metal ion impurities can be introduced in the process of emulsion grain formation or physical ripening. Examples of compounds used include cadmium, zinc, lead, copper, thallium, salts such as bismuth, or Group VIII elements iron, ruthenium, rhodium, palladium, osmium,
Examples thereof include salts of iridium and platinum, or complex salts. Of these metals, lead, iridium, bismuth and rhodium are preferred. The addition amount of these compounds may vary depending on the purpose, but is 10 ^-9 to 10 ^-2 mol (more preferably 10 ^-7 mol) with respect to the silver halide.
10 to ³ mol) is preferred. For the method of incorporating these metals, see US Pat. Nos. 3,761,276 and 43,954.
No. 78 and JP-A-59-216136.

The silver halide emulsion used in the present invention is
Usually, it is preferable that chemical sensitization and spectral sensitization are performed. Regarding the chemical sensitization method, treatment such as sulfur sensitization typified by unstable sulfur compound addition, noble metal sensitization typified by gold sensitization, reduction sensitization, or selenium sensitization is performed alone or in combination. be able to. As the compound used for the chemical sensitization, those described in JP-A No. 62-215272, page 18, lower right column to page 22, upper right column of the specification are preferably used. In the chemical sensitization treatment, as described in JP-A-1-197742, in the presence of a mercapto compound, JP-A-1-254946, JP-A-2-69738, and JP-A-2-273735.
Thiosulfinic acid, sulfinic acid, and sulfite may be added as described in the publication. The chemical sensitization method for core particles is described in JP-A-2-199450 and 2-19.
The method described in Japanese Patent No. 9449 can be used. A detailed specific example is given in Research Disclosure No. 17643-III (issued in December 1978)
There is also a patent described on page 23. Spectral sensitization is performed for the purpose of imparting spectral sensitivity in a desired light wavelength region to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye that absorbs light in a wavelength range corresponding to the desired spectral sensitivity, that is, a so-called spectral sensitizing dye. Examples of the spectral sensitizing dye include FM Harm
er `` Heterocyclic compounds-Cyanine dyes and rela
ted compounds "(John Wiley & Sons (NewYork, Londo
n) Published by the company, 1964). Specific examples of the compound and the spectral sensitization method are described in JP-A-62-215272, No. 2
Those described on page 2, upper right column to page 38 are preferably used. A detailed specific example is given in Research Disclosure No. There are also patents described on pages 23 to 24 of 17643-IV (issued in December 1978).

The non-pre-fogged internal latent image type silver halide emulsion preferably used in the present invention will be described. An internal latent image type silver halide emulsion which has not been fogged beforehand is an emulsion in which the surface of silver halide grains is not fogged and which contains a silver halide which mainly forms a latent image inside the grain. Specifically, the silver halide emulsion is fixed on the transparent support in a fixed amount (0.5 to 3 g / m 2).
² ) Apply and expose to light for a fixed time of 0.01 to 10 seconds, and in the following developer (internal type developer),
When developed at 0 ° C. for 5 minutes, the maximum density measured by a usual photographic density measuring method was the same as the above coating, and the silver halide emulsion exposed in the same manner was developed in the following developing solution (surface type developing solution). Those having a density at least 5 times higher than the maximum density obtained when developed at 18 ° C. for 6 minutes are preferable, and those having a density at least 10 times higher are more preferable. (Internal type developer) Metol 2.0 g Sodium sulfite (anhydrous) 90.0 g Hydroquinone 8.0 g Sodium carbonate (monohydrate) 52.8 g KBr 5.0 g KI 0.5 g Water was added to 1000 ml (Surface type development) liquid) metol 2.5 g L-ascorbic acid _{10.0g NaBO 2 · 4H 2 O 35.0g} KBr 1.0g water to make 1000ml

Specific examples of the internal latent image type silver halide emulsion include, for example, conversion type silver halide emulsions described in US Pat. No. 2,592,250; or US Pat. Nos. 3,761,276, 3,850,637 and 3,923,513. , 4035185 and 43954.
78, 4504570, JP-A-52-
No. 156614, No. 55-127549, No. 53-6
0222, 59-208540, 60-107.
641, 61-3137, and 62-215.
No. 272, German Patent No. 2332802c2, Research Disclosure No. 235
10 (issued November 1983), page 236; U.S. Pat.
No. 27; JP-A Nos. 63-10160 and 63-47766, and Japanese Patent Application No. 1-2467, which relate to silver chlorobromide core-shell emulsions; Sho 63-191145,
And cores described in JP-A-1-52146 /
Shell type silver halide emulsions can be mentioned. The internal latent image type silver halide grains which have not been fogged in the present invention are preferably core / shell type. The molar ratio of the internal latent image type core / shell silver halide emulsion is 20 /.
It is particularly preferably 1 or less and 1/100 or more.

The photographic emulsion used in the present invention contains an antifoggant or stabilizer for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. You can For specific examples, see Research Disclosure No.
17643-VI (issued in December 1978) and E.I.
J. Birr, "Stabilization of Photographic Silv
er Halide Emulsion "(Focal Press), 1974.

In the present invention, various color couplers can be used in addition to the above-mentioned yellow coupler. Typical examples of useful color couplers include pyrazolone or pyrazoloazole compounds and open-chain or heterocyclic ketomethylene compounds. Specific examples of these magenta and cyan couplers that can be used in the present invention are described in "Research Disclosure" No. 17643 (1
Issued December 1978) Page 25, Item VII-D, ibid. 1
8717 (issued in November 1979) and Japanese Patent Laid-Open No. 62-
It is described in the compounds described in JP-A-215272 and the patents cited therein. The 5-pyrazolone-based magenta coupler which can be preferably used in the present invention is a 5-pyrazolone-based coupler in which the 3-position is substituted with an arylamino group or an acylamino group (among others, a sulfur atom-eliminating type two-equivalent coupler). More preferred are pyrazoloazole-based couplers, of which US Pat. No. 372 is particularly preferred.
Pyrazolo [5,1-c] described in 5067
[1,2,4] triazoles and the like are preferable, but the imidazo [1,3] described in U.S. Pat. No. 4,500,630 is preferred in view of low yellow sub-absorption of a coloring dye and light fastness.
2-b] pyrazoles are more preferred and are described in US Pat.
40654, pyrazolo [1,5-b] [1,
2,4] triazole is particularly preferred. Examples of cyan couplers that can be preferably used in the present invention include naphthol-based and phenol-based couplers described in US Pat. Nos. 2,474,293 and 4,052,212
It is a phenolic cyan coupler having an alkyl group of ethyl group or more at the meta position of the phenol nucleus described in U.S. Pat. No. 3,772,002, and other 2,5-diacylamino-substituted phenolic couplers have the color image fastness. Is preferred.

Colored couplers for correcting unnecessary absorption in the short wavelength region of the dyes formed, couplers in which the coloring dyes have an appropriate diffusivity, non-color couplers, and development inhibitors released in association with the coupling reaction. DIR couplers and polymerized couplers can also be used. Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are Research Disclosure N
o. 17643, Patents described in VII to F, JP-A-57-151944, 57-154234, and 60.
-184248, those described in U.S. Pat. No. 4,248,962 and JP-A-63-146035.
Those described in the publication are preferred. Examples of couplers that release a nucleating agent or a development accelerator in an image during development include British Patent Nos. 2097140 and 2131188.
Each specification, JP-A-59-157638 and JP-A-59-1
No. 70840, International Application Publication (WO) 88/01
The one described in Japanese Patent No. 402 is preferable. The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the photosensitive silver halide, preferably 0.01 to 0.5 mol for the yellow coupler and 0.03 for the magenta coupler. Mole to 0.5 mole,
For cyan couplers, it is 0.02-1.0 mol.

As the binder or protective colloid that can be used in the emulsion layer and the non-photosensitive layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. . In the light-sensitive material of the present invention, an antifoggant or a color mixing inhibitor can also be used. Typical examples thereof include the compounds described in JP-A No. 62-215272, pages 185 to 193. Examples of the compound releasing a photographically useful group include JP-A-63-153540 and 63-25955.
No. 5, JP-A-2-61636, and JP-A-2-2440.
41, the compound of each statement of 2-308240 are mentioned. In the present invention, a color forming enhancer can be used for the purpose of improving the color forming property of the coupler. Typical examples of the compounds are JP-A-62-215272, 121 to 12.
Those described on page 5 can be mentioned. To the light-sensitive material of the present invention, an ultraviolet absorber, a plasticizer, a fluorescent brightening agent, a matting agent, an air antifoggant, a coating aid, a film hardener, an antistatic agent, a slipperiness improving agent, etc. may be added. it can. Typical examples of these additives are listed in Research Disclosure No. 17
643VII-XIII (issued December 1978) 2
5 to 27, and 18716 (issued in November 1979), pages 647 to 651.

The color photographic light-sensitive material of the present invention preferably has at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on the support. And it is preferable that the non-photosensitive layer is provided adjacent to these layers. The order of each layer of the red-sensitive emulsion layer, the green-sensitive emulsion layer and the blue-sensitive emulsion layer can be arbitrarily selected as required. The preferred order of layer arrangement is red-sensitive, green-sensitive, blue-sensitive from the support side or green-sensitive, red-sensitive and blue-sensitive from the support side. Further, each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. . It is usual that the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler. It is also possible to use different combinations such as mixed use.
As described above, the light-sensitive material of the present invention is provided with a non-light-sensitive layer in addition to the silver halide emulsion layer. Examples of such layers include a protective layer, an intermediate layer, a filter layer, an antihalation layer, There are auxiliary layers such as a back layer and a white reflective layer.

The color photographic light-sensitive material of the present invention preferably contains a nucleating agent. The nucleating agent functions as a development accelerator when the color photographic light-sensitive material is a normal color photographic light-sensitive material (for example, a color negative film). Further, in the direct positive color photographic light-sensitive material which is a preferred embodiment of the present invention, the nucleating agent acts during surface development processing of an internal latent image type silver halide emulsion which has not been fogged in advance to form a direct positive image. Work. It is a substance used when carrying out the so-called "chemical fog method". The nucleating agent is a silver halide emulsion layer,
Alternatively, it is contained in at least one of adjacent non-photosensitive layers (for example, an intermediate layer, an undercoat layer or a back layer),
It is preferably contained in the silver halide emulsion layer together with the yellow coupler represented by the above formula (Y) according to the present invention. Examples of the nucleating agent that can be used in the present invention include those described in Research Disclosure, No.
22534 (January 1983), pp. 50-54, same magazine, N
o. 15162 (November 1976) pp. 76-77, No. 23510 (November 1983) 346-35
Examples thereof include quaternary heterocyclic compounds described on page 2, hydrazine compounds, and the like. Two or more kinds of these nucleating agents may be used in combination. The nucleating agent used in the present invention is
A quaternary heterocyclic compound represented by the following formula (N-I) or a hydrazine compound represented by (N-II) is preferable.

[0103]

[Chemical 32]

In the above formula (N-I), Z ³¹ represents a non-metal atom group necessary for forming a 5- to 6-membered heterocyclic group. R ³¹ represents an aliphatic group. R ³² represents a hydrogen atom, an aliphatic group or an aromatic group. However, the Z ^31, R ³¹ and R ³² are substituted heather and R ³² may form a ring with the heterocyclic ring completed by Z ^31, further R ³¹ and R ^32, At least one of the groups represented by Z ³¹ contains an alkynyl group, an acyl group, a hydrazine group or a hydrazone group, or R ³¹ and R ³² form a 6-membered ring to form a dihydropyridinium skeleton. May be. Y represents a counter ion for charge balance, and n is 0
Or represents 1.

[0105]

[Chemical 33]

In the above formula (N-II), R ⁴¹ represents an aliphatic group, an aromatic group or a heterocyclic group. R ⁴² is a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group,
It represents an aryloxy group or an amino group. G represents a carbonyl group, a sulfonyl group, a sulfinyl group, a phosphoryl group or an iminomethylene group (HN = C =). R ⁴³ and R ⁴⁴ are both hydrogen atoms, or one is a hydrogen atom and the other is one of an alkylsulfonyl group, an arylsulfonyl group or an acyl group (provided that G, R ⁴² and R ⁴⁴ are G, A hydrazone structure (= N-N = C =) may be formed in a form including R ⁴² , R ⁴⁴ and hydrazine nitrogen Note that the quaternary heterocyclic compound represented by the formula (N-I) is not particularly limited. Japanese Patent Laid-Open No. 2-90154 or Japanese Patent Laid-Open No. 3-90154
It is described in Japanese Patent No. 155543. In addition, the formula (N−I
The hydrazine compound represented by I) is disclosed in JP-A-2-90.
No. 154 or JP-A-3-95546.

Typical nucleating agents represented by the above formulas (NI) and (N-II) are as follows. (N-I-1) 7- (3-Cyclohexylmethoxythiocarbonylaminobenzamide) -10-propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate (N-I-2) 6- ( 3-Ethoxythiocarbonylaminobenzamido) -1-propargyl-2,3-trimethylenequinolinium trifluoromethanesulfonate (N-I-3) 6-ethoxythiocarbonylamino-2
-Methyl-1-propargylquinolinium trifluoromethanesulfonate (N-I-4) 7- [3- (5-mercaptotetrazol-1-yl) benzamide] -10-propargyl-
1,2,3,4-Tetrahydroacridinium perchlorate (N-II-1) 1-formyl-2- {4- [3- {3-
[3- (5-Mercaptotetrazol-1-yl) phenyl] ureido} benzsulfonamide] phenyl} hydrazine (N-II-2) 1-formyl-2- {4- [3- (5-
Mercaptotetrazol-1-yl) benzenesulfonamide] phenyl} hydrazine

In the present invention, it is preferable to use the quaternary heterocyclic compound and the hydrazine compound in combination. In the present invention, the addition amount of the nucleating agent varies depending on the characteristics of the silver halide emulsion actually used, the chemical structure of the nucleating agent and the developing conditions, and therefore can be varied over a wide range. About 1 x 1 per mole of silver
A range of 0 ^-8 moles to about 1 x 10 ^-2 moles is practically useful, with about 1 x 10 ^-5 moles to about 1 x 10 moles per silver mole being preferred.
^-3 mol range.

In the present invention, the "optical fog method" may be carried out separately from the "chemical fog method". The entire exposure in the "light fog method", that is, the fog exposure is performed after imagewise exposure, before color development processing or during color development processing. That is, the imagewise exposed light-sensitive material is exposed in a color developing solution or in a pre-bath of the color developing solution, or is taken out from these solutions and dried before being exposed. Is most preferred.
As a light source for fogging exposure, for example, Japanese Patent Laid-Open No. 56-1
A light source having a high color rendering property (as close as possible to white) as described in JP-A-37350 and JP-A-58-70223 is preferable. The illuminance of light is 0.01 to 2000 lux, preferably 0.05 to 30 lux, more preferably 0.0.
5-5 looks is suitable. The light-sensitive material using a higher-sensitivity emulsion is preferred to have low illuminance.
The illuminance may be adjusted by changing the luminous intensity of the light source, or by changing the light exposure by various filters, the distance between the light-sensitive material and the light source, or the angle between the light-sensitive material and the light source. Further, the illuminance of the above-mentioned fogging light can be continuously or stepwise increased from a low illuminance to a high illuminance. It is preferable to immerse the light-sensitive material in a color developing solution or a solution of its pre-bath so that the solution sufficiently penetrates into the emulsion layer of the light-sensitive material before irradiation with light. The time from the penetration of the liquid to the light fog exposure is generally 2 seconds to 2
Minutes, preferably 5 seconds to 1 minute, more preferably 10 seconds to 3
0 seconds. The exposure time for fogging is generally 0.01 second to 2 minutes, preferably 0.1 second to 1 minute, more preferably 1 second to 40 seconds.

In the direct positive color photographic light-sensitive material which is a preferred embodiment of the present invention, when the above nucleating agent is used, it is preferable to use a nucleating accelerator for promoting the action of the nucleating agent. A nucleation accelerator does not substantially function as a nucleating agent, but accelerates the action of the nucleating agent to increase the maximum density of the direct positive image and / or obtain a certain maximum density of the direct positive image. Means a substance that has the function of accelerating the development time required. In the present invention, JP-A-2-890
The nucleation accelerator described in JP 48 can be preferably used. The nucleation accelerator may be contained in at least one of the internal latent image type silver halide emulsion layer which is not fogged in advance or the adjacent non-photosensitive layer (intermediate layer or protective layer). The nucleation accelerator is preferably contained in the silver halide emulsion together with the yellow coupler represented by the formula (Y) and the nucleating agent. The addition amount of the nucleation accelerator is preferably 10 ⁻⁶ to 10 ⁻² mol, and more preferably 10 ⁻⁵ to 10 ⁻² mol, per mol of silver halide.
The nucleation accelerator may be contained in the processing solution (that is, the developing solution or its pre-bath), in which case it is preferably 10 ^-8 to 10 ^-3 mol, and more preferably 1 liter of the processing solution. It is 10 ⁻⁷ to 10 ⁻⁴ mol.

Known photographic additives that can be used in the present invention are described in Research Disclosure No. 1764
3 (Dec. 1978) and No. 3 of the same. 18716 (1
(November 979), and the relevant parts are summarized in the table below. Additive type RD17643 RD18716 ───────────────────────────── 1 Chemical sensitizer, page 23, page 648, right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, pages 23 to 24, page 648, right column ~ Supersensitizer, page 649, right column 4 Whitening agent, page 24 5 Fog inhibitor, pages 24 to 25, page 649, right column ~ Stabilizer, page 650, right column 6 light absorber, page 25 right column, page 649 right column ~ filter dye, page 650 left column, ultraviolet absorber 7 stain inhibitor page 25 right column 8 dye image stabilizer 25 page 9 hardening agent 26 page 651 left column 10 Binder page 26 Same as above ─────────────────────────────

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are made of a flexible support usually used for photographic light-sensitive materials, such as a flexible support such as plastic film, paper and cloth, or a rigid material such as glass, pottery and metal. It is coated on a support.
What is useful as the flexible support is a film made of a semi-synthetic or synthetic polymer such as cellulose nitrate, cellulose acetate, cellulose acetate acetate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, a baryter layer or an α-olefin polymer. Examples include paper coated or laminated with (eg, polyethylene, polypropylene, ethylene / butene copolymer). The support may be colored with a dye or pigment. For coating silver halide photographic emulsion layers and other hydrophilic colloid layers,
For example, various known methods such as a dip coating method, a roller coating method, a curtain coating method and an extrusion coating method can be used. Also, if necessary, US Pat.
No. 1294, No. 2761791, No. 352652
Multiple layers may be simultaneously coated by the method described in each specification such as No. 8 and No. 3508947.

Next, a color image forming method using the color photographic light-sensitive material of the present invention will be described. The color image forming method of the present invention forms a color image by subjecting the above color photographic light-sensitive material to image exposure, and then performing development processing with a developer containing a specific color developing agent represented by the formula (D). It is characterized by The development processing method may be a conventionally known method. Various exposure means can be used for exposing the light-sensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination light source or the writing light source.
Natural light (sunlight), incandescent lamp, halogen atom sealed lamp, mercury lamp, fluorescent lamp and flash light source such as strobe or metal burning flash bulb or semiconductor laser,
Light emitting diodes and plasma light sources can also be used as recording light sources. In addition, a phosphor screen (CRT or the like) emitted from a phosphor excited by an electron beam or the like, a liquid crystal (LC
D) or lanthanum-doped lead titan zirconate (PLZT) or the like may be used as an exposure means in which a linear or planar light source is combined with a microshutter array. The spectral distribution used for exposure can be adjusted with a color filter as needed. In particular, use high-density beam light as a light source such as various lasers such as gas lasers (He-Ne laser, Ar laser, He-Cd laser) and semiconductor lasers, and move it relative to the photosensitive material. An exposing means of a so-called scanning exposure method (scanner method) for exposing an image by means of is preferable for exposing the light-sensitive material of the present invention. As a scanning exposure apparatus, for example, a color copying machine AP-5 manufactured by Fuji Photo Film Co., Ltd.
000 can be used.

In the case of exposure by the scanning exposure system, the time for exposing silver halide is the time required for exposing a certain minute area. As this minute area, the minimum unit for controlling the light quantity from digital data is generally used, and is called a pixel. Therefore, the exposure time per pixel varies depending on the size of the pixel. The size of this pixel depends on the pixel density.
It is 2000 dpi. In the direct positive color photographic light-sensitive material of the present invention, the pixel size is set to 1 pixel when the pixel density is 400 dpi, and the exposure time per pixel is 10 ^-3 seconds or less (preferably 10 ^-6 to 10 ^-4). Scanning exposure under the condition of (seconds).

The color developing agent used in the color image forming method of the present invention is represented by the following formula (D).

[0116]

[Chemical 34]

Examples of the alkyl group represented by R ^D1 include an alkyl group having 1 to 8 carbon atoms.
As such examples, methyl, ethyl, butyl or methoxyethyl are preferred. Examples of the alkylene group represented by R ^D2 include an alkylene group having 2 to 6 carbon atoms. As such an example, ethylene or trimethylene is preferable. Specific examples of the developing agent represented by formula (D) are shown below.

[0118]

[Chemical 35]

[0119]

[Chemical 36]

In the present invention, the compound represented by the above (D-2) or (D-3) is preferable. The above formula (D)
The amount of the color developing agent represented by is preferably about 0.1 g to about 20 g, and more preferably about 0.5 to about 10 g per liter of the developing solution. An aromatic primary amine type color developing agent other than the above may be used in combination, but if the developing agent represented by the formula (D) is 50
It is preferable that the content is at least mol%. The developing solution used in the color image forming method of the present invention is the same as the conventional color developing solution except that the developing agent is the above specific compound. The development processing method is also the same as the development processing method known per se, except that the above-described developing solution is used. The photographic light-sensitive material after the above color development processing is usually bleached,
A desilvering process consisting of a fixing process is performed, and after desilvering process,
Generally, washing and / or stabilization treatment is performed. Regarding the above-mentioned series of processing steps, JP-A-3-12
The method described on pages 380 to 381 of Japanese Patent No. 0537 can be preferably used.

The color photographic light-sensitive material of the present invention has various uses, but is suitable for making color prints, color copies and color proofs. The color proof making method of the present invention can use a conventional color proof making method other than using the color photographic light-sensitive material of the present invention as described above. That is, the color proof making method of the present invention is
The color photographic light-sensitive material of the present invention is subjected to color separation and halftone image conversion, using a cyan plate halftone dot image film, an magenta halftone dot image film, a yellow plate halftone dot image film and a black halftone dot image film, This is a method of forming a color image by sequentially exposing with red light, green light and blue light and then performing color development processing as described above. As an apparatus for carrying out such a method, there is, for example, a Fine Checker 850H (exposure time: about 0.02 to 0.3 seconds) manufactured by Fuji Photo Film Co., Ltd.

[0122]

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

[Example 1] (Preparation of solid dispersion S-1 of fine powder dye) Water 21.7 m
1, 3% of a 5% aqueous solution of p-octylphenoxyethanesulfonate sodium and 5% aqueous solution of p-octylphenoxypoly (polymerization degree 10) oxyethylene ether 0.5
700g capacity pot mill (vibrating ball mill)
(OB type, manufactured by Chuo Kakoki Co., Ltd.). 1.0 g of the dye (III-3) shown below and 50 ml of zirconium oxide beads (diameter 1 mm) were further added to this, and dispersed for 2 hours. The average particle size of the fine powder of the obtained dye is 0.
It was 2 μm. 12.5 of the dispersion thus obtained
% Gelatin aqueous solution, and the beads were filtered to prepare a solid dispersion S-1 of fine powder dye.

(Preparation of Solid Dispersion S-2 to 16 of Fine Powder Dye) The same as in the preparation of the solid dispersion S-1 of fine powder dye, except that the dye was changed as shown in Table 1 below. And solid dispersion S-2 of fine powder dyes corresponding to
~ 16 were prepared. The average particle size of the fine powders of the respective dyes obtained was all 0.2 μm.

[0125]

[Table 1] Table 1 ──────────────────────────────────── Dispersion Dye Dispersion Dye Mix Weight Ratio ──────────────────────────────────── S-1 III-3 S-11 III-12 S -2 I-4 S-12 III-13 S-3 II-7 S-13 II-23 / III-3 / II-2 (1: 1: 1) S-4 II-8 S-14 II-24 / III-8 / II-15 (1: 1: 1) S-5 II-15 S-15 III-12 / III-10 (1: 1) S-6 II-21 S-16 III-13 / I -4 / IV-7 (1: 1: 1) S-7 IV-2 S-8 IV-6 S-9 II-23 S-10 II-24 ────────────── ───────────────────────

[0126]

[Chemical 37]

[0127]

[Chemical 38]

[0128]

[Chemical Formula 39]

[0129]

[Chemical 40]

[0130]

[Chemical 41]

(Preparation of Sample 101) On the front side of a paper support (thickness 100 μm) laminated on both sides with polyethylene,
The following 1st to 11th layers and the 12th to 1st layers on the back side
A color photographic light-sensitive material having three layers coated was prepared (comparative sample). For the polyethylene coated on the first layer, titanium oxide (4 g / m ² ) was used as a white pigment, and a slight amount (0.0
03 g / m ² ) of ultramarine blue as a bluing dye (the surface chromaticity of the support is L *, a *, b *, 88.0, −
0.20, -0.75).

(Photosensitive layer composition) The components and coating amount (g /
m ² ) is shown. However, the addition amount of the sensitizing dye is shown by mol per mol of silver. For silver halide, the coating amount in terms of silver is shown. The emulsion used for each layer was prepared according to the production method of the emulsion EM-1 described later by changing the grain forming temperature to change the grain size. However, as the emulsion for the 11th layer, a Lippmann emulsion not surface-sensitized was used. First layer (anti-halation layer) Black colloidal silver 0.10 Gelatin 0.40 Color mixing inhibitor (Cpd-7) 0.05 Color mixing inhibitor solvent (Solv-4, 5 equivalents) 0.12 Second layer ( Intermediate layer) Gelatin 0.40 Dye (Cpd-32) 0.005 Third layer (red sensitive layer) Red sensitizing dye (ExS-1, 2, 3, each equivalent amount, 5.4 × 10 ^-4 in total) Bromide spectrally sensitized by (average grain size: 0.41 μm, grain size distribution: 10%, octahedron) 0.25 gelatin 0.40 cyan coupler (ExC-1, 2, 3 1: 1: 0.2) 0.30 Anti-fading agent (Equivalent amounts of Cpd-1, 2, 3, 4, 30) 0.18 Anti-staining agent (Cpd-5, 15) 0.003 Coupler dispersion medium (Cpd-6) ) 0.30 Coupler solvent (Equivalent amounts of Solv-1, 3, 5) 0.12

Fourth Layer (Intermediate Layer) Gelatin 0.70 Color Mixing Inhibitor (Cpd-7) 0.08 Color Mixing Inhibitor Solvent (Solv-4, 5 Equivalent Amount) 0.16 Polymer Latex (Cpd-8) 0 .10 Fifth Layer (Green Sensitive Layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS- ^4, 2.6 × 10 ⁻⁴ ) (average particle size: 0.40 μm, particle size distribution 10%) , Octahedron) 0.20 gelatin 0.70 magenta coupler (ExM-1, 2, 3 each equivalent) 0.11 yellow coupler (ExY-1) 0.03 anti-fading agent (Cpd-9, 26, 30, 31 is each equal amount) 0.15 Anti-staining agent (Cpd-10, 11, 12, 13 in the ratio of 10: 7: 7: 1) 0.025 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Equivalent amounts of Solv-4 and 6) 0.15 Sixth layer Intermediate layer) The same as the fourth layer

Seventh Layer (Yellow Filter Layer) Yellow colloidal silver (particle size: 100A) 0.12 Gelatin 0.70 Color mixing inhibitor (Cpd-7) 0.03 Color mixing inhibitor solvent (Solv-4, 5 etc.) Amount) 0.10 Polymer latex (Cpd-8) 0.07 8th layer (intermediate layer) Same as 4th layer 9th layer (blue sensitive layer) Blue sensitizing dye (ExS-5, 6 each equivalent amount, total) Silver bromide (average grain size: 0.70 μm, grain size distribution 11%, octahedron) 0.40 gelatin 0.80 yellow coupler (ExY-1, 2) spectrally sensitized with 3.5 × 10 ⁻⁴ ). 3 is an equal amount) 0.35 Anti-fading agent (Cpd-14) 0.10 Anti-fading agent (Cpd-30) 0.05 Anti-staining agent (Cpd-5, 15 in a ratio of 1: 5) 0 0.007 Coupler dispersion medium (Cpd-6) 0.0 Coupler solvent (Solv-2) 0.10 10th layer (ultraviolet absorbing layer) Gelatin 1.00 Ultraviolet absorber (Equivalent amounts of Cpd-2, 4, 16) 0.50 Color-mixing inhibitor (Cpd-7, 17) 0.03 Dispersion medium (Cpd-6) 0.02 UV absorber solvent (Equivalent amounts of Solv-2 and 7) 0.08 Anti-irradiation dye (Cpd-18, 19, 20, 21) , 27 in the ratio of 10: 10: 13: 15: 20) 0.05 11th layer (protective layer) Fine grain silver iodobromide (99 mol% silver bromide, average size 0.05 μm) 0.03 Polyvinyl alcohol Acrylic modified copolymer of 0.01 (molecular weight: 50,000) Equal amounts of polymethylmethacrylate particles (average particle size: 2.4 μm) and silicon oxide (average particle size: 5 μm) 0.05 Gelatin 0.05 Chin hardener (H-1, the H-2 each eq) 0.18

Twelfth Layer (Back Layer) Gelatin 2.50 Ultraviolet Absorber (Equivalent Cpd-2, 4, 16) 0.50 Dye (Equivalent Equivalent of Cpd-18, 19, 20, 21, 27) ) 0.06 13th layer (back layer protective layer) Polymethylmethacrylate particles (average particle size 2.4 μm) and silicon oxide (average particle size 5 μm) in equal amounts 0.05 gelatin 2.00 gelatin hardening agent ( H-1 and H-2 are equal amounts) 0.14

(Preparation of Emulsion EM-1) An aqueous solution of potassium bromide and an aqueous solution of silver nitrate containing 3 × 10 ⁻⁸ mol of rhodium bromide and 3 × 10 ⁻⁶ mol of iridium chloride ammonium salt per 1 mol of silver were mixed with 1 mol of silver. It was added simultaneously to the gelatin aqueous solution to which 0.3 g of 3,4-dimethyl-1,3-thiazoline-2-thione was added per mole at 65 ° C. for 15 minutes with vigorous stirring, and the average particle size was 0. 23 μm octahedral silver bromide grains were obtained. 6m per mole of silver in this emulsion
g sodium thiosulfate and 7 mg chloroauric acid (tetrahydrate)
Were sequentially added, and chemical sensitization was performed by heating at 75 ° C. for 80 minutes. The grains thus obtained were used as cores for further growth in the same precipitation environment as in the first time, and finally an octahedral monodisperse core / shell silver bromide emulsion having an average grain size of 0.4 μm was obtained. To this emulsion, 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) were added per mol of silver, and the mixture was heated at 60 ° C. for 60 minutes for chemical sensitization.
An internal latent image type silver halide emulsion was obtained.

Each photosensitive layer contains (ExZK-
1) and (ExZK-2) are 10 ^-3 % by weight and 10 ^-2 % by weight, respectively, with respect to silver halide, and Cpd is used as a nucleation accelerator.
Each of -22, 28 and 29 was used at 10 ^-2 % by weight. Furthermore, in each layer, an alkanol XC (Du
Pont) and sodium alkylbenzene sulfonate as coating aids and succinate and Magef.
ac F-120 (manufactured by Dainippon Ink and Chemicals, Inc.) was used. In the layers containing silver halide and colloidal silver, Cpd-23, 24, and 25 were used as stabilizers in equal amounts. The compounds used in the above sample preparation are shown below. In addition,
The film thickness of the sample 101 on the photosensitive layer side (the thickness of the laminate on the support) was 9.5 μm.

[0138]

[Chemical 42]

[0139]

[Chemical 43]

[0140]

[Chemical 44]

[0141]

[Chemical formula 45]

[0142]

[Chemical formula 46]

[0143]

[Chemical 47]

[0144]

[Chemical 48]

[0145]

[Chemical 49]

[0146]

[Chemical 50]

[0147]

[Chemical 51]

[0148]

[Chemical 52]

[0149]

[Chemical 53]

Solv-1 di (2-ethylhexyl)
Sebacate Solv-2 Trinonyl Phosphate Solv-3 Di (3-methylhexyl) Phthalate Solv-4 Tricresyl Phosphate Solv-5 Dibutyl Phthalate Solv-6 Trioctyl Phosphate Solv-7 Di (2-ethylhexyl) Phthalate H-11 , 2-Bis (vinylsulfonylacetamide) ethane H-2 4,6-dichloro-2-hydroxy-
1,3,5-Triazine / Na salt ExZK-17- (3-ethoxythiocarbonylaminobenzamide) -9-methyl-10 propargyl-
1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate ExZK-2 2- [4- {3- [3- {3- [5-
{3- [2-chloro-5- (1-dodecyloxycarbonylethoxycarbonyl) phenylcarbamoyl] -4
-Hydroxy-1-naphthylthio} tetrazole-1-
Ill] phenyl} ureido] benzenesulfonamide}
Phenyl] -1-formylhydrazine

(Preparation of Sample 102) In the preparation of Sample 101, the yellow couplers (ExY-2, 3) contained in the ninth layer (blue-sensitive layer) were replaced with the following yellow couplers (Y-4) according to the present invention. ) (Replaced with equimolar)
Sample 102 is the same as Sample 101 except for the above.
(Comparative sample) was prepared. (Preparation of Samples 103 and 104) In the preparation of Sample 102, instead of the yellow coupler (Y-4) of the present invention, the following yellow coupler (Y) of the present invention was used.
Samples 103 and 104 (comparative samples) corresponding to each sample were prepared in the same manner as the sample 102, except that each of the compounds was changed to (-11) or (Y-15) (replaced by equimolar amount).

[0152]

[Chemical 54]

[0153]

[Chemical 55]

(Preparation of Sample 105) In the preparation of Sample 104, instead of the yellow colloidal silver contained in the seventh layer (yellow filter layer), the fine powder dye solid dispersion (S-9 prepared above) was prepared. ) (Yellow dye: II-2
A sample 105 (sample of the present invention) was prepared in the same manner as the sample 104 except that 3) was added so that the content was 0.4 g / m ² . (Preparation of Samples 106 and 107) In the preparation of Sample 105, the fine powder dye solid dispersion (S-9) (yellow dye) contained in the seventh layer (yellow filter layer) was prepared in place of the above. Fine powder dye solid dispersion (S-1
0) or (S-11), except for the above sample 1
Samples 106 and 107 (samples of the present invention) corresponding to each sample were prepared in the same manner as in 05. (Preparation of Sample 108) In preparation of the sample 105,
Instead of the black colloidal silver contained in the first layer (antihalation layer), the fine powder dye solid dispersion (S-13) (II-23 / III-3 / II-2 = 1: 1 prepared above is prepared.
1: 1) so that the compound content is 0.2 g / m ² and in the fourth layer (intermediate layer) a fine powder dye solid dispersion (S
-1) (III-3) whose compound content is 0.03 g /
A sample 108 (sample of the present invention) was prepared in the same manner as the sample 105 except that it was added so as to have m ² . (Preparation of Samples 109 and 110) In the preparation of Sample 108, the fine powder dye solid dispersion (S-13) (II-23 / II) contained in the first layer (antihalation layer).
Fine powder dye solid dispersion (S-15 or S-16) (I-3 / II-2 = 1: 1: 1) prepared above (black dye)
Samples 109 and 110 (samples of the present invention) corresponding to each sample were prepared in the same manner as the sample 108 except that the above was changed. (Preparation of Sample 111) In preparation of the sample 108,
Sample 108 was prepared in the same manner as in Sample 108 except that the yellow coupler (Y-7) shown below was used instead of the yellow coupler contained in the ninth layer (blue-sensitive layer).
Sample 111 (sample of the present invention) was prepared.

[0155]

[Chemical 56]

The characteristics of each sample (silver halide photographic light-sensitive material) prepared above are shown in Table 2 below.

[0157]

[Table 2] Table 2 ──────────────────────────────────── 1st layer 4th layer 7th Layer 9th Layer Anti-Halle Intermediate Layer Yellow Yellow Sample No. Solution Filter Coupler ──────────────────────────────────── 101 (Comparison) Black colloidal silver Yellow colloidal silver ExY -2,3 102 (Comparison) Same as above Y-4 103 (Comparison) Same as above Same as above Y-11 104 (Comparison) Same as above Same as above Y-15 ──────────────────── ───────────────── 105 (present invention) Same as above S-9 Y-15 106 (present invention) Same as above S-10 Same as above 107 (present invention) Same as above S-11 Same as above 108 (Invention) S-13 S-1 S-9 Same as above 109 (Invention) S-15 Same as above Same as above Same as above 110 (Invention) S-16 Same as above Same as above Same as above 111 (Invention) S-13 Same above Same as above Y-7 ─ ────────────────────────────────── ─

[Evaluation as direct positive color photographic light-sensitive material] Each sample prepared as described above was subjected to 2854 ° K.
Light having a color temperature of 600 cms was exposed for 1/10 seconds through a continuous wedge. After exposure, color development processing was performed under the processing conditions shown below.

[Processing conditions] Using an automatic processor, continuous processing was carried out by the method described below until the cumulative replenishment amount of the solution became 3 times the tank capacity.

──────────────────────────────────── Treatment process time Temperature Tank capacity Replenishment amount ─── ───────────────────────────────── color development 135 sec 38 ° C. 28 liters 240 ml / m ² bleach-fixing 40 seconds 35 ℃ 11 liters 320 ml / m ² water washing (1) 40 seconds 35 ℃ 7 liters ----- water washing (2) 40 seconds 35 ℃ 7 liters 320 liters / m ² drying 30 seconds 80 ℃ ──────────── ─────────────────────────

The replenishing system for washing water was a so-called countercurrent replenishing system in which the washing bath (2) was replenished and the overflow solution of the washing bath (2) was introduced into the washing bath (1). At this time, the amount of the bleach-fix solution carried from the bleach-fix by the light-sensitive material to the washing bath (1) was 35 ml / m ² .

The composition of each processing solution was as follows. ──────────────────────────────────── Color developer A Tank liquid Replenisher ─────── ────────────────────────────── D-sorbit 0.15g 0.20g sodium naphthalenesulfonate 0.15g 0.20g Formalin condensate Nitrilotris (methylenephosphonic acid) pentasodium salt 1.8 g 1.8 g Diethylenetriaminepentaacetic acid 0.5 g 0.5 g 1-hydroxyethylidene-0.15 g 0.15 g 1,1-diphosphonic acid diethylene glycol 12.0 ml 16 0.0 ml Benzyl alcohol 14.0 ml 18.5 ml Potassium bromide 0.70 g --- Benzotriazole 0.005 g 0.007 g Sodium sulfite 5.6 g 7.4 g Hydro Sylamine / 1/2 sulfate 4.5 g 6.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 6.0 g 8.0 g Triethanolamine 6.0 g 8.0 g Potassium carbonate 30.0 g 25.0 g Optical brightener (diaminostilbene type) 1.3 g 1.7 g Water was added 1000 ml 1000 ml ───────────── ──────────────────────── pH (25 ℃) 10.25 10.75 (pH adjustment with KOH or sulfuric acid) ─────── ─────────────────────────────

──────────────────────────────────── Bleach-fixing solution Tank solution Replenishing solution ──── ──────────────────────────────── Ethylenediamine 4 Acetic acid ・ 2 sodium ・ dihydrate 4.0g Ethylenediamine 4 in the tank liquid Acetic acid-Fe (III) -55.0 g Same ammonium dihydrate Ammonium thiosulfate (750 g / liter) 168 ml Sodium p-toluenesulfinate 30.0 g Ammonium bisulfite 35.0 g 3-Mercapto-1,2,4-triazole 0.5g Ammonium sulfate 10.0g Add water 1000ml ──────────────────────────────────── pH ( 25 ℃) pH adjustment with ammonia water or acetic acid 6.20 ────────────────────────────────────

──────────────────────────────────── Rinsing water Both tank liquid and replenishing liquid ─── ────────────────────────────────── Chlorinated sodium isocyanurate 0.02g Deionized water (conductivity 5μs / cm or less) 1000 ml pH 6.5 ─────────────────────────────────────

(1) Measurement of minimum density (Dmin) The minimum density (Dmin) was determined by measuring the reflection density of the sample obtained after color development. The reflection density is
Each sample was measured using blue, green, and red filters to obtain a characteristic curve. Each density (R, G, B) in the minimum density part of the obtained characteristic curve was evaluated as the value of the minimum density (whiteness). (2) Evaluation of raw storability Each of the samples 101 to 111 prepared above was stored (incubated) for 10 days under the conditions of a temperature of 45 ° C. and a humidity of 55% RH, and then subjected to the above exposure, and the color development processing solution described above. A was used for development processing. The minimum concentration of the incubated sample with respect to the non-incubated sample was measured by the same method as above, and the difference (ΔDmin) was determined. Usually, it is preferable that ΔDmin does not change. The above results are shown in Table 3.

[0166]

[Table 3] Table 3 ──────────────────────────────────── Sample minimum density (white background) (Dmin ) Raw storability (ΔDmin) No. Cyan Magenta Yellow Cyan Magenta Yellow ──────────────────────────────────── (Comparative Example) 101 0.12 0.15 0.15 +0.03 +0.02 +0.03 102 0.12 0.15 0.14 +0.03 +0.03 +0.02 103 0.13 0.15 0.15 +0.03 +0.02 +0.03 104 0.12 0.14 0.15 +0.03 +0.02 +0.02 ───────────────────────────── (Invention example) 105 0.12 0.13 0.13 +0.01 0.0 +0.01 106 0.12 0.13 0.13 +0.01 +0.01 +0. 01 107 0.12 0.12 0.13 0.0 0.0 +0.01 108 0 10 0.13 0.12 +0.01 +0.01 0.0 109 109 0.10 0.12 0.13 +0.01 0.0 0.0 110 110 0.10 0.13 0.13 +0.01 0. 0 0.0 111 0.10 0.13 0.12 +0.01 0.0 0.0 ──────────────────────────── ─────────

As is clear from the results shown in Table 3, when the direct positive color photographic light-sensitive material according to the present invention (Samples 105 to 111 of the present invention) was used, the minimum image density was low and the raw storage stability was low. There is little variation in the minimum image density of.

[Example 2] [Evaluation as color photographic light-sensitive material] Each sample used in Example 1 was subjected to exposure and color development processing in the same manner as in Example 1 described above, and then treated with a processing solution. I investigated the effect.
However, the color developing solution is the color developing solution A and the color developing solution B used in the above-mentioned Example 1 [4- [N-as the color developing agent.
Same as color developer A except that ethyl-N- (β-hydroxyethyl) amino] aniline sulfuric acid / 1/2 hydrate was used and tank solution was 4.2 g / liter and replenisher was 5.6 g / liter. Sample 10 used in Example 1 above
After exposing 1 to a development rate of 15%, 40% of the sample
m ² was treated, and predetermined replenishment was performed to preliminarily fatigue both treatment solutions. The results are shown in Table 4 below.

[0169]

[Table 4] Table 4 ──────────────────────────────────── Color developer A Color developer B Sample Minimum image density (Dmin) Minimum image density (Dmin) No. Cyan Magenta Yellow Cyan Magenta Yellow ──────────────────────────────────── (Comparative Example) 101 0.13 0.12 0.12 0.12 0.11 0.11 102 0.16 0.14 0.15 0.14 0.13 0.14 103 0.11 0.12 0.14 0.10 0.11 0.12 104 0.11 0.12 0.12 0.10 0.11 0.11 ───────────────────────────── ──────── (Invention example) 105 0.11 0.11 0.11 0.10 0.10 0.10 106 0.11 0.10 0.11 0.10 0.10 0.1. 10 107 0.10 0.10 0.11 0.10 0.10 0.10 ──────────────────── ────────────────

As is clear from the results shown in Table 4, the color developer B containing the developing agent represented by the formula (D) according to the present invention is used even if the treatment liquid is fatigued. In this case, an image having a lower minimum image density can be obtained.

[Example 3] Among the samples used in Example 1 above, Sample 101, Sample 108, and Sample 111 were used, and a halftone image was obtained using a Fine Checker FC850II manufactured by Fuji Photo Film Co., Ltd. After adhering the plate-making film, red exposure (SC-60 filter manufactured by Fuji Photo Film Co., Ltd.), green exposure (BPB-53 filter manufactured by Fuji Photo Film Co., Ltd.), and blue exposure (BPN45 manufactured by Fuji Photo Film Co., Ltd.) SC-42
Each exposure of (filter) was performed sequentially. At that time, a plate-making film for cyan image and black image was made to adhere during red exposure, a plate-making film for magenta image and black image at the time of green exposure, and a plate-making film for yellow image and black image at the time of blue exposure. A color proof was created in this way. The image formation in this case is the color development processing (color development solution B) according to the second embodiment.
Was used). The minimum halftone dot area of each image of the color proof obtained as described above was observed with a 100 times magnifying glass. The results are shown in Table 5 below.

[0172]

[Table 5] Table 5 ──────────────────────────────────── Reproduced minimum halftone image Cyan image Green exposure maximum density (Dmax) Sample standard exposure 2 times increase Standard green exposure No. Yellow Magenta Cyan Cyan Exposure doubled ──────────────────────────────────── 101 3% or more 3% 3% or more 5% or more 1.8 1.6 108 2% 2% 2% 2% 1.8 1.8 111 2% 2% 2% 2% 1.8 1.8 ──────── ─────────────────────────────

As is clear from the results shown in Table 5, the color photographic light-sensitive material according to the present invention (Sample No. 10 of the present invention).
Nos. 8 and 111) were preferable, as compared with the comparative sample 101, the change in cyan halftone dot reproducibility and the maximum density due to changes in green exposure were small.

[Example 4] As a light source, a helium-neon gas laser (wavelengths 633 nm and 543 nm) and an argon laser (wavelength 458 nm) were used.
A device that can perform sequential scanning exposure (substantial exposure time of about 5 × 10 ⁻⁵ seconds) on a sample while moving a light flux with a diameter of 80 μm at a pitch of 0 μm in a scanning exposure of 1.6 m / s perpendicularly to the scanning direction. Assembled Using this device, the comparative sample 1
01 and the samples 108 and 111 were exposed and then processed using the above-mentioned processing liquid B, and the reproducibility of the halftone image of the obtained image was evaluated. As a result, the color photographic light-sensitive materials of the present invention (invention samples 108 and 111) were able to satisfactorily reproduce up to 2% of halftone dot images, while the color photographic light-sensitive material of the comparative example (comparative sample 101) had 3%. Only halftone images could be reproduced.

Example 5 (Preparation of Samples 112 to 118) Sample 10 of the above Example 1
8 was prepared in the same manner as in Sample 108, except that the solid dispersion of the fine powder dye added to the first layer, the fourth layer and the seventh layer was changed as shown in Table 6 below. Samples 112 to 118 (samples of the present invention) corresponding to the above were prepared.

[0176]

[Table 6] Table 6 ──────────────────────────────────── Composition of non-photosensitive layer Sample No. ． 1st layer 4th layer 7th layer ──────────────────────────────────── 112 S-13 S -2 S-11 113 S-14 S-3 S-12 114 S-15 S-4 S-9 115 S-16 S-5 S-10 116 S-15 S-6 S-11 117 S-14 S. -7 S-12 118 S-13 S-8 S-9 ──────────────────────────────────── ─

Each sample prepared as described above was subjected to exposure and color development processing in the same manner as in Example 1 above. As a result, good results similar to those in Example 1 were obtained.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G03F 3/10 B 8004-2H

Claims (5)

[Claims] 1. A support having at least one blue-sensitive layer, at least one green-sensitive layer and at least one non-photosensitive layer containing a silver halide grain and a color coupler. In the silver halide color photographic light-sensitive material, the color coupler of the blue light-sensitive layer is an acetamide type yellow coupler represented by the following formula (Y): [In the formula (Y), R ^Y1 represents a substituent excluding a hydrogen atom,
Q is a 3- to 5-membered hydrocarbon ring together with C, or N,
Represents a non-metal atom group necessary for forming a 3- to 5-membered heterocycle containing at least one heteroatom selected from S, O and P in the ring, and R ^Y2 represents an alkyl group, an aryl group or Represents a heterocyclic group, and X ^Y represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of a color developing agent. However, R ^Y1 may combine with Q to form a polycycloalkyl group which is a bicycloalkyl group or more. ] And a layer containing fine powder of a dye represented by the following formula (I) as the above non-photosensitive layer. [Chemical 2] [In the formula (I), D represents a compound having a chromophore, X
Represents a dissociative proton bonded to D directly or through a divalent linking group or a group having a dissociative proton, and y
Represents an integer of 1 to 7. ] 2. The silver halide grain is an internal latent image type silver halide grain which has not been fogged in advance.
The color photographic light-sensitive material described in. 3. A color photographic light-sensitive material according to claim 1 or 2, after imagewise exposure, the following formula (D): [In the formula, R ^D1 represents an alkyl group and R ^D2 represents an alkylene group, provided that R ^D1 and R ^D2 may be linked to each other to form a ring. ] The development processing using the developing agent shown by these is the color image forming method characterized by the above-mentioned. 4. A cyan plate halftone dot image film, a magenta plate halftone dot image film, and a yellow plate halftone dot image film obtained by color separation and halftone image conversion of the color photographic light-sensitive material according to claim 1 or 2. And a black halftone dot image film, which are sequentially exposed to red light, green light, and blue light, and then color-developed. 5. A color image forming process, which comprises subjecting the color photographic light-sensitive material according to claim 1 or 2 to scanning exposure for an exposure time of 10 ⁻³ seconds or less per pixel, and then performing color development processing. Method.