JPH06230513A - Direct positive color photographic sensitive material, color image forming method and color proof forming method - Google Patents

Abstract

PURPOSE:To provide the direct positive color photographic sensitive material with which images having a high yellow image density and low density in white parts are obtainable and which is adequate for formation of a color proof. CONSTITUTION:This direct positive color photographic sensitive material has blue sensitive layers, green sensitive layers and red sensitive layers contg. internal latent image type silver halide particles which are not previously fogged and color couplers. The couplers of the blue sensitive layers are the yellow couplers expressed by formula I or formula II. Fogging agents or development accelerators or compds. which release their precursors are incorporated in correspondence to developing silver at the time of development into at least one layer of the photosensitive layers or nonphotosensitive layers. In the image forming method and color proof forming method, such photosensitive materials are used. In the formulas, X1 and X2 respectively denote an alkyl group, aryl group or heterocyclic group; X3 denotes an org. residue forming a nitrogenous heterocyclic group together with.N-; Y denotes an aryl group or heterocyclic group; Z denotes a group which is eliminated when the couplers expressed by this formula react with the oxidant of the main developing agent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a color photographic light-sensitive material containing a novel yellow coupler and a compound which releases a fogging agent or a development accelerator or a precursor thereof, and a color image forming method and color using the same. Regarding proof making method.

[0002]

2. Description of the Related Art The process of working a color printed matter includes the steps of color-separating a color original and converting it into a halftone dot image to form a transmission halftone image. A printing plate is made from the obtained transmission type halftone dot image. 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-56-56).
501217, 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. . JP-A-56-104335
The publication discloses a method for producing a color proof using a color photographic light-sensitive material, and this method has great advantages in terms of process simplicity and low cost, and is excellent in tone reproduction. There are features. 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 ( This is a method in which each color of Y) and black (B) is sequentially contact-exposed so that a color negative is printed on a color paper, and then a designated color development processing is performed to obtain a color proof. This method has a feature that the process is simple and easy to be automated 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. Many positive-positive type photosensitive materials are used. Among them, direct positive type color photographic light-sensitive materials, which have been rapidly progressing in practical use technology in recent years, are attracting attention 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 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 in which a photographic light-sensitive material is subjected to surface development after image exposure, after being subjected to a fog treatment or while being subjected to a fog treatment to directly obtain a positive image. The internal latent image type silver halide photographic emulsion which has not been previously fogged is a type of halide having a photosensitive nucleus mainly inside the silver halide emulsion and a latent image is mainly formed inside the grain upon exposure. A silver photographic light-sensitive material. Various techniques have been known so far in this field. For example, US Pat.
No. 0, No. 2466957, No. 2497875, No. 2
No. 588898, No. 3317322, No. 376126
6, 37,96577 and British Patent No. 11513.
63, No. 1155053, No. 1011062, etc. are the main ones. The formation mechanism of the direct positive image is explained as follows. That is, when imagewise exposure is carried out, a so-called internal latent image is formed on the silver halide, and by subjecting it to a fog treatment, the surface desensitizing action due to this internal production works (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. Image (positive image)
Is formed. The fog treatment method includes a so-called "chemical fog method" which uses a nucleating agent, and a "light fog method" which exposes the entire surface of the photosensitive layer.

The formation of a direct positive color image is carried out by image-exposing an internal latent image type silver halide light-sensitive material which has not been previously fogged as described above, and then, for example, in the presence of a nucleating agent, surface color development processing is carried out. Then, desilvering processing (bleaching, fixing (or bleach-fixing) processing), and further normal washing and /
Alternatively, it is achieved by performing a stabilizing treatment. These series of processes are usually carried out using a system including the above-mentioned process steps, so that the process time is set to be extremely short. However, in direct positive image formation, the developing speed is slower than in the case of a normal negative type,
It takes a long processing time, and therefore, when a positive image is directly formed using the above system, sufficient development processing is not carried out, and therefore, the maximum density of the obtained image is not sufficient. There is a problem. In order to solve such a problem, there has been proposed a method of increasing the maximum image density of a direct positive image by increasing the processing speed. For example, a method of increasing the pH and / or solution temperature of the developer to shorten the developing time, a hydroquinone derivative described in US Pat. No. 3,227,552, or a mercapto compound described in JP-A-60-170843 is used. Method, a method of subjecting a silver halide grain (particularly, a core / shell type) to a surface chemical sensitization treatment, or European Patent Publication No. 0278986A1 and International Publication WO8.
There is a method disclosed in JP-A-8 / 01402 in which a light-sensitive material contains a compound which releases a fogging agent or a development accelerator or a precursor thereof in response to developed silver during development. International Publication WO88 / 01402 describes that a higher maximum image density can be obtained by using a compound which releases a fogging agent or the like corresponding to developed silver during development.

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 coupler. The coupler used is a coupler having a high coupling speed and a high coloring density in a short time. It is desired that the coloring property is good so as to give The hue of the dye thus produced is desired to exhibit good color reproducibility with little side absorption. In particular, in color proofing applications, since the color image is represented by halftone dots, the maximum image density is high (the gradation is hard), and the hues of yellow, magenta, and cyan are close to the hue of the printing ink. It is necessary. With respect to the yellow coupler, conventionally, an acylacetamide type yellow coupler having a pivalyl group as an acyl group has been used as a preferable one (see JP-A-2-220049). However, according to the study of the present inventors, the conventionally used acylacetamide type yellow coupler having the above-mentioned pivaloyl group has a problem that the color density is low. Therefore, it is not always suitable for the purpose of producing a color proof. Further, in this yellow coupler, even when a compound which releases a fogging agent or a development accelerator as described above is used, the improvement of the maximum image density is not sufficiently satisfactory, and especially in the application of color proofing. Improvement is desired.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to have a high maximum image density (hard gradation), close to the hue of printing ink, and excellent in color reproducibility (having high whiteness). (EN) It is intended to provide a color photographic light-sensitive material capable of obtaining a yellow color image, a color image forming method and a color proof making method using the light-sensitive material.

[0007]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made extensive studies in search of a yellow coupler which meets the above-mentioned object, and as a result, selectively use the specific yellow coupler represented by the above formula. Further, it was found that the above object can be achieved by using the yellow coupler and a specific compound in combination, and further by using the yellow coupler in combination with a specific developing agent, thereby completing the present invention. did. The present invention comprises a blue-sensitive layer (blue-sensitive emulsion layer) and a green-sensitive layer (green-sensitive emulsion layer) containing an internal latent image type silver halide grain not previously fogged and a color image-forming coupler on a support. And a red-sensitive layer (red photosensitive emulsion layer), and a direct positive color photographic light-sensitive material comprising at least one non-light-sensitive layer adjacent thereto, wherein the color image-forming coupler of the blue-sensitive layer is represented by the following formula ( 1), (2): General formula (1)

[0008]

[Chemical 4]

General formula (2)

[0010]

[Chemical 5]

(Wherein X ₁ and X ₂ each represent an alkyl group, an aryl group or a heterocyclic group, X ₃ represents an organic residue forming a nitrogen-containing heterocyclic group together with> N-, and Y represents an aryl group. Group or a heterocyclic group, Z represents a group which is released when the coupler represented by the general formula reacts with an oxidized product of a developing agent), and contains at least one yellow coupler represented by Or at least one of the non-photosensitive layers contains a compound which releases a fogging agent or a development accelerator or a precursor thereof in correspondence with developed silver during development, a direct positive color photographic light-sensitive material. . The present invention also provides the above color true light-sensitive material by the following formula (D):

[0012]

[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. ) In the color image forming method, the development processing is performed using a developing agent. The present invention further relates to the above-mentioned color photographic light-sensitive material, which has undergone color separation and halftone image conversion, and has a cyan halftone dot image film, a magenta halftone dot image film, a yellow halftone dot image film, and a black halftone dot image film. using,
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 above color photographic light-sensitive material is subjected to scanning exposure for an exposure time of 10 ⁻³ seconds or less per pixel, and then color development processing.

The preferred embodiments of the color photographic light-sensitive material of the present invention will be described below.

(1) A layer in which the yellow coupler represented by the above formula (1) or (2) and the compound releasing the fogging agent or the development accelerator or their precursors are the same layer (more preferably halogenated). Silver emulsion layer). (2) In the above (1), the emulsion layer further contains a nucleating agent.

[0016]

EFFECT OF THE INVENTION By using the color photographic light-sensitive material of the present invention containing the novel yellow coupler and a compound which releases a fogging agent, a development accelerator or a precursor thereof, a yellow image having a high color density can be obtained. . The hue of the obtained color image is a yellow image having a color reproducibility (high whiteness) close to that of printing ink and is particularly suitable for producing a color proof.

The color photographic light-sensitive material of the present invention will be described below. The color photographic light-sensitive material of the present invention contains a novel yellow coupler and a compound which releases a fogging agent, a development accelerator or a precursor thereof as described above. The color photographic light-sensitive material includes various types that form a yellow color-developing (dye) image by a coupling reaction between the yellow coupler and an oxidant produced by color development processing. In particular,
Color negative film, color positive film (color reversal film, color print film),
Color reversal paper, color auto positive film, or color auto positive paper are available. However, the yellow dye image obtained by the color photographic light-sensitive material of the present invention is particularly advantageous when it is used as a color copy image or a color proof image, and therefore, a color auto positive paper (direct positive color photographic light-sensitive material).
It is advantageous to use as.

In the color photographic light-sensitive material of the present invention, at least one silver halide emulsion layer and at least one light-insensitive layer are provided on a support. Then, each of the yellow coupler represented by the above formula (Ya) and the compound that releases the fogging agent, the development accelerator or the precursor thereof is contained in at least one layer of the emulsion layer or the non-photosensitive layer. . It is preferable that the yellow coupler and the release compound such as the fogging agent are contained together in the same layer, and particularly it is preferable that they are contained together in the silver halide emulsion layer. Below, the said structural component is demonstrated in order.

The couplers represented by the general formulas (1) and (2) will be described in detail. When X ₁ and X ₂ represent an alkyl group, they have 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
Is a linear, branched, cyclic, saturated, unsaturated, substituted or unsubstituted alkyl group. Examples of alkyl groups include methyl, ethyl, propyl, butyl, cyclopropyl, allyl, t-octyl, i-butyl, dodecyl, 2-hexyldecyl. When X ₁ and X ₂ represent a heterocyclic group, the hetero atom having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, for example, at least one nitrogen atom, oxygen atom or sulfur atom is contained in the range of 3 to 12, preferably 5 or It is a 6-membered, saturated or unsaturated, substituted or unsubstituted, monocyclic or condensed ring heterocyclic group. Examples of the heterocyclic group include 3-pyrrolidinyl, 1,2,4-triazol-3-yl, 2-pyridyl, 4-pyrimidinyl,
3-pyrazolyl, 2-pyrrolyl, 2,4-dioxo-
1,3-imidazolidin-5-yl, pyranyl and the like can be mentioned.

When X ₁ and X ₂ represent an aryl group,
It represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms. Typical examples of the aryl group are phenyl and naphthyl. When X ₃ represents a nitrogen-containing heterocyclic group formed together with> N-, the heterocyclic group has 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms and is a hetero atom other than a nitrogen atom, such as an oxygen atom or a sulfur atom. May be a substituted or unsubstituted, saturated or unsaturated, monocyclic or condensed-ring heterocyclic group having a 3- to 12-membered ring, preferably a 5- or 6-membered ring. Examples of this heterocyclic group are pyrrolidino, piperidino, morpholino, 1-
Piperazinyl, 1-indolinyl, 1,2,3,4-tetrahydroquinolin-1-yl, 1-imidazolidinyl, 1-pyrazolyl, 1-pyrrolinyl, 1-pyrazolidinyl, 2,3-dihydro-1-indazolyl, 2-isoindolinyl , 1-indolyl, 1-pyrrolyl, 4-thiazin-S, S-dioxo-4-yl or benzoxazin-4-yl.

When X ₁ and X _{2 each} represent a substituted alkyl, aryl or heterocyclic group having a substituent, and when the nitrogen-containing heterocyclic group formed with X ₃ with> N- has a substituent, The following are mentioned as an example of those substituents. Halogen atom (eg fluorine atom, chloro atom), alkoxycarbonyl group (C2-3)
0, preferably 2-20. For example, methoxycarbonyl,
Dodecyloxycarbonyl, hexadecyloxycarbonyl), an acylamino group (having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, for example, acetamide, tetradecanamide,
2- (2,4-di-t-amylphenoxy) butanamide, benzamide), sulfonamide group (having 1 to 3 carbon atoms)
0, preferably 1-20. For example, methanesulfonamide, dodecanesulfonamide, hexadecylsulfonamide, benzenesulfonamide), a carbamoyl group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, N-butylcarbamoyl, N, N-diethylcarbamoyl), N-
Sulfonylcarbamoyl group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, N-mesylcarbamoyl, N-dodecylsulfonylcarbamoyl), sulfamoyl group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, N-butylsulfafa Moyl, N-dodecylsulfamoyl, N-hexadecylsulfamoyl, N-3- (2,4-di-t
-Amylphenoxy) butylsulfamoyl, N, N-
Diethylsulfamoyl), alkoxy group (C1-C1)
30, preferably 1-20. For example, methoxy, hexadecyloxy, isopropoxy), aryloxy group (C6-20, preferably 6-10. For example, phenoxy, 4-methoxyphenoxy, 3-t-butyl-4-hydroxyphenoxy, naphthoxy), aryl Oxycarbonyl group (C7-21, preferably 7-11. For example, phenoxycarbonyl), N-acylsulfamoyl group (C2-30, preferably 2-20. For example, N
-Propanoylsulfamoyl, N-tetradecanoylsulfamoyl), a sulfonyl group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, methanesulfonyl, octanesulfonyl, 4-hydroxyphenylsulfonyl, dodecanesulfonyl), alkoxy. Carbonylamino group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, ethoxycarbonylamino), cyano group, nitro group, carboxyl group, hydroxyl group, sulfo group, alkylthio group (having 1 to 30 carbon atoms, preferably 1 to 30 carbon atoms) 20. For example, methylthio,
Dodecylthio, dodecylcarbamoylmethylthio),

A ureido group (having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as N-phenylureido, N-hexadecylureido), an aryl group (having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, such as phenyl or naphthyl). , 4-methoxyphenyl), a heterocyclic group (having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, 3 to 12, containing at least one hetero atom such as a nitrogen atom, oxygen atom, or sulfur atom).
A monocyclic or condensed ring, preferably a 5- or 6-membered ring.
For example, 2-pyridyl, 3-pyrazolyl, 1-pyrrolyl,
2,4-dioxo-1,3-imidazolidin-1-yl, 2-benzoxazolyl, morpholino, indolyl), alkyl group (having 1 to 30 carbon atoms, preferably 1 to 2 carbon atoms)
0, straight chain, branched, cyclic, saturated, unsaturated, for example, methyl, ethyl, isopropyl, cyclopropyl, t-pentyl, t-octyl, cyclopentyl, t-butyl, s
-Butyl, dodecyl, 2-hexyldecyl) acyl group (having 1 to 30 carbon atoms, preferably 2 to 20. For example, acetyl, benzoyl), acyloxy group (having 2 to 30 carbon atoms,
Preferably 2 to 20. For example, propanoyloxy, tetradecanoyloxy), arylthio group (having 6 to 2 carbon atoms)
0, preferably 6-10. For example, phenylthio, naphthylthio), sulfamoylamino group (having 0 to 30 carbon atoms,
Preferably 0-20. For example, N-butylsulfamoylamino, N-dodecylsulfamoylamino, N-phenylsulfamoylamino) or N-sulfonylsulfamoyl group (having 1 to 30 carbon atoms, preferably 1 to 2 carbon atoms).
0. Examples thereof include N-mesylsulfamoyl, N-ethanesulfonylsulfamoyl, N-dodecanesulfonylsulfamoyl, and N-hexadecanesulfonylsulfamoyl. The above substituents may further have a substituent. Examples of the substituent include the substituents mentioned here. Among the above, preferred substituents include an alkoxy group, a halogen atom, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, a sulfonamide group, a nitro group, an alkyl group or an aryl group.

When Y represents an aryl group in the general formulas (1) and (2), it has 6 to 20 carbon atoms, preferably 6 to 20 carbon atoms.
And 10 substituted or unsubstituted aryl groups. Phenyl and naphthyl groups are typical examples. When Y represents a heterocyclic group in the general formulas (1) and (2), it has the same meaning as described when X ₁ or X ₂ represents a heterocyclic group. When Y represents a substituted aryl group or a substituted heterocyclic group, examples of the substituent include, for example, the above X.
Examples of the case where ₁ has a substituent include the substituents listed above. As a preferred example of the substituent which Y has, one of the substituents is a halogen atom, an alkoxycarbonyl group, a sulfamoyl group, a carbamoyl group, a sulfonyl group, an N-sulfonylsulfamoyl group, an N-acylsulfamoyl group, Alkoxy group, acylamino group,
This is when it is an N-sulfonylcarbamoyl group, a sulfonamide group or an alkyl group. A particularly preferred example of Y is a phenyl group having at least one substituent in the ortho position.

The group represented by Z in the general formulas (1) and (2) may be any conventionally known coupling-off group. Preferred Z is a nitrogen-containing heterocyclic group that binds to the coupling position at a nitrogen atom, an aryloxy group, an arylthio group, a heterocyclic oxy group, a heterocyclic thio group, an acyloxy group, a carbamoyloxy group, an alkylthio group or a halogen atom. Can be mentioned. These leaving groups are non-photographic useful groups or photographic useful groups or precursors thereof (eg, development inhibitors, development accelerators, desilvering accelerators, fogging agents, dyes, hardeners, couplers, oxidized developing agents). Scavenger, fluorescent dye, developing agent or electron transfer agent). When Z is a photographically useful group, those conventionally known are useful. For example, U.S. Pat. Nos. 4,248,962, 4,409,323, 4,438,193, 4,421,845 and 46,185.
No. 71, No. 4652516, No. 4861701, No. 4782012, No. 4857440, No. 48471.
No. 85, No. 4477563, No. 4438193, No. 4628024, No. 4618571, No. 47419.
94, European Published Patent No. 193389A, 3
The photographically useful group described in 48139A or 272573A or a leaving group (for example, a timing group) for releasing the group is used.

When Z represents a nitrogen-containing heterocyclic group bonded to the coupling position at the nitrogen atom, it preferably has 1 to 1 carbon atoms.
5, preferably 1-10, 5- or 6-membered, substituted or unsubstituted, saturated or unsaturated, monocyclic or condensed-ring heterocyclic group. The hetero atom may contain an oxygen atom or a sulfur atom in addition to the nitrogen atom. Preferred specific examples of the heterocyclic group are 1-pyrazolyl, 1
-Imidazolyl, pyrrolino, 1,2,4-triazol-2-yl, 1,2,3-triazol-1-yl, benzotriazolyl, benzimidazolyl, imidazolidin-2,4-dione-3-yl, Oxazolidine-2,
4-dione-3-yl, 1,2,4-triazolidine-
3,5-dione-4-yl, imidazolidin-2,4
5-trion-3-yl, 2-imidazolinone-1-yl, 3,5-dioxomorpholino or 1-indazolyl. When these heterocyclic groups have a substituent, examples of the substituent include the substituents listed as the substituents which the group represented by the above X ₁ group may have. As a preferred substituent, one of the substituents is an alkyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an acylamino group, a sulfonamide group, an aryl group, a nitro group, a carbamoyl group, a cyano group or This is when it is a sulfonyl group.

When Z represents an aromatic oxy group, it is preferably a substituted or unsubstituted aromatic oxy group having 6 to 10 carbon atoms. A substituted or unsubstituted phenoxy group is particularly preferable. When it has a substituent, examples of the substituent include
Examples thereof include the substituents enumerated as the substituents which the group represented by X ₁ may have. Among them, a preferred substituent is a case where at least one substituent is an electron-withdrawing substituent, and examples thereof include a sulfonyl group, an alkoxycarbonyl group, a sulfamoyl group, a halogen atom, a carbamoyl group, a nitro group and a cyano group. Alternatively, an acyl group can be used. When Z represents an aromatic thio group,
It is preferably a substituted or unsubstituted aromatic thio group having 6 to 10 carbon atoms. Particularly preferred is a substituted or unsubstituted phenylthio group. When it has a substituent, examples of the substituent include the substituents listed as the substituents which the group represented by X ₁ may have. Among them, a preferable substituent is at least one substituent,
This is when it is an alkyl group, an alkoxy group, a sulfonyl group, an alkoxycarbonyl group, a sulfamoyl group, a halogen atom, a carbamoyl group, or a nitro group.

When Z represents a heterocyclic oxy group, the portion of the heterocyclic group contains 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and contains at least one hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom. It is a substituted or unsubstituted, saturated or unsaturated, monocyclic or condensed-ring heterocyclic group having 1 to 12, preferably 5 or 6 membered ring. Examples of the heterocyclic oxy group include a pyridyloxy group, a pyrazolyloxy group, or a furyloxy group. When it has a substituent, examples of the substituent include the substituents listed as the substituents which the group represented by X ₁ may have. Among them, a preferable substituent is an alkyl group, an aryl group, a carboxyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an acylamino group, a sulfonamide group, a nitro group. , A carbamoyl group or a sulfonyl group.

When Z represents a heterocyclic thio group, the portion of the heterocyclic group contains at least one hetero atom having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as a nitrogen atom, an oxygen atom or a sulfur atom. It is a substituted or unsubstituted, saturated or unsaturated, monocyclic or condensed-ring heterocyclic group having 1 to 12, preferably 5 or 6 membered ring. Examples of the heterocyclic thio group include tetrazolylthio group, 1,3,4
-Thiadiazolylthio group, 1,3,4-oxadiazolylthio group, 1,3,4-triazolylthio group, benzimidazolylthio group, benzothiazolylthio group, or 2
A pyridylthio group. When it has a substituent,
Examples of the substituent include the substituents enumerated as the substituents which the group represented by X ₁ may have. Among them, preferable substituents include at least one of the substituents being an alkyl group, an aryl group, a carboxyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group,
This is when it is an acylamino group, a sulfonamide group, a nitro group, a carbamoyl group, a heterocyclic group or a sulfonyl group.

When Z represents an acyloxy group, it is preferably a monocyclic or condensed ring substituted or unsubstituted aromatic acyloxy group having 6 to 10 carbon atoms or 2 to 2 carbon atoms.
30 is preferably a substituted or unsubstituted aliphatic acyloxy group of 2 to 20. When these have a substituent,
Examples of the substituent include the substituents enumerated as the substituents which the group represented by X ₁ may have. When Z represents a carbamoyloxy group, it has 1 carbon atom.
-30, preferably 1-20 aliphatic, aromatic, heterocyclic, substituted or unsubstituted carbamoyloxy groups. For example, N, N-diethylcarbamoyloxy, N-
Phenylcarbamoyloxy, 1-imidazolylcarbonyloxy or 1-pyrrolocarbonyloxy. When these have a substituent, examples of the substituent include the substituents enumerated as the substituents which the group represented by X1 may have. When Z represents an alkylthio group, it has 1 to 30 carbon atoms, preferably 1 to
20 is a linear, branched, cyclic, saturated, unsaturated, substituted or unsubstituted alkylthio group. When it has a substituent, examples of the substituent include the substituents listed as the substituents which the group represented by X ₁ may have.

Next, a particularly preferred range of the couplers represented by the general formulas (1) and (2) will be described below. The group represented by X ₁ in the general formula (1) is preferably an alkyl group. Particularly preferably, it has 1 to 10 carbon atoms.
Is an alkyl group. The group represented by Y in the general formulas (1) and (2) is preferably an aromatic group. Particularly preferred is a phenyl group having at least one substituent at the ortho position. The explanation of the substituent includes those explained as the substituent which may be possessed when Y is an aromatic group. The description of the preferable substituents is also the same. General formula (1)
And the group represented by Z in (2) is preferably 5
And a 6-membered nitrogen-containing heterocyclic group that bonds to the coupling position at a nitrogen atom, an aromatic oxy group, a 5- or 6-membered heterocyclic oxy group, or a 5- or 6-membered heterocyclic thio group. Preferred couplers in the general formulas (1) and (2) are represented by the following general formulas (3), (4) or (5). General formula (3)

[0031]

[Chemical 7]

General formula (4)

[0033]

[Chemical 8]

General formula (5)

[0035]

[Chemical 9]

In the formula, Z has the same meaning as described in the general formula (1), X ₄ represents an alkyl group, X ₅ represents an alkyl group or an aromatic group, and Ar represents at least one ortho-position. Represents a phenyl group having a substituent, X ₆
Is -C (R ₁ R ₂₎ represents an organic residue forming a -N <with a nitrogen-containing Hajime Tamaki (monocyclic or condensed), X ₇ -
Represents an organic residue forming a nitrogen-containing heterocyclic group (monocycle or condensed ring) together with C (R ₃ ) = C (R ₄ ) -N <,
R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom or a substituent. In the general formulas (3) to (5), X _{4 to} X ₇ , Ar
The detailed description and the preferred range of the groups represented by and Z have the same meanings as those described in the corresponding ranges in the description of the general formulas (1) and (2). When R _{1 to} R ₄ represent a substituent, the examples of the substituent that X ₁ may have are listed. Particularly preferred couplers in the above general formula are the couplers represented by the general formula (4) or (5). The couplers represented by the general formulas (1) to (5) are represented by X ₁ to
2 in the groups represented by X ₇ , Y, Ar, R _{1 to} R ₄ and Z, which are bonded to each other via a divalent or higher valent group;
Multimers or higher multimers (eg telomers or polymers) may be formed. In this case, the number of carbon atoms shown in each of the above substituents may be out of the specified range. The couplers represented by the general formulas (1) to (5) are preferably non-diffusion couplers. The diffusion-resistant type is a coupler having a group in the molecule that makes the molecular weight sufficiently large in order to immobilize it in the layer to which the molecule is added. Usually, the total carbon number is 8 to 30, preferably 10 to 2.
An alkyl group having 0 or an aryl group having a substituent having a total carbon number of 4 to 20 is used. These diffusion resistant groups may be substituted in any of the molecules, or may have a plurality of groups. Specific examples of the yellow couplers represented by formulas (1) to (5) are shown below, but the invention is not limited thereto.

[0037]

[Chemical 10]

[0038]

[Chemical 11]

[0039]

[Chemical 12]

[0040]

[Chemical 13]

[0041]

[Chemical 14]

[0042]

[Chemical 15]

[0043]

[Chemical 16]

[0044]

[Chemical 17]

[0045]

[Chemical 18]

[0046]

[Chemical 19]

[0047]

[Chemical 20]

[0048]

[Chemical 21]

[0049]

[Chemical formula 22]

[0050]

[Chemical formula 23]

[0051]

[Chemical formula 24]

[0052]

[Chemical 25]

[0053]

[Chemical formula 26]

[0054]

[Chemical 27]

[0055]

[Chemical 28]

[0056]

[Chemical 29]

[0057]

[Chemical 30]

The yellow couplers of the present invention represented by the general formulas (1) to (5) can be synthesized by the following routes. Synthesis example-1

[0059]

[Chemical 31]

Synthesis of intermediate B 357.5 g (3.0 mol) of compound A, compound B39
6.3 g (3.0 mol) was dissolved in 1.2 l of ethyl acetate and 0.6 l of dimethylformamide. While stirring, a solution of 631 g (3.06 mol) of dicyclohexylcarbodiimide in acetonitrile (400 ml) was added at 15 to 35 ° C.
It was dripped at. After reacting at 20 to 30 ° C. for 2 hours, the precipitated dicyclohexylurea was collected by filtration. 500 ml of ethyl acetate and 1 liter of water were added to the filtrate, and the aqueous layer was removed. Next, the organic layer was washed with water twice with 1 liter of water. The organic layer was dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure to obtain 692 g (98.9%) of Intermediate A as an oily substance. 692 g (2.97 mol) of Intermediate A was dissolved in 3 l of ethyl alcohol, and 430 g of 30% sodium hydroxide was added dropwise at 75 to 80 ° C while stirring. After dropping, at the same temperature, 30
After reacting for minutes, the precipitated crystals were collected by filtration. (Yield 6
58 g) The crystals were suspended in 5 l of water, and 300 ml of concentrated hydrochloric acid was added dropwise at 40 to 50 ° C with stirring. After stirring at the same temperature for 1 hour, the crystals were collected by filtration to obtain 579 g of Intermediate B (9
5%) was obtained. (Decomposition point 127 ° C.) Synthesis of intermediate D 45.1 g (0.22 mol) of intermediate B, compound C86.
6 g (0.2 mol) was dissolved in 400 ml of ethyl acetate and 200 ml of dimethylacetamide. With stirring, a solution of 66 g (0.32 mol) of dicyclohexylcarbodiimide in acetonitrile (100 ml) was added dropwise at 15 to 30 ° C. After reacting at 20 to 30 ° C. for 2 hours, the precipitated dicyclohexylurea was collected by filtration. Ethyl acetate 400 in the filtrate
ml, 600 ml of water, and after removing the water layer, add 2
It was washed with water twice. The organic layer was dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure to obtain 162 g of an oily substance.
This oily substance was mixed with 100 ml of ethyl acetate and 300 ml of n-hexane.
Crystallized from ml, 108 g of intermediate D (87.1%)
Obtained. (Melting point 132-134 ° C)

[0061]

[Table 1]

Synthesis of Exemplified Coupler Y-7 49.6 g (0.08 mol) of Intermediate D was dissolved in 300 ml of dichloromethane. Sulfuryl chloride 11.
4 g (0.084 mol) was added dropwise with stirring at 10 to 15 ° C. After reacting for 30 minutes at the same temperature, 200 g of a 5% aqueous sodium bicarbonate solution was added dropwise to the reaction mixture.
The organic layer was separated, washed with 200 ml of water, and dried over anhydrous sodium sulfate. Dichloromethane was distilled off under reduced pressure to obtain 47 g of an oily substance. 47 g of this oily substance was dissolved in 200 ml of acetonitrile, and 28.4 g (0.2
2 mol) and 22.2 g (0.22 mol) of triethylamine were added with stirring. After reacting for 4 hours at 40 to 50 ° C., the mixture was poured into 300 ml of water, and the precipitated oily substance was extracted with 300 ml of ethyl acetate. The organic layer was washed with 200 g of 5% aqueous sodium hydroxide solution, and then twice more with 300 ml of water.
Washed with water. The organic layer was acidified with dilute hydrochloric acid, washed twice with water, and concentrated under reduced pressure to give a residue. (Yield 70 g) The obtained oily substance was crystallized with a mixed solvent of 50 ml of ethyl acetate and 100 ml of n-hexane to give 47.8 g (80%) of Exemplified Coupler 1.
%)Obtained. (Melting point 145-7 ° C)

[0063]

[Table 2]

Synthesis Example-2

[0065]

[Chemical 32]

Synthesis of Intermediate E 90.3 g of Intermediate B (0.44 mol), Compound E187
g (0.4 mol) was dissolved in 500 ml of ethyl acetate and 300 ml of dimethylformamide. With stirring, dicyclohexylcarbodiimide 131.9 g (0.64 mol)
Acetonitrile solution (200 ml) was added dropwise at 15 to 30 ° C. After reacting at 20 to 30 ° C. for 2 hours, the precipitated dicyclohexylurea was collected by filtration. Ethyl acetate 5 in the filtrate
After adding 00 ml and 600 ml of water and removing the aqueous layer, the organic layer was washed twice with water. The organic layer was dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure to obtain 281 g of an oily substance. This was dissolved by heating with 1.5 l of n-hexane, and insoluble materials were removed by filtration. The n-hexane solution was cooled with water, and the precipitated intermediate E was collected by filtration. Yield 243.4 g (93%) melting point 103-5 ° C.

[0067]

[Table 3]

Synthesis of Exemplified Coupler Y-16 39.3 g (0.06 mol) of Intermediate E was dissolved in 200 ml of dichloromethane. Sulfuryl chloride 8.7 was added to this solution.
g (0.064 mol) was added dropwise with stirring at 10 to 15 ° C. After reacting for 30 minutes at the same temperature, 200 g of a 4% aqueous sodium hydrogencarbonate solution was added dropwise to the reaction mixture. The organic layer was separated, washed with 200 ml of water, and dried over anhydrous sodium sulfate. Dichloromethane was distilled off under reduced pressure to obtain 41.3 g of an oily substance. 41.3 g of this oily substance was added to 100 ml of acetonitrile and 200 ml of dimethylacetamide.
After dissolving in ml, 20.8 g (0.16 mol) of compound D and 16.2 g of triethylamine were added with stirring. Thirty
After reacting at -40 ° C for 3 hours, pour into 400 ml of water,
The precipitated oily substance was extracted with 300 ml of ethyl acetate. The organic layer was washed with 300 g of 2% sodium hydroxide and then twice more. The organic layer was acidified with diluted hydrochloric acid, washed twice with water, and concentrated under reduced pressure to obtain 42 g of a residue. This was crystallized with 200 ml of methanol, and the exemplified coupler Y-16 was mixed with 3 ml.
Obtained 9.8 g (85%). (Melting point 110 to 112 ° C)

[0069]

[Table 4]

Synthesis Example-3

[0071]

[Chemical 33]

Synthesis of Intermediate F 104.7 g (0.51 mol) of Intermediate B, Compound F18
7.5 g (0.5 mol) was dissolved in 1 l of ethyl acetate and 400 ml of dimethylformamide. With stirring, a solution of 107.3 g (0.525 mol) of dicyclohexylcarbodiimide in 100 ml of dimethylformamide (15 ml) was added.
It was added dropwise at 30 ° C. After reacting at 20 to 30 ° C for 1 hour, 500 ml of ethyl acetate was added, the mixture was heated to 50 to 60 ° C, and dicyclohexylurea was collected by filtration. 500 water in the filtrate
ml was added, the aqueous layer was removed, and the mixture was washed twice with water. The organic layer was dried over anhydrous sodium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain 290 g of an oily substance. This oily substance was heated with 1 liter of ethyl acetate and 2 liters of methanol, insoluble matter was removed by filtration, and the filtrate was water-cooled, and crystals of Intermediate F were precipitated, and were collected by filtration. Yield 267 g (95%) melting point 163- 4
℃

[0073]

[Table 5]

Synthesis of Intermediate G 114.0 g (0.2 mol) of Intermediate F were dissolved in 500 ml of dichloromethane. Sulfuryl chloride 28.
4 g (0.21 mol) was added dropwise with stirring at 10 to 15 ° C. After reacting for 30 minutes at the same temperature, 500 g of a 6% aqueous sodium hydrogencarbonate solution was added dropwise to the reaction mixture. The organic layer was separated, washed with 500 ml of water and dried over anhydrous sodium sulfate. When dichloromethane was distilled off under reduced pressure, intermediate G was precipitated as crystals and was collected by filtration. Yield 108.6g (91%)

Synthesis of Exemplified Coupler Y-12 Intermediate G 29.8 g (0.05 mol) was dissolved in dimethylformamide 80 ml, compound D 12.9 g (0.1 mol) was added, and then triethylamine 10.1 g (0 .1
0 mol) was added dropwise with stirring at 20 to 30 ° C. 40
After reacting at ˜45 ° C. for 1 hour, 300 ml of ethyl acetate and 200 ml of water were added. The organic layer was washed twice with 400 g of 2% sodium hydroxide and then once more. The organic layer was acidified with diluted hydrochloric acid, washed twice with water, and concentrated under reduced pressure to obtain 34 g of a residue. This was crystallized with a mixed solvent of 50 ml of ethyl acetate and 150 ml of n-hexane to give an exemplary coupler Y-.
19 g of 12 was obtained. The crystals were recrystallized with 120 ml of a mixed solvent having an ethyl acetate / n-hexane = 1/3 vol ratio to obtain 15 g (43.5%) of Exemplified coupler Y-12. (Melting point 135-6 ° C)

[0076]

[Table 6]

Synthesis Example-4

[0078]

[Chemical 34]

Synthesis of Exemplified Coupler Y-49 Compound 27.0 g (0.15 mol) and triethylamine 15.2 g (0.15 mol) were dissolved in 50 ml of dimethylformamide. 29.8 g of intermediate G in this mixture
A solution of (0.05 mol) in dimethylformamide (30 ml) was added dropwise with stirring. After reacting for 4 hours at 30 to 40 ° C., 400 ml of ethyl acetate and 300 ml of water were added.
The organic layer was washed with 400 g of a 2% aqueous sodium hydroxide solution and then twice more. The organic layer was acidified with dilute hydrochloric acid, washed twice with water, and dried over anhydrous sodium sulfate. The ethyl acetate was distilled off under reduced pressure to obtain 54 g of a residue. This was crystallized with 300 ml of a mixed solvent of ethyl acetate / methanol (1/2 vol ratio), and the exemplified coupler Y-49 was collected by filtration. The obtained crystals were recrystallized with 200 ml of a mixed solvent of ethyl acetate / methanol (1/2 vol ratio) to give Exemplified coupler Y-49 at 28.8.
g (77.8%) was obtained. Melting point 190-191 ° C

[0080]

[Table 7]

The amount of the yellow coupler represented by the above formula (1) or (2) used in the light-sensitive material is generally in the range of 1 × 10 ^-5 mol to 1 × 10 ^-2 mol per 1 m ² of the light-sensitive material. And preferably in the range of 1 × 10 ⁻⁴ mol to 10 ⁻³ mol, and more preferably 2 × 10 ⁻⁴ mol to 10 ⁻³ mol.

Next, a compound (hereinafter referred to as an FR compound) used in the color photographic light-sensitive material of the present invention, which releases a fogging agent or a development accelerator or a precursor thereof.
Will be described in detail. As the fogging agent or the development accelerator (hereinafter referred to as FA), a reducing compound (hydrazine, hydrazinde, hydrazone, hydroquinone, catechol, p-aminophenol, p-
Phenylenediamine, 1-phenyl-3-pyrazolidinone, enamine, aldehyde, polyamine, acetylene,
Aminoborane, a tetrazolium salt, a quaternary salt such as ethylenebispyridinium salt, etc.) and a compound capable of forming silver sulfide during development (for example, thiourea, thioamide, dithiocarbamate, rhodanine, thiohydantoin, thiazolidinethione; Compounds having a partial structure of SCN =) and the like.

The FP compounds that can be used in the present invention include the following. (i) A coupler that releases FA or a precursor thereof by coupling with an oxidation product of an aromatic primary amine developing agent. (ii) A coupler which is coupled with an oxidation product of an aromatic primary amine developing agent to give a diffusible coupling product, and the coupling product functions as FA or a precursor thereof. (iii) A redox compound that releases FA or a precursor thereof by a redox reaction with an oxidation product of an aromatic primary amine developing agent or a subsequent reaction of the reaction. The above compounds (i), (ii) and (iii) are represented by the following general formulas (I), (II) and (III), respectively. (I) Cp- (TIME) _n- FA (II) BALL-Cp- (TIME) _n- FA (III) RED- (TIME) _n- FA In the above formula, Cp is an aromatic primary amine development. Represents a coupler residue capable of undergoing a coupling reaction with an oxidized form of a drug. B
ALL represents a diffusion-resistant group which can be separated from Cp by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. RED represents a compound residue capable of undergoing a redox reaction with an oxidized product of an aromatic primary amine developing agent. TIME
Represents a timing group that further releases FA after leaving Cp or RED by a coupling reaction. n represents 0 or 1, and FA is, when n is 0,
It is a group which can be separated from Cp or RED by a coupling reaction, and a group which can be released from TIME when n is 1 (in the case of the compound represented by (II) in the above formula, F is
A may not be released from Cp or TIME after the coupling reaction. Here, FA represents a so-called fogging agent or development accelerator which acts on silver halide grains during development to generate fog nuclei capable of initiating development. Examples of FA include a group that acts reductively on silver halide grains during development to produce fog nuclei or a group that acts on silver halide grains to produce silver sulfide nuclei which are fog nuclei that can initiate development. be able to.

Preferred groups for FA include groups having adsorptivity for silver halide grains and can be represented as follows. AD- (L) _m -X AD represents a group having adsorptivity to silver halide, L represents a divalent group, and m represents 0 or 1.
X represents a reducing group or a group capable of acting on silver halide to form silver sulfide. However, when X is the latter, it may also have the function of AD, and in this case, AD- (L) _m- is not always necessary. When FA is a group represented by AD- (L) _m -X, TIM
The position of binding to E, Cp or RED is AD- (L) _m
It may be any position in -X. In the general formula (I), −
(TIME) _n -FA binds to the coupling position of Cp, and the bond is cleaved during the coupling reaction. In the general formula (II), BALL is bonded to the coupling position of Cp, and the bond is cleaved during the coupling reaction. Further, since-(TIME) _n -FA is bonded to the non-coupling position of Cp, the bond is not immediately cleaved by the coupling. In the general formula (III),-(TIME) _n -FA is bonded to a position at which RED can be released from RED by a redox reaction with an oxidized aromatic primary amine developing agent or a subsequent reaction thereof.
On the other hand, the group represented by TIME may be a trivalent group in the case of the general formula (I). That is, one of the trivalent bonds binds to FA, one of the remaining two bonds to the coupling position of Cp, and the other one binds to the uncoupling position of Cp. . The compound having such a structure is characterized in that, at the time of the coupling reaction with the aromatic primary amine developing agent, the bond with TIME that is bonded to the coupling site is cut off, but the compound is bonded to the non-coupling site. The bond with the existing TIME is not cleaved, and the bond portion (anion) of the cleaved TIME cleaves the bond with FA by electron transfer and / or intramolecular nucleophilic substitution reaction of TIME to cleave FA. It can be released. Therefore, in the case of such compounds,
In addition to being a trivalent group, it is necessary to have a structure capable of releasing FA by intramolecular electron transfer and / or intramolecular nucleophilic substitution reaction.

The general formulas (I), (II) and (III) will be described in more detail below. In the general formula (I),
The coupler residue represented by Cp is yellow as described below,
In addition to magenta and cyan couplers, it has a partial structure of non-color coupler and black coupler. Here, a typical example of the yellow coupler among the couplers is described in US Pat.
No. 75057, No. 2407210, No. 3265506.
No. 2, No. 2298443, No. 3048194, No. 34
No. 47928 and the like. Among the yellow couplers, acylacetamide derivatives such as benzoylacetanilide and pivaloylacetanilide are preferable. Therefore, as the yellow coupler residue (Cp), those represented by the following general formulas (Ia) and (IIa) are preferable.

[0086]

[Chemical 35]

In addition, * represents a bonding position of the FA group or TIME group (the same applies to the following general formula (XVa)). Here, R ¹ represents a non-diffusible group having 8 to 32 carbon atoms, and R ² and R ³ are each independently a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group or a non-diffusible group having 8 to 32 carbon atoms. Represents a diffusible group. p is an integer of 1 to 4,
q represents an integer of 1 to 5. When p and q are 2 or more, R ² and R ³ may be the same or different from each other.

Representative examples of magenta couplers are shown in US Pat. Nos. 2,600,788, 2,369,489 and 234.
No. 3703, No. 2311082, No. 3152896
No. 35, 194529, 3062653, 29.
No. 08573, Japanese Patent Publication No. 47-27411,
JP-A-59-171956 and 59-162548.
No. 60-33552, No. 60-43659, No. 60-172982, and the like.
Of the magenta couplers, pyrazolone or pyrazoloazoles (pyrazolopyrazole, pyrazoloimidazole, pyrazolotriazole, pyrazolotetrazole, etc.)
Is preferred. Therefore, the magenta coupler residue (C
As p), those represented by the following general formulas (IIIa), (IVa) and (Va) are preferable.

[0089]

[Chemical 36]

Here, R ¹¹ represents a diffusion resistant group having 8 to 32 carbon atoms, and R ¹² represents a halogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, or a substituted phenyl group. Z represents a nonmetallic atom group necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring), The substituent may be a diffusion resistant group.

Typical examples of cyan couplers are US Pat. Nos. 2,772,162, 2,895,826 and 3,0028.
No. 36, No. 3034892, No. 2474293, No. 2423730, No. 2367531, and No. 30.
No. 41236, JP-A-56-99341,
57-155538, 57-204545, 58-189154, and 59-31953,
58-118643, 58-187928, 58-213748, U.S. Pat. No. 4,333,399.
No. 9 specification and the like. Of those cyan couplers, phenols or naphthols are preferable. Therefore, the cyan coupler residue (Cp) has the following general formulas (IVa), (VIIa), (VIIIa) and (IXa)
Those represented by are preferred.

[0092]

[Chemical 37]

Here, R ²¹ represents a diffusion resistant group having 8 to 32 carbon atoms, R ²² represents a halogen atom, a lower alkyl group or a lower alkoxy group, and r represents an integer of 1 to 3. r
When is 2 or more, R ^{22 s} may be the same or different.

Cp may be a so-called colorless coupler. Typical examples of colorless couplers are described in US Pat. Nos. 3,912,513 and 4,048,67,
It is described in JP-A No. 52-152721.
Representative examples of these non-color-forming coupler residues have skeletons represented by the following general formulas (Xa), (XIa) and (XIIa).

[0095]

[Chemical 38]

Here, R ³¹ represents a diffusion resistant group having 8 to ³² carbon atoms, and R ³² represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group.

[0097]

[Chemical Formula 39]

Here, R ³¹ represents a diffusion resistant group having 8 to 32 carbon atoms, and V represents an oxygen atom, a sulfur atom or --N.
Represents an (R ³³ ) -group. R ³³ is a hydrogen atom or has 1 carbon atom
Represents an alkyl group of 32.

[0099]

[Chemical 40]

Here, R ⁴¹ and R ⁴² are each independently an alkoxycarbonyl group, aminocarbonyl group, acyl group, alkoxysulfonyl group, alkoxysulfinyl group, sulfamoyl group, sulfinamoyl group, sulfonyl group, sulfinyl group, cyano group, It represents an ammonium mill group, a nitrogen-containing heterocycle bonded by a nitrogen atom, and the like.
R ⁴¹ and R ⁴² may combine to form a 5- or 6-membered ring.

In addition to the above, Cp may be a color-forming coupler residue which forms a black color by reacting with an oxidized product of a developing agent. Examples of those couplers include US Pat.
939231, 2181944, 233310.
No. 6, 4126461, West German patent (OL
S) 2644194 and 2650764. Specifically, those coupler residues are represented by the following general formulas (XIIIa), (XIVa) and (XVa).

[0102]

[Chemical 41]

R ⁵¹ is an alkyl group having 3 to 20 carbon atoms or a phenyl group (the phenyl group is substituted with a hydrogen group, a halogen atom, an amino group, an alkyl group having 1 to 20 carbon atoms or an alkoxy group). May be used). R ⁵² and R ⁵³ are each independently a hydrogen atom, a halogen atom,
It represents an alkyl group or an alkenyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. R ⁵⁴ represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group or another monovalent organic group, and r represents an integer of 1 to 3. When r is 2 or more, R ⁵⁴ may be the same as or different from each other.

Cp represented by the above general formulas (Ia) to (XVa) may form a multimer other than the dimer at a portion other than the coupling site, and may be bonded to the polymer at that portion. You may have.

In the general formula (II), the coupler residue represented by Cp has the structure represented by the above general formulas (Ia) to (XVa), and BALL is bound to the * mark, and -(TIME) _n -FA is bound to one of the sites.

In the general formula (II), the nondiffusible group represented by BALL is a polymer having a size and shape giving non-diffusibility to the coupler and having a plurality of leaving groups linked to each other. It may have an alkyl group and / or an aryl group that imparts non-diffusibility. In the latter case, the total number of carbon atoms in the alkyl group and / or aryl group is preferably about 8 to 32. B
ALL has a group for bonding to the coupling position of Cp, and typical examples thereof include -O- and -S.
-, - N = N -, - OCO -, - OSO 2 -, and is -N constituting the hetero ring =.

In the general formula (III), the group represented by RED has a skeleton of hydroquinone, catechol, o-aminophenol or p-aminophenol, and is an oxidation product of an aromatic primary amine developing agent and redox. React and subsequently undergo alkaline hydrolysis to-(TIME) _n -FA
It represents a group that releases a group (in the following general formulas (XVIa) to (XXIa), this is abbreviated as “FR”).

Specific examples thereof are represented by general formulas (XVIa) to (XXIa).

[0109]

[Chemical 42]

[0110]

[Chemical 43]

In the above formula, R ⁶¹ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group,
Aryloxy group, alkylthio group, arylthio group,
Cyano group, alkoxycarbonyl group, carbamoyl group,
It represents a sulfamoyl group, a carboxyl group, a sulfo group, a sulfonyl group, an acyl group, a carbonamido group, a sulfonamide group or a heterocyclic group, r represents an integer of 1 to 3, and p represents an integer of 1 to 4. When p and r are 2 or more, R ⁶¹ may be the same or different from each other, and two vic-positions are bonded to each other to form a benzene ring or a 5- to 7-membered heterocycle. It may be formed. R ⁶² represents an alkyl group, an aryl group, an acyl group, a carbamoyl group, a sulfonyl group or a sulfamoyl group. T ¹ represents a hydrogen atom or a group capable of splitting off upon hydrolysis under alkaline conditions. When two T ^1's are present in the molecule, they may be different from each other. As a typical example of T ¹ , a hydrogen atom,
Examples thereof include an acyl group, a sulfonyl group, an alkoxycarbonyl group, a carbamoyl group and an oxalyl group.

The timing group represented by TIME is described in US Pat. No. 4,248,962, JP-A-57-56.
No. 837, etc., the compound is released from Cp or BED by a coupling reaction or a redox reaction, and then FA is released by an intramolecular substitution reaction, British Patent 20
72363A, JP-A-57-154234, 57.
No. 188035, No. 56-114946, No. 57-
56837, 58-209736, 58-20
No. 9737, No. 58-209738, No. 58-209
Nos. 740 and 58-98728, which release FA by electron transfer through a conjugated system, and oxidation of aromatic primary amine developers as disclosed in JP-A-57-111536. Examples thereof include those that are coupling components capable of releasing FA by a coupling reaction with the body. These reactions may be carried out in one step or in multiple steps.

Further, as described above, a trivalent TIME that binds to the coupling site and the non-coupling site and FA is also preferable (an example of incorporation into a yellow coupler is disclosed in JP-A-58-209740). Have been described).

When FA is a group containing AD- (L) _m -X, AD may be directly bonded to the carbon atom at the coupling position, or L or X may be eliminated by a coupling reaction. If possible, these may be bound to the coupling carbon. What is known as a so-called 2-equivalent leaving group may be interposed between the coupling carbon and AD. These 2-equivalent leaving groups include an alkoxy group (eg methoxy), an aryloxy group (eg phenoxy), an alkylthio group (eg ethylthio), an arylthio group (eg phenylthio), a heterocyclic oxy group (eg tetrazolyloxy), Heterocyclic thio groups (eg pyridylthio), heterocyclic groups (eg hydantoinyl, pyrazolyl, triazolyl, benzotriazolyl). In addition, those described in British Patent Publication No. 2011391 can be used as FA.

The group capable of adsorbing to silver halide represented by AD is a nitrogen-containing heterocycle having a dissociable hydrogen atom (pyrrole, imidazole, pyrazole, triazole, tetrazole, benzimidazole, benzopyrazole, benzotriazole). , Lauryl, tetraazaindene, imidazotetrazole, pyrazolotriazole, pentaazaindene, etc.), a heterocycle having at least one nitrogen atom and another heteroatom (oxygen atom, sulfur atom, selenium atom, etc.) in the ring ( Oxazoles, thiazoles, thiazolines, thiazolidines, thiadiazoles, benzothiazoles, benzoxazoles, benzselenazoles, etc.), mercapto group-containing heterocycles (2-mercaptobenzthiazole, 2-mercaptopyrimidine, 2-mercaptobenzoxy). Sol, 1-phenyl-5-mercaptotetrazole, etc.), quaternary salt (quaternary salt of tertiary amine, pyridine, quinoline, benzthiazole, benzimidazole, benzoxazole, etc.), thiophenols, alkylthiols (cysteine, etc.) ), And = NC
Examples thereof include compounds having an S- partial structure (for example, thiourea, dithiocarbamate, thioamide, rhodanine, thiazolidinethione, thiohydantoin, and thiobarbituric acid).

[0116] Alkylene As the divalent linking group represented by L in the FA, alkenylene, phenylene, naphthylene, -O -, - S -, - SO -, - SO 2 -, - N = N
-, Carbonyl, amide, thioamide, sulfonamide, ureido, thioureido, heterocycle and the like. If one of the divalent linking groups constituting L is cleavable by the action of components in the developing solution (eg, hydroxide ion, hydroxylamine, sulfite ion, etc.), the fogging effect can be controlled. It can also be deactivated.

The group represented by X is a reducing compound (hydrazine, hydrazide, hydrazone, hydroquinone, catechol, p-aminophenol, p-phenylenediamine, 1-phenyl-3-pyrazolidinone, enamine, aldehyde, polyamine, acetylene. , Aminoborane, tetrazolium salts, quaternary salts such as ethylenebispyridinium salts, etc.) or compounds capable of forming silver sulfide during development (eg, thiosulfate, thioamide, dithiocarbamate, rhodanine, thiohydantoin, thiazolidinethione). , = NCS- partial structure, etc.) and the like. Among the groups represented by X, some of the groups capable of forming silver sulfide at the time of development have an adsorptivity for silver halide grains, and can also serve as an adsorptive group AD. The FR compounds used in the present invention and examples thereof are described in JP-A Nos. 57-150845, 59-50439, 59-157638, 59-170840 and 6
0-37556, 60-147029, 60-
It is described in each specification such as 128446.

An example of AD is shown below. The free bond is −
It binds to (L) _m- X and-(TIME) _n- .

Specific examples of the compounds used in the present invention are shown below.

[0120]

[Chemical 44]

[0121]

[Chemical formula 45]

[0122]

[Chemical formula 46]

[0123]

[Chemical 47]

[0124]

[Chemical 48]

[0125]

[Chemical 49]

[0126]

[Chemical 50]

[0127]

[Chemical 51]

[0128]

[Chemical 52]

[0129]

[Chemical 53]

[0130]

[Chemical 54]

[0131]

[Chemical 55]

[0132]

[Chemical 56]

[0133]

[Chemical 57]

[0134]

[Chemical 58]

[0135]

[Chemical 59]

[0136]

[Chemical 60]

[0137]

[Chemical formula 61]

[0138]

[Chemical formula 62]

[0139]

[Chemical formula 63]

The FR compound described above may be contained in any of the layers constituting the light-sensitive material, but is preferably contained in the silver halide emulsion layer. The addition amount of the FR compound used in the present invention is in the range of 10 ^-9 to 10 ^-1 mol, preferably 1 mol per 1 mol of silver halide contained in the FR compound-containing layer or the adjacent layer. It is in the range of 10 ⁻⁵ to 10 ⁻¹ mol.

When the FR compound is incorporated in the silver halide emulsion layer, a known method (for example, US Pat.
22027 specification) is utilized. For example, a method of dissolving in the following solvent and then dispersing in a hydrophilic colloid is used.

Examples of the solvent that can be used include the following. Phthalic acid alkyl ester (eg, dibutyl phthalate, dioctyl phthalate), phosphoric acid ester (eg, diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid ester (eg, acetyl citric acid) Tributyl), benzoic acid ester (eg, octyl benzoate), alkylamide (eg, diethyllaurylamide), fatty acid ester (eg, dibutoxyethylsuccinate, diethylazelate), trimesic acid ester (eg,
(Tributyl trimesate) or the like, or a boiling point of about 30 ° C.
Organic solvent at 150 ° C., for example, lower alkyl acetate such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone,
β-ethoxyethyl acetate, methyl cellosolve acetate, etc.

The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used. In addition, Japanese Patent Publication Sho 51-3985
The dispersion method using a polymer described in JP-A-51-59943 and JP-A-51-59943 can also be used. When the FR compound has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

The pre-fogged internal latent image type silver halide emulsion of the present invention 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 grains. More specifically, the silver halide emulsion is fixed on the transparent support in a fixed amount (0.5
~ 3 g / m ² ) and exposed to light for a fixed time of 0.01 to 10 seconds to give the following developer (internal developer)
When developed at 20 ° C. for 5 minutes, the maximum density measured by an ordinary photographic density measuring method was the same as the above, and the silver halide emulsion exposed in the same manner was developed with the following developing solution (surface type developing solution). Among them, 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-added 1000 ml Surface type developer Metol 2.5 g L-ascorbic acid 10.0 g NaBO ₂ .4H ₂ O 35.0 g KBr 1.0 g Water added 1000 ml

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, 56-22681, 59-2085
No. 40, No. 60-107641, No. 61-1337.
No. 62-215272, German Patent No. 2332802c2, Research Disclosure No. 23510 (issued in November 1983)
Patent disclosed on page 236; Specification of U.S. Pat. No. 4,789,627, which further has a silver chloride shell; JP-A 63-10160 and 6 regarding silver chlorobromide core-shell emulsion.
JP-A-3-47766 and Japanese Patent Application No. 1-2467
The core / shell type silver halide emulsions described in JP-A-63-191145 and JP-A-1-52146 relating to emulsions doped with metal ions 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. Further, the molar ratio of the silver halide of the core to the shell of the internal latent image type core / shell silver halide emulsion is 20/1 or less, and particularly preferably 1/100 or more.

The internal latent image type silver halide grains which have not been fogged in advance include Mn, Cu, Zn, Cd, Pb and Bi.
Alternatively, at least one metal selected from the group consisting of metals belonging to Group VIII of the periodic table may be incorporated. The amount of Mn, Cu, Zn, Cd, Pb, Bi or a metal belonging to Group VIII of the periodic table contained in the internal latent image type silver halide grains not previously fogged is 10 ⁻ per mol of silver halide. ⁹ to 10 ^-2 mol is preferred, 10
^-7 to 10 ^-3 mol is more preferable. P among the above metals
The use of b (lead), Ir (iridium), Bi (bismuth) and Rh (rhodium) is preferred. These metals are mixed reaction liquid in the form of a solution in which the metal (metal ion) is dissolved in an aqueous solution or an organic solvent when silver halide grains are formed while mixing and stirring a silver ion solution and an aqueous halogen solution. It can be incorporated in the silver halide grains by adding it (or coexisting in an aqueous halogen solution). Alternatively, after the silver halide grains are formed, they can be incorporated into the emulsion in the form of an aqueous solution of the above metal or a solution of the above metal dissolved in an organic solvent. In this case, it may be further covered with silver halide. The above-mentioned metal is usually added in the form of a metal complex salt or a metal compound such as an oxyacid salt or an organic acid salt of the metal. For the method of incorporating these metals, see US Pat. Nos. 3,761,276 and 4,
395478 and JP-A-59-216136
It is described in Japanese Patent Publication No.

The silver halide grains used in the present invention have a cubic shape, an octahedron shape, a dodecahedron shape and a tetradecahedron shape (JP-A-2-22).
3948), irregular crystal forms such as spheres, and JP-A-1-131547.
Emulsions in which tabular grains having a length / thickness ratio value of 5 or more, particularly 8 or more, described in JP-A No. 1-158429, occupy 50% or more of the total projected area of the grains may be used. . Further, it may be an emulsion having a composite form of these various crystal systems, or an emulsion composed of a mixture thereof. The composition of silver halide includes silver chloride, silver bromide, and mixed silver halide, and the silver halide preferably used in the present invention does not contain silver iodide or may contain silver iodide. 3 mol%
The following are silver (iodo) silver bromide, (iodo) silver chloride or (iodo) silver bromide. The average grain size of the silver halide grains (the grain diameter in the case of spherical grains or grains close to spheres, the vertical length in the case of cubic grains, and the average length based on the projected surface) is 1.5 μm. Hereinafter, 0.1 μm or more is preferable, but 1.2 μm or less is particularly preferable,
It is 0.2 μm or more. The particle size distribution may be narrow or wide, but in order to improve graininess, sharpness, etc., the number or weight of particles is within ± 40% of the average particle size, preferably within 30%, and most preferably ±. It is preferred to use in the present invention so-called "monodisperse" silver halide emulsions having a narrow grain size distribution such that 90% or more, especially 95% or more of all grains fall within 20%.

Further, in order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes or emulsions having the same size in the emulsion layers having substantially the same color sensitivity are used. A plurality of different particles can be mixed in the same layer or multilayer-coated 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 emulsion used in the present invention is preferably chemically sensitized inside or on the surface thereof by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization or the like alone or in combination. The chemical sensitization method for core particles is described in JP-A-2-199450 and JP-A-2-199449.
The method described in the publication can be used. JP-A-1-
In the presence of a mercapto compound as described in JP-A-197742, JP-A-1-254946 and JP-A-2-6.
You may add thiosulfinic acid, a sulfinic acid, and a sulfite as described in 9738 and 2-273735 gazette. For specific examples, see Research Disclosure No. 17643-III (issued in December 1978), page 23, etc.

The photographic emulsion used in the present invention is spectrally sensitized with a photographic sensitizing dye in a conventional manner. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes, and these dyes can be used alone or in combination. Further, the above dye and supersensitizer may be used in combination. For specific examples, see Research
Disclosure magazine No. 17643-IV (issued in December 1978), pages 23-24, etc. The photographic emulsion used in the present invention includes a photosensitive material manufacturing process,
An antifoggant or stabilizer may be incorporated for the purpose of preventing fog during storage or photographic processing or stabilizing photographic performance. For specific examples, see Research Disclosure No. 17643-VI
(Issued in December 1978) and E.I. J. By Birr
"Stabiliaution of Photographic Silver Hailde Emul
sion "(Focal Press), 1974.

In the present invention, various color couplers may be used in addition to the yellow coupler represented by the above formula (1) or (2). Typical examples of useful color couplers include naphthol or phenol compounds,
There are pyrazolone or pyrazoloazole compounds and open-chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are "Research Disclosure".
Magazine No. 17643 (issued December 1978) page 25, VI
Item I-D, ibid. 18717 (issued in November 1979)
And the compounds described in JP-A-62-215272 and the patents cited therein. Yellow couplers preferably used in the present invention include, for example, US Pat. Nos. 3,933,501 and 4,022,620.
Nos. 4,326,024, 4,401,752, respective specifications, Japanese Patent Publication No. 58-10739, and British Patent No. 142.
Those described in the specifications of No. 5020 and No. 1476760 are preferable.

Colored couplers for correcting unnecessary absorption in the short wavelength region of the dyes produced, couplers in which the coloring dyes have an appropriate diffusibility, non-color couplers, and development inhibitors released in association with the coupling reaction. DIR couplers and polymerized couplers can also be used. A coupler which releases a photographically useful residue upon coupling is also preferably used in the present invention. DIR couplers that release development inhibitors are Research Disclosure N
o. 17643, patents described in paragraphs VII to F, JP-A-57-151944, 57-154234, and 60-
Preferred are those disclosed in 184248, U.S. Pat. No. 4,248,962, and those disclosed in JP-A-63-146035. 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 or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. The light-sensitive material of the present invention includes
A color fog preventing agent or a color mixing preventing agent can also be used. Typical examples of these are JP-A-62-215272 and 185.
The compounds described on page 193 can be mentioned. As a compound that releases a photographically useful group, there is disclosed in Japanese Patent Laid-Open No.
No. 3-153540, No. 63-259555,
Japanese Patent Laid-Open Nos. 2-61636, 2-244041, and 2
The compounds described in each publication of -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 include those described in JP-A No. 62-215272, pages 121 to 125. Dyes which prevent irradiation and halation may be used in the light-sensitive material of the present invention (for example, the compounds described in JP-A Nos. 2-85850 and 2-89047) may be used. May be a solid microcrystal dispersion method.), Ultraviolet absorbers, plasticizers, optical brighteners, matting agents, air antifoggants, coating aids, hardening agents, antistatic agents and slipperiness improvers. Etc. can be added. Typical examples of these additives are Research
Disclosure magazine No. 17643VII to XIII (1
Issued December 1978) pages 25-27, and 1871
6 (issued in November 1979), pages 647-651.

The light-sensitive material of the present invention has at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer on the support. The order of these layers can be arbitrarily selected as necessary. The preferred order of layer arrangement is from the support side to red-sensitive, green-sensitive, and blue-sensitive or from the support side to green-sensitive, red-sensitive, and blue-sensitive. 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, but in some cases, the green-sensitive layer contains a yellow coupler and a magenta coupler. It is also possible to use different combinations such as mixed use. In the light-sensitive material of the present invention, in addition to the silver halide emulsion layer, an auxiliary layer such as a non-light-sensitive layer such as a protective layer, an intermediate layer, a filter layer, an antihalation layer, a back layer and a white reflective layer may be appropriately provided. preferable.

The fog treatment of the photographic light-sensitive material of the present invention is carried out by the following "optical fog method" and / or "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 the light source for the fogging exposure, for example, JP-A-56-137350 and JP-A-58-70223 are used.
A light source having a high color rendering property (as close to white as possible) as described in each publication is preferable. The illuminance of light is 0.01 to 20
00 lux, preferably 0.05 to 30 lux, more preferably 0.05 to 5 lux 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 permeation of the liquid to the light fog exposure is generally 2 seconds to 2 minutes, preferably 5 seconds to 1 minute, and more preferably 10 seconds to 30 seconds. The exposure time for fogging is generally 0.01 seconds to 2 minutes, preferably 0.1.
Seconds to 1 minute, more preferably 1 second to 40 seconds.

In the present invention, the nucleating agent used when the so-called "chemical fog method" is applied can be contained in the photosensitive material or in the processing solution for the photosensitive material. A method in which it is contained in a light-sensitive material is preferably used. Here, the nucleating agent is a substance which acts when the surface latent image processing of the internal latent image type silver halide emulsion which has not been fogged in advance and directly forms a positive image. In the present invention, the fog treatment is preferably performed using a nucleating agent. When it is contained in the light-sensitive material, it is preferably added to the internal latent image type silver halide emulsion layer, but as long as it is diffused during coating or during processing and the nucleating agent is adsorbed on silver halide, It may be added to a layer such as an intermediate layer, an undercoat layer or a back layer. Examples of the nucleating agent that can be used in the present invention include, for example, Research Disclosure Magazine,
No. 22534 (January 1983), pp. 50-54, ibid., No. 15162 (November 1976) 76-77
Page, the same magazine No. 23510 (November 1983) 346-
Examples thereof include quaternary heterocyclic compounds and hydrazine compounds described on page 352. Two or more kinds of these nucleating agents may be used in combination.

In the present invention, the nucleating agents described in the following publications can be preferably used. That is, a quaternary heterocyclic compound represented by the general formula (N-I) described on pages 510 to 514 of JP-A-3-155543 and a general formula described on pages 60-65 of JP-A-3-95546. A hydrazine compound represented by (N-II);
Representative nucleating agents represented by the above general formulas (N-I) 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. When the nucleating agent is added to the processing solution, it is contained in the developing solution or the low pH pre-bath as described in JP-A-58-178350. When a nucleating agent is added to the treatment liquid, the amount used is 10 ^-8 to 10 ^-1 per liter.
The amount is preferably mol, and more preferably 10 ⁻⁷ to 10 ⁻³ mol. In the present invention, the nucleating agent may be contained in the hydrophilic colloid layer adjacent to the silver halide emulsion layer, but is preferably contained in the silver halide emulsion layer. The amount added 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, but it is about 1 × per mol of silver in the silver halide emulsion. A range of 10 ⁻⁸ to about 1 × 10 ⁻² mol is practically useful, with a preferred range of about 1 × 10 ⁻⁵ to about 1 × 10 ⁻³ mol per mol of silver.

When a nucleating agent is used, it is preferable to use a nucleating accelerator for promoting the action of the nucleating agent. The nucleation accelerator does not substantially function as a nucleating agent,
It refers to a substance that promotes the action of a nucleating agent to increase the maximum density of a direct positive image and / or accelerates the development time necessary to obtain a certain maximum density of a direct positive image. Such a nucleation accelerator has at least one mercapto group which may be optionally substituted with an alkali metal atom or an ammonium group. Thiadiazoles, oxadiazoles, benzotriazoles, tetrazaindenes, triazaindenes and pentazaindenes and compounds described in JP-A-63-106656, pages 5 to 16 can be mentioned. . In addition, JP-A-63-
No. 226652, No. 63-106656, No. 63-8
The compounds described in No. 740 can be mentioned.

Two or more of these nucleation accelerators can be used in combination. The nucleation accelerator can be contained in the light-sensitive material or the processing solution, but in the light-sensitive material, it may be contained in the internal latent image type silver halide emulsion or other hydrophilic colloid layers (intermediate layer, protective layer, etc.). Preferably contained in Particularly preferred is in a silver halide emulsion or its adjacent layer. 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. When the nucleation accelerator is added to the processing solution, that is, the developing solution or its pre-bath, it is preferably 10 ^-8 to 10 ^-3 mol, and more preferably 10 ^-7 to 10 ^-4 mol per liter. is there.

Known photographic additives that can be used in the present invention are described in Research Disclosure No. 17643
(December 1978) and the same No. 18716 (197
(November 1997), 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 24 Page 5 antifoggant page 24-25 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 anti-stain agent 25 Page right column 8 Dye image stabilizer page 25 9 Hardener 26 page 651 Left column 10 Binder 26 page 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 such as a plastic film, paper or cloth usually used for photographic light-sensitive materials or a rigid support such as glass, earthenware or metal. It is coated on a support.
What is useful as a flexible support is a film, paralayer or α-olefin polymer made of a semi-synthetic or synthetic polymer such as cellulose nitrate, cellulose acetate, cellulose acetate acetate, polystyrene, polyvinyl chloride, polyethylene terephthalate, and polycarbonate. 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
No. 8, No. 3508947 and the like may be used to simultaneously apply multiple layers.

The invention of a color image forming method using the direct positive color photographic light-sensitive material will be described below. The direct positive color photographic light-sensitive material of the present invention can be subjected to development processing by a conventionally known development processing method after imagewise exposure, but it is preferably processed by another color image forming method of the present invention. The color image forming method of the present invention is characterized in that after the above direct positive color photographic light-sensitive material is imagewise exposed, it is processed with a development processing solution containing a color developing agent represented by the formula (D) to obtain a positive color image. .

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. Flash light sources such as natural light (sunlight), incandescent lamps, halogen atom filled lamps, mercury lamps, fluorescent lamps and strobes or metal burning flash bulbs are common. A gas, a dye solution or a semiconductor laser, a light emitting diode, or a plasma light source which emits light in a wavelength range from ultraviolet to infrared can also be used as the recording light source. In addition, a linear or planar micro-shutter array using a phosphor screen (CRT, etc.) emitted from a phosphor excited by an electron beam, liquid crystal (LCD), lanthanum-doped lead titan zirconate (PLZT), or the like. It is also possible to use an exposure means combining the above light sources. If necessary, the spectral distribution used for exposure can be adjusted with a color filter. In particular, by using a high-density beam light such as a gas laser (He-Ne laser, Ar laser, He-Cd laser) or various lasers such as a semiconductor laser as a light source, and moving this light beam relative to a photosensitive material. An exposure means of so-called scanning exposure system (scanner system) for imagewise exposure is preferable for exposing the direct positive color photographic light-sensitive material of the present invention. As the scanning exposure device, for example, a color copying machine AP-5000 manufactured by Fuji Photo Film Co., Ltd. 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 each 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 is
A practical range depending on the pixel density is 50 to 200.
It is 0 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 for this 1 pixel is 10 ^−3.
Scanning exposure is preferably performed under the condition of not more than seconds (preferably 10 ⁻⁶ to 10 ⁻⁴ seconds).

In the general formula (D) showing the developing agent used in the present invention, R ^D1 preferably has 1 to 1 carbon atoms.
The alkyl group of 8 and particularly preferable ones are a methyl group, an ethyl group, a butyl group, a methoxymethyl group and the like. R ^D2 is preferably an alkylene group having 2 to 6 carbon atoms, and particularly preferable ones are an ethylene group and a trimethylene group. Preferred specific examples of the developing agent represented by formula (D) are shown below.

[0167]

[Chemical 64]

[0168]

[Chemical 65]

The amount of the developing agent represented by formula (D) used is preferably about 0.1 g to about 20 g, and more preferably about 0.5 g 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 it is preferable that the developing solution contains the developing agent represented by the general formula (D) in an amount of 50 mol% or more. The developing solution used in the development processing method of the present invention is the same as the conventional color developing solution except that the developing agent is the above-mentioned 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 generally subjected to desilvering treatment including bleaching and fixing treatment, and further, after desilvering treatment, washing and / or stabilization treatment is generally performed. Regarding the series of processing steps described above, Japanese Patent Application Laid-Open No. HEI 3
The methods described on pages 380 to 381 of JP-A-120537 can be preferably used.

The direct positive color photographic light-sensitive material of the present invention comprises
There are various uses, but color printing, color copying,
Suitable for making color proofs. The method for producing a color proof of the present invention is a method for producing a color proof by utilizing a conventional method for producing a color proof, in addition to using the direct positive color photographic light-sensitive material of the present invention as described above. That is, the method for producing a color proof of the present invention is a cyan halftone dot image film, a magenta halftone dot image film, a yellow halftone dot image film obtained by subjecting the direct positive color photographic light-sensitive material of the present invention to color separation and halftone image conversion. And a black halftone dot image film, which is sequentially exposed to red light, green light and blue light, and then subjected to color development processing as described above to form a color image. This method is, for example, a fine checker F manufactured by Fuji Photo Film Co., Ltd.
It can be easily performed by using C850H (exposure time: about 0.02 to 0.3 seconds).

[0171]

【Example】

Example 1 Preparation of Sample 101 A paper support (thickness 10) laminated on both sides with polyethylene.
(0 micron), the following 1st layer or 11th layer was applied to the front side, and the 12th to 13th layers were applied to the back side to form a color photographic light-sensitive material. The polyethylene coated on the first layer contains titanium oxide (4 g / m ² ) as a white pigment and a trace amount (0.003 g / m ² ) of ultramarine as a bluing dye (the chromaticity of the surface of the support is L 88 in the ^* , a ^* , and b ^* systems.
It was 0, -0.20, -0.75.

(Photosensitive layer composition) The components and coating amount (g /
m ² unit). However, the addition amount of the sensitizing dye is shown in mol per mol of silver. For silver halide, the coating amount in terms of silver is shown. The emulsion used for each layer is Emulsion E described below.
It was made by changing the particle size by changing the temperature according to the manufacturing method of M-1. However, as the emulsion for the 11th layer, a Lippmann emulsion which was not surface-chemically sensitized was used.

First Layer (Antihalation Layer) Black Colloidal Silver ...... 0.10 Color Mixing Inhibitor (Cpd-7) ...... 0.05 Color Mixing Inhibitor Solvent (Solv-4, 5 Equivalents) ...... 0. 12 Gelatin ... 0.70

Second layer (intermediate layer) Gelatin: 0.70 Dye (Cpd-32): 0.005

Third Layer (Red Sensitive Layer) Silver bromide spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3 equivalents 5.4 × 10 ⁻⁴ ) (average grain size 0.40 μ, Grain size distribution 10%, octahedron) ...... 0.25 gelatin ...... 0.70 Cyan coupler (ExC-1, 2, 3 1: 1: 0.2) ...... 0.30 Anti-fading agent (Cpd- 1,2,3,4,30 each equivalent) ...... 0.18 stain inhibitor (Cpd-5,15 each equivalent) ...... 0.003 coupler dispersion medium (Cpd-6) ...... 0.30 coupler Solvent (Equivalent amounts of Splv-1, 3, 5) ... 0.12

4th layer (intermediate layer) Gelatin: 1.00 Color mixing inhibitor (Cpd-7): 0.08 Color mixing agent solvent (Solv-4, 5 equivalents): 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 grain size 0.40 μ, grain size distribution 10%, eight) 0.20 Gelatin ...... 1.00 Magenta coupler (ExM-1, 2 each equivalent) ...... 0.11 Yellow coupler (ExY-1) ...... 0.03 Anti-fading agent (Cpd-9, 26) , 30 and 31 are each equivalent) 0.15 Anti-staining agent (Cpd-10, 11, 12, 13 in 10: 7: 7: 1 ratio) ... 0.025 Coupler dispersion medium (Cpd-6) ) ...... 0.05 Coupler solvent (Solv-4, 6 each equivalent) ...... 0.15

6th layer (intermediate layer) Same as 4th layer

Seventh Layer (Blue Sensitive Layer) Silver bromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6 each equivalent weight 3.5 × 10 ⁻⁴ ) (average grain size 0.60 μ, grain size Distribution 11%, octahedral) 0.32 Gelatin 0.80 Yellow coupler (ExY-2, 3 equivalents) 0.35 Anti-fading agent (Cpd-14) 0.10 Anti-fading Agent (Cpd-30) ... 0.05 Anti-staining agent (Cpd-5, 15 in 1: 5 ratio) ... 0.007 Coupler dispersion medium (Cpd-6) ... 0.05 Coupler solvent (Splv- 2) ...... 0.10

Eighth layer (ultraviolet absorber-containing layer) Gelatin: 0.60 Ultraviolet absorber (equal amounts of Cpd-2, 4, 16) 0.40 Color-mixing inhibitor (Cpd-7, 17) Amount) ... 0.03 Dispersion medium (Cpd-6) ... 0.02 UV absorber solvent (Solv-2, 7 each equivalent amount) ... 0.08 Anti-irradiation dye (Cpd-18, 19, 20) , 21, 27 in the ratio of 10: 10: 13: 15: 20) .... 0.05

Ninth Layer (Protective Layer) Fine grain silver iodobromide (silver bromide 99 mol%, average size 0.05 μ) ... 0.03 Acrylic modified copolymer of polyvinyl alcohol (molecular weight 50,000) ...... 0 .01 Polymethylmethacrylate particles (average particle size 2.4μ) and silicon oxide (average particle size 5μ) Equivalent ... 0.05 Gelatin ... 0.05 Gelatin hardening agent (H-1, H-2 etc.) Amount) ...... 0.18

10th Layer (Back Layer) Gelatin ... 2.50 Ultraviolet Absorber (Equivalent Amount of Cpd-2, 4, 16) 0.50 Dye (Cpd-18, 19, 20, 21, 27) Equal amount) ... 0.06

Eleventh Layer (Back Layer Protective Layer) Polymethylmethacrylate particles (average particle size 2.4 μ) and silicon oxide (average particle size 5 μ) Equivalent ... 0.05 Gelatin ... 2.00 Gelatin hardener (Equivalent amount of H-1 and H-2) ... 0.14

Preparation of Emulsion EM-1 An aqueous solution of potassium bromide and silver nitrate was simultaneously added to an aqueous gelatin solution at 65 ° C. over 15 minutes with vigorous stirring,
Octahedral silver bromide grains having an average grain size of 0.23 μm were obtained. At this time, 0.3 g of 3,4-dimethyl-1,3 per mol of silver was used.
-Thiazolin-2-thione was added. 1 silver in this emulsion
Chemical sensitization was carried out by sequentially adding 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) per mol and heating at 75 ° C. for 80 minutes. Using the particles thus obtained as a core, the particles are further grown in the same precipitation environment as the first time,
Finally, an octahedral monodisperse core / shell silver bromide emulsion having an average grain size of 0.4 μ was obtained. Coefficient of variation of particle size is about 10%
Met. To this emulsion were added 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mol of silver.
The mixture was heated at 0 ° C. for 60 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion.

ExZK-1 is used as a nucleating agent in each photosensitive layer.
And ExZK-2 are 10 ^-3 for silver halide,
10 ^-2 % by weight, Cpd-22, 28 as a nucleation accelerator,
29 were used at 10 ^-2 wt% each. Further, alkanol XC (Du Pont) and sodium alkylbenzenesulfonate were used as emulsification / dispersion aids in each layer, and succinate and Magefac F-120 (manufactured by Dainippon Ink and Chemicals) were used as coating aids. In the silver halide and colloidal silver-containing layer, (Cpd-23, 24 and 25 equivalent amounts) was used as a stabilizer. This sample was designated as sample number 101. The compounds used in the examples are shown below.

[0186]

[Chemical formula 66]

[0187]

[Chemical formula 67]

[0188]

[Chemical 68]

[0189]

[Chemical 69]

[0190]

[Chemical 70]

[0191]

[Chemical 71]

[0192]

[Chemical 72]

[0193]

[Chemical formula 73]

[0194]

[Chemical 74]

[0195]

[Chemical 75]

[0196]

[Chemical 76]

Solv-1 Di (2-ethylhexyl) sebacate Solv-2 Trinonyl Phosphate Solv-3 Di (3-methylhexyl) phthalate Solv-4 Tricresyl Phosphate Solv-5 Dibutylphthalate Solv-6 Trioctyl Phosphate Solv- 7 Di (2-ethylhexyl) phthalate

H-1 1,2-bis (vinylsulfonylacetamido) ethane H-2 4,6-dichloro-2-hydroxy-
1,3,5-triazine Na salt

ExZK-1 7- (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-todecyloxycarbonylethoxycarbonyl) phenylcarbamoyl] -4
-Hydroxy-1-naphthylthio} tetrazole-1-
Ill] phenyl} ureido] benzenesulfonamide}
Phenyl] -1-olmylhydrazine

(Preparation of Samples 1 to 5) In preparation of the above-mentioned Sample 101, instead of the yellow coupler (ExY-2, 3) contained in the seventh layer (blue sensitive layer), yellow shown in Table 8 was used. Corresponding samples 1 to 6 (samples of the present invention) were prepared in the same manner as the sample 101, except that the coupler was changed and the same amount was added.

[Evaluation as color photographic light-sensitive material] Each sample prepared as described above was measured at 2854 ° K, 100
Exposure was performed through the wedge for 1/10 seconds with light having a color temperature of CMS. After exposure, color development processing was performed under the processing conditions shown below.

[Processing conditions] Processing step time Temperature Color development 135 seconds 38 ° C. Bleach fixing 60 34 ° C. Water washing (1) 40 32 ° C. Water washing (2) 40 32 ° C. Dry 30 80 ° C.

Color developer A D-Sorbit 0.15 g Sodium naphthalenesulfonate / formalin condensate 0.15 g Nitrilotris (methylenephosphonic acid) pentasodium salt 1.8 g Ethylenetriaminepentaacetic acid 0.5 g 1-Hydroxyethylidene -1,1-Diphosphonic acid 0.15 g Diethylene glycol 12.0 ml Benzyl alcohol 13.5 ml Potassium bromide 0.70 g Benzotriazole 0.003 g Sodium sulfite 2.4 g Disodium-N, N-bis (sulfonate) hydroxyl Amine 8.0 g Triethanolamine 6.0 g N-Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 6.0 g Potassium carbonate 30.0 g Optical brightener (diaminostilbe System) 1.3 g Water was added 1000 ml pH (25 ° C) (pH adjusted with KOH or sulfuric acid) 10.30

Bleach-fixing solution Ethylenediaminetetraacetic acid ・ disodium ・ dihydrate 4.0 g Ethylenediaminetetraacetic acid ・ Fe (III) ・ Ammonium ・ dihydrate 55.0 g Ammonium thiosulfate (750 g / l) 168 ml p-toluenesulfin Sodium acid salt 30.0 g Ammonium sulfite 35.0 g 5-Mercapto-1,3,4-triazole 0.5 g Ammonium sulfate 10.0 g Water was added to 1000 ml pH (25 ° C) (pH adjustment with ammonia water or acetic acid) ) 6.50

Washing water Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.50

The density of the yellow image of each sample obtained by performing the above processing was measured, and the maximum density (Dmax) and the minimum density (Dmin) were obtained. The results are shown in Table 8 below.

Table 8 Sample No. 7th layer yellow image density Low coupler maximum density Minimum density 101 (Comparative example) ExY-2, 3 2.03 0.13 1 (invention) Y-2 2.160 .12 2 (present invention example) Y-7 2.17 0.12 3 (present invention example) Y-14 2.19 0.12 4 (present invention example) Y-30 2.18 0.12 5 (present Invention Example) Y-42 2.17 0.12 6 (Invention Example) Y-52 2.19 0.12

As is apparent from the results shown in Table 8 above, when the color photographic light-sensitive materials containing the yellow coupler according to the present invention (Samples 1 to 6 of the present invention) were used, they were used for comparison including the conventional yellow coupler. It is possible to obtain a yellow image having a higher maximum (image) density and a lower minimum (image) density than the color photographic light-sensitive material (Comparative Sample 101).

Example 2 (Preparation of Samples 7 to 9) In the preparation of Sample 101 of Example 1 above, the compounds (I-8, II-3, and III-) which release the following fogging agents and the like into the seventh layer were prepared. Samples 7 to 9 (comparative samples) were prepared in the same manner as Sample 101, except that 6) was added in an amount of 0.3 g / m ² .

(Preparation of Samples 10 to 12) In the preparation of Sample 3 described above, the same amount of the compound (I-8, II-3, and III-6) that releases the fogging agent used above was added to the seventh layer. Samples 10 to 12 (samples of the present invention) corresponding to each sample were prepared in the same manner as sample 3 except for the above. For each sample prepared as described above, in the same manner as in Example 1 above,
Exposure and color development processing were performed. Then, the density of the obtained yellow image of each sample was measured by the same method as in Example 1 above, and the maximum density (Dmax) and the minimum density (Dmin) were obtained. The results are shown in Table 9 below. In addition, Table 9 also shows the data of the sample 101 obtained in Example 1.

Table 9 Sample No. 7th layer No. 7th layer Yellow image density Low coupler Compound maximum density Minimum density 101 (Comparative example) ExY-2, 3 ... 2.03 0.13 7 (Comparative example) ExY-2, 3 I-8 2.06 0.13 8 (〃) 〃 II-3 2.07 0.13 9 (〃) 〃 III-6 2.06 0.13 10 (Example of the present invention) Y- 14 I-8 2.27 0.11 11 (〃) 〃 II-3 2.28 0.11 12 (〃) 〃 III-6 2.30 0.11 As is clear from the results shown in Table 9 above. And a color photographic light-sensitive material containing the above compound (samples 10 to 12 of the invention).
Is used, a yellow image having a high maximum image density and a low minimum image density can be obtained.

Example 3 (Evaluation as color photographic light-sensitive material) Each sample (101 (comparative sample), 10 (inventive sample) and 1 of Example 2 above.
2 (invention sample)) in the same manner as in Example 2 above.
Exposure and color development processing were performed. However, as the color developing solution, color developing solution B having the following composition was used in place of color developing solution A. Then, the density of the obtained yellow image of each sample was measured by the same method as in Example 1 above, and the maximum density (Dmax) and the minimum density (Dmin) were obtained. The results are shown in Table 10 below. In addition, in Table 10, above-mentioned Example 2
The data obtained by (using color developer A) are also shown.

Color developer BD-Sorbit 0.15 g sodium naphthalenesulfonate / formalin condensate 0.15 g nitrilotris (methylenephosphonic acid) pentasodium salt 1.8 g diethylenetriaminepentaacetic acid 0.5 g 1-hydroxyethylidene- 1,1-Diphosphonic acid 0.15 g Diethylene glycol 12.0 ml Benzyl alcohol 13.5 ml Potassium bromide 0.70 g Benzotriazole 0.003 g Sodium sulfite 2.8 g Hydroxylamine 1/2 sulfate (sulphonate) hydroxylamine 4.5 g Triethanolamine 6.5 g 4- [N-Ethyl-N- (β-hydroxyethyl) amino] aniline Sulfuric acid / 1/2 hydrate 4.2 g Potassium carbonate 30.0 g Optical brightener (Diaminostilbene type) 1.3 g Add water to 1,000 ml pH (25 ° C) (pH adjusted with KOH or sulfuric acid) 10.35

Table 10 Sample No. 7th layer No. 7th layer color development Yellow image density Low coupler compound Developer maximum density Minimum density 101 (Comparative example) ExY-2, 3 ... A 2.03 0.13 101 (〃) ExY-2, 3 ...... B 1.96 0.12 10 (Example of the present invention) Y-14 I-8 A 2.27 0.11 10 (〃) B 〃 B 2.31 0.10 12 (Examples of the present invention) III-6 A 2.30 0.11 12 (〃) 〃 〃 B 2.35 0.10 As is clear from the results shown in Table 10 above, the yellow coupler according to the present invention was used. When the color photographic light-sensitive materials containing the same (Samples 7 and 9 of the present invention) are used and processed with a color developing solution containing a specific developing agent according to the present invention, the maximum (image) density is higher and the minimum (image) density is higher. It is possible to obtain a yellow image having a low image quality.

Example 4 Among the samples used in the above Example 2, Sample 101, Sample 10 and Sample 12 were used, and a plate making film having a halftone image was used using a fine checker FC850H manufactured by Fuji Photo Film Co., Ltd. , And then 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 and SC- manufactured by Fuji Photo Film Co., Ltd.) 42 filters) were sequentially exposed. At that time, a plate-making film for an unimage and a black image was overlapped with each other during red exposure, a plate-making film for a magenta image and a black image was overlapped during green exposure, and a plate-making film for a yellow image and a black image was further overlapped during blue exposure. A color proof was created in this way. In addition,
The image formation in this case was performed according to the color development processing (processing using the color developing solution B) according to Example 3 above. The minimum halftone dot area of the color-proof yellow image obtained as described above was observed with a 100-fold magnifying glass. The results are shown in Table 11 below.

Table 11 Sample No. 7th layer No. 7th layer Color development Yellow image low coupler compound Developer Minimum dot area 101 (Comparative example) ExY-2, 3 ... B 3% or more 10 (Invention) Example) Y-14 I-8 B 2% 12 (Example of the present invention) 〃 III-6 B 2%

As is clear from the results shown in Table 11 above, the color photographic light-sensitive materials containing the yellow coupler of the present invention (Samples 10 and 12 of the present invention) were able to reproduce up to 2% halftone dot image. The color photographic light-sensitive material of Comparative Example (Comparative Sample 101) could not reproduce a halftone dot image of 2% and could reproduce only a halftone dot image of 3% or more.

Example 5 As a light source, a helium-neon gas laser (wavelength 63
3 nm and 543 nm) and argon laser (wavelength 4
58 nm), a light flux with a diameter of 80 μm at a pitch of 100 μm is moved perpendicularly to the scanning direction by a scanning exposure of 1.6 m / s, and a sequential scanning exposure (substantial exposure time of about 5 × 10 ⁻⁵ I assembled a device that can. Using this apparatus, the comparative sample 101 and the sample 10 were exposed and then treated with the treatment liquid B, and the reproducibility of the halftone image of the obtained image was evaluated. As a result, the color photographic light-sensitive material of the present invention (Invention sample 10) was able to satisfactorily reproduce up to a 2% halftone dot image, while the color photographic light-sensitive material of the comparative example (Comparative sample 101) was 4% halftone dot. I could only reproduce the image.

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Claims (4)

[Claims] 1. A blue-sensitive layer, a green-sensitive layer and a red-sensitive layer containing an internal latent image type silver halide grain not previously fogged and a color image-forming coupler on a support, and a non-photosensitive layer adjacent thereto. In a direct positive color photographic light-sensitive material having at least one of each of the following, the blue-sensitive layer color image-forming coupler is represented by the following formula (1) or (2): general formula (1) General formula (2) (In the formula, X ₁ and X ₂ each represent an alkyl group, an aryl group or a heterocyclic group, X ₃ represents an organic residue forming a nitrogen-containing heterocyclic group with> N-, and Y represents an aryl group or a heterocyclic group. Represents a cyclic group, and Z represents a group which leaves when the coupler represented by the general formula reacts with an oxidized product of a developing agent.), And contains at least one yellow coupler represented by
And at least one of the above-mentioned photosensitive layer or non-photosensitive layer
A direct positive color photographic light-sensitive material, wherein the layer contains a compound which releases a fogging agent or development accelerator or a precursor thereof in response to developed silver. 2. The color photographic light-sensitive material according to claim 1 having the following formula (D): (Wherein 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). A method for forming a color image, which comprises processing. 3. The cyan photographic halftone dot image film, the magenta halftone dot image film, the yellow halftone dot image film, and the black ink plate obtained by color separation and halftone image conversion of the color photographic light-sensitive material according to claim 1. Using halftone image film,
A method for producing a color proof, which comprises sequentially exposing with red light, green light, and blue light, and then performing color development processing. 4. A color image forming method, which comprises subjecting the color photographic light-sensitive material according to claim 1 to scanning exposure for an exposure time of 10 ⁻³ seconds or less per pixel, and then performing color development processing.