JPH05150432A - Image forming method - Google Patents

Abstract

PURPOSE:To obtain a cyan image and a yellow image good in color development hue (color reproducibility) and superior in color development performance. CONSTITUTION:The direct positive color photographic sensitive material has nonprefogged internal latent image type silver halide emulsion layers each containing a cyan coupler represented by formula I and an acylacetanilide type yellow coupler represented by formula II, and this photographic sensitive material is processed with a developing agent represented by formula III. In formulae I-III, Y is a nonmetallic atomic group necessary to form a 3-to 8-membered hetero ring together with the N atom without directly combining with this; L is alkylene; Z is H or a group to be released by coupling; Ar is aryl; R<21> is a univalent group except H and does not combine with Q<21> to form a ring; Q<21> is a nonmetallic atomic group necessary to form a ring together with the C atom; R<41> is alkyl; and R<42> is alkylene.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method using a direct positive color photographic light-sensitive material utilizing an internal latent image type silver halide emulsion, which makes it possible to directly obtain a positive image. More specifically, the present invention relates to an image forming method using a direct positive color photographic light-sensitive material suitable for producing a color proof used for plate inspection and adjustment in color plate making and printing processes.

[0002]

BACKGROUND OF THE INVENTION Photographic processes for obtaining direct positive images without the need for reversal processing steps or negative films are well known. As a method for forming a positive image using a conventionally known direct positive color silver halide photographic light-sensitive material, there is a method using an internal latent image type silver halide emulsion which has not been fogged in advance. This method is a method for directly obtaining a positive color image by subjecting a photographic light-sensitive material to image development and then performing surface development after or after fog treatment. The internal latent image type silver halide photographic emulsion which is not previously fogged is a type of halogenated type in which a silver halide grain has a photosensitive nucleus mainly inside and a latent image is mainly formed inside the grain by exposure. A silver photographic emulsion. Various techniques have been known so far in this field. For example, US Pat. No. 2,592.
No. 250, No. 2466957, No. 2497875,
No. 2588982, No. 3317322, No. 3761
No. 266, No. 3761276, No. 3796577 and British Patent No. 11513363, No. 1155053.
Nos. 1011062 and 1011062 are the main ones. The formation mechanism of the direct positive image is explained as follows. That is, when imagewise exposure is performed, a so-called internal latent image is formed on the silver halide, and then a fog treatment is performed to cause a surface desensitizing action due to the internal latent image (that is, the halogen in the exposed portion is affected). Development nuclei (fog nuclei are not generated on the surface of silver halide), development nuclei are selectively generated only on the surface of unexposed areas of silver halide, and then normal surface development processing is performed to unexpose the unexposed areas. A photographic image (positive image) is formed on. The fog treatment method includes a so-called "light fog method" for exposing the entire photosensitive layer, and a "chemical fog method" for using a nucleating agent. A direct positive color silver halide photographic light-sensitive material using an internal latent image type silver halide emulsion which has not been previously fogged as described above has been accepted in recent years due to the simplicity of its processing step and has been used for copy applications and the like. Is coming.

The working process of the color printed matter includes the steps of color-separating a color original and converting it into a halftone dot image to produce a transmission type halftone dot image. A printing plate is made from the obtained transmission type halftone dot image, but prior to this, the final printed matter (main printing)
There is a step of inspecting the state, characteristics, etc., and performing necessary calibration (color calibration). As a color proofing method, conventionally, a method of preparing 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-56-50121).
7 and 59-97140). However, all of these methods require superposition and transfer of images, and also require superposition and transfer of a plurality of figures, and the process is complicated and requires a lot of time and cost. .. JP-A-56-104335 discloses that
A method of producing a color proof using a color photographic light-sensitive material has been disclosed, and this method has major advantages in terms of simplicity of process and low cost, and is also characterized by excellent tone reproducibility. The method for producing a color proof using the above color photographic light-sensitive material uses a silver halide color photographic light-sensitive material of a coloring method having a continuous tone, to which 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 the features that the process is simple and easy to automate as compared with the various methods described above. There are several possible silver halide color photographic light-sensitive materials that can be used in such color proofs. Among them, the transmission type black and white halftone image used in the production process of the color printed matter described above is often a positive type especially in Japan and Europe, and therefore, as a silver halide color photographic light-sensitive material for color proofing. A lot of posi-positive type photosensitive materials are used. Among them, the direct positive type color photographic light-sensitive material, which has been rapidly advanced in practical use technology in recent years, has been attracting attention as being most suitable for use in color proof because of its ease of processing.

A positive color image can be obtained by subjecting a light-sensitive material containing a yellow, magenta and cyan color image forming coupler in different color-sensitive light-sensitive layers as described above to image development and then color development processing. it can.
The color development process causes a coupling reaction between the oxidized product of the developing agent and the coupler to produce a color dye, which forms a positive color image. In this case, it is desired that the coupler used is one having a good color forming property (high maximum density) so that the coupling speed is as high as possible and a high color forming density is provided in a limited time. Further, it is desired that the color-developing dye thus produced is a yellow, magenta, or cyan dye having a small amount of sub-absorption and gives a color image having good color reproducibility. In particular, in the use of the color proof as described above, the points of color developability and color reproducibility are especially important, and it is desirable to use a coupler and a color developing agent satisfying such conditions. Conventionally, acylacetanilide type yellow couplers, 2,5-diacylaminophenol type cyan couplers and pyrazoloazole type magenta couplers are known as color image forming couplers used directly in positive color photographic light-sensitive materials. For example, Japanese Patent Laid-Open No. 2-22
Japanese Patent No. 0049 discloses that an acyl group has a pivaloyl type [(C
H _{3) 3} CCO-] acyl acetanilide yellow coupler and 2,5 diacylaminophenol cyan couplers directly included in the photosensitive layer positive photographic light-sensitive material is disclosed is. Further, the above publication describes an example in which a pyrazoloazole-based magenta coupler is also used together with the yellow coupler and the cyan coupler.
Further, JP-A-3-196037 discloses a specific cyan coupler, and it is described that this coupler can be directly used in a positive photosensitive material.

[0005]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide an image forming method capable of obtaining a cyan image and a yellow image having an excellent hue (color reproducibility) and an excellent color development. It is to be.

[0006]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted extensive studies as to a coupler and a color developing agent which give a color image which is more advantageous for producing a color proof as described above. It was found that the above object can be achieved by using a specific cyan coupler, a specific yellow coupler, and a specific developing agent shown in Japanese Patent Publication No. 196037 in combination to complete the present invention.
The present invention comprises at least one layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer each containing an internal latent image type silver halide grain not previously fogged and a color image-forming coupler on a support. A direct positive color photographic light-sensitive material, wherein the color image-forming coupler of the red-sensitive layer is represented by the following formula (C):

[0007]

[Chemical 4]

[In the formula, Y is a nonmetallic atomic group forming a 3- to 8-membered heterocycle with a nitrogen atom, and in the heterocycle, a carbonyl group is not directly bonded to the nitrogen atom; L is an alkylene. Is a group; Z is a hydrogen atom or a coupling-off group; Ar is an aryl group; and Y, L, Z and Ar may have a substituent. ] The cyan coupler represented by the formula [1], and the color image-forming coupler of the blue-sensitive layer has an acyl group represented by the following formula (I):

[0009]

[Chemical 5]

[In the formula, R ²¹ represents a monovalent group, and Q
²¹ represents a non-metal atom group necessary for forming a 3- to 5-membered hydrocarbon ring or a 3- to 5-membered heterocyclic ring together with C, provided that R ²¹ is not a hydrogen atom, and It does not combine with Q ²¹ to form a ring. ] A direct positive color photographic light-sensitive material which is an acylacetanilide type yellow coupler represented by the following formula (D):

[0011]

[Chemical 6]

[Wherein R ⁴¹ represents an alkyl group, and R ⁴²
Represents an alkylene group, provided that R ⁴¹ and R ⁴² may combine with each other to form a ring. ] The image forming method is characterized in that development processing is performed using a developing agent.

The preferred embodiments of the present invention are as follows.

(1) In the above formula (C), the heterocyclic group formed by Y together with the nitrogen atom is 1-pyrrolyl, 1-imidazolyl, 1-pyrazolyl, 1,2,3-triazol-1-yl, 1 , 2,4-triazol-1-yl,
1,2,4-triazol-1-yl, 1,2,4-triazol-4-yl, 1,2,3-triazol-1
-Yl, 1,2,3,4-tetrazol-1-yl,
1,2,3,4-tetrazol-2-yl, 4-pyridone-1-yl, indol-1-yl, indazole-
1-yl, benzimidazol-1-yl, benzotriazol-1-yl, benzotriazol-2-yl,
Carbazolyl, purin-1-yl or xanthine-1
-Yl (each group may have a substituent).

(2) In the above formula (C), L is an alkylene group represented by the following formula (La).

[0016]

[Chemical 7]

[Wherein R ¹ and R ² are each a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or an alkoxycarbonyl group; m
Is an integer of 1 to 6; and when m is 2 or more, a plurality of —CR ¹ R ² — may be different. ]

(3) In the above formula (C), Z is a hydrogen atom, a halogen atom, a group represented by the following formula (Za) or a group represented by the following formula (Zb).

[0019]

[Chemical 8]

[Wherein R ⁴ is a halogen atom, a cyano group,
A nitro group, an alkyl group, an alkoxy group, an alkylthio group, an alkylsulfonyl group, an arylsulfonyl group, a carbonamido group, a sulfonamide group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group or a carboxyl group; n is an integer of 0 to 5 And when n is 2 or more, plural R ^{4 s} may be different. ]

[0021]

[Chemical 9]

[In the formula, R ⁵ and R ⁶ are each a hydrogen atom or a monovalent group; T is —CO—, —SO
-, - SO ₂ - or - (PO) R ⁸ - is a; R ⁷ and R ⁸ are each a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, an alkenyloxy group, is an aryl group or an amino group: p is an integer of 1 to 6; and when p is 2 or more, a plurality of —CR ⁵ R ⁶
-May be different. ]

(4) In the above formula (C), Ar represents an aryl group, a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, a cyano group, a nitro group, an amino group,
Alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, acyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl Having a substituent selected from the group consisting of a group, a carbonamido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, a ureido group, an alkoxycarbonylamino group, a sulfamoylamino group, an alkoxysulfonyl group, an imide group and a heterocyclic group. ..

(5) The acylacetanilide type yellow coupler is represented by the following formula (Y).

[0025]

[Chemical 10]

[In the formula (Y), R ²¹ represents a monovalent substituent except a hydrogen atom. Q ²¹ represents a non-metal atomic group necessary for forming a 3- to 5-membered hydrocarbon ring or a 3- to 5-membered heterocycle with C. R ²² represents a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkyl group or an amino group. R ²³ represents a substitutable group on the benzene ring. X ²¹ represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. P represents an integer of 0 to 4. However, when P is plural, plural R ²³ may be the same or different. (6) In the above (5), Q ²¹ represents a nonmetallic atom group necessary for forming a 3-membered hydrocarbon ring with C. (7) In the above (5), X ²¹ is a heterocyclic group or an aryloxy group. (8) In the above (5), R ²² is a halogen atom (particularly chlorine atom) or an alkoxy group. (9) In the above (5), R ²³ is an alkoxy group, an alkoxycarbonyl group, a carbonamide group or a sulfonamide group. (10) In the formula (D), R ⁴¹ is ethyl.

[0027]

The direct positive color photographic light-sensitive material containing the specific cyan coupler and the yellow coupler having a specific acyl group is developed by using the specific developing agent to form a conventional photosensitive material combination. It is possible to obtain a cyan image and a yellow image having a good coloring hue (good color reproducibility) and a good coloring property, as compared with the above. In particular, in the image obtained by the combination of the present invention, the unnecessary absorption density of each of the cyan image and the yellow image is decreased, and the coloring density is also increased, so that an excellent color image satisfying both the coloring hue and the coloring density can be obtained. .. Therefore,
A light-sensitive material suitable for making a color proof can be provided.

[Detailed Description of the Invention] The image forming method of the present invention will be described below. The direct positive color photographic light-sensitive material used in the image forming method of the present invention comprises a light-sensitive layer (a light-sensitive emulsion layer) having three different color sensitivities, namely a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer on a support. ) Is provided at least one layer. Each photosensitive layer contains an internal latent image type silver halide grain and a color image forming coupler (color coupler) which have not been fogged in advance. In the red layer,
As described above, the cyan coupler represented by the formula (C) is included. The blue sensitive layer contains the specific acylacetanilide type yellow coupler.

The cyan coupler and the yellow coupler used in the above photographic light-sensitive material will be described in detail below in order.

The cyan coupler is represented by the following formula.

[0031]

[Chemical 11]

In the above formula (C), Y is a non-metal atomic group forming a 3- to 8-membered heterocycle with a nitrogen atom.
However, the carbonyl group in the heterocycle is not directly bonded to the nitrogen atom. L is an alkylene group. Z
Is a hydrogen atom or a coupling-off group. Ar is an aryl group. And Y, L, Z and Ar may have a substituent. In the present specification, the above heterocycle may be represented by X as follows.

[0033]

[Chemical 12]

Hereinafter, X, Y, L, Z and Ar will be sequentially described in detail.

The above X is preferably a 5- to 7-membered heterocycle. The total number of carbon atoms in X is preferably 1 to 30, and more preferably 1 to 24. In addition to the nitrogen atom in the above formula (X), a hetero atom (eg,
Other nitrogen, oxygen, sulfur, selenium, tellurium) may be contained. Further, X may form a condensed ring.

Examples of X include 1-pyrrolyl, 1-imidazolyl, 1-pyrazolyl, 1,2,3-triazol-1-yl, 1,2,4-triazol-1-yl,
1,2,4-triazol-1-yl, 1,2,4-triazol-4-yl, 1,2,3-triazol-1
-Yl, 1,2,3,4-tetrazol-1-yl,
1,2,3,4-tetrazol-2-yl, 4-pyridone-1-yl (above, monocycle), indol-1-yl,
Examples include indazol-1-yl, benzimidazol-1-yl, benzotriazol-1-yl, benzotriazol-2-yl, carbazolyl and purin-1-yl, and xanthin-1-yl (above, condensed ring). it can.

X may have a substituent. Examples of the substituent include a halogen atom, nitro group, cyano group, carboxyl group, alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, sulfonyl group, amino group. , An alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, a ureido group and an alkoxycarbonylamino group.

X is preferably 1-imidazolyl, 1
-Pyrazolyl, 1,2,4-triazol-1-yl,
1,2,3-triazol-1-yl, 1,2,3,4
-Tetrazol-1-yl, 1,2,3,4-tetrazol-2-yl, benzimidazol-1-yl, benzotriazol-1-yl or benzotriazol-
2-yl. X is particularly preferably 1-pyrazolyl, 1,2,4-triazol-1-yl, 1,2,3
-Triazol-1-yl, 1,2,3,4-tetrazol-2-yl or benzotriazol-2-yl.

In the formula (C), L is an alkylene group. The number of carbon atoms in L is preferably 1 to 30, and more preferably 1 to 18.

L may have a substituent. Examples of the substituent include a halogen atom, an aryl group, an alkoxy group, an aryloxy group and an alkoxycarbonyl group.

It is particularly preferable that L is an alkylene group represented by the following formula (La).

[0042]

[Chemical 13]

In the formula (La), R ¹ and R ² are
Each is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or an alkoxycarbonyl group. m is an integer of 1 to 6. And m is 2
In the above case, a plurality of —CR ¹ R ² — may be different.

R ¹ and R ² are preferably each a hydrogen atom, an alkyl group or an aryl group. m
Is preferably an integer of 1 to 3, and more preferably 1.

In the formula (C), Z is a hydrogen atom or a coupling-off group. The coupling-off group means a group (including an atom having a function of leaving) which has a function of leaving from a phenol nucleus when the cyan coupler of the formula (C) undergoes a coupling reaction with a color developing agent.

Examples of preferred coupling-off groups are halogen atom, --OR ⁴ , --SR ⁴ , and --O (CO).
_{^{R 4, -OSO 2 R 4,}} -NH (CO) R 4, -NH
(CO) SR ⁴ , -O (CO) OR ⁴ , -O (CO) N
HR ⁴ , an arylazo group (having 6 to 30 carbon atoms) and a heterocyclic group (having 1 to 30 carbon atoms), which serves as a coupling active position (position at which it bonds to the phenol nucleus) of a nitrogen atom.
Example, succinimide, phthalimide, hydantoinyl,
Pyrazolyl, 2-benztriazolyl) can be mentioned. R ⁴ is an alkyl group (having 1 to 3 carbon atoms).
6), an alkenyl group (having 2 to 36 carbon atoms), a cycloalkyl group (having 3 to 36 carbon atoms), an aryl group (having 6 to 36 carbon atoms) or a heterocyclic group (having 2 to 36 carbon atoms). .. These groups may have a substituent. Examples of the substituent include a halogen atom, hydroxyl group, carboxyl group, sulfo group, cyano group, nitro group, amino group, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group. , Alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, acyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, alkoxycarbonylamino Group, sulfamoylamino group, alkoxysulfonyl group, imido group and heterocyclic group.

Z is preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group or an alkylthio group. Z is a hydrogen atom, a halogen atom, the following formula (Z
It is more preferably a group represented by a) or a group represented by the following formula (Zb).

[0048]

[Chemical 14]

In the formula (Za), R ⁴ is a halogen atom, a cyano group, a nitro group, an alkyl group, an alkoxy group,
It is an alkylthio group, an alkylsulfonyl group, an arylsulfonyl group, a carbonamido group, a sulfonamide group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group or a carboxyl group. n is an integer of 0 to 5. When n is 2 or more, plural R ^{4 s} may be different.

In the formula (Za), R ⁴ is a halogen atom, an alkyl group (eg, methyl, t-butyl, t-octyl, pentadecyl), an alkoxy group (eg, methoxy, n).
-Butoxy, n-octyloxy, benzyloxy, methoxyethoxy), carbonamide group (eg, acetamide, 3-carboxypropanamide) or sulfonamide group (eg, methanesulfonamide, toluenesulfonamide, p-dodecyloxysulfonamide) ) Is preferable. Alkyl or alkoxy groups are particularly preferred. It is preferable that n is 0 or 1.

In the formula (Zb), R ⁵ and R ⁶ are
Each is a hydrogen atom or a monovalent group. T is -C
O -, - SO -, - SO 2 - or - (PO) R ⁸ - is. R ⁷ and R ⁸ are each a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, an alkenyloxy group, an aryloxy group or an amino group (including a substituted amino group). p is an integer of 1 to 6. And
When p is 2 or more, a plurality of —CR ⁵ R ⁶ — may be different.

In the formula (Zb), examples of the monovalent group represented by R ⁵ or R ⁶ include alkyl groups (eg, methyl, ethyl, n-butyl, ethoxycarbonylmethyl,
Benzyl, n-decyl, n-dodecyl), aryl groups (eg, phenyl, 4-chlorophenyl, 4-methoxyphenyl), acyl groups (eg, acetyl, decanoyl, benzoyl, pivaloyl) and carbamoyl groups (eg, N-
Examples thereof include ethylcarbamoyl and N-phenylcarbamoyl). It is particularly preferable that each of R ⁵ and R ⁶ is a hydrogen atom, an alkyl group or an aryl group. T is, -CO- or -SO ₂ - is preferably, and particularly preferably -CO-. R ⁷
Is an alkyl group, an alkoxy group, an alkenyloxy group,
It is preferably an aryloxy group or an amino group. Alkoxy groups and amino groups (including substituted amino groups) are particularly preferred. p is preferably 1, 2 or 3 and particularly preferably 1.

In the formula (C), Ar is an aryl group. The carbon atom number of Ar is preferably 6 to 36, and more preferably 6 to 15.

Ar preferably has a substituent. Examples of the substituent include a halogen atom, hydroxyl group, carboxyl group, sulfo group, cyano group, nitro group, amino group, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group. , Alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, acyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, alkoxycarbonylamino Group, sulfamoylamino group, alkoxysulfonyl group, imido group and heterocyclic group.

As a substituent of Ar, a halogen atom (fluorine, chlorine, bromine, iodine), a cyano group, a nitro group, an alkyl group (eg, methyl, t-butyl, trifluoromethyl, trichloromethyl), an alkoxy group ( Example, methoxy, ethoxy, butoxy, trifluoromethoxy), alkylsulfonyl group (eg, methylsulfonyl, propylsulfonyl, butylsulfonyl, benzylsulfonyl), arylsulfonyl group (eg, phenylsulfonyl, p-tolylsulfonyl, p-chlorophenylsulfonyl) ), Acyl group (eg, acetyl, benzoyl), alkoxycarbonyl group (eg, methoxycarbonyl, butoxycarbonyl), sulfonamide group (eg, methanesulfonamide, trifluoromethanesulfonamide, toluenesulfonamide), carba Yl group (e.g., N, N- dimethylcarbamoyl, N- phenylcarbamoyl) and sulfamoyl group (e.g., N, N- diethylsulfamoyl, N- phenylsulfamoyl) are preferred. A halogen atom, a cyano group, trifluoromethyl, an alkylsulfonyl group, an arylsulfonyl group and a sulfonamide group are more preferable.

Ar is 4-cyanophenyl, 4-cyano-3-halogenophenyl, 3-cyano-4-halogenophenyl, 4-alkylsulfonylphenyl, 4-alkylsulfonyl-3-halogenophenyl, 4-alkylsulfonyl- 3-alkoxyphenyl, 3-alkoxy-
4-alkylsulfonylphenyl, 3,4-dihalogenophenyl, 4-halogenophenyl, 3,4,5-trihalogenophenyl, 3,4-dicyanophenyl, 3-cyano-4,5-dihalogenophenyl, 4- Particularly preferred is trifluoromethylphenyl or 3-sulfonamidophenyl. Most preferred are 4-cyanophenyl, 3-cyano-4-halogenophenyl, 4-cyano-3-halogenophenyl, 3,4-dicyanophenyl and 4-alkylsulfonylphenyl.

Below, X (X-1) to (X-24), L
(L-1) to (L-24), Z (Z-1) to (Z-5
9) and specific examples of Ar (Ar-1) to (Ar-18).

[0058]

[Chemical 15]

[0059]

[Chemical 16]

[0060]

[Chemical 17]

[0061]

[Chemical 18]

[0062]

[Chemical 19]

[0063]

[Chemical 20]

[0064]

[Chemical 21]

[0065]

[Chemical formula 22]

[0066]

[Chemical formula 23]

[0067]

[Chemical formula 24]

[0068]

[Chemical 25]

[0069]

[Chemical formula 26]

[0070]

[Chemical 27]

Specific examples of the cyan coupler represented by the formula (C) are shown in Table 1 below.

[0072]

[Table 1]

A typical synthetic route of the cyan coupler represented by the formula (C) is shown below.

[0074]

[Chemical 28]

The above R is a hydrogen atom or a lower alkyl group (eg, methyl, ethyl). Q is a leaving group (eg, fluorine, chlorine, bromine, iodine, methanesulfonyloxy, p-
Toluene sulfonyloxy). Y, L, Z and Ar have the same definitions as in formula (C).

Compound c is synthesized by the nucleophilic substitution reaction of compound a and compound b. It is preferable to use triethylamine, N-methylmorpholine, diazabicycloundecene, sodium carbonate or potassium carbonate as the base. The reaction proceeds even without a solvent, but a solvent such as acetonitrile, acetone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N′-dimethylimidazolin-2-one, toluene or tetrahydrofuran is used. May be. Reaction temperature is usually -20
C. to 150.degree. C., preferably 20.degree. C. to 100.degree.

When R is a lower alkyl group, compound c
Is hydrolyzed to induce compound d. For the hydrolysis, an aqueous solution of an inorganic base such as sodium hydroxide, potassium hydroxide or sodium carbonate is used. A water-miscible solvent such as methanol, ethanol, or tetrahydrofuran may be added to the aqueous solution as a reaction solvent. Reaction temperature is usually -20
C. to 100.degree. C., preferably 0.degree. C. to 80.degree.

The compound d can be converted to the compound e by using thionyl chloride, phosphorus oxychloride, phosphorus pentachloride, oxalyl chloride or the like. The reaction proceeds without a solvent, but methylene chloride, chloroform, carbon tetrachloride,
A solvent such as dichloroethane, toluene, N, N-dimethylformamide, N, N-dimethylacetamide may be used. The reaction temperature is generally -20 ° C to 150 ° C, preferably -10 ° C to 80 ° C.

The compound f can be synthesized by a known method (US Pat. No. 4,333,999 and JP-A-60-35731, 61-2757, 61).
-42658 and 63-208562).

The reaction between the compound e and the compound f proceeds without a solvent, but acetonitrile, ethyl acetate, tetrahydrofuran, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, N, N'-dimethyl is used. A solvent such as imidazolin-2-one may be used.
The reaction temperature is generally -20 ° C to 150 ° C, preferably -1.
The temperature is 0 ° C to 80 ° C. Pyridine, imidazole, N,
A weak base such as N-dimethylaniline may be added.

The cyan coupler represented by the formula (C) can also be synthesized by direct dehydration condensation reaction of the compound d and the compound f. In this reaction, as a condensing agent, N, N'-
Dicyclohexylcarbodiimide, carbonyldiimidazole or the like can be used.

Next, a synthesis example of the cyan coupler represented by the formula (C) is shown.

[Synthesis Example 1] Synthesis of cyan coupler (C-1) 5-phenyl-1,2,3,4-tetrazole 14.6
g and 34.6 g of potassium carbonate, 200 ml of N, N-dimethylacetamide was added, and 33.5 g of ethyl 2-bromotetradecanoate while stirring on a steam bath.
Was dripped. After the dropping, the mixture was heated with stirring for 3 hours and cooled. Add 300 ml of ethyl acetate to the reaction mixture and add 3 ml with 400 ml of water.
It was washed with water once and extracted. The ethyl acetate solution was concentrated with an evaporator, and the residue was dissolved in 200 ml of ethanol.
Sodium hydroxide 10 in ethanol solution with stirring at room temperature
A 50 ml solution of g of water was added dropwise, and the mixture was further stirred for 5 hours.
Dilute hydrochloric acid was added to the reaction solution to make it acidic, and then ethyl acetate 300 was added.
ml was added, and the mixture was washed with 400 ml of water three times and extracted.
The ethyl acetate solution was concentrated with an evaporator, and 300 ml of acetonitrile was added to the residue to dissolve it. The acetonitrile solution was gradually cooled, and the precipitated white crystals were filtered to obtain 35 g of 2- (5-phenyl-1,2,3,4-tetrazol-1-yl) tetradecanoic acid.

22.4 g of 2- (5-phenyl-1,2,3,4-tetrazol-1-yl) tetradecanoic acid and 0.2 ml of N, N-dimethylformamide were dissolved in 60 ml of methylene chloride and stirred at room temperature. 7.9 ml of lower oxalyl chloride was added dropwise. After stirring for 2 hours, the mixture was concentrated under reduced pressure to obtain oily 2- (5-phenyl-1,2,3,4-tetrazol-2-yl) tetradecanoic acid chloride.

5-amino-4-chloro-2- [3- (4
-Cyanophenyl) ureido] phenol (US Pat.
Synthesized by the method described in No. 333999) 16.
1 g was dissolved in 200 ml of N, N-dimethylacetamide, and 2- (5-phenyl-1,2,2
3,4-Tetrazol-2-yl) tetradecanoic acid chloride was added dropwise. After dropping, the mixture was stirred for 2 hours and transferred to a separating funnel. 300 ml of ethyl acetate and 500 ml of water were added for extraction, the ethyl acetate solution was washed with dilute hydrochloric acid and then with an aqueous sodium hydrogen carbonate solution, and then concentrated. 300 ml of acetonitrile was added to the concentrate, dissolved by heating, and then crystallized. The precipitated crystals are filtered, washed with acetonitrile, and dried to obtain the desired cyan coupler (C-3) crystals 2
9.1 g was obtained. The structure of the coupler was confirmed by ¹ H NMR spectrum, mass spectrum and elemental analysis. The melting point was 176 to 185 ° C.

The photographic material preferably contains 1 × 10 ^{-5 to} 1 × 10 ^-2 mol, and more preferably 1 × 10 ^{-4 to} 5 × 10 ^-3 mol, of the above-mentioned cyan coupler per m ^2. It is preferable to contain 2 × 10 ^{−4 to} 1 × 10 ⁻³ mol.

Next, the acylacetanilide type yellow coupler having an acyl group represented by the above formula (I) will be described in detail. The acylacetanilide type yellow coupler used in the present invention is preferably a compound represented by the following formula (Y).

[0088]

[Chemical 29]

In the above formula (Y), R ²¹ represents a monovalent substituent except a hydrogen atom. Q ²¹ represents a non-metal atomic group necessary for forming a 3- to 5-membered hydrocarbon ring or a 3- to 5-membered heterocycle with C. R ²² represents a hydrogen atom, a halogen atom (fluorine, chlorine, bromine, iodine; the same applies hereinafter in the explanation of the formula (Y)), an alkoxy group, an aryloxy group, an alkyl group or an amino group. R ²³ represents a substitutable group on the benzene ring. X ²¹ represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized product of an aromatic primary amine developing agent (hereinafter referred to as a leaving group). P is 0
Represents an integer of ~ 4. However, when P is plural, plural R
²³ may be the same as or different from each other. ]

When the substituent in the formula (Y) is an alkyl group or contains an alkyl group, unless otherwise specified, the alkyl group may be substituted with a straight chain, branched chain or cyclic group. Means an optionally substituted alkyl group. In the present invention, the alkyl group includes an aralkyl group. Examples of alkyl groups include methyl, isopropyl, t-butyl, cyclopentyl, t-pentyl, cyclohexyl, 2-ethylhexyl, 1,1,3,3-tetramethylbutyl, dodecyl, hexadecyl, benzyl, trifluoromethyl, hydroxy. Mention may be made of methylmethoxyethyl, ethoxycarbonylmethyl and phenoxyethyl.

When the substituent in the formula (Y) is or contains an alkenyl group, unless otherwise specified, the alkenyl group may be linear, branched or cyclic, and may be substituted. Also means an alkenyl group.
Examples of alkenyl groups include allyl, 3-cyclohexenyl, oleyl.

When the substituent in the formula (Y) is an aryl group or includes an aryl group, the aryl group means a monocyclic or condensed ring aryl group which may be substituted, unless otherwise specified. To do. Examples of aryl groups are phenyl, 1-naphthyl, p-tolyl, o-tolyl, p-chlorophenyl, 4-methoxyphenyl, 8-
Quinolyl, 4-hexadecyloxyphenyl, pentafluorophenyl, p-hydroxyphenyl, p-cyanophenyl, 3-pentadecylphenyl, 2,4-di-t.
-Pentylphenyl, p-methanesulfonamidophenyl, 3,4-dichlorophenyl may be mentioned.

When the substituent in the formula (Y) is a heterocyclic group or contains a heterocyclic group, the heterocyclic group is selected from O, N, S, P, Se and Te unless otherwise specified. It means a 3- to 8-membered optionally substituted monocyclic or condensed-ring heterocyclic group containing at least one heteroatom in the ring. Examples of the heterocyclic group are 2-furyl, 2-pyridyl, 4-pyridyl, 1-pyrazolyl, 1-imidazolyl, 1-benzotriazolyl, 2-benzotriazolyl, succinimide, phthalimide, 1-benzyl-.
2,4-imidazolidindione-3-yl can be mentioned.

Hereinafter, R ²¹ , R ²² in the formula (Y),
R ²³ , Q ²¹ and X ²¹ will be described in detail.

R ²¹ is a halogen atom, a cyano group, an alkyl group (more preferably an alkyl group having 1 to 30 carbon atoms), an alkenyl group (more preferably 2 to 30 carbon atoms).
Alkenyl group), an alkoxy group (more preferably an alkoxy group having 1 to 30 carbon atoms), an aryl group (more preferably an aryl group having 6 to 30 carbon atoms), an aryloxy group (more preferably 6 carbon atoms). ~ 30 aryloxy groups) are preferred. These may have a substituent (or atom). Examples of the substituent (or atom) include a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a nitro group, an amino group, a carbonamido group, a sulfonamide group and an acyl group.

It is more preferable that R ¹¹ is a halogen atom, an alkyl group (particularly methyl) or an alkenyl group.

The above Q ²¹ is a hydrocarbon ring having 3 to 30 carbon atoms, which may be substituted with any of 3 to 5 members, together with a carbon atom, or a hetero ring selected from at least one of N, S, O and P. It represents a group of non-metal atoms necessary for forming a heterocycle having 2 to 30 carbon atoms containing atoms in the ring. The ring formed by Q ²¹ together with the carbon atom may contain an unsaturated bond in the ring. Examples of the ring formed by Q ²¹ together with the carbon atom include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclopropene ring, a cyclobutene ring, a cyclopentene ring,
Examples thereof include an oxetane ring, an oxolane ring, a 1,3-dioxolane ring, a thietane ring, a thiolane ring and a pyrrolidine ring. Further, examples of the substituent include a halogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an aryl group, an acyl group, an alkoxy group, an aryloxy group,
Examples thereof include a cyano group, an alkoxycarbonyl group, an alkylthio group and an arylthio group.

The above Q ²¹ has 3 to 5 rings formed together with carbon atoms.
It is preferably a group of non-metal atoms necessary for forming a 5-membered hydrocarbon ring (particularly preferably a 3-membered hydrocarbon ring).

Preferred specific examples of the acyl group represented by the formula (I) are shown below.

[0100]

[Chemical 30]

[0101]

[Chemical 31]

[0102]

[Chemical 32]

R ²² is a halogen atom (more preferably a chlorine atom or a fluorine atom), which may be substituted with 1 to 30 carbon atoms (more preferably 1 to 30 carbon atoms).
8) alkoxy group (eg, methoxy, ethoxy, methoxyethoxy, butoxy), an aryloxy group having 6 to 30 carbon atoms (more preferably 6 to 24 carbon atoms) (eg, phenoxy, p-tolyloxy, p-methoxy). Phenoxy), 1 to 30 carbon atoms (more preferably 1 to 1 carbon atoms)
6) alkyl groups (eg, methyl, trifluoromethyl,
Ethyl, isopropyl, t-butyl), carbon number 2-30
(More preferably, an alkenyl group having 2 to 6 carbon atoms (eg, allyl) or an amino group having 0 to 30 carbon atoms is preferable. Further, examples of these substituents include a halogen atom, an alkyl group, an alkynyl group, an alkoxy group, and an aryloxy group. The above R ²² is
A chlorine atom, methoxy or trifluoromethyl is particularly preferred.

Examples of the group capable of substituting on the benzene ring represented by R ²³ include a halogen atom, an alkyl group,
Alkenyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, ureido group, sulfamoyl Amino group, alkoxycarbonylamino group, alkoxysulfonyl group, nitro group, heterocyclic group, cyano group, acyl group, acyloxy group, alkylsulfonyloxy group,
And an arylsulfonyloxy group.

R ²³ is preferably the following atom or group. Halogen atom, any of which may be substituted, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or 1 to carbon atoms
30 alkoxy group, C2-30 alkoxycarbonyl group, C7-30 aryloxycarbonyl group, C1-30 carbonamido group, C1-3
0 sulfonamide group, C1-30 carbamoyl group, C0-30 sulfamoyl group, C1-3
0 alkylsulfonyl group, C 6-30 arylsulfonyl group, C 1-30 ureido group, C 0
To a sulfamoylamino group, a C2 to C30 alkoxycarbonylamino group, a C1 to C30 heterocyclic group, a C1 to C30 acyl group, and a C1 to C30 alkylsulfonyloxy group, An arylsulfonyloxy group having 6 to 30 carbon atoms.

As the above-mentioned substituent, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group. Group, arylsulfonyl group, acyl group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonylamino group, sulfamoylamino group, ureido group, cyano group, nitro group, acyloxy group, alkoxycarbonyl group, Examples thereof include an aryloxycarbonyl group, an alkylsulfonyloxy group and an arylsulfonyloxy group.

R ²³ is preferably a halogen atom, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonamido group, a sulfonamide group, a carbamoyl group or a sulfamoyl group. Particularly preferred is an alkoxy group, an alkoxycarbonyl group, a carbonamide group or a sulfonamide group. R above
²³ is preferably substituted at the meta or para position on the benzene ring with respect to the acetamide bond (-CHCONH-).

The above P is preferably 1 or 2.

As an example of the group (leaving group) represented by X ²¹ which can be split off by the coupling reaction with the oxidation product of the aromatic primary amine developing agent, a nitrogen atom is bonded to the coupling active position. Examples thereof include a heterocyclic group, an aryloxy group, an arylthio group, an acyloxy group, an alkylsulfonyloxy group, an arylsulfonyloxy group, a heterocyclic oxy group and a halogen atom.

X ²¹ is preferably a heterocyclic group or an aryloxy group which is bonded to the coupling active position by a nitrogen atom.

When X ²¹ represents a heterocyclic group, X ²¹ is an optionally substituted 5- to 7-membered monocyclic or condensed heterocyclic ring, and preferred examples thereof include succinimide and malein. Imide, phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4
-Triazole, tetrazole, indole, indazole, benzimidazole, benzotriazole, imidazolidine-2,4-dione, oxazolidine-2,4
-Dione, thiazolidine-2,4-dione, imidazolidin-2-one, oxazolidin-2-one, thiozolidin-2-one, benzimidazolin-2-one, 2-
Pyrrolin-5-one, 2-imidazolin-5-one, indoline-2,3-dione, 2,6-dioxypurine,
Parabanic acid, 1,2,4-triazolidine-3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone,
6-pyridazone-2-pyrazone, 2-amino-1,3
4-thiazolidine and 2-imino-1,3,4-thiazolidin-4-one can be mentioned.

Examples of the substituents of these heterocycles include halogen atom, hydroxyl group, nitro group, cyano group, carboxyl group, sulfo group, alkyl group, alkenyl group, aryl group, alkoxy group, aryloxy group,
Alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group,
Aryloxycarbonyl group, acyl group, acyloxy group, amino group, carbonamido group, sulfonamide group,
Examples thereof include a carbamoyl group, a sulfamoyl group, a ureido group, an alkoxycarbonylamino group and a sulfamoylamino group.

[0113] The X ²¹ is, when an aryloxy group, X ²¹ is an aryloxy group having 6 to 30 carbon atoms and preferably, selected from the group of substituents listed when the X ²¹ is a heterocyclic group It may be substituted with a group.

As the substituent of the aryloxy group, for example, a halogen atom, a cyano group, a nitro group, a carboxyl group, a trifluoromethyl group, an alkoxycarbonyl group,
A carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group or a cyano group is preferable.

The above X ²¹ is represented by the following formulas (X ²¹ -1) and (X
²¹ -2) or (still more preferably X ²¹ -3) is a heterocyclic group or an aryloxy group represented by.

[0116]

[Chemical 33]

In the formula (X ²¹ -1), Z ²¹ means the following groups.

[0118]

[Chemical 34]

Here, R ²⁴ , R ²⁵ , R ²⁸ and R ²⁹ are each a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group or amino. Represents a group. R ²⁶ and R ²⁷ are a hydrogen atom, an alkyl group,
It represents an aryl group, an alkoxy group, an alkylsulfonyl group, an arylsulfonyl group or an alkoxycarbonyl group. R ³⁰ and R ³¹ represent a hydrogen atom, an alkyl group or an aryl group. R ³⁰ and R ³¹ may combine with each other to form a benzene ring. R ²⁴ and R ²⁵ , R ²⁵ and R ²⁶ , R ²⁶ and R ²⁷ or R ²⁴ and R ²⁸ are bonded to each other,
A ring (eg, cyclobutane, cyclohexane, cycloheptane, cyclohexene, pyrrolidine, piperidine) may be formed. The above Z ²¹ is preferably the following groups.

[0120]

[Chemical 35]

The heterocyclic group represented by the above formula (X ²¹ -1) has 2 to 30, preferably 4 to 20 and more preferably 5 to 16 carbon atoms.

[0122]

[Chemical 36]

Here, at least one of R ³² and R ³³ is a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, a carboxyl group, an alkoxycarbonyl group,
A group selected from a carbonamido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group or an acyl group (provided that the other is a hydrogen atom, an alkyl group or an alkoxy group). Good). R ³⁴ is R ³² or R ³³
Represents a group having the same meaning as. m represents an integer of 0 to 2. The aryloxy group represented by the above (X ²¹ -2) has 6 to 30, preferably 6 to 24, and more preferably 6 to 15 carbon atoms.

[0124]

[Chemical 37]

Here, W represents, together with N, a non-metal atom group necessary for forming a pyrrole ring, a pyrazole ring, an imidazole ring or a triazole ring. The above ring may have a substituent. Preferred examples of such a substituent include a halogen atom, nitro group, cyano group, alkoxycarbonyl group, alkyl group, aryl group, amino group, alkoxy group, aryloxy group or carbamoyl group. The heterocyclic group represented by the above (X ²¹ -3) has 2 to 30 carbon atoms, preferably 2 carbon atoms.
-24, more preferably 2-16.

The above X ²¹ is particularly preferably the heterocyclic group represented by the above formula (X ²¹ -1).

The yellow coupler represented by the formula (Y) has substituents R ²¹ , Q ²¹ , X ²¹ or

[0128]

[Chemical 38]

In the above, a dimer or a multimer of more than one may be formed which are bound to each other via a divalent or higher valent group. In this case, the number of carbon atoms shown in each of the above-mentioned substituents may be outside the specified range. less than,
Specific examples of the yellow coupler represented by the formula (Y) are shown below.

[0130]

[Chemical Formula 39]

[0131]

[Chemical 40]

[0132]

[Chemical 41]

[0133]

[Chemical 42]

[0134]

[Chemical 43]

[0135]

[Chemical 44]

[0136]

[Chemical 45]

[0137]

[Chemical 46]

[0138]

[Chemical 47]

[0139]

[Chemical 48]

[0140]

[Chemical 49]

The yellow coupler represented by the formula (Y) is
It can be synthesized by the following synthesis method.

[0142]

[Chemical 50]

Here, the compound (a) is treated with j. Chem. S
oc. (C), 1968, 2548, j. Am. Che
m. Soc. , 1934, 56, 2710, Synth
sis, 1971, 258, J. Org. Chem.
1978, 43, 1729, CA, 1960, 66, 1
It is synthesized by the method described in 8533y or the like. The following compounds (b), (C), (d), (e) and (f) can be synthesized by a conventionally known method.

The compound (b) is synthesized in a solvent (using thionyl chloride, oxalyl chloride or the like without solvent or methylene chloride, chloroform, carbon tetrachloride, dichloroethane, toluene, N, N-dimethylformamide,
(N, N-dimethylacetamide, etc.). The reaction temperature is generally -20 ° C to 150 ° C, preferably -10 ° C to 80 ° C. Compound (c)
Is synthesized by converting ethyl acetoacetate into an anion using magnesium methoxide and adding the compound (b) therein. The synthesis is carried out without solvent or using tetrahydrofuran, ethyl ether or the like. The reaction temperature is generally -20 ° C to 60 ° C, preferably -10 ° C to 3
It is in the range of 0 ° C. Compound (d) is synthesized by reacting compound (c) with ammonia as a base, aqueous NaHCO ₃ solution, aqueous sodium hydroxide solution or the like without solvent or in a solvent such as methanol, ethanol or acetonitrile. The reaction temperature is usually -20 ° C.
To 50 ° C, preferably -10 ° C to 30 ° C.
The compound (e) is synthesized by reacting the compound (d) and the compound (g) without a solvent. The reaction temperature is generally 100 ° C to 150 ° C, preferably 100 ° C to 120 ° C.
The range is.

When X ²¹ is not a hydrogen atom, compound (f) is synthesized by introducing a leaving group X ²¹ after chlorination or bromination. Compound (e) is converted to a chloro substitution product with sulfuryl chloride, N-chlorosuccinimide, etc. in a solvent (dichloroethane, carbon tetrachloride, chloroform, methylene chloride, tetrahydrofuran, etc.), or bromo substitution with bromine, N-succinimide, etc. The body. The reaction temperature is -2
It is in the range of 0 ° C to 70 ° C, preferably -10 ° C to 50 ° C. Next, chloro-substituted, or bromo-substituted product and the proton adduct H-X ²¹ and a solvent leaving group (methyl chloride, chloroform, tetrahydrofuran, acetone, acetonitrile, dioxane, N- methylpyrrolidone, N, N'
Dimethylimidazolidin-2-one, N, N-dimethylformamide, N, N-dimethylacetamide, etc.),
Reaction temperature -20 to 150 ° C, preferably -10 to 10
By reacting at 0 ° C., the compound (f) (yellow coupler according to the present invention) can be obtained. At this time,
A base such as triethylamine, N-ethylmorpholine, tetramethylguanidine, potassium carbonate, sodium hydroxide or sodium hydrogen carbonate may be used.

Examples of synthesizing couplers are shown below. Synthesis Example 1 (Compound Y-17) Gotkis, D.M. et al. Am. Chem. S
oc. 1-methylcyclopropanecarboxylic acid 25 synthesized by the method described in 1934, 56, 2710.
g, methylene chloride 100 cc, and N, N-dimethylformamide 1 cc, 38.1 g of oxalyl chloride was added dropwise at room temperature over 30 minutes. After dropping, react at room temperature for 2 hours, and under aspirator reduced pressure,
By removing methylene chloride and excess oxalyl chloride, an oily substance of 1-methylcyclopropanecarbonyl chloride was obtained. 100 cc of methanol was added dropwise to a mixture of 6 g of magnesium and 2 cc of carbon tetrachloride at room temperature over 30 minutes. Then, after heating under reflux for 2 hours, 32.6 g of ethyl 3-oxobutanoate was added dropwise over 30 minutes under heating under reflux. After the dropping, the mixture was heated under reflux for further 2 hours, and methanol was completely distilled off under reduced pressure of an aspirator. Tetrahydrofuran 100 cc was added to the reaction product and dispersed, and 1-methylcyclopropanecarbonyl chloride obtained above was added dropwise at room temperature. After reacting for 30 minutes, the reaction solution was extracted with 300 cc of ethyl acetate and diluted sulfuric acid water, washed with water, the organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off to give 2- (1-methylcyclopropanecarbonyl). Oil of ethyl-3-oxobutanoate 55.
3 g was obtained. A solution of ethyl 2- (1-methylcyclopropanecarbonyl) -3-oxobutanoate (55 g) and ethanol (160 cc) was stirred at room temperature, and 30% aqueous ammonia (60 cc) was added dropwise thereto over 10 minutes. Then, the mixture is stirred for 1 hour, extracted with 300 cc of ethyl acetate, diluted hydrochloric acid, neutralized, washed with water, the organic layer is dried over anhydrous sodium sulfate, and then the solvent is distilled off to give (1-methylcyclopropanecarbonyl) ethyl acetate 43 g of oil was obtained. (1-
34 g of an oily product of methylcyclopropanecarbonyl) ethyl acetate and N- (3-amino-4-chlorophenyl) -2
4 (4.5 g) of-(2,4-di-t-pentylphenoxy) butanamide was heated to reflux at an internal temperature of 100 to 120 ° C under reduced pressure of an aspirator. After reacting for 4 hours, the reaction solution was purified by column chromatography with a mixed solvent of n-hexane and ethyl acetate to obtain 49 g of Exemplified Compound Y-17 as a viscous oil. The structure of the compound was confirmed by mass spectrum, NMR spectrum and elemental analysis.

Synthesis Example 2 (Exemplified Compound Y-1) 22.8 g of Exemplified Compound Y-17 was treated with 300 ml of methylene chloride.
Dissolve in cc, and under cooling with ice, 5.4 g of sulfuryl chloride.
Was added dropwise over 10 minutes. After reacting for 30 minutes, the reaction solution was washed well with water, dried over anhydrous sodium sulfate, and then concentrated.
A chloride of Exemplified Compound Y-17 was obtained. 1-benzyl-5
-Ethoxyhydantoin 18.7 g, triethylamine 11.2 cc, and N, N-dimethylformamide 50
A solution of the above-illustrated chloride of the exemplified compound Y-17 dissolved in 50 cc of N, N-dimethylformaldehyde was added dropwise to the cc solution at room temperature over 30 minutes. Then, after hydration at 40 ° C. for 4 hours, the reaction solution was diluted with ethyl acetate 30 times.
After extraction with 0 cc and washing with water, 2% triethylamine aqueous solution 3
It was washed with water at 00 cc and then neutralized with dilute hydrochloric acid.
After drying the organic layer over anhydrous sodium sulfate, the solvent was distilled off and the obtained oily substance was crystallized from a mixed solvent of n-hexane and ethyl acetate. The precipitated crystals were filtered, washed with a mixed solvent of n-hexane and ethyl acetate, and dried to give crystals of Exemplified compound Y-1 (22.8 g). The structure of the compound was confirmed by mass spectrum, NMR spectrum and elemental analysis. The melting point was 132 to 3 ° C.

The yellow coupler represented by the above formula (Y) may be used alone or in combination of two or more kinds. Further, these may be used as a mixture with a known coupler as a yellow coupler. The amount of the yellow coupler represented by the formula (Y) used in the light-sensitive material is 1 × 10 ⁻⁵ mol to 1 × m ² of the light-sensitive material.
A range of 10 ^-2 mol is general, preferably 1 x 1
It is in the range of 0 ⁻⁴ mol to 10 ⁻³ mol, more preferably 2 × 10 ⁻⁴ mol to 10 ⁻³ mol.

The prefogged 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 forms a latent image mainly inside the grains. However, more specifically, a certain amount of silver halide emulsion (0.5
To 3 g / m ²⁾ was applied, the following developer giving exposure at fixed time of 0.01 to 10 seconds to in (internal developer), 20 ° C., conventional photographic density when developed 5 minutes The maximum density measured by the measuring method is the maximum obtained when a silver halide emulsion coated in the same amount as above and exposed in the same manner is developed at 18 ° C. for 6 minutes in the following developer (surface type developer). Those having a concentration of at least 5 times greater than the concentration are preferred, and those having a concentration of at least 10 times greater are preferred. 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 0.5 g L-ascorbic acid 10.0 g NaBO ₂ .4H ₂ O 35.0 g KBr 1.0 g Water was added to 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-52-1
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), page 236; specification of U.S. Pat. No. 4,789,627, further having a silver chloride shell; JP-A-63-10160 relating to silver chlorobromide core-shell emulsions;
JP-A-63-47766 and Japanese Patent Application No. 1-24
No. 67; Japanese Patent Application Laid-Open No. 63-191145 and Japanese Patent Application Laid-Open No. 1-5214 relating to emulsions doped with metal ions.
Examples thereof include core / shell type silver halide emulsions described in JP-A No. The internal latent image type silver halide grains which have not been fogged in the present invention are preferably core / shell type. The internal latent image type core / shell silver halide emulsion has a silver halide core / shell molar ratio of 20/1 or less and 1/10.
0 or more is particularly preferable.

The internal latent image type silver halide grains which have not been fogged beforehand 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 in 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 metal is usually added in the form of a complex salt of the metal 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, octahedral, dodecahedral or tetradecahedral shape (JP-A-2-22).
3948), an irregular crystal form such as a sphere, and JP-A-1-131547.
Emulsions in which tabular grains having a length / thickness ratio value of 5 or more, particularly 8 or more, which occupy 50% or more of the total projected area of the grains, may be used. .. Further, it may be an emulsion having a complex form of these various crystal systems, or an emulsion comprising 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. ± 20%
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 the grains are contained therein.

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 are used in the emulsion layers having substantially the same color sensitivity. It is possible to mix a plurality of different particles in the same layer or to coat multiple layers in different layers. Furthermore, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be mixed or laminated and used.

The silver halide emulsion used in the present invention is preferably chemically sensitized in its grain interior or surface 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 (197
Issued in December, 1996) See patents on pages 23-24. The photographic emulsion used in the present invention may contain an antifoggant or stabilizer for the purpose of preventing fog during the production process of a light-sensitive material, storage or photographic processing, or stabilizing photographic performance. For a detailed example,
For example, Research Disclosure No. 1764
3-VI (issued in December 1978) and E.I. J. B
irr by "Stabiliaution of Photographic Silver Hai
lde Emulsion "(Focal Press), published in 1974.

In the present invention, various color couplers may be used in addition to the cyan coupler represented by (C) and the yellow coupler represented by (Y). Typical examples of useful color couplers are naphthol or phenol compounds, pyrazolone or virazoloazole 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 described in "Research Disclosure" No. 17643 (19
Issued December 1978), page 25, section VII-D, ibid. 1
8717 (issued in November 1979) and Japanese Patent Laid-Open No. 62-
No. 215,272 and the patents cited therein. The 5-pyrazolone-based magenta coupler preferably used in the present invention is a 5-pyrazolone-based magenta coupler in which 5-position is substituted with an arylamino group or an acylamino group.
It is a pyrazolone-based coupler (among others, a sulfur atom-elimination type two-equivalent coupler). More preferred are pyrazoloazole-based couplers, and among them, US Pat. No. 37250.
67. Pyrazolo [5,1-c] [1,
2,4] triazoles and the like are preferable, but the imidazo [1,2-
b] Pyrazoles are more preferred and are described in US Pat.
No. 654, pyrazolo [1,5-b] [1,2,
4] Triazole is particularly preferable.

Colored couplers for correcting unnecessary absorption in the short wavelength region of the dyes formed, couplers in which the coloring dyes have an appropriate diffusivity, non-color couplers, and development inhibitors released in association with the coupling reaction. DIR couplers and polymerized couplers can also be used. 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 VII to F, JP-A-57-151944, 57-154234, and 60.
-184248, JP-A-63-146035 and those described in U.S. Pat. No. 4,248,962.
Those described in the publication are preferred. Examples of couplers that release a nucleating agent or a development accelerator in an image during development include British Patent Nos. 2097140 and 2131188.
Each specification, JP-A-59-157638, 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
An antifoggant or a color mixing inhibitor 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, 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 that prevent irradiation or 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. Solid fine crystal dispersion method may be used.), UV absorber, plasticizer, fluorescent whitening agent, matting agent, air antifoggant, coating aid, film hardening agent, antistatic agent, slipperiness improver, etc. Can be added. Typical examples of these additives are Research
Disclosure magazine No. 17643VII-XII
Item I (published December 1978), pages 25-27, and 18716 (published November 1979), pages 647-651.

The light-sensitive material of the present invention has at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on the support. The order of these layers can be arbitrarily selected as required. The preferred order of layer arrangement is red-sensitive, green-sensitive, blue-sensitive from the support side or green-sensitive, red-sensitive and blue-sensitive from the support side. 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, 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 dried. 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. Light-sensitive materials using higher sensitivity emulsions are preferred to have low illuminance. The illuminance may be adjusted by changing the luminous intensity of the light source, or by changing the photosensitivity by various filters, the distance between the photosensitive material and the light source, or the angle between the photosensitive material and the light source. Further, the illuminance of the above-mentioned fogging light can be increased from low illuminance to high illuminance continuously or stepwise. 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 and used is preferable. Here, the nucleating agent is a substance which acts when the surface latent image of an internal latent image type silver halide emulsion which has not been fogged in advance is subjected to a direct image formation. 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 to 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, No. 23510 (November 1983) 346
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, 510 of JP-A-3-155543
To 514, a quaternary heterocyclic compound represented by the general formula (N-I), and 60 to 60 of JP-A-3-95546.
The hydrazine compound represented by the general formula (N-II) on page 65; typical nucleating agents represented by the 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 a developing solution or a low pH pre-bath as described in JP-A-58-178350. When the 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. A nucleation accelerator does not substantially function as a nucleating agent,
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 optionally substituted with an alkali metal atom or an ammonium group, thiadiazoles, oxadiazoles, benzotriazoles, tetrazaindenes, Examples thereof include triazaindenes and pentazaindenes, and the compounds described in JP-A-63-106656, pages 5 to 16. In addition, JP-A-63-
No. 226652, No. 63-106656, No. 63-8
The compounds described in No. 740 can be mentioned.

These nucleation accelerators can be used in combination of two or more kinds. The nucleation accelerator can be contained in the light-sensitive material or in the processing solution, but in the light-sensitive material, it can be used in internal latent image type silver halide emulsions and 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 amount of the nucleation accelerator added 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 (19
(November 1979), 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 to supersensitizer, page 649, right column 4 whitening agent, page 24 5 Fog inhibitor, pages 24 to 25, page 649, right column to stabilizing agent, page 650, right column 6 Light absorber, page 25, right column, page 649, right column ~ Filter dye, page 650, left column UV absorber 7 Stain inhibitor, page 25, right column 8 Dye image stabilizer, page 25, 9 Hardener, page 26, page 651, left column 10 Binder page 26 Same as above ─────────────────────────────

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are made of a flexible support 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 the flexible support is a film made of a semi-synthetic or synthetic polymer such as cellulose nitrate, cellulose acetate, cellulose acetate acetate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, a baryter layer or an α-olefin polymer. Examples include paper coated or laminated with (for example, 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, etc. may be used to simultaneously apply multiple layers.

Next, an image forming method using the above direct positive color photographic light-sensitive material will be described. In the image forming method of the present invention, the above light-sensitive material is subjected to image exposure and then treated with a developing treatment liquid containing a color developing agent represented by the following formula (D),
It is characterized by obtaining a positive color image.

[0168]

[Chemical 51]

Examples of the alkyl group represented by R ⁴¹ include alkyl groups having 1 to 8 carbon atoms.
As such examples, methyl, ethyl, butyl or methoxyethyl are preferred. Examples of the alkylene group represented by R ⁴² include an alkylene group having 2 to 6 carbon atoms. As such an example, ethylene or trimethylene is preferable. Specific examples of the developing agent represented by formula (D) are shown below.

[0170]

[Chemical 52]

[0171]

[Chemical 53]

In the present invention, the compounds represented by the above (D-2) or (D-3) are preferable. An aromatic primary amine color developing agent other than the above may be used in combination. The amount of the color developing agent used is preferably about 0.1 g to about 20 g, and more preferably about 0.5 to about 10 g per liter of the developing solution. 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 above-mentioned series of processing steps, see 38 of JP-A-3-120537.
The method described on pages 0 to 381 can be preferably used.

[0173]

EXAMPLES The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. (Preparation of Sample 101) The following 1st to 11th layers are multilayer-coated on the front side of a paper support (thickness 100 μm) laminated on both sides with polyethylene, and the 12th to 13th layers are multilayer coated on the back side. A photosensitive material (comparative sample) was prepared. For the polyethylene coated on the first layer, titanium oxide (4 g / m
² ) as a white pigment and a small amount (0.003 g / m ² )
² ) Ultramarine blue is included as a bluing dye (the chromaticity of the surface of the support is 88.0, -0.20,-in L *, a *, b * system).
It was 0.75). (Photosensitive layer composition) The components and the coating amount (g / m ² ) are shown below. 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 was prepared by changing the grain size by changing the grain formation temperature according to the production method of emulsion EM-1 described later. However, as the emulsion of the 11th layer, a Lippmann emulsion which was not surface-sensitized was used.

First Layer (Antihalation Layer) Black Colloidal Silver 0.10 Color Mixing Inhibitor (Cpd-7) 0.05 Gelatin 0.70 Second Layer (Intermediate Layer) Gelatin 0.70 Third Layer (Red Sensitive Layer) ) Silver bromide spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3, each equivalent amount, 5.4 × 10 ⁻⁴ in total) (average grain size: 0.4 μm, grain size distribution: 10) %, Octahedron) 0.25 gelatin 1.00 cyan coupler (ExC-1) 0.30 anti-fading agent (Equivalent amounts of Cpd-1, 2, 3, 4 and 30) 0.18 anti-stain agent (Cpd) -5) 0.003 Coupler dispersion medium (Cpd-6) 0.03 Coupler solvent (Solv-1) 0.24

Fourth Layer (Intermediate Layer) Gelatin 1.00 Color Mixing Inhibitor (Cpd-7) 0.08 Color Mixing Inhibitor Solvent (Solv-2, 3 in Equivalent Amounts) 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 μm, grain size distribution 10) %, Octahedron) 0.25 gelatin 0.80 magenta coupler (Equivalent amounts of ExM-1, 2) 0.11 yellow coupler (ExY-1) 0.03 anti-fading agent (Cpd-9, 26, 30) Each equivalent amount) 0.15 Anti-staining agent (Cpd-10, 11, 12, 13 in a 10: 7: 7: 1 ratio) 0.025 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv- 2, 4 each equal amount) 0.15 6th layer (intermediate) ) Same as the 4th layer 7th layer (intermediate layer) Gelatin 2.30 Color-mixing inhibitor (Cpd-7) 0.14 Color-mixing inhibitor solvent (Solv-2, 3 in equal amounts) 0.45 Polymer latex (Cpd) -8) 0.14 Eighth Layer (Blue Sensitive Layer) Silver bromide (average grain size) spectrally sensitized with a blue sensitizing dye (ExS-5, 6 equivalents, total 3.5 × 10 ⁻⁴ ). : 0.60 μm, Particle size distribution 11%, Octahedron) 0.40 Gelatin 0.80 Yellow coupler (Equivalent of ExY-1, 2) 0.35 Anti-fading agent (Cpd-14) 0.10 Anti-fading Agent (Cpd-30) 0.05 Stain inhibitor (Cpd-5, 15 in a ratio of 1: 5) 0.007 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-1) 0.10

Ninth layer (UV absorbing layer) Gelatin 1.00 UV absorber (equal amounts of Cpd-2, 4, and 16) 0.50 Color-mixing inhibitor (equal amounts of Cpd-7 and 17). 03 Dispersion medium (Cpd-6) 0.02 UV absorber solvent (Solv-1, 5 in each equivalent amount) 0.08 Anti-irradiation dye (Cpd-18, 19, 20, 21, 27 10:10: 13:15:20 ratio) 0.05 10th layer (protective layer) Fine silver chlorobromide (97 mol% silver chloride, average size 0.1 μm) 0.03 Acrylic modified copolymer of polyvinyl alcohol 01 (Molecular weight: 50,000) Equal amounts of polymethylmethacrylate particles (average particle size: 2.4 μm) and silicon oxide (average particle size: 5 μm) 0.05 Gelatin 1.80 Gelatin hardening agent (H-1, H -2 Equivalent amount) 0.18 11th layer (back layer) Gelatin 2.50 UV absorber (Equivalent amount of Cpd-2, 4, 16) 0.50 Dye (Cpd-18, 19, 20, 21, 27) 0.06 12th layer (back layer protective layer) Polymethylmethacrylate particles (average particle size: 2.4 μm) and silicon oxide (average particle size: 5 μm) are each equivalent 0.05 gelatin 2 0.000 Gelatin hardening agent (Equivalent amounts of H-1 and H-2) 0.14

(Preparation of Emulsion EM-1) An aqueous solution of potassium bromide and silver nitrate was added to 0.3 g of 3,4-per mol of silver.
Dimethyl-1,3-thiazoline-2-thione was added simultaneously to the aqueous gelatin solution with vigorous stirring at 65 ° C. for 15 minutes to obtain octahedral silver bromide grains having an average grain size of 0.23 μm. It was 6 per mole of silver in this emulsion
Chemical sensitization was performed by sequentially adding mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) and heating at 75 ° C. for 80 minutes. The grains thus obtained were used as cores for further growth in the same precipitation environment as in the first time, and finally an octahedral monodisperse core / shell silver bromide emulsion having an average grain size of 0.4 μm was obtained. The coefficient of variation of particle size was about 10%. To this emulsion, 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) were added per mol of silver, and the mixture was heated at 60 ° C. for 60 minutes to carry out chemical sensitization treatment. A silver halide emulsion was obtained. In each light-sensitive layer, ExZK-1 and ExZK-2 as nucleating agents were added by 10 ^-3 % by weight and 10 ^-2 % by weight with respect to the silver halide, and Cpd-22, 28, 29 as nucleating accelerators, respectively. 10 ⁻² wt% was used. Further, for each layer, alkanol XC (Du Pont) and sodium alkylbenzene sulfonate were used as emulsification / dispersion aids, and succinate and Magefac F-120 (manufactured by Dainippon Ink and Chemicals, Inc.) were used as coating aids. Equal amounts of Cpd-23, 24, and 25 were used as stabilizers in the silver halide and colloidal silver-containing layers. The compounds used in the preparation of the above sample are shown below.

[0178]

[Chemical 54]

[0179]

[Chemical 55]

[0180]

[Chemical 56]

[0181]

[Chemical 57]

[0182]

[Chemical 58]

[0183]

[Chemical 59]

[0184]

[Chemical 60]

[0185]

[Chemical formula 61]

[0186]

[Chemical formula 62]

[0187]

[Chemical 63]

[0188]

[Chemical 64]

[0189]

[Chemical 65]

[0190]

[Chemical 66]

[0191]

[Chemical 67]

[0192]

[Chemical 68]

Solv-1 di (2-ethylhexyl)
Sebacate Solv-2 Trinonyl Phosphate Solv-3 Di (3-methylhexyl) Phthalate Solv-4 Tricresyl Phosphate Solv-5 Dibutyl Phthalate Solv-6 Trioctyl Phosphate Solv-7 Di (2-ethylhexyl) Phthalate H-11 , 2-Bis (vinylsulfonylacetamide) ethane H-2 4,6-dichloro-2-hydroxy-
1,3,5-Triazine / Na salt ExZK-17- (3-ethoxythiocarbonylaminobenzamide) -9-methyl-10-propargyl-1,2,3
4-Tetrahydroacridinium trifluoromethanesulfonate ExZK-2 2- [4- {3- [3- {3- [5- {3- [2-chloro-5- (1-dodecyloxycarbonylethoxycarbonyl) phenyl) Carbamoyl] -4-hydroxy-1
-Naphthylthio} tetrazol-1-yl] phenyl}
Ureido] benzenesulfonamide} phenyl] -1-
Formyl hydrazine

(Preparation of Sample 102) In the preparation of Sample 101, the cyan coupler (ExC-1) contained in the third layer (red sensitive layer) was changed to the cyan coupler (ExC-2) shown below. Sample 102 was prepared in the same manner as Sample 101, except that it was replaced with equimolar amount.

[0195]

[Chemical 69]

(Preparation of Samples 103 and 104) In the preparation of Sample 101 above, the cyan coupler (ExC-1) contained in the third layer (red sensitive layer) was replaced by the cyan coupler (C-3 or Samples 103 and 104 corresponding to each other were prepared in the same manner as the sample 101, except that it was changed to C-7) (replaced by equimolar amount).

[0197]

[Chemical 70]

(Preparation of Sample 105) In the preparation of Sample 103, the yellow couplers (ExY-1 and ExY-2) contained in the eighth layer (blue-sensitive layer) were replaced with the yellow couplers (Y- Sample 105 was prepared in the same manner as Sample 103 except that it was replaced with 28 (replaced with equimolar amount).
It was created.

[0199]

[Chemical 71]

(Preparation of Sample 106) In the preparation of Sample 104, the yellow couplers (ExY-1 and ExY-2) contained in the eighth layer (blue-sensitive layer) were replaced with the yellow couplers (Y- 29) Sample 10 was prepared in the same manner as Sample 104, except that
Created 6.

[0201]

[Chemical 72]

[Evaluation as direct positive color photographic light-sensitive material] With respect to each silver halide color photographic light-sensitive material (Samples 101 to 106) prepared as described above, color reproducibility and color development were evaluated by the following methods. It was (Evaluation of color reproducibility) After the sample was made to develop a single color in each of the hues of yellow and cyan to obtain a color-developed image (dye image), the peak density of each dye image was 2.0.
Λ _700nm yellow) and λ _420nm (cyan)
The absorption density at the wavelength of (unnecessary absorption density) was measured and evaluated using a spectrophotometer. (Evaluation of color developability) The maximum color density of the above sample was measured by a densitometer (X
-Rite310RT, manufactured by X-Rite) was used for measurement and evaluation.

The image forming method using the above light-sensitive material is as follows.
The following process was followed. Comparative Example 1 (1) As a color developing agent contained in the color developing solution,
N-ethyl-N- (β-methanesulfonamidoethyl)
-3-Methyl-4-aminoaniline sulfate was used.

[Example 1] (2) The color developing agent contained in the color developing solution was changed to [N
-Ethyl-N-β- (methanesulfonamidoethyl)-
3-Ethyl-4-aminoaniline sulfate]] (D-2; mother liquor: 4.3 g, replenisher:
The image forming method according to the present invention was performed in the same manner as in Comparative Example 1 except that the amount was changed to 5.6 g).

Example 2 (3) Instead of the color developing agent D-2 contained in the color developing solution of the above (2), the following compound D-3 (mother liquor:
The image forming method according to the present invention was carried out in the same manner as in the above (2) except that 4.6 g and a replenishing solution: 6.1 g) were used.

[0206]

[Chemical formula 73]

[Color Development Processing] The above exposed sample was continuously processed by the method described below using an automatic processor until the cumulative replenishment amount of the solution became 3 times the tank capacity. ──────────────────────────────────── Treatment process time Temperature Tank capacity Replenishment amount ─────── ────────────────────────────── color development 135 sec 38 ° C. 28 liters 240 ml / m ² bleach-fixing 40 seconds 35 ° C. 11 liters 320 ml / m ² water washing (1) 40 seconds 35 ° C. 7 liters −−− water washing (2) 40 seconds 35 ° C. 7 liters 320 ml / m ² drying 30 seconds 80 ° C. ─────────────── ────────────────────── The replenishing method of the washing water is such that the washing bath (2) is replenished, and the overflow liquid of the washing bath (2) is washed ( The so-called countercurrent replenishment method, which leads to 1), was adopted. At this time, the amount of each processing solution carried out by the light-sensitive material was 35 ml / m ² .

──────────────────────────────────── Color developer developer tank liquid replenisher ──── ──────────────────────────────── D-Sorbit 0.15g 0.20g Sodium naphthalenesulfonate ・ 0.15g 0 20g Formalin condensate nitrilotris (methylenephosphonic acid) 1.8g 1.8g pentasodium salt diethylenetriaminepentaacetic acid 0.50g 0.50g 1-hydroxyethylidene-1,1-0.15g 0.15g diethylene glycol diethylene glycol 12. 0 ml 16.0 ml Benzyl alcohol 13.5 ml 18.0 ml Potassium bromide 0.70 g --- Benzotriazole 0.003 g 0.004 g Sodium sulfite 2.8 g 0.7 g Hydroxylamine 1/2 sulfate 6.0 g 5.3 g Triethanolamine 6.0 g 8.0 g N-ethyl-N- (β-methanesulfone 6.4 g 8.5 g amidoethyl) -3-methyl-4 -Aminoaniline sulfate potassium carbonate 30.0 g 25.0 g Optical brightener (diaminostilbene type) 1.3 g 1.7 g Water was added 1000 ml 1000 ml ───────────────── ──────────────────── pH (25 ℃) 10.35 10.93 (pH adjusted with KOH or sulfuric acid) ─────────── ──────────────────────────

──────────────────────────────────── Bleach-fixing solution Tank solution Replenishing solution ──── ──────────────────────────────── Ethylenediamine 4 acetic acid ・ 4.0g Same as mother liquor 2 sodium ・ dihydrate ethylenediamine 4 Acetic acid / Fe (III) /55.0 g Ammonium / dihydrate Ammonium thiosulfate (750 g / l) 168 ml Sodium p-toluenesulfinate 30.0 g Ammonium sulfite 35.0 g 5-Mercapto-1,3,4-triazole 5g Ammonium nitrate 10.0g Water added 1000ml ──────────────────────────────────── pH (25 ℃ ) (PH adjusted with ammonia water or acetic acid 6.20 ────────────────────────────────────

──────────────────────────────────── Rinsing water [both tank liquid and replenisher] ─ ─────────────────────────────────── Sodium chlorinated isocyanurate 0.02g Deionized water (conductivity 5 μs / cm or less) 1000 ml ───────────────────────────────────── pH 6.50 ─── ──────────────────────────────────

The above results are shown in Table 2 (comparative example) and Table 3.
And shown in Table 4.

[0212]

[Table 2] Table 2 (1) When N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate is used as a color developing agent ─────── ───────────────────────────── Unnecessary absorption density Maximum color density Cyan Yellow Cyan Yellow Cyan Yellow Sample No. Coupler Coupler (λ _420nm ) (λ _700nm ) Dmax Dmax ──────────────────────────────────── 101 ExC -1ExY-1 0.72 0.11 2.05 2.15 ExY-2 ──────────────────────────────── ───── 102 ExC-2ExY-1 0.50 0.11 1.84 2.15 ExY-2 ──────────────────────── ──────────── 103 C-3 ExY-1 0.50 0.11 2.24 2.14 ExY-2 ───────────────── ──────────────────── 104 C-7 ExY-1 0.51 0.11 2.28 2.15 ExY-2 ───────── ──────────────── ─────────── 105 C-3 Y-28 0.52 0.10 2.25 2.39 ───────────────────── ──────────────── 106 C-7 Y-29 0.52 0.10 2.28 2.38 ─────────────── ─────────────────────

[0213]

[Table 3] Table 3 (2) When the color developing agent D-2 is used ──────────────────────────────── ───── Unnecessary absorption density Maximum coloring density Cyan Yellow Cyan Yellow Cyan Yellow Sample No. Coupler Coupler (λ _420nm ) (λ _700nm ) Dmax Dmax ──────────────────────────────────── 101 ExC -1ExY-1 0.72 0.11 2.07 2.19 (Comparative example) ExY-2 ──────────────────────────── ───────── 102 ExC-2ExY-1 0.50 0.11 1.90 2.18 (Comparative example) ExY-2 ──────────────── ──────────────────── 103 C-3 ExY-1 0.47 0.11 2.26 2.18 (Comparative example) ExY-2 ──── ──────────────────────────────── 104 C-7 ExY-1 0.48 0.11 2.30 2. 17 (Comparative example) ExY-2 ─── ──────────────────────────────── (Example of the present invention) 105 C-3 Y-28 0.47 0.08 2.27 2.42 106 C-7 Y-29 0.47 0.08 2.28 2.42 ────────────────────────── ───────────

[0214]

[Table 4] Table 4 (3) When the color developing agent D-3 is used ──────────────────────────────── ───── Unnecessary absorption density Maximum coloring density Cyan Yellow Cyan Yellow Cyan Yellow Sample No. Coupler Coupler (λ _{420 nm} ) (λ _{700 nm} ) Dmax Dmax ──────────────────────────────────── The present invention Example 105 C-3 Y-28 0.47 0.08 2.28 2.41 106 C-7 Y-29 0.47 0.08 2.28 2.40 ───────────── ─────────────────────────

As is clear from the results shown in Tables 2 to 4, according to the image forming method of the present invention, the unnecessary absorption density is low (excellent in color hue, that is, good color reproducibility) and the maximum image Yellow and cyan images with high density (excellent in color development) can be obtained.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] February 1, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0165

[Correction method] Change

[Correction content]

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 (19
(November 1979), 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 to supersensitizer, page 649, right column 4, whitening agent, page 24 5, antifoggant, pages 24 to 25, page 649, right column, stabilizer, page 650, right Column 6 Light absorber, Page 25 Right column, Page 649 Right column, Filter dye, Page 650, Left column UV absorber 7 Stain inhibitor, Page 25 Right column 8, Dye image stabilizer, Page 25 9 Hardener, Page 26, 651 Left column 10 Binder page 26 Same as above ────────────────────────────── In addition to the above UV absorbers, triazine compounds (for example,
Kai 46-3335, European Published Patent No. 520,938
No. A), benzophenone compounds (European publication)
The one described in Japanese Patent No. 521,823A) is preferably used.
it can.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0176

[Correction method] Change

[Correction content]

Ninth Layer (UV Absorption Layer) Gelatin 1.00 UV absorber (Equivalent amount of Cpd-2 , 4 , 16 , 31, 32 ) 0.50 Anti-color mixing agent (Cpd-7, 17 etc.) Amount) 0.03 Dispersion medium (Cpd-6) 0.02 UV absorber solvent (Equivalent amounts of Solv-1, 5) 0.08 Anti-irradiation dye (Cpd-18, 19, 20, 21, 27) 10:10: 13:15:20 ratio) 0.05 10th layer (protective layer) Fine grain silver chlorobromide (silver chloride 97 mol%, average size 0.1 μm) 0.03 Acrylic modification of polyvinyl alcohol Polymer 0.01 (Molecular weight: 50,000) Polymethylmethacrylate particles (average particle size: 2.4 μm) and silicon oxide (average particle size: 5 μm) are equal amounts of each 0.05 Gelatin 1.80 Gelatin hardening agent (H 0.18 11th layer (back layer) Gelatin 2.50 UV absorber (Equivalent amounts of Cpd-2, 4 and 16) 0.50 Dye (Cpd-18, 19) , 20, 21, and 27) 0.06 12th layer (back layer protective layer) Polymethylmethacrylate particles (average particle size: 2.4 μm) and silicon oxide (average particle size: 5 μm), etc. Amount 0.05 Gelatin 2.00 Gelatin hardening agent (Equivalent amounts of H-1 and H-2) 0.14

[Submission date] February 1, 1993

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0189

[Correction method] Change

[Correction content]

[0189]

[Chemical 65]

Claims (1)

[Claims] 1. A support is provided with at least one of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer each containing an internal latent image type silver halide grain not previously fogged and a color image-forming coupler. Which is a direct positive color photographic light-sensitive material, wherein the color image-forming coupler of the red-sensitive layer is represented by the following formula (C): [In the formula, Y is a nonmetallic atomic group forming a 3- to 8-membered heterocycle with a nitrogen atom, and in the heterocycle, a carbonyl group is not directly bonded to the nitrogen atom; L is an alkylene group. Z is a hydrogen atom or a coupling-off group; Ar is an aryl group; and Y, L, Z and Ar may have a substituent. ] The cyan coupler represented by the formula [1], and the color image-forming coupler of the blue-sensitive layer has an acyl group represented by the following formula (I): [In the formula, R ²¹ represents a monovalent group, and Q ²¹ represents, together with C,
Represents a group of non-metal atoms necessary to form a 3- to 5-membered hydrocarbon ring or a 3- to 5-membered heterocycle, provided that R ²¹ is not a hydrogen atom and is bonded to Q ²¹ ; It does not form a ring. ] A direct positive color photographic light-sensitive material which is an acylacetanilide type yellow coupler represented by the following formula (D): [In the formula, R ⁴¹ represents an alkyl group and R ⁴² represents an alkylene group, provided that R ⁴¹ and R ⁴² may be linked to each other to form a ring. ] The image forming method characterized by performing development processing using the developing agent shown by these.