JPH063778A - Color photographic sensitive material, color image forming method, and production of color proof - Google Patents

Abstract

PURPOSE:To increase the max. density and to obtain good whiteness by incorporating an acylacetoamide-type yellow coupler and a necleus-producing agent into at least one layer of the emulsion layer or nonphotosensitive layers. CONSTITUTION:This silver halide color photographic sensitive material has at least each one layer of silver halide emulsion layer and nonphotosensitive layer on a supporting body. At least one layer of the emulsion layer and nonphotosensitive layers contains an acylacetoamide-type yellow coupler having an acyl group expressed by the formula. Moreover, at least one layer of the emulsion layer and nonphotosensitive layers contains a necleus-producing agent. In the formula, RY<1> is a substituent, QY<1> is nonmetal atoms necessary to form a six-member heteroring or five-member heterocyclic ring containing two heteroatoms with C. Thereby, the obtd. yellow coupler has high color developing property, and the use amt. of the nucleus generating agent can be decreased.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color photographic light-sensitive material containing a novel yellow coupler and a nucleating agent, and a color image forming method and a color proof making method using the same.

[0002]

2. Description of the Related Art The process of working a color printed matter includes the steps of color-separating a color original and converting it into a halftone dot image to form a transmission halftone image. A printing plate is made from the obtained transmission type halftone dot image, and prior to this, there is a step of inspecting the state, characteristics, etc. of the final printed matter (actual printing) and performing necessary proofing (color proofing). As a color proofing method, conventionally, a method of making a printing plate and making a test print has been used. However, in recent years, various color proofs have been produced for the purpose of speeding up the calibration process and reducing costs. As a method for producing a color proof, a photopolymer, a diazo method, a surprint method using a photoadhesive polymer, an overlay method and the like are known (for example, US Pat. No. 3,582,327, JP-A-56-56).
501217, 59-97140). However, all of these methods require superposition and transfer of images, and also require superposition and transfer of a plurality of figures, and the process is complicated and requires a lot of time and cost. . JP-A-56-104335
The publication discloses a method for producing a color proof using a color photographic light-sensitive material, and this method has a great merit in terms of process simplicity and low cost, and is excellent in tone reproducibility. There are features. The color proofing method using the above color photographic light-sensitive material uses a silver halide color photographic light-sensitive material of a coloring method having a continuous gradation, and a magenta (M) color, cyan (C) color, yellow ( This is a method in which each color of Y) and black (B) is sequentially contact-exposed so that a color negative is printed on a color paper, and then a designated color development processing is performed to obtain a color proof. This method has the features that the steps are simple and easy to automate as compared with the various methods described above. There are several possible silver halide color photographic light-sensitive materials that can be used in such color proofs. Among them, the transmission type black and white halftone image used in the production process of the color printed matter described above is often a positive type especially in Japan and Europe, and therefore, as a silver halide color photographic light-sensitive material for color proofing. Posi-positive type photosensitive materials are often used. Among them, direct positive type color photographic light-sensitive materials, which have been rapidly progressing in practical use technology in recent years, are attracting attention as being most suitable for use in color proof because of the ease of processing.

As a method for forming a positive image using a conventionally known direct positive silver halide photographic light-sensitive material, there is a method using an internal latent image type silver halide emulsion which has not been fogged in advance. This method is a method in which a photographic light-sensitive material is subjected to surface development after image exposure, after being subjected to a fog treatment or while being subjected to a fog treatment to directly obtain a positive image. The internal latent image type silver halide photographic emulsion which has not been previously fogged is a type of halogenated type in which a silver halide grain has a photosensitive nucleus mainly inside and a latent image is mainly formed inside the grain by exposure. A silver photographic light sensitive emulsion. Various techniques have been known so far in this field. For example, US Pat.
No. 0, No. 2466957, No. 2497875, No. 2
No. 588898, No. 3317322, No. 376126
6, 37,96577 and British Patent No. 11513.
63, No. 1155053, No. 1011062, etc. are the main ones. The formation mechanism of the direct positive image is explained as follows. That is, when imagewise exposure is carried out, a so-called internal latent image is formed on the silver halide, and by subjecting it to a fog treatment, a surface desensitizing action due to this internal latent image works (that is, halogenation in an exposed portion is performed). (Development nuclei (fog nuclei) are not generated on the surface of silver), development nuclei are selectively generated only on the surface of unexposed areas of silver halide, and then normal surface development treatment is performed to unexposed areas. Photo image (positive image)
Is formed. The fog treatment method includes a so-called "chemical fog method" which uses a nucleating agent, and a "light fog method" which exposes the entire surface of the photosensitive layer. As the nucleating agent, for example, Research Disclosure Magazine, No. 22534 (1983 1
P. 50-54, same magazine, No. 15162 (1976)
Nov., pp. 76-77, No. 23510 (19
(November 1983) Quaternary heterocyclic compounds described on pages 346 to 352, hydrazine compounds and the like are known.

With the diversification of direct positive color photographic light-sensitive material applications as described above, the demands on the obtained image (image quality) become more and more severe, and the maximum image density is high and the minimum image density is low, that is, It is desired that the image has a large ratio between the maximum image density and the minimum image density.
Particularly in the applications of color copying and color proof, it is important to obtain a high color reproducibility by increasing the maximum image density and decreasing the minimum image density. In the system using the nucleating agent as described above, the highlight portion of the characteristic curve of the obtained image tends to be softened. For this reason, the minimum image density (Dmin) increases with the actual exposure amount, which may cause a decrease in whiteness. As an effective method for suppressing such a decrease in whiteness, there is a method in which the amount of the nucleating agent used is reduced to make the highlight portion harder. However, in this way, the maximum density (Dmax) is reduced. There is a problem that it is easy.

By the way, a positive color image is formed by forming a coloring dye by a coupling reaction between an oxidized product of a developing agent and a coupler. Conventionally, as a yellow coupler, an acylacetamide type yellow coupler having a pivaloyl group as an acyl group has been preferably used (see, for example, JP-A-2-220049). However, the acylacetamide type yellow coupler having a pivaloyl group as described above has a problem that the color developability is low. Therefore, in the light-sensitive material using the conventional yellow coupler as described above, it is difficult to obtain a yellow image having a sufficiently high maximum density, and it is also difficult to improve the whiteness by reducing the amount of the nucleating agent described above. There was room for further improvement in applications such as color copying and color proofing.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a color photographic light-sensitive material which gives a yellow color image having a high maximum density and good whiteness, and a color image forming method. Another object of the present invention is to provide a method for producing a color proof that can obtain a yellow colored image having a hue close to that of the printing ink (having good color reproducibility).

[0007]

The first invention of the present invention is as follows:
In a silver halide color photographic light-sensitive material in which at least one silver halide emulsion layer and at least one non-light-sensitive layer are provided on a support, the following formula ( A silver halide containing an acylacetamide type yellow coupler having an acyl group represented by Ya), and at least one of the emulsion layer and the non-photosensitive layer containing a nucleating agent. It is found in color photographic light-sensitive materials.

[0008]

[Chemical 7]

[In the formula (Ya), R ^Y1 represents a substituent,
Q ^Y1 represents a non-metallic atomic group necessary for forming a 6-membered heterocycle with C or a 5-membered heterocycle containing two heteroatoms. ]

A second invention of the present invention comprises the above color photographic light-sensitive material, which is represented by the following formula (D):

[0011]

[Chemical 8]

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

A third invention of the present invention is a cyan plate halftone dot image film, a magenta halftone dot image film, a yellow halftone dot image film obtained by color separation and halftone image conversion of the above color photographic light-sensitive material. And a black proof halftone image film, which is sequentially exposed by red light, green light and blue light, and then color development processing is performed. A fourth invention of the present invention is a color image forming method characterized in that the above color photographic light-sensitive material is subjected to color development processing after scanning exposure with an exposure time of 10 ^-3 seconds or less per pixel.

The preferred embodiments of the present invention will be described below.

(1) The acyl group represented by the above formula (Ya) is represented by the following formula (Ya-1).

[0016]

[Chemical 9]

(In the above formula, Z ^Y1 represents a hetero atom selected from N, S, O and P, R ^Y4 represents a substituent, Q ^Y2 represents Z ^Y1 and a carbon atom together with a 6-membered member. Heterocycle, or Z ^Y1 , represents a non-metal atomic group necessary for forming a 5-membered heterocycle containing two heteroatoms together with carbon atoms.) (2) In formula (Y), R ^Y1 is halogen. An atom, a cyano group, an alkyl group, an alkenyl group, an alkoxy group, an alkylthio group, an alkylamino group, an alkylcarbonyl group, an aryl group, or an aryloxy group. (3) In the formula (Y), R ^Y2 is chlorine atom, trifluoromethyl, methoxy, phenoxy, p-tolyloxy or p-methoxyphenoxy. (4) In the color photographic light-sensitive material according to claim 1, the formula (Y
An acylacetamide type yellow coupler having an acyl group represented by a) and a nucleating agent are contained in the same layer (more preferably, a silver halide emulsion layer). (5) In the color photographic light-sensitive material according to claim 2, the formula (Y
a) The acylacetamide type yellow coupler having an acyl group represented by a) and the nucleation accelerator are in the same layer (more preferably, an emulsion layer containing an internal latent image type silver halide grain which has not been fogged in advance). include. (6) The color photographic light-sensitive material has at least one each of a red light-sensitive emulsion layer, a green light-sensitive emulsion layer and a blue light-sensitive emulsion layer.

[0018]

As described above, the color photographic light-sensitive material of the present invention contains an acylacetamide type yellow coupler characterized by an acyl group and a nucleating agent. This yellow coupler exhibits a high color-forming property, and therefore a yellow image having a high maximum density can be obtained. Therefore, the amount of the nucleating agent used can be reduced, and a yellow image with high whiteness can be realized while maintaining a high maximum density. Further, since the obtained yellow image is an image having a hue close to that of the printing ink (having good color reproducibility), it is particularly suitable as a material for producing a color proof.

[Detailed Description of the Invention] The color photographic light-sensitive material of the present invention will be described below. The color photographic light-sensitive material of the present invention contains a novel yellow coupler and a nucleating agent as described above. The color photographic light-sensitive material includes various types that form a yellow color-developing (dye) image by a coupling reaction between the yellow coupler and an oxidant produced by color development processing.
Specific examples include a color negative film, a color positive film (color reversal film, a film for color printing), a color reversal paper, a color auto positive film, or a color auto positive paper. However, the yellow dye image obtained with the color photographic light-sensitive material of the present invention is particularly advantageous when used as a color copy image or a color proof image, and therefore, as a color auto positive paper (direct positive color photographic light-sensitive material). It is advantageous to use.

In the color photographic light-sensitive material of the present invention, at least one silver halide emulsion layer and at least one light-insensitive layer are provided on a support. Each of the acylacetamide type yellow coupler having an acyl group represented by the formula (Ya) and the nucleating agent is contained in at least one of the emulsion layer and the non-photosensitive layer. The yellow coupler and the nucleating agent are preferably contained together in the same layer, and particularly preferably the yellow coupler and the nucleating agent are contained together in the silver halide emulsion layer. Further, as described above, the color photographic light-sensitive material of the present invention is an embodiment in which the silver halide emulsion layer is an emulsion layer containing internal latent image type silver halide grains which have not been fogged in advance, that is, a direct positive color photographic light-sensitive material. In this embodiment, the acylacetamide type yellow coupler having an acyl group represented by the formula (Ya), the nucleating agent, and the nucleating accelerator are added to the emulsion layer or the non-photosensitive layer. It is preferably contained in at least one of the layers. Also in this case, it is preferable that all of the yellow coupler, the nucleating agent and the nucleation accelerator are contained together in the same layer. In particular, the yellow coupler, the nucleating agent and the nucleation accelerator are particularly preferable. Are preferably simultaneously contained in an emulsion layer containing internal latent image type silver halide grains which have not been previously fogged. The yellow coupler will be described below.

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

[0022]

[Chemical 10]

In the formula (Y), R ^Y1 represents a substituent. Q ^Y1 represents, together with C, a non-metal atom group necessary for forming a 6-membered heterocycle or a 5-membered heterocycle containing 2 heteroatoms. R ^Y2 represents a hydrogen atom, a halogen atom (fluorine, chlorine, bromine, iodine; the same applies hereinafter in the description of formula (Y)), an alkoxy group, an aryloxy group, an alkyl group, an amino group or a heterocyclic group. R ^Y3 represents a substitutable group on the benzene ring. X ^Y1 represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized product of an aromatic primary amine developing agent (hereinafter, leaving group). P represents an integer of 0 to 4. However, when P is plural, plural R ^Y3 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, the alkyl group is linear, branched or cyclic, unless otherwise specified. 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 formula (Y) is or contains an alkenyl group, unless otherwise specified, the alkenyl group may be linear, branched or cyclic, substituted. Also means an alkenyl group.
Examples of alkenyl groups include allyl, 3-cyclohexenyl, oleyl.

When the substituent in 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-.
Mention may be made of 2,4-imidazolidindione-3-yl.

Hereinafter, R ^Y1 , R ^Y2 in the formula (Y),
R ^Y3 , Q ^Y1 and X ^Y1 will be described in detail. First, the expression (Y
The acyl group represented by a) will be described first. R ^Y1 is a halogen atom, a cyano group, an alkyl group having 1 to 30 carbon atoms (more preferably 1 to 8 carbon atoms), an alkoxy group having 1 to 30 carbon atoms (more preferably 1 to 8 carbon atoms) An alkylthio group having 1 to 30 carbon atoms (more preferably 1 to 8 carbon atoms), 1 to 30 carbon atoms (more preferably 1 to 30 carbon atoms)
8) Alkylamino group, C1-30 (more preferably C1-8) alkylcarbonyl group, C6-30 (more preferably C6-24) aryl group, carbon number 6 to 30 (more preferably 6 to 2 carbon atoms)
The aryloxy group of 4) is preferable. These groups may have a substituent (or atom). Examples of the substituent (or atom) include a halogen atom, an alkyl group, an alkoxy group, a nitro group, an amino group, a carbonamido group,
A sulfonamide group and an acyl group can be mentioned.
R ^Y1 may also be a ballast group, or R
^Y1 may combine with Q ^Y1 to form a bicyclo ring.

It is more preferable that R ^Y1 is a halogen atom (fluorine, chlorine, bromine), an alkyl group (ethyl, methyl), an alkoxy group (especially methoxy), an alkylthio group (especially methylthio).

The above Q ^Y1 is N, S, O together with carbon atoms.
And a 6-membered heterocycle containing at least one heteroatom selected from P in the ring, or a 5-membered heterocycle containing two heteroatoms selected from N, S, O and P in the ring. Represents the group of non-metal atoms required to form. The ring formed by Q ^Y1 together with the carbon atom may contain an unsaturated bond in the ring, and may be substituted or unsubstituted. When it is substituted, the substituent is the same as the substituent described for R ^Y3 described later. Further, it may be substituted with an oxo group (═O), and the substituents may be bonded to each other to form a ring. In the present invention, in the ring formed by Q ^Y1 together with the carbon atom, it is preferable that the 2-position of the carbonyl-substituted carbon (β-position when viewed from the carbonyl group) is a hetero atom. That is, it is preferable to have an acyl group represented by the following formula (Ya-1).

[0031]

[Chemical 11]

In the above formula, Z ^Y1 represents a hetero atom selected from N, S, O and P, R ^Y4 represents a substituent, and Q ^Y2 represents a 6-membered complex with Z ^Y1 and a carbon atom. A ring, or Z ^Y1 , represents a non-metal atomic group necessary for forming a 5-membered heterocycle containing two heteroatoms together with a carbon atom. The above R ^Y4 has the same meaning as the substituent described above for R ^Y1 ,
Q ^Y2 has the same ^meaning as described in the above formula (Ya) of Q ^Y1 .

The preferred specific examples of the acyl group represented by the formula (Ya) are described below.

[0034]

[Chemical 12]

[0035]

[Chemical 13]

[0036]

[Chemical 14]

[0037]

[Chemical 15]

R ^Y2 is a halogen atom, which may be substituted, and has 1 to 30 carbon atoms (more preferably,
An alkoxy group having 1 to 18 carbon atoms, an aryloxy group having 6 to 30 carbon atoms (more preferably 6 to 24 carbon atoms),
An alkyl group having 1 to 30 carbon atoms (more preferably 1 to 6 carbon atoms), an amino group having 0 to 30 carbon atoms or 1 to carbon atoms
A heterocyclic group having 30 (more preferably 1 to 24 carbon atoms) is preferable. In addition, examples of these substituents include a halogen atom, an alkyl group, an alkoxy group, and an aryloxy group. The preferred specific examples of the group represented by R ^Y2 are described below.

[0039]

[Chemical 16]

R ^Y2 is a chlorine atom, trifluoromethyl, methoxy, phenoxy, p-tolyloxy or p
-Methoxyphenoxy is particularly preferred.

Examples of the group represented by R ^Y3 that can be substituted on the benzene ring include a halogen atom, an alkyl 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, sulfamoylamino group, Alkoxycarbonylamino group, alkoxysulfonyl group,
Examples thereof include a nitro group, a heterocyclic group, a cyano group, an acyl group, an acyloxy group, an alkylsulfonyloxy group, and an arylsulfonyloxy group.

The above R ^Y3 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 aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, and 2 to 2 carbon atoms
30 alkoxycarbonyl group, C7-30 aryloxycarbonyl group, C1-30 carbonamido group, C1-30 sulfonamide group, C1
˜30 carbamoyl group, 0 to 30 carbon sulfamoyl group, 1 to 30 carbon alkylsulfonyl group, 6 to 30 carbon arylsulfonyl group, 1 to 30 carbon ureido group, 0 to 30 carbon atom A sulfamoylamino group, an alkoxycarbonylamino group having 2 to 30 carbon atoms,
A heterocyclic group having 1 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, an alkylsulfonyloxy group having 1 to 30 carbon atoms, and an arylsulfonyloxy group having 6 to 30 carbon atoms.

Examples of the substituent include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group and an aryl group. Sulfonyl 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, aryloxycarbonyl group A group, an alkylsulfonyloxy group and an arylsulfonyloxy group.

R ^Y3 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 a sulfamoyl group, an alkoxycarbonyl group, a carbonamide group or a sulfonamide group. R above
^Y3 is preferably substituted at the meta position or para position on the benzene ring with respect to the acetamide bonding group (-CHCONH-).

The above P is preferably 1 or 2. The preferred specific examples of the group represented by R ^Y3 are described below.

[0046]

[Chemical 17]

[0047]

[Chemical 18]

As an example of a group (leaving group) represented by X ^Y1 which can be split off by a coupling reaction with an oxidation product of an aromatic primary amine developing agent (leaving group), 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 ^Y1 is preferably a heterocyclic group or an aryloxy group which is bonded to the coupling active position by a nitrogen atom.

When X ^Y1 represents a heterocyclic group, X ^Y1 is an ^optionally substituted 5- to 7-membered monocyclic or condensed-ring heterocycle, and preferable 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, thiazolidin-2-one, benzimidazolin-2-one, benzoxazolin-2-one, benzothiazolin-2-one , 2-pyrrolin-5-one, 2-imidazoline-5-
On, indoline-2,3-dione, 2,6-dioxypurine, parabanic acid, 1,2,4-triazolidine-
3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone, 6-pyridazone-2-pyrazone, 2-amino-1,3,4-thiazolidine, 2-imino-1,3,4
-Thiazolidin-4-one may be mentioned.

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

[0052] The X ^Y1 is, when an aryloxy group, X ^Y1 is preferably an aryloxy group having 6 to 30 carbon atoms, wherein X ^Y1 is selected from the group of substituents mentioned case 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 ^Y1 is represented by the following formulas (X ^Y1 -1), (X
^The heterocyclic group represented by ^Y1-2 ) or (XY1-3) or the aryloxy group is more preferred.

[0055]

[Chemical 19]

In the above formula (X ^Y1-1 ), Z ^Y2 means the following groups.

[0057]

[Chemical 20]

Here, R ^Y5 , R ^Y6 , R ^Y9 and R ^Y10 are
It represents 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 an amino group. R ^Y7 and R ^Y8 represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an alkylsulfonyl group, an arylsulfonyl group or an alkoxycarbonyl group. R ^Y11 and R ^Y12 represent a hydrogen atom, an alkyl group or an aryl group. R ^Y11 and R ^Y12 are
They may combine with each other to form a benzene ring. R ^Y5 and R
^Y6 , R ^Y6 and R ^Y7 , R ^Y7 and R ^Y8, or R ^Y5 and R ^Y9 may be bonded to each other to form a ring (eg, cyclobutane, cyclohexane, cycloheptane, cyclohexene, pyrrolidine, piperidine). The above Z ^Y2 is preferably the following groups.

[0059]

[Chemical 21]

The heterocyclic group represented by the above formula (X ^Y1 -1) has 2 to 30, preferably 4 to 20 and more preferably 5 to 16 carbon atoms.

[0061]

[Chemical formula 22]

Here, at least one of R ^Y13 and R ^Y14 is a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, a carboxyl group, an alkoxycarbonyl group, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group. , An alkylsulfonyl group, an arylsulfonyl group or an acyl group (however, the other may be a hydrogen atom, an alkyl group or an alkoxy group). R ^Y15 represents a group having the same meaning as R ^Y13 or R ^Y14 . m represents an integer of 0 to 2. The aryloxy group represented by the above (X ^Y1 -2) has 6 to 30, preferably 6 to 24, and more preferably 6 to 15 carbon atoms.

[0063]

[Chemical formula 23]

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 ^Y1 -3) has 2 to 30 carbon atoms, preferably 2 carbon atoms.
-24, more preferably 2-16.

It is particularly preferable that X ^Y1 is a heterocyclic group represented by the following formula (X ^Y1 -1).

The yellow coupler represented by the formula (Y) has substituents R ^Y1 , Q ^Y1 , X ^Y1 or

[0067]

[Chemical formula 24]

In, a dimer or a multimer having more than one valence may be formed to bond with each other. In this case, the number of carbon atoms shown in each of the above substituents may be out of the specified range. Specific examples of the heterocyclic group represented by the formula X ^Y1 are shown below.

[0069]

[Chemical 25]

[0070]

[Chemical formula 26]

[0071]

[Chemical 27]

[0072]

[Chemical 28]

[0073]

[Chemical 29]

Specific examples of the yellow coupler represented by the formula (Y) are shown below.

[0075]

[Chemical 30]

[0076]

[Chemical 31]

[0077]

[Chemical 32]

[0078]

[Chemical 33]

[0079]

[Chemical 34]

[0080]

[Chemical 35]

[0081]

[Chemical 36]

[0082]

[Chemical 37]

[0083]

[Chemical 38]

[0084]

[Chemical Formula 39]

[0085]

[Chemical 40]

[0086]

[Chemical 41]

[0087]

[Chemical 42]

[0088]

[Chemical 43]

[0089]

[Chemical 44]

[0090]

[Chemical formula 45]

[0091]

[Chemical formula 46]

[0092]

[Chemical 47]

[0093]

[Chemical 48]

[0094]

[Chemical 49]

[0095]

[Chemical 50]

[0096]

[Chemical 51]

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 synthesis examples of the yellow coupler according to the present invention are shown below. Synthesis Example 1 (Synthesis of Compound Y-29) Compound Y-29 can be synthesized by the following synthetic route.

[0099]

[Chemical 52]

(1) Pyruvate ethyl ester was added to 2,
After acetalization with 4-pentyldiol, 17.2 g of compound A obtained by hydrolysis was added to 50 ml of methylene chloride and N, N′-dimethylformamide 1
Dissolve in 1 ml, and under ice-cooling, add oxalyl chloride 1 to it.
0.5 ml was added dropwise. After stirring at room temperature for 1 hour, all the solvents were distilled off under reduced pressure to obtain a carboxylic acid chloride of compound A. (2) 40 g of methanol was added to 2.4 g of active magnesium.
To the magnesium methoxide obtained by dropping ml, 13.1 g of ethyl 3-oxobutanoate was added, and the mixture was refluxed for 2 hours. After the methanol was distilled off under reduced pressure, the carboxylic acid chloride of the compound A was added dropwise with 50 ml of tetrahydrofuran and refluxed for 30 minutes. After post-treatment by a conventional method, column chromatography gave Compound B (17.1 g) as an oil. (3) Compound B was added to a solution of 100 ml of ethanol and 20 ml of aqueous ammonia (30%), and the mixture was stirred at 50 ° C. for 30 minutes. Post-treatment was carried out by a conventional method to obtain 13.8 g of an oily substance of β-keto ester (Compound C). (4) Compound C 13.8 g and 2,4-dichloro-5-
21.3 g of dodecyloxycarbonylaniline was heated at 120 ° C. without solvent. After 1 hour, the mixture was further heated and reacted under reduced pressure for 1 hour, and then the reaction product was purified by column chromatography using a mixed solvent of n-hexane and ethyl acetate to obtain 22.8 g of compound D. (5) Compound D (22.8 g) was dissolved in methylene chloride (300 ml), and sulfuryl chloride (5.67 g) was added dropwise under ice cooling. After reacting for 30 minutes, all the solvents were distilled off under reduced pressure, and N, N-dimethylformamide (100 ml) was added thereto.
18.7 g of 1-benzyl-5-ethoxyhydantoin,
And 12 ml of triethylamine were added and reacted at 40 ° C. for 2 hours. After post-treatment by a conventional method, the product is purified by column chromatography to obtain the objective compound Y
19.2 g of -29 was obtained as an oil. The structure of the obtained compound was confirmed by mass spectrum, NMR spectrum and elemental analysis.

Synthesis Example 2 (Synthesis of Exemplified Compound Y-10) Compound A used in the synthesis of Exemplified Compound Y-29
Compound E shown below was used in place of
2-Methoxy-5- [2- (2,4-di-t) instead of 4-dichloro-5-dodecyloxycarbonylaniline
Exemplified compound Y-10 was obtained in the same manner except that -amylphenoxy) butanoic acid amide] aniline was used. The structure of the obtained compound was confirmed by mass spectrum, NMR spectrum and elemental analysis.

[0102]

[Chemical 53]

Synthesis Example 3 (Synthesis of Exemplified Compound Y-66) (1) 2-Methyl-1,3-dioxolane-2-carboxylic acid synthesized by the method described in J. Chem. Soc., 1959, 477. 38.1 g of oxalyl chloride was added dropwise to a mixture of 33 g, methylene chloride 100 ml, and N, N-dimethylformamide 1 ml at room temperature over 30 minutes.
After the dropping, the mixture was reacted at room temperature for 2 hours, and then methylene chloride and excess oxalyl chloride were removed under reduced pressure of an aspirator to obtain an oily substance of 2-methyl-1,3-dioxolane-2-carbonyl chloride. . (2) 100 ml of methanol was added dropwise to a mixture of 6 g of magnesium and 2 ml 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 under heating under reflux for 30 minutes. 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 ml) was added to the reaction product to disperse it, and the previously obtained 2-methyl-1,3-dioxolane-2-carbonyl chloride was added dropwise thereto at room temperature. After reacting for 30 minutes, the reaction solution was extracted with 300 ml of ethyl acetate and diluted sulfuric acid water, washed with water, and the organic layer was dried over anhydrous sodium sulfate, and then the solvent was distilled off to give 2- (2-methyl-1,3,3). An oily product of ethyl-dioixolane-2-carbonyl) -3-oxobutanoate 63.
3 g was obtained. (3) 2- (2-methyl-1,3-dioxolane-2-
A solution of 63 g of ethyl carbonyl) -3-oxobutanoate and 160 ml of ethanol was stirred at room temperature, and then stirred therein.
60 ml of% ammonia water was added dropwise over 10 minutes. Then, the mixture was stirred for 1 hour, extracted with 300 ml of ethyl acetate, diluted sulfuric acid aqueous solution, neutralized, washed with water, and the organic layer was dried over anhydrous sodium sulfate, and then the solvent was distilled off (2-methyl-1,3- Dioxolane-2-carbonyl) ethyl acetate oil 5
0 g was obtained. (4) 2-Methyl-1,3-dioxolane-obtained above
An internal temperature of 100 g of 40 g of ethyl 2-carbonyl) acetate and 44.5 g of N- (3-amino-4-chlorophenyl) -2- (2,4-di-t-pentylphenoxy) butanamide.
The mixture was heated to reflux under reduced pressure of an aspirator at ˜120 ° C. Four
After reacting for a time, the reaction solution was purified by column chromatography with a mixed solvent of n-hexane and ethyl acetate,
51 g of Exemplified compound Y-66 was obtained as a viscous oil. The structure of the obtained compound was confirmed by mass spectrum, NMR spectrum and elemental analysis.

Synthesis Example 4 (Synthesis of Exemplified Compound Y-36) (1) 24.0 g of Exemplified Compound (Y-66) obtained above was dissolved in 300 ml of methylene chloride, and sulfuryl chloride of 5. 4g was dripped over 10 minutes. After reacting for 30 minutes, the reaction solution was thoroughly washed with water, dried over anhydrous sodium sulfate, and concentrated to obtain a chloride of Exemplified Compound Y-33. (2) 1-benzyl-5-ethoxyhydantoin 18.
7 g, triethylamine 11.2 ml, and N, N-
A solution of the chloride of Exemplified Compound Y-33 synthesized above in 50 ml of N, N-dimethylformamide was dropped into a mixed solution of 50 ml of dimethylformamide at room temperature over 30 minutes. Then, after reacting for 4 hours at 40 ° C., the reaction solution was extracted with 300 ml of ethyl acetate, washed with water,
Further, it was washed with 300 ml of a 2% triethylamine aqueous solution and then neutralized with dilute sulfuric acid water. The organic layer was dried over anhydrous sodium sulfate and the solvent was distilled off to obtain an oily substance which 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 then dried to obtain 23.4 g of crystals of Exemplified compound Y-25. The structure of the obtained compound was confirmed by mass spectrum, NMR spectrum and elemental analysis.

Synthesis Example 5 (Synthesis of Exemplified Compound Y-67) (1) 2-Methyl-1,3-dithiolane-2-synthesized by the method described in Tetrahedoron, 1968, 24, 24,5293.
41 g of carboxylic acid was added to 2-methyl-1,3 of Synthesis Example 3 above.
By using as a raw material instead of dioxolane-2-carboxylic acid and performing the same operation as in Synthesis Example 3, N-
51 g of [2-chloro-5- (2- (2,4-di-t-pentylphenoxy) butanamide) phenyl] -2- (2-methyl-1,3-dithiolane-2-carbonyl) acetamide was obtained as an amorphous substance. Got as. (2) Next, this N- [2-chloro-5- (2-
25.3 g of (2,4-di-t-pentylphenoxy) butanamido) phenyl] -2- (2-methyl-1,3-dithiolane-2-carbonyl) acetamide was used in place of Exemplified Compound Y-66 in Synthesis Example 4. Was used as a raw material in the same manner and was subjected to the same reaction treatment, and then the obtained oil was purified by column chromatography with a mixed solvent of n-hexane and ethyl acetate to give Exemplified Compound Y-67 as a viscous oil. 27.2 g was obtained. The structure of the obtained compound was confirmed by mass spectrum, NMR spectrum and elemental analysis.

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

The amount of the yellow coupler represented by the above formula (Y) in the photosensitive material is 1 per 1 m ² of the photosensitive material.
The range of x10 ^-5 mol to 1 x 10 ^-2 mol is general,
It is preferably in the range of 1 × 10 ⁻⁴ mol to 10 ⁻³ mol, more preferably 2 × 10 ⁻⁴ mol to 10 ⁻³ mol.

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

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

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

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

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

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

In the silver halide emulsion used in the present invention, various polyvalent metal ion impurities can be introduced in the process of emulsion grain formation or physical ripening. Examples of compounds used include cadmium, zinc, lead, copper, thallium, salts such as bismuth, or Group VIII elements iron, ruthenium, rhodium, palladium, osmium,
Examples thereof include salts of iridium and platinum, or complex salts. Of these metals, lead, iridium, bismuth and rhodium are preferred. The amount of these compounds added may vary depending on the purpose, but it is 10 ^-9 to 10 ^-2 mol (more preferably 10 ^-7 to 1) with respect to the silver halide.
0 ^-3 mol) are preferred. For the method of incorporating these metals, see US Pat. Nos. 3,761,276 and 4,395,478.
And Japanese Patent Application Laid-Open No. 59-216136.

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

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

Specific examples of the internal latent image type silver halide emulsion include, for example, conversion type silver halide emulsions described in US Pat. No. 2,592,250; or US Pat. Nos. 3,761,276, 3,850,637 and 3,923,513. , 4035185 and 43954.
78, 4504570, JP-A-52-
No. 156614, No. 55-127549, No. 53-6
0222, 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;
No. 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 concerning 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 core / shell silver halide molar ratio of 20/1 or less and 1/10.
0 or more is particularly preferable.

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

In the present invention, various color couplers can be used in addition to the above-mentioned yellow coupler. Typical examples of useful color couplers include pyrazolone or pyrazoloazole compounds and open-chain or heterocyclic ketomethylene compounds. Specific examples of these magenta and cyan couplers that can be used in the present invention are described in "Research Disclosure" No. 17643 (1
Issued December 1978) Page 25, Item VII-D, ibid. 1
8717 (issued in November 1979) and Japanese Patent Laid-Open No. 62-
It is described in the compounds described in JP-A-215272 and the patents cited therein. The 5-pyrazolone-based magenta coupler which can be preferably used in the present invention is a 5-pyrazolone-based coupler in which the 3-position is substituted with an arylamino group or an acylamino group (among others, a sulfur atom-eliminating type two-equivalent coupler). More preferred are pyrazoloazole-based couplers, of which US Pat. No. 372 is particularly preferred.
Pyrazolo [5,1-c] described in 5067
[1,2,4] triazoles and the like are preferable, but the imidazo [1,3] described in U.S. Pat. No. 4,500,630 is preferred in view of low yellow sub-absorption of a coloring dye and light fastness.
2-b] pyrazoles are more preferred and are described in US Pat.
40654, pyrazolo [1,5-b] [1,
2,4] triazole is particularly preferred. Examples of cyan couplers that can be preferably used in the present invention include naphthol-based and phenol-based couplers described in U.S. Pat. Nos. 2,474,293 and 4,052,212, and phenols described in U.S. Pat. No. 3,777,002. It is a phenolic cyan coupler having an alkyl group of ethyl group or more at the meta position of the nucleus, and other 2,5-
A diacylamino-substituted phenol coupler is also preferable in terms of color image fastness.

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

As the binder or protective colloid that can be used in the emulsion layer and the non-photosensitive layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. . In the light-sensitive material of the present invention, an antifoggant or a color mixing inhibitor can also be used. Typical examples thereof include the compounds described in JP-A No. 62-215272, pages 185 to 193. Examples of the compound releasing a photographically useful group include JP-A-63-153540 and 63-25955.
No. 5, JP-A-2-61636, and JP-A-2-2440.
41, the compound of each statement of 2-308240 are mentioned. In the present invention, a color forming enhancer can be used for the purpose of improving the color forming property of the coupler. Typical examples of the compounds are JP-A-62-215272, 121 to 12.
Those described on page 5 can be mentioned. 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 listed in Research Disclosure No. 17643
Items VII to XIII (issued in December 1978) 25 to 2
7 pages, and 18716 (issued in November 1979) 6
47-651.

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

The color photographic light-sensitive material of the present invention contains a nucleating agent. The nucleating agent functions as a development accelerator when the color photographic light-sensitive material is a normal color photographic light-sensitive material (for example, a color negative film).
Further, in the direct positive color photographic light-sensitive material which is a preferred embodiment of the present invention, the nucleating agent acts during surface development processing of an internal latent image type silver halide emulsion which has not been fogged in advance to form a direct positive image. Work. It is a substance used when carrying out the so-called "chemical fog method". The nucleating agent is a silver halide emulsion layer or an adjacent non-photosensitive layer (for example, an intermediate layer, an undercoat layer or a back layer).
According to the present invention, which is contained in at least one layer of
It is preferably contained in the silver halide emulsion layer together with the acylacetamide type coupler having an acyl group represented by the formula (Ya). Examples of the nucleating agent that can be used in the present invention include those described in Research Disclosure, No. 22534 (January 1983) 50-5
P. 4, ibid., No. 15162 (November 1976) 7
Pages 6 to 77, No. 23510 (November 1983)
Mon) Quaternary heterocyclic compounds described on pages 346 to 352, hydrazine compounds, and the like. Two or more kinds of these nucleating agents may be used in combination. The nucleating agent used in the present invention is preferably a quaternary heterocyclic compound represented by the following formula (NI) or a hydrazine compound represented by (N-II).

[0124]

[Chemical 54]

In the above formula (N-I), Z ³¹ represents a nonmetallic atom group necessary for forming a 5- or 6-membered heterocyclic group. R ³¹ represents an aliphatic group. R ³² represents a hydrogen atom, an aliphatic group or an aromatic group. However, the above Z ³¹ , R ³¹
And R ³² may be substituted, and R ³² may combine with the heterocyclic ring completed by Z ³¹ to form a ring, and R ^32
At least one of the groups represented by ³¹ and R ³² and Z ³¹ contains an alkynyl group, an acyl group, a hydrazine group or a hydrazone group, or R ³¹ and R ³² form a 6-membered ring, and A pyridinium skeleton may be formed.
Y represents a counterion for charge balance, and n
Represents 0 or 1.

[0126]

[Chemical 55]

In the above formula (N-II), R ⁴¹ represents an aliphatic group, an aromatic group or a heterocyclic group. R ⁴² is a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group,
It represents an aryloxy group or an amino group. G represents a carbonyl group, a sulfonyl group, a sulfinyl group, a phosphoryl group or an iminomethylene group (HN = C =). R ⁴³ and R ⁴⁴ are both hydrogen atoms, or one is a hydrogen atom and the other is one of an alkylsulfonyl group, an arylsulfonyl group or an acyl group (provided that G, R ⁴² and R ⁴⁴ are G, R ^42, R ⁴⁴ and hydrazine nitrogen hydrazone in a form including a structure (= N-N = C = ) may be formed.). The quaternary heterocyclic compound represented by formula (N-I) is described in JP-A-2-90154 or JP-A-3-155543. In addition, the formula (N
The hydrazine compound represented by formula (II) is described in JP-A-2-9
No. 0154, or Japanese Patent Laid-Open No. 3-95546.

Typical nucleating agents represented by the above formulas (NI) and (N-II) are as follows. (N-I-1) 7- (3-cyclohexylmethoxythiocarbonylaminobenzamide) -10-propargyl-1,2,3,3
4-Tetrahydroacridinium trifluoromethanesulfonate (N-I-2) 6- (3-ethoxythiocarbonylaminobenzamido) -1-propargyl-2,3-trimethylenequinolinium trifluoromethanesulfonate (N-I) -3) 6-Ethoxythiocarbonylamino-2-methyl-1-
Propargylquinolinium trifluoromethanesulfonate (N-I-4) 7- [3- (5-mercaptotetrazol-1-yl)
Benzamide] -10-propargyl-1,2,3,4
-Tetrahydroacridinium perchlorate (N-II-1) 1-formyl-2- {4- [3- {3- [3- (5-mercaptotetrazol-1-yl) phenyl] ureido} benzsulfonamide] phenyl } Hydrazine (N-II-2) 1-formyl-2- {4- [3- (5-mercaptotetrazol-1-yl) benzenesulfonamide] phenyl} hydrazine

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

In the present invention, the "optical fog method" may be carried out in addition to the "chemical fog method".
The entire exposure in the "light fog method", that is, the fog exposure is performed after imagewise exposure, before color development processing or during color development processing. That is, the imagewise exposed light-sensitive material is exposed in a color developing solution or in a pre-bath of the color developing solution, or is taken out from these solutions and dried before being exposed. Is most preferred. As the light source for the fogging exposure, for example, JP-A-56-137 is used.
A light source having a high color rendering property (as close to white as possible) as described in JP-A-350 and JP-A-58-70223 is preferable. The illuminance of light is 0.01 to 2000 lux, preferably 0.05 to 30 lux, and more preferably 0.05 to
5 looks is suitable. The light-sensitive material using a higher-sensitivity emulsion is preferred to have low illuminance. The illuminance may be adjusted by changing the luminous intensity of the light source, or by changing the light exposure by various filters, the distance between the light-sensitive material and the light source, or the angle between the light-sensitive material and the light source. Further, the illuminance of the above-mentioned fogging light can be continuously or stepwise increased from a low illuminance to a high illuminance. It is preferable to immerse the light-sensitive material in a color developing solution or a solution of its pre-bath so that the solution sufficiently penetrates into the emulsion layer of the light-sensitive material before irradiation with light. The time from the penetration of the liquid to the light fog exposure is generally 2 seconds to 2 minutes,
It is preferably 5 seconds to 1 minute, more preferably 10 seconds to 30 seconds. The exposure time for fogging is generally 0.0
It is 1 second to 2 minutes, preferably 0.1 second to 1 minute, and more preferably 1 second to 40 seconds.

In the direct positive color photographic light-sensitive material of the preferred embodiment of the present invention, when the above nucleating agent is used, it is preferable to use a nucleating accelerator for promoting the action of the nucleating agent. A nucleation accelerator does not substantially function as a nucleating agent, but accelerates the action of the nucleating agent to increase the maximum density of the direct positive image and / or obtain a certain maximum density of the direct positive image. Means a substance that has the function of accelerating the development time required. The nucleation accelerator used in the present invention is represented by the following formula (I) or (II).

[0132]

[Chemical 56]

In the formula (I), Q ¹¹ is 5 member or 6
Represents a group of atoms necessary for forming a member heterocycle (the heterocycle may be condensed with a carbon aromatic ring or a heteroaromatic ring). M represents a hydrogen atom, an alkali metal atom, an ammonium group, or a group capable of cleaving under alkaline conditions.

[0134]

[Chemical 57]

In formula (II), Q ¹² represents an atomic group necessary for forming a 5-membered or 6-membered heterocycle capable of forming an imino silver (heterocycle is a carbon aromatic ring or a heteroaromatic ring). It may be condensed). M represents a hydrogen atom, an alkali metal atom, an ammonium group, or a group capable of cleaving under alkaline conditions. The nucleation accelerator will be briefly described below. First, the nucleation accelerator represented by the above formula (I) will be described. The atomic group necessary for forming the 5- or 6-membered heterocycle represented by Q ¹¹ is at least one atom of carbon atom, nitrogen atom, oxygen atom, sulfur atom, and selenium atom. Examples of the heterocycle include tetrazole, triazole, imidazole, thiadiazole,
Oxadiazole, selenadiazole, oxazole,
Thiazole, benzoxazole, benzthiazole,
Benzimidazole, pyrimidine, triazaindene,
Mention may be made of tetraazaindene and pentaazaindene. These heterocyclic groups may further have a substituent. Examples of the alkali metal atom represented by M include sodium and potassium, and examples of the ammonium group include trimethylammonium and dimethylbenzylammonium.
Examples of the group capable of cleaving under alkaline conditions (hydrogen atom or group capable of becoming an alkali metal atom) include acetyl, dianoethyl, and methanesulfonylethyl. Next, the nucleation accelerator represented by the above formula (II) will be described. The atomic group necessary for forming the 5-membered or 6-membered heterocycle represented by Q ¹² capable of forming iminosilver is the same as the atom constituting Q ¹¹ . Examples of the heterocycle include indazole, benzimidazole, benzotriazole, benzoxazole, benzthiazole, imidazole, thiazole, oxazole, triazole, tetrazole, triazaindene,
Mention may be made of pentaazaindene, diazaindene, pyrazole, and indole. These heterocyclic groups may further have a substituent. M has the same meaning as the group represented by the above formula (I). In the present invention,
The nucleation accelerator shown below can be preferably used.

[0136]

[Chemical 58]

Two or more of the nucleation accelerators may be used in combination. The details of the nucleation accelerator represented by the above formula (I) or (II) are described in JP-A-2-89048.
It is described in Japanese Patent Publication No. The nucleation accelerator is contained in at least one of the internal latent image type silver halide emulsion layer which has not been fogged in advance or the adjacent non-photosensitive layer (intermediate layer or protective layer). The nucleation accelerator is represented by the above formula (CaI)
Alternatively, it is preferably contained in the silver halide emulsion together with a cyan coupler represented by the formula (CbI) and a nucleating agent. The addition amount of the nucleation accelerator is preferably 10 ⁻⁶ to 10 ⁻² mol, and more preferably 10 ⁻⁵ to 10 ⁻² mol, per mol of silver halide. The nucleation accelerator may be contained in the processing solution (that is, the developing solution or its pre-bath). In that case, 10 ⁻⁸ to 10 ⁻⁸ per 1 liter of the processing solution.
^-3 mol is preferable, and 10 ^-7 to 10 ^-4 mol is more preferable.

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

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are made of a flexible support 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 (eg, polyethylene, polypropylene, ethylene / butene copolymer). The support may be colored with a dye or pigment. For coating silver halide photographic emulsion layers and other hydrophilic colloid layers,
For example, various known methods such as a dip coating method, a roller coating method, a curtain coating method and an extrusion coating method can be used. Also, if necessary, US Pat.
No. 1294, No. 2761791, No. 352652
Multiple layers may be simultaneously coated by the method described in each specification such as No. 8 and No. 3508947.

Next, a color image forming method using the color photographic light-sensitive material of the present invention will be described. The color image forming method of the present invention forms a color image by subjecting the above color photographic light-sensitive material to image exposure, and then performing development processing with a developer containing a specific color developing agent represented by the formula (D). It is characterized by The development processing method may be a conventionally known method. Various exposure means can be used for exposing the light-sensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination light source or the writing light source.
Natural light (sunlight), incandescent lamp, halogen atom sealed lamp, mercury lamp, fluorescent lamp and flash light source such as strobe or metal burning flash bulb or semiconductor laser,
Light emitting diodes and plasma light sources can also be used as recording light sources. In addition, a phosphor screen (CRT or the like) emitted from a phosphor excited by an electron beam or the like, a liquid crystal (LC
D) or lanthanum-doped lead titan zirconate (PLZT) or the like may be used as an exposure means in which a linear or planar light source is combined with a microshutter array. The spectral distribution used for exposure can be adjusted with a color filter as needed. In particular, use high-density beam light as a light source such as various lasers such as gas lasers (He-Ne laser, Ar laser, He-Cd laser) and semiconductor lasers, and move it relative to the photosensitive material. An exposure means of a so-called scanning exposure system for imagewise exposure by is preferable for exposing the light-sensitive material of the present invention. As the scanning exposure device, for example, a color copying machine AP-5000 manufactured by Fuji Photo Film Co., Ltd. can be used.

A scanner system such as DP460 manufactured by Dainippon Screen is also preferable. In the case of exposure by a scanning exposure method (scanner method), the time for exposing silver halide is the time required for exposing a certain minute area. As this minute area, the minimum unit for controlling the light quantity from digital data is generally used, and is called a pixel. Therefore, the exposure time per pixel varies depending on the size of the pixel. The size of this pixel depends on the pixel density, and is practically 50 to 2000 dpi. In the direct positive color photographic light-sensitive material of the present invention,
When the pixel density is 400 dpi, the pixel size is 1 pixel, and scanning exposure is performed under the condition that the exposure time per pixel is 10 ⁻³ seconds or less (preferably 10 ⁻⁶ to 10 ⁻⁴ seconds).

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

[0143]

[Chemical 59]

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

[0145]

[Chemical 60]

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

The color photographic light-sensitive material of the present invention has various uses, but is suitable for producing color prints, color copies, color proofs and color displays. The color proof making method of the present invention can use a conventional color proof making method other than using the color photographic light-sensitive material of the present invention as described above. That is, the method for producing a color proof of the present invention comprises
By using color separation and halftone image conversion, using a cyan halftone dot image film, a magenta halftone dot image film, a yellow halftone dot image film and a black halftone dot image film, with red light, green light and blue light This is a method of forming a color image by performing color development processing as described above after sequential exposure. An apparatus for carrying out such a method is, for example, Fine Checker 8 manufactured by Fuji Photo Film Co., Ltd.
50II (exposure time: about 0.02 to 1.0 seconds).

[0148]

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

Example 1 (Preparation of Sample 101) The following 1st to 11th layers were formed on the front side of a paper support (thickness 100 μm) laminated on both sides with polyethylene, and 12th to 13th layers were formed on the back side. A color photographic light-sensitive material having multiple layers coated was prepared (comparative sample). 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 ) The 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 coating amount (g /
m ² ) is shown. However, the addition amount of the sensitizing dye is shown by mol per mol of silver. For silver halide, the coating amount in terms of silver is shown. The emulsion used for each layer was prepared according to the production method of the emulsion EM-1 described later by changing the grain forming temperature to change the grain size. However, as the emulsion for the ninth layer, a Lippmann emulsion which was not surface-sensitized was used. 1st layer (anti-halation layer) Black colloidal silver 0.10 Gelatin 0.70 Color mixture inhibitor (Cpd-7) 0.05 Color mixture inhibitor solvent (Solv-4 and 5 are equal amounts) 0.12 Second layer (Intermediate layer) Gelatin 0.70 Dye (Cpd-32) 0.005 Third layer (red sensitive layer) Red sensitizing dye (ExS-1, 2, 3, each equal amount, 5.4 × 10 ^{−4 in} total) ) Spectrally sensitized silver bromide (average grain size: 0.40 μm, grain size distribution: 10%, octahedron) 0.25 gelatin 0.70 cyan coupler (ExC-1, 2, 3 to 0.30) (1: 1: 0.2 ratio) Anti-fading agent (Equivalent amounts of Cpd-1, 2, 3, 4, 30) 0.18 Anti-staining agent (Equivalent amounts of Cpd-5, 15) 0.1. 003 Coupler dispersion medium (Cpd-6) 0.3 Coupler solvent (Solv-1, 3, 5 Amount) 0.12

Fourth layer (intermediate layer) Gelatin 1.00 Color mixing inhibitor (Cpd-7) 0.08 Color mixing inhibitor solvent (Solv-4, 5 equivalents) 0.16 Polymer latex (Cpd-8) 0 .10 Fifth Layer (Green Sensitive Layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS- ^4, 2.6 × 10 ⁻⁴ ) (average particle size: 0.4 μm, particle size distribution 10%) , Octahedron) 0.20 Gelatin 1.00 Magenta coupler (Equivalent amounts of ExM-1 and 2) 0.11 Yellow coupler (ExY-1) 0.03 Anti-fading agent (Cpd-9, 26, 30, 31) 0.15 Anti-staining agent (Cpd-10, 11, 12, 13 in 10: 7: 7: 1 ratio) 0.025 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv -4 and 6 are equal amounts) 0.15 6th layer (medium) Layer) same as that of the fourth layer

Seventh Layer (Blue Sensitive Layer) Silver bromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6 equivalents, 3.5 × 10 ⁻⁴ in total) (average grain size: 0. 6 μm, particle size distribution 11%, octahedron) 0.32 gelatin 0.80 yellow coupler (equal amounts of ExY-1, 2, and 3) 0.35 anti-fading agent (Cpd-14) 0.10 anti-fading agent (Cpd-30) 0.05 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-2) 0.10 Eighth layer (ultraviolet absorbing layer) Gelatin 0.60 Ultraviolet absorber (Cpd-2, 4) , 16 are each equal amount) 0.40 Color mixing inhibitor (Cpd-7, 17 is each equal amount) 0.03 Dispersion medium (Cpd-6) 0.02 UV absorber solvent (Solv-2, 7 is each equal amount) Amount) 0.08 Anti-irradiation dye (Cpd-18, 19, 20) 21 and 27 in a ratio of 10: 10: 13: 15: 20) 0.05 9th layer (protective layer) Fine grain silver iodobromide (99 mol% of silver bromide, average size 0.05 μm) 0.03 Polyvinyl Alkyl-modified copolymer of alcohol 0.01 (Molecular weight: 50,000) Equal amounts of polymethylmethacrylate particles (average particle size: 2.4 μm) and silicon oxide (average particle size 5 μm) 0.05 Gelatin 0.05 Gelatin Hardener (Equivalent amounts of H-1 and H-2) 0.18

10th layer (back layer) Gelatin 2.50 UV absorber (Equivalent amount of Cpd-2, 4, 16) 0.50 Dye (Equivalent amount of Cpd-18, 19, 20, 21, 27) ) 0.06 11th layer (back layer protective layer) Polymethylmethacrylate particles (average particle size 2.4 μm) and silicon oxide (average particle size 5 μm) in equal amounts 0.05 gelatin 2.00 gelatin hardener ( H-1 and H-2 are equal amounts) 0.14

(Preparation of Emulsion EM-1) An aqueous solution of potassium bromide and silver nitrate was vigorously added to an aqueous gelatin solution containing 0.3 g of 3,4-dimethyl-1,3-thiazoline-2-thione added per mol of silver. The mixture was added simultaneously with stirring at 65 ° C. over 15 minutes to obtain octahedral silver bromide grains having an average grain size of 0.23 μm. 6m per mole of silver in this emulsion
g sodium thiosulfate and 7 mg chloroauric acid (tetrahydrate)
Were sequentially added, and chemical sensitization was performed by heating at 75 ° C. for 80 minutes. The grains thus obtained were used as cores for further growth in the same precipitation environment as in the first time, and finally an octahedral monodisperse core / shell silver bromide emulsion having an average grain size of 0.4 μm was obtained. The coefficient of variation of particle size was about 10%. To this emulsion were added 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mol of silver.
Chemical sensitization was performed by heating at 0 ° C. for 60 minutes to obtain an internal latent image type silver halide emulsion.

Each photosensitive layer contains (ExZK-
1) and (ExZK-2) were used at 10 ^-3 % by weight and 10 ^-2 % by weight, respectively, based on the silver halide. Further, each layer has an alkanol XC (Du Pont) as an emulsification dispersion aid.
And sodium alkylbenzenesulfonate as a coating aid, succinate and Magefac F-1
20 (manufactured by Dainippon Ink and Chemicals, Inc.) was used. For the layer containing silver halide and colloidal silver, a stabilizer (Cp
d-23, 24, and 25 were used in equal amounts). The compounds used in the above sample preparation are shown below.

[0156]

[Chemical formula 61]

[0157]

[Chemical formula 62]

[0158]

[Chemical formula 63]

[0159]

[Chemical 64]

[0160]

[Chemical 65]

[0161]

[Chemical formula 66]

[0162]

[Chemical formula 67]

[0163]

[Chemical 68]

[0164]

[Chemical 69]

[0165]

[Chemical 70]

[0166]

[Chemical 71]

[0167]

[Chemical 72]

[0168]

[Chemical formula 73]

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

(Preparation of Samples 1 to 6) In the preparation of Sample 101, instead of the yellow couplers (ExY-1, 2 and 3) contained in the seventh layer (blue sensitive layer), the following compounds are shown. Yellow coupler (Y-4, 6, 10, 12,
Samples 1 to 6 (samples of the present invention) corresponding to each sample were prepared in the same manner as the sample 101 except that the same amount was added instead of 24 and 28).

[0171]

[Chemical 74]

[0172]

[Chemical 75]

[0173]

[Chemical 76]

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

[0175]

──────────────────────────────────── Color developer A ──────── ───────────────────────────── D-sorbit 0.15g sodium naphthalenesulfonate 0.15g formalin condensate nitrilotris (methylene Phosphonic acid) 1.8 g pentasodium salt ethylenetriaminepentaacetic acid 0.5 g 1-hydroxyethylidene-1,1-0.15 g diphosphonic acid diethylene glycol 12.0 ml benzyl alcohol 13.5 ml potassium bromide 0.70 g benzotriazole 0.003 g Sodium sulfite 2.4 g Disodium-N, N-bis 8.0 g (sulfonate) hydroxylamine triethanolamine 6.0 g N-ethyl-N (Β-Methanesulfone 6.0 g Amidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid / monohydrate potassium carbonate 30.0 g Optical brightener (diaminostilbene type) 1.3 g Water added 1000 ml ──────────────────────────────────── pH (25 ℃) (pH adjusted with KOH or sulfuric acid) 10 30 ─────────────────────────────────────

──────────────────────────────────── Bleach-fixing solution ───────── ──────────────────────────── Ethylenediaminetetraacetic acid ・ 2 sodium ・ dihydrate 4.0g Ethylenediaminetetraacetic acid ・ Fe (III) ・55.0 g ammonium dihydrate ammonium thiosulfate (750 g / liter) 168 ml sodium p-toluenesulfinate 30.0 g ammonium sulfite 35.0 g 5-mercapto-1,3,4-triazole 0.5 g ammonium sulfate 10.0 g water In addition 1000 ml ──────────────────────────────────── pH (25 ℃) (with ammonia water or acetic acid) pH adjustment) 6.50 ───────── ───────────────────────────

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

The density of the yellow image of each sample obtained by performing the above processing was measured, and the maximum density (Dmax) and the minimum density (Dmin) were obtained. The results are shown in Table 1 below.

[0180]

[Table 1] Table 1 ──────────────────────────────────── 7th layer yellow image density Sample No. Yellow coupler maximum density minimum density ──────────────────────────────────── 101 (Comparative example) ExY-1 2, 3 1.95 0.11 1 (Example of the present invention) Y-4 2.16 0.10 2 (Example of the present invention) Y-6 2.20 0.10 3 (Example of the present invention) Y-10 2 .21 0.10 4 (invention example) Y-12 2.19 0.10 5 (invention example) Y-24 2.21 0.10 6 (invention example) Y-28 2.20 0.10 ────────────────────────────────────

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

Example 2 (Preparation of Samples 7 to 10) In the preparation of Sample 1, Sample 2, Sample 3 and Sample 4 of Example 1 above, each photosensitive layer [third
Layer (red sensitive layer), fifth layer (green sensitive layer) and seventh (blue sensitive layer)]
In the same manner as in the above samples, except that the nucleation accelerator shown below was added to the silver halide in an amount of 10 ^-2 % by weight.
It was created. (Preparation of Sample 102) In the preparation of Sample 101 of Example 1 described above, each photosensitive layer [third layer (red sensitive layer), fifth layer (green sensitive layer) and seventh (blue sensitive layer)] A sample 102 (comparative sample) was prepared in the same manner as the sample 101, except that the nucleation accelerator shown in 1 was added in an amount of 10 ^-2 % by weight based on the silver halide.

[0183]

[Chemical 77]

[Evaluation as color photographic light-sensitive material] Each sample prepared as described above was subjected to exposure and color development processing in the same manner as in Example 1 above. Then, the density of the yellow image of each obtained sample was measured by the same method as in Example 1 above, and the maximum density (Dmax) and the minimum density (Dmin) were obtained. The results are shown in Table 2 below. In addition,
Table 2 also shows the data of the sample 101 obtained in Example 1.

[0185]

[Table 2] Table 2 ───────────────────────────────────── For each photosensitive layer of the seventh layer Yellow image Sample No. Yellow coupler Nucleation accelerator Maximum concentration Minimum concentration ──────────────────────────────────── 101 (Comparative example ) ExY -1,2,3 --- 1.95 0.11 102 (Comparative example) ExY -1,2,3 A-1 2.05 0.10 ───────────── ──────────────────────── 7 (Example of the present invention) Y-4 A-1 2.29 0.08 8 (Example of the present invention) Y- 6 A-2 2.33 0.08 9 (Invention Example) Y-10 A-3 2.25 0.08 10 (Invention Example) Y-12 A-6 2.26 0.08 ──── ────────────────────────────────

As is clear from the results shown in Table 2, when the color photographic light-sensitive materials (Samples 7 to 10 of the invention) containing the nucleation accelerator are used, the maximum (image) density is higher and It is possible to obtain a yellow image having a lower minimum (image) density.

[Example 3] [Evaluation as color photographic light-sensitive material] Each sample (102 (comparative sample), 7 (inventive sample) and 9) of Example 2 above.
(Invention sample) was subjected to exposure and color development processing in the same manner as in Example 2 above. However, as the color developing solution, a color developing solution B having the following composition is used instead of the color developing solution A.
Was used. Then, the density of the yellow image of each obtained sample was measured by the same method as in Example 1 above, and the maximum density (Dmax) and the minimum density (Dmin) were obtained. The results are shown in Table 3 below. In addition, in Table 3, the data obtained in Example 2 (using color developer A) is also shown.

──────────────────────────────────── Color developer B ──────── ───────────────────────────── D-sorbit 0.15g sodium naphthalenesulfonate 0.15g formalin condensate nitrilotris (methylene Phosphonic acid) 1.8 g pentasodium salt diethylenetriaminepentaacetic acid 0.5 g 1-hydroxyethylidene-1,1-0.15 g diphosphonic acid diethylene glycol 12.0 ml benzyl alcohol 13.5 ml potassium bromide 0.70 g benzotriazole 0.003 g sulfite Sodium 2.8g Hydroxylamine 1/2 sulfate 4.5g (sulfonate) Hydroxylamine Triethanolamine 6.5g 4- [ -Ethyl-N- (β-4.2g Hydroxyethyl) amino] aniline Sulfuric acid / 1/2 hydrate Potassium carbonate 30.0g Optical brightener (diaminostilbene type) 1.3g Water added 1000ml ──── ──────────────────────────────── pH (25 ℃) (pH adjusted with KOH or sulfuric acid) 10.35 ── ───────────────────────────────────

[0189]

[Table 3] Table 3 ──────────────────────────────────── For each photosensitive layer of the seventh layer Color development Yellow image Sample No. Yellow coupler Nucleation accelerator Maximum concentration Minimum concentration ───────────────────────────────────── 102 ( Comparative Example) ExY -1,2,3 A-1 A 2.04 0.12 102 (Comparative Example) ExY -1,2,3 A-1 B 1.95 0.11 7 (Invention Example) Y- 4 A-1 A 2.29 0.08 7 (Invention example) Y-4 A-1 B 2.33 0.07 9 (Invention example) Y-10 A-3 A 2.25 0.08 9 (Inventive Example) Y-10 A-3 B 2.36 0.07 ───────────────────────────────── ────

As is apparent from the results shown in Table 3 above, the color photographic light-sensitive materials containing the yellow couplers of the present invention (Samples 7 and 9 of the present invention) were used, and the specific developing agent of the present invention was used. When processed with a color developer containing
It is possible to obtain a yellow image having a higher maximum (image) density and a lower minimum (image) density.

[Example 4] Of the samples used in Example 2 above, Sample 102, Sample 7 and Sample 10 were used, and
Fine checker FC8 manufactured by Fuji Photo Film Co., Ltd.
50II was used to bring a plate-making film having a halftone image into close contact with it, and then red exposure (Fuji Photo Film Co., Ltd. SC
-60 filter), green exposure (Fuji Photo Film Co., Ltd. BPB-53 filter), and blue exposure (Fuji Photo Film Co., Ltd. BPN45 and SC-42 filter) were sequentially performed. At that time, the plate making film of cyan image and black image at the time of red exposure, the plate making film of magenta image and black image at the time of green exposure,
Further, at the time of blue exposure, a plate-making film for yellow image and a plate for black image were overlapped and brought into close contact. A color proof was created in this way. The image formation in this case was performed according to the color development processing (processing using the color developing solution B) according to Example 3 described above. The minimum halftone dot area of the color-proof yellow image obtained as described above was observed with a 100-fold magnifying glass. The results are shown in Table 4 below.

[0192]

[Table 4] Table 4 ──────────────────────────────────── For each photosensitive layer of the seventh layer Color development Yellow image sample No. Yellow coupler Nucleation accelerator Developing solution Minimum halftone dot area ───────────────────────────────────── 102 ( Comparative Example) ExY -1,2,3 A-1 B 3% or more 7 (Invention Example) Y-4 A-1 B 2% 10 (Invention Example) Y-12 A-6 B 2% ─── ──────────────────────────────────

As is clear from the results shown in Table 4, the color photographic light-sensitive materials containing the yellow coupler according to the present invention (Samples 7 and 10 of the present invention) were able to reproduce up to 2% halftone dot image. However, the color photographic light-sensitive material of Comparative Example (Comparative Sample 102) cannot reproduce up to 2% halftone dot image, and
Only half-tone dot images could be reproduced.

[Embodiment 5] As a light source, a helium-neon gas laser (wavelengths 633 nm and 543 nm) and an argon laser (wavelength 458 nm) were used.
A device that can perform sequential scanning exposure (substantial exposure time of about 5 × 10 ⁻⁵ seconds) on a sample while moving a light flux with a diameter of 80 μm at a pitch of 0 μm in a scanning exposure of 1.6 m / s perpendicularly to the scanning direction. Assembled Using this device, the comparative sample 1
After 01 and Sample 7 were exposed, they were processed using the above-mentioned processing liquid B, and the reproducibility of the halftone image of the obtained image was evaluated. As a result, the color photographic light-sensitive material of the present invention (Invention sample 7) was able to satisfactorily reproduce up to 2% halftone dot image, while the color photographic light-sensitive material of Comparative example (Comparative sample 101) was 4%
I was able to reproduce only the halftone dot image.

[Example 6] (Preparation of Samples 11 to 13) In preparation of Sample 7 of Example 2 described above, each photosensitive layer [third layer (red sensitive layer), fifth layer (green sensitive layer) and 7 (blue sensitive layer)]
Samples 11 to 13 (samples of the present invention) corresponding to each sample were prepared in the same manner as the above sample except that only xZK-1 was used and the addition amount was changed as shown in Table 5 below. (Preparation of Samples 103 to 105) In the preparation of Sample 102 described above, it was added to each photosensitive layer [third layer (red sensitive layer), fifth layer (green sensitive layer) and seventh (blue sensitive layer)]. Nucleating agent E
In the same manner as in Sample 102, except that only xZK-1 was used and the addition amount was changed as shown in Table 5 below,
Samples 103 to 105 (comparative samples) corresponding to each were prepared.

[Evaluation as color photographic light-sensitive material] Each sample prepared as described above was subjected to exposure and color development processing in the same manner as in Example 1 above. However, as the color developing solution, the color developing solution B was used instead of the color developing solution A. Then, the density of the yellow image of each obtained sample was measured by the same method as in Example 1 above, and the maximum density (Dmax) and the minimum density (Dmin) were obtained. The results are shown in Table 5 below.

[0197]

[Table 5] Table 5 ──────────────────────────────────── 7th layer nucleating agent Addition amount Yellow image Sample No. Yellow coupler (wt% / AgX) Maximum density Minimum density ──────────────────────────────────── 103 ( Comparative Example ExY -1,2,3 5 × 10 ^-2 2.26 0.14 104 (Comparative Example) ExY -1,2,3 1 × 10 ^-2 1.90 0.11 105 (Comparative Example) ExY -1,2,3 5 × 10 ^-3 1.70 0.09 ────────────────────────────────── ─── 11 (Example of the present invention) Y-4 5 × 10 ^-2 2.39 0.08 12 (Example of the present invention) Y-4 1 × 10 ^-2 2.30 0.07-13 (Example of the present invention) Y -4 5 × 10 ^-3 2.21 0.07 ─────────────────────────────────────

As is clear from the results shown in Table 5, in the color photographic light-sensitive materials containing the yellow coupler according to the present invention (Samples 11 to 13 of the present invention), the minimum amount due to the variation of the addition amount of the nucleating agent was observed. There is almost no increase in concentration, and there is little decrease in maximum concentration. Therefore, an image with good whiteness can be obtained. On the other hand, a color photographic light-sensitive material containing a conventionally used yellow coupler (Comparative Samples 103 to 10)
In 5), the minimum concentration decreases due to the variation in the amount of the nucleating agent added, but the maximum concentration also decreases.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location G03C 7/407 7/413 G03F 3/10 B 8004-2H

Claims (6)

[Claims] 1. A silver halide color photographic light-sensitive material comprising at least one silver halide emulsion layer and at least one light-insensitive layer on a support, wherein the emulsion layer or at least one light-insensitive layer is provided. To
An acylacetamide type yellow coupler having an acyl group represented by the following formula (Ya) is contained, and at least one of the emulsion layer or the non-photosensitive layer contains a nucleating agent. Silver halide color photographic light-sensitive material. [Chemical 1] [In the formula (Ya), R ^Y1 represents a substituent, and Q ^Y1 represents a 6-membered heterocycle together with C, or 5 heterocycles containing 2 heteroatoms.
Represents a group of non-metal atoms necessary to form a member heterocycle. ] 2. The silver halide emulsion layer is an emulsion layer containing internal latent image type silver halide grains which have not been fogged in advance, and at least one of the emulsion layer and the non-photosensitive layer has the following formula: The color photographic light-sensitive material according to claim 1, further comprising a nucleation accelerator represented by (I) or (II). [Chemical 2] [In the formula (I), Q ¹¹ represents an atomic group necessary for forming a 5- or 6-membered heterocycle (the heterocycle may be condensed with a carbon aromatic ring or a heteroaromatic ring). , M represents a hydrogen atom, an alkali metal atom, an ammonium group, or a group capable of cleaving under alkaline conditions. ] [Chemical 3] [In the formula (II), Q ¹² represents an atomic group necessary for forming a 5-membered or 6-membered heterocycle capable of forming an imino silver (the heterocycle is a carbon aromatic ring or a heteroaromatic ring condensed with each other). And M represents a hydrogen atom, an alkali metal atom, an ammonium group, or a group that cleaves under alkaline conditions. ] 3. The color photographic light-sensitive material according to claim 1, wherein the nucleating agent is represented by the following formula (N-I) or (N-II). [Chemical 4] [In the formula (N-I), Z ³¹ represents a nonmetallic atom group necessary for forming a 5- or 6-membered heterocyclic group, R ³¹ represents an aliphatic group, and R ³² represents a hydrogen atom. represents an aliphatic group or an aromatic group (provided that the Z ^31, R ³¹ and R ³² may be substituted, also R ³² is forms a ring by combining with heterocyclic ring completed by Z ³¹ And R ³¹ and R ³² ,
At least one of the groups represented by Z ³¹ contains an alkynyl group, an acyl group, a hydrazine group or a hydrazone group, or R ³¹ and R ³² form a 6-membered ring to form a dihydropyridinium skeleton. , Y represents a counterion for charge balance, and n is 0 or 1
Represents ] [Chemical 5] [In the formula (N-II), R ⁴¹ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ⁴² represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group or an amino group. And G represents a carbonyl group, a sulfonyl group, a sulfinyl group, a phosphoryl group or an iminomethylene group (HN = C =), and R ⁴³ and R ⁴⁴ are both hydrogen atoms, or one is a hydrogen atom and the other is an alkylsulfonyl group. A group, an arylsulfonyl group or an acyl group (provided that G, R ⁴² and R ⁴⁴ are
A hydrazone structure (= NN = C =) may be formed in a form including G, R ⁴² , R ⁴⁴ and hydrazine nitrogen. )] 4. The color photographic light-sensitive material according to claim 1, claim 2 or claim 3 is represented by the following formula (D): [In the formula, R ^D1 represents an alkyl group and R ^D2 represents an alkylene group, provided that R ^D1 and R ^D2 may be linked to each other to form a ring. ] The development processing using the developing agent shown by these is the color image forming method characterized by the above-mentioned. 5. A cyan plate halftone dot image film, a magenta halftone dot image film, and a yellow plate obtained by color separation and halftone image conversion of the color photographic light-sensitive material according to claim 1, 2, or 3. A method for producing a color proof, comprising using a halftone dot image film and a black halftone dot image film to sequentially expose with a red light, a green light and a blue light, and then to develop a color. 6. The color photographic light-sensitive material according to claim 1, 2 or 3 is subjected to color development processing after scanning exposure for an exposure time of 10 ⁻³ seconds or less per pixel. Color image forming method.