JPH0627610A - Color photogrphic sensitive material, color image forming method, and color proof forming method - Google Patents

Abstract

PURPOSE:To improve hue development by using a specified acylacetamido type yellow coupler for the color image-forming coupler of a blue-sensitive layer and a specified cyan coupler for the coupler of a red-sensitive layer. CONSTITUTION:The color, image-forming coupler of the blue-sensitive layer is the acylacetamido type yellow coupler having the acyl group represented by formula I and that of the red-sensitive layer is represented by formula II. In formulae I and II, RY<1> is a substituent: QY<1> is a nonmetallic atomic group necessary to form a 6-membered hetero ring or a 5-membered 2 hetero atomcontaining hetero ring together with the C atom; RC<1> is H, halogen, or alkyl; RC<2> alkyl, aryl, or a heterocyclic group; RC<3> is H, halogen, alkyl, alkoxy, or the like; and XC<1> is H or a group to be released by coupling with the oxidation product of a developing agent.

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 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.

A positive color image can be obtained by subjecting a light-sensitive material containing yellow, magenta and cyan color image forming couplers in light-sensitive layers having different color sensitivities to image development and then color development processing. The color development process causes a coupling reaction between the oxidized product of the developing agent and the coupler to produce a color dye, which forms a positive color image. In this case, the coupler to be used is desired to have a good color forming property such that the coupling speed is as high as possible and a high color forming density is provided in a limited time. Further, it is desired that the generated color-developing dye is a yellow, magenta or cyan dye having a small amount of sub-absorption and gives a color image having good color reproducibility. Further, it is desired that the color image thus formed has good storage stability. That is, the color-developing dye of each hue of the obtained color image generally tends to cause fading or discoloration due to various factors such as humidity, heat, and light, but the speed of fading or discoloration is as slow as possible, and the fading or discoloration speed is as low as possible. Is as uniform as possible over the entire image area, and it is desired that the color balance of the residual dye image does not change.

Conventional color image-forming couplers used in positive color photographic light-sensitive materials include acylacetamide type yellow couplers having a pivaloyl group as an acyl group, 2,5-diacylaminophenol cyan couplers and pyra. A zoloazole-based magenta coupler is known (JP-A-2-220049).
Issue). However, according to the study by the present inventor, among the couplers disclosed in the above publications, in particular, the yellow coupler has an unnecessary absorption of a green light region, and the three colors described in the above publications. The color image (dye image) obtained by the combination of the couplers is not sufficiently storable, especially with respect to light (that is, the fading or discoloring speed of the dye image is different), and therefore the color balance of the residual dye image is It turns out that it has a problem of easy collapse.

As a method for solving the above problems, there has been proposed a method of using a specific combination of couplers for each color (Japanese Patent Publication No. 52-7344).
No. 59-57238 or 60-23255.
No. 0 publications). However, even if these methods are used, the resulting color developability is poor, the hue of the color forming dye is poor, and the variation in the color balance of the residual dye image is not sufficiently improved.

[0007]

DISCLOSURE OF THE INVENTION The object of the present invention is to obtain a good hue of hue (good color reproducibility) and to maintain the image (especially, fluctuation of color balance due to fading or discoloration by light). It is an object of the present invention to provide a color photographic light-sensitive material which is advantageous in producing a color proof and which can obtain an improved color image, and a color image forming method.

[0008]

SUMMARY OF THE INVENTION The present invention comprises:
Including silver halide grains and color imaging couplers,
In a silver halide color photographic light-sensitive material having at least one of each of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer, the color image-forming coupler of the blue-sensitive layer is an acyl represented by the following formula (Ya). An acylacetamide type yellow coupler having a group,

[0009]

[Chemical 5]

[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. The color image forming coupler of the red-sensitive layer is represented by the following formula (C)
Cyan coupler represented by

[0011]

[Chemical 6]

[In the formula (C), R ^C1 represents a hydrogen atom, a halogen atom or an alkyl group, R ^C2 represents an alkyl group, an aryl group or a heterocyclic group, and R ^C3 represents a hydrogen atom, a halogen atom or an alkyl group. , An alkoxy group, an aryloxy group or a carbonamido group, and X ^C1 represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of a developing agent. ] It is in the color photographic light-sensitive material characterized by being. Further, the present invention provides the above color photographic light-sensitive material by the following formula (D):

[0013]

[Chemical 7]

[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. ] The color image forming method is characterized in that development processing is carried out using a color developing agent. Furthermore, the present invention provides a color photographic light-sensitive material, which has been subjected to color separation and halftone image conversion, 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. Use,
A method for producing a color proof is characterized in that color development processing is performed after sequential exposure with red light, green light and blue light. Furthermore, there is provided a color image forming method characterized in that the above color photographic light-sensitive material is subjected to scanning exposure for an exposure time of 10 ⁻³ seconds or less per pixel and then color development processing.

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

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

[0017]

[Chemical 8]

(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 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 formula (C), X ^C1 is a halogen atom (particularly chlorine).

[0020]

The acylacetamide type yellow coupler having an acyl group represented by the above formula (Ya) and the cyan coupler represented by the above formula (C) both have a good coloring hue and good color reproducibility. There is. Therefore, the use of these couplers can provide a light-sensitive material suitable for producing a color proof. Further, the obtained image has a good storability and gives a color image with little variation in the color balance of the residual dye image. Further, the above formula (M)
By combining it with the magenta coupler represented by the formula (1), a light-sensitive material having higher usability as a color proof can be provided. In particular, in forming a color image, a color image having better color reproducibility and good storability can be obtained by processing with a color development processing solution represented by the formula (D) containing a specific developing agent. .

[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 specific cyan coupler as described above. This color photographic light-sensitive material includes various types which form yellow and cyan color-developed (dye) images by a coupling reaction between each of the yellow coupler and the cyan coupler and an oxidant generated by the 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 combination of the yellow and cyan dye images 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, a color auto positive paper (direct positive color photographic image) is used. It is advantageous to use it as a photosensitive material).

The color photographic light-sensitive material of the present invention has at least one three-color light-sensitive layer (light-sensitive emulsion layer) having different color sensitivities of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer on a support. It is provided. Each light-sensitive layer contains a silver halide grain and a color image-forming coupler, and the blue-sensitive layer contains an acylacetamide type yellow coupler having an acyl group represented by the formula (Ya) as described above. The red-sensitive layer contains a cyan coupler represented by the formula (C). Further, in the present invention, it is preferable that the green-sensitive layer contains a magenta coupler represented by the formula (M). The color image-forming coupler represented by the above formula, which is used in the color photographic light-sensitive material of the present invention, will be described below in order.

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).

[0024]

[Chemical 9]

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, and may be 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 contains 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 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.

More preferably, 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 the carbon atom.
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).

[0033]

[Chemical 10]

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 Z ^Y1 and a carbon atom together with a 6-membered complex 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 .

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

[0036]

[Chemical 11]

[0037]

[Chemical 12]

[0038]

[Chemical 13]

[0039]

[Chemical 14]

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.

[0041]

[Chemical 15]

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 which 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 above-mentioned 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.

[0048]

[Chemical 16]

[0049]

[Chemical 17]

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, 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 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 heterocyclic ring, and preferred examples thereof include succinimide and malein. Imide, phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4
-Triazole, tetrazole, indole, indazole, benzimidazole, benzotriazole, imidazolidine-2,4-dione, oxazolidine-2,4
-Dione, thiazolidine-2,4-dione, imidazolidin-2-one, oxazolidin-2-one, 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, aryloxycarbonyl group, acyl group, acyloxy group, amino group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, alkoxycarbonylamino group, Mention may be made of sulfamoylamino groups.

[0054] 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 expressed 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.

[0057]

[Chemical 18]

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

[0059]

[Chemical 19]

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.

[0061]

[Chemical 20]

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

[0063]

[Chemical 21]

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.

[0065]

[Chemical formula 22]

Here, W represents a non-metal atom group necessary for forming a pyrrole ring, a pyrazole ring, an imidazole ring or a triazole ring together with N. 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

[0069]

[Chemical formula 23]

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

[0071]

[Chemical formula 24]

[0072]

[Chemical 25]

[0073]

[Chemical formula 26]

[0074]

[Chemical 27]

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

[0076]

[Chemical 28]

[0077]

[Chemical 29]

[0078]

[Chemical 30]

[0079]

[Chemical 31]

[0080]

[Chemical 32]

[0081]

[Chemical 33]

[0082]

[Chemical 34]

[0083]

[Chemical 35]

[0084]

[Chemical 36]

[0085]

[Chemical 37]

[0086]

[Chemical 38]

[0087]

[Chemical Formula 39]

[0088]

[Chemical 40]

[0089]

[Chemical 41]

[0090]

[Chemical 42]

[0091]

[Chemical 43]

[0092]

[Chemical 44]

[0093]

[Chemical formula 45]

[0094]

[Chemical formula 46]

[0095]

[Chemical 47]

[0096]

[Chemical 48]

[0097]

[Chemical 49]

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.

[0100]

[Chemical 50]

(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 1 m of N, N-dimethylformamide.
Dissolve in 1 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.

[0103]

[Chemical 51]

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. Into a mixture of 33 g, 100 ml of methylene chloride, and 1 ml of N, N-dimethylformamide, 38.1 g of oxalyl chloride was added dropwise 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 was added thereto under ice cooling. 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) used 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.

Next, the cyan coupler represented by the following formula (C) will be described in detail.

[0110]

[Chemical 52]

In the above formula (C), R ^C1 is a hydrogen atom,
Halogen atom (F, Cl, Br, I) or C1-C1
18 represents an optionally substituted linear, branched, or cyclic alkyl group. Here, examples of the substituent on the alkyl group include a halogen atom, an aryl group, an alkoxy group, and an aluroxy group.

In the formula (C), R ^C2 is a linear, branched, or cyclic alkyl group having 1 to 36 carbon atoms (preferably 4 to 30) which may be substituted, and 6 to 36 carbon atoms. (Preferably 12 to 30), which may be substituted, represents an aryl group or a heterocyclic group having 2 to 36 carbon atoms (preferably 12 to 30). Here, the heterocyclic group means at least one N, O, S, P, Se and T in the ring.
It represents a heterocyclic group which may form a 5- to 7-membered condensed ring having a hetero atom selected from e. Examples of these are 2-furyl, 2-thienyl, 2-pyridyl, 4-
Pyridyl, 4-pyrimidyl, 2-imidazolyl, 4-quinolyl and the like can be mentioned.

R ^C2 may have a substituent. Examples of the substituent include halogen atom, cyano group, nitro group, carboxyl group, sulfo group, alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, aryl. Examples include a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a carbonamido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an imide group, a ureido group, an alkoxycarbonylamino group or a sulfamoylamino group. Yes (above referred to as Substituent Group A). Of these, examples of preferable substituents include an aryl group, a heterocyclic group, an aryloxy group,
It is an alkylsulfonyl group, an arylsulfonyl group or an imide group.

In the formula (C), R ^C3 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 16 carbon atoms (preferably 1 to 8), an alkoxy group having 1 to 16 carbon atoms (preferably 1 to 8), Aryloxy group having 6 to 24 carbon atoms (preferably 6 to 18) or 1 to 24 carbon atoms (preferably 1 to 1)
It represents the carbonamido group of 8). The above group may be substituted with a substituent selected from the above substituent group A.

In the formula (C), X ^C1 represents a hydrogen atom or a coupling-off group capable of leaving by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. Examples of the coupling-off group include a halogen atom, a sulfo group, an alkoxy group having 1 to 36 carbon atoms (preferably 1 to 24), an aryloxy group having 6 to 36 carbon atoms (preferably 6 to 24), and a carbon number. 2-36 (preferably 2-24) acyloxy groups, having 1-36 carbon atoms (preferably 1-2)
4) Alkylsulfonyl group, C6-C36 (preferably 6-24) arylsulfonyl group, C1-C3
6 (preferably 2 to 24) alkylthio group, carbon number 6
To 36 (preferably 6 to 24) arylthio group, C4 to C36 (preferably 4 to 24) imide group, C1 to C36 (preferably 1 to 24) carbamoyloxy group or C1 to C3 36 (preferably 2 to 24) heterocyclic groups bonded to the coupling active position at the nitrogen atom (for example, pyrazolyl, imidazolyl, 1,2,4-triazol-1-yl, tetrazolyl) can be mentioned.
Here, the above groups may be substituted with a substituent selected from the above substituent group A.

Preferred examples of R ^C1 , R ^C2 , R ^C3 and X ^C1 of the formula (C) are shown below.

The above R ^C1 is preferably F, Cl or an alkyl group substituted with at least one halogen atom, and particularly preferably —C (CF ₂ ) _m F or —C.
It is a group represented by (CF ₂ ) _n H. Here, m and n each represent an integer of 1 to 16 (preferably 1 to 8).

R ^C2 is preferably an alkyl group, and particularly preferably an alkyl group substituted at the 1-position with an aryloxy group, an alkylsulfonyl group, an arulesulfonyl group, an imide group or a heterocyclic group.

The above R ^C3 is preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methoxy group or an acetamide group, and particularly preferably a hydrogen atom.

X ^C1 is preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group or a heterocyclic thio group, more preferably a hydrogen atom or a chlorine atom, and particularly a chlorine atom. Is.

Below, R ^C1 , R ^C2 and R in the formula (C) are represented.
Specific examples of ^C3 and X ^C1 are shown below.

Examples of R ^C1 ; F, Cl, --CF ₃ ,-(CF
₂ ) ₂ F,-(CF ₂ ) ₄ F,-(CF ₂ ) ₆ F,-
_{(CF 2) 8 F, -CF} 2 H, - (CF 2) 3 H, -
_{(CF 2) 5 H, -} (CF 2) 7 H, - (CF 2) 9
_{H, -CF 2 Cl, - (} CF 2) 3 Cl

Examples of R ^C2 ;

[0124]

[Chemical 53]

[0125]

[Chemical 54]

Examples of R ^C3 : H, F, Cl, --CH ₃ , --C
_{H (CH 3) 2, -OCH} 3, -OCF 3, -OCH 2
_{CH 2 OCH 3, -NHCOCH 3,} -NHCOCF
_{3, -NHCOC 4 H 9 -t (} t represents tertiary.),

[0127]

[Chemical 55]

Examples of X ^C1 ; H, F, Cl, --SO ₃ H,-
_{CH 2 COOCH 3, -OCH 2 CH} 2 CH 2 COO
_{H, -OCH 2 CONHCH 2 CH 2} OOCH 3, -O
_{PO (OC 2 H 5) 2} , -OCOCH 3, -OSO 2 C
_{H 3, -OCONHC 2 H 5,} -SCH 2 COOH, -
SCH ₂ CH ₂ COOH,

[0129]

[Chemical 56]

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

[0131]

[Chemical 57]

[0132]

[Chemical 58]

[0133]

[Chemical 59]

[0134]

[Chemical 60]

[0135]

[Chemical formula 61]

The cyan coupler represented by the above formula (C) can be synthesized by the method described in US Pat. No. 2,895,826 or JP-A Nos. 51-6551 and 61-69065.

The amount of the cyan coupler represented by the above formula (C) used in the photosensitive material is 1 per 1 m ² of the photosensitive material.
× 10 ^-5 in the range of mole to 1 × 10 ^-2 mol, preferably, 1 × 10 ^-4 mol to 5 × 10 ^-2 mols, more preferably 2 × 10 ^-4 mol to 1 × 10 ^- It is in the range of ³ moles.

Next, the magenta coupler represented by the following formula (M) will be described in detail.

[0139]

[Chemical formula 62]

Preferred skeletons among the coupler skeletons represented by the above formula (M) are represented by the following formulas (MI) to (MV).

[0141]

[Chemical formula 63]

(MI) 1H-imidazo [1,2-
b] pyrazole (M-II) 1H-pyrazolo [1,5-b] [1,2,
4] triazole (M-III) 1H-pyrazolo [1,5-c] [1,2,
4] triazole (M-IV) 1H-pyrazolo [1,5-d] tetrazole (MV) 1H-pyrazolo [1,5-a] benzimidazole

R ^M1 in the above formulas (MI) to (MV),
R ^M2 , R ^M3 , R ^M4 and X ^M1 each represent a substituent. Hereinafter, these substituents will be described in detail. R ^M1 is a hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, hydroxy group, nitro group, carboxyl group, sulfo group, amino group, alkoxy group, aryloxy group, acylamino group, alkylamino group. Group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group Represents an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonylamino group, an imide group, a heterocyclic thio group, a sulfinyl group, a phosphonyl group, an aryloxycarbonyl group, an acyl group or an azolyl group. R ^M1 may form a bis form via a divalent group.

The substituent represented by R ^M1 will be described in more detail. Examples of the halogen atom include a chlorine atom and a bromine atom. The alkyl group represents, for example, a linear, branched, or cyclic alkyl group having 1 to 32 carbon atoms. The alkyl group includes an aralkyl group. Specific examples thereof include methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3- (3-pentadecylphenoxy) propyl, 3- {4- {2- [4
-(4-Hydroxyphenylsulfonyl) phenoxy]
Dodecanamido} phenyl} propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl, 3-
Mention may be made of (2,4-di-t-amylphenoxy) propyl. The alkenyl group includes a linear, branched, or cyclic one having 1 to 32 carbon atoms. The alkynyl group includes a straight chain or branched chain having 1 to 32 carbon atoms.

Examples of the above aryl group include phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, 2,4,6-trimethylphenyl and 3-tridecanamide-2,4,6. -Trimethylphenyl, and 4-
Mention may be made of tetradecanamidophenyl. Examples of the heterocyclic group include 2-furyl, 2-thienyl, 2-pyrimidinyl, and 2-benzothiazolyl. Examples of the alkoxy group include methoxy, ethoxy, 2-methoxyethoxy, 2-
Mention may be made of dodecylethoxy and 2-methanesulfonylethoxy. Examples of the aryloxy group include phenoxy, 2-methylphenoxy, 4-
Mention may be made of t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy and 3-methoxycarbamoyl. Examples of the acylamino group include acetamide, benzamide, tetradecanamide, 2- (2,4-di-t-amylphenoxy) butanamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide, and 2- {4- (4-
Hydroxyphenylsulfonyl) phenoxy} decanamide may be mentioned.

Examples of the alkylamino group include:
Mention may be made of methylamino, butylamino, dodecylamino, diethylamino and methylbutylamino. Examples of the arylamino group include phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, and 2
-Chloro-5- {2- (3-t-butyl-4-hydroxyphenoxy) dodecanamide) anilino may be mentioned. Examples of the ureido group include phenylureido, methylureido, and N, N-dibutylureido. Examples of the sulfamoylamino group include N, N-dipropylsulfamoylamino and N-methyl-N-decylsulfamoylamino. Examples of the alkylthio group include methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, and 3- (4-t-butylphenoxy) propylthio. Examples of the arylthio group include phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio,
Mention may be made of 2-carboxyphenylthio and 4-tetradecanomidophenylthio. Examples of the alkoxycarbonylamino group include methoxycarbonylamino and tetradecyloxycarbonylamino. Examples of the sulfonamide group include methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, and 2-
Mention may be made of methoxy-5-t-butylbenzenesulfonamide.

Examples of the carbamoyl group include N
-Ethylcarbamoyl, N, N-butylcarbamoyl,
N- (2-dodecyloxyethyl) carbamoyl, N-
Methyl-N-dodecylcarbamoyl, and N- {3-
Mention may be made of (2,4-di-t-amylphenoxy) propyl} carbamoyl. Examples of the sulfamoyl group include N-ethylsulfamoyl, N, N-
Mention may be made of dipropylflufamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, and N, N-diethylsulfamoyl. Examples of the sulfonyl group include methanesulfonyl, octanesulfonyl, benzenesulfonyl, and toluenesulfonyl. Examples of the alkoxycarbonyl group include:
Mention may be made of methoxycarbonyl, butoxycarbonyl, dodecyloxycarbonyl and octadecyloxycarbonyl. Examples of the heterocyclic oxy group include 1-phenyltetrazole-5-oxy and 2
-Tetrahydropyranyloxy may be mentioned.
Examples of the azo group include phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, and 2-hydroxy-4-propanoylphenylazo.

Examples of the acyloxy group include acetoxy. Examples of the carbamoyloxy group include N-methylcarbamoyloxy and N-phenylcarbamoyloxy. Examples of the silyloxy group include trimethylsilyloxy and dibutylmethylsilyloxy. Examples of the aryloxycarbonylamino group include phenoxycarbonylamino. Examples of the imide group include N-
Mention may be made of succinimide, N-phthalimide and 3-octadecenylsuccinimide. Examples of the heterocyclic thio group include 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, and 2-pyridylthio.

Examples of the sulfinyl group include dodecanesulfinyl, 3-pentadecylphenylsulfinyl, and 3-phenoxypropylsulfinyl. Examples of the phosphonyl group include phenoxyphosphonyl, octyloxyphosphonyl, and phenylphosphonyl. Examples of the aryloxycarbonyl group include phenoxycarbonyl. Examples of the acyl group include acetyl, 3-phenylpropanoyl, benzoyl, and 4-dodecyloxybenzoyl. Examples of the azolyl group include imidazolyl, pyrazolyl, 3-chloro-pyrazole-1-
And triazolyl.

Of these substituents, the group capable of further having a substituent may have a substituent or a halogen atom linked by a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom. Among these substituents, R ^M1 is an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, a ureido group, a urethane group,
Alternatively, an acylamino group is preferable.

R ^M2 represents a group similar to the substituents exemplified for the above R ^M1 , and is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfinyl group, an acyl group. Alternatively, a cyano group is preferable.

R ^M3 represents a group similar to the substituents exemplified for the above R ^M1 , and is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl. A group, a carbamoyl group, or an acyl group is preferable, and an alkyl group, an aryl group, a heterocyclic group, an alkylthio group, or an arylthio group is more preferable.

R ^M4 represents a group similar to the substituents exemplified for the above R ^M1 , and is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, a carbamoyl group or a sulfamoyl group. A group, a sulfonyl group, an acyl group, an acylamino group, an alkoxycarbonylamino group, a sulfonamide group, a sulfamoylamino group, or a cyano group is preferable. n is 1
Represents an integer of 4 and is preferably an integer of 1 to 3.

X ^M1 represents a hydrogen atom or a group (including an atom) capable of splitting off upon reaction with an oxidized product of an aromatic primary amine color developing agent. Examples of such a releasable group or atom include a halogen atom, an alkoxy group,
Aryloxy group, acyloxy group, alkyl or aryl sulfonyloxy group, acylamino group, alkyl or aryl sulfonamide group, alkoxycarbonyloxy group, aryloxycarbonyloxy group,
Examples thereof include an alkylthio group, an arylthio group, a heterocyclic thio group, a carbamoylamino group, a 5- or 6-membered nitrogen-containing heterocyclic group, an imide group and an arylazo group. These groups may be further substituted with other organic substituents.

Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the alkoxy group include ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy and ethoxycarbonylmethoxy. Examples of the aryloxy group include 4-methylphenoxy, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarbonylphenoxy, 4-methoxycarbonylphenoxy, 3
Mention may be made of -acetylaminophenoxy and 2-carboxyphenoxy. Examples of the acyloxy group include acetoxy, tetradecanoyloxy and benzoyloxy.

Examples of the above-mentioned alkyl or arylsulfonyloxy group include methanesulfonyloxy and toluenesulfonyloxy.
Examples of the acylamino group include dichloroacetylamino and heptafluorobutyrylamino. Examples of the alkyl or aryl sulfonamide group include methanesulfonamino, trifluoromethanesulfonamino and p-toluenesulfonamino. Examples of the alkoxycarbonyloxy group include ethoxycarbonyloxy and benzyloxycarbonyloxy. Examples of the aryloxycarbonyloxy group include a phenoxycarbonyloxy group.

Examples of the alkyl, aryl or heterocyclic thio group include dodecylthio, 1-carboxydodecylthio, phenylthio and 2-butoxy-5-tert-.
Mention may be made of octylphenylthio, 2-benzyloxycarbonylaminophenylthio, and tetrazolylthio. As the carbamoylamino group,
For example, N-methylcarbamoylamino and N-phenylcarbamoylamino can be mentioned. Examples of the 5- or 6-membered nitrogen-containing heterocyclic group include 1-imidazolyl, 1-pyrazolyl, 1,2,4-triazol-1-yl, tetrazolyl, 3,5-dimethyl-1-
Pyrazolyl, 4-cyano-1-pyrazolyl, 4-methoxycarbonyl-1-pyrazolyl, 4-acetylamino-
1-pyrazolyl and 1,2-dihydro-2-oxo-
1-pyridyl can be mentioned. Examples of the imide group include succinimide and hydantoinyl. Examples of the arylazo group include phenylazo and 4-methoxyphenylazo.

In addition to these, X ^M1 may also take the form of a bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom. Further, X ^M1 may contain a photographically useful group such as a development inhibitor or a development accelerator.

X ^M1 is preferably a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, or a 5- or 6-membered nitrogen-containing heterocycle bonded to the coupling active position with a nitrogen atom. X ^M1 is particularly preferably a halogen atom, a substituted aryloxy group, a substituted arylthio group or a substituted 1-pyrazolyl group.

Specific examples of the magenta coupler represented by the formula (M) are shown below.

[0161]

[Chemical 64]

[0162]

[Chemical 65]

[0163]

[Chemical formula 66]

[0164]

[Chemical formula 67]

[0165]

[Chemical 68]

[0166]

[Chemical 69]

[0167]

[Chemical 70]

[0168]

[Chemical 71]

[0169]

[Chemical 72]

[0170]

[Chemical formula 73]

[0171]

[Chemical 74]

[0172]

[Chemical 75]

[0173]

[Chemical 76]

[0174]

[Chemical 77]

[0175]

[Chemical 78]

[0176]

[Chemical 79]

[0177]

[Chemical 80]

[0178]

[Chemical 81]

[0179]

[Chemical formula 82]

[0180]

[Chemical 83]

[0181]

[Chemical 84]

[0182]

[Chemical 85]

[0183]

[Chemical 86]

[0184]

[Chemical 87]

[0185]

[Chemical 88]

[0186]

[Chemical 89]

[0187]

[Chemical 90]

The method for synthesizing the magenta coupler represented by the above formula (M) is described in the following documents. Formula (M-
The compound represented by 1) is described in U.S. Pat. No. 4,500,630, and the compound represented by the formula (M-II) is described in U.S. Pat. Nos. 4,540,654 and 4,705,863, and JP-A-61-58163. -65245, 62-209
Nos. 457 and 62-249155, the compound represented by the formula (M-III) is described in JP-B-47-2741.
No. 1 and U.S. Pat. No. 3,725,067, the compound represented by the formula (M-IV) is described in JP-A-60-3355.
It can be synthesized according to the methods described in JP-A-2.

The amount of the magenta coupler represented by the above formula (M) used in the photosensitive material is 1 per 1 m ² of the photosensitive material.
× 10 ^-5 in the range of mole to 1 × 10 ^-2 mol, preferably 1 × 10 ^-5 mol to 5 × 10 ^-3 mols, more preferably, 5 × 10 ^-5 mol to 2 × 10 ^- It is in the range of ³ moles.

The silver halide emulsion containing silver halide grains used in the color photographic light-sensitive material of the present invention is a so-called surface latent image type emulsion or latent image in which a latent image is mainly formed on the surface of the silver halide grains. May be any of the so-called internal latent image type emulsions, which are mainly formed inside the silver halide grains. 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 different halogen compositions, 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 or There are particles having a structure in which parts of different compositions are bonded on the surface), and these can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use either of the latter two rather than the particles having a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the structure as described above, the boundary between different portions in the halogen composition is an unclear boundary because a mixed crystal is formed due to the composition difference even if the boundary is clear. Alternatively, it may be one that positively has a continuous structural change. Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide /
A silver chloride ratio can be used. This ratio is
Wide range depending on the purpose, but the silver chloride ratio is 2%
The above is preferable.

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

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

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

The silver chlorobromide emulsion used in the present invention is described in P. Glaf
Chides "Chimie et Photograph-ique" (Paul Mon
tel, 1967), GF Duffin, "(Photog
raph-ic Emulsion Chemistry "(Focal Press, 1
966), V. L. Zelikman et al, "Making a
nd Coating Photographic Emulsion "(Focal Press, Inc., 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used, and as a method of reacting the soluble silver salt and the soluble halogen salt, any method such as a one-sided mixing method, a simultaneous mixing method, and a combination thereof may be used. You may use. It is also possible to use a method of forming particles in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg 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 addition amount of these compounds may vary depending on the purpose, but is 10 ^-9 to 10 ^-2 mol (more preferably 10 ^-7 mol) with respect to the silver halide.
10 to ³ mol) is preferred. For the method of incorporating these metals, see US Pat. Nos. 3,761,276 and 43,954.
No. 78 and JP-A-59-216136.

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

The emulsion containing the non-pre-fogged internal latent image type silver halide grains 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, a certain amount of silver halide emulsion (0.5
To 3 g / m ²⁾ was applied, the following developer giving exposure at fixed time of 0.01 to 10 seconds to in (internal developer), 20 ° C., conventional photographic density when developed 5 minutes The maximum density measured by the measuring method is the maximum obtained when a silver halide emulsion coated in the same amount as above and exposed in the same manner is developed at 18 ° C. for 6 minutes in the following developer (surface type developer). Those having a concentration of at least 5 times greater than the concentration are preferred, and those having a concentration of at least 10 times greater are preferred. Internal type developer Metol 2.0 g Sodium sulfite (anhydrous) 90.0 g Hydroquinone 8.0 g Sodium carbonate (monohydrate) 52.8 g KBr 5.0 g KI 0.5 g Water-added 1000 ml Surface type developer Metol 2 .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 production 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.

Various couplers such as the yellow coupler, the cyan coupler and the magenta coupler described above can be used in the color photographic light-sensitive material of the present invention. A colored coupler for correcting unnecessary absorption in the short wavelength region of the dye to be produced, a coupler in which the coloring dye has an appropriate diffusivity,
Colorless couplers, DIR couplers that release development inhibitors with the coupling reaction and polymerized couplers can also be used. Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. The DIR coupler releasing a development inhibitor is Research Disclosure No. 17643, VII ~
Patents described in paragraph F, JP-A-57-151944, JP-A-57-154234 and JP-A-60-184248, those described in U.S. Pat. No. 4,248,962 and JP-A-63-146035. Those that have been processed are preferred. As a coupler which releases a nucleating agent or a development accelerator in an image form at the time of development, British Patent No. 20971
40, No. 2131188, each specification, JP-A-59-
Those described in JP-A Nos. 157638, 59-170840 and WO-A-88 / 01402 are preferable.

In the light-sensitive material of the present invention, in addition to the emulsion layer described above,
A non-photosensitive layer (eg, an intermediate layer) is usually provided.
As the binder or protective colloid that can be used in these emulsion layers and non-photosensitive layers, 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. As a compound which releases a photographically useful group, JP-A-63-153540 is known.
No. 63-259555, JP-A-2-616.
No. 36, No. 2-244041, and No. 2-308240. In the present invention, a color forming enhancer can be used for the purpose of improving the color forming property of the coupler. A representative example of the compound is JP-A-62-21527.
No. 2, page 121-125. The light-sensitive material of the present invention contains dyes for preventing irradiation and halation (for example, JP-A-2-85850).
The compounds described in JP-A Nos. 2-89047 and 2-89047 may be used. A solid microcrystal dispersion method may be used as the dispersion method of the dye. ), UV absorbers, plasticizers, optical brighteners, matting agents, air antifoggants, coating aids, hardeners,
An antistatic agent, a slipperiness improving agent, etc. can be added.
Typical examples of these additives are listed in Research Disclosure No. 17643VII-XIII (1978
25-27 pages, and 18716 (1 December)
(Published November 997) pp. 647-651.

The color photographic light-sensitive material of the present invention 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. . In some cases, a yellow coupler and a magenta coupler may be mixed and used in the green-sensitive layer. As described above, the light-sensitive material of the present invention is usually 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 and an antihalation layer. There are auxiliary layers such as a back layer and a white reflective layer.

The color photographic light-sensitive material of the present invention preferably contains a nucleating agent. The nucleating agent functions as a development accelerator when the color photographic light-sensitive material is a normal color photographic light-sensitive material (for example, a color negative film). Further, in the direct positive color photographic light-sensitive material which is a preferred embodiment of the present invention, the nucleating agent acts during surface development processing of an internal latent image type silver halide emulsion which has not been fogged in advance to form a direct positive image. Work. It is a substance used when carrying out the so-called "chemical fogging method". The nucleating agent is a silver halide emulsion layer,
Alternatively, it may be contained in any of the adjacent non-photosensitive layers (for example, an intermediate layer, an undercoat layer or a back layer), but it is preferably contained in the silver halide emulsion layer together with the coupler. Examples of the nucleating agent that can be used in the present invention include, for example, Research Disclosure Magazine,
No. 22534 (January 1983), pp. 50-54, ibid., No. 15162 (November 1976) 76-77
Page, No. 23510 (November 1983) 346
Quaternary heterocyclic compounds described on page 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 represented by the formula (N- which is described in JP-A-2-90154 or JP-A-3-155543.
I)) quaternary heterocyclic compounds, or JP-A-2-
A hydrazine compound represented by the formula (N-II) described in JP-A-90154 or JP-A-3-95546 is preferable.

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

In the present invention, it is preferable to use the quaternary heterocyclic compound and the hydrazine compound in combination. In the present invention, the addition amount of the nucleating agent varies depending on the characteristics of the silver halide emulsion actually used, the chemical structure of the nucleating agent and the developing conditions, and therefore can be varied over a wide range. About 1 x 1 per mole of silver
A range of 0 ^-8 moles to about 1 x 10 ^-2 moles is practically useful, with about 1 x 10 ^-5 moles to about 1 x 10 moles per silver mole being preferred.
^-3 mol range. The nucleating agent may be added to the treatment liquid. In particular, it is effective when directly performing the fogging process on the positive color photographic light-sensitive material. In this case, it is preferable to add it to a low pH pre-bath as described in JP-A-58-178350. When the nucleating agent is added to the treatment liquid, the amount used is preferably 10 ^-8 to 10 ^-1 mol per liter of the treatment liquid, and 10 ^-7 to 10 ^-3.
Molar is more preferred.

In the present invention, the direct fog processing of the positive color photographic light-sensitive material is carried out in combination with the "chemical fog method" using the above nucleating agent or separately in the "light fog method".
You may carry out using. The overall exposure in the "light fog method", that is, fog exposure is performed after imagewise exposure, before color development processing or during color development processing. That is, the imagewise exposed light-sensitive material is exposed in a color developing solution or in a pre-bath of the color developing solution, or is taken out from these solutions and dried before being exposed. Is most preferred. As a light source for fogging exposure,
For example, JP-A-56-137350 and JP-A-58-702.
A light source having a high color rendering property (as close to white as possible) as described in JP-A No. 23 is preferable. The illuminance of light is 0.01-
2000 lux, preferably 0.05 to 30 lux, more preferably 0.05 to 5 lux is suitable. The light-sensitive material using a higher-sensitivity emulsion is preferred to have low illuminance. The illuminance may be adjusted by changing the luminous intensity of the light source, or by changing the light exposure by various filters, the distance between the light-sensitive material and the light source, or the angle between the light-sensitive material and the light source. Further, the illuminance of the fogging light can be increased from low illuminance to high illuminance continuously or stepwise. It is preferable to immerse the light-sensitive material in a color developing solution or a solution of its pre-bath so that the solution sufficiently penetrates into the emulsion layer of the light-sensitive material before irradiation with light. The time from the permeation of the liquid to the light exposure is generally 2 seconds to 2 minutes, preferably 5 seconds to 1
Minutes, more preferably 10 seconds to 30 seconds. The exposure time for fogging is generally 0.01 second to 2 minutes, preferably 0.1 second to 1 minute, more preferably 1 second to 40 seconds.

In the embodiment of the color photographic light-sensitive material of the present invention, particularly the direct positive color photographic light-sensitive material, when the above nucleating agent is used, a nucleating accelerator for promoting the action of the nucleating agent is used. Is preferred. A nucleation accelerator does not substantially function as a nucleating agent, but accelerates the action of the nucleating agent to increase the maximum density of the direct positive image and / or obtain a certain maximum density of the direct positive image. Means a substance that has the function of accelerating the development time required. In the present invention, the nucleation accelerator described in JP-A-2-89048 can be preferably used. The nucleation accelerator is a silver halide emulsion layer or an adjacent non-photosensitive layer (intermediate layer, protective layer, etc.)
Although it may be contained in any of the above, it is preferably contained in the silver halide emulsion together with the coupler and the nucleating agent. The amount of nucleation accelerator added is 1 per mol of silver halide.
0 ^-6 to 10 ^-2 mol is preferable, and more preferably 10 ^-5.
It is about 10 ^-2 mol. The nucleation accelerator may be contained in the processing solution (that is, the developing solution or its pre-bath), in which case it is preferably 10 ^-8 to 10 ^-3 mol, and more preferably 1 liter of the processing solution. It is 10 ⁻⁷ to 10 ⁻⁴ mol.

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

In the color photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are flexible supports generally used for photographic light-sensitive materials such as plastic films, papers and cloths, or rigid such as glass, pottery and metal. 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 the silver halide photographic emulsion layer and other hydrophilic colloid layers, various known methods such as dip coating method, roller coating method, curtain coating method and extrusion coating method can be used. Also, if necessary, US Patent No. 2
No. 681294, No. 2761791, No. 3526
Multiple layers may be simultaneously coated by the method described in each specification such as No. 528 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. If necessary, the spectral distribution used for exposure can be adjusted with a color filter. 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 color photographic light-sensitive material of the present invention, the pixel size when the pixel density is 400 dpi is 1 pixel,
The exposure time per pixel is 10 ^-3 seconds or less (preferably,
Scan exposure is performed under the condition of 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).

[0214]

[Chemical Formula 91]

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 color developing agent represented by formula (D) are shown below.

[0216]

[Chemical Formula 92]

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: 0.02 to 1.0 seconds).

[0219]

EXAMPLES The present invention will be described more specifically 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. The layers were overcoated to prepare a color photographic light-sensitive material (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 ) Ultramarine blue is included as a bluing dye (the surface chromaticity of the support is 8 *, -0.20,-in L *, a *, b * system).
It was 0.75). (Photosensitive layer composition) The components and the coating amount (g / m ² ) are shown below. However, the addition amount of the sensitizing dye is shown 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 in accordance with the method for producing the emulsion EM-1 described later, by changing the grain forming temperature to change the grain size. However, as the emulsion of the 11th layer, a Lippmann emulsion which was not surface-sensitized was used.

First Layer (Antihalation Layer) Black Colloidal Silver 0.10 Color Mixing Inhibitor (Cpd-7) 0.05 Gelatin 0.70 Second Layer (Intermediate Layer) Gelatin 0.70 Third Layer (Red Sensitive Layer) ) Silver bromide spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3, each equivalent amount, 5.4 × 10 ⁻⁴ in total) (average grain size: 0.4 μm, grain size distribution: 10) %, Octahedron) 0.25 gelatin 1.00 cyan coupler (ExC-1, 2 to 3: 7 ratio) 0.30 anti-fading agent (Cpd-1, 2, 3, 4, 30 in equal amounts) 0.18 Anti-staining agent (Cpd-5) 0.003 Coupler dispersion medium (Cpd-6) 0.03 Coupler solvent (Solv-1, 2, and 3 are equal amounts) 0.12

Fourth Layer (Intermediate Layer) Gelatin 1.00 Color Mixing Inhibitor (Cpd-7) 0.08 Color Mixing Inhibitor Solvent (Solv-4, 5 and Equivalent Amount) 0.16 Polymer Latex (Cpd-8) 0.10 Fifth layer (green sensitive layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS- ^4, 2.6 × 10 ⁻⁴ ) (average grain size: 0.40 μm, grain size distribution 10) %, Octahedron) 0.25 gelatin 0.80 magenta coupler (Equivalent amounts of ExM-1, 2) 0.11 yellow coupler (ExY-1) 0.03 anti-fading agent (Cpd-9, 26, 30) Each equivalent) 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- Equivalent to 4, 6) 0.15

6th layer (intermediate layer) Same as 4th layer 7th layer (yellow filter layer) Yellow colloidal silver (particle size 100Å) 0.12 Gelatin 0.70 Color mixing inhibitor (Cpd-7) 0.03 Color mixing Inhibitor solvent (Equivalent amounts of Solv-4 and 5) 0.10 Polymer latex (Cpd-8) 0.07 8th layer (intermediate layer) Same as 4th layer 9th layer (blue sensitive layer) Blue sensitization Silver bromide (average grain size: 0.60 μm, grain size distribution 11%, octahedron) 0.40 spectrally sensitized with a dye (ExS-5, 6 equivalents, 3.5 × 10 ⁻⁴ in total) 0.40 Gelatin 0.80 Yellow coupler (Equivalent to ExY-1, 2) 0.35 Anti-fading agent (Cpd-14) 0.10 Anti-fading agent (Cpd-30) 0.05 Anti-staining agent (Cpd-5, 15 in 1: 5 ratio) 0.007 coupler Dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-2) 0.10

10th layer (ultraviolet absorbing layer) Gelatin 1.00 Ultraviolet absorber (equal amounts of Cpd-2, 4, 16) 0.50 Anti-color mixing agent (equal amounts of Cpd-7, 17) 0. 03 Dispersion medium (Cpd-6) 0.02 UV absorber solvent (Equivalent amounts of Solv-2, 7) 0.08 Anti-irradiation dye (Cpd-18, 19, 20, 21, 27 10:10: 13:15:20 ratio) 0.05 11th layer (protective layer) Fine grain silver chlorobromide (97 mol% silver chloride, average size 0.1 μm) 0.03 Acrylic modified copolymer of polyvinyl alcohol 01 (Molecular weight: 50,000) Polymethylmethacrylate particles (average particle size: 2.4 μm) and silicon oxide (average particle size: 5 μm) in equal amounts 0.05 gelatin 1.80 gelatin hardening agent (H-1, H) − 0.18 12th layer (back layer) gelatin 2.50 UV absorber (Equivalent amount of Cpd-2, 4, 16) 0.50 Dye (Cpd-18, 19, 20, 21, 27 is each equal amount) 0.06 13th layer (back layer protective layer) Polymethylmethacrylate particles (average particle size: 2.4 μm) and silicon oxide (average particle size: 5 μm) are each equal amount 0.05 gelatin 2.00 Gelatin hardening agent (equal amounts of H-1 and H-2) 0.14

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

[0226]

[Chemical formula 93]

[0227]

[Chemical 94]

[0228]

[Chemical 95]

[0229]

[Chemical 96]

[0230]

[Chemical 97]

[0231]

[Chemical 98]

[0232]

[Chemical 99]

[0233]

[Chemical 100]

[0234]

[Chemical 101]

[0235]

[Chemical 102]

[0236]

[Chemical 103]

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

(Preparation of Sample 102) In the preparation of Sample 101, the yellow couplers (ExY-1 and ExY-2) contained in the ninth layer (blue-sensitive layer) were replaced with the yellow couplers (Y- Sample 102 was prepared in the same manner as Sample 101, except that it was changed to 4) (replaced with equimolar amount).
Was prepared (comparative sample). (Preparation of Sample 103) In preparation of the sample 101,
Cyan coupler (E) contained in the third layer (red sensitive layer)
Sample 103 was prepared in the same manner as Sample 101 (comparative sample) except that xC-1 and ExC-2) were changed to cyan couplers (C-1) shown below (replaced with equimolar amounts). (Preparation of Sample 104) In preparation of the sample 101,
Samples except that the magenta couplers (ExM-1 and ExM-2) contained in the fifth layer (green-sensitive layer) were changed to magenta couplers (M-41) shown below (replaced by equimolar amounts). Sample 104 was prepared in the same manner as 101 (comparative sample).

[0239]

[Chemical 104]

(Preparation of Sample 105) In preparation of Sample 101, the yellow couplers (ExY-1 and ExY-2) contained in the ninth layer (blue-sensitive layer) were replaced with the above-mentioned yellow coupler (Y-4). , Magenta couplers (ExM-1 and ExM- contained in the fifth layer (green layer))
2) in the magenta coupler (M-41), and the cyan coupler (Ex in the third layer (red-sensitive layer)).
C-1 and ExC-2) are the above cyan couplers (C-
A sample 105 was prepared in the same manner as the sample 101, except that each sample was changed to 1) (replaced with an equimolar amount) (sample of the present invention).

(Preparation of Sample 106) The yellow coupler (Y-4) shown below was used as the yellow coupler (Y-4) contained in the ninth layer (blue sensitive layer) in the preparation of Sample 105.
-19) except that it was changed to (19) (replaced with equimolar amount)
Sample 106 was prepared in the same manner as 05 (sample of the present invention). (Preparation of Sample 107) In preparation of the sample 105,
The magenta coupler (M-41) contained in the fifth layer (green-sensitive layer) is the magenta coupler (M-7) shown below.
Sample 105 except that it was changed to 2) (replaced with equimolar amount)
Sample 107 was prepared in the same manner as (Sample of the present invention). (Preparation of Sample 108) In preparation of the sample 105,
Cyan coupler (C) contained in the third layer (red sensitive layer)
A sample 108 was prepared in the same manner as the sample 105 except that the cyan coupler (C-4) shown below was replaced (replaced with an equimolar amount) (sample of the present invention). (Preparation of Samples 109 and 110) In the preparation of Sample 108, the yellow coupler (Y-4) contained in the ninth layer (blue sensitive layer) is shown below as a yellow coupler (Y
-38 or 50) except that it was changed (replaced with equimolar amounts) in the same manner as sample 108
09 and 110 were prepared (invention sample).

[0242]

[Chemical 105]

[0243]

[Chemical formula 106]

[Evaluation as color photographic light-sensitive material] With respect to each silver halide color photographic light-sensitive material (Samples 101 to 110) prepared as described above, color reproducibility and image storability were evaluated. The image forming method using these photosensitive materials was carried out according to the following processing.

(Evaluation of Color Reproducibility) A sample was made to develop a single color in each of the hues of yellow, magenta and cyan to obtain a color image (dye image). Then, for each dye image of each hue, λ ₇₀₀ (yellow), λ ₆₆₀ (magenta) and λ
Absorption density at ₄₂₀ (cyan) wavelength (unnecessary absorption density)
Was measured and evaluated using a spectrophotometer.

(Evaluation of image storability) The following photofading test was conducted and evaluated. After image exposure of the sample, color development processing was performed to obtain a full-color developed image, which was then exposed to a fluorescent lamp (30,000 lux) for 2 weeks, and the yellow, magenta and cyan densities of the obtained image were changed to blue light and green. Light and red light densitometer (X-Rite310RT, X-
Rite Co., Ltd.), and the difference between the measured values of the yellow and cyan densities (ΔD _GR and ΔD _GB ) with respect to the portion having a magenta density of 1.5 was evaluated.

[Color development processing] Using the automatic processor, the cumulative replenishment amount of the solution is 3 times the tank capacity by the method described below.
It processed continuously until it doubled.

──────────────────────────────────── Treatment process time Temperature Mother liquor tank capacity Replenishment amount ── ────────────────────────────────── Color development 135 seconds 38 ° C 11 liters 300 ml / m ² Bleach-fixing 40 seconds 33 ° C. 3 liters 300 ml / m ² water washing (1) 40 seconds 33 ° C. 3 liters −2− water washing (2) 40 seconds 33 ° C. 3 liters 320 ml / m ² drying 30 seconds 80 ° C. ─────────── ──────────────────────────

The replenishing system for washing water was a so-called countercurrent replenishing system in which the washing bath (2) was replenished and the overflow solution of the washing bath (2) was introduced into the washing bath (1). At this time, the carry-in amount of the bleach-fixing solution from the bleach-fixing bath to the washing bath (1) by the light-sensitive material was 35 ml / m ² , and the ratio of the replenishing amount of washing water to the carry-in amount of the bleach-fixing solution was 9.1 times. It was

The composition of each processing solution was as follows. ──────────────────────────────────── Color developer Mother solution Replenisher ──────── ──────────────────────────── D-sorbit 0.15g 0.20g sodium naphthalenesulfonate ・ 0.15g 0.20g formalin condensation Product Ethylenediaminetetrakis 1.5 g 1.5 g Methylenephosphonic acid Diethylene glycol 12.0 ml 16.0 ml Benzyl alcohol 13.5 ml 18.0 ml Potassium bromide 0.70 g --- Benzotriazole 0.003 g 0.004 g Sodium sulfite 2.4 g 3 .2 g N, N-bis (carboxymethyl) 4.0 g 5.3 g Hydrazine D-glucose 2.0 g 2.4 g Triethanolamine 6.0 g 8.0 g -Ethyl-N- (β-methane 6.4 g 8.5 g sulfonamidoethyl) -3-methyl-4-aminoaniline sulfate potassium carbonate 30.0 g 25.0 g optical brightener (diaminostilbene type) 1.0 g 1.2g Add water 1000ml 1000ml ──────────────────────────────────── pH (25 ℃) 10.25 11.00 ────────────────────────────────────

──────────────────────────────────── Bleach-fixing solution Mother solution Replenishing solution ───── ────────────────────────────────────── Ethylenediaminetetraacetic acid ・ 2.0g Same as the mother liquor ・ Dihydrate of ethylenediaminetetraacetic acid -Fe (III) -70.0 g ammonium dihydrate ammonium thiosulfate (700 g / liter) 180 ml sodium p-toluenesulfinate 45.0 g sodium bisulfite 35.0 g 5-mercapto-1,3,4-triazole 0. 5g Ammonium nitrate 10.0g Add water 1000ml ───────────────────────────────────── pH (25 ℃ ) 6.10 ────────────── ──────────────────────

[Washing Water] Both the mother liquor and the replenisher were supplied with tap water using an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and an OH type anion exchange resin (Amberlite IR-400). Water was passed through a packed mixed-bed column to adjust the concentration of calcium and magnesium ions to 3 mg / liter or less, and subsequently, 20 mg / liter of sodium diisocyanurate dichloride and 0.15 g / liter of sodium sulfate were added. PH of this liquid
Was in the range of 6.5 to 7.5.

The above results are shown in Table 1 below.

[0254]

[Table 1] Table 1 ──────────────────────────────────── Unnecessary absorption density Color coupler YMC Image storability Sample No. YMC (700nm) (660nm) (420nm) △ D _GR △ D _GB ─────────────────────────── ─────────── (Comparative example) 101 ExY-1,2 ExM-1,2 ExC-1,2 0.12 0.16 0.42 +0.02 -0.05 102 Y-4 ExM-1,2 ExC-1 , 2 0.11 0.16 0.42 +0.02 +0.02 103 ExY-1,2 ExM-1,2 C-1 0.12 0.16 0.38 +0.01 -0.05 104 ExY-1,2 M-41 ExC-1,2 0.12 0.13 0.42 +0.07- 0.02 ──────────────────────────────────── (Example of the present invention) 105 Y-4 M-41 C -1 0.11 0.13 0.38 +0.01 +0.02 106 Y-19 M-41 C-1 0.10 0.13 0.38 +0.02 +0.01 107 Y-4 M-72 C-1 0.11 0.13 0.38 +0.01 +0.02 108 Y-4 M-41 C- 0.11 0.13 0.37 +0.01 +0.02 109 Y-38 M-41 C-4 0.10 0.13 0.37 +0.01 +0.02 110 Y-50 M-41 C-4 0.11 0.13 0.38 +0.01 +0.01 ───────── ────────────────────────────

As is clear from the results shown in Table 1, a color photographic light-sensitive material prepared by using the yellow coupler according to the present invention and combining a specific cyan coupler and a magenta coupler (invention samples 105 to 105). 11
0) gives an image in which the unnecessary absorption density is low (that is, the color hue is excellent and the color reproducibility is good), and the density difference between the dye images after the photobleaching test is small (that is, the color balance is not disturbed). On the other hand, comparative samples (101-10
In 4), the unwanted absorption density is high in any of the color dye images, and the density difference between the dye images after the photobleaching test is large.

Example 2 (1) The following image forming method was carried out using the samples 101, 105 and 106. And it evaluated by the method similar to the evaluation method performed in the said Example 1. Example 1 above
In the color developing solution, the color developing agent contained in the color developing solution was replaced by the compound (D) shown below instead of [N-ethyl-N-β- (methanesulfonamidoethyl) -3-ethyl-4-aminoaniline sulfate]. -2; The image forming method was carried out in the same manner as in Example 1 except that the mother liquor: 4.3 g and the replenisher: 5.6 g) were used. (2) The following image forming method was carried out using the samples 105 and 106. And it evaluated by the method similar to the evaluation method performed in the said Example 1. In the above Example 1, the color developing agent contained in the color developing solution was [N-
Ethyl-N-β- (methanesulfonamidoethyl) -3
-Ethyl-4-aminoaniline sulfate], the following compound (D-3; mother liquor: 4.6 g, replenisher: 6.
The image forming method was carried out in the same manner as in Example 1 except that 1 g) was changed.

[0257]

[Chemical formula 107]

The above results are shown in Table 2 below.

[0259]

[Table 2] Table 2 ──────────────────────────────────── Unnecessary absorption density Color coupler Y M C Image storability Sample No. YMC (700nm) (660nm) (420nm) △ D _GR △ D _GB ─────────────────────────── ─────────── (Comparative example) 101 ExY-1,2 ExM-1,2 ExC-1,2 0.11 0.13 0.38 +0.04 -0.08 ───────────── ──────────────────────── (Example of the present invention) (When a color developing agent (D-2) is used 105 Y-4 M-41 C -1 0.08 0.10 0.34 +0.01 +0.02 106 Y-19 M-41 C-1 0.07 0.10 0.34 +0.01 +0.02 109 Y-38 M-41 C-4 0.08 0.10 0.34 +0.02 +0.01 110 Y-50 M-41 C-4 0.09 0.10 0.34 +0.02 +0.02 ─────────────────────────────────── (Inventive Example) (When a color developing agent (D-3) is used 105 Y-4 M-41 C-1 0.08 0.10 0.34 +0.01 +0.03 106 Y-19 M-41 C-1 0.08 0.10 0.34 + 0.02 +0.02 109 Y-38 M-41 C-4 0.08 0.10 0.34 +0.02 +0.02 110 Y-50 M-41 C-4 0.08 0.10 0.34 +0.02 +0.03 ───────────── ───────────────────────

As is clear from the results shown in Table 2 above, the samples of the present invention (105, 106, 109 and 11).
0) is used and an image forming method including development processing using a specific color developing agent is carried out, the unnecessary absorption density is further reduced, and the density difference between the dye images after the photobleaching test is also reduced. It gets smaller. On the other hand, when the image forming method is carried out using the comparative sample (101), the unnecessary absorption density is lowered, but the density difference between the dye images after the photobleaching test is large, and the color balance is largely lost. .

[Example 3] Of the samples used in Example 1 above, Sample 101 and Sample 105 were used to make a fine checker FC850II manufactured by Fuji Photo Film Co., Ltd.
After making a plate-making film having a halftone image in close contact with the same, red exposure (SC-60 manufactured by Fuji Photo Film Co., Ltd.
Filter), green exposure (Fuji Photo Film Co., Ltd. BPB-53 filter), and blue exposure (Fuji Photo Film Co., Ltd. BPN45 and SC-42 filter)
Each exposure was sequentially performed. At that time, a plate-making film for cyan image and black image was made to adhere during red exposure, a plate-making film for magenta image and black image at the time of green exposure, and a plate-making film for yellow image and black image at the time of blue exposure. A color proof was created in this way. The image formation in this case was carried out by using the following color developing solution (processing solution B).

──────────────────────────────────── Color developer (Processing liquid B) ─── ───────────────────────────────── D-Sorbit 0.15g Sodium naphthalenesulfonate 0.15g Formalin condensate Nitrilotris (methylenephosphonic 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 sodium sulfite 2.8 g hydroxylamine 1/2 sulfate 4.5 g (sulfonate) hydroxylamine triethanolamine 6.5 g 4- [N-ethyl-N- (β-4.2g hydroxyethyl) amino] aniline sulfuric acid / 1/2 hydrate potassium carbonate 30.0g optical brightener (diaminostilbene type) 1.3g water 1000 ml ──────────────────────────────────── pH (25 ℃) (pH adjusted with KOH or sulfuric acid) 10.35 ─────────────────────────────────────

The minimum halftone dot area of the yellow image of the color proof obtained as described above was observed with a magnifying power of 100. As a result, a color photographic light-sensitive material containing a yellow coupler and a cyan coupler according to the present invention (Invention Sample 10
5) was able to reproduce up to 2% halftone images, but the color photographic light-sensitive material of the comparative example (Comparative Sample 101) could not reproduce up to 2% halftone images, and only 3% or more halftone images. I couldn't reproduce it.

[Embodiment 4] As a light source, a helium-neon gas laser (wavelengths 633 nm and 543 nm) and an argon laser (wavelength 458 nm) were used.
A device that can perform sequential scanning exposure (substantial exposure time of about 5 × 10 ⁻⁵ seconds) on a sample while moving a light flux with a diameter of 80 μm at a pitch of 0 μm in a scanning exposure of 1.6 m / s perpendicularly to the scanning direction. Assembled Using this device, the comparative sample 1
01 and the sample 109 were exposed and then processed using the 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 109) was able to reproduce well up to 2% halftone dot image, but the color photographic light-sensitive material of Comparative example (Comparative sample 101)
Was able to reproduce only up to 4% halftone dot image.

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

Claims (5)

[Claims] 1. A silver halide color photographic light-sensitive material comprising, on a support, at least one of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer each containing silver halide grains and a color image-forming coupler. The color image-forming coupler of the blue-sensitive layer is represented by the following formula (Y
an acylacetamide type yellow coupler having an acyl group represented by a), wherein [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. The color image forming coupler of the red-sensitive layer is represented by the following formula (C)
Cyan coupler represented by [In the formula (C), R ^C1 represents a hydrogen atom, a halogen atom or an alkyl group, R ^C2 represents an alkyl group, an aryl group or a heterocyclic group, and R ^C3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. , An aryloxy group or a carbonamido group, and X ^C1 represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of a developing agent. ] The color photographic light-sensitive material characterized by being 2. The silver halide grains are internal latent image type silver halide grains which have not been fogged in advance, and the color image forming coupler of the green-sensitive layer is a magenta coupler represented by the following formula (M). The color photographic light-sensitive material according to claim 1, wherein [Chemical 3] [In the formula (M), R ^M1 represents a hydrogen atom or a substituent,
Z ^M1 represents a group of non-metal atoms necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms (the azole ring may have a substituent (including a condensed ring)) , X ^M1 represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of a developing agent. ] 3. A color photographic light-sensitive material according to claim 1 or 2 is prepared 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 color image forming method characterized by carrying out development processing using the color developing agent shown by these. 4. A cyan plate halftone dot image film, a magenta plate halftone dot image film, and a yellow plate halftone dot image film obtained by subjecting the color photographic light-sensitive material according to claim 1 or 2 to color separation and halftone image conversion. And a black halftone dot image film, which are sequentially exposed to red light, green light, and blue light, and then color-developed. 5. A color image forming process, which comprises subjecting the color photographic light-sensitive material according to claim 1 or 2 to scanning exposure for an exposure time of 10 ⁻³ seconds or less per pixel, and then performing color development processing. Method.