JPH0611810A - Forming method of color picture image - Google Patents

Abstract

PURPOSE:To provide a method for forming color picture image with high contrast in density, and good whiteness, and its yellow is similar to the hue of printing ink, and especially the method is suitable for color proof formation. CONSTITUTION:A color picture image is formed by exposing a silver halide color photographic sensitive material having an emulsion layer and a nonphotosensitive layer on a supporting body, or exposing and monochromatically developing, then treating the photosensitive material by fogging or color developing. The emulsion layer or nonphotosensitive layer contains an acetoamide yellow coupler having an acyl group expressed by formula. In formula, RY<1> is a substituent, QY<1> is nonmetal atoms necessary to form a six-member heteroring with C or five-member heteroring including two heteroatoms.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a color image forming method utilizing a silver halide color photographic light-sensitive material containing a novel yellow coupler. The present invention particularly relates to a positive color image forming method.

[0002]

2. Description of the Related Art The process of working a color printed matter includes the steps of color-separating a color original and converting it into a halftone dot image to form a transmission halftone image. A printing plate is made from the obtained transmission type halftone dot image. Prior to this, there is a step of inspecting the state, characteristics, etc. of the final printed matter (actual printing) and performing necessary proofing (color proofing). As a color proofing method, conventionally, a method of making a printing plate and making a test print has been used. However, in recent years, various color proofs have been produced for the purpose of speeding up the calibration process and reducing costs. As a method for producing a color proof, a photopolymer, a diazo method, a surprint method using a photoadhesive polymer, an overlay method and the like are known (for example, US Pat. No. 3,582,327, JP-A-56-56).
501217, 59-97140). However, all of these methods require superposition and transfer of images, and also require superposition and transfer of a plurality of figures, and the process is complicated and requires a lot of time and cost. . JP-A-56-104335
The publication discloses a method for producing a color proof using a color photographic light-sensitive material, and this method has 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 color image by using a conventionally known direct positive silver halide photographic light-sensitive material, there is a method of using an internal latent image type silver halide emulsion which has not been fogged in advance. This method is a method of obtaining a positive color image on the photographic light-sensitive material by performing color development (surface development) after the photographic light-sensitive material is subjected to image exposure, after being subjected to fog treatment or while being subjected to fog treatment. . The internal latent image type silver halide photographic emulsion which has not been previously fogged is a type of halide having a photosensitive nucleus mainly inside the silver halide grain and a latent image is mainly formed inside the grain upon exposure. A silver photographic light sensitive emulsion. Various techniques have been known so far in this field. For example, U.S. Pat. Nos. 2,592,250, 2,466,957, 2,497,875, and 2,588,89.
82, 3,317,322, 3,761,266, 3,795,677 and British Patent No. 1151,363,
The main ones are those described in the respective specifications of Nos. 1155053 and 1011062. The formation mechanism of the direct positive image is explained as follows. That is,
When the 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 the internal latent image works (that is, when the silver halide in the exposed portion is exposed). (Development nuclei (fog nuclei) are not generated on the surface), development nuclei are selectively generated only on the surface of the silver halide in the unexposed area, and then the normal surface development treatment is performed to obtain a photographic image (Positive image) is formed. The fog treatment method includes a so-called "chemical fog method", which uses a fog agent (usually called a nucleating agent), and a "light fog method", which exposes the entire surface of the photosensitive layer. There is. After the above color development processing,
Usually, desilvering is performed, followed by washing with water and drying.

In the color reversal image forming method, a photographic light-sensitive material is subjected to image exposure, and then black-and-white development processing is performed. Then, color development processing is performed after the reversal processing or while performing the reversal processing to form a positive color image on the photographic light-sensitive material. Is the way to get. By the above image exposure processing, a latent image is formed on the silver halide in the exposed area. The silver halide in the exposed area is developed by the black and white development process to form a silver image. A latent image is formed on the silver halide remaining in the unexposed area by the reversal process. "Chemical fogging method" that uses a fogging agent for the reversal process
There is a "light fog method" that uses full exposure. By the color development processing, the silver halide in the unexposed area is color-developed to form a color image. After the above color development processing, desilvering processing is usually performed to remove the silver image. Then wash with water,
A drying process is performed.

In the color photographic light-sensitive material used in the positive color image forming method as described above, the demand for the obtained image (image quality) becomes more and more strict with the diversification of its use, and the maximum image density is high. Further, it is desired that the image has a low minimum image density, that is, a ratio of the maximum image density to the minimum image density is large. Especially for color copy, color proof, or color display applications that use direct positive color imaging methods,
It is important to obtain high color reproducibility by increasing the maximum image density and decreasing the minimum image density. In the system using the so-called "chemical fogging method" using the above-mentioned fogging agent, the gradation of the highlight portion of the specific curve of the obtained image tends to be soft. For this reason, the minimum image density (Dmin) increases with the actual exposure amount, which may cause a decrease in whiteness. As an effective method of suppressing such a decrease in whiteness, there is a method of reducing the amount of the fog-improving agent used to make the gradation of the highlight portion harder. In this way, the maximum density (Dmax) However, there is a problem that it is easy to decrease.

By the way, a positive color image is formed by the formation of a coloring dye by a coupling reaction between an oxidized product of a developing agent and a coupler. Conventionally, as a yellow coupler, an acylacetamide type yellow coupler having a pivaloyl group as an acyl group has been preferably used (see, for example, JP-A-2-220049). However, the acylacetamide type yellow coupler having a pivaloyl group as described above has a problem that the color developability is low. In order to obtain a high maximum image density, it is conceivable to increase the amount of fogging agent or increase the amount of fogging light, but this is not preferable because the minimum image density increases. For this reason, it is difficult to obtain a yellow image having a sufficiently high maximum density and a sufficiently low minimum density with a light-sensitive material using the conventional yellow coupler as described above, and therefore, particularly in applications such as color copying and color proofing. There was room for improvement.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a color image forming method which gives a yellow color image having a high maximum density and a good whiteness. It is also an object of the present invention to provide a color image forming method suitable for producing a color proof, in which a yellow colored image having a hue close to that of a printing ink (having good color reproducibility) can be obtained.

[0008]

SUMMARY OF THE INVENTION The present invention comprises:
A silver halide color photographic light-sensitive material comprising at least one silver halide emulsion layer containing an internal latent image type silver halide grain not previously fogged and at least one light-insensitive layer is exposed after imagewise exposure. Then, in the method of forming a color image by subsequent color development processing or by exposing the entire surface during the color development processing, at least one of the emulsion layer or the non-photosensitive layer is represented by the following formula (Y
The color image forming method is characterized by containing an acylacetamide type yellow coupler having an acyl group represented by a).

[0009]

[Chemical 4]

[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. ]

In the present invention, a silver halide color photographic light-sensitive material comprising at least one silver halide emulsion layer containing silver halide grains and at least one light-insensitive layer is provided on a support after imagewise exposure. In the method of forming a color image by black-and-white development, then full exposure, and then color development processing, or by full exposure during color development processing, at least one layer of the emulsion layer or the non-photosensitive layer, A color image forming method is characterized by containing an acylacetamide type yellow coupler having an acyl group represented by the following formula (Ya).

[0012]

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

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

[0016]

[Chemical 6]

(In the above formula, Z ^Y1 represents a hetero atom selected from N, S, O and P, R ^Y4 represents a substituent, Q ^Y2 represents Z ^Y1 and a carbon atom together with a 6-membered member. Heterocycle, or Z ^Y1 , represents a non-metal atomic group necessary for forming a 5-membered heterocycle containing two heteroatoms together with carbon atoms.) (2) In formula (Y), R ^Y1 is halogen. An atom, a cyano group, an alkyl group, an alkenyl group, an alkoxy group, an alkylthio group, an alkylamino group, an alkylcarbonyl group, an aryl group, or an aryloxy group. (3) In the formula (Y), R ^Y2 is chlorine atom, trifluoromethyl, methoxy, phenoxy, p-tolyloxy or p-methoxyphenoxy.

(4) In the color photographic light-sensitive material according to claim 1 or 2, an acylacetamide type yellow coupler having an acyl group represented by the formula (Ya) is contained in the silver halide emulsion layer. (5) The color photographic light-sensitive material has at least one blue-sensitive emulsion layer and contains an acylacetamide type yellow coupler having an acyl group represented by the above formula (Ya) in the blue-sensitive emulsion layer. (6) The color photographic light-sensitive material has at least one each of a red light-sensitive emulsion layer, a green light-sensitive emulsion layer and a blue light-sensitive emulsion layer. (7) Whole surface exposure is performed using a light source having a high color rendering property.

[0019]

As described above, the color photographic light-sensitive material used in the color image forming method of the present invention contains an acylacetamide type yellow coupler having a characteristic acyl group. By the image forming method according to the present invention, the yellow coupler exhibits a high color-forming property, so that a yellow image having a high maximum density can be obtained, and particularly, a gradation in a low density region corresponding to a highlight portion is hard, A yellow image with high whiteness can be realized. Further, since the obtained yellow image has a hue close to that of the printing ink, it is particularly suitable for producing a color proof.

[Detailed Description of the Invention] The color image forming method of the present invention will be described below. The color image forming method of the present invention is characterized by using a color photographic light-sensitive material containing a novel yellow coupler as described above.
Therefore, a conventionally known method is used for the processing step itself of the color image forming method. The color image forming method of the present invention includes the following two aspects. (1) A silver halide color photographic light-sensitive material in which at least one silver halide emulsion layer containing internal latent image type silver halide grains which have not been fogged and a non-photosensitive layer are provided on a support. Is subjected to image-wise exposure and then to full-surface exposure, and then subjected to color development processing, or to full-exposure during color development processing, followed by desilvering processing (bleaching / fixing), washing and drying to form a positive color image. Method. (2) A silver halide color photographic light-sensitive material in which at least one silver halide emulsion layer containing silver halide grains and one non-light-sensitive layer are provided on a support.
After image exposure, black and white development, then full exposure, then color development processing, or full exposure during color development processing, followed by desilvering (bleaching / fixing), water washing, and drying to obtain a positive color image. How to form.

The color photographic light-sensitive material used in the above method of the present invention is provided with at least one silver halide emulsion layer and at least one light-insensitive layer on a support.
An acylacetamide type yellow coupler having an acyl group represented by the formula (Ya) is contained in at least one of the emulsion layer and the non-photosensitive layer. The yellow coupler is preferably contained in the silver halide emulsion layer. The yellow coupler will be described below.

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

[0023]

[Chemical 7]

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

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

When the substituent in 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 alkenyl group, an alkoxy group, a nitro group, an amino group, a carbonamido group, a sulfonamide group and an acyl group. R ^Y1 may be a ballast group,
Alternatively, 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).

[0032]

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

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

[0035]

[Chemical 9]

[0036]

[Chemical 10]

[0037]

[Chemical 11]

[0038]

[Chemical 12]

The above 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. Examples of these substituents include a halogen atom, an alkyl group, an alkenyl group, an alkoxy group,
And an aryloxy group. less than,
Preferred specific examples of the group represented by R ^Y2 are described below.

[0040]

[Chemical 13]

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.

As the above-mentioned substituent, 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, 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.

[0047]

[Chemical 14]

[0048]

[Chemical 15]

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.

The above X ^Y1 is preferably a heterocyclic group or an aryloxy group which is bonded to the coupling active position with 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, aryloxycarboni group, acyl group, acyloxy group, amino group,
Examples thereof include carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, alkoxycarbonylamino group and sulfamoylamino group.

[0053] The X ^Y1 is, when an aryloxy group, X ^Y1 is preferably an aryloxy group having 6 to 30 carbon atoms, wherein X ^Y1 is selected from the group of substituents mentioned case a heterocyclic group It may be substituted with a group.

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

The above X ^Y1 is represented by the following formulas (X ^Y1 -1) and (X
^The heterocyclic group represented by ^Y1-2 ) or (XY1-3) or the aryloxy group is more preferred.

[0056]

[Chemical 16]

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

[0058]

[Chemical 17]

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 (for example, cyclobutane, cyclohexane, cycloheptane, cyclohexene, pyrrolidine, piperidine). The above Z ^Y2 is preferably the following groups.

[0060]

[Chemical 18]

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.

[0062]

[Chemical 19]

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.

[0064]

[Chemical 20]

Here, W represents, together with N, a non-metal atom group necessary for forming a pyrrole ring, a pyrazole ring, an imidazole ring or a triazole ring. The above ring may have a substituent. Preferred examples of such a substituent include a halogen atom, nitro group, cyano group, alkoxycarbonyl group, alkyl group, aryl group, amino group, alkoxy group, aryloxy group or carbamoyl group. The heterocyclic group represented by the above (X ^Y1 -3) has 2 to 30 carbon atoms, preferably 2 carbon atoms.
-24, more preferably 2-16.

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

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

[0068]

[Chemical 21]

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

[0070]

[Chemical formula 22]

[0071]

[Chemical formula 23]

[0072]

[Chemical formula 24]

[0073]

[Chemical 25]

[0074]

[Chemical formula 26]

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

[0076]

[Chemical 27]

[0077]

[Chemical 28]

[0078]

[Chemical 29]

[0079]

[Chemical 30]

[0080]

[Chemical 31]

[0081]

[Chemical 32]

[0082]

[Chemical 33]

[0083]

[Chemical 34]

[0084]

[Chemical 35]

[0085]

[Chemical 36]

[0086]

[Chemical 37]

[0087]

[Chemical 38]

[0088]

[Chemical Formula 39]

[0089]

[Chemical 40]

[0090]

[Chemical 41]

[0091]

[Chemical 42]

[0092]

[Chemical 43]

[0093]

[Chemical 44]

[0094]

[Chemical formula 45]

[0095]

[Chemical formula 46]

[0096]

[Chemical 47]

[0097]

[Chemical 48]

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 49]

(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 50]

Synthesis Example 3 (Synthesis of Exemplified Compound Y-66) (1) 2-Methyl-1,3-dioxolane-2-carboxylic acid synthesized by the method described in J. Chem. Soc., 1959, 477. 38.1 g of oxalyl chloride was added dropwise to a mixture of 33 g, methylene chloride 100 ml, and N, N-dimethylformamide 1 ml at room temperature over 30 minutes.
After the dropping, the mixture was reacted at room temperature for 2 hours, and then methylene chloride and excess oxalyl chloride were removed under reduced pressure of an aspirator to obtain an oily substance of 2-methyl-1,3-dioxolane-2-carbonyl chloride. . (2) 100 ml of methanol was added dropwise to a mixture of 6 g of magnesium and 2 ml of carbon tetrachloride at room temperature over 30 minutes. Then, after heating under reflux for 2 hours, 32.6 g of ethyl 3-oxobutanoate was added dropwise under heating under reflux for 30 minutes. After the dropping, the mixture was heated under reflux for further 2 hours, and methanol was completely distilled off under reduced pressure of an aspirator. Tetrahydrofuran (100 ml) was added to the reaction product to disperse it, and the previously obtained 2-methyl-1,3-dioxolane-2-carbonyl chloride was added dropwise thereto at room temperature. After reacting for 30 minutes, the reaction solution was extracted with 300 ml of ethyl acetate and diluted sulfuric acid water, washed with water, and the organic layer was dried over anhydrous sodium sulfate, and then the solvent was distilled off to give 2- (2-methyl-1,3,3). An oily product of ethyl-dioixolane-2-carbonyl) -3-oxobutanoate 63.
3 g was obtained. (3) 2- (2-methyl-1,3-dioxolane-2-
A solution of 63 g of ethyl carbonyl) -3-oxobutanoate and 160 ml of ethanol was stirred at room temperature, and then stirred therein.
60 ml of% ammonia water was added dropwise over 10 minutes. Then, the mixture was stirred for 1 hour, extracted with 300 ml of ethyl acetate, diluted sulfuric acid aqueous solution, neutralized, washed with water, and the organic layer was dried over anhydrous sodium sulfate, and then the solvent was distilled off (2-methyl-1,3- Dioxolane-2-carbonyl) ethyl acetate oil 5
0 g was obtained. (4) 2-Methyl-1,3-dioxolane-obtained above
An internal temperature of 100 g of 40 g of ethyl 2-carbonyl) acetate and 44.5 g of N- (3-amino-4-chlorophenyl) -2- (2,4-di-t-pentylphenoxy) butanamide.
The mixture was heated to reflux under reduced pressure of an aspirator at ˜120 ° C. Four
After reacting for a time, the reaction solution was purified by column chromatography with a mixed solvent of n-hexane and ethyl acetate,
51 g of Exemplified compound Y-66 was obtained as a viscous oil. The structure of the obtained compound was confirmed by mass spectrum, NMR spectrum and elemental analysis.

Synthesis Example 4 (Synthesis of Exemplified Compound Y-36) (1) 24.0 g of Exemplified Compound (Y-66) obtained above was dissolved in 300 ml of methylene chloride, and sulfuryl chloride 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 processing steps of the color image forming method of the present invention will be described in order.

As described above, the color image forming method of the present invention includes two methods. (1) A step of exposing the photographic light-sensitive material to the entire surface after image exposure, and then performing color development processing, or exposing the entire surface during color development processing, and further desilvering (bleaching / fixing), washing with water, and drying Direct positive color image forming method. (2) The photographic light-sensitive material is subjected to image-wise exposure, black-and-white development, then full-surface exposure, and then color development processing, or full-exposure during color development processing, followed by desilvering (bleaching / fixing), washing with water, A color reversal image forming method including a step of drying. In addition, during the above-mentioned treatment process, a water washing treatment or the like is further appropriately performed. Image exposure, overall exposure, color development, and subsequent desilvering (bleaching) in the above processing steps
Each processing step including steps is common to the above two systems. These processing steps will be described in detail below.

[Image exposure] Various exposure means can be used for image exposure of the photographic light-sensitive material. 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. When carrying out the color image forming method of the present invention,
When the pixel density is 400 dpi, the pixel size is set to 1 pixel, and scanning exposure can be performed under the condition that the exposure time per pixel is 10 ⁻³ seconds or less (more preferably 10 ⁻⁶ to 10 ⁻⁴ seconds). preferable.

When the color image forming method of the present invention is carried out, color separation and halftone image conversion, cyan halftone dot image film, magenta halftone dot image film, yellow halftone dot image film and black ink are used as exposure methods. A color proof can be prepared by using a plate halftone image film and sequentially exposing it with red light, green light and blue light. As an apparatus for carrying out such a method, for example, Fine Checker 850II manufactured by Fuji Photo Film Co., Ltd. (exposure time: about 0.02-
1.0 second).

[Black-and-white development processing] Black-and-white development is carried out according to the above (2).
Image forming method. Black and white developer
Contains a developing agent. Examples of the developing agent include dihydroxybenzenes (eg, hydroquinone, hydroquinone monosulfonate), 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4).
-Hydroxymethyl-3-pyrazolidone), aminophenols (eg, N-methyl-p-aminophenol),
Examples thereof include ascorbic acid and a condensed heterocyclic compound having a 1,2,3,4-tetrahydroquinoline ring and an indole ring (described in US Pat. No. 4,067,872).
As the developing agent, two or more kinds of compounds may be used in combination. The amount of developing agent used is 1 × 10 ^-5 per liter of black and white developer.
To 1 mole. In the black and white developing solution, in addition to the developing agent, a preservative (eg, sulfite, bisulfite), a silver halide solvent, a buffer (eg, carbonate, boric acid, borate, alkanolamine), Alkaline agents (eg, hydroxides, carbonates), solubilizers (eg, polyethylene glycols, their esters), pH adjusters (eg, organic acids such as acetic acid),
Sensitizer (eg, quaternary ammonium salt), development accelerator (eg,
Thioether compound), surfactant, defoaming agent, hardener,
A viscosity imparting agent, an antifoggant, a swelling inhibitor (eg, sodium sulfate, potassium sulfate), a chelating agent and the like can be added. The pH value of the black and white developer is 8.5 to 11.5.
Is preferable, and more preferably 9.0 to 10.5. The replenishment amount of black and white developer is photographic material 1
It is preferably 50 ml to 500 ml, and more preferably 50 ml to 330 ml per m ² . The processing time of the black and white development step is preferably 20 seconds to 3 minutes, and more preferably 25 seconds to 75 seconds. The treatment temperature is preferably 30 ° C to 50 ° C, more preferably 35 ° C to 45 ° C.

[Overall Exposure] In the “light fog method”, the entire exposure, that is, fog exposure is performed after image exposure, before color development processing or during color development processing in the image forming method (1). . That is, the imagewise exposed light-sensitive material is exposed in a color developing solution or in a pre-bath of the color developing solution, or is taken out from these solutions and dried before being dried. Most preferred. 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
It is 1 minute, more preferably 10 seconds to 30 seconds. The illuminance of light is 0.01 to 2000 lux, preferably 0.05.
-30 lux, more preferably 0.05-5 lux is suitable. 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 image forming method (2), the fog exposure is performed after the image exposure, after the black and white development processing, before the color development processing or during the color development processing. That is, the imagewise exposed light-sensitive material is immersed in a color developing solution or in a pre-bath of the color developing solution, or is taken out from these solutions and exposed before drying, but is exposed from the pre-bath of the color developing solution. Most preferably, the exposure is carried out afterward and before entering the color developing solution. Specifically, it is preferable that the light fog is performed after the first washing with water or during the first washing with water. When it is performed during the first washing with water, 45 seconds or more have passed since the start of the first washing with water. It is preferable to carry out after. The light illuminance is not particularly limited, but 30 lux or more is preferable, and 100 lux or more is more preferable. Exposure time is 5 seconds or more when the illuminance is 100 lux,
It is preferably 15 seconds or more. As the light source for the fogging exposure, for example, JP-A-56-137350 and 58-
A light source having a high color rendering property (as close to white as possible) as described in each of the 70223 publications, for example, a fluorescent lamp, a tungsten lamp, a halogen lamp or the like is preferable. The wavelength of the light source is preferably 400 to 700 nm. It is to be noted that a light-sensitive material using an emulsion having higher sensitivity is preferable 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.

[Color development processing] The color development processing can be carried out by using a conventional color developing solution, and the following formula (D) is used.
It is preferable to use a developer containing a color developing agent represented by

[0117]

[Chemical 51]

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

[0119]

[Chemical 52]

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. When the color developing agent represented by the above formula (D) is used, an aromatic primary amine type color developing agent other than this may be used in combination, but it is represented by the formula (D) in the developer. 50 developing agents
It is preferable that the content is at least mol%. The photographic light-sensitive material after the above color development processing is generally subjected to desilvering treatment including bleaching and fixing treatment, and further, after desilvering treatment, washing and / or stabilization treatment is generally performed. For the above series of processing steps, the method described on pages 380 to 381 of JP-A-3-120537 can be preferably used.

The method of the present invention can be preferably used for producing color prints, color copies, color proofs and color displays.

The color photographic light-sensitive material used in the color image forming method of the present invention will be described below. The silver halide emulsion used in the color photographic light-sensitive material is a so-called surface latent image type emulsion in which the latent image is mainly formed on the surface of the silver halide grain, or the latent image is mainly formed inside the silver halide grain, It is a so-called internal latent image type emulsion. For the color photographic light-sensitive material used in the above-mentioned image forming method (1), an emulsion containing internal latent image type silver halide grains which has not been fogged in advance is used. The internal latent image type silver halide grains not previously fogged will be described later.

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

A so-called high silver chloride emulsion having a high silver chloride content is preferably used for a light-sensitive material suitable for rapid processing. The silver chloride content of the high silver chloride emulsion is preferably 90 mol% or more,
95% or more is more preferable. In such a high silver chloride emulsion, a structure having a silver bromide localized layer in the inside and / or on the surface of the silver halide grain 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%. 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 a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0. The thickness is preferably 1 μm to 2 μm (more preferably 0.2 μm to 1.2 μm). Further, the particle size distribution thereof is preferably a so-called monodisperse coefficient of variation of 20% or less (standard deviation of particle size distribution divided by average particle size), preferably 15% or less. In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodispersed silver halide emulsions having different grain sizes or a plurality of emulsions having the same size but different sensitivities are used in the emulsion layers having substantially the same color sensitivity. The particles can be mixed in the same layer or multi-layered in different layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or laminated and used.

The silver halide grains contained in the photographic emulsion have a regular crystal form such as a cube, octahedron, dodecahedron or tetradecahedron, spherical,
It is possible to use a material having an irregular crystal shape such as a plate shape, or a material having a composite shape of these. It may also be a mixture of those having various crystal forms. In the present invention, among these, the particles having the above-mentioned regular crystal form are contained in an amount of 50% or more, preferably 70% or more, more preferably 90% or more. In addition to these, an emulsion having tabular grains having an average aspect ratio (circular equivalent diameter / thickness) of 5 or more, preferably 8 or more as a projected area exceeding 50% of all grains can 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 and the like may be used, and as a format for reacting the soluble silver salt and the soluble halogen salt, any method such as a one-sided mixing method, a simultaneous mixing method, and a combination thereof may be used. You may use. It is also possible to use a method of forming particles in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg constant in the liquid phase in which silver halide is produced, that is,
A so-called controlled double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

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

The silver halide emulsion used in the present invention is
Usually, it is preferable that chemical sensitization and spectral sensitization are performed. Regarding the chemical sensitization method, treatment such as sulfur sensitization typified by unstable sulfur compound addition, noble metal sensitization typified by gold sensitization, reduction sensitization, or selenium sensitization is performed alone or in combination. be able to. As the compound used for chemical sensitization, those described in JP-A No. 62-215272, from page 18, lower right column to page 22, upper right column of the specification are preferably used. In the above 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. In the present invention, a dye that absorbs light in the wavelength range corresponding to the desired spectral sensitivity,
It is preferable to add a so-called spectral sensitizing dye. Examples of spectral sensitizing dyes include, for example, “Heterocyclic compounds-Cyanine dyes and related” by FM Harmer.
compounds ”(John Wiley & Sons (New York, London)
The one described in the company publication, 1964) can be mentioned. As specific examples of compounds and the spectral sensitization method, those described in JP-A-62-215272, page 22, upper right column to page 38 are preferably used. A detailed specific example is given in Research Disclosure No. 17643-IV (issued in December 1978)
There are also patents described on pages 23 to 24.

The internal latent image type silver halide emulsion which has not been fogged in advance 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 silver halide emulsion is coated on a transparent support in a fixed amount (0.5 to 3 g / m ² ) and exposed to light for a fixed time of 0.01 to 10 seconds. When developed in an internal developer) at 20 ° C. for 5 minutes, the maximum density measured by a usual photographic density measuring method is the same amount as above, and the silver halide emulsion exposed similarly is subjected to the following developer ( In a surface type developer, a developer having a concentration at least 5 times higher than the maximum concentration obtained when developed at 18 ° C. for 6 minutes is preferable, and more preferably at least 1.
It has a 0-fold higher concentration. 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 emulsion
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 relating to emulsions doped with metal ions.
Examples thereof include core / shell type silver halide emulsions described in JP-A No. The internal latent image type silver halide grains which have not been fogged in the present invention are preferably core / shell type. The internal latent image type core / shell silver halide emulsion has a 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.

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

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

As the binder or protective colloid that can be used in the emulsion layer or the non-photosensitive layer of the light-sensitive material, gelatin is advantageously used, but other hydrophilic colloids can also be used. A color fog preventing agent or a color mixing preventing agent can also be used in the light-sensitive material. 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-63-1535 can be used.
40, No. 63-259555, JP-A No. 2-6
No. 1636, No. 2-244041, No. 2-30824
The compounds described in each publication of No. 0 can be mentioned. In the present invention, a color forming enhancer can be used for the purpose of improving the color forming property of the coupler. Representative examples of compounds are disclosed in JP-A-62-215.
No. 272, pages 121-125. Dyes for preventing irradiation and halation are used in the light-sensitive material (for example, JP-A-2-85850 and 2).
The compounds described in each publication of -89047 may be used. A solid microcrystal dispersion method may be used as the dispersion method of the dye. ), An ultraviolet absorber, a plasticizer, a fluorescent whitening agent, a matting agent, an air fog preventing agent, a coating aid, a film hardening agent, an antistatic agent, a slipperiness improving agent and the like can be added. Typical examples of these additives are listed in Research Disclosure No. 17643 VII to XIII (December 1978)
25-27 pages, and 18716 (1979)
(November, 2013) pp. 647-651.

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

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

In the photographic light-sensitive material used in the method of the present invention, the photographic emulsion layer and other layers are a flexible support usually used for photographic light-sensitive materials, such as a flexible support such as plastic film, paper, cloth or glass, ceramics. , Coated on a rigid support such as metal. 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. (Eg polyethylene, polypropylene,
It is a paper or the like coated or laminated with an 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 Pat. Nos. 2,681,294 and 2,761,791.
Nos. 3,526,528 and 3,508,947 may be applied simultaneously to form multiple layers.

[0139]

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

(Preparation of Sample 101) On the front side of a paper support (thickness 100 μm) laminated on both sides with polyethylene,
The following 1st to 11th layers and the 12th to 1st layers on the back side
A color photographic light-sensitive material having three layers coated was prepared. For the polyethylene coated on the first layer, titanium oxide (4 g / m
² ) as a white pigment and a small amount (0.003 g / m ² )
² ) The ultramarine blue is included as a bluing dye (the chromaticity of the surface of the support is 88.0, -0.20,-in L *, a *, b * system).
It was 0.75).

(Photosensitive layer composition) The components and coating amount (g /
m ² ) is shown. However, the addition amount of the sensitizing dye is shown by mol per mol of silver. For silver halide, the coating amount in terms of silver is shown. The emulsion used for each layer was prepared according to the production method of the emulsion EM-1 described later by changing the grain forming temperature to change the grain size. However, as the emulsion for the ninth layer, a Lippmann emulsion which was not surface-sensitized was used. 1st layer (anti-halation layer) Black colloidal silver 0.10 Gelatin 0.70 Color mixing inhibitor (Cpd-7) 0.05 Color mixing inhibitor solvent (Solv-4, 5 and each equivalent amount) 0.12 Second layer (Intermediate layer) Gelatin 0.70 Dye (Cpd-32) 0.005 Third layer (red sensitive layer) Red sensitizing dye (ExS-1, 2, 3, each equal amount, total 5.4 × 10 ⁻⁴⁾ ) Spectrally sensitized silver bromide (average grain size: 0.40 μm, grain size distribution: 10%, octahedron) 0.25 gelatin 0.70 cyan coupler (ExC-1, 2, 3 to 0.30 Anti-fading agent (Equivalent amounts of Cpd-1, 2, 3, 4, 30) 0.18 Anti-staining agent (Equivalent amounts of Cpd-5, 15) 0.1. 003 Coupler dispersion medium (Cpd-6) 0.3 Coupler solvent (Solv-1, 3, 5 Amount) 0.12

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

Seventh Layer (Blue Sensitive Layer) Silver bromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6 equivalents, 2.5 × 10 ⁻⁴ in total) (average grain size: 0. 6 μm, particle size distribution 11%, octahedron) 0.30 gelatin 0.50 yellow coupler (equal amounts of ExY-1, 2, and 3) 0.40 anti-fading agent (Cpd-14) 0.10 anti-fading agent (Cpd-30) 0.05 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-2) 0.10 Eighth layer (ultraviolet absorbing layer) Gelatin 0.60 Ultraviolet absorber (Cpd-2, 4) , 16 are each equal amount) 0.40 Color mixing inhibitor (Cpd-7, 17 is each equal amount) 0.03 Dispersion medium (Cpd-6) 0.02 UV absorber solvent (Solv-2, 7 is each equal amount) Amount) 0.08 Anti-irradiation dye (Cpd-18, 19, 20) 21 and 27 in a ratio of 10: 10: 13: 15: 20) 0.05 9th layer (protective layer) Fine grain silver iodobromide (99 mol% of silver bromide, average size 0.05 μm) 0.03 Polyvinyl Alkyl-modified copolymer of alcohol 0.01 (Molecular weight: 50,000) Equal amounts of polymethylmethacrylate particles (average particle size: 2.4 μm) and silicon oxide (average particle size 5 μm) 0.05 Gelatin 0.05 Gelatin Hardener (Equivalent amounts of H-1 and H-2) 0.18

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

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

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

[0147]

[Chemical 53]

[0148]

[Chemical 54]

[0149]

[Chemical 55]

[0150]

[Chemical 56]

[0151]

[Chemical 57]

[0152]

[Chemical 58]

[0153]

[Chemical 59]

[0154]

[Chemical 60]

[0155]

[Chemical formula 61]

[0156]

[Chemical formula 62]

[0157]

[Chemical formula 63]

[0158]

[Chemical 64]

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

(Preparation of Samples 102-107) Sample 1 above
In the preparation of No. 01, instead of the yellow couplers (ExY-1, 2 and 3) contained in the seventh layer (red-sensitive layer), the yellow couplers shown below were changed and added in an equimolar amount. Samples 102 to 107 corresponding to each sample were prepared in the same manner as the sample 101 except for the above.

[0161]

[Chemical 65]

[0162]

[Chemical formula 66]

[0163]

[Chemical formula 67]

(Preparation of Samples 108 to 114) Sample 1 above
01 to 107, the nucleating agent (Ex
Samples 108 to 114 corresponding to the samples 101 to 107 were prepared in the same manner as the samples 101 to 107 except that ZK-1 and ExZK-2) were not added.

[Example 1] [Formation of color image] The following image forming method was carried out using each sample prepared as described above. (1) For each sample of 101 to 107, 2854
After exposure with light having a color temperature of K and 100 CMS through a wedge for 1/10 seconds, color development processing was performed under the following processing conditions (image formation using a chemical fogging method). (2) For each sample of 108 to 114, 2854
After exposure through a wedge for 1/10 seconds with light having a color temperature of K and 100 CMS, color development processing was performed under the processing conditions shown below. And 20 seconds after the start of color development,
10 with a high color rendering light source (fluorescent lamp) with a color temperature of 5200K
The entire surface was exposed for 2 seconds (image formation using a light fog method).

[0166]

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

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

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

The density of the yellow image of each sample obtained by carrying out the above image forming method was measured, and the maximum density (Dma
x) and the minimum density (Dmin) were determined. Further, the gradation of the low density portion was obtained as follows. The difference between the exposure doses (E) giving the respective densities of Dmin + 0.2 and Dmin + 0.02 was obtained by the logarithmic exposure dose, and was made to be Δlog E. The smaller the value is, the harder the image is and the better the foot is cut. The results are shown in Table 1 below.

[0171]

[Table 1] Table 1 ──────────────────────────────────── The maximum light density of the seventh layer of the sample Minimum density Gradation No. of low density area Cyan coupler Fogging (Dmax) (Dmin) △ log E (relative value) ───────────────────────────────── ─── (Comparative Example) 101 ExY-1,2,3 None 2.10 0.11 100 102 Y-4 None 2.20 0.10 92 103 Y-6 None 2.18 0.11 96 104 Y- 8 None 2.21 0.10 92 105 Y-27 None 2.21 0.11 92 106 Y-28 None 2.20 0.11 96 107 Y-37 None 2.18 0.11 92 ───── ─────────────────────────────── (Comparative example) 108 ExY-1,2,3 Yes 2.12 0.11 96 ──────────────────────────────────── (Example of the present invention) 109 Y-4 Yes 2.32 0. 09 69 110 Y-6 Yes 2.30 0.10 65 111 Y-8 Yes 2.35 0.09 73 112 Y-27 Yes 2.36 0.09 69 113 Y-28 Yes 2.32 0.10 65 114 Y-37 Yes 2.30 0.09 65 ─────────────────────────────────────

As is clear from the results shown in Table 1 above, a light-sensitive material containing a specific yellow coupler was used,
In addition, by carrying out the image forming method (109 to 114) according to the present invention using the light fogging method, the maximum compared to the image forming method (101 to 108) using the chemical fogging method, which was carried out as a comparison. (Image) High density,
Further, it is possible to obtain a yellow image having a low minimum (image) density and excellent gradation in the low density portion.

[Example 2] [Formation of color image] Of the samples used in Example 1, the samples 108, 110 and 111 were exposed and color-developed in the same manner as in Example 1. And the entire surface was exposed. However, as the color developing solution, color developing solution B having the following composition was used in place of color developing solution A. And
The density of the yellow image of each of the obtained samples was measured by the same method as in Example 1 above, and the maximum density (Dmax) and the minimum density (Dmin) were determined. The results are shown in Table 2 below.
In Table 2, the above-mentioned Example 1 (using color developer A) was used.
The data obtained in 1. is also shown. Also, the gradation of low density area
For g E, the value of Sample 108 of Example 1 was set to 100.

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

[0175]

[Table 2] Table 2 ───────────────────────────────────── Maximum color density of the 7th layer of the sample Minimum density Gradation No. of low density area Yellow coupler Developer (Dmax) (Dmin) △ log E (relative value) ───────────────────────────────── (Comparative example) 108 ExY-1,2,3 A 2.12 0.11 100 108 ExY-1,2,3 B 2.10 0.11 102 ──────────── ───────────────────────── (Example of the present invention) 110 Y-6 A 2.30 0.10 68 110 110 Y-6 B 2.40 0.09 58 111 Y-8 A 2.32 0.10 76 111 Y-8 B 2.40 0.09 55 ─────────────────────── ──────────────

As is clear from the results shown in Table 2 above, when a sample containing a specific yellow coupler was used and the image forming method according to the present invention using the light fog method was carried out, color development processing was performed. By using a processing solution containing a specific developing agent as the solution, the maximum (image)
It is possible to obtain a yellow image having high density, low minimum (image) density, and excellent whiteness with excellent gradation in the low density portion.

[Example 3] Of the samples used in Example 1 above, a plate-making film having a halftone dot image was brought into close contact with each of the samples 108, 110 and 111, followed by red exposure (Fuji Photo Film Co., Ltd.). (SC-60 filter manufactured by Fuji Photo Film Co., Ltd.), green exposure (BPB-53 filter manufactured by Fuji Photo Film Co., Ltd.), and blue exposure (BPN45 and SC-42 filter manufactured by Fuji Photo Film Co., Ltd.) were sequentially performed. At that time, a plate-making film for cyan image and black image was overlapped during red exposure, a plate-making film for magenta image and black image was overlapped for green exposure, and a plate-making film for yellow image and black image was further overlapped during blue exposure. Further, the exposure amount at the time of blue exposure was slightly corrected because the sensitivity was different for each sample. A color proof was created in this way. The image formation in this case is the same as that in the second embodiment.
The color development processing (processing using the color developing solution B) and the entire surface exposure processing according to the above were performed. The maximum density (Dmax) and the minimum density (Dmin) of the yellow image of the color proof obtained as described above were measured. The minimum dot area is 10
It was observed with a magnifying power of 0. Furthermore, the white background was subjected to a sensitive evaluation. The results are shown in Table 3 below.

[0178]

[Table 3] Table 3 ──────────────────────────────────── Maximum concentration of the 7th layer of the sample Minimum No. of minimum white background Yellow coupler (Dmax) (Dmin) Halftone dot area Sensitive evaluation ──────────────────────────────────── ( Comparative example) 108 ExY-1,2,3 1.55 0.14 3% Poor ─────────────────────────────── ────── (Example of the present invention) 110 Y-6 1.70 0.12 2% excellent 111 Y-8 2.74 0.12 2% excellent ────────────── ───────────────────────

As is clear from the results shown in Table 3 above, when a sample containing a specific yellow coupler was used and the image forming method according to the present invention using the light fog method was carried out, color development processing was performed. By using a processing solution containing a specific developing agent as the solution, the maximum (image)
It is possible to obtain a yellow image having high density, low minimum (image) density, and excellent gradation in the low density portion.

Example 4 As a light source for image exposure, a helium-neon gas laser (wavelengths 633 nm and 54) was used.
3 nm) and an argon laser (wavelength 458 nm) are used, and a light flux with a diameter of 80 μm is 1.6 at a pitch of 100 μm.
While moving vertically with respect to the scanning direction by scanning exposure of m / s, sequential scanning exposure on the sample (substantial exposure time of about 5 × 10 ⁻⁵
I assembled a device that can. Using this apparatus, of the samples used in Example 1 above, each sample of 108 and 111 was subjected to image exposure and subjected to the same processing as in Example 2, and the reproducibility of the obtained halftone image. Was evaluated. as a result,
When a sample containing a specific yellow coupler (Y-8) was used and the image forming method according to the present invention utilizing the light fogging method was carried out, even a halftone dot image of 2% could be reproduced well. In the case of using a sample containing a conventional yellow coupler (ExY-1,2,3) and performing an image forming method for comparison using the light fogging method, up to 4% halftone dot image is obtained. I could only reproduce it. Also, this result and Example 2
From the comparison with the above results, it can be seen that when the color image forming method of the present invention is carried out, the image reproducibility is further improved when the image exposure is carried out with an exposure time of substantially 10 ⁻³ seconds or less.

(Preparation of Sample 201) The following 1st to 14th layers were applied to the front side of a paper support (thickness: 100 μm) laminated on both sides with polyethylene, and 15th to 16th layers were applied to the back side. Then, a positive type color photographic light-sensitive material was directly prepared. For the polyethylene coated on the first layer, titanium oxide (4 g / m ² ) was used as a white pigment, and a trace amount (0.
(003 g / m ² ) ultramarine as a bluing dye (the surface chromaticity of the support is 88.0 in L *, a *, b * systems,
It was -0.20 and -0.75). (Composition of photosensitive layer) Components and coating amount (g / m ² unit) below
Indicates. 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 is the emulsion EM-
According to the production method of 1, the particle size was changed by changing the temperature during particle formation. However, as the emulsion for the 14th layer, a Lippmann emulsion not surface-sensitized was used.

First Layer (Antihalation Layer) Black Colloidal Silver 0.10 Gelatin 0.70 Second Layer (Intermediate Layer) Gelatin 0.70 Third Layer (Low Sensitivity Red Sensitive Layer) Red Sensitizing Dye (ExS-1) Silver bromide (average grain size: 0.25 μm, grain size distribution: [coefficient of variation] 8%, octahedron) spectrally sensitized with 2, 3 and each equivalence meter 3.8 × 10 ⁻⁴ ) 0 .04 silver chlorobromide spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3, each equivalence meter 3.8 × 10 ⁻⁴ ) (silver chloride 5 mol%, average grain size: 0.04). 40 μm, particle size distribution: [variation coefficient] 10%, octahedron) 0.08 gelatin 1.00 cyan coupler (ExC-1, 2, 3 in a ratio of 0.30 1: 1: 0.2) fading prevention Agent (Equivalent amounts of Cpd-1, 2, 3, and 4) 0.18 Antistain agent (Cpd-5) 0.003 Coupler dispersion medium (Cpd-6) 0.03 Coupler solvent (Equivalent amounts of Solv-1, 2, and 3) 0.12 Fourth layer (high-sensitivity red-sensitive layer) Red sensitizing dye (ExS-1, 2, 3. Silver bromide spectrally sensitized with each equivalence meter 3.8 × 10 ⁻⁴ (average grain size: 0.6 μm, grain size distribution: [variation coefficient] 15%, octahedron) 0.14 Gelatin 1.00 Cyan coupler (ExC-1, 2, 3 in a ratio of 0.30 1: 1: 0.2) Anti-fading agent (Cpd-1, 2, 3, 4 in equal amounts) 0.18 Coupler dispersion medium (Cpd-6) 0.03 Coupler solvent (Equivalent amounts of Solv-1, 2 and 3) 0.12 Fifth layer (intermediate layer) Gelatin 1.00 Color mixture inhibitor (Cpd-7) 0. 08 Color-mixing inhibitor solvent (Solv-4, 5 in each equivalent amount) 0.16 Polymer latex (Cpd-8) 0.10

Sixth Layer (Low Sensitivity Green Sensitive Layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS- ^4, 2.6 × 10 ⁻⁴ ) (average grain size: 0.25 μm, grain Size distribution: [variation coefficient] 8%, octahedron) 0.04 Silver chlorobromide (5 mol% silver chloride, spectrally sensitized with a green sensitizing dye (ExS- ^4, 2.6 × 10 ⁻⁴ ). Average particle size: 0.40 μm, particle size distribution: [variation coefficient] 10%, octahedron) 0.06 gelatin 0.80 magenta coupler (equal amounts of ExM-1, 2, 3) 0.11 anti-fading agent ( Cpd-9, 26 in equal amounts) 0.15 Antistain (Cpd-10, 11, 12, 13 in 10: 7: 7: 1 ratio) 0.025 Coupler dispersion medium (Cpd-6) 0 .05 coupler solvent (equal amounts of Solv-4 and 6) 0.15 7th layer (high-sensitivity green-sensitive layer) green Sensitive dye (ExS-4,2.6 × 10 ^-4) in spectrally sensitized silver bromide (average grain size: 0.65 .mu.m, particle size distribution: [variation coefficient] 16%, octahedral) 0. 10 Gelatin 0.80 Magenta coupler (ExM-1, 2 and 3 equivalent amounts) 0.11 Anti-fading agent (Cpd-9 and 26 equivalent amounts) 0.15 Anti-staining agent (Cpd-10, 11 and 12) , 13 at a ratio of 10: 7: 7: 1) 0.025 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-4, 6 in equal amounts) 0.15 Eighth layer (intermediate layer) ) Same as the 5th layer 9th layer (yellow filter layer) Yellow colloidal silver (particle size 100Å) 0.12 Gelatin 0.70 Color mixture inhibitor (Cpd-7) 0.03 Color mixture inhibitor solvent (Solv-4, 5) 0.10 polymer latex (C pd-8) 0.07 10th layer (intermediate layer) Same as 5th layer

Eleventh Layer (Low Sensitivity Blue Sensitive Layer) Silver bromide (average grain) spectrally sensitized with a blue sensitizing dye (equal amounts of ExS-5 and ExS-5, total 3.5 × 10 ⁻⁴ ) Size: 0.40 μm, particle size distribution: [variation coefficient] 8%, octahedron) 0.07 Spectral sensitization with blue sensitizing dye (ExS-5, 6 in equal amounts, total 3.5 × 10 ⁻⁴ ). Sensitive silver bromide (silver chloride 8 mol%, average grain size: 0.60 μm, grain size distribution: [variation coefficient] 11%, octahedron) 0.12 gelatin 0.80 yellow coupler (ExY-1, 2 is each equal amount) 0.40 Anti-fading agent (Cpd-14) 0.10 Anti-staining agent (Cpd-5, 15 in a ratio of 1: 5) 0.007 Coupler dispersion medium (Cpd-6) 0. 05 Coupler solvent (Solv-2) 0.10 12th layer (high-sensitivity blue-sensitive layer) Blue sensitizing dye (ExS-5 6 each equal amounts, total 3.5 × 10 ^-4) in spectrally sensitized silver chloride (average particle size: 0.85 .mu.m, particle size distribution: [coefficient of variation] 1 8%, cubic) 0.13 Gelatin 0.60 Yellow coupler (ExY-1, 2 in equal amounts) 0.35 Anti-fading agent (Cpd-14) 0.10 Anti-staining agent (Cpd-5, 15 in a ratio of 1: 5) 0. 007 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-2) 0.10 13th layer (UV absorbing layer) Gelatin 1.00 UV absorber (Equivalent amounts of Cpd-2, 4 and 16) 0.50 Color mixing inhibitor (Equivalent amounts of Cpd-7 and 17) 0.03 Dispersion medium (Cpd-6) 0.02 Ultraviolet absorber solvent (Equivalent amounts of Solv-2 and 7) 0.08 Irradiation Preventive dye (Cpd-18, 19, 20, 21, 27 10:10 13: 15: 20 ratio) 0.05

Fourteenth Layer (Protective Layer) Fine silver chlorobromide (97 mol% silver chloride, average size 0.1 μm) 0.03 Acrylic modified copolymer of polyvinyl alcohol (molecular weight: 50,000) 0.01 Polymethylmethacrylate Equivalent amount of particles (average particle size: 2.4 μm) and silicon oxide (average particle size: 5 μm) 0.05 Gelatin 1.80 Gelatin hardening agent (Equivalent amounts of H-1 and H-2) 18 15th layer (back layer) Gelatin 2.50 Ultraviolet absorber (Equivalent amounts of Cpd-2, 4, 16) 0.50 Dye (Equivalent amount of Cpd-18, 19, 20, 21, 27) 0 0.06 16th layer (back layer protective layer) Polymethylmethacrylate particles (average particle size: 2.4 μm) and silicon oxide (average particle size: 5 μm) in equal amounts 0.05 gelatin 2.00 gelatin hardener ( -1, the equivalent amount of H-2) 0.14

Preparation of Silver Halide Emulsion (Preparation of Emulsion EM-1) An aqueous solution of potassium bromide and silver nitrate was vigorously stirred in an aqueous gelatin solution at 75 ° C. at 15 ° C.
At the same time, they were added all at once to obtain a silver halide solution containing octahedral silver bromide grains having an average grain size of 0.40 μm. Then 0.3 g of 3,4-dimethyl-1,3-per mol of silver
Thiazoline-2-thione was added. To this emulsion, 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) were sequentially added per mol of silver, and the mixture was heated at 75 ° C. for 80 minutes for chemical sensitization. Using the grains thus obtained as a core, silver halide grains were further grown in the same precipitation environment as in the first time, and finally the average grain size was 0.
A 7 μm octahedral monodisperse core / shell silver bromide emulsion was obtained.
The coefficient of variation of particle size was about 10%. To this emulsion were added 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mol of silver, and the mixture was mixed at 60 ° C. for 60 minutes.
A chemical sensitization treatment was performed by heating for 1 minute to obtain an internal latent image type silver halide emulsion. ExZK is used as a nucleating agent in each photosensitive layer.
-1 and ExZK-2 for silver halide respectively 10
^-3 wt%, 10 ^-2 wt%, Cpd-2 as a nucleation accelerator
^10-2 was used. Further, in each layer, alkanol XC (Du Pont) and sodium alkylbenzene sulfonate were used as an emulsification / dispersion aid, and succinate and Magefac F-120 (manufactured by Dainippon Ink and Chemicals, Inc.) were used as coating aids. Cpd-2 is used as a stabilizer for the layer containing silver halide and colloidal silver.
Equal amounts of 3, 24, and 25 were used. The sample number of this sample was 201. The compounds used in the above sample preparation are shown below.

[0187]

[Chemical 68]

[0188]

[Chemical 69]

[0189]

[Chemical 70]

[0190]

[Chemical 71]

[0191]

[Chemical 72]

[0192]

[Chemical formula 73]

[0193]

[Chemical 74]

[0194]

[Chemical 75]

[0195]

[Chemical 76]

[0196]

[Chemical 77]

[0197]

[Chemical 78]

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-ethoxythiocarbonylaminobenzamido) -9-methyl-10-propargyl-1,2,3,3
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 Samples 202 and 203) In the preparation of Sample 201, the yellow coupler (ExY-1) contained in the 11th layer (low sensitivity blue sensitive layer) and the 12th layer (high sensitivity blue sensitive layer). , 2) was replaced with the yellow coupler (Y-7, 33) shown below (substituting with an equimolar amount), and samples 202 and 203 corresponding to each were prepared in the same manner as the sample 201.

[0201]

[Chemical 79]

(Preparation of Samples 204 to 206) Sample 2 above
In the preparation of 01 to 203, the nucleating agent ExZ is added to each photosensitive layer.
Samples 204 to 206 corresponding to the samples 201 to 203 were prepared in the same manner as the samples 201 to 203 except that K-1 and ExZK-2 were not added.

[Color image formation] [Example 5] An image forming method as described below was carried out using each of the samples prepared as described above. 201-2
Each sample of No. 06 was exposed to light having a color temperature of 5200K through a wedge for 1/10 seconds, and then subjected to color development processing under the following processing conditions (image formation using a chemical fog method). However, 204 to 206 of the above samples
After 20 seconds from the start of color development, each sample was subjected to full exposure for 10 seconds by a high color rendering light source (fluorescent lamp) having a color temperature of 5200K.

Before the treatment was started, the image-exposed AP copy paper (manufactured by Fuji Photo Film Co., Ltd.) was used for continuous treatment until the cumulative replenishment amount of the solution became three times the tank volume. Then, the sample was developed. ──────────────────────────────────── Treatment process time Temperature Tank capacity Replenishment amount ─────── ────────────────────────────── Color development 135 seconds 38 ° C 11 liters 350 ml / m ² Bleaching fixing 40 seconds 34 ° C 3 liters 300 ml / m ² water washing (1) 40 seconds 32 ° C. 3 liters −−− water washing (2) 40 seconds 32 ° C. 3 liters 350 ml / m ² drying 30 seconds 80 ° C. ─────────────── ────────────────────── The replenishing method of the washing water is such that the washing bath (2) is replenished and the overflow liquid of the washing bath (2) is washed ( The so-called countercurrent replenishment system, which leads to 1), was adopted. At this time, the carry-out amount of each processing solution by the light-sensitive material was 35 ml / m ² . The composition of each treatment liquid is as follows.

──────────────────────────────────── Color developer developer tank liquid replenishment amount ──── ──────────────────────────────── D-Sorbit 0.15g 0.20g Sodium naphthalenesulfonate ・ 0.15g 0 20 g Formalin condensate Nitrilotris (methylenephosphonic acid) 1.8 g 1.80 g Pentasodium salt Ethylenetriaminepentaacetic acid 0.5 g 0.50 g 1-Hydroxyethylidene-1,1-0.15 g 0.15 g Diphosphonic acid diethylene glycol 12 0.0 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. g Disodium-N, N-bis 8.0 g 10.6 g (sulfonate) hydroxylamine triethanolamine 6.0 g 8.0 g N-ethyl-N- (β-methanesulfone 6.0 g 8.0 g amidoethyl) -3 -Methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate potassium carbonate 30.0 g 25.0 g optical brightener (diaminostilbene type) 1.3 g 1.7 g Water added 1000 ml 1000 ml ───── ─────────────────────────────── pH (25 ℃) 10.30 10.79 (pH adjusted with KOH or sulfuric acid) ────────────────────────────────────

──────────────────────────────────── Bleach-fixing solution Tank solution Replenishing solution ──── ─────────────────────────────────────── Ethylenediaminetetraacetic acid ・ 2 sodium ・ dihydrate 4.0g Same as tank liquid Ethylenediamine Tetraacetic acid / Fe (III) /55.0 g Ammonium / dihydrate Ammonium thiosulfate (750 g / l) 168 ml Sodium p-toluenesulfinate 30.0 g Ammonium sulfite 35.0 g 5-Mercapto-1,3,4-triazole 0 0.5 g Ammonium sulfate 10.0 g Water was added 1000 ml ──────────────────────────────────── pH (25 ℃) (pH adjustment with ammonia water or acetic acid) 6.50 ─────────────────────────────────────

──────────────────────────────────── [Washing water] (Same as mother liquor and replenisher) ) ──────────────────────────────────── Sodium chlorinated isocyanurate 0.020 g Deionized water ( Conductivity 5μs / cm or less) 1000ml pH 6.5 ─────────────────────────────────────

The density of the yellow image of each sample obtained by carrying out the above image forming method was measured, and the maximum density (Dma
x) and the minimum density (Dmin) were determined. Further, the gradation of the low density portion was obtained as follows. The difference between the exposure doses (E) giving the respective densities of Dmin + 0.2 and Dmin + 0.02 was obtained by the logarithmic exposure dose, and was made to be Δlog E. Sample 201 was set as 100 and shown as a relative value. The smaller the value is, the harder the image is and the better the foot is cut. The results are shown in Table 4 below.

[0209]

[Table 4] Table 4 ──────────────────────────────────── Maximum total concentration of the seventh layer of the sample Minimum density Gradation No. of low density area Cyan coupler exposure (Dmax) (Dmin) △ log E (relative value) ─────────────────────────────────── (Comparative Example) 201 ExY-1,2 None 2.31 0.16 100 202 Y-7 None 2.34 0.16 95 203 Y-33 None 2.36 0.16 98 ────── ────────────────────────────── (Comparative example) 204 ExY-1, 2 Yes 2.36 0.16 93 ── ────────────────────────────────── (Invention example) 205 Y-7 Yes 2.51 0.14 78 206 Y-33 Yes 2.51 0.14 75 ─────────────────────────────────────

As is clear from the results shown in Table 4, a light-sensitive material containing a specific yellow coupler was used,
And by carrying out the image forming method (Sample 205 and Sample 206) according to the present invention using the light fogging method,
Compared to the image forming method (Samples 201 to 204) using the chemical fogging method, which is performed as a comparison, the maximum (image)
It is possible to obtain a yellow image having high density, low minimum (image) density, and excellent gradation in the low density portion.

(Preparation of Sample 301) A paper support having a thickness of 220 μm laminated on both sides with polyethylene was multilayer-coated with the following first to twelfth layers to prepare a color photographic material. To the polyethylene coated on the first layer, 15% by weight of anatase type titanium dioxide white was added as a white pigment, and a slight amount of ultramarine blue was added as a bluing dye. The chromaticity of the surface of the support was (L *, a *, b *) color system and was 89.0, -0.18 and -0.73, respectively.

(Composition of each layer) The components of each layer and the coating amount (g / m ² ) are shown below. However, for silver halide, the coating amount in terms of silver is shown. First layer (gelatin layer) Gelatin 0.30 Second layer (antihalation layer) Black colloidal silver 0.07 Gelatin 0.50 Third layer (low sensitivity red sensitive layer) Red sensitizing dye (1, 2, 3 each) Silver chloroiodobromide spectrally sensitized with (equal amount) (1 mol% silver chloride, 4 mol% silver iodide, average particle size 0.3 μm, dispersion coefficient 10%, cubic, core-iodine core-shell structure) 0 .05 silver chloroiodobromide spectrally sensitized with a red sensitizing dye (equal amounts of 1, 2, and 3) (silver chloride 1 mol%, silver iodide 4 mol%, average particle size 0.5 μm, dispersion coefficient 12%, cubic) 0.08 Gelatin 1.00 Cyan coupler 1 0.14 Cyan coupler 2 0.07 Anti-fading agent 1 0.03 Anti-fading agent 2 0.03 Anti-fading agent 3 0.03 Dispersion medium (for coupler) ) 0.03 Di (2-ethylhexyl) phthalate (solvent for coupler) 0 .02 Trinonyl phosphate (solvent for coupler) 0.02 Di (3-methylhexyl) phthalate (solvent for coupler) 0.02 Development accelerator 0.05 Fourth layer (high-sensitivity red-sensitive layer) Red sensitizing dye ( 1,2,3) spectrally sensitized silver iodobromide (silver iodide 6 mol%, average grain size 0.8 μm, dispersion coefficient 18%, tabular (aspect ratio = 8), core iodide type core shell Structure) 0.15 Gelatin 1.00 Cyan coupler 1 0.20 Cyan coupler 2 0.10 Anti-fading agent 1 0.05 Anti-fading agent 2 0.05 Anti-fading agent 3 0.05 Dispersion medium (for coupler) 0. 03 Di (2-ethylhexyl) phthalate (solvent for coupler) 0.033 Trinonyl phosphate (solvent for coupler) 0.033 Di (3-methylhexyl) phthalate (solvent for coupler) 0.033 Development accelerator 0.05

Fifth layer (intermediate layer) Magenta colloidal silver 0.02 Gelatin 1.00 Color mixing inhibitor 1 0.04 Color mixing inhibitor 2 0.04 Tricresyl phosphate (solvent for color mixing inhibitor) 0.08 Dibutyl phthalate (Solvent for color mixing inhibitor) 0.08 Polyethyl acrylate latex (Molecular weight of 10,000 to 100,000) 0.10 Sixth layer (low sensitivity green sensitive layer) Silver chloroiodobromide spectrally sensitized with the green sensitizing dye 1. (Silver chloride 1 mol%, silver iodide 2.5 mol%, average particle size 0.28 μm, dispersion coefficient 6%, cubic, core iodine type core-shell structure) 0.03 Spectral sensitized with green sensitizing dye 1. Silver chloroiodobromide (silver chloride 1 mol%, silver iodide 2.5 mol%, average particle size 0.45 μm, dispersion coefficient 10%, cubic) 0.05 gelatin 0.80 magenta coupler 1 0.05 magenta Color 2 0.05 Anti-fading agent 4 0.10 Anti-staining agent 1 0.05 Anti-staining agent 2 0.05 Anti-staining agent 3 0.001 Anti-staining agent 4 0.01 Dispersion medium (for coupler) 0.05 Tri Cresyl phosphate (solvent for coupler) 0.075 Trioctyl phosphate (solvent for coupler) 0.075 7th layer (high-sensitivity green-sensitive layer) Silver iodobromide spectrally sensitized with green sensitizing dye 1 (iodination Silver 3.5 mol%, average particle size 0.8 μm, dispersion coefficient 18%, tabular (aspect ratio = 8), uniform iodine type 0.10 gelatin 0.80 magenta coupler 1 0.05 magenta coupler 20 .05 anti-fading agent 4 0.10 anti-staining agent 3 0.001 anti-staining agent 4 0.01 dispersion medium (for coupler) 0.05 tricresyl phosphate (solvent for coupler) 0 075 trioctyl phosphate (coupler solvent) 0.075

Eighth layer (yellow filter layer) Yellow colloidal silver 0.14 Gelatin 1.00 Color mixing inhibitor 1 0.06 Tricresyl phosphate (solvent for color mixing inhibitor) 0.075 Dibutyl phthalate (solvent for color mixing inhibitor) ) 0.075 polyethyl acrylate latex (molecular weight 10,000 to 100,000) 0.10 9th layer (low-sensitivity blue-sensitive layer) chloroiodobromide spectrally sensitized with a blue sensitizing dye (equal amounts of 1 and 2) Silver (1 mol% silver chloride, 3.5 mol% silver iodide, average particle size 0.38 μm, dispersion coefficient 10%, cubic, core-iodine type core-shell structure) 0.07 Blue sensitizing dye (1 and 2 each) Silver chloroiodobromide spectrally sensitized with (equal amount) (silver chloride 1 mol%, silver iodide 3.5 mol%, average particle size 0.55 μm, dispersion coefficient 10%, cubic, core iodide type core-shell structure ) 0.10 Chin 0.50 Yellow coupler 1 0.10 Yellow coupler 2 0.10 Anti-fading agent 5 0.10 Anti-staining agent 3 0.001 Dispersion medium (for coupler) 0.05 Trinonyl phosphate (solvent for coupler) 0.05 10th layer (high-sensitivity blue-sensitive layer) Silver iodobromide spectrally sensitized with a blue sensitizing dye (equal amounts of 1 and 2) (3.5 mol% silver iodide, average particle size 1.3 μm, dispersion) Coefficient 20%, tabular (aspect ratio = 12), core iodine type core-shell structure) 0.25 gelatin 1.00 yellow coupler 1 0.20 yellow coupler 2 0.20 anti-fading agent 5 0.10 anti-staining agent 3 0.002 Dispersion medium (for coupler) 0.15 Trinonyl phosphate (solvent for coupler) 0.10

Eleventh layer (UV absorbing layer) Gelatin 1.50 UV absorbing agent 1 0.50 UV absorbing agent 2 0.50 Dispersion medium (for UV absorbing agent) 0.15 Di (2-ethylhexyl) phthalate (UV absorbing Solvent for agent) 0.075 Trinonyl phosphate (solvent for ultraviolet absorber) 0.075 Dye 1 (for prevention of irradiation) 0.01 Dye 2 (for prevention of irradiation) 0.01 Dye 3 (for prevention of irradiation) 0.01 Dye 4 (for prevention of irradiation) 0.01 12th layer (protective layer) Gelatin 0.90 1,2-bis (vinylsulfonylacetamide) ethane (gelatin hardener) 0.085 4,6-dichloro- 2-hydroxy 1,3,5-triazine sodium salt (gelatin hardener) 0.085 non-photosensitive silver halide (chlorobromide , Silver bromide 3 mol%, average particle size 0.2 [mu] m) 0.02 modified Poval 0.05

Further, for each layer, alkanol XC (manufactured by Du Pont) and sodium alkylbenzenesulfonate were used as emulsifying dispersants, and succinate and Magfac F-120 (manufactured by Dainippon Ink and Chemicals) were used as coating aids. I was there. The following stabilizers 1, 2 and 3 were used in the layer containing silver halide or colloidal silver. The photographic material thus prepared was designated as Sample No. 301.

The compounds used for preparing the photographic material are shown below.

[0218]

[Chemical 80]

[0219]

[Chemical 81]

[0220]

[Chemical formula 82]

[0221]

[Chemical 83]

[0222]

[Chemical 84]

[0223]

[Chemical 85]

[0224]

[Chemical 86]

[0225]

[Chemical 87]

[0226]

[Chemical 88]

[0227]

[Chemical 89]

(Preparation of Samples 302 to 307) Sample 3 above
In the preparation of No. 01, the yellow couplers 1 and 2 contained in the 9th and 10th layers were used in Example 1 to obtain the yellow couplers (Y-4, 6, 8, 27, 28 and 3).
Sample 30 above except for the change to 7) (substitution with equimolar amount)
Samples 302 to 307 corresponding to each in the same manner as 1
It was created.

[Formation of Color Image] [Example 6] An image forming method as described below was carried out using each of the samples prepared as described above. Each sample obtained as described above is exposed through a wedge for sensitometry at a light source of 3200 ° K, and then processed by an automatic processor under the following conditions to form an image on a photographic material. did.

──────────────────────────────────── Treatment process time Temperature Mother liquor tank capacity Replenishment amount ── ────────────────────────────────── Black and white development 75 seconds 38 ℃ 8 liters 330ml / m ² First water washing ( 1st bath) 45 seconds 33 ° C 5 liters None 1st water washing (2nd bath) 45 seconds 33 ° C 5 liters 5000 ml / m ² Reverse exposure 15 seconds (100 lux) Color development 135 seconds 38 ° C 15 liters 500 ml / m ² 2 water washing 45 seconds 33 ℃ 5 liter 1000ml / m ² bleach-fixing (1st bath) 60 seconds 38 ℃ 7 liter None bleach-fixing (2nd bath) 60 seconds 38 ℃ 7 liter 220ml / m ² 3rd water washing (1st bath) ) 45 seconds 33 ° C 5 liters None 3rd water washing (second bath) 45 seconds 33 ° C 5 liters None 3rd Washing (Third bath) 45 sec 33 ° C. 5 liters 5000 ml / m ² Drying 45 sec 75 ℃ ───────────────────────────── ───────

The first and third washing steps are
Each was a countercurrent washing method. That is, in the first rinsing step, rinsing water was poured into the second bath, and the overflow liquid was led to the first bath. In the third washing step, washing water was poured into the third bath, the overflow solution was introduced into the second bath, and the overflow solution in the second bath was introduced into the first bath.

The composition of each processing solution is shown below.

──────────────────────────────────── Black and White Developer Mother Solution Replenisher ───── ─────────────────────────────── Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 1.0 g 1.0 g Diethylenetriamine pentaacetic acid / 5 sodium salt 3.0 g 3.0 g Potassium sulfite 30.0 g 30.0 g Potassium thiocyanate 1.2 g 1.2 g Potassium carbonate 35.0 g 35.0 g Potassium hydroquinone monosulfonate 25.0 g 25 0.0 g 1-phenyl-4-hydroxymethyl-4-methyl-4-methyl-3-pyrazolidone 2.0 g 2.0 g potassium bromide 0.5 g None potassium iodide 5.0 mg None ───────── ──────── ─────────────────── Add water 1000ml 1000ml pH (adjusted with hydrochloric acid or potassium hydroxide) 9.60 9.70 ───────── ────────────────────────────

──────────────────────────────────── Color developer Mother solution Replenisher ───── ─────────────────────────────── Benzyl alcohol 15.0 ml 18.0 ml Diethylene glycol 12.0 ml 14.0 ml 3,6- Dithia-1,8-octane-diol 0.20 g 0.25 g Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 0.5 g 0.5 g Diethylenetriamine 5 acetic acid-5 sodium salt 2.0 g 2.0 g Sodium sulfite 2.0 g 2.5 g Hydroxylamine sulfate 3.0 g 3.6 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-aminoaniline sulfate 5.0 g 8.0 g Optical brightening Agent (diaminosti Ben series) 1.0 g 1.2 g Potassium bromide 0.5 g None Potassium iodide 1.0 mg None ──────────────────────────── ────────── Add water 1000ml 1000ml pH (adjusted with hydrochloric acid or potassium hydroxide) 10.25 10.40 ─────────────────── ─────────────────

──────────────────────────────────── Bleach-fixing solution Mother solution Replenishing solution ───── ─────────────────────────────── ethylenediaminetetraacetic acid ・ 2 sodium ・ dihydrate 5.0g 5.0g ethylenediaminetetraacetic acid Fe (III) ammonium monohydrate 80.0 g 80.0 g sodium sulfite 15.0 g 15.0 g ammonium thiosulfate aqueous solution (700 ml / l) 160 ml 160 ml 2-mercapto-1,3,4-triazole 0.5 g 0.5g ──────────────────────────────────── Add water 1000ml 1000ml pH (acetic acid or ammonia Adjust with water) 6.50 6.50 ───────────────── ──────────────────

The density of the yellow image of each sample obtained by carrying out the above-mentioned image forming method was measured, and the maximum density (Dma
x) and the minimum density (Dmin) were determined. Further, the gradation of the lowest density portion was obtained in the same manner as in Example 1 above. The results are shown in Table 5 below.

[0237]

[Table 5] Table 5 ──────────────────────────────────── Maximum of the 9th and 10th layers Density Minimum density Gradation of low density area Sample No. Yellow coupler (Dmax) (Dmin) △ log E (relative value) ──────────────────────────────────── — 301 (Comparative example) ExY-1, 2.22 0.11 100 ───────────────────────────────── ──── 302 (invention example) Y-4 2.35 0.10 74 303 (invention example) Y-6 2.34 0.10 71 304 (invention example) Y-8 2.38 0. 10 77 305 (Example of the present invention) Y-27 2.38 0.10 74 306 (Example of the present invention) Y-28 2.34 0.10 69 307 (Example of the present invention) Y-37 2.34 0.10 71 ────────────────────────────────────

As is apparent from the results shown in Table 5 above, the color reversal image forming method (Samples 301 to 307) according to the present invention using a sample containing a specific yellow coupler.
By carrying out, a yellow image having a higher maximum (image) density, a lower minimum (image) density and an excellent gradation in the low density portion is obtained as compared with the image forming method (sample 301) carried out as a comparison. be able to.

Claims (5)

[Claims] 1. A silver halide color photograph in which at least one silver halide emulsion layer containing an internal latent image type silver halide grain not previously fogged and a non-light-sensitive layer are provided on a support. After imagewise exposing the photosensitive material,
In the method of forming a color image by exposing the entire surface and then performing color development processing, or by exposing the entire surface during color development processing, at least one layer of the emulsion layer or the non-photosensitive layer is represented by the following formula (Ya). A color image forming method, which comprises an acylacetamide type yellow coupler having an acyl group represented by the formula. [Chemical 1] [In the formula (Ya), R ^Y1 represents a substituent, and Q ^Y1 represents a 6-membered heterocycle together with C, or 5 heterocycles containing 2 heteroatoms.
Represents a group of non-metal atoms necessary to form a member heterocycle. ] 2. A silver halide color photographic light-sensitive material comprising at least one silver halide emulsion layer containing silver halide grains and a non-photosensitive layer on a support, after imagewise exposure, followed by black and white development. And then expose the entire surface,
Then, in the method for forming a color image by color development processing or by exposing the entire surface during color development processing, an acyl group represented by the following formula (Ya) is formed on at least one layer of the emulsion layer or the non-photosensitive layer. A method for forming a color image, which comprises an acylacetamide type yellow coupler having [Chemical 2] [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. ] 3. The color image forming method according to claim 1, wherein the color development processing is performed using a processing solution containing a color developing agent represented by the following formula (D). [Chemical 3] [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. ] 4. 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 obtained by subjecting the image exposure to color separation and halftone image conversion. 3. The color image forming method according to claim 1, wherein the sequential exposure is performed with red light, green light, and blue light. 5. The color image forming method according to claim 1, wherein the image exposure is scanning exposure for an exposure time of 10 ⁻³ seconds or less per pixel.