JPH04362631A - Direct positive color photographic sensitive material and image forming method - Google Patents

Abstract

PURPOSE:To provide a direct positive color photographic sensitive material capable of giving a color image having a fine developed hue (satisfactory color reproducibility) and improved shelf stability by which a change of the color balance by fading due to light is especially suppressed. CONSTITUTION:Blue-, green- and red-sensitive layers each contg. an unprefogged internal latent image type silver halide emulsion and a color coupler are formed on a base to obtain a direct positive color photographic sensitive material. The color couplers contained in the layers are a yellow coupler represented by formula I, a magenta coupler represented by formula II and a cyan coupler represented by formula III and these couplers are used in combination.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a direct positive color photographic material that makes it possible to directly obtain a positive image using an internal latent image type silver halide emulsion, and an image forming method using the same. In particular, the present invention relates to a direct positive color photographic material suitable for creating color proofs used for plate inspection and inspection in color plate making and printing processes, and an image forming method using the same.

0002

BACKGROUND OF THE INVENTION Photographic methods for obtaining direct positive images without the need for reversal processing steps or negative film are well known.

As a method for producing a positive image using a conventionally known direct positive color silver halide photographic light-sensitive material, there is a method using an internal latent image type silver halide emulsion which has not been fogged in advance. This method is a method in which a photographic light-sensitive material is subjected to surface development after image exposure, after being subjected to fogging treatment, or while being subjected to fogging treatment, to directly obtain a positive color image.

The above-mentioned internal latent image type silver halide photographic emulsion which is not fogged in advance is a type in which photosensitive nuclei are mainly inside the silver halide grains, and a latent image is mainly formed inside the grains upon exposure. A silver halide photographic emulsion.

[0005] Various techniques are known to date in this field. For example, US Patent Nos. 2,592,250, 2,466,957, 2,497,875, and 258
No. 8982, No. 3317322, No. 3761266, No. 3761276, No. 3796577 and British Patent No. 1151363, No. 1150553, No. 10
The main ones are those described in the specifications of No. 11062.

The mechanism for forming a direct positive image is explained as follows. That is, when imagewise exposed, a so-called internal latent image is generated on the silver halide, and then by performing a fogging treatment, a surface desensitization effect due to this internal latent image is activated (i.e., the silver halide in the exposed area is development nuclei (fogging nuclei) are not generated on the surface of the silver halide), but development nuclei are selectively generated only on the surface of the silver halide in the unexposed areas, and then by performing normal surface development processing, the unexposed areas become photographic. An image (positive image) is formed. The above-mentioned fogging treatment methods include a method called "photofogging method" in which the entire photosensitive layer is exposed to light, and a method called "chemical fogging method" using a nucleating agent.

In recent years, direct positive color silver halide photographic light-sensitive materials using internal latent image type silver halide emulsions that are not fogged in advance have been accepted for their simplicity of processing process, and have been used for copying purposes, etc. It has been used for

[0008] The process of producing color printed matter includes the steps of color-separating a color original and converting it into a halftone image to create a transmission halftone image. A printing plate is made from the obtained transmission halftone image, but prior to this, the final printed matter (actual printing)
There is a process of inspecting the condition, characteristics, etc., and performing necessary calibration (color calibration). Conventionally, the color proofing method has been to create a printing plate and make a trial print. However, in recent years, various color proofs have been created in order to speed up the proofreading process and reduce costs.

Known methods for producing color proofs include photopolymers, diazo methods, surprint methods and overlay methods using photo-adhesive polymers (for example, US Pat. No. 3,582,327, Japanese Unexamined Patent Publication No. 56-
501217, 59-97140). However, all of these methods require overlapping and transferring images, and the process is complicated, requiring a lot of time and cost, as it is necessary to overlay and transfer multiple images. .

[0010] JP-A-56-104335 discloses a method for producing a color proof using a color photosensitive material, and this method has great advantages in terms of simple process and low cost. Moreover, it has features such as excellent tone reproducibility.

The method for producing a color proof using the above-mentioned color photographic light-sensitive material uses a silver halide color photographic light-sensitive material of a color development method having continuous gradations, and a magenta (M) color photographic material is used.
The color, cyan (C), yellow (Y), and ink (B) color plates are sequentially exposed in close contact like printing a color negative onto color paper, and then subjected to specified color development processing to obtain a color proof. It's a method. This method has features that the process is simpler and easier to automate than the various methods mentioned above.

There are several possible silver halide color photographic materials that can be used for such color proofs. Among these, the transmission black-and-white dot images used in the production process of color printed matter mentioned above are often positive, especially in Japan and Europe, so they are not suitable for use as silver halide color photographic materials for color proofing. Positive-positive photosensitive materials are often used. Among them, the above-mentioned direct positive type color photographic materials, whose practical technology has been rapidly progressing in recent years, are attracting attention as being most suitable for color proofing applications because of their ease of processing.

[0013]

[Problems to be Solved by the Invention] Positive color images are produced by image-wise exposing a photosensitive material containing yellow, magenta, and cyan color image-forming couplers in photosensitive layers with different color sensitivities, as described above, and then subjecting it to a color development process. It can be obtained by doing. The color development process causes a coupling reaction between the oxidized form of the developing agent and the coupler to produce a coloring dye, which forms a positive color image. In this case, the coupler used is desired to have a coupling rate as fast as possible and a good color forming property that provides high color density in a limited amount of time. It is desired that the coloring dyes produced are yellow, magenta, and cyan dyes with little side absorption and provide color images with good color reproducibility.

[0014] Furthermore, it is desired that the color image formed in this manner has good storage stability. In other words, the coloring pigments of each hue of the resulting color image are generally affected by humidity, heat,
Fading or discoloration tends to occur due to various factors such as light, but the rate of fading or discoloration should be as slow as possible, and the rate of fading or discoloration should be as uniform as possible over the entire image area, and the color balance of the remaining dye image should be maintained. It is hoped that this will not change.

Conventionally, known color image forming couplers used in direct positive color photographic materials include acylacetanilide type yellow couplers, 2,5-diacylaminophenol type cyan couplers and pyrazoloazole type magenta couplers. . For example, JP-A-2-220049 discloses a direct positive photographic material containing an acylacetanilide type yellow coupler and a 2,5-diacylaminophenol type cyan coupler in the photosensitive layer. This publication describes a color photographic material using a pyrazoloazole magenta coupler together with the above-mentioned yellow coupler and cyan coupler. However, according to the inventor's study, among the couplers disclosed in the above-mentioned publications, in particular,
Regarding cyan couplers, there is little absorption in the unnecessary blue light region, but among these, those with good coloring properties have absorption wavelengths closer to the short wavelength side and have absorption in the unnecessary green light region; However, there is a problem that color development is low when the color is in the appropriate range, and the color images (dye images) obtained with the combination of the three color couplers described in the above-mentioned publication have poor storage stability, especially It has been found that the storage properties against light are not sufficient (that is, the fading or discoloration speeds of the dye images are different), and therefore, the color balance of the remaining dye images tends to be disturbed.

As a method for solving the above problems, a method has been proposed in which a specific combination of couplers is used for each color (Japanese Patent Publication No. 52-7344).
No. 59-57238 or No. 60-23255
0 publications). However, even when these methods are used, the coloring properties obtained are poor, the hue of the coloring dyes is poor, and the variation in color balance of the residual dye image is not improved to a sufficiently satisfactory degree.

[0017] Therefore, an object of the present invention is to provide a color that has good color development (good color reproducibility) and improved image storage stability (particularly, variations in color balance caused by fading or discoloration due to light). It is an object of the present invention to provide a direct positive color photographic material suitable for preparing a color proof, from which an image can be obtained.

[0018]

[Means for solving the problem] As a result of the inventor's studies,
It has been found that the above-mentioned problems can be solved by the selective use of the three color couplers used. That is, the inventors have discovered that the above object can be achieved by using a combination of specific couplers for each coupler, and have completed the present invention.

The present invention provides at least one layer each of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer containing an internal latent image type silver halide emulsion and a color image-forming coupler which have not been fogged in advance on a support. In the direct positive color photographic light-sensitive material, the color image-forming coupler in the blue-sensitive layer has the following formula (Y):

[0020]

[Chemical formula 8]

[In the formula, R1 represents an aryl group or a tertiary alkyl group, and R2 represents an alkyl group, an aryl group,
represents an alkoxy group, aryloxy group, dialkylamino group, alkylthio group or arylthio group, R3
represents a group that can be substituted on the benzene ring, X1 represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized product of a developing agent, and k represents an integer from 0 to 4, provided that, When k is plural, the plural R3's may be the same or different. ], and the color image forming coupler of the green-sensitive layer has the following formula (M):

[0022]

[Chemical formula 9]

[In the formula, R4 represents an alkyl group or an aryl group, and Z represents a group of nonmetallic atoms necessary to form a 5-membered azole ring containing 2 to 4 nitrogen atoms (the azole ring is (which may have a substituent (including a fused ring)), X2 represents a hydrogen atom or a group capable of being separated by a coupling reaction with an oxidized product of a developing agent;
When 4 is an alkyl group, X2 is not a halogen atom. ], and the color image forming coupler of the red-sensitive layer has the following formula (Cy):

0
024]

[Chemical formula 10]

[In the formula, R5 represents a hydrogen atom, a halogen atom, or an alkyl group, R6 represents an alkyl group, an aryl group, or a heterocyclic group, and R7 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryloxy group. group or a carbonamide group, and X3 represents a hydrogen atom or a group capable of being separated by a coupling reaction with an oxidized product of a developing agent. ] A direct positive color photographic material characterized by being a cyan coupler represented by:

Further, the present invention provides the above-mentioned direct positive color photographic material with the following formula (D):

[0027]

[Chemical formula 11]

[In the formula, R8 represents an alkyl group, and R
9 represents an alkylene group, provided that R8 and R9 may be connected to each other to form a ring. ] An image forming method characterized by carrying out a development process using a developing agent shown in the following.

Preferred embodiments of the photographic material of the present invention are as follows. (1) In formula (Y), R1 is a 2- or 4-alkoxyaryl group or tert-butyl. (2) In formula (Y), R2 is methyl, ethyl, alkoxy group, aryloxy group or dialkylamino group. (3) In formula (Y), R3 is an alkoxy group, an alkoxycarbonyl group, a carbonamide group, a sulfonamide group, a carbamoyl group or a sulfamoyl group. (4) In formula (Y), X1 is a heterocyclic group or an aryloxy group.

(5) In formula (M), the coupler skeleton is of the following formula (M-II):

[0031]

[Chemical formula 12]

##STR1## and R11 is an alkyl group (especially 2-phenoxyethyl).

In formula (6) (Cy), X3 is a halogen atom (especially chlorine).

(7) In formula (D), R8 is ethyl.

[0035]

Effects of the Invention: Three color couplers: a yellow coupler represented by the formula (Y), a magenta coupler represented by the formula (M), and a cyan coupler represented by the formula (Cy) (both of these three color couplers absorb By using the direct positive color photographic light-sensitive material of the present invention, which has a wavelength closer to the short wavelength side), the color development hue is good (good color reproducibility), and the image storage stability is good (the color of the residual dye image is It is possible to obtain a full-color image (with little variation in balance). In particular, when forming a color image, a full-color image with better color reproducibility and better storage stability can be obtained by processing with a color developing solution containing a specific developing agent represented by the above formula (D). . Therefore, a photosensitive material suitable for creating color proofs can be provided.

The direct positive color photographic material of the present invention will be explained below. The direct positive color photographic light-sensitive material of the present invention has at least one three-color light-sensitive layer (light-sensitive emulsion layer) having different color sensitivities, that is, a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, provided on a support. It becomes. Each photosensitive layer contains an internal latent image type silver halide emulsion and a color image-forming coupler that have not been previously fogged. As described above, the color image-forming coupler is composed of a yellow coupler represented by the formula (Y), a magenta coupler represented by the formula (M), and a cyan coupler represented by the formula (Cy). The cyan coupler is contained in the red-sensitive layer, the magenta coupler is contained in the green-sensitive layer, and the yellow coupler is contained in the blue-sensitive layer.

The three color image-forming couplers represented by the above formulas used in the photographic material of the present invention will be explained below in order.

The yellow coupler represented by the following formula (Y) will be explained in detail below.

[0039]

[Chemical formula 13]

In the above formula (Y), the aryl group represented by R1 is an aryl group having 6 to 24 carbon atoms (
For example, phenyl, p-tolyl, o-tolyl, 4-methoxyphenyl, 2-methoxyphenyl, 4-butoxyphenyl, 4-octyloxyphenyl, 4-hexadecyloxyphenyl, 1-naphthyl) are preferred.

The tertiary alkyl group represented by R1 is an alkyl group having 4 to 24 carbon atoms (eg, tert-butyl, tert-pentyl, tert-hexyl, 1,1
, 3,3-tetramethylbutyl, 1-adamantyl, 1
, 1-dimethyl-2-chloroethyl, 2-phenoxy-
2-propyl, bicyclo[2,2,2]octane-1-
) is preferred.

In the above formula (Y), the alkyl group represented by R2 is an alkyl group having 1 to 24 carbon atoms (
Examples: methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, n-octyl, n-hexadecyl,
benzyl) is preferred.

The aryl group represented by R2 is:
Aryl groups having 6 to 24 carbon atoms (eg, phenyl, p-tolyl, o-tolyl, 4-methoxyphenyl) are preferred.

The alkoxy group represented by R2 is preferably an alkoxy group having 1 to 24 carbon atoms (eg, methoxy, ethoxy, butoxy, n-octyloxy, n-tetradecyloxy, benzyloxy, methoxyethoxy).

The aryloxy group represented by R2 is an aryloxy group having 6 to 24 carbon atoms (eg, phenoxy, p-tolyloxy, o-tolyloxy, p-methoxyphenoxy, p-dimethylaminophenoxy, m-
pentadecylphenoxy) is preferred.

The dialkylamino group represented by R2 is preferably a dialkylamino group having 2 to 24 carbon atoms (eg, dimethylamino, diethylamino, pyrrolidino, piperidino, morpholino).

The alkylthio group represented by R2 is preferably an alkylthio group having 1 to 24 carbon atoms (eg, methylthio, butylthio, n-octylthio, n-hexadecylthio).

The arylthio group represented by R2 is preferably an arylthio group having 6 to 24 carbon atoms (eg, phenylthio, 4-methoxyphenylthio, 4-tert-butylphenylthio, 4-dodecylphenylthio).

In the above formula (Y), the following groups are preferable as the groups (including atoms) that can be substituted on the benzene ring represented by R3. Halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, ureido group, Sulfamoylamino group, alkoxycarbonylamino group, nitro group, heterocyclic group, cyano group, acyl group, acyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group;

Preferred examples of the halogen atoms are fluorine, chlorine, bromine and iodine.

[0051] The alkyl group has 1 to 24 carbon atoms.
Alkyl groups (eg, methyl, tert-butyl, n-dodecyl) are preferred.

The above aryl group has 6 to 24 carbon atoms.
aryl groups (eg, phenyl, p-tolyl, p-dodecyloxyphenyl) are preferred.

The alkoxy group has 1 to 2 carbon atoms.
4 alkoxy groups (e.g., methoxy, n-butoxy, n-
octyloxy, n-tetradecyloxy, benzyloxy, methoxyethoxy) are preferred.

The above aryloxy group has 6 carbon atoms.
~24 aryloxy groups (e.g., phenoxy, p-te
rt-butylphenoxy, 4-butoxyphenoxy) are preferred.

The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 24 carbon atoms (eg, ethoxycarbonyl, dodecyloxycarbonyl, 1-(dodecyloxycarbonyl)ethoxycarbonyl).

The aryloxycarbonyl group mentioned above is an aryloxycarbonyl group having 7 to 24 carbon atoms (for example,
phenoxycarbonyl, 4-tert-octylphenoxycarbonyl, 2,4-di-tert-pentylphenoxycarbonyl) are preferred.

[0057] The carbon amide group has 1 carbon atom.
Carbonamide groups with ~24 substituents (e.g., acetamido, pivaloylamino, benzamide, 2-ethylhexanamide, tetradecaneamide, 1-(2,4-
di-tert-pentylphenoxy)butanamide, 3
-(2,4-di-tert-pentylphenoxy)butanamide, 3-dodecylsulfonyl-2-methylpropanamide) are preferred.

[0058] The above sulfonamide group has 1 carbon number.
Sulfonamide groups having ~24 substituents (eg, methanesulfonamide, p-toluenesulfonamide, hexadecanesulfonamide) are preferred.

The above carbamoyl group has 1 to 1 carbon atoms.
Carbamoyl group having 24 substituents (e.g., N-methylcarbamoyl, N-tetradecylcarbamoyl, N,
N-dihexylcarbamoyl, N-octadecyl-N-
Methylcarbamoyl, N-phenylcarbamoyl) are preferred.

The above-mentioned sulfamoyl group is an unsubstituted sulfamoyl group or a sulfamoyl group having a substituent having 1 to 24 carbon atoms (eg, N-methylsulfamoyl, N-phenylsulfamoyl, N-acetylsulfamoyl, N- Propanoylsulfamoyl, N-hexadecylsulfamoyl, N,N-dioctylsulfamoyl) are preferred.

The alkylsulfonyl group is preferably an alkylsulfony group having 1 to 24 carbon atoms (eg, methylsulfonyl, benzylsulfonyl, hexadecylsulfonyl).

The above arylsulfonyl includes arylsulfonyl having 6 to 24 carbon atoms (eg, phenylsulfonyl, p-tolylsulfonyl, p-dodecylsulfonyl,
p-methoxysulfonyl) is preferred.

The above ureido group has 1 to 24 carbon atoms.
A ureido group having a substituent (e.g., 3-methylureido, 3-phenylureido, 3,3-dimethylureido,
3-tetradecylureido) is preferred.

The above-mentioned sulfamoylamino group is preferably an unsubstituted sulfamoylamino group or a sulfamoylamino group having a substituent having 1 to 24 carbon atoms (eg, N,N-dimethylsulfamoylamino).

The alkoxycarbonylamino group mentioned above is an alkoxycarbonylamino group having 2 to 24 carbon atoms (
For example, methoxycarbonylamino, isobutoxycarbonylamino, dodecyloxycarbonylamino) are preferred.

The above heterocyclic group is preferably a heterocyclic group having 1 to 24 carbon atoms (eg, 4-pyridyl, 2-thienyl, phthalimide, octadecylsuccinimide).

The above acyl group includes an acyl group having 1 to 24 carbon atoms (eg, acetyl, benzoyl, dodecanoyl)
is preferred.

The above acyloxy group has 1 to 1 carbon atoms.
24 acyloxy groups (eg, acetoxy, benzoyloxy, dodecanoyloxy) are preferred.

The alkylsulfonyloxy group mentioned above is an alkylsulfonyloxy group having 1 to 24 carbon atoms (for example,
Methylsulfonyloxy, hexadecylsulfonyloxy) are preferred.

The arylsulfonyloxy group mentioned above is an arylsulfonyloxy group having 6 to 24 carbon atoms (for example,
p-toluenesulfonyloxy, p-dodecylphenylsulfonyloxy) are preferred.

In the above formula (Y), k is preferably an integer of 1 or 2 (more preferably 1).

In the above formula (Y), it is a group that can be separated by a coupling reaction with the oxidized product of the developing agent represented by X1, and specifically, the following atoms or groups can be mentioned. Halogen atom, heterocyclic group, aryloxy group, arylthio group, acyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, heterocyclicoxy group;

[0073] Examples of the above halogen atoms include fluorine,
Chlorine, bromine and iodine are preferred.

Examples of the above heterocyclic group include those having 1 to 2 carbon atoms.
A heterocyclic group that is bonded to the coupling active position through 4 nitrogen atoms is preferred.

The above arylthio group has 6 carbon atoms.
~24 arylthio groups (e.g., phenylthio, p-te
rt-butylphenylthio, p-chlorophenylthio,
p-carboxyphenylthio) is preferred.

The above acyloxy group has 1 to 1 carbon atoms.
24 acyloxy groups (acetoxy, bezoyloxy,
dodecanoyloxy) is preferred.

The alkylsulfonyloxy group mentioned above is an alkylsulfonyloxy group having 1 to 24 carbon atoms (for example,
Methylsulfonyloxy, butylsulfonyloxy, dodecylsulfonyloxy) are preferred.

The above arylsulfonyloxy group includes an arylsulfonyloxy group having 6 to 24 carbon atoms (eg,
benzenesulfonyloxy, p-chlorophenylsulfonyloxy) are preferred.

[0079] The above heterocyclic oxy group has 1 to 1 carbon atoms.
24 heterocyclic oxy groups (e.g., 3-pyridyloxy, 1-
phenyl-1,2,3,4-tetrazol-5-yloxy) is preferred.

Among the above groups, a heterocyclic group or an aryloxy group in which the nitrogen atom is bonded to the coupling active position is more preferred.

When X1 represents a heterocyclic group with a nitrogen atom bonded to the coupling active position, X1 represents a heteroatom selected from oxygen, sulfur, phosphorus, nitrogen, phosphorus, selenium and tellurium in addition to the nitrogen atom. May contain 5-7
(The heterocycle is an optionally substituted monocyclic ring or a fused ring).

Examples of the above heterocyclic groups include succinimide, maleimide, 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, oxazolin-2-one, thiazolin-2-one, benzimidazolin-2-one, benzoxazolin-2-one, benzothiazolin-2-one one, 2-pyrrolin-5-one, 2-imidazolin-5-one, indoline-2,3-dione, 2,6-dioxypurine, parabanic acid, 1,2,4-triazolidine-3,
Examples include 5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone, 6-pyridazone, and 2-pyrazone. These heterocycles may be substituted.

Examples of substituents include hydroxyl group, carboxyl group, sulfo group, amino group (eg, amino, N-
methylamino, N,N-dimethylamino, N,N-diethylamino, anilino, pyrrolidino, piperidino, morpholino). Another example is
There are the substituents listed as examples of R3 above.

[0084] X1 is an aryloxy group (having 6 to 2 carbon atoms)
When X1 is a heterocyclic group, the aryloxy group may be substituted with a group or atom selected from the group of substituents listed above when X1 is a heterocyclic group.

These substituents (or atoms) include:
The following are preferred. Carboxyl group, sulfo group, cyano group, nitro group, alkoxycarbonyl group, halogen atom, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, alkyl group, alkylsulfonyl group, arylsulfonyl group, acyl group;

008
6] Next, examples of substituents more preferably used in the present invention will be described for R1, R2, R3 and X1.

R1: 2- or 4-alkoxyaryl group (eg, 4-methoxyphenyl, 4-butoxyphenyl, 2-methoxyphenyl), tert-butyl, and among these, tert-butyl is most preferred.

R2; methyl, ethyl, alkoxy group,
An aryloxy group, a dialkylamino group, and among these, a methyl, ethyl, alkoxy group, aryloxy group or dimethylamino group is preferred.

R3; alkoxy group, alkoxycarbonyl group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group,

When X1 represents the above heterocyclic group, X1
can preferably be represented by the following formula (X1-A).

[0091]

[Chemical formula 14]

In the above (X1-A), Z1 is
Represents the following group.

[0093]

[Chemical formula 15]

In the group represented above, the above R21
, R22, R25 and R26 represent 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; represents an atom, an alkyl group, an aryl group, an alkylsulfonyl group, an arylsulfonyl group, or an alkoxycarbonyl group; R27 and R28 above represent a hydrogen atom, an alkyl group, or an aryl group; provided that R27 and R28 are bonded to each other and A benzene ring may be formed, and R21 and R22, R
22 and R23, R23 and R24, and R21 and R25 may be bonded to each other to form a ring (eg, cyclobutane, cyclohexane, cycloheptane, cyclohexene, pyrrolidine, piperidine).

Among the heterocyclic groups represented by the formula (X1-A), particularly preferred are those in which Z1 is represented by the following group.

[0096]

[Chemical formula 16]

The total number of carbon atoms in the heterocyclic group represented by formula (X1-A) is 2 to 24, preferably 4 to 20, more preferably 5 to 16.

Examples of the heterocyclic group represented by formula (X1-A) include succinimide, maleimide, phthalimide, 1-methylimidazoline-2,4-dione-3
-yl, 1-benzylimidazolidi-2,4-dione-
3-yl, 5,5-dimethyloxazolidine-2,4-
Dion-3-yl, 5-methyl-5-propyloxazolidin-2,4-dion-3-yl, 5,5-dimethylthiazolidin-2,4-dion-3-yl, 5,5-dimethylimidazolidine- 2,4-dion-3-yl, 3
-methylimidazolidinetrion-1-yl, 1,2,
4-triazolidine-3,5-dion-4-yl, 1-
Methyl-2-phenyl-1,2,4-triazolidine-
3,5-dione-4-yl, 1-benzyl-2-phenyl-1,2,4-triazolidine-3,5-dione-4
-yl, 5-hexyloxy-1-methylimidazolidin-2,4-dion-3-yl, 1-benzyl-5-ethoxyimidazolidin-2,4-dion-3-yl, 1
-benzyl-5-dodecyloxyimidazolidine-2,
Mention may be made of 4-dione-3-yl.

Among the above heterocyclic groups, imidazolidin-2,4-dion-3-yl (especially 1-benzyl-imidazolidin-2,4-dion-3-yl)
is most preferred.

[0100] When X1 represents an aryloxy group,
The following groups are preferred. 4-carboxyphenoxy, 4-
Methylsulfonylphenoxy, 4-(4-benzyloxyphenylsulfonyl)phenoxy, 4-(4-hydroxyphenylsulfonyl)phenoxy, 2-chloro-4
-(3-chloro-4-hydroxyphenylsulfonyl)
Phenoxy, 4-methoxycarbonylphenoxy, 2-
Chloro-4-methoxycarbonylphenoxy, 2-acetamido-4-methoxycarbonylphenoxy, 4-isopropoxycarbonylphenoxy, 4-cyanophenoxy, 2-[N-(2-hydroxyethyl)carbamoyl]phenoxy, 4-nitrophenoxy, 2,5-dichlorophenoxy, 2,3,5-trichlorophenoxy,
4-methoxycarbonyl-2-methoxyphenoxy, 4
-(3-carboxypropanamide)phenoxy;

0
101 The coupler represented by formula (Y) has the above R1,
1 or

[0102]

[Chemical formula 17]

[0103] A dimer or a multimer of more than two molecules may be formed by bonding to each other via a divalent or divalent or more divalent group. In this case, the number of carbon atoms in each of the above substituents may be outside the specified range.

When the coupler represented by formula (Y) forms a multimer, a typical example is a single or copolymer of an addition-polymerizable ethylenically unsaturated compound (yellow color-forming monomer) having a yellow dye-forming residue. be. In this case, the multimer contains a repeating unit represented by the following formula (Y-I), and one or more of these repeating units may be contained in the multimer, and non-color-forming ethylene type as a copolymerization component. It may also be a copolymer containing one or more monomers.

[0105]

[Chemical formula 18]

[In the formula, R represents a hydrogen atom, a chlorine atom, or an alkyl group having 1 to 4 carbon atoms; A is -CONH
-, -COO- or a substituted or unsubstituted phenylene group; B represents a substituted or unsubstituted alkylene group, phenylene group or aralkylene group; L is
-CONH-, -NHCONH-, -NHCOO-, -
NHCO-, -OCONH-, -NH-, -COO-,
-OCO-, -CO-, -0-, -S-, -SO2 -
, -NHSO2- or -SO2NH-;
and a, b and c represent 0 or 1; Q is
R1, X1 or of the compound represented by formula (Y)

[
0107]

[Chemical formula 19]

[0108] This represents a yellow coupler residue from which a hydrogen atom has been removed. ]

As the multimer, a copolymer of a yellow color-forming monomer represented by a repeating unit (coupler unit) represented by formula (Y-I) and a non-color-forming ethylenic monomer shown below is preferred.

Examples of non-color forming ethylenic monomers that do not undergo a coupling reaction with the oxidized form of a developing agent (usually an aromatic primary amine developing agent) include the following. Acrylic acid, α-chloroacrylic acid, α-alkylacrylic acid (e.g., methacrylic acid), amides or esters derived from these acrylic acids (e.g., acrylamide, methacrylamide, n-butylacrylamide,
tert-butylacrylamide, diacetone acrylamide, methyl acrylate, ethyl acrylate, n
-propyl acrylate, n-butyl acrylate, t
ert-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), vinyl esters (e.g. vinyl acetate, vinyl pro- pionate and vinyl laurate), acrylonitrile,
methacrylonitrile, aromatic vinyl compounds (e.g. styrene and its derivatives, e.g. vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic ester, N-
Vinyl-2-pyrrolidone, N-vinylpyridine and 2
- and 4-vinylpyridine, etc.

Among the above, acrylic esters, methacrylic esters, and maleic esters are particularly preferred. The non-color-forming ethylene monomer used here is
Two or more types can also be used together. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, methyl acrylate and diacetone acrylamide, etc. can be used.

As is well known in the field of polymer couplers, the ethylenically unsaturated monomer to be copolymerized with the vinyl monomer corresponding to the formula (Y-I) depends on the physical properties of the copolymer formed. and/or chemical properties (eg, solubility, compatibility with the binder (eg, gelatin) of the photographic colloid composition, its flexibility, thermal stability, etc.) are selected to be favorably influenced.

The yellow coupler used in the present invention is:
A lipophilic polymer coupler obtained by polymerizing a vinyl monomer to provide a coupler unit represented by the above formula (Y-I) is dissolved in an organic solvent and then emulsified and dispersed in an aqueous gelatin solution in the form of latex. Alternatively, it may be produced by direct emulsion polymerization.

A method of emulsifying and dispersing a lipophilic polymer coupler in the form of latex in an aqueous gelatin solution is described in US Pat. No. 3,518,200, and emulsion polymerization is described in
The methods described in US Pat. No. 4,080,211 and US Pat. No. 3,370,952 can be used.

Specific examples of R3 and X1 for the yellow image forming coupler represented by formula (Y) are shown below, but the present invention is not limited to these examples. A specific example of X1 will be shown.

[0116]

[C20]

[0117]

[C21]

[0118]

[C22]

[0119]

[C23]

[0120]

[C24]

[0121]

[C25]

[0122]

[C26]

A specific example of R3 is shown below.

[0124]

[C27]

[0125]

[C28]

[0126]

[C29]

[0127]

[C30]

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

[0129]

[Chemical formula 31]

[0130]

[C32]

[0131]

[Chemical formula 33]

[0132]

[C34]

[0133]

[C35]

[0134]

[C36]

[0135]

[C37]

[0136]

[C38]

[0137]

[C39]

[0138]

[C40]

[0139]

[C41]

[0140]

[C42]

[0141]

[C43]

[0142]

[C44]

[0143]

[C45]

[0144]

[C46]

[0145]

[C47]

[0146]

[C48]

[0147]

[C49]

[0148]

[C50]

[0149]

[C51]

[0150]

[C52]

[0151]

[C53]

[0152]

[C54]

[0153]

[C55]

[0154]

[C56]

[0155]

[C57]

[0156]

[C58]

[0157]

[C59]

[0158]

[C60]

[0159]

[C61]

[0160]

[C62]

[0161]

[C63]

[0162]

[C64]

[0163]

[C65]

[0164]

[C66]

The above couplers can be synthesized by conventional known synthesis methods. For example, JP-A-63-123
Examples include the synthesis method described in Japanese Patent No. 047.

The above yellow couplers may be used alone or in combination of two or more. It may also be used in combination with other known yellow couplers.

The amount of the above-mentioned yellow coupler according to the present invention used in the photosensitive material is 1×1 per m2 of the photosensitive material.
The range is from 0-5 mol to 1 x 10-2 mol, preferably from 1 x 10-4 mol to 5 x 10-3 mol, more preferably from 2 x 10-4 mol to 1 x 10-3 mol. The range is 3 moles.

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

[0169]

[C67]

Among the coupler skeletons represented by the above formula (M), preferred skeletons are shown by the following formula.

[0171]

[C68]

1H-imidazo[1,2-b]pyrazole

[0173]

[C69]

1H-pyrazolo[1,5-b][1,2,
4] Triazole

[0175]

[C70]

1H-pyrazolo[1,5-c][1,2,
4] Triazole

[0177]

[C71]

1H-pyrazolo[1,5-d]tetraazole

In the above formulas (M-I) to (M-IV), R11 represents an alkyl group or an aryl group. R1
The alkyl group represented by 1 is a straight chain, branched chain or cyclic alkyl group having 1 to 32 carbon atoms. These groups may have organic substituents or halogen atoms linked via carbon, oxygen, nitrogen or sulfur atoms.

Examples of the above alkyl groups include methyl, ethyl, propyl, isopropyl, tert-butyl, tridecyl, 2-methanesulfonylethyl, 2-phenoxyethyl, 2-ethoxyethyl, 2-acetylaminoethyl, 2-( Mention may be made of 2,4-di-tert-amylphenoxy)ethyl, ethoxycarbonylmethyl, 2,2,2-trifluoroethyl, 2-(1-phthalimidoyl)ethyl, and 2-hydroxyethyl. Among these, methyl, ethyl, 2-phenoxyethyl and 2-ethoxyethyl are preferred.

The aryl group represented by R11 is:
A phenyl group having one or more electron-donating groups, specific examples of which include 2-methoxyphenyl, 2,4-dimethoxyphenyl, 2,6-dimethoxyphenyl, 2,4,
6-trimethoxyphenyl, 2,6-dimethoxy-4-
Examples include methylphenyl, 2-4-di(N,N-dimethylamino)phenyl, and 2-methyl-4-(N,N-dimethylamino)phenyl. Among these,
2-methoxyphenyl, 2,4-dimethoxyphenyl and 2,6-dimethoxyphenyl groups are preferred.

In formulas (M-1) to (M-IV), R
12 represents a hydrogen atom, an alkyl group or an aryl group. The alkyl group and aryl group may further have an organic substituent or a halogen atom connected via a carbon atom, oxygen atom, nitrogen atom or sulfur atom.

Examples of the alkyl group represented by R12 are methyl, ethyl, isopropyl, tert-butyl, tridecyl, 3-(4-acylaminophenyl)propyl, 3-(4-alkylsulfonamidophenyl)propyl, 3 -(4-arylsulfonamidophenyl)
Propyl, 2-acylaminoethyl, 2-alkylsulfonamidoethyl, 2-arylsulfonamidoethyl, 2-acylamino-1-methylethyl, 2-alkylsulfonamido-1-methylethyl, 2-arylsulfonamido-1- Methyl ethyl, acylaminomethyl,
Mention may be made of alkylsulfonamidomethyl, arylsulfonamidomethyl, 1-acylaminoethyl, 1-alkylsulfonamidoethyl or 1-arylsulfonamidoethyl. Among these, 2-acylaminoethyl, 2-arylsulfonamidoethyl,
2-acylamino-1-methylethyl, 2-arylsulfonamidoethyl-1-methylethyl, arylsulfonamidoethyl and 1-arylsulfonamidomethyl are preferred.

Examples of the aryl group represented by R12 include phenyl, 3 or 4 acylaminophenyl, 3 or 4-alkylsulfonamidophenyl, 3 or 4
-arylsulfonamidophenyl, 3-acylamino-2,4,6-trimethylphenyl, 3-alkylsulfonamido-2,4,6-trimethylphenyl and 3
-arylsulfonamido-2,4,6-trimethylphenyl. Among these, 3-acylaminophenyl, 3-arylsulfonamidophenyl, 3-acylamino-2,4,6-trimethylphenyl, and 3-arylsulfonamido-2,4,6-trimethylphenyl are preferred.

In formulas (M-I) to (M-IV), R
13 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, or a cyano group .

Among these, an alkoxycarbonyl group or a carbamoyl group is preferred.

Examples of the alkyl group represented by R13 include straight chain or branched alkyl groups having 1 to 32 carbon atoms (
Examples, methyl, ethyl, propyl, isopropyl, ter
(t-butyl, tridecyl, trifluoromethyl, heptafluoropropyl, 2-methanesulfonylethyl).

An example of the cycloalkyl group represented by R13 is cyclopentyl.

Examples of the aralkyl group represented by R13 include 3-(3-pentadecylphenoxy)propyl,
Mention may be made of 3-{4-{2-[4-(4-hydroxyphenylsulfonyl)phenoxy]propyl, 2-ethoxytridecyl and 3-(2,4-di-tert-amylphenoxy)propyl.

Examples of the aryl group represented by R13 include phenyl, pentafluorophenyl, pentachlorophenyl, 4-tert-butylphenyl, 2,4-di-tert-amylphenyl and 4-tetradecanamidophenyl. can.

Examples of the heterocyclic group represented by R13 include 2-furyl, 2-thienyl, 2-pyrimidinyl and 2-benzothiazolyl.

Examples of the alkoxycarbonyl group represented by R13 include methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl and octadecyloxycarbonyl.

Examples of the carbamoyl group represented by R13 include N-ethylcarbamoyl, N,N-dibutylcarbamoyl, N-(2-dodecyloxyethyl)carbamoyl, N-methyl-N-dodecylcarbamoyl and N-{3 -(2,4-di-tert-amylphenoxy)propyl}carbamoyl.

Examples of the sulfamoyl group represented by R13 include N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N-(2-dodecyloxyethyl)sulfamoyl, N-ethyl-N-dodecylsulfamoyl. Mention may be made of moyl and N,N-diethylsulfamoyl.

Examples of the sulfonyl group represented by R13 include metasulfonyl, octanesulfonyl, benzenesulfonyl and toluenesulfonyl.

When R13 is an aryl group, X represents a hydrogen atom or a group (including atoms) that can be separated in reaction with an oxidized product of an aromatic primary amine color developing agent. Such removable groups or atoms include, for example, halogen atoms, alkoxy, aryloxy, acyloxy, alkyl or arylsulfonyloxy, acylamino, alkyl or arylsulfonamide groups, alkoxycarbonyloxy, aryloxy Examples include a carbonyloxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, a carbamoylamino group, a 5- or 6-membered nitrogen-containing heterocyclic group, an imide group, and an arylazo group. These groups may be further substituted with other organic substituents.

Examples of the halogen atom include fluorine atom, chlorine atom and bromine atom.

Examples of the alkoxy group include ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy and ethoxycarbonylmethoxy.

[0199] As the above aryloxy group, for example, 4
Mention may be made of -methylphenoxy, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarboxyphenoxy, 3-acetylaminophenoxy and 2-carboxyphenoxy.

[0200] Examples of the above acyloxy group include acetoxy, tetradecanoyloxy and benzoyloxy.

Examples of the alkyl or arylsulfonyloxy group include methanesulfonyloxy and toluenesulfonyloxy.

Examples of the above acylamino group include dichloroacetylamino and heptafluorobutyrylamino.

[0203] Examples of the alkyl or arylsulfonamide group include methanesulfonamino, trifluoromethanesulfonamino and p-toluenesulfonamino.

Examples of the alkoxycarbonyloxy group include ethoxycarbonyloxy and benzyloxycarbonyloxy.

[0205] Examples of the above aryloxycarbonyloxy group include phenoxycarbonyloxy group.

Examples of the alkyl, aryl or heterocyclic thio group include dodecylthio, 1-carboxydodecylthio, phenylthio, 2-butoxy-5-ter
Mention may be made of t-octylphenylthio and tetrazolylthio.

Examples of the carbamoylamino group include N-methylcarbamoylamino and N-phenylcarbamoylamino.

Examples of the 5- or 6-membered nitrogen-containing heterocyclic group include imidazolyl, pyrazolyl, triazolyl, tetrazolyl and 1,2-dihydro-2-oxo-1-pyridyl.

[0209] Examples of the imide group include succinimide and hydantoinyl.

Examples of the arylazo group include phenylazo and 4-methoxyphenylazo.

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

When R13 is an aryl group, X is preferably a halogen atom, an aryloxy group, an alkyl or arylthio group, or a 5- or 6-membered nitrogen-containing heterocycle bonded to the coupling active position via a nitrogen atom. . It is particularly preferred that X is a halogen atom or an alkyl or arylthio group.

When R13 is an alkyl group, X represents a leaving group excluding a halogen atom from among the leaving groups described for the case where R13 is an aryl group. When R13 is an alkyl group, X is preferably an alkyl or arylthio group, a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active position via a nitrogen atom, and more preferably an arylthio group.

In the present invention, (M-I) to (M-IV
), preferred is (M-II) or (M-III), particularly preferred is (M-II).

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

[0216]

[C72]

[0217]

[C73]

[0218]

[C74]

[0219]

[C75]

[0220]

[C76]

[0221]

[C77]

[0222]

[C78]

[0223]

[C79]

[0224]

[C80]

[0225]

[Chemical formula 81]

[0226]

[C82]

[0227]

[Chemical formula 83]

[0228]

[Chemical formula 84]

[0229]

[Chemical formula 85]

[0230]

[C86]

[0231]

[Chemical formula 87]

[0232]

[Chemical formula 88]

[0233]

[Chemical formula 89]

[0234]

[C90]

[0235]

[Chemical formula 91]

[0236]

[C92]

[0237]

[C93]

[0238]

[C94]

[0239]

[C95]

[0240] The magenta coupler according to the present invention is disclosed in JP-A-62-209457, JP-A-63-250368, JP-A-63-307453, and JP-A-2-115183.
It can be synthesized according to the method described in publications such as No.

The amount of the magenta coupler according to the present invention used in the photosensitive material is 1×10 −
The amount ranges from 5 mol to 1 x 10-2 mol, preferably 1
The range is from x10-5 mol to 5 x 10-3 mol, more preferably from 5 x 10-5 mol to 2 x 10-3 mol.

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

[0243]

[C96]

In the above formula (Cy), R5 is a hydrogen atom, a halogen atom (F, Cl, Br, I), or an optionally substituted linear, branched or cyclic group having 1 to 18 carbon atoms. represents an alkyl group. Here, examples of substituents on the alkyl group include a halogen atom, an aryl group, an alkoxy group, and an alluroxy group.

[0245] In formula (Cy), R6 has 1 to 1 carbon atoms.
36 (preferably 4 to 30) optionally substituted,
Straight chain, branched chain or cyclic alkyl group, carbon number 6
-36 (preferably 12-30) optionally substituted aryl group or carbon number 2-36 (preferably 12
~30) represents a heterocyclic group. Here, the term "heterocyclic group" refers to a heterocyclic group which may form a 5- to 7-membered condensed ring having at least one heteroatom selected from N, O, S, P, Se, and Te in the ring. represent. Examples of these include 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 4-pyrimidyl, 2-imidazolyl, 4-quinolyl, and the like.

R6 may have a substituent. Examples of substituents include halogen atoms, cyano groups, nitro groups, carboxyl groups, sulfo groups, alkyl groups, aryl groups, heterocyclic groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkylsulfonyl groups, and aryl groups. Examples include sulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, carbonamido group, sulfonamido group, carbamoyl group, sulfamoyl group, imido group, ureido group, alkoxycarbonylamino group or sulfamoylamino group. (hereinafter referred to as substituent group A). Examples of preferable substituents among these are aryl group, heterocyclic group, aryloxy group,
It is an alkylsulfonyl group, an arylsulfonyl group or an imido group.

In formula (Cy), R7 is a hydrogen atom,
Halogen atom, alkyl group having 1 to 16 carbon atoms (preferably 1 to 8), alkoxy group having 1 to 16 carbon atoms (preferably 1 to 8), aryloxy group having 6 to 24 carbon atoms (preferably 6 to 18) group or carbon number 1 to 24 (preferably 1
~18) represents a carbonamide group. The above group may be substituted with a substituent selected from the above substituent group A.

In formula (Cy), X3 represents a hydrogen atom or a coupling-off group capable of being separated by a coupling reaction with an oxidized product of an aromatic primary amine developer. Examples of coupling-off groups include halogen atoms, sulfo groups, alkoxy groups having 1 to 36 carbon atoms (preferably 1 to 24), aryloxy groups having 6 to 36 carbon atoms (preferably 6 to 24 carbon atoms), and aryloxy groups having 6 to 36 carbon atoms (preferably 6 to 24 carbon atoms). 2-36 (preferably 2-24)
acyloxy group, carbon number 1-36 (preferably 1-2
4) an alkylsulfonyl group, an arylsulfonyl group having 6 to 36 carbon atoms (preferably 6 to 24 carbon atoms), and an arylsulfonyl group having 1 to 3 carbon atoms;
6 (preferably 2 to 24) alkylthio groups, 6 carbon atoms
-36 (preferably 6-24) arylthio group, C4-36 (preferably 4-24) imide group, C1-36 (preferably 1-24) carbamoyloxy group, or C1-36 (preferably 1-24) carbamoyloxy group 36 (preferably 2 to 24) heterocyclic groups (eg pyrazolyl, imidazolyl, 1,2,4-triazol-1-yl, tetrazolyl) bonded to the coupling active position via the nitrogen atom can be mentioned. Here, the above group may be substituted with a substituent selected from the substituent group A.

[0249] R5, R6, R7 of formula (Cy)
Examples of preferred groups for and X3 are shown below.

The above R5 is preferably F, Cl or an alkyl group substituted with at least one halogen atom, particularly preferably represented by -C(CF2)mF or -C(CF2)nH It is the basis. Here, m and n each represent an integer of 1 to 16 (preferably 1 to 8).

The above R6 is preferably an alkyl group, particularly preferably an alkyl group substituted at the 1-position with an aryloxy group, an alkylsulfonyl group, an allursulfonyl group, an imide group, or a heterocyclic group.

The above R7 is preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methoxy group or an acetamido group, and particularly preferably a hydrogen atom.

The above X3 is preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, or a heterocyclic thio group, more preferably a hydrogen atom or a chlorine atom, and especially a chlorine atom. be.

[0254] R5 and R6 in formula (Cy) are as follows:
, R7 and X3 are shown below.

Example of R5; F, Cl, -CF3, -(CF2)2 F, -(C
F2 )4 F, -(CF2)6 F, -(CF2
)8F, -CF2H, -(CF2)3H, -(
CF2)5H, -(CF2)7H, -(CF2
)9H, -CF2Cl, -(CF2)3Cl

[0256] Example of R6;

0257]

[C97]

[0258]

[C98]

0259]

[C99]

0260]

[Chemical formula 100]

Examples of R7; H, F, Cl, -CH3, -CH(CH3)2
, -OCH3, -OCF3, -OCH2 CH2
OCH3, -NHCOCH3, -NHCOCF3
, -NHCOC4 H9 -t (t represents tertiary),

0262]

[Chemical formula 101]

Example of X3; H, F, Cl, SO3 H, -CH2 COOCH3
, -OCH2 CH2 CH2 COOH, -OCH
2 CONHCH2 CH2 OOCH3, -OPO(
OC2H5)2, -OCOCH3, -OSO2
CH3, -OCONHC2H5, -SCH2
COOH, -SCH2CH2 COOH,

0264

[Chemical formula 102]

0265]

[Chemical formula 103]

A specific example of the cyan coupler represented by the formula (Cy) will be shown below.

0267]

[Chemical formula 104]

0268

[Chemical formula 105]

0269]

[Chemical formula 106]

0270]

[Chemical formula 107]

0271]

[Chemical formula 108]

0272]

[Chemical formula 109]

0273

[Chemical formula 110]

0274]

[Chemical formula 111]

0275]

[Chemical formula 112]

0276]

[Chemical formula 113]

0277]

[Chemical formula 114]

[0278]

[Chemical formula 115]

0279]

[Chemical formula 116]

0280]

[Chemical formula 117]

0281]

[Chemical formula 118]

0282]

[Chemical formula 119]

0283

[Chemical formula 120]

0284

[Chemical formula 121]

0285]

[Chemical formula 122]

0286]

[Chemical formula 123]

The cyan coupler represented by the above formula (Cy) can be synthesized by the method described in US Pat.

The amount of cyan coupler represented by the above formula (Cy) used in the photosensitive material is in the range of 1 x 10-5 mol to 1 x 10-2 mol per m2 of the photosensitive material,
Preferably, the range is from 1 x 10-4 mol to 5 x 10-2 mol, more preferably from 2 x 10-4 mol to 1 x 10-3 mol.
It is in the molar range.

The unfogged internal latent image type silver halide emulsion used in the present invention contains silver halide grains whose surfaces are not fogged and which forms latent images mainly inside the grains. More specifically, a silver halide emulsion is deposited on a transparent support in a certain amount (
0.5 to 3 g/m2), exposed to light for a fixed time of 0.01 to 10 seconds, and developed in the following developer (internal type developer) at 20°C for 5 minutes. The maximum density measured by the photographic density measurement method is obtained when a silver halide emulsion coated in the same amount as above and exposed in the same manner is developed in the following developer (surface type developer) at 18°C for 6 minutes. preferably at least 5 times greater, more preferably at least 1
It has a concentration 0 times greater.

0290 Internal type developer Metol

2.0g Sodium sulfite (anhydrous)
90.0g
hydroquinone
8.0g
Sodium carbonate (monohydrate)
52.8g KB
r
5.0g
KI

Add 0.5g water

1000cc surface type developer Metol

2.5g L-ascorbic acid
10.
0g NaBO2 ・4H2 O
35.0
g KBr

Add 1.0g water

1000cc

Specific examples of internal latent image type emulsions include conversion type silver halide emulsions described in US Pat. No. 2,592,250, US Pat. Nos. 3,761,276 and 3,850,637,
No. 3923513, No. 4035185, No. 4395
Specifications of No. 478 and No. 4504570, Japanese Unexamined Patent Publication No. 1983
-156614, 55-127549, 53-
No. 50222, No. 56-22681, No. 59-208
No. 540, No. 60-107641, No. 61-3137
No. 62-215272, Research Disclosure Magazine No. No. 23510 (issued in November 1983) on page 236, as well as U.S. Pat.
-47766, Japanese Patent Application No. 1-2467, JP-A-63-191145 concerning emulsion doped with metal ions,
Examples include core/shell type silver halide emulsions described in JP-A-1-52146. The molar ratio of silver halide between the core and the shell of the internal latent image type core-shell silver halide emulsion is particularly preferably 20/1 or less and 1/100 or more.

[0292] The internal latent image type silver halide grains which are not fogged in advance include Mn, Cu, Zn, Cd, Pd, and Bi.
Alternatively, at least one metal selected from the group consisting of metals belonging to Group VIII of the periodic table may be incorporated.

[0293] Mn, Cu, Zn, Cd, Pd, which are contained in internal latent image type silver halide grains that have not been fogged in advance,
The amount of Bi or metal belonging to Group VIII of the periodic table is preferably 10-9 to 10-2 mol, more preferably 10-7 to 10-3 mol, per mol of silver halide.

Among the metals mentioned above, particular preference is given to using lead, iridium and bismuth and rhodium.

When these metals are mixed with a silver ion solution and an aqueous halogen solution to form silver halide grains, the metal ions can be made to coexist in the form of an aqueous solution or an organic solvent solution and incorporated into the grains. Alternatively, after forming the grains, metal ions may be added in the form of an aqueous or organic solvent solution and then further coated with silver halide.

[0296] Methods for incorporating these metals are described in US Pat. No. 3,761,276, US Pat.

[0297] The shapes of the silver halide grains used in the present invention are cubic, octahedral, dodecahedral, and dodecahedral (Japanese Patent Application Laid-open No. 2-22
3948), irregular crystal shapes such as spherical, and JP-A-1-13154.
No. 7, No. 1-158429, even when using an emulsion in which tabular grains with a length/thickness ratio of 5 or more, particularly 8 or more, account for 50% or more of the total projected area of the grains. good. Further, emulsions having composite forms of these various crystal systems or mixtures thereof may be used.

[0298] The composition of silver halide includes silver chloride, silver bromide, and mixed silver halide, and the silver halide preferably used in the present invention does not contain silver iodide or contains silver iodide. At most, 3 mol% or less of salt (iodine) silver bromide, (
silver chloride or silver bromide.

The average grain size of silver halide grains (in the case of spherical or nearly spherical grains, the grain diameter is taken as the grain size, and in the case of cubic grains, the vertical length is taken as the grain size, and expressed as an average based on the projected surface). , 1.5 μm or less, 0.1 μm
It is preferably at least m, but particularly preferably at most 1.2 μm and at least 0.2 μm. The particle size distribution may be narrow or wide, but in order to improve granularity and sharpness, the particle number or weight should be within ±40% of the average particle size, preferably within 30%, most preferably ± It is preferable to use in the present invention a so-called "monodisperse" silver halide emulsion having a narrow grain size distribution in which 90% or more, especially 95% or more of all grains fall within 20%.

In order to satisfy the target gradation of a light-sensitive material, two or more types of monodispersed silver halide emulsions with different grain sizes or two or more types of monodisperse silver halide emulsions with different grain sizes are used in an emulsion layer having substantially the same color sensitivity, or two or more types of monodispersed silver halide emulsions with the same size and sensitivity are used. A plurality of particles having different properties can be mixed in the same layer or coated in separate layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions may be mixed or layered for use.

The silver halide emulsion used in the present invention can be chemically sensitized inside or on the grains by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization, etc. alone or in combination. As the chemical sensitization method for the core particles, methods described in Japanese Patent Application Laid-Open Nos. 2-199450 and 2-199449 can be used. Japanese Patent Application Publication No. 197742
In the presence of a mercapto compound as described in No. 1-254946, No. 2-69738, No. 2-2
Thiosulfinic acid, sulfinic acid, and sulfite may be added as described in each publication of No. 73735. For detailed examples, see Research Disclosure Magazine No. 176
43-III (published in December 1978), page 23, etc.

The photographic emulsion used in the present invention is spectrally sensitized with a photographic sensitizing dye in a conventional manner. Particularly useful dyes are those belonging to cyanine dyes, merocyanine dyes and complex merocyanine dyes, which may be used alone or in combination. Further, the above dyes and supersensitizers may be used in combination. For detailed specific examples, please refer to research
Disclosure magazine No. 17643-IV (197
It is in the patent described on pages 23-24 (published in December 1998).

[0303] The photographic emulsion used in the present invention may contain an antifoggant or a stabilizer for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Can be done. For detailed specific examples, see Research Disclosure Magazine No.
17643-VI (issued December 1978) and E
．． J. “Stabilization o” by Birr
f Photographic Silver Hai
'lde Emulsion' (Focal Pres.
s), published in 1974.

In the present invention, various color couplers can be used in combination in addition to the yellow coupler represented by the formula (Y), the magenta coupler represented by the formula (M), and the cyan coupler represented by the formula (Cy). can. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolone or virazoloazole compounds, and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in combination in the present invention are given in "Research Disclosure" magazine No. 17643 (19
(Published December 1978) Page 25, Section VII-D, No. 1
8717 (issued in November 1979) and JP-A-62-
No. 215,272 and the patents cited therein.

[0305] Colored couplers for correcting unnecessary absorption in the short wavelength region of the generated dyes, couplers in which coloring dyes have appropriate diffusivity, colorless couplers, and releasing development inhibitors along with coupling reactions. DIR couplers and polymerized couplers can also be used.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are described in Research Disclosure no. 17643, patents described in sections VII to F, JP-A-57-151944, JP-A-57-
154234, 60-184248, US Pat. No. 4,248,962, and JP-A-63-146035 are preferred.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

[0308] In the light-sensitive material of the present invention, a color antifogging agent or a color mixing inhibitor can be used. Representative examples of these are described in JP-A-62-215272, pages 185-193.

Compounds that release photographically useful groups include:
JP 63-153540, JP 63-259555, JP 2-61636, JP 2-244041
No. 2-308240.

[0310] A color enhancer can be used in the present invention for the purpose of improving the color development of the coupler. Representative examples of compounds are JP-A-62-215272, 121-125.
Examples include those listed on page.

The photosensitive material of the present invention contains dyes that prevent irradiation and halation (for example, JP-A-2-85
Compounds described in No. 850 and No. 2-89047 may also be used. Further, as a dye dispersion method, a solid microcrystal dispersion method may be used. ), ultraviolet absorbers, plasticizers, optical brighteners, matting agents, air antifogging agents, coating aids, hardeners, antistatic agents, slipperiness improvers, etc. can be added. Representative examples of these additives are listed in Research Disclosure magazine no. 17643 VII-XIII (197
18716 (published in December 2008), pages 25-27, and
Published in November 1979) on pages 647-651.

The light-sensitive material of the present invention has at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as necessary. The preferred layer arrangement order is red sensitivity, green sensitivity, blue sensitivity from the support side, or green sensitivity, red sensitivity, blue sensitivity from the support side.
I have a blue sensibility. Further, each of the above emulsion layers may be made up of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may exist between two or more emulsion layers having the same color sensitivity. . Usually, 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 mixing them.

[0313] In addition to the silver halide emulsion layer, the light-sensitive material according to the present invention is preferably provided with auxiliary layers such as a protective layer, an intermediate layer, a filter layer, an antihalation layer, a backing layer, and a white reflective layer.

[0314] In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are as described in Research Disclosure Magazine No. 1
7643VVII (issued December 1978), page 28, and the supports described in European Patent No. 0102253 and Japanese Unexamined Patent Publication No. 61-97655. Also, Research Disclosure Magazine No. 176
It is also possible to use the coating method described in section 43XV, pages 28-29.

The fogging treatment of the present invention is carried out by the following "photofogging method" and/or "chemical fogging method". The entire surface exposure in the "light fogging method", that is, the fogging exposure, is
This is carried out after imagewise exposure, after or during color development. That is, the imagewise exposed photosensitive material is immersed in a color developer or a pre-bath of a color developer, or is taken out from these solutions and exposed before drying. is most preferred.

[0316] As a light source for fogging exposure, a light source with high color rendering properties (as close to white as possible) as described in, for example, Japanese Patent Laid-Open Nos. 56-137350 and 58-70223 is preferable. The appropriate illuminance of the light is 0.01 to 2000 lux, preferably 0.05 to 30 lux, more preferably 0.05 to 5 lux. The more sensitive a light-sensitive material uses an emulsion, the more preferable it is to be exposed to light at a lower illuminance. The illuminance may be adjusted by changing the luminous intensity of the light source, or by changing the exposure using various filters, the distance between the photosensitive material and the light source, or the angle between the photosensitive material and the light source. Further, the illuminance of the fogging light can be increased continuously or stepwise from low illuminance to high illuminance.

[0317] It is preferable to immerse the light-sensitive material in a color developer or its pre-bath solution, and irradiate the light-sensitive material after the solution has sufficiently penetrated into the emulsion layer of the light-sensitive material. The time from when the liquid penetrates to when the light fog exposure is carried out is generally 2 seconds to 2 minutes, preferably 5 seconds to 1 minute, and more preferably 10 seconds to 30 seconds. The exposure time for fogging is generally 0.01 seconds to 2 minutes, preferably 0.1 seconds to 1 minute, and more preferably 1 second to 40 seconds.

In the present invention, the nucleating agent used in the so-called "chemical fogging method" can be contained in the light-sensitive material or in the processing solution for the light-sensitive material. Preferably, it is used by incorporating it into a photosensitive material.

Here, the nucleating agent is a substance that acts to directly form a positive image during surface development of an internal latent image type silver halide emulsion that has not been fogged in advance. In the present invention, the fogging treatment is preferably performed using a nucleating agent. When it is added to a light-sensitive material, it is preferably added to the internal latent image type silver halide emulsion layer, but as long as the nucleating agent is adsorbed to the silver halide by diffusion during coating or processing, it may be added to the internal latent image type silver halide emulsion layer. For example, it may be added to an intermediate layer, an undercoat layer or a back layer.

[0320] Furthermore, two or more types of nucleating agents may be used in combination. Nucleating agents that can be used in the present invention include, for example, Research Disclosure Magazine, No. 2253
4 (January 1983) pp. 50-54, same magazine, No. 15
162 (November 1976) pp. 76-77, same magazine No.
23510 (November 1983), pages 346-352, quaternary heterocyclic compounds, hydrazine compounds, and the like.

[0321] Examples of the quaternary heterocyclic nucleating agent include US Pat. No. 3,615,615, US Pat.
No. 4738, No. 3759901, No. 3854956, No. 4094683, No. 4306016, specifications of British Patent No. 1283835, Japanese Patent Publication No. 49-38164, No. 52-19452, No. 52-47326, Japanese Unexamined Patent Publication No. 52-4732 -69613, 52-3426, 55-
138742, 60-11837, and the aforementioned Research Disclosure magazine, No. 22
534, Comrade No. 23213 (issued August 1983 2
67-270). Furthermore, as a highly active quaternary salt compound, JP-A No. 63-12104
No. 2, No. 63-301942, JP-A-1-19113
No. 2, Patent Application No. 63-255360, No. 63-2305
Those described in No. 89 and No. 63-255361 can be used.

In the present invention, a nucleating agent represented by the following general formula [Fa] is preferably used. Hereinafter, the nucleating agent represented by the general formula [Fa] will be explained in detail.

0323]

[Chemical formula 124]

In the general formula [Fa], the heterocycle completed by Z2 is, for example, quinolinium, benzothiazolium, benzimidazolium, pyridinium, thiazolinium, thiazolium, naphthothiazolium, selenazolium, benzoselenazolium, imidazo Mention may be made of the following: trizolium, tetrazolium, indolenium, pyrrolinium, acridinium, phenanthridinium, isoquinolinium, oxazolium, naphthoxazolium and benzoxazolium nuclei.

Substituents for Z2 include alkyl groups, alkenyl groups, aralkyl groups, aryl groups, alkynyl groups, hydroxy groups, alkoxy groups, aryloxy groups, halogen atoms, amino groups, alkylthio groups, arylthio groups, acyloxy groups, Acylamino group, sulfonyl group,
Sulfonyloxy group, sulfonylamino group, carbonylamino group, carboxyl group, acyl group, carbamoyl group, sulfamoyl group, sulfo group, cyano group, ureido group, urethane group, carbonate group, hydrazine group, hydrazone group, or imino group, etc. can be given. As the substituent for Z2, for example, at least one substituent is selected from the above substituents, but if two or more are selected, they may be the same or different. Moreover, the above-mentioned substituents may be further substituted with these substituents. Furthermore, as a substituent for Z2, a heterocyclic quaternary ammonium group completed with Z2 via a suitable linking group L may be included. In this case, it takes a so-called dimer structure.

Preferred examples of the heterocycle completed by Z2 include quinolinium, benzothiazolium, benzimidazolium, pyridinium, acridinium, phenanthridinium, and isoquinolinium nuclei. More preferred are quinolinium and benzothiazolium, most preferred is quinolinium.

[0327] The aliphatic group of R31 and R32 has 1 carbon number.
~18 unsubstituted alkyl groups and substituted alkyl groups in which the alkyl moiety has 1 to 18 carbon atoms. Examples of the substituent include those described as the substituent for Z2.

[0328] The aromatic group represented by R32 has 6 to 6 carbon atoms.
Examples of the 20 groups include phenyl group and naphthyl group. Examples of the substituent include those described as the substituent for Z2. R32 is preferably an aliphatic group, most preferably a methyl group, a substituted methyl group, or a ring formed by bonding with a heterocycle completed by Z2.

At least one of the groups represented by R31, R32 and Z2 has an alkynyl group, an acyl group, a hydrazine group, or a hydrazone group, or R
31 and R32 form a 6-membered ring to form a dihydropyridinium skeleton, which may be substituted with the group described above as a substituent for the group represented by Z2.

[0330] At least one of the groups or substituents on the ring represented by R31, R32 and Z2 is an alkynyl group or an acyl group, or R31 and R32 are linked to form a dihydropyridinium skeleton. Preferably, it further contains at least one alkynyl group, most preferably a propargyl group.

[0331] At least one of the substituents R31, R32 and Z2 preferably has a group represented by the following formula. Formula: X12-(L11)m - Here, X12 represents an adsorption promoting group to silver halide, L11 represents a divalent linking group, and m represents 0 or 1. In the present invention, it is preferable that Z2 has a group represented by the above formula as a substituent.

Preferred examples of the adsorption promoting group to silver halide represented by X12 include a thioamide group, a mercapto group, and a 5- to 6-membered nitrogen-containing heterocyclic group. These may be substituted with the substituents listed as substituents for Z2. The thioamide group is preferably an acyclic thioamide group (eg, thiourethane group, thiourido group, etc.).

The mercapto group of X12 is a heterocyclic mercapto group (for example, 5-mercaptotetrazole, 3
-mercapto-1,2,4-triazole, 2-mercapto-1,3,4-thiadiazole, 2-mercapto-
1,3,4-oxadiazole, etc.) are preferred.

[0334] The 5- to 6-membered nitrogen-containing heterocycle represented by can give.

The divalent linking group represented by L11 is an atom or atomic group containing at least one of C, N, S, and O. Specifically, for example, alkylene group, alkenylene group, alkynylene group, arylene group, -O-,
-S-, -NH-, -CO-, -SO2- (these groups may have a substituent), etc. alone or in combination. Examples of combinations include:
-COO-, -CONH-, -SO2 NH-, -OC
ONH-, -NHCONH-, -NHSO2NH-,
-alkylene-CONH-, -arylene-SO2N
H-, -arylene-NHCONH-, -arylene-
CONH-, etc. are preferred. In the present invention, the divalent linking group represented by L11 is more preferably -arylene-SO2NH-, -arylene-NHCONH-, or -arylene-CONH-.

Counter ions Y for charge balance include, for example, bromide ion, chloride ion, iodide ion, p-toluenesulfonate ion, ethylsulfonate ion, perchlorate ion, trifluoromethanesulfonate ion,
Examples include thiocyanine ion, boron tetrafluoride ion, and phosphorus hexafluoride ion. Among these, bromide ion, iodide ion, perchlorate ion or trifluoromethanesulfonate ion are preferred, and more preferably,
These are iodide ion, perchlorate ion, or trifluoromethanesulfonate ion.

[0337] These compounds and their synthesis methods can be found in, for example, Research Disclosure (Research D).
isclosure) magazine, No. 22,534 (19
Published in January 1983, pp. 50-54), and No. 23,
Patent cited in 213 (Published August 1983, pp. 267-270), Japanese Patent Publication No. 49-38164, No. 5
No. 2-19452, No. 52-47326, Japanese Unexamined Patent Publication No. 1973
-69163 Publication, Publication No. 52-3426, Publication No. 55-1
No. 38742, No. 60-11837, U.S. Patent No. 43
It is described in the 06016 specification and the 4471044 specification.

Specific examples of the nucleating agent represented by the general formula [Fa] are listed below, but the invention is not limited thereto.

0339]

[Chemical formula 125]

0340]

[Chemical formula 126]

0341]

[Chemical formula 127]

0342]

[Chemical formula 128]

0343]

[Chemical formula 129]

0344

[Chemical formula 130]

0345]

[Chemical formula 131]

0346]

[Chemical formula 132]

0347]

[Chemical formula 133]

0348

[Chemical formula 134]

0349]

[Chemical formula 135]

0350]

[Chemical formula 136]

0351]

[Chemical formula 137]

0352]

[Chemical formula 138]

0353]

[Chemical formula 139]

0354]

[Chemical formula 140]

0355]

[Chemical formula 141]

0356]

[Chemical formula 142]

0357]

[Chemical formula 143]

0358]

[Chemical formula 144]

[0359] As the hydrazine compound, for example, the above-mentioned Research Disclosure magazine No. 15,162
(Published in November 1976) Pages 76-77 and magazine No.
．． 23,510 (issued November 1983) 346-35
Examples include those listed on page 2. More specifically, those described in the following patent specifications can be mentioned. First, examples of hydrazine-based nucleating agents having silver halide adsorption groups include, for example, US Pat. No. 4,030,925;
Same No. 4080207, Same No. 4031127, Same No. 3
No. 718470, No. 4269929, No. 4276
No. 364, No. 4278748, No. 4385108
No. 4459347, British Patent No. 2011391
No. B, JP-A-54-74729, JP-A No. 55-16353
No. 3, No. 55-74536, and No. 60-1797
Examples include those described in No. 34 and No. 63-231441.

[0360] Other hydrazine-based nucleating agents include, for example, JP-A-57-86829, US Pat.
No. 8, No. 4478928, and No. 256378
Examples include the compounds described in No. 5 and No. 2588982.

As highly active hydrazine compounds, JP-A-63-231441, JP-A-63-234244, JP-A-63-234245, JP-A-63-234246, JP-A-6
3-204256, JP-A No. 2-18558, JP-A No. 1-
Examples include compounds described in Japanese Patent No. 131557.

[0362] Representative hydrazine-based nucleating agents are shown below. (B-1) 1-formyl-2-{4-[3-(2-
methoxyphenyl)ureido]phenyl}hydrazine,
(B-2) 1-formyl-2-{4-[3-(5-
Mercaptotetrazol-1-yl)benzamido]phenyl}hydrazine, (B-3) 1-formyl-2-[4-{3-[3-
(5-mercaptotetrazol-1-yl)phenyl]
ureido}phenyl]hydrazine,

[0363] As the nucleating agent, quaternary heterocyclic compounds are preferable as they greatly exhibit the effects of the present invention, as described above. Note that a quaternary heterocyclic compound and a hydrazine compound may be used together. When the nucleating agent is added to the processing solution, it may be contained in the developer solution or a low pH prebath as described in JP-A-58-178350. When adding a nucleating agent to the processing solution, the amount used is 10 liters per liter.
-8 to 10-1 mol is preferable, more preferably 10-
It is 7 to 10-3 mol.

In the present invention, the nucleating agent may be contained in the hydrophilic colloid layer adjacent to the silver halide emulsion layer, but it is preferably contained in the silver halide emulsion layer. The amount added varies depending on the characteristics of the silver halide emulsion used in practice, the chemical structure of the nucleating agent, and the development conditions, so it can vary over a wide range, but it is approximately 1x per mole of silver in the silver halide emulsion. 10-8 mol to about 1×1
A range of 0-2 moles is useful in practice, with a preferred range of about 1.times.10@-7 moles to about 1.times.10@-3 moles per mole of silver.

[0365] When using a nucleating agent, it is preferable to use a nucleating promoter to promote the action of the nucleating agent. A nucleation accelerator is a substance that has virtually no function as a nucleation agent, but
A substance that acts to enhance the action of a nucleating agent to increase the maximum density of a direct positive image and/or to speed up the development time required to obtain a given maximum density of a direct positive image.

Such nucleation accelerators include tetrazaindenes, triazaindenes and pentazaindenes having at least one mercapto group optionally substituted with an alkali metal atom or an ammonium group. and JP-A No. 63-106656, Nos. 5-1
Examples include the compounds described on page 6. Also, JP-A No. 63-226652, No. 63-106656, No. 6
Examples include the compounds described in No. 3-8740.

[0367] Specific examples of the nucleation accelerator are given below.

0368

[Chemical formula 145]

0369]

[Chemical formula 146]

0370]

[Chemical formula 147]

0371]

[Chemical formula 148]

0372]

[Chemical formula 149]

0373]

[Chemical formula 150]

0374]

[Chemical formula 151]

0375]

[Chemical formula 152]

0376]

[Chemical formula 153]

[0377] The nucleation accelerator can be contained in the light-sensitive material or in the processing solution, but in the light-sensitive material, the nucleation accelerator can be incorporated into internal latent image type silver halide emulsions and other hydrophilic colloid layers (
It is preferable to include it in an intermediate layer, a protective layer, etc.). Particularly preferred is a layer in or adjacent to a silver halide emulsion.

The amount of the nucleation accelerator added is preferably 10-6 to 10-2 mol, more preferably 10-5 to 10-2 mol, per mol of silver halide.

[0379] When the nucleation accelerator is added to the processing solution, that is, the developer or its pre-bath, 1 liter/liter of the nucleation promoter is added.
Preferably 0-8 to 10-3 mol, more preferably 1
It is 0-7 to 10-4 mol.

[0380] Two or more types of nucleation accelerators can also be used in combination.

[0381] Known photographic additives that can be used in the present invention are those listed in the aforementioned Research Disclosure No. 17643
(December 1978) and the same No. 18716 (19
(November 1979), and the relevant sections are summarized in the table below.

0382 Additive type RD
17643 RD18716 ─
──────────────────────────
─── 1 Chemical sensitizer
Page 23 Page 648 Right column
2 Sensitivity enhancer
Same as above
3 Spectral sensitizer, 23-2
Page 4 Page 648 Right column ~
supersensitizer
Page 649 right column 4 increase
Whitening agent page 24
5 Antifoggant
Pages 24-25 Page 649 Right column ~
stabilizer
Page 650 right column
6 Light absorbers, 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 2
Page 5 9 Hardener
Page 26 Page 651 Left column
10 Binder 2
Page 6 Same as above
────────────────────────
──────

[0383] In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are formed of a flexible support such as plastic film, paper, or cloth, or a rigid support such as glass, ceramic, or metal, which is commonly used in photographic light-sensitive materials. applied to the body. Useful as flexible supports are films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polymers. (For example, paper coated with or laminated with polyethylene, polypropylene, ethylene/butene copolymer), etc. The support may be colored using dyes or pigments.

For coating the silver halide photographic emulsion layer and other hydrophilic colloid layers, various known methods can be used, such as dip coating, roller coating, curtain coating, and extrusion coating. . In addition, as necessary, U.S. Patent No. 2681294, U.S. Patent No. 276179
Multiple layers may be applied simultaneously by the methods described in No. 1, No. 3,526,528, No. 3,508,947, etc.

Next, the color development processing method will be explained. The internal latent image type silver halide emulsion-containing light-sensitive material of the present invention can be developed directly into a positive image by using a surface developer. A surface developer is one in which the development process is substantially induced by latent images or fog nuclei on the surface of silver halide grains.

[0386] The color developer used in the present invention contains:
Contains aromatic primary amine color developing agent. Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto. (1) N,N-diethyl-p-phenylenediamine, (
2) 2-amino-5-diethylaminotoluene, (3)
2-amino-5-(N-ethyl-N-laurylamino)
Toluene, (4) 4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline, (5) 2-methyl-4
-[N-ethyl-N-(β-hydroxyethyl)amino]aniline, (6) 4-amino-3-methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl]-aniline, Among these, compounds represented by (2), (4), (5) and (6) are preferred.

[0387] These p-phenylenediamine derivatives may also be salts such as sulfates, hydrochlorides, sulfites, and p-toluenesulfonates. Such examples include (7) N-ethyl-N-β-(methanesulfonamidoethyl)-3-ethyl-4 aminoaniline sulfate, (8
) N-ethyl-hydroxyethyl-4-aminoaniline sulfate, and the like.

Furthermore, a compound represented by the following formula (D) can be used as an aromatic primary amine color developing agent.

0389]

[Chemical formula 154]

Examples of the alkyl group represented by R8 above include alkyl groups having 1 to 8 carbon atoms, with methyl, ethyl, butyl or methoxyethyl being preferred. The alkylene group represented by R9 above includes alkylene groups having 2 to 6 carbon atoms, with ethylene or trimethylene being preferred. Specific examples of the developing agent represented by the above formula (D) are shown below.

0391

[Chemical formula 155]

0392]

[Chemical formula 156]

0393

[Chemical formula 157]

0394

[Chemical formula 158]

0395]

[Chemical formula 159]

0396

[Chemical formula 160]

0397]

[Chemical formula 161]

0398

[Chemical formula 162]

In the present invention, compounds represented by (D-2) or (D-3) are particularly preferred. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to about 20 g, more preferably about 0.5 g to about 10 g, per liter of developer.

[0400] Color developers also require sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl compound sulfite adducts as preservatives. It can be added accordingly. The preferred amount added is 0.5g to 10g per liter of color developer.
, more preferably 1 g to 5 g.

[0401] As compounds that directly preserve the developing agent, various hydroxylamines, JP-A-63-4
Hydroxamic acids described in Publication No. 3138, No. 63-17
Hydrazines described in Publication No. 0642 and JP-A-2-64
Hydrazine derivatives and hydroxylamine derivatives described in JP-A No. 632, phenols described in JP-A-63-44657 and JP-A-63-58443, JP-A No. 63-58443;
α-Hydroxyketones and α described in Publication No.-44656
-aminoketones and/or 63-3624
It is preferable to add various saccharides described in Publication No. 4. In addition, in combination with the above compounds, JP-A-63-4235, JP-A-63-24254, JP-A-63-21647, JP-A-63-
No. 146040, No. 63-27841, and No. 63
Monoamines described in various publications such as No.-25654, JP-A-63-30845, JP-A-63-146040, and JP-A-6
Diamines described in various publications such as No. 3-43439, polyamines described in JP-A-63-21647 and JP-A-63-26655, polyamines described in JP-A-63-44655, Nitroxy radicals described in JP-A-63-53551, JP-A-63-43
140 and 63-53549, oximes described in JP-A-63-56654, and tertiary amines described in JP-A-63-239447. is preferable.

[0402] As other preservatives, JP-A-57-44
Various metals described in JP-A-148 and JP-A-57-53749, salicylic acids described in JP-A-59-180588, alkanolamines as described in JP-A-54-3532, JP-A-56-94349. Polyethyleneimines described in the above publication, aromatic polyhydroxy compounds described in US Pat. No. 3,746,544, and the like may be contained as necessary.

The content of these compounds in the color developer is preferably as follows per liter of color developer:
0.5g to 50g, more preferably 1.0 to 30g,
Particularly preferably, it is 1.5 g to 20 g.

[0404] These compounds may be present in the photosensitive material. In addition, it can be present not only in color developers, but also in bleaching and bleach-fixing solutions, water washing, or water washing substitute stabilizing solutions.
It is possible to impart good performance by acting on the color developing agent present in each solution (due to being brought in from the color developing solution, etc.) and its oxidized product.

[0405] The color developer used in the present invention preferably has a pH of 9 to 12, more preferably 9 to 11.0, and the color developer may contain compounds of other known developer components. be able to.

[0406] In order to maintain the above pH, it is preferable to use various buffers. Carbonates, phosphates, tetraborates, and hydroxybenzoates are especially soluble as buffering agents.
Excellent buffering ability in the high pH range of pH 9.0 or higher.

Specific examples of buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate,
Trisodium phosphate, tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), o-
Examples include potassium hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.

[0408] The amount of the buffer added to the color developer is 0.
．． It is preferably 1 mol/liter or more, especially 0
．． It is preferably 1 mol/liter to 0.4 mol/liter.

[0409] In addition, various chelating agents can be used in the color developer as an agent for preventing precipitation of calcium or magnesium, or to improve the stability of the color developer.

[0410] The chelating agent is preferably an organic acid compound, and examples thereof include aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids. Specific examples are shown below, but the invention is not limited to these. Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2- diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic acid,
Ethylenediamine orthohydroxyphenylacetic acid, 2
-phosphonobutane-1,2,4-tricarboxylic acid, 1-
Hydroxyethylidene-1,1-diphosphonic acid, N,N
'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid, 1,2-dihydroxybenzene-3,5-disulfonic acid. Two or more of these chelating agents may be used in combination, if necessary.

[0411] These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example, it is about 0.1 g to 10 g per liter.

[0412] Any development accelerator can be added to the color developer if necessary. However, the color developer used in the present invention preferably does not substantially contain benzyl alcohol from the viewpoints of formulation properties and prevention of color staining. Here, "substantially" means that the developer contains less than 2 milliliters per liter of developer, preferably not at all.

Other development accelerators include:
No. 16088, No. 37-5987, No. 38-7826
No. 44-12380, No. 45-9019, and U.S. Pat. No. 3,813,247, etc.;
p-phenylenediamine compounds represented by No. 0-15554, JP-A-50-137726, and JP-B No. 44-
30074, JP-A-56-156826 and JP-A-56-156826
Quaternary ammonium salts represented by No. 2-43429, etc., U.S. Patent Nos. 2,494,903 and 3,128,18
No. 2, No. 4,230,796, No. 3,253,919
No. 41-11431, U.S. Patent No. 2,482
, No. 546, No. 2,596,926 and No. 3,58
Amine compounds described in No. 2,346, etc., Japanese Patent Publication No. 37-Sho.
No. 16088, No. 42-25201, U.S. Patent No. 3,
No. 128,183, Special Publication No. 41-11431, No. 42
Polyalkylene oxides shown in -23883 and U.S. Patent No. 3,532,501, etc., and others 1-
Phenyl-3-pyrazolidones, imidazoles, etc. can be added as necessary.

In the present invention, any antifoggant (or development inhibitor) can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, and 5-nitrobenzotriazole.
Representative examples include nitrogen-containing heterocyclic compounds such as chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

[0415] The color developer used in the present invention may contain a fluorescent brightener. As the fluorescent whitening agent, 4,4'-diamino-2,2'-disulfostilbene compounds are preferred. The amount added is 0 to 5 g/liter, preferably 0.1 g to 4 g/liter.

[0416] Also, if necessary, alkylsulfonic acid,
Various surfactants such as aryphosphonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added.

[0417] The processing temperature of the color developer of the present invention is 20~
The temperature is 50°C, preferably 30-40°C. Processing time is 2
The time is 0 seconds to 5 minutes, preferably 30 seconds to 2 minutes. The smaller the amount of replenishment, the better, but 100 per m2 of photosensitive material.
~1500 ml, preferably 100-800 ml. More preferably, it is 100 ml to 400 ml.

Next, the desilvering process will be explained. The desilvering process is generally performed using any process such as bleaching process-fixing process, fixing process-bleach-fixing process, bleaching process-bleach-fixing process, bleach-fixing process, etc. Good too. The process period of the desilvering process is 1 minute 30 seconds or less, more preferably 15 seconds to 60 seconds.

(Desilvering step) The bleaching solution, bleach-fixing solution and fixing solution used in the desilvering step will be explained. As the bleaching agent used in the bleaching solution or bleach-fixing solution, any bleaching agent can be used, but in particular organic complex salts of iron(III) (e.g., aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid) Complex salts of phosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or organic acids such as ecunic acid, tartaric acid and malic acid; sulfates; hydrogen peroxide and the like are particularly preferred from the viewpoint of bleaching power and prevention of environmental pollution.

Aminopolycarboxylic acids, aminopolyphosphonic acids useful for forming organic complexes of iron(III),
Or, to list organic phosphonic acids or their salts, ethylenediaminetetraacetic acid, diethyleneditriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, imino Examples include diacetic acid, glycol ether diamine tetraacetic acid, and the like.

These compounds include sodium, potassium,
Either lithium or ammonium salt may be used. Among these compounds, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid,
, 3-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferred because of their high bleaching power.

Among these, organic complex salts of iron (III) can be prepared using ferric phosphate or the like and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid from the viewpoint of rapid processing. A ferric ion complex salt may be formed in solution. Further, the chelating agent may be used in excess of the amount required to form the ferric ion complex. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.01 to 1.0 mol/liter, preferably 0.05 to 0.50 mol/liter.

Various compounds can be used as bleach accelerators in the bleach solution, bleach-fix solution and/or their prebath. For example, US Pat. No. 3,893,858,
German Patent No. 1290812, JP-A-53-9
Publication No. 5630, Research Disclosure No. 171
No. 29 (July 1978 issue), compounds having a mercapto group or disulfide bond, and
No. 506, JP-A-52-20832, JP-A No. 53-327
Thiourea compounds described in No. 35, US Pat. No. 3,706,561, and halides such as iodine and bromide ions are preferred because they have excellent bleaching power.

[0424] In addition, the bleach or bleach-fix solution used in the present invention may contain bromides (for example, potassium bromide, sodium bromide, ammonium bromide) or chlorides (for example,
Rehalogenating agents such as potassium chloride, sodium chloride, ammonium chloride) or iodides (eg, ammonium iodide) can be included. Boric acid, borax, if necessary
One or more inorganic acids and organic acids having pH buffering capacity such as sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, and these Alkali metal or ammonium salts or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The fixing agent used in the bleach-fixing solution or fixing solution according to the present invention is a known fixing agent, namely, a thiosulfate such as sodium thiosulfate or ammonium thiosulfate; or a thiocyanic acid such as sodium thiocyanate or ammonium thiocyanate. Salt; ethylene bisthioglycolic acid, 3,6-
These are water-soluble silver halide dissolving agents such as thioether compounds such as dithia-1,8-octanediol and thioureas, and these can be used alone or in combination of two or more. Also, JP-A-55-155354
A special bleach-fixing solution consisting of a combination of the fixing agent described in the above publication and a large amount of a halide such as potassium iodide may also be used.

In the present invention, it is preferred to use thiosulfates, especially ammonium thiosulfates. The amount of fixing agent per liter is preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.0 mol. The pH range of the bleach-fixing solution or fixing solution is preferably 3 to 10, more preferably 5 to 10.
-9 is preferable.

The bleach-fix solution may also contain various other fluorescent brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

[0428] The bleach-fix solution and fixing solution in the present invention contain sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (eg, ammonium bisulfite, sodium bisulfite, etc.) as preservatives. It is preferable to contain a sulfite ion releasing compound such as potassium bisulfite, etc.), metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). The content of these compounds is preferably about 0.02 to 0.0.50 mol/liter, more preferably 0.04 to 0.0.50 mol/liter in terms of sulfite ion.
It is 0.40 mol/liter.

[0429] As a preservative, sulfite is generally added, but ascorbic acid, carbonyl bisulfite adducts, carbonyl compounds, etc. may also be added.

[0430] Furthermore, buffering agents, optical brighteners, chelating agents,
Antifoaming agents, antifungal agents, etc. may be added as necessary.

Water Washing and/or Stabilization In the processing of the present invention, water washing and/or stabilization processing is generally carried out after desilvering processing such as fixing or bleach-fixing.

[0432] The amount of washing water in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the purpose, the washing water temperature, the number of washing tanks (number of stages), the replenishment method such as countercurrent, forward flow, etc.
It can be set in a wide range depending on various other conditions. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is as follows:
Journal of the Society of Motion Picture and Television Engineers (
Journal of the Society of
Motion Picture and Television
ion Engineers) Volume 64, P248
-253 (May 1955 issue). Normally, the number of stages in multistage countercurrent system is 2 to 6.
is preferable, and 2 to 4 are particularly preferable.

[0433] According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, for example, from 0.5 liters to 1 liter or less per 1 m2 of photosensitive material. The increased residence time of water in the tank causes problems such as bacteria propagation and the resulting floating matter adhering to the photosensitive material. In the processing of the color light-sensitive material of the present invention, the method for reducing calcium and magnesium described in JP-A No. 62-288838 can be used very effectively as a solution to such problems. Also, isothiazolone compounds and thiabendazoles described in JP-A No. 57-8542, JP-A No. 61-8542,
Chlorine disinfectants such as chlorinated sodium isocyanurate described in No. 120145, benzotriazole, copper ions, etc. described in JP-A-61-267761, "Chemistry of antibacterial and antifungal agents" by Hiroshi Horiguchi, hygiene technology “Sterilization of microorganisms,”
It is also possible to use the fungicides described in "Bactericidal and Antifungal Techniques" and "Encyclopedia of Antibacterial and Antifungal" edited by the Japan Antibacterial and Antifungal Society.

Furthermore, in the washing water, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softener can be used.

[0435] The above-mentioned water washing step can be followed or the stabilizing solution can be directly treated without going through the water washing step. A compound having an image stabilizing function is added to the stabilizing solution, such as an aldehyde compound typified by formalin, a buffer for adjusting the membrane pH suitable for dye stabilization, and an ammonium compound. In addition, in order to prevent the proliferation of bacteria in the solution and to impart antifungal properties to the photographic material after processing, the various disinfectants and antifungal agents described above can be used.

[0436] Furthermore, surfactants, optical brighteners, and hardeners can also be added. In the processing of the photosensitive material of the present invention, when stabilization is performed directly without a water washing step, known methods described in JP-A-57-8543, JP-A-58-14834, JP-A-60-220345, etc. All can be used.

Others: 1-hydroxyethylidene-1,
It is also a preferred embodiment to use a chelating agent such as 1-diphosphonic acid or ethylene diamino tetramethylene phosphonic acid, or a magnesium or bismuth compound.

[0438] In the present invention, a so-called rinsing solution can also be used as a washing solution or a stabilizing solution used after the desilvering treatment.

[0439] The pH of the water washing step or stabilization step is 4 to 1.
0, preferably 5-8. The temperature can be set variously depending on the use and characteristics of the photosensitive material, but generally it is between 15 and 45
℃, preferably 20 to 40℃. The time can be set arbitrarily, but a shorter time is preferable. Preferably 30 seconds to 3 minutes,
More preferably, the time is 30 seconds to 2 minutes. The smaller the amount of replenishment, the better from the viewpoints of running costs, reduced emissions, ease of handling, etc., and the effects of the present invention are also greater.

A specific preferred amount of replenishment is 0.5 to 50 times, preferably 3 to 40 times, the amount brought in from the pre-bath per unit area of the photosensitive material. Or it is 1 liter or less, preferably 500 ml or less per m2 of photosensitive material. Further, replenishment may be performed continuously or intermittently.

[0441] The liquid used in the water washing and/or stabilization step was
Furthermore, it can also be used in a pre-process. As an example of this, we can reduce the overfloat of flush water by using a multi-stage countercurrent method.
The amount of waste liquid can be reduced by flowing the concentrated liquid into the bleach-fixing bath, which is a pre-bath, and replenishing the bleach-stabilizing bath with concentrated liquid.

[0442] The direct positive color photographic material of the present invention is
Although it has various uses, it is particularly suitable for creating color proofs.

[0443] Various exposure means can be used to expose the photosensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination or writing light source. Natural light (sunlight)
, incandescent lamps, halogen-filled lamps, mercury vapor lamps, fluorescent lamps, and flash light sources such as strobes or metal-fired flashbulbs are common. Gaseous, dye solution or semiconductor lasers, light emitting diodes and plasma light sources emitting light in the wavelength range from ultraviolet to infrared can also be used as recording light sources. In addition, fluorescent screens (such as CRT) and liquid crystals (such as CRTs) emitted from fluorescent substances excited by electron beams, etc.
An exposure means that combines a linear or planar light source with a micro-shutter array using lanthanum-doped lead titanium zirconate (PLZT) or the like can also be used. If necessary, the spectral distribution used for exposure can be adjusted using color filters. In addition, Fuji Photo Film (
The scanning exposure method used in the color copier AP-5000 manufactured by Co., Ltd. can be used.

0444]

[Examples] The present invention will be explained in more detail below with reference to Examples. However, the present invention is not limited to these examples.

[Example 1] (Preparation of sample 101) Paper support laminated on both sides with polyethylene (thickness 100 μm)
) on the front side, layer 1 to 11 below, and layer 1 on the back side.
A color photographic material (
A comparison sample) was prepared. The polyethylene on the first layer coating side contains titanium oxide (4 g/m2) as a white pigment and a trace amount (0.003 g/m2) of ultramarine as a blue-tinged dye (the chromaticity of the surface of the support is L* , a*, b* system were 88.0, -0.20, -0.75).

(Photosensitive layer composition) The components and coating amount (g/
m2). However, the amount of sensitizing dye added is expressed in moles per mole of silver. Regarding silver halide, the coating amount is shown in terms of silver. The emulsions used in each layer were prepared by changing the grain size by changing the grain formation temperature according to the method for manufacturing emulsion EM-1 described below. However, as the emulsion for the 11th layer, a Lippmann emulsion whose surface was not chemically sensitized was used.

0447 First layer (antihalation layer) Black colloidal silver

0.10 Color mixing prevention agent (Cpd-7)

0.05 gelatin

0.70

0448 Second layer (middle layer) Gelatin

0.70

3rd layer (red sensitive layer) Red sensitizing dye (ExS-1, 2, 3, equal amounts of each,
Silver bromide spectrally sensitized with a total of 5.4 x 10-4 (average grain size: 0.4 μm, grain size distribution: 10%, octahedral)

0.25 Gelatin

1.00 Cyan coupler (3:7 ratio of ExC-1 and 2)
0.30 Antifading agent (Cpd-1, 2
, 3, 4, 30 in equal amounts) 0.18 Stain inhibitor (Cpd-5)
0.003 Coupler dispersion medium (Cpd-6)
0.03 Coupler solvent (equal amounts of Solv-1, 2, and 3)
0.12

0450 4th layer (middle layer) Gelatin

1.00 Color mixing prevention agent (Cpd-7)

0.08 Color mixing inhibitor solvent (Solv-
Equal amounts of 4 and 5) 0.16
Polymer latex (Cpd-8)
0.10

0451
] 5th layer (green sensitive layer) Green sensitizing dye (ExS-4, 2.6×10-4
) spectrally sensitized silver bromide (average grain size: 0.40 μm, grain size distribution 10%)
, octahedron) 0.25 Gelatin
0.80
Magenta coupler (equal amounts of ExM-1 and 2)
0.11 Yellow coupler (ExY-1)
0.03 Anti-fading agent (Cp
Equal amounts of d-9, 26, and 30) 0
．． 15 Stain inhibitor (Cpd-10, 11,
12 and 13 in a 10:7:7:1 ratio)

0.025 Coupler dispersion medium (Cpd-6
)
0.05 coupler solvent (Solv-4, 6
Equal amount of each) 0.15

[
0452] 6th layer (middle layer) Same as 4th layer

0453 7th layer (yellow filter layer) Yellow colloidal silver (particle size 100 Å)
0.12 Gelatin
0.70
Color mixing inhibitor (Cpd-7)
0.03
Color mixing inhibitor solvent (equal amounts of Solv-4 and Solv-5)
0.10 Polymer latex (Cpd-8)
0.07

0454] 8th layer (middle layer) Same as 4th layer

9th layer (blue sensitive layer) Blue sensitizing dye (Equivalent amounts of ExS-5 and 6,
Spectrally sensitized with a total of 3.5 x 10-4)
Silver bromide (average particle size: 0.60 μm,
Particle size distribution 11%, octahedral)
0.40 Gelatin
0.8
0 Yellow coupler (equal amounts of ExY-1 and 2) 0.35 Anti-fading agent (Cpd-14)
0.10 Anti-fading agent (Cpd-30)
0.05 Stain inhibitor (Cpd-5, 15 in a 1:5 ratio) 0
．． 007 Coupler dispersion medium (Cpd-6)
0.
05 Coupler solvent (Solv-2)
0.10

0456 Layer 10 (ultraviolet absorbing layer) Gelatin

1.00 Ultraviolet absorber (Cpd-2,
Equal amounts of 4 and 16) 0.50
Color mixing inhibitor (Equivalent amounts of Cpd-7 and 17)
0.03 Dispersion medium (C
pd-6)
0.02 Ultraviolet absorber solvent (equal amounts of Solv-2 and Solv-7)
0.08 Anti-irradiation dye (
Cpd-18, 19, 20, 21, 27 in the ratio of 10:10: 13:15:20)

0.05

11th layer (protective layer) Fine grain silver chlorobromide (silver chloride 97 mol%,
average size 0.1μm)
0.03
Acrylic modified copolymer of polyvinyl alcohol
0.01 (molecular weight: 5
0000) Equal amounts of polymethyl methacrylate particles (average particle size: 2.4 μm) and silicon oxide (average particle size: 5 μm)

0.05 gelatin

1.80
Gelatin hardening agent (equal amounts of H-1 and H-2)
0.18

0458 12th layer (back layer) Gelatin

2.50 Ultraviolet absorber (Cpd-2,
Equal amounts of 4 and 16) 0.50
Dye (equal amounts of Cpd-18, 19, 20, 21, 27) 0.06

0459 13th layer (back layer protective layer) Polymethyl methacrylate particles (
Average particle size: 2.4 μm) and silicon oxide
(Average particle size: 5 μm) in equal amounts of each
0.05 gelatin

2.00
Gelatin hardening agent (equal amounts of H-1 and H-2)
0.14

(Emulsion E
How to make M-1) Add an aqueous solution of potassium bromide and silver nitrate simultaneously to an aqueous gelatin solution over 15 minutes at 65°C with vigorous stirring to obtain octahedral silver bromide particles with an average particle size of 0.23 μm. Ta. At this time, 0.3 per mole of silver
g of 3,4-dimethyl-1,3-thiazoline-2-thione were added. A chemical sensitization treatment was performed by sequentially adding 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) per mole of silver to this emulsion and heating at 75° C. for 80 minutes. The thus obtained grains were used as cores and further grown in the same precipitation environment as in the first precipitation to finally obtain an octahedral monodispersed core/shell silver bromide emulsion with an average grain size of 0.4 μm. The coefficient of variation in particle size was approximately 10%. To this emulsion were added 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mole of silver, and
A chemical sensitization treatment was performed by heating for a minute to obtain an internal latent image type silver halide emulsion.

[0461] Each photosensitive layer contained ExZK-1 as a nucleating agent.
and ExZK-2 to silver halide at 10-3, respectively.
wt%, 10-2 wt%, Cpd-2 as nucleation accelerator
2, 28, and 29 were each used in an amount of 10-2% by weight. Furthermore, alkanol XC (Du
Pont) and sodium alkylbenzene sulfonate, succinate ester and Magef as coating aids.
ac F-120 (manufactured by Dainippon Ink and Chemicals Co., Ltd.)
was used. As a stabilizer in the silver halide and colloidal silver containing layer,
Equivalent amounts of Cpd-23, 24, and 25 were used. The compounds used to create the above samples are shown below.

0462]

[Chemical formula 163]

0463]

[Chemical formula 164]

0464

[Chemical formula 165]

0465]

[Chemical formula 166]

0466]

[Chemical formula 167]

0467]

[Chemical formula 168]

0468]

[Chemical formula 169]

0469]

[Chemical formula 170]

0470]

[Chemical formula 171]

0471]

[Chemical formula 172]

0472]

[Chemical formula 173]

0473]

[Chemical formula 174]

0474]

[Chemical formula 175]

0475]

[Chemical formula 176]

0476]

[Chemical formula 177]

0477]

[Chemical formula 178]

0478]

[Chemical formula 179]

0479]

[Chemical formula 180]

0480]

[Chemical formula 181]

0481]

[Chemical formula 182]

0482]

[Chemical formula 183]

0483]

[Chemical formula 184]

0484]

[Chemical formula 185]

0485]

[Chemical formula 186]

0486]

[Chemical formula 187]

0487]

[Chemical formula 188]

0488]

[Chemical formula 189]

0489]

[Chemical formula 190]

0490]

[Chemical formula 191]

0491

[Chemical formula 192]

0492]

[Chemical formula 193]

0493

[Chemical formula 194]

0494

[Chemical formula 195]

0495]

[Chemical formula 196]

0496]

[Chemical formula 197]

0497]

[Chemical formula 198]

0498

[Chemical formula 199]

0499]

[C200]

0500]

[C201]

0501]

[C202]

0502]

[C203]

0503]

[C204]

0504 Solv-1 Di(2-ethylhexyl) sebacate

0505 Solv-2 trinonyl phosphate

0506 Solv-3 Di(3-methylhexyl) phthalate

0507 Solv-4 tricresyl phosphate

0508 Solv-5 dibutyl phthalate

Solv-6 trioctyl phosphate

[
0510 Solv-7 di(2-ethylhexyl) phthalate

H-1 1,2-bis(vinylsulfonylacetamido)ethane

H-2 4,6-dichloro-2-hydroxy-1,3,5-triazine/Na salt

ExZK-1 7-(3-ethoxythiocarbonylaminobenzamide)-9-methyl-10-propargyl-1,2,3,4
-Tetrahydroacridinium trifluoromethanesulfonate

ExZK-2 2-[4-{3-[3-{3-[5-{3-[2-chloro-5-(1-dodecyloxycarbonylethoxycarbonyl)phenylcarbamoyl]-4-hydroxy- 1
-naphthylthio}tetrazol-1-yl]phenyl}
ureido]benzenesulfonamide}phenyl]-1-
Formylhydrazine

(Preparation of Sample 102) In the preparation of Sample 101, the cyan couplers (ExC-1 and ExC-2) contained in the third layer (red-sensitive layer) were replaced with the following cyan couplers (Cy- Sample 102 was prepared in the same manner as Sample 101 (comparative sample) except that 1) was changed (replaced with equimolar amounts).

0516]

[C205]

(Preparation of Sample 103) In the preparation of Sample 101, the magenta couplers (ExM-1 and ExM-2) contained in the fifth layer (green-sensitive layer) were replaced with the magenta couplers (M-2) shown below. Sample 10 was prepared in the same manner as Sample 101 except that 22) was changed (replaced with equimolar amounts).
3 was prepared (comparative sample).

0518]

[C206]

(Preparation of Sample 104) In the preparation of Sample 101, the yellow couplers (ExY-1 and ExY-2) contained in the ninth layer (blue-sensitive layer) were replaced with the following yellow couplers (Y- Sample 10 was prepared in the same manner as Sample 101 except that 31) was changed (replaced with equimolar amounts).
4 (comparative sample).

0520]

[C207]

(Preparation of Sample 105) In preparing the above sample 101, the cyan couplers (ExC-1 and ExC-2) contained in the third layer (red sensitive layer) were replaced with the above cyan coupler (Cy-1). , magenta couplers (ExM-1 and ExM-2) contained in the fifth layer (green-sensitive layer)
) to the above magenta coupler (M-22), and the ninth
Yellow coupler (Ex
Y-1 and ExY-2) with the above yellow coupler (Y-1 and ExY-2)
Sample 105 was prepared in the same manner as Sample 101 (sample of the present invention), except that -31) were changed (replaced with equimolar amounts).

(Preparation of Sample 106) In preparing Sample 105, the cyan coupler (Cy-1) contained in the third layer (red sensitive layer) was replaced with the cyan coupler (Cy-1) shown below.
Sample 1 except that y-4) was changed (replaced with equimolar)
Sample 106 was created in the same manner as 05 (sample of the present invention)
.

0523]

[C208]

(Preparation of Sample 107) In the preparation of Sample 105, the magenta coupler (M-22) contained in the fifth layer (green-sensitive layer) was replaced with the magenta coupler (M-23) shown below ( Sample 107 was prepared in the same manner as Sample 105 (sample of the present invention), except that the amount was replaced with an equimolar amount.

0525]

[C209]

(Preparation of Sample 108) In preparing Sample 105, the yellow coupler (Y-31) contained in the ninth layer (blue-sensitive layer) was replaced with the yellow coupler (Y-34) shown below ( Sample 108 (sample of the present invention) was prepared in the same manner as Sample 105, except that the amount was replaced with an equimolar amount.

0527]

[Chemical formula 210]

[Evaluation as a Direct Positive Color Photographic Material] Each of the silver halide color photographic materials (Samples 101 to 108) prepared as described above was evaluated for color reproducibility and image storage stability. The image forming method using these photosensitive materials was performed according to the following process.

(Evaluation of color reproducibility) After obtaining a colored image (dye image) by monochromating the sample in each hue of yellow, magenta, and cyan, λ700 (yellow) and λ660 ( The absorption density (unnecessary absorption density) at wavelengths of magenta) and λ400 (cyan) was measured and evaluated using a spectrophotometer.

(Evaluation of Image Preservability) The following photofading test was conducted and evaluated. After image exposure of the sample, a color development process was performed to obtain a full-color image, which was then exposed to fluorescent light (30,000 lux) for two weeks, and the yellow, magenta, and cyan densities of the resulting image were compared with blue light, green light, and green light. Densitometer (X-Rite310RT, X-
(manufactured by Rite), and evaluated by the difference in the measured values of yellow and cyan densities (ΔDG-R and ΔDG-B) for a portion with a magenta density of 1.5.

[Color development processing] Using the method described below using an automatic developing machine, the cumulative replenishment amount of the solution is 3 of the tank capacity.
Continued processing until doubled.

0532] ──────────────────────────
──────────── Treatment process Time Temperature Mother liquor tank capacity
Replenishment amount ────────────
────────────────────────
Color development 135 seconds 38℃
11 liters 300ml/m2 Bleach fixing 40 seconds 33℃
3 liters 300ml/m2 water washing (1)
40 seconds 33℃ 3 liters --- Water washing (2
) 40 seconds 33℃ 3 liters 320ml/m2 drying
30 seconds 80℃────────
──────────────────────────
───

0533 The washing water replenishment method is the washing bath (2)
The overflow liquid from the washing bath (2) is refilled to the washing bath (2).
A so-called countercurrent replenishment method was adopted, which leads to 1). At this time, the amount of bleach-fix solution brought in from the bleach-fix bath to the washing bath (1) by the photosensitive material was 35 ml/m2, and the ratio of the amount of washing water replenishment to the amount of bleach-fix solution brought in was 9.1 times. .

[0534] The composition of each treatment liquid was as follows. ──────────────────────────
──────────── Color developer
Mother liquor
Refill fluid────────────
────────────────────────
D-Sorvit
0.15g 0.20g
Sodium naphthalene sulfonate 0
．． 15g 0.20g Formalin condensate Ethylenediaminetetrakis
1.5g 1.5g Methylenephosphonic acid Diethylene glycol
12.0ml 16.0ml Benzyl alcohol
13.5ml 18.0ml Potassium bromide
0.70g --- Benzotriazole 0
．． 003g 0.004g Sodium sulfite 2
．． 4g 3.2g N,N-bis(carboxymethyl) 4.0g
5.3g hydrazine D-glucose
2.0g 2.4
g Triethanolamine
6.0g 8.0g
N-ethyl-N-(β-methane
6.4g 8.5g Sulfonamidoethyl)-3-methyl-4-aminoaniline sulfate Potassium carbonate
30.0g 25.0g Fluorescent brightener (diaminostilbene type) 1.0g
Add 1.2g water
1000ml
1000ml────────────────
──────────────────── pH (
25℃)
10.25 11.00──────
──────────────────────────
──────

0535] ──────────────────────────
──────────── Bleach-fix solution

Mother liquid Replenisher──────
──────────────────────────
────── Ethylenediaminetetraacetic acid・
2.0g Same as mother liquor Disodium dihydrate Ethylenediaminetetraacetic acid Fe(III)
70.0g
Ammonium dihydrate ammonium thiosulfate (700g/liter) 18
0ml Sodium p-toluenesulfinate
45.0g Sodium bisulfite
3
5.0g 5-mercapto-1,3,4-triazole 0.5g Ammonium nitrate
1
Add 0.0g water
1000ml───
──────────────────────────
──────── pH (25℃)
6
．． 10──────────────────────
──────────────

0536 “Washing water”
Both the mother liquor and the replenisher were mixed with tap water using H-type strongly acidic cation exchange resin (Amberlite IR-120 manufactured by Rohm and Haas).
B) and OH type anion exchange resin (Amberlite I)
Water was passed through a mixed bed column packed with R-400) to reduce the concentration of calcium and magnesium ions to 3 mg/liter or less, and then 20 mg/liter of sodium isocyanurate dichloride and 0.15 g/liter of sodium sulfate were added. Added. The pH of this liquid was in the range of 6.5 to 7.5.

[Example 2] (1) Above samples 101 and 10
The following image forming method was carried out using No. 5 and No. 108. Then, evaluation was performed using the same evaluation method as that used in Example 1 above. In Example 1 above, the color developing agent contained in the color developer was replaced with [N-ethyl-N-β-(methanesulfonamidoethyl)-3-ethyl-4-aminoaniline sulfate] as shown below. The compound shown (D-2
An image forming method was carried out in the same manner as in Example 1, except that the mother liquor: 4.3 g and the replenisher solution: 5.6 g) were used.

0538]

[Chemical formula 211]

(2) The following image forming method was carried out using the above samples 105 and 108. Then, evaluation was performed using the same evaluation method as that used in Example 1 above. In Example 1 above, the color developing agent contained in the color developer was replaced with [N-ethyl-N-β-(methanesulfonamidoethyl)-3-ethyl-4-aminoaniline sulfate] as shown below. An image forming method was carried out in the same manner as in Example 1, except that the following compound (D-3; mother liquor: 4.6 g, replenisher: 6.1 g) was used.

0540]

[C212]

[0541] The above results are summarized in Tables 1 and 2 below.

0542]

[Table 1]

0543]

[Table 2]

As is clear from the results shown in Tables 1 and 2, the direct positive photographic materials (samples 105 to 108 of the present invention) prepared using the yellow, magenta and cyan couplers according to the present invention had the following properties: The unnecessary absorption density is low (that is, the developed color hue is excellent and the color reproducibility is good), and the density difference between each dye image after the photofading test is small (that is, the color balance is small). On the other hand, comparative samples (101~
No. 104) has a high unnecessary absorption density in any of the colored dye images, and the difference in density between each dye image after the photofading test is large. Further, when the image forming method is carried out using the samples of the present invention (105 and 108), the unnecessary absorption density is further reduced, and the density difference between each dye image after the photofading test is also further reduced. On the other hand, when the image forming method was carried out using comparative sample (101), the unnecessary absorption density decreased, but the density difference between each dye image after the photofading test was large.
The color balance is greatly distorted.

Claims (2)

[Claims] 1. A support is provided with at least one layer each of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer each containing an internal latent image type silver halide emulsion and a color image-forming coupler which have not been fogged in advance. In the direct positive color photographic light-sensitive material, the color image-forming coupler of the blue-sensitive layer has the following formula (Y): [Formula 1] [wherein R1 represents an aryl group or a tertiary alkyl group, R2 represents an alkyl group, represents an aryl group, an alkoxy group, an aryloxy group, a dialkylamino group, an alkylthio group, or an arylthio group, R3 represents a group that can be substituted on the benzene ring, and X1 represents a hydrogen atom or a coupling with an oxidized form of a developing agent. It represents a group that can be separated by reaction, and k represents an integer of 0 to 4. However, when k is a plurality of R3's, the plurality of R3's may be the same or different. ], and the color image forming coupler of the green-sensitive layer is represented by the following formula (M
): [Formula 2] [In the formula, R4 represents an alkyl group or an aryl group, and Z represents a group of nonmetallic atoms necessary to form a 5-membered azole ring containing 2 to 4 nitrogen atoms ( (The azole ring may have a substituent (including a fused ring)), X2 represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized developing agent, provided that R4 is an alkyl group. In this case, X2 is not a halogen atom. ], and the color image forming coupler of the red-sensitive layer has the following formula (Cy): [In the formula, R5 represents a hydrogen atom, a halogen atom or an alkyl group, and R6 represents an alkyl group] group, aryl group or heterocyclic group, R7 is a hydrogen atom, a halogen atom,
It represents an alkyl group, an alkoxy group, an aryloxy group, or a carbonamide group, and X3 represents a hydrogen atom or a group capable of being separated by a coupling reaction with an oxidized product of a developing agent. ] A direct positive color photographic material characterized by being a cyan coupler represented by: 2. At least one layer each of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer containing an internal latent image type silver halide emulsion and a color image-forming coupler which have not been fogged in advance is provided on a support. , the color image-forming coupler of the blue-sensitive layer has the following formula (Y): [Formula 4, R1 represents an aryl group or a tertiary alkyl group, and R2 represents an alkyl group, an aryl group, an alkoxy group, an aryl group] represents an oxy group, dialkylamino group, alkylthio group or arylthio group, R3 represents a group that can be substituted on the benzene ring, and X11 represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized product of a developing agent. and k represents an integer from 0 to 4, provided that when k is a plurality of R3's, the plurality of R3's may be the same or different. ], and the color image forming coupler of the green-sensitive layer is represented by the following formula (M
): [Formula 5] [In the formula, R4 represents an alkyl group or an aryl group, and Z represents a group of nonmetallic atoms necessary to form a 5-membered azole ring containing 2 to 4 nitrogen atoms ( The azole ring may have a substituent (including a fused ring), X2
represents a hydrogen atom or a group capable of being separated by a coupling reaction with an oxidized product of a developing agent. However, when R4 is an alkyl group, X2 is not a halogen atom. ], and the color image forming coupler of the red-sensitive layer has the following formula (Cy): [In the formula, R5 represents a hydrogen atom, a halogen atom or an alkyl group, and R6 represents an alkyl group] group, aryl group or heterocyclic group, R7 is a hydrogen atom, a halogen atom,
It represents an alkyl group, an alkoxy group, an aryloxy group, or a carbonamide group, and X3 represents a hydrogen atom or a group capable of being separated by a coupling reaction with an oxidized product of a developing agent. A direct positive color photographic light-sensitive material which is a cyan coupler represented by the following formula (D): [In the formula, R8 represents an alkyl group and R9 represents an alkylene group, provided that R8 and R9 are mutually They may be connected to form a ring. ] An image forming method characterized by carrying out a development process using a developing agent represented by: