JPH05303162A - Direct positive color photographic sensitive material, and color image and color proof forming method - Google Patents

Abstract

PURPOSE:To enhance hue and color developing performances and to lower a minimum density by selectively using a specified cyan coupler. CONSTITUTION:A red-sensitive layer contains at least one kind of cyan dye stuff image-forming coupler represented by formula I or II in which each of RC<11> and RC<12> is an electron-attractive group; ZC<11> is -NH- or -CH(RC<13>)-, ZC<12> is -C(RC<14>)= or -N=; ZC<13> is-C(RC<15>)= or -N=, RC<13> is an electron-attractive group, each of RC<14> and RC<15> is H or a substituent, XC<11> is H or a group to be released by coupling with the oxidation product of an aromatic primary amine color developing agent RC<21> is H or a substituent, RC<22> is a substituent, ZC<21> is a nonmetallic atomic group necessary to form a 6-membered N-containing hetero-cyclic ring, and XC<21> is H or a group to be released by coupling with the oxidation product of an aromatic primary amine color developing agent.

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 light-sensitive material utilizing an internal latent image type silver halide emulsion, a color image forming method using the same, and a color proof making, which makes it possible to directly obtain a positive image. Regarding the method.

[0002]

BACKGROUND OF THE INVENTION Photographic methods for obtaining direct positive images without the need for reversal processing steps or negative films are well known.
As a method for forming a positive image using a conventionally known direct positive color silver halide photographic light-sensitive material, there is a method using an internal latent image type silver halide emulsion which has not been fogged in advance. This method is a method of directly obtaining a positive color image by subjecting a photographic light-sensitive material to image development, surface-developing after or after fogging, or while performing fogging. The internal latent image type silver halide photographic emulsion which is not previously fogged is a type of halogenated type in which a silver halide grain has a photosensitive nucleus mainly inside and a latent image is mainly formed inside the grain by exposure. A silver photographic emulsion. Various techniques have been known so far in this field. For example, US Pat. No. 2,592,250.
Nos. 2466957, 2497875, 25
No. 88982, No. 3317322, No. 3761266
Nos. 3,761,276, 3,796,577 and British Patent Nos. 1,153,163, 1,150,553 and 10,
Those described in each specification of No. 11062 are the main ones. The formation mechanism of the direct positive image is explained as follows. That is, when imagewise exposure is performed, a so-called internal latent image is formed on the silver halide, and then a fog treatment is performed to cause a surface desensitizing action due to the internal latent image (that is, the halogen in the exposed portion is affected). Development nuclei (fog nuclei are not generated on the surface of silver halide), development nuclei are selectively generated only on the surface of unexposed silver halide,
Thereafter, a normal surface development process is performed to form a photographic image (positive image) on the unexposed portion. The fog treatment method includes a so-called "light fog method" for exposing the entire photosensitive layer, and a "chemical fog method" for using a nucleating agent. A direct positive color silver halide photographic light-sensitive material using an internal latent image type silver halide emulsion which has not been previously fogged as described above has recently been accepted as having a simple processing step, and thus, a color copy or a color plate, It has been used for printing plate inspection, making color proof for checking, etc.

The working process of a color printed matter includes the steps of color-separating a color original document and converting it into a halftone dot image to form a transmissive halftone image. A printing plate is made from the obtained transmission type halftone dot image, but prior to this, the final printed matter (main printing)
There is a step of inspecting the state, characteristics, etc., and performing necessary calibration (color calibration). As a color proofing method, conventionally, a method of preparing a printing plate and making a test print has been used. However, in recent years, various color proofs have been produced for the purpose of speeding up the calibration process and reducing costs.
As a method for producing a color proof, a photopolymer, a diazo method, a surprint method using a photoadhesive polymer, an overlay method and the like are known (for example, US Pat. No. 3,582,327, JP-A-56-50121).
7 and 59-97140). However, all of these methods require superposition and transfer of images, and also require superposition and transfer of a plurality of figures, and the process is complicated and requires a lot of time and cost. .. JP-A-56-104335 discloses that
A method of producing a color proof using a color photographic light-sensitive material has been disclosed, and this method has major advantages in terms of simplicity of process and low cost, and is also characterized by excellent tone reproducibility. The method for producing a color proof using the above color photographic light-sensitive material uses a silver halide color photographic light-sensitive material of a coloring method having a continuous tone, to which magenta (M) color, cyan (C) color, yellow ( This is a method in which each color of Y) and black (B) is sequentially contact-exposed so that a color negative is printed on a color paper, and then a designated color development processing is performed to obtain a color proof. This method has the features that the process is simple and easy to automate as compared with the various methods described above. There are several possible silver halide color photographic light-sensitive materials that can be used in such color proofs. Among them, the transmission type black and white halftone image used in the production process of the color printed matter described above is often a positive type especially in Japan and Europe, and therefore, as a silver halide color photographic light-sensitive material for color proofing. Many positive-positive type photosensitive materials are used. Among them, the direct positive type color photographic light-sensitive material, which has been rapidly advanced in practical use technology in recent years, has been attracting attention as being most suitable for use in color proof because of its ease of processing.

A positive color image can be obtained by subjecting a light-sensitive material containing yellow, magenta and cyan color image forming couplers in different light-sensitive layers as described above to image development and then color development processing. it can.
The color development process causes a coupling reaction between the oxidized product of the developing agent and the coupler to produce a color dye, which forms a positive color image. In this case, the coupler to be used is desired to have a good color forming property such that the coupling speed is as high as possible and a high color forming density is given in a limited time. Further, it is desired that the color-developing dye thus produced is a yellow, magenta, or cyan dye having a small amount of sub-absorption and gives a color image having good color reproducibility. Further, in terms of color reproducibility, it is important to reduce the minimum image density to realize high whiteness. Conventionally,
Acylacetanilide yellow couplers, 2,5-diacylaminophenol cyan couplers and pyrazoloazole magenta couplers are known as color image-forming couplers used directly in positive color photographic light-sensitive materials. For example, in JP-A-2-220049, an acyl group has a pivaloyl type [(CH ₃ ) ₃ CC
O-], a direct positive photographic light-sensitive material containing an acylacetanilide yellow coupler and a 2,5-diacylaminophenol cyan coupler in a light-sensitive layer is disclosed. Further, the above publication describes an example in which a pyrazoloazole-based magenta coupler is also used together with the yellow coupler and the cyan coupler. Further, the above-mentioned publication describes adding a highly active hydroquinone compound to the emulsion layer.

[0005]

However, according to the study by the present inventor, even if the coupler and the hydroquinone compound disclosed in the above publication are used, the coloring hue,
Both the color development and whiteness are not sufficiently satisfactory,
Further improvements are desired. Therefore, an object of the present invention is to provide a direct positive color photographic light-sensitive material having a good color hue (good color reproducibility), an excellent color developability, and a low minimum density (good whiteness). Another object of the present invention is to provide a color image forming method and a color proof forming method using the above direct positive color photographic light-sensitive material.

[0006]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made extensive studies in search of a cyan coupler which meets the above-mentioned object, and as a result, selectively use a specific cyan coupler represented by the above formula. Further, it was found that the above object can be achieved by using the above cyan coupler and a specific compound in combination, and further by using the above cyan coupler and a specific developing agent in combination, thereby completing the present invention. did. The present invention comprises a blue-sensitive layer (blue-sensitive emulsion layer), a green-sensitive layer (green-sensitive emulsion layer) containing an internal latent image type silver halide grain not previously fogged and a color image-forming coupler on a support. And a red-sensitive layer (red light-sensitive emulsion layer), and a non-light-sensitive layer adjacent thereto, in a direct positive color photographic light-sensitive material, the color image-forming coupler of the red-sensitive layer is represented by the following formula ( CaI) or (CbI):

[0007]

[Chemical 7]

[In the formula, R ^C11 and R ^C12 each independently represent an electron-withdrawing group having a Hammett's substituent constant σ _P value of 0.2 or more. However, the sum of the sigma _P value of sigma _P value and R ^C12 of R ^C11 is 0.65 or more. Z ^C11 is -N
Represents H- or -CH (R ^C13 )-. Z ^C12 is -C (R
^C14 ) = or -N =. Z ^C13 is -C (R ^C15 ) =
Or represents -N =. R ^C13 is Hammett's substituent constant σ
_It represents an electron-withdrawing group having a _P value of 0.2 or more. R ^C14 and R ^C15 each independently represent a hydrogen atom or a substituent. X ^C11 represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine color developing agent].

[0009]

[Chemical 8]

[In the formula, R ^C21 represents a hydrogen atom or a substituent. R ^C22 represents a substituent. Z ^{C2 1} represents a non-metal atom group necessary for forming a nitrogen-containing 6-membered heterocycle. However, the heterocycle has at least one dissociative group. X
^C21 represents a group capable of splitting off by a coupling reaction with a hydrogen atom or an oxidized product of an aromatic primary amine color developing agent]], a direct positive color photograph characterized by containing at least one cyan coupler It is a photosensitive material.

In another aspect of the present invention, the color image forming coupler of the green-sensitive layer of the above direct positive color photographic light-sensitive material has the following formula (M):

[0012]

[Chemical 9]

[In the formula, R ^M represents a hydrogen atom or a substituent, and Z ^M is necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms together with the carbon atom and the nitrogen atom to be bonded. Represents a non-metal atom group, the azole ring may have a substituent (including a condensed ring), and X ^M is a hydrogen atom or a group capable of splitting off during a coupling reaction with an oxidized product of a developing agent. The present invention is a direct positive color photographic light-sensitive material which is a magenta coupler represented by

In still another aspect of the present invention, at least one of the blue-sensitive layer, green-sensitive layer, red-sensitive layer and non-light-sensitive layer of the above direct positive color photographic light-sensitive material has the following formula (HQ1) or (HQ2):

[0015]

[Chemical 10]

[In the formula, R ^Q1 and R ^Q2 each independently represent a hydrogen atom or a group capable of releasing a hydroxyl group upon cleavage of a bond with an oxygen atom during development, and R ^Q3 , R ^Q4 and R ^Q6 are each Independently, hydrogen atom, halogen atom, sulfo group, carboxyl group, cyano group, alkyl group, alkenyl group, aryl group, acylamino group, sulfonamide group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, Acyloxy group, sulfonyl group, carbamoyl group, alkoxycarbonyl group,
Represents a sulfamoyl group, a ureido group, a urethane group or a carbonic acid ester group, and R ^Q5 represents the same group as the group represented by R ^Q3 or an aryl group bonded via a linking group, provided that R ^Q5 represents when the same groups as those represented by the R ^Q3, the R ^Q3 and R ^Q4 or R ^Q5 and R ^Q6 may form a carbocyclic or heterocyclic ring in cooperation, and the R ^Q3
When at least one of R ^Q6 to R ^Q6 is not a hydrogen atom and R ^{Q3 to} R ^Q6 is composed only of a hydrogen atom and an alkyl group, at least one of the alkyl groups has 6 or more carbon atoms, and R ^Q3 The total number of carbon atoms in R ^Q6 is 15 or less. ]

[0017]

[Chemical 11]

[Wherein, R ^{Q11 to} R ^Q16 are each independently a hydrogen atom, a halogen atom, a sulfo group, a carboxyl group, a cyano group, an alkyl group, an alkenyl group, an aryl group, an acylamino group, a sulfonamide group, an alkoxy group. Represents an aryloxy group, an alkylthio group, an arylthio group, an acyl group, an acyloxy group, a sulfonyl group, a carbamoyl group, an alkoxycarbonyl group, or a sulfamoyl group, and represents the above R ^Q11 and R ^Q12 or R ^Q14 and R
^Q15 may together form a carbocycle or a heterocycle; R ^Q17 and R ^Q18 are each independently a hydrogen atom,
It represents an alkyl group, an aryl group or a heterocyclic group, and the above R ^Q17 and R ^Q18 may together form a carbocycle or a heterocycle. ] The above-mentioned direct positive color photographic light-sensitive material containing at least one hydroquinone derivative represented by

In still another aspect of the present invention, after the above direct positive color photographic light-sensitive material is imagewise exposed, the following formula (D):

[0020]

[Chemical 12]

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

Still another aspect of the present invention is a cyan plate halftone dot image film, a magenta halftone dot image film, a yellow halftone dot image film and a black ink plate obtained by subjecting the above color photographic light-sensitive material to color separation and halftone image conversion. It is a method for producing a color proof, which comprises sequentially exposing with a red light, a green light and a blue light using a halftone image film and then performing a color development process.

In still another aspect of the present invention, there is provided a color image forming method, which comprises subjecting the above direct positive color photographic light-sensitive material to scanning exposure for an exposure time of 10 ^-3 seconds or less per pixel, and then performing color development processing. is there.

[0024]

By using the direct positive color photographic light-sensitive material of the present invention containing the cyan coupler represented by the above formula (CaI) or (CbI), the coloring hue is good (good color reproducibility), and It is possible to obtain a cyan image with good color development. Further, the cyan coupler and the above formula (M)
When used together with the magenta coupler represented by, the unnecessary absorption density of each of the cyan image and the magenta image is reduced, and the color density is also increased, so that an excellent color image satisfying both the hue and the color density can be obtained. In particular, when the hydroquinone derivative represented by the formula (HQ1) or (HQ2) is used in combination, the minimum concentration is decreased and a high whiteness is obtained. Further, when forming a color image, when the color developing treatment solution represented by the formula (D) and containing a specific developing agent is used, the above effect becomes more remarkable, and therefore, a photosensitive material suitable for producing a color proof is obtained. Material can be provided.

The direct positive color photographic light-sensitive material of the present invention will be described below. In the direct positive color photographic light-sensitive material of the present invention, at least one light-sensitive layer (light-sensitive emulsion layer) having three different color sensitivities of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer is provided on a support. It becomes. Each photosensitive layer contains an internal latent image type silver halide grain and a color image forming coupler (color coupler) which have not been fogged in advance. As described above, the red-sensitive layer contains the cyan coupler represented by the formula (CaI) or (CbI).
Further, the green-sensitive layer preferably contains the magenta coupler represented by the formula (M).

The cyan coupler represented by the formula (CaI) or (CbI) used in the photographic light-sensitive material of the present invention will be described in detail below. First, the cyan coupler represented by the following formula (CaI) will be described.

[0027]

[Chemical 13]

In the above formula (CaI), R ^C11 and R ^C12 are each independently Hammett's substituent constant σ _P
The value represents an electron-withdrawing group having a value of 0.2 or more. However, R
The sum of the sigma _P value of sigma _P value and R ^C12 of ^C11 is 0.65 or more. Z ^C11 represents —NH— or —CH (R ^C13 ) —. Z ^C12 represents -C (R ^C14 ) = or -N =.
Z ^C13 represents -C (R ^C15 ) = or -N =. R ^C13
Represents an electron-withdrawing group having a Hammett's substituent constant σ _P value of 0.2 or more. R ^C14 and R ^C15 each independently represent a hydrogen atom or a substituent. X ^C11 represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine color developing agent.

The cyan coupler represented by the above formula (CaI) is specifically represented by the following formulas (CaII) to (CaIX).

[0030]

[Chemical 14]

(Wherein R ^C11 , R ^C12 , R ^C13 , R
^C14 , R ^C15 and X ^C11 have the same meanings as in the above formula (CaI). )

In the present invention, the formulas (CaII), (Ca
Cyan couplers represented by III) or (CaIV) are preferable, and cyan couplers represented by formula (CaIII) are particularly preferable.

Each of R ^C11 , R ^C12 and R ^C13 is an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.20 or more. Preferably, each σ _p value is 0.3
It is an electron-withdrawing group of 5 or more, and more preferably an electron-withdrawing group having a σ _p value of 0.60 or more. The upper limit is an electron-withdrawing group having a σ _P value of 1.0 or less. Further, the sum of the σ _p value of R ^{C11 and} the σ _p value of R ^C12 is preferably 0.70 or more, and the upper limit is about 1.8.

Hammett's rule was used in L.L. in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb put forward by Hammett, which is widely accepted today. The substituent constants obtained by Hammett's rule are σ _p value and σ _m
There are values, and these values are found in many common books. For example, J. A. Dean edition `` Lange's Hand book of che
mistry "12th edition, 1979 (Mc Graw-Hill) and" Special Issue on Chemistry ", No. 122, pages 96-103, 1979.
Detailed in the year (Nankodo). In the present invention, R ^C11 and R ^C12
And R ^C13 are limited by the Hammett's substituent constant σ _p value, but this does not mean that the values known in the literatures described in these publications are limited only to certain substituents, and that value is unknown in the literature. However, as a matter of course, it is included as long as it is included in the range when measured based on the Hammett's rule.

Specific examples of R ^C11 , R ^C12 and R ^C13 which are electron withdrawing groups having a σ _p value of 0.20 or more are:
Acyl group, acyloxy group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl Group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, halogenated alkoxy group, halogenated aryloxy group, halogenated alkylamino group, halogenated alkylthio group, Examples thereof include an aryl group, a heterocyclic group, a halogen atom, an azo group, or a selenocyanate group, which has a σ _p value of 0.20 or more and is substituted with an electron withdrawing group other than the above. Among these substituents, the group which can have a substituent is represented by R described later.
^It may further have a substituent such as ^C14 .

The above-mentioned R ^C11 , R ^C12 and R ^C13 will be described in more detail. As the acyl group, for example,
Mention may be made of acetyl, 3-phenylpropanoyl, benzoyl and 4-dodecyloxybenzoyl. Examples of the acyloxy group may include acetoxy.

Examples of the carbamoyl group include carbamoyl, N-ethylcarbamoyl, N-phenylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl and N- (4-n-pentadecaneamide). Phenylcarbamoyl, N-methyl-N-dodecylcarbamoyl, and N- {3- (2,
4-di-t-amylphenoxy) propyl} carbamoyl can be mentioned.

Examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl and iso-
Propyloxycarbonyl, tert-butyloxycarbonyl, iso-butyloxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, diethylcarbamoylethoxycarbonyl, perfluorohexylethoxycarbonyl, and 2-decyl-hexyloxycarbonylmethoxycarbonyl. Can be mentioned.

Examples of the aryloxycarbonyl group include phenoxycarbonyl and 2,4-di-tert.
-Amylphenoxycarbonyl can be mentioned.
Examples of the dialkylphosphono group include dimethylphosphono. Examples of the diarylphosphono group include diphenylphosphono. Examples of the diarylphosphinyl group include diphenylphosphinyl. Examples of the alkylsulfinyl group include 3-phenoxypropylsulfinyl. Examples of the arylsulfinyl group include 3-pentadecylphenylsulfinyl.

Examples of the alkylsulfonyl group include:
Mention may be made of methanesulfonyl and octanesulfonyl. Examples of the arylsulfonyl group include benzenesulfonyl and toluenesulfonyl. Examples of the sulfonyloxy group include methanesulfonyloxy and toluenesulfonyloxy. Examples of the acylthio group include acetylthio and benzoylthio.

As the sulfamoyl group, for example, N-
Mention may be made of ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, and N, N-diethylsulfamoyl. .. Examples of the thiocarbonyl group include methylthiocarbonyl and phenylthiocarbonyl.

The halogenated alkyl group is, for example,
Examples thereof include trifluoromethyl and heptafluoropropyl. Examples of the halogenated alkoxy group may include trifluoromethyloxy. Examples of the halogenated aryloxy group include pentafluorophenyloxy. Examples of the halogenated alkylamino group include N, N-di- (trifluoromethyl) amino. Examples of the halogenated alkylthio group include difluoromethylthio,
Mention may be made of 1,1,2,2-tetrafluoroethylthio.

Examples of the aryl group substituted with an electron-withdrawing group other than the above having a σ _p value of 0.20 or more include, for example,
2,4-dinitrophenyl, 2,4,6-trichlorophenyl and pentachlorophenyl can be mentioned.
Examples of the heterocyclic group include 2-benzoxazolyl,
2-Benzothiazolyl, 1-phenyl-2-benzimitazolyl, 5-chloro-1-tetrazolyl, 1-pyrrolyl can be mentioned. Examples of the halogen atom include a chlorine atom and a bromine atom. Examples of the azo group include phenylazo.

Typical σ _p values of electron withdrawing groups are cyano group (0.66), nitro group (0.78), trifluoromethyl group (0.54), acetyl group (0.5
0), trifluoromethanesulfonyl (0.92), methanesulfonyl group (0.72), benzenesulfonyl group (0.70), methanesulfinyl group (0.49), carbamoyl group (0.36), methoxycarbonyl group (0.45), pyrazolyl group (0.37), methanesulfonyloxy group (0.36), dimethoxyphosphoryl group (0.60), sulfamoyl group (0.57) and the like.

R ^C11 , R ^C12 and R ^C13 are preferably electron withdrawing groups having a σ _p value of 0.35 or more. Examples of these are acyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, halogenated alkyl group. , Halogenated alkyloxy groups, halogenated alkylthio groups, halogenated aryloxy groups, halogenated aryl groups, aryl groups substituted with two or more nitro groups, and heterocyclic groups. Among them, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group and a halogenated alkyl group are preferable, and a cyano group, an alkoxycarbonyl group which is unsubstituted or substituted with a fluorine atom, an alkoxycarbonyl group or a carbamoyl group, an unsubstituted or alkyl group or More preferred is an aryloxycarbonyl group substituted with an alkoxy group.

More preferably in the present invention, R ^C11 ,
At least one of R ^C12 and R ^C13 has a σ _p value of 0.60.
These are electron withdrawing groups. Examples of the electron-withdrawing group having a σ _p value of 0.60 or more include a nitro group, a cyano group, and an arylsulfonyl group. A cyano group is particularly preferable as R ^C11 .

R ^C14 and R ^C15 each independently represent a hydrogen atom or a substituent (including atoms). Examples of the substituent include a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkyl, an aryl or a heterocyclic thio group, an acyloxy group, a carbamoyloxy group, a silyloxy group. Group, sulfonyloxy group, acylamino group, alkylamino group, arylamino group, ureido group, sulfamoylamino group, alkenyloxy group, formyl group, alkyl,
Aryl or heterocyclic acyl group, alkyl, aryl or heterocyclic sulfonyl group, alkyl, aryl or heterocyclic sulfinyl group, alkyl, aryl or heterocyclic oxycarbonyl group, alkyl, aryl or heterocyclic oxycarbonylamino group, sulfonamide group, Carbamoyl group, sulfamoyl group, phosphonyl group, imido group, azolyl group, hydroxy group, cyano group,
Examples thereof include a carboxy group, a nitro group, a sulfo group and an unsubstituted amino group. The alkyl group, aryl group or heterocyclic group contained in these groups may be further substituted with the substituents exemplified for R ^C14 above.

The above-mentioned R ^C14 and R ^C15 will be described in more detail. Examples of the halogen atom include a chlorine atom and a bromine atom. Examples of the aliphatic group include a linear or branched alkyl group having 1 to 36 carbon atoms, an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, and a cycloalkenyl group. Examples of these are methyl, ethyl, propyl, isopropyl, tert-butyl, tridecyl, 2-methanesulfonylethyl, 3- (3-pentadecylphenoxy) propyl, 3- {4- {2- [4-
(4-hydroxyphenylsulfonyl) phenoxy] dodecanamide} phenyl} propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl, and 3- (2,4-di-tert-amylphenoxy) propyl).

The aryl group is preferably an aryl group having 6 to 36 carbon atoms, for example, phenyl, naphthyl, 4-hexadecyloxyphenyl, 4-tert-butylphenyl, 2,4-di-tert-amylphenyl, 4- Tetradecanamidophenyl, and 3- (2,4-tert-amylphenoxyacetamido) phenyl. Examples of the heterocyclic group include 3-pyridyl, 2-furyl and 2
-Thienyl, 2-pyridyl, 2-pyrimidinyl, and 2-benzothiazolyl. Alkoxy groups include, for example, methoxy, ethoxy, 2-methoxyethoxy, 2-dodecyloxyethoxy, and 2-methanesulfonylethoxy.

Examples of the aryloxy group include phenoxy, 2-methylphenoxy, 4-tert-butylphenoxy, 2,4-di-tert-amylphenoxy, 2-chlorophenoxy, 4-cyanophenoxy and 3-nitrophenoxy. , 3-tert-butyloxycarbamoylphenoxy, and 3-methoxycarbamoylphenoxy. Examples of the heterocyclic oxy group include 2-benzimidazolyloxy and 1-phenyltetrazole-5.
-Oxy, and 2-tetrahydropyranyloxy. Examples of the alkyl, aryl or heterocyclic thio group include methylthio, ethylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3
-Phenoxypropylthio, 3- (4-tert-butylphenoxy) propylthio, phenylthio, 2-butoxy-5-tert-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio , 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,4-triazole-6-thio, and 2-pyridylthio.

Examples of the acyloxy group include acetoxy and hexadecanoyloxy. Examples of the carbamoyloxy group include N-ethylcarbamoyloxy and N-phenylcarbamoyloxy. Examples of the silyloxy group include trimethylsilyloxy and dibutylmethylsilyloxy. Examples of the sulfonyloxy group include dodecylsulfonyloxy.

Examples of the acylamino group include acetamide, benzamide, tetradecanamide, 2-
(2,4-tert-amylphenoxyacetamide, 2-
[4- (4-Hydroxyphenylsulfonyl) phenoxy)] decanamide, isopentadecanamide, 2-
(2,4-di-tert-amylphenoxy) butanamide, and 4- (3-tert-butyl-4-hydroxyphenoxy) butanamide. Alkylamino groups include, for example, methylamino, butylamino, dodecylamino, dimethylamino, diethylamino, and methylbutylamino. Examples of the arylamino group include phenylamino, 2-chloroanilino, 2-chloro-5-tetradecanamidoanilino, N
-Acetylanilino, 2-chloro-5- [α-2-tert
-Butyl-4-hydroxyphenoxy) dodecanamide] anilino, and 2-chloro-5-dodecyloxycarbonylanilino. Examples of the ureido group include methylureido, phenylureido, N,
N-dibutyl ureido, and dimethyl ureido are mentioned.

Examples of the sulfamoylamino group include N, N-dipropylsulfamoylamino and N-methyl-N-decylsulfamoylamino. Examples of the alkenyloxy group include 2-propenyloxy. Examples of the alkyl, aryl or heterocyclic acyl group include acetyl, benzoyl, 2,4-di-tert-amylphenylacetyl, 3-
Phenylpropanoyl, and 4-dodecyloxybenzoyl. Examples of the alkyl, aryl or heterocyclic sulfonyl group include methanesulfonyl,
Octane sulfonyl, benzene sulfonyl, and toluene sulfonyl.

Examples of the sulfinyl group include octansulfinyl, dodecylsulfinyl, dodecanesulfinyl, phenylsulfinyl, 3-pentadecylphenylsulfinyl, and 3-phenoxypropylsulfinyl. Alkyl, aryl or heterocyclic oxycarbonyl groups include, for example, methoxycarbonyl, butoxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, and phenoxycarbonyl. Examples of the alkyl, aryl or heterocyclic oxycarbonylamino group include methoxycarbonylamino, tetradecyloxycarbonylamino, phenoxycarbonylamino and 2,
4-di-tert-butylphenoxycarbonylamino is mentioned.

Examples of the sulfonamide group include methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, and 2-methoxy-5-.
tert-Butylbenzenesulfonamide may be mentioned. Examples of the carbamoyl group include N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, and N- [3- (2,4- J-te
rt-Amylphenoxy) propyl] carbamoyl. Examples of the sulfamoyl group include N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylflufamoyl, and N, N-. Diethylsulfamoyl may be mentioned.

Examples of the phosphonyl group include phenoxyphosphonyl, octyloxyphosphonyl, and phenylphosphonyl. Examples of the imide group include N-succinimide, hydantoinyl, N-phthalimide, and 3-octadecenylsuccinimide. Examples of the azolyl group include imidazolyl, pyrazolyl, 3-chloro-pyrazol-1-yl,
And triazolyl.

The following are preferred as R ^C14 and R ^C15 . Alkyl group, aryl group, heterocyclic group, cyano group, nitro group, acylamino group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, Sulfamoyl group, sulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group,
Phosphonyl group, acyl group, azolyl group.

More preferably, it is an alkyl group or an allure group, and more preferably, an alkyl group or an aryl group having at least one alkoxy group, sulfonyl group, sulfamoyl group, carbamoyl group, acylamide group or sulfonamide group as a substituent. is there. Particularly preferred is an alkyl group or an aryl group having at least one acylamide group or sulfonamide group as a substituent.

X ^C11 represents a hydrogen atom or a group (hereinafter, simply referred to as “leaving group”) which leaves when the coupler reacts with the oxidation product of the aromatic primary amine color developing agent. The leaving group is a halogen atom, an aromatic azo group, or an alkyl group, an alur group or a heterocyclic group, an alkyl or arylsulfonyl group, an arylsulfinyl group which is bonded to a coupling position via an oxygen, nitrogen, sulfur or carbon atom. , Alkyl, aryl or heterocyclic carbonyl groups, and heterocyclic groups attached to the coupling position at the nitrogen atom. Examples of these include halogen atoms, alkoxy groups, aryloxy groups,
Acyloxy group, alkyl or aryl sulfonyloxy group, acylamino group, alkyl or aryl sulfonamide group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl, aryl or heterocyclic thio group, carbamoylamino group, arylsulfinyl group, arylsulfonyl Group, a 5-membered or 6-membered nitrogen-containing heterocyclic group, an imide group, and an arylazo group. The alkyl group, aryl group or heterocyclic group contained in these leaving groups may be further substituted with the substituents mentioned above for R ^C14 , and when these substituents are two or more, they are the same. Or they may be different. Further, these substituents may further have the substituents described above for R ^C14 .

The leaving group will be described in more detail.
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Alkoxy groups include, for example, ethoxy, dodecyloxy, methoxyethyl, carbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, and ethoxycarbonylmethoxy. As an aryloxy group,
Examples include 4-methylphenoxy, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarboxyphenoxy, 3-acetylaminophenoxy, and 2-carboxyphenoxy. Examples of acyloxy groups include acetoxy, tetradecanoyloxy, and benzoyloxy.

Examples of the alkyl or arylsulfonyloxy group include methanesulfonyloxy and toluenesulfonyloxy. Examples of the acylamino group include dichloroacetylamino and heptafluorobutyrylamino. Alkyl or aryl sulfonamide groups include, for example, methanesulfonamino, trifluoromethanesulfonamino, and p-toluenesulfonylamino.
Examples of the alkoxycarbonyloxy group include ethoxycarbonyloxy and benzyloxycarbonyloxy. Examples of the aryloxycarbonyloxy group include phenoxycarbonyloxy.

Examples of the alkyl, aryl or heterocyclic thio group include ethylthio, 2-carboxyethylthio, dodecylthio, 1-carboxydodecylthio, phenylthio, 2-butoxy-5-tert-octylphenylthio, and tetrazolylthio. Be done. Examples of the arylsulfonyl group include 2-butoxy-5-te.
Examples include rt-octylphenylsulfonyl. Examples of the arylsulfinyl group include 2-butoxy-5
And -tert-octylphenylsulfinyl.
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. Examples of the imide group include succinimide and hydantoinyl. Examples of the arylazo group include phenylazo,
And 4-methoxyphenylazo.

The above groups may be further substituted with the groups mentioned as the substituents for R ^C14 . Further, there is a bis-type coupler obtained by bonding a 4-equivalent coupler with an aldehyde or a ketone as a leaving group that bonds to the coupling position via a carbon atom. The leaving group of the present invention may contain a photographically useful group such as a development inhibitor and a development accelerator.

The leaving group is a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, an arylsulfonyl group, an arylsulfinyl group,
A 5-membered or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active position with a nitrogen atom is preferable, and an arylthio group is particularly preferable.

Next, the cyan coupler represented by the following formula (CbI) will be described.

[0067]

[Chemical 15]

In the above formula (CbI), R ^C21 represents a hydrogen atom or a substituent. R ^C22 represents a substituent. Z
^C21 represents a non-metal atomic group necessary for forming a nitrogen-containing 6-membered heterocycle. However, the heterocycle has at least one dissociative group. X ^C21 represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine color developing agent.

Examples of the substituents in R ^C21 and R ^C22 include the substituents mentioned above in R ^C14 . In the present invention, at least one of R ^C21 and R ^C22 is preferably an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.20 or more, and more preferably σ _p value of 0.35. The electron withdrawing group of at least 0.60 is more preferable. Particularly preferably, R ^C21 and R
^At least one of ^C22 is a cyano group. The electron-withdrawing group corresponding to the Hammett's substituent constant σ _p value is as described above in R ^C11 .

Z ^C21 represents a group of non-metal atoms necessary to form a nitrogen-containing 6-membered heterocycle. However, the heterocycle has at least one dissociative group. Examples of the four divalent linking groups constituting such a nitrogen-containing 6-membered heterocycle include, for example, -NH-, -N (R)-, -N =, -CH (R)-,-.
CH =, -C (R) =, -CO-, -S-, -SO-,
—SO ₂ — (R represents a substituent, and
Substituents listed in ^C14 may be mentioned). Examples of the dissociative group include those having an acidic proton such as -NH- and -CH (R)-. Preferably, the pKa in water is 3 to 1
It has a value of 2. X ^C21 has the same ^meaning as X ^C11 described above.

The coupler represented by the above formula (CbI) is
Those represented by the following formulas (CbII) to (CbXIX) are preferable, and couplers represented by the formulas (CbII), (CbIII) or (CbVIII) are more preferable.

[0072]

[Chemical 16]

[0073]

[Chemical 17]

In the above formula, R ^C21 , R ^C22 and X
^C21 has the same meaning as in formula (CbI).
R ^C23 , R ^C25 , R ^C26 , R ^C27 and R ^C28 each represent a hydrogen atom or a substituent, and R ^C24 represents a substituent. EW
G represents an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.35 or more. R ^C23 , R ^C24 , R ^C25 , R ^C26 , R
Substituents for ^C27 and R ^C28 are the same as those mentioned above for R ^C14 . The electron-withdrawing group represented by EWG is the same as those listed for R ^C11 above.

In the cyan coupler represented by the formula (CaI) or (CbI), each substituent on the mother nucleus has the formula (CaI).
I) or (CbI) is contained in the cyan coupler skeleton to form a dimer or higher polymer, or a polymer chain is contained to form a homopolymer or a copolymer. May be. The homopolymer or copolymer containing a polymer chain means an addition polymer having a cyan coupler residue represented by the formula (CaI) or (CbI), a homopolymer or copolymer of an ethylenically unsaturated compound. Is a typical example.
In this case, one or more kinds of the cyan color-forming repeating unit having a cyan coupler residue represented by the formula (CaI) or (CbI) may be contained in the polymer, and an acrylic ester may be contained as a copolymerization component. A methacrylic acid ester, a maleic acid ester, or a copolymer containing one or more non-color-forming ethylene type monomers that do not couple with the oxidation product of an aromatic primary amine color developing agent. Good.

Specific examples of the coupler represented by the formula (CaI) are shown below. The substituents used in these specific examples are as follows.

[0077]

[Chemical 18]

[0078]

[Chemical 19]

[0079]

[Chemical 20]

[0080]

[Chemical 21]

[0081]

[Chemical formula 22]

[0082]

[Chemical formula 23]

[0083]

[Table 1] Table 1 ──────────────────────────────────── CaII R ^C11 R ^C12 R ^C14 R ^C15 X ^C11 ──────────────────────────────────── 1 (9) (4) (4) ( 49) (1) 2 (4) (18) (9) (25) (1) 3 (16) (4) (4) (48) (1) 4 (4) (20) (8) (25) (37) 5 (18) (4) (4) (25) (28) 6 (4) (40) (11) (25) (1) ──────────────── ─────────────────────

[0084]

[Chemical formula 24]

[0085]

[Table 2] Table 2 ──────────────────────────────────── CaIII R ^C11 R ^C12 R ^C14 X ^C11 ──────────────────────────────────── 1 (8) (4) (46) (1) 2 (4) (18) (26) (1) 3 (4) (20) (25) (1) 4 (4) (36) (25) (1) 5 (4) (35) (25) ( 1) 6 (4) (19) (25) (1) 7 (4) (13) (46) (1) 8 (4) (23) (47) (28) 9 (4) (13) (27) ) (29) 10 (4) (17) (50) (30) 11 (4) (35) (27) (32) 12 (4) (16) (42) (24) 13 (4) (12) (43) (34) 14 (4) (9) (52) (33) ─────────────────────────────── ─────

[0086]

[Chemical 25]

[0087]

[Table 3] Table 3 ──────────────────────────────────── CaIV R ^C11 R ^C12 R ^C15 X ^C11 ──────────────────────────────────── 1 (9) (4) (49) (2) 2 (4) (18) (45) (1) 3 (4) (13) (39) (31) 4 (4) (35) (51) (34) 5 (4) (38) (14) ( 37) 6 (4) (20) (25) (1) 7 (4) (15) (50) (2) 8 (4) (22) (48) (10) ────────── ────────────────────────────

[0088]

[Chemical formula 26]

[0089]

[Table 4] Table 4 ──────────────────────────────────── Ca V R ^C11 R ^C12 X ^C11 ──────────────────────────────────── 1 (4) (21) (1) ──── ────────────────────────────────

[0090]

[Chemical 27]

[0091]

[Table 5] Table 5 ──────────────────────────────────── CaVI R ^C11 R ^C12 R ^C13 R ^C14 R ^C15 X ^C11 ──────────────────────────────────── 1 (4) (9) (5 ) (51) (3) (11) ─────────────────────────────────────

[0092]

[Chemical 28]

[0093]

[Table 6] Table 6 ──────────────────────────────────── CaVII R ^C11 R ^C12 R ^C13 R ^C14 X ^C11 ──────────────────────────────────── 1 (5) (4) (4) ( 42) (1) 2 (5) (4) (4) (44) (31) ────────────────────────────── ───────

[0094]

[Chemical 29]

[0095]

[Table 7] Table 7 ──────────────────────────────────── CaVIII R ^C11 R ^C12 R ^C13 R ^C15 X ^C11 ──────────────────────────────────── 1 (9) (4) (4) ( 44) (1) ─────────────────────────────────────

[0096]

[Chemical 30]

[0097]

[Table 8] Table 8 ──────────────────────────────────── CaIX R ^C11 R ^C12 R ^C13 X ^C11 ──────────────────────────────────── 1 (4) (18) (4) (1) 2 (4) (41) (4) (10) ─────────────────────────────────────

Specific examples of the coupler represented by the formula (CbI) are shown below. The substituents used in these specific examples are as follows.

[0099]

[Chemical 31]

[0100]

[Chemical 32]

[0101]

[Chemical 33]

[0102]

[Chemical 34]

[0103]

[Chemical 35]

[0104]

[Chemical 36]

[0105]

[Chemical 37]

[0106]

[Chemical 38]

[0107]

[Table 9] Table 9 ──────────────────────────────────── CbII R ^C21 R ^C22 R ^C23 R ^C24 X ^C21 ──────────────────────────────────── 1 (14) (31) (13) ( 21) (1) 2 (14) (31) (13) (21) (3) 3 (88) (31) (22) (21) (3) 4 (42) (31) (12) (21) (3) 5 (12) (31) (15) (21) (3) 6 (31) (31) (19) (21) (3) 7 (31) (31) (20) (21) (3 ) 8 (16) (40) (13) (21) (1) 9 (9) (31) (14) (21) (3) 10 (8) (31) (14) (21) (3) 11 (43) (43) (13) (23) (3) 12 (14) (31) (19) (23) (74) 13 (25) (31) (19) (23) (77) 14 (14 ) (45) (67) (23) (79) 5 (25) (31) (66) (23) (83) 16 (14) (31) (68) (23) (91) ─────────────────── ──────────────────

[0108]

[Chemical Formula 39]

[0109]

[Table 10] Table 10 ──────────────────────────────────── CbIII R ^C21 R ^C22 R ^C23 R ^C26 X ^C21 ──────────────────────────────────── 1 (14) (31) (44) ( 21) (1) 2 (14) (31) (44) (21) (3) 3 (14) (31) (44) (1) (1) 4 (18) (31) (45) (1) (3) 5 (31) (31) (45) (1) (3) 6 (31) (31) (42) (1) (1) 7 (14) (31) (37) (1) (3 ) 8 (15) (31) (38) (1) (3) 9 (16) (31) (39) (1) (3) 10 (43) (43) (39) (1) (3) 11 (31) (43) (44) (1) (3) 12 (45) (31) (44) (1) (3) 13 (7) (31) (44) (72) (3) 14 (14 ) (31) (38) 72) (3) 15 (10) (44) (1) (69) (3) 16 (87) (31) (44) (1) (82) 17 (14) (31) (44) (1) (83) 18 (88) (31) (38) (1) (76) 19 (14) (31) (37) (1) (80) 20 (14) (31) (40) (1) (91 ) ────────────────────────────────────

[0110]

[Chemical 40]

[0111]

[Table 11] Table 11 ──────────────────────────────────── CbIV R ^C21 R ^C22 R ^C24 X ^C21 ──────────────────────────────────── 1 (14) (31) (13) (1) 2 (25) (31) (19) (3) 3 (43) (31) (28) (80) 4 (31) (14) (27) (83) ──────────── ─────────────────────────

[0112]

[Chemical 41]

[0113]

[Table 12] Table 12 ──────────────────────────────────── Cb V R ^C21 R ^C22 R ^C23 X ^C21 ──────────────────────────────────── 1 (14) (31) (13) (1 ) 2 (25) (31) (20) (3) 3 (43) (31) (30) (79) 4 (31) (14) (29) (84) ─────────── ───────────────────────────

[0114]

[Chemical 42]

[0115]

[Table 13] Table 13 ──────────────────────────────────── CbVI R ^C21 R ^C22 R ^C23 X ^C21 ──────────────────────────────────── 1 (14) (31) (28) (1) 2 (25) (31) (27) (3) 3 (43) (31) (19) (81) 4 (31) (14) (12) (82) ──────────── ─────────────────────────

[0116]

[Chemical 43]

[0117]

[Table 14] Table 14 ──────────────────────────────────── CbVII R ^C21 R ^C22 R ^C26 X ^C21 ──────────────────────────────────── 1 (14) (31) (9) (1) 2 (25) (31) (13) (3) 3 (43) (31) (27) (80) 4 (31) (14) (28) (85) ──────────── ─────────────────────────

[0118]

[Chemical 44]

[0119]

[Table 15] Table 15 ──────────────────────────────────── CbVIII R ^C21 R ^C22 R ^C25 X ^C21 ──────────────────────────────────── 1 (14) (31) (29) (1) 2 (8) (31) (14) (1) 3 (37) (31) (21) (1) 4 (49) (31) (21) (3) 5 (25) (37) (21) ( 1) 6 (31) (31) (8) (1) 7 (14) (38) (21) (1) 8 (42) (42) (14) (1) 9 (13) (31) (14 ) (1) 10 (14) (31) (13) (74) 11 (14) (31) (9) (75) 12 (14) (31) (8) (76) 13 (31) (14) (13) (78) 14 (31) (31) (12) (79) 15 (42) (14) (19) (80) 16 (42) (31) (20) (81) 17 (14) ( 31) (8) (82 18 (31) (31) (8) (83) 19 (14) (31) (19) (84) 20 (31) (14) (9) (91) ──────────── ──────────────────────────

[0120]

[Chemical 45]

[0121]

[Table 16] Table 16 ──────────────────────────────────── CbIX R ^C21 R ^C22 R ^C27 R ^C28 X ^C21 ──────────────────────────────────── 1 (14) (31) (27) ( 27) (1) 2 (25) (31) (27) (27) (3) 3 (43) (31) (28) (28) (81) 4 (31) (14) (28) (28) (84) ─────────────────────────────────────

[0122]

[Chemical 46]

[0123]

[Table 17] Table 17 ──────────────────────────────────── Cb X R ^C21 R ^C22 R ^C23 R ^C24 EWG X ^C21 ───────────────────────────────────── 1 (14) (31) (13 ) (21) (31) (1) 2 (25) (31) (19) (23) (31) (3) 3 (43) (31) (67) (23) (43) (79) 4 ( 31) (14) (62) (23) (31) (82) ────────────────────────────────── ───

[0124]

[Chemical 47]

[0125]

[Table 18] Table 18 ──────────────────────────────────── CbXI R ^C21 R ^C22 R ^C23 R ^C26 EWG X ^C21 ──────────────────────────────────── 1 (14) (31) (44) (21) (31) (1) 2 (25) (31) (45) (1) (43) (3) 3 (43) (31) (44) (72) (31) (80) 4 (31 ) (14) (1) (69) (31) (83) ─────────────────────────────────── ──

[0126]

[Chemical 48]

[0127]

[Table 19] Table 19 ──────────────────────────────────── CbXII R ^C21 R ^C22 R ^C24 EWG X ^C21 ──────────────────────────────────── 1 (14) (31) (19) (43 ) (1) 2 (25) (31) (13) (31) (3) 3 (43) (31) (27) (31) (81) 4 (31) (14) (28) (43) ( 84) ────────────────────────────────────

[0128]

[Chemical 49]

[0129]

[Table 20] Table 20 ──────────────────────────────────── CbXIII R ^C21 R ^C22 R ^C23 EWG X ^C21 ──────────────────────────────────── 1 (14) (31) (20) (31 ) (1) 2 (25) (31) (13) (31) (3) 3 (43) (31) (24) (43) (79) 4 (31) (14) (30) (31) ( 85) ────────────────────────────────────

[0130]

[Chemical 50]

[0131]

[Table 21] Table 21 ──────────────────────────────────── CbXIV R ^C21 R ^C22 R ^C23 EWG X ^C21 ──────────────────────────────────── 1 (14) (31) (19) (31 ) (1) 2 (25) (31) (12) (43) (3) 3 (43) (31) (27) (31) (80) 4 (31) (14) (28) (31) ( 82) ────────────────────────────────────

[0132]

[Chemical 51]

[0133]

[Table 22] Table 22 ──────────────────────────────────── CbXV R ^C21 R ^C22 R ^C26 EWG X ^C21 ──────────────────────────────────── 1 (14) (31) (13) (43 ) (1) 2 (25) (31) (9) (31) (3) 3 (43) (31) (28) (31) (87) 4 (31) (14) (27) (43) ( 83) ────────────────────────────────────

[0134]

[Chemical 52]

[0135]

[Table 23] Table 23 ──────────────────────────────────── CbXVI R ^C21 R ^C22 R ^C25 EWG X ^C21 ──────────────────────────────────── 1 (14) (31) (8) (31 ) (1) 2 (25) (31) (9) (31) (3) 3 (43) (31) (13) (43) (79) 4 (31) (14) (19) (31) ( 84) ────────────────────────────────────

[0136]

[Chemical 53]

[0137]

[Table 24] Table 24 ──────────────────────────────────── CbXVII R ^C21 R ^C22 R ^C27 R ^C28 EWG X ^C21 ───────────────────────────────────── 1 (14) (31) (27) (27) (31) (1) 2 (25) (31) (27) (27) (43) (3) 3 (43) (31) (28) (28) (31) (80) 4 (31 ) (14) (28) (28) (31) (85) ────────────────────────────────── ──

[0138]

[Chemical 54]

[0139]

[Table 25] Table 25 ──────────────────────────────────── CbXVIII R ^C21 R ^C22 R ^C23 R ^C24 X ^C21 ──────────────────────────────────── 1 (14) (31) (13) ( 21) (1) 2 (25) (31) (28) (21) (3) 3 (43) (31) (19) (23) (81) 4 (31) (14) (67) (23) (83) ────────────────────────────────────

[0140]

[Chemical 55]

[0141]

[Table 26] Table 26 ──────────────────────────────────── CbXIX R ^C21 R ^C22 R ^C23 R ^C26 X ^C21 ──────────────────────────────────── 1 (14) (31) (44) ( 21) (1) 2 (25) (31) (45) (1) (3) 3 (43) (31) (38) (72) (79) 4 (31) (14) (40) (1) (84) ─────────────────────────────────────

The compound according to the present invention and the intermediate thereof can be synthesized by a known method. For example, J.Am.Chem.Soc., 80,5332 (1958), J.Ame.Chem., 81
No., 2452 (1959), J. Am. Chem. Soc., 112, 2465 (1990), Or
g.Synth., I 270 (1941), J.Chem.Soc., 5149 (1962), Hetr
ocyclic., 27, 2301 (1988), Rec.Trav.chim., 80,1075
It can be synthesized by the method described in (1961) and the like, the literature cited therein or a similar method.

Next, a specific synthesis example will be shown.

(Synthesis Example 1) The exemplified compound (CaIII-2) was synthesized by the following route.

[0145]

[Chemical 56]

2-Amino-4-cyano-3-methoxycarbonylpyrrole (1a) (66.0 g, 0.4 mol)
3,5-dichlorobenzoyl chloride (2a) (83.2 g, 0.4 mol) was added to the dimethylacetamide (300 ml) solution of the above at room temperature, and the mixture was stirred for 30 minutes. Water was added to this and extraction was performed twice with ethyl acetate.
The organic layers were collected, washed with water and saturated saline, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was recrystallized from acetonitrile (300 ml) to obtain compound (3a) (113 g, 84%).

Compound (3a) (101.1 obtained above)
Powder of potassium hydroxide (252 g, 4.5 mol) was added to a dimethylformamide (200 ml) solution of g, 0.3 mol) at room temperature and stirred well. Hydroxylamine-0-sulfonic acid (237 g,
2.1 mol), be careful not to raise the temperature suddenly,
It was added little by little and stirred for 30 minutes after the addition. Further 0.1N
A hydrochloric acid aqueous solution was added dropwise to neutralize while observing the pH test paper.
The obtained solution was extracted three times with ethyl acetate, the organic layer was washed with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (developing solvent; hexane: ethyl acetate = 2: 1) to give compound (4a) (9.50 g, 9%).

The compound (4a) thus obtained (7.04 g, 2)
Carbon tetrachloride (9 cc) was added to an acetonitrile (30 ml) solution of (0 mmol) at room temperature, triphenylphosphine (5.76 g, 22 mmol) was subsequently added, and the mixture was heated under reflux for 8 hours. After cooling, water was added and the mixture was extracted 3 times with ethyl acetate. The organic layer was washed with water and saturated saline and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and silica gel column chromatography (developing solvent;
Purification with hexane: ethyl acetate = 4: 1) gave compound (5a) (1.13 g, 17%).

1.8 g of the obtained compound (5a) and 2-
12.4 g of octyl octanol (6a) was dissolved in 2.0 ml of sulfolane, and 1.5 g of titanium isopropoxide was further added. After keeping the reaction temperature at 110 ° C. and reacting for 1.5 hours, ethyl acetate was added and the mixture was washed with water. After drying the ethyl acetate layer, it was distilled off,
The residue was purified by column chromatography to obtain 1.6 g of the desired exemplary compound (CaIII-2).

(Synthesis Example 2) Exemplified compound (CbIII-3) was synthesized by the following route.

[0151]

[Chemical 57]

2-Amino-3-cyano-4-phenylpyrrole (Compound a) 1 obtained by condensing 2-aminoacetophenone hydrochloride and malononitrile in the presence of an alkali.
8.3 g and diethyl ethoxyethylidene malonate 2
5.3 g of ethanol was dispersed in 300 ml of ethanol, 22.0 ml of a 28% methanol solution of sodium methylate was added thereto, and the mixture was heated under reflux for 5 hours. After cooling, ethyl acetate was added, the mixture was washed with water, the organic solvent was concentrated, and the precipitated crystals were collected by filtration to obtain 11.6 g of compound b. Then, 50 ml of 2-hexyldecanol and 2.0 g of Ti (Oi-Pr) ₄ were added thereto, and the mixture was heated at an oil bath temperature of 130 to 140 ° C for 6 hours. After cooling, the product was purified by silica gel chromatography (developing solvent; hexane: ethyl acetate = 1: 1) to obtain 14.7 g of the desired exemplary compound (CbIII-3) as a pale yellow oily substance.

The above cyan couplers may be used alone or in combination of two or more. Also, it may be used in combination with other known couplers. The above formula (CaI)
Alternatively, the amount of the cyan coupler represented by (CbI) used in the light-sensitive material is 1 × 10 ⁻⁵ per 1 m ² of the light-sensitive material.
It ranges from 1 mol to 1 × 10 ^-2 mol, preferably 1 ×.
The range of 10 ⁻⁴ mol to 5 × 10 ⁻² mol, more preferably,
It is in the range of 2 × 10 ⁻⁴ mol to 1 × 10 ⁻³ mol.

The magenta coupler which is preferable as the color image-forming coupler contained in the green-sensitive layer of the direct positive color photographic light-sensitive material of the present invention will be described below. This magenta coupler is a magenta coupler represented by the following formula (M).

[0155]

[Chemical 58]

[Wherein, R ^M represents a hydrogen atom or a substituent, and Z ^M is necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms together with the carbon atom and the nitrogen atom to be bonded. Represents a non-metal atom group, the azole ring may have a substituent (including a condensed ring), and X ^M is a hydrogen atom or a group capable of splitting off during a coupling reaction with an oxidized product of a developing agent. Represents]. Among the magenta couplers represented by the formula (M), a particularly preferable magenta coupler is represented by the following formula (M
-I) having a 1 H -imidazo [1,2- b ] pyrazole skeleton, represented by the following formula (M-II)
H -pyrazolo [1,5- b ] [1,2,4] triazole skeleton, 1 represented by the following formula (M-III)
H -pyrazolo [5,1- c ] [1,2,4] triazole skeleton, 1 H represented by the following formula (M-IV)
-A compound having a pyrazolo [1,5- d ] tetrazole skeleton and a compound having a 1 H -pyrazolo [1,5- a ] benzimidazole skeleton represented by the following formula (MV).

[0157]

[Chemical 59]

The above formulas (M-I), (M-II), (M-II)
I), (M-IV) and (M-V) in each formula R ^M1 ,
R ^M2 , R ^M3 , R ^M4 , n ^M and X ^M will be described in detail. R ^M1 is a hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, hydroxy group, nitro group, carboxy group, sulfo group, amino group, alkoxy group, aryloxy group, acylamino group, alkylamino group. Group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group,
Sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, allyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxy It represents a carbonyl group, an acyl group, or an azolyl group, and R ^M1 may be a divalent group to form a bis form.

More specifically, R ^M1 is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom), an alkyl group (eg, a straight chain or branched chain alkyl group having 1 to 32 carbon atoms, an aralkyl group, an alkenyl group). Group, alkynyl group, cycloalkyl group, cycloalkenyl group, and specifically, for example, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3-
(3-Pentadecylphenoxy) propyl, 3- {4-
{2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecanamide} phenyl} propyl, 2-
Ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl); aryl groups (eg phenyl, 4-t-butylphenyl, 2,4-di-t-amyl Phenyl, 2,
4,6-Trimethylphenyl, 3-tridecanamide-
2,4,6-trimethylphenyl, 4-tetradecanamidophenyl); a heterocyclic group (for example, 2-furyl, 2
-Thienyl, 2-pyrimidinyl, 2-benzothiazolyl); cyano group, hydroxy group, nitro group, carboxy group, sulfo group, amino group, alkoxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy, 2 -Methanesulfonylethoxy); an aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3
-Methoxycarbamoyl); an acylamino group (for example,
Acetamide, benzamide, tetradecanamide, 2
-(2,4-di-t-amylphenoxy) butanamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide; alkylamino group (Eg, methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino); anilino group (eg, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino, 2
-Chloro-5-dodecyloxycarbonylanilino, N
-Acetylanilino, 2-chloro-5- {2- (3-t
-Butyl-4-hydroxyphenoxy) dodecanamide} anilino); ureido group (for example, phenylureido, methylureido, N, N-dibutylureido); sulfamoylamino group (for example, N, N-dipropylsulfamoylamino) , N-methyl-N-decylsulfamoylamino); alkylthio group (for example, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3- (4-
t-butylphenoxy) propylthio); an arylthio group (for example, phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio,
2-carboxyphenylthio, 4-tetradecanamidophenylthio); alkoxycarbonylamino group (for example, methoxycarbonylamino, tetradecyloxycarbonylamino); sulfonamide group (for example, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy-5-t-butylbenzenesulfonamide); a carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl). Carbamoyl, N-methyl-N-dodecylcarbamoyl, N- {3
-(2,4-di-t-amylphenoxy) propyl} carbamoyl); a sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl,
N- (2-dodecyloxyethyl) sulfamoyl, N
-Ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl); sulfonyl group (eg, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl); alkoxycarbonyl group (eg, methoxycarbonyl, butyloxycarbonyl) , Dodecyloxycarbonyl, octadecyloxycarbonyl); heterocyclic oxy group (for example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy); azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pi) Valoylaminophenylazo,
2-hydroxy-4-propanoylphenylazo); acyloxy group (eg acetoxy); carbamoyloxy group (eg N-methylcarbamoyloxy, N-
Phenylcarbamoyloxy); silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy); aryloxycarbonylamino group (eg,
Phenoxycarbonylamino); imide group (eg, N
-Succinimide, N-phthalimide, 3-octadecenylsuccinimide); heterocyclic thio group (for example, 2-
Benzothiazolylthio, 2,4-diphenoxy-1,
3,5-triazole-6-thio, 2-pyridylthio); sulfinyl group (eg, dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl); phosphonyl group (eg, phenoxyphosphonyl, octyloxyphosphonyl) , Phenylphosphonyl); aryloxycarbonyl groups (eg phenoxycarbonyl); acyl groups (eg acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl); or azolyl groups (eg imidazolyl, pyrazolyl, 3 -Chloropyrazol-1-yl, triazolyl).

Among these substituents, the group capable of further having a substituent may have an organic substituent or a halogen atom linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. Good. Among these substituents, preferred R ^M1 is an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, a ureido group,
Examples thereof include urethane group and acylamino group.

R ^M2 is a group similar to the substituents exemplified for R ^M1 , and preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfinyl group, Examples thereof include an acyl group and a cyano group. R ^M3 is R ^M1
Is a group similar to the substituents exemplified for, preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group,
Examples thereof include an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, a carbamoyl group and an acyl group, and more preferably,
Examples thereof include an alkyl group, an aryl group, a heterocyclic group, an alkylthio group and an arylthio group. Also, R
^M4 is a group similar to the substituents exemplified for R ^M1 ,
Preferably, hydrogen atom, alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, sulfonyl group, acyl group, acylamino group, alkoxycarbonylamino group, sulfonamide group. , Sulfamoylamino group, cyano group and the like.

N represents an integer of 1 to 4, preferably 1 to 3. X ^M represents a hydrogen atom or a group capable of splitting off during a coupling reaction with an oxidized product of a developing agent (particularly, an aromatic primary amine color developing agent). Examples of the splittable group include a halogen atom and an alkoxy group. , Aryloxy group, acyloxy group, alkyl or aryl sulfonyloxy group, acylamino group, alkyl or aryl sulfonamide group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl, aryl or heterocyclic thio group, carbamoylamino group, 5 And 6-membered nitrogen-containing heterocyclic groups, imide groups, arylazo groups, etc., and these groups may be further substituted with the groups exemplified as the substituents of R ^M1 . More specifically, the group capable of splitting off in the reaction with the oxidized product of the developing agent represented by X ^M includes a halogen atom (eg, fluorine atom, chlorine atom, bromine atom); an alkoxy group (eg, ethoxy, Dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, ethoxycarbonylmethoxy); aryloxy group (for example, 4-methylphenoxy, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxy) Carbonylphenoxy, 4-methoxycarbonylphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy); acyloxy groups (eg acetoxy, tetradecanoyloxy, benzoyloxy); alkyl or arylsulfonyl groups Si group (for example, methanesulfonyloxy, toluenesulfonyloxy); Acylamino group (for example, dichloroacetylamino, heptafluorobutyrylamino); Alkyl or aryl sulfonamide group (for example, methanesulfonamino, trifluoromethanesulfonamino, p -Toluenesulfonylamino); an alkoxycarbonyloxy group (for example, ethoxycarbonyloxy, benzyloxycarbonyloxy); an aryloxycarbonyloxy group (for example, phenoxycarbonyloxy); an alkyl, aryl or heterocyclic thio group (for example, dodecylthio,
1-carboxydodecylthio, phenylthio, 2-butoxy-5-t-octylphenylthio, 2-benzyloxycarbonylaminophenylthio, tetrazolylthio); carbamoylamino group (for example, N-methylcarbamoylamino, N-phenylcarbamoylamino) ;
5- or 6-membered nitrogen-containing heterocyclic group (for example, 1-imidazolyl, 1-pyrazolyl, 1,2,4-triazol-1-yl, tetrazolyl, 3,5-dimethyl-1-
Pyrazolyl, 4-cyano-1-pyrazolyl, 4-methoxycarbonyl-1-pyrazolyl, 4-acetylamino-
1-pyrazolyl, 1,2-dihydro-2-oxo-1-
Pyridyl); imide groups (eg succinimide, hydantoinyl); arylazo groups (eg phenylazo, 4-methoxyphenylazo) and the like.

In addition to these, X ^M is a leaving group bonded via a carbon atom, which is an aldehyde or a ketone.
It may take the form of a bis-type coupler obtained by condensing an equal amount of coupler. Further, X ^M may contain a photographically useful group such as a development inhibitor and a development accelerator. Preferred as X ^M are a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, and a 5-membered or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active position with a nitrogen atom. A halogen atom, a substituted aryloxy group, a substituted arylthio group,
Alternatively, it is a substituted 1-pyrazolyl group.

Specific examples of the magenta coupler represented by the formula (M) are shown below, but the invention is not limited to these compounds.

[0165]

[Chemical 60]

[0166]

[Chemical formula 61]

[0167]

[Chemical formula 62]

[0168]

[Chemical 63]

[0169]

[Chemical 64]

[0170]

[Chemical 65]

[0171]

[Chemical 66]

[0172]

[Chemical 67]

[0173]

[Chemical 68]

[0174]

[Chemical 69]

[0175]

[Chemical 70]

[0176]

[Chemical 71]

[0177]

[Chemical 72]

[0178]

[Chemical formula 73]

[0179]

[Chemical 74]

[0180]

[Chemical 75]

[0181]

[Chemical 76]

[0182]

[Chemical 77]

[0183]

[Chemical 78]

[0184]

[Chemical 79]

[0185]

[Chemical 80]

[0186]

[Chemical 81]

[0187]

[Chemical formula 82]

[0188]

[Chemical 83]

[0189]

[Chemical 84]

[0190]

[Chemical 85]

[0191]

[Chemical formula 86]

[0192]

[Chemical 87]

[0193]

[Chemical 88]

The magenta coupler represented by the formula (M) is
It can be synthesized by the synthetic method described in the following documents. For example, the compound represented by the formula (M-I) is described in U.S. Pat. No. 4,500,630, and the compound represented by the formula (M-II) is disclosed in U.S. Pat. Nos. 4,540,654 and 4,705,863.
61-65245, 62-209457, 62-249155 and the like disclose compounds represented by the formula (M-III) in JP-B-47.
-27411 and U.S. Pat. No. 3,725,067, the formula (M-
The compounds represented by IV) can be synthesized by the synthetic methods described in JP-A-60-33552 and the like.

The magenta coupler represented by the above formula (M) may be used alone or in combination of two or more kinds. Furthermore, these magenta couplers,
You may use it, mixing with another well-known magenta coupler. The amount of the magenta coupler represented by the above formula (M) used in the photosensitive material is 1 × 10 ⁻⁵ per 1 m ² of the photosensitive material.
It is generally in the range of 1 to 10 × ² mol, preferably 1 × 10 ⁻⁴ to 10 ⁻³ mol, more preferably 2 × 1.
It is in the range of 0 ^-4 mol to 10 ^-3 mol.

The pre-fogged internal latent image type silver halide emulsion of the present invention is an emulsion in which the surface of silver halide grains is not fogged and which contains a silver halide which mainly forms a latent image inside the grains. However, more specifically, a certain amount of silver halide emulsion (0.5
To 3 g / m ²⁾ was applied, the following developer giving exposure at fixed time of 0.01 to 10 seconds to in (internal developer), 20 ° C., conventional photographic density when developed 5 minutes The maximum density measured by the measuring method is the maximum obtained when a silver halide emulsion coated in the same amount as above and exposed in the same manner is developed at 18 ° C. for 6 minutes in the following developer (surface type developer). Those having a concentration of at least 5 times greater than the concentration are preferred, and those having a concentration of at least 10 times greater are preferred.

Internal type developer Metol 2.0 g Sodium sulfite (anhydrous) 90.0 g Hydroquinone 8.0 g Sodium carbonate (monohydrate) 52.8 g KBr 5.0 g KI 0.5 g Water-added 1000 ml Surface type developer metol 2.5 g L-ascorbic acid _{10.0g NaBO 2 · 4H 2 O 35.0g} KBr 1.0g water to make 1000ml

Specific examples of the internal latent image type silver halide emulsion include, for example, conversion type silver halide emulsions described in US Pat. No. 2,592,250; or US Pat. Nos. 3,761,276, 3,850,637 and 3,923,513. , 4035185 and 43954.
78, 4504570, JP-A-52-1
No. 156614, No. 55-127549, No. 53-6
0222, 56-22681, 59-2085
No. 40, No. 60-107641, No. 61-1337.
No. 62-215272, German Patent No. 2332802c2, Research Disclosure No. 23510 (issued in November 1983), page 236; specification of U.S. Pat. No. 4,789,627, further having a silver chloride shell; JP-A-63-10160 relating to silver chlorobromide core-shell emulsions;
JP-A-63-47766 and Japanese Patent Application No. 1-24
No. 67; Japanese Patent Application Laid-Open No. 63-191145 and Japanese Patent Application Laid-Open No. 1-5214 relating to emulsions doped with metal ions.
Examples thereof include core / shell type silver halide emulsions described in JP-A No. The internal latent image type silver halide grains which have not been fogged in the present invention are preferably core / shell type. The internal latent image type core / shell silver halide emulsion has a silver halide core / shell molar ratio of 20/1 or less and 1/10.
0 or more is particularly preferable.

The internal latent image type silver halide grains which have not been fogged beforehand include Mn, Cu, Zn, Cd, Pb and Bi.
Alternatively, at least one metal selected from the group consisting of metals belonging to Group VIII of the periodic table may be incorporated. The amount of Mn, Cu, Zn, Cd, Pb, Bi or a metal belonging to Group VIII of the periodic table contained in the internal latent image type silver halide grains not previously fogged is 10 ⁻ per mol of silver halide. ⁹ to 10 ^-2 mol is preferred, 10
^-7 to 10 ^-3 mol is more preferable. P among the above metals
The use of b (lead), Ir (iridium), Bi (bismuth) and Rh (rhodium) is preferred. These metals are mixed reaction liquid in the form of a solution in which the metal (metal ion) is dissolved in an aqueous solution or an organic solvent when silver halide grains are formed while mixing and stirring a silver ion solution and an aqueous halogen solution. It can be incorporated in the silver halide grains by adding it (or coexisting in an aqueous halogen solution). Alternatively, after the silver halide grains are formed, they can be incorporated in the emulsion in the form of an aqueous solution of the above metal or a solution of the above metal dissolved in an organic solvent. In this case, it may be further covered with silver halide. The above metal is usually added in the form of a complex salt of the metal or a metal compound such as an oxyacid salt or an organic acid salt of the metal. For the method of incorporating these metals, see US Pat. Nos. 3,761,276 and 4,
395478 and JP-A-59-216136
It is described in Japanese Patent Publication No.

The silver halide grains used in the present invention have a cubic shape, an octahedron shape, a dodecahedron shape and a tetradecahedron shape (JP-A-2-22).
3948), an irregular crystal form such as a sphere, and JP-A-1-131547.
Emulsions in which tabular grains having a length / thickness ratio value of 5 or more, particularly 8 or more, which occupy 50% or more of the total projected area of the grains, may be used. .. Further, it may be an emulsion having a complex form of these various crystal systems, or an emulsion comprising a mixture thereof. The composition of silver halide includes silver chloride, silver bromide, and mixed silver halide, and the silver halide preferably used in the present invention does not contain silver iodide or may contain silver iodide. 3 mol%
The following are silver (iodo) silver bromide, (iodo) silver chloride or (iodo) silver bromide. The average grain size of the silver halide grains (the grain diameter in the case of spherical grains or grains close to spheres, the vertical length in the case of cubic grains, and the average length based on the projected surface) is 1.5 μm. Hereinafter, 0.1 μm or more is preferable, but 1.2 μm or less is particularly preferable,
It is 0.2 μm or more. The particle size distribution may be narrow or wide, but in order to improve graininess, sharpness, etc., the number or weight of particles is within ± 40% of the average particle size, preferably within 30%, and most preferably ±. It is preferred to use in the invention so-called "monodisperse" silver halide emulsions with a narrow grain size distribution such that 90% or more, especially 95% or more of all grains fall within 20%.

In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes or emulsions having the same size are used in the emulsion layers having substantially the same color sensitivity. It is possible to mix a plurality of different particles in the same layer or to coat multiple layers in different layers. Furthermore, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be mixed or laminated and used.

The silver halide emulsion used in the present invention is preferably chemically sensitized in the inside or the surface of the grain by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization or the like alone or in combination. The chemical sensitization method for core particles is described in JP-A-2-199450 and JP-A-2-199449.
The method described in the publication can be used. JP-A-1-
In the presence of a mercapto compound as described in JP-A-197742, JP-A-1-254946 and JP-A-2-6.
You may add thiosulfinic acid, a sulfinic acid, and a sulfite as described in 9738 and 2-273735 gazette. For specific examples, see Research Disclosure No. 17643-III (issued in December 1978), page 23, etc.

The photographic emulsion used in the present invention is spectrally sensitized with a photographic sensitizing dye in a conventional manner. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes, and these dyes can be used alone or in combination. Further, the above dye and supersensitizer may be used in combination. For more specific examples, see Research
Disclosure magazine No. 17643-IV (197
Issued in December, 1996) See patents on pages 23-24. The photographic emulsion used in the present invention may contain an antifoggant or stabilizer for the purpose of preventing fog during the production process of a light-sensitive material, storage or photographic processing, or stabilizing photographic performance. For a detailed example,
For example, Research Disclosure No. 1764
3-VI (issued in December 1978) and E.I. J. B
irr by "Stabiliaution of Photographic Silver Hai
lde Emulsion "(Focal Press), published in 1974.

In the present invention, the above formula (CaI) is used.
Or a cyan coupler represented by (CbI) and a formula (M)
In addition to the magenta coupler represented by, various color couplers may be used. Typical examples of useful color couplers are naphthol or phenol compounds, pyrazolone or virazoloazole compounds and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are described in "Research Disclosure" N.
o. 17643 (published December 1978) page 25, VI
Item I-D, ibid. 18717 (issued in November 1979) and the compounds described in JP-A No. 62-215272 and the patents cited therein. Examples of yellow couplers preferably used in the present invention include US Pat. Nos. 3,933,501 and 402,262.
No. 0, No. 4326024, No. 4401754, each specification, Japanese Patent Publication No. 58-10739, British Patent No. 14
Those described in the specifications of No. 25020 and No. 1476760 are preferable.

The blue-sensitive layer of the direct positive photographic light-sensitive material of the present invention,
At least one of the green-sensitive layer, the red-sensitive layer, and the non-photosensitive layer,
It is preferable that at least one hydroquinone derivative represented by the formula (HQ1) or (HQ2) is contained.

First, the compound represented by the above general formula (HQ1) will be described in detail. In the above formula (HQ1), examples of the group represented by R ^Q1 and R ^Q2 which releases a hydroxyl group upon cleavage of a bond with an oxygen atom during development processing include an acyl group, an alkoxycarbonyl group, an aminocarbonyl group, or Further, the groups described in JP-A-59-197037 or 59-201057 can be mentioned. Examples of the acyl group include an acetyl group, a chloroacetyl group, a dichloroacetyl group, a benzoyl group, a 4-cyanobenzoyl group and a 4-oxopentanoyl group. Examples of the alkoxycarbonyl group include an ethoxycarbonyl group, a phenoxycarbonyl group and a 4-methoxybenzyloxycarbonyl group. Examples of the aminocarbonyl group include a methylaminocarbonyl group, a 4-nitrophenylaminocarbonyl group, a 2-pyridylaminocarbonyl group, and a 1-imidazolylcarbonyl group.

Further, the group represented by R ^Q1 and R ^Q2, which is released from the hydroxyl group upon cleavage of the bond with the oxygen atom during the development treatment, is a linking group bonded to R ^Q3 , R ^Q4 and R ^Q6 , or R ^Q5. May combine with to form a 5- to 7-membered ring. As such an _{example, * - COCH 2 CH 2 -} **, * - COCH
₂ CH ₂ CH ₂ -**, * -COCH ₂ SCH _2- *
_{*, * - CONHCH 2 - **} , * - COOCH 2 - *
*, * -CONHCH ₂ CH ₂ -**, * -CH ₂ CH
₂ SCH ₂ -**, * -CH ₂ CH ₂ COCH _2- *
_{*, * - COCH 2 O -} **, * - COCONH - **
Can be mentioned. Here, * is bonded to the oxygen atom of hydroquinone, and ** is R ^Q3 , R ^Q4 and R ^Q6 , or R ^Q5
Represents the position of bonding to the hydroquinone skeleton via the linking group bonded to. R ^Q1 and R ^Q2 are preferably hydrogen atoms.

In the above formula (HQ1), examples of the halogen atom represented by R ^Q3 , R ^Q4 and R ^Q6 include a chlorine atom, a bromine atom and a fluorine atom. R
^The alkyl group represented by ^Q3 , ^RQ4 and ^RQ6 is an alkyl group having 1 to 30 (preferably 1 to 15) carbon atoms, for example, methyl, sec-butyl, t-butyl, t-pentyl, t-hexyl. , Cyclohexyl, t-octyl, benzyl and the like. ^Examples of the alkenyl group represented by R ^Q3 , R ^Q4 and R ^Q6 include an allyl group. Examples of the aryl group represented by R ^Q3 , R ^Q4 and R ^Q6 include aryl groups having 6 to 30 (preferably 6 to 15) carbon atoms, such as phenyl and p-tolyl. Examples of the acylamino group represented by R ^Q3 , R ^Q4 and R ^Q6 include acylamino groups having 2 to 30 (preferably 2 to 15) carbon atoms, for example, groups such as acetylamino and benzoylamino. The sulfonamide group represented by R ^Q3 , R ^Q4 and R ^Q6 has 1 to 1 carbon atoms.
There may be mentioned 30 (preferably 1 to 15) sulfonamide groups such as methanesulfonamide and benzenesulfonamide groups. Examples of the alkoxy group represented by R ^Q3 , R ^Q4 and R ^Q6 include alkoxy groups having 1 to 30 carbon atoms (preferably 1 to 15), such as methoxy, butoxy, benzyloxy and dodecyloxy groups. it can.

The aryloxy group represented by R ^Q3 , R ^Q4 and R ^Q6 has 6 to 30 carbon atoms (preferably 6 to 1 carbon atoms).
The aryloxy group of 5), for example, groups such as phenoxy and p-methoxyphenoxy can be mentioned. R ^Q3 ,
The alkylthio group represented by R ^Q4 and R ^Q6 is an alkylthio group having 1 to 30 (preferably 1 to 15) carbon atoms,
For example, groups such as butylthio and decylthio can be mentioned. Examples of the arylthio group represented by R ^Q3 , R ^Q4 and R ^Q6 include arylthio groups having 6 to 30 (preferably 6 to 15) carbon atoms, such as phenylthio and p-hexyloxyphenylthio groups. .. R ^Q3 ,
The acyl group represented by R ^Q4 and R ^Q6 has 2 to 2 carbon atoms.
There may be mentioned 30 (preferably 2 to 15) acyl groups, for example, groups such as acetyl, benzoyl, hexanoyl and the like. Examples of the acyloxy group represented by R ^Q3 , R ^Q4, and R ^Q6 include acyloxy groups having 2 to 30 (preferably 2 to 15) carbon atoms, for example, groups such as acetyloxy and benzoyloxy. The sulfonyl group represented by R ^Q3 , R ^Q4 and R ^Q6 has 1 to 30 carbon atoms.
(Preferably 1 to 15) sulfonyl groups, for example, groups such as methanesulfonyl, benzenesulfonyl and the like can be mentioned. The carbamoyl group represented by R ^Q3 , R ^Q4 and R ^Q6 has 1 to 30 carbon atoms (preferably 1 to 15).
A carbamoyl group having a substituent of, for example, a group such as N, N-diethylcarbamoyl or N-phenylcarbamoyl can be given. The alkoxycarbonyl group represented by R ^Q3 , R ^Q4 and R ^Q6 has 2 to 30 carbon atoms.
(Preferably 2 to 15) alkoxycarbonyl groups such as methoxycarbonyl and butoxycarbonyl groups can be mentioned.

The sulfamoyl group represented by R ^Q3 , R ^Q4 and R ^Q6 is an unsubstituted or substituted sulfamoyl group having 1 to 30 (preferably 1 to 15) carbon atoms, for example, N, N-dipropyls. A group such as rufamoyl or N-phenylsufamoyl can be added. R ^Q3 , R ^Q4
And the ureido group represented by R ^Q6 has 1 to 2 carbon atoms.
Ureido groups having 0 (preferably 1 to 15) substituents, for example, groups such as 3-methylureido, 3-isopropylureido, 3-cyclohexylureido, 3-hexadecylureido and 3-phenylureido are mentioned. it can. The urethane group represented by R ^Q3 , R ^Q4 and R ^Q6 is a urethane group having 2 to 20 carbon atoms (preferably 2 to 15), such as methoxycarbonylamino, t-butyloxycarbonylamino, dodecyloxydicarbonniamino. And groups such as phenoxycarbonylamino. The carbonic acid ester group represented by R ^Q3 , R ^Q4 and R ^Q6 has 2 to 20 carbon atoms (preferably 2 to 20 carbon atoms).
The carbonate ester group of 15), for example, groups such as ethoxycarbonyloxy and phenoxycarbonyloxy can be mentioned. R ^Q5 represents the same group as the group represented by R ^Q3 , or an aryl group bonded through a linking group.

The above R ^Q3 , R ^Q4 , R ^Q5 and R ^Q6 may have a substituent. ^Examples of the substituent include a group substituting for R ^Q8 described later. However, R ^Q5 is above R ^Q3
When it represents the same group as the group represented by, the above R ^Q3 and R ^Q4
R ^Q5 and R ^Q6 may be combined with each other to form a carbocycle or a heterocycle. Also, when the R ^Q5 represents the same groups as those represented by the R ^Q3, the R ^Q3, R ^Q4, R
^When at least one of ^Q5 and R ^Q6 is not a hydrogen atom and R ^Q3 , R ^Q4 , R ^Q5 and R ^Q6 are composed of only a hydrogen atom and an alkyl group, at least one of the alkyl groups has a carbon number. 6 or more, and the total number of carbon atoms of R ^Q3 , R ^Q4 , R ^Q5 and R ^Q6 is 15 or less (preferably 4 to 1).
3, more preferably 7 to 13). The above formula (HQ
In 1), when R ^Q5 represents the same group group and represented by R ^Q3, the R ^Q3, R ^Q4, R ^Q5 and R ^Q6 is a hydrogen atom,
A halogen atom, an alkyl group, an aryl group, an alkoxy group, a cyano group, an acylamino group or an alkylthio group is preferable, and a hydrogen atom, an alkyl group, an alkoxy group or an acylamino group is more preferable.

In the above formula (HQ1), R ^Q5 is preferably a group represented by the following formula (HQ1-a).

[0213]

[Chemical 89]

[Wherein, R ^Q7 represents a substitutable group on the benzene ring, R ^Q8 represents an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a heterocyclic group or an amino group, and L represents a divalent group. Represents a connecting group, and p represents an integer of 1 to 3, m represents an integer of 0 to 4, provided that m is 2
In the above case, a plurality of R ^Q7 may be the same or different. Examples of the group represented by R ^Q7 that can be substituted on the benzene ring include the same groups as the groups represented by R ^Q3 described above. Among these, a halogen atom, an alkyl group, an aryl group, an acylamino group, a sulfamoyl group, a sulfonamide group, an alkoxy group, an alkylthio group, a ureido group or a urethane group is preferable, and an alkyl group, an alkoxy group or a sulfamoyl group is more preferable. A group or an acylamino group. In the present invention, m
Is preferably 0 or 1. As mentioned above, R ^Q3 , R
The total carbon number of ^Q4 and R ^Q6 and R ^Q7 is preferably 50 or less, more preferably 35 or less, and particularly 20.
It is below.

The divalent linking group represented by L above is
An atom or atomic group containing at least one of C, N, S and O. Specifically, (1) alkylene group (preferably having 1 to 12 carbon atoms, for example, methylene, ethylene, trimethylene, etc.), (2) alkenylene group (preferably having 2 to 12 carbon atoms, for example, vinylene) , Butylene, etc.), (3) alkynylene group (preferably having a carbon number of 2
12, eg ethynylene, butynylene etc.),
(4) Arylene group (preferably having 6 to 10 carbon atoms, for example, phenylene, naphthylene, etc.), (5) -O
-, (6) -S-, (7) -NH-, (8) -CO-,
And (9) —SO ₂ — (these groups may have a substituent) or the like, or a combination thereof. Specific examples of the above combination include, for example, (1
0) -NHCO-, (11) -OCO-, (12) -N
_{HSO 2 -, (13) -OCO} -NH -, (14) -N
HCO-O-, (15) -NHCO-NH-, (16)
-OCO-O -, (17) -NHSO 2 -NH- and,
(1) a combination of - (4) and (5) to (17) (e.g., -NHCO- (alkylene) -, - NHSO ₂ -
(Alkylene)-, -NHCONH- (alkylene)-
Etc.) can be mentioned. In the present invention, L
Is an alkylene (in _{particular, -CH 2 -), - NHCO-} ,
_{-NHSO 2 -, - NHCONH-, NHSO} 2 NH-
And -NHCO- (alkylene)-are preferable, and -NH
CO- is particularly preferred. p is preferably 1 to 2, and particularly 1
Is.

The alkyl group represented by R ^Q8 above is
Mention may be made of alkyl groups having 1 to 30 carbon atoms, such as methyl, ethyl, butyl, isopropyl, t-butyl, cyclohexyl, octyl and hexadecyl.
The alkenyl group represented by R ^Q8 has 2 to 2 carbon atoms.
Mention may be made of 30 alkenyl groups, such as allyl, 2-pentenyl and octadecenyl. Examples of the alkynyl group represented by R ^Q8 include an alkynyl group having 2 to 30 carbon atoms, for example, propargyl.
The aryl group represented by R ^Q8 has 6 to 3 carbon atoms.
Mention may be made of 0 aryl groups, for example phenyl and naphthyl. The heterocyclic group represented by R ^Q8 is a 3- to 12-membered heterocyclic ring containing at least one hetero atom selected from nitrogen atom, oxygen atom, sulfur atom or selenium. Such examples include pyridyl, triazinyl, uracil, pyrrolyl, thienyl, furanyl, oxazolyl, thiazolyl, imidazolyl, pyrazolylyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl, pyrrolidinyl and morpholinyl. The above R ^Q8 may have a substituent (including atoms). As the substituent, an alkyl group (having 1 to 18 carbon atoms), an alkenyl group (having 2 to 1 carbon atoms)
8), an alkynyl group (having 2 to 18 carbon atoms), an aralkyl group (having 7 to 20 carbon atoms), an aryl group (having 6 to 20 carbon atoms),
Hydroxyl group, alkoxy group (having 1 to 18 carbon atoms), aryloxy group (having 6 to 20 carbon atoms), halogen atom, amino group, alkylthio group (having 1 to 18 carbon atoms), arylthio group (having 6 to 20 carbon atoms), Acyloxy group (C1
~ 18), sulfonyloxy group (C1-18), acylamino group (C1-18), sulfonamide group (C1-18), carboxyl group, alkoxycarbonyl group (C2-18), Aryloxycarbonyl group (7 to 20 carbon atoms), acyl group (1 to 2 carbon atoms)
0), carbamoyl group (having a substituent having 1 to 20 carbon atoms), sulfamoyl group (unsubstituted or having a substituent having 1 to 20 carbon atoms), sulfo group, cyano group, ureido group (having 1 to 20 carbon atoms). Having a substituent), a urethane group (having 2 to 20 carbon atoms), and a carbonic acid ester group (having 2 to 2 carbon atoms).
0) can be mentioned. The above R ^Q8 is preferably an alkyl group (having 1 to 16 carbon atoms (preferably 1 to 10, more preferably 8 to 10)) or an aryl group (phenyl).

Specific examples of the compound represented by the formula (HQ1) are shown below.

[0218]

[Chemical 90]

[0219]

[Chemical Formula 91]

[0220]

[Chemical Formula 92]

[0221]

[Chemical formula 93]

[0222]

[Chemical 94]

[0223]

[Chemical 95]

Synthesis examples of the compound represented by the above formula (HQ1) are shown below. Synthesis of Compound (HQ1-2) To 100 ml of acetoniryl, 15.3 g of 2,5-dimethoxyaniline and 10.1 g of triethylamine were added, and 37 g of 2-dodecanesulfonamide benzoic acid chloride was further added with stirring under ice cooling. After further reacting at room temperature for 2 hours, 50 ml of water was added, and the precipitated crystals were collected by filtration, washed with water, and dried at 50 ° C. The obtained solid was added to 200 ml of toluene, and aluminum chloride 40 was added.
g was added and reacted at 120 ° C. for 5 hours. The obtained reaction product was added little by little to ice water, followed by extraction with ethyl acetate and washing with water three times, and then the organic layer was concentrated under reduced pressure.
The residue was dissolved in 150 ml of isopropyl alcohol, 500 ml of n-hexane was added, and the precipitated crystals were collected by filtration to obtain 39 g of the desired product (yield 82%).

Next, the compound represented by the following formula (HQ2) will be described in detail. In the general formula (HQ2), the groups represented by R ^{Q11 to} R ^Q16 are the same as the groups represented by R ^Q3 described above. R ^Q11 and R ^Q12, and R ^Q14 and R ^{Q1 5} may together form a carbocycle or a heterocycle, and R ^{Q11 to} R ^{Q1 6} are the same as the above R.
^It may be substituted with the substituents ^{listed as} the substituents for ^Q3 . The alkyl group represented by R ^Q17 and R ^Q18 is an alkyl group having 1 to 40 carbon atoms, for example, methyl,
Mention may be made of groups such as i-bropyr, undecyl, benzyl and the like. The aryl group represented by R ^Q17 and R ^Q18 is an aryl group having 6 to 40 carbon atoms, for example,
Examples thereof include groups such as phenyl and p-tolyl.
Examples of the heterocyclic group represented by R ^Q17 and R ^Q18 above include
A heterocyclic group having 1 to 40 carbon atoms, for example, a pyridin-2-yl group can be mentioned. In addition, R ^Q17 and R ^Q18 described above may together form a carbocycle or a heterocycle. R above
^Q17 and R ^Q18 may be further substituted with an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a sulfo group, a carboxyl group, an amide group, a carbamoyl group, or a halogen atom. Furthermore, the compound of formula (HQ2) may form a bis form (tetrakis form as the hydroquinone part) in R ^Q17 and / or R ^Q18 . In the above formula (HQ2), R ^{Q1 to} R ^Q16 are preferably hydrogen atoms, halogen atoms, alkyl groups, aryl groups, acylamino groups or alkylthio groups. More preferably, it is a hydrogen atom, an alkyl group or an acylamino group. R ^Q17 and R ^Q18 are preferably a hydrogen atom or an alkyl group, and it is also preferable that R ^Q17 and R ^Q18 together form a carbocycle. More preferably, R ^Q17 is a hydrogen atom and R ^Q18 is a hydrogen atom or an alkyl group.
The total number of carbon atoms of R ^{Q11 to} R ^Q18 is 60 or less, preferably 5 to 45, more preferably 10 to 30.

Specific examples of the compound represented by the formula (HQ2) are shown below.

[0227]

[Chemical 96]

[0228]

[Chemical 97]

[0229]

[Chemical 98]

[0230]

[Chemical 99]

[0231]

[Chemical 100]

[0232]

[Chemical 101]

[0233]

[Chemical 102]

The compounds represented by the above formula (HQ1) or (HQ2) may be used alone or in combination of two or more kinds. In addition, the formula (HQ
The compounds represented by 1) and (HQ2) may be used in combination.
The compound represented by the formula (HQ1) or (HQ2) is
Generally 1 × 10 ⁻⁸ mol / m ² to 1 m ^{2 of the} light-sensitive material
1 × 10 ⁻² mol / m ² , preferably 1 × 10 ⁻⁷ mol / m
² to 1 × 10 ⁻³ mol / m ² , more preferably 1 × 10
It is used in the range of ⁻⁶ mol / m ² to 1 × 10 ⁻⁴ mol / m ² .

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

As the binder or protective colloid that can be used in the emulsion layer or the intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. The light-sensitive material of the present invention includes
An antifoggant or a color mixing inhibitor can also be used. Typical examples of these are JP-A-62-215272 and 185.
The compounds described on page 193 can be mentioned. As a compound that releases a photographically useful group, Japanese Patent Laid-Open No.
No. 3-153540, No. 63-259555,
Japanese Patent Laid-Open Nos. 2-61636, 2-244041, and 2
The compounds described in each publication of -308240 are mentioned. In the present invention, a color forming enhancer can be used for the purpose of improving the color forming property of the coupler. Typical examples of the compounds include those described in JP-A No. 62-215272, pages 121 to 125. Dyes which prevent irradiation and halation may be used in the light-sensitive material of the present invention (for example, the compounds described in JP-A Nos. 2-85850 and 2-89047) may be used. Solid fine crystal dispersion method may be used.), Ultraviolet absorber, plasticizer, fluorescent whitening agent, matting agent, air antifoggant, coating aid, film hardening agent, antistatic agent, slipperiness improver, etc. Can be added. Typical examples of these additives are Research
Disclosure magazine No. 17643VII-XII
Item I (published December 1978), pages 25-27, and 18716 (published November 1979), pages 647-651.

The light-sensitive material of the present invention has at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer on the support. The order of these layers can be arbitrarily selected as required. The preferred order of layer arrangement is red-sensitive, green-sensitive, blue-sensitive from the support side or green-sensitive, red-sensitive and blue-sensitive from the support side. Each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. .. It is usual that the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but in some cases, the green-sensitive layer contains a yellow coupler and a magenta coupler. It is also possible to use different combinations such as mixed use. In the light-sensitive material of the present invention, in addition to the silver halide emulsion layer, a non-light-sensitive layer, such as a protective layer, an intermediate layer, a filter layer, an antihalation layer, a back layer, and a white reflective layer may be appropriately provided. preferable.

The fog treatment of the photographic light-sensitive material of the present invention is carried out by the following "optical fog method" and / or "chemical fog method". The entire exposure in the "light fog method", that is, the fog exposure is performed after imagewise exposure, before color development processing or during color development processing. That is, the imagewise exposed light-sensitive material is exposed in a color developing solution or in a pre-bath of the color developing solution, or is taken out from these solutions and dried before being dried. Is most preferred. As the light source for the fogging exposure, for example, JP-A-56-137350 and JP-A-58-70223 are used.
A light source having a high color rendering property (as close to white as possible), as described in each publication, is preferable. The illuminance of light is 0.01 to 20
00 lux, preferably 0.05 to 30 lux, more preferably 0.05 to 5 lux is suitable. Light-sensitive materials using higher sensitivity emulsions are preferred to have low illuminance. The illuminance may be adjusted by changing the luminous intensity of the light source, or by changing the photosensitivity by various filters, the distance between the photosensitive material and the light source, or the angle between the photosensitive material and the light source. Further, the illuminance of the above-mentioned fogging light can be increased from low illuminance to high illuminance continuously or stepwise. It is preferable to immerse the light-sensitive material in a color developing solution or a solution of its pre-bath so that the solution sufficiently penetrates into the emulsion layer of the light-sensitive material before irradiation with light. The time from the permeation of the liquid to the light fog exposure is generally 2 seconds to 2 minutes, preferably 5 seconds to 1 minute, and more preferably 10 seconds to 30 seconds. The exposure time for fogging is generally 0.01 seconds to 2 minutes, preferably 0.1.
Seconds to 1 minute, more preferably 1 second to 40 seconds.

In the present invention, the nucleating agent used when the so-called "chemical fog method" is applied can be contained in the light-sensitive material or in the processing liquid for the light-sensitive material. A method in which it is contained in a light-sensitive material and used is preferable. Here, the nucleating agent is a substance which acts when the surface latent image of an internal latent image type silver halide emulsion which has not been fogged in advance is subjected to a direct image formation. In the present invention, the fog treatment is preferably performed using a nucleating agent. When it is contained in the light-sensitive material, it is preferably added to the internal latent image type silver halide emulsion layer, but as long as it is diffused during coating or during processing and the nucleating agent is adsorbed to silver halide, It may be added to a layer such as an intermediate layer, an undercoat layer or a back layer. Examples of the nucleating agent that can be used in the present invention include, for example, Research Disclosure Magazine,
No. 22534 (January 1983), pp. 50-54, ibid., No. 15162 (November 1976) 76-77
Page, No. 23510 (November 1983) 346
Quaternary heterocyclic compounds and hydrazine compounds described on page 352. Two or more kinds of these nucleating agents may be used in combination.

In the present invention, the nucleating agents described in the following publications can be preferably used. That is, a quaternary heterocyclic compound represented by the general formula (N-I) described on pages 510 to 514 of JP-A-3-155543 and a general formula described on pages 60-65 of JP-A-3-95546. A hydrazine compound represented by (N-II);
Representative nucleating agents represented by the above general formulas (N-I) and (N-II) are as follows. (N-I-1) 7- (3-Cyclohexylmethoxythiocarbonylaminobenzamide) -10-propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate (N-I-2) 6- ( 3-Ethoxythiocarbonylaminobenzamido) -1-propargyl-2,3-trimethylenequinolinium trifluoromethanesulfonate (N-I-3) 6-ethoxythiocarbonylamino-2
-Methyl-1-propargylquinolinium trifluoromethanesulfonate (N-I-4) 7- [3- (5-mercaptotetrazol-1-yl) benzamide] -10-propargyl-
1,2,3,4-tetrahydroacridinium perchlorate (N-II-1) 1-formyl-2- {4- [3- {3-
[3- (5-Mercaptotetrazol-1-yl) phenyl] ureido} benzsulfonamide] phenyl} hydrazine (N-II-2) 1-formyl-2- {4- [3- (5-
Mercaptotetrazol-1-yl) benzenesulfonamide] phenyl} hydrazine

In the present invention, it is preferable to use the quaternary heterocyclic compound and the hydrazine compound in combination. When the nucleating agent is added to the processing solution, it is contained in a developing solution or a low pH pre-bath as described in JP-A-58-178350. When the nucleating agent is added to the treatment liquid, the amount used is 10 ^-8 to 10 ^-1 per liter.
The amount is preferably mol, and more preferably 10 ⁻⁷ to 10 ⁻³ mol. In the present invention, the nucleating agent may be contained in the hydrophilic colloid layer adjacent to the silver halide emulsion layer, but is preferably contained in the silver halide emulsion layer. The amount added varies depending on the characteristics of the silver halide emulsion actually used, the chemical structure of the nucleating agent and the developing conditions, and therefore can be varied over a wide range, but it is about 1 × per mol of silver in the silver halide emulsion. A range of 10 ⁻⁸ to about 1 × 10 ⁻² mol is practically useful, with a preferred range of about 1 × 10 ⁻⁵ to about 1 × 10 ⁻³ mol per mol of silver.

When a nucleating agent is used, it is preferable to use the nucleating accelerator for promoting the action of the nucleating agent. A nucleation accelerator does not substantially function as a nucleating agent,
A substance that promotes the action of a nucleating agent to increase the maximum density of a direct positive image and / or accelerates the development time necessary to obtain a certain maximum density of a direct positive image. Such a nucleation accelerator has at least one mercapto group optionally substituted with an alkali metal atom or an ammonium group, thiadiazoles, oxadiazoles, benzotriazoles, tetrazaindenes, Examples thereof include triazaindenes and pentazaindenes, and the compounds described in JP-A-63-106656, pages 5 to 16. In addition, JP-A-63-
No. 226652, No. 63-106656, No. 63-8
The compounds described in No. 740 can be mentioned.

Two or more kinds of these nucleation accelerators can be used in combination. The nucleation accelerator can be contained in the light-sensitive material or in the processing solution, but in the light-sensitive material, it can be used in internal latent image type silver halide emulsions and other hydrophilic colloid layers (intermediate layer, protective layer, etc.). Preferably contained in Particularly preferred is in a silver halide emulsion or its adjacent layer. The amount of the nucleation accelerator added is preferably 10 ⁻⁶ to 10 ⁻² mol, and more preferably 10 ⁻⁵ to 10 ⁻² mol, per mol of silver halide. When the nucleation accelerator is added to the processing solution, that is, the developing solution or its pre-bath, it is preferably 10 ^-8 to 10 ^-3 mol, and more preferably 10 ^-7 to 10 ^-4 mol per liter. is there.

Known photographic additives that can be used in the present invention are described in Research Disclosure No. 17643
(December 1978) and the same No. 18716 (19
(November 1979), and the relevant parts are summarized in the table below. Additive type RD17643 RD18716 ───────────────────────────── 1 Chemical sensitizer page 23, page 648, right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, pages 23 to 24, page 648, right column to supersensitizer, page 649, right column 4 whitening agent, page 24 5 Fog inhibitor, pages 24 to 25, page 649, right column to stabilizing agent, page 650, right column 6 Light absorber, page 25, right column, page 649, right column ~ Filter dye, page 650, left column UV absorber 7 Stain inhibitor, page 25, right column 8 Dye image stabilizer, page 25, 9 Hardener, page 26, page 651, left column 10 Binder page 26 Same as above ─────────────────────────────

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are made of a flexible support such as a plastic film, paper or cloth usually used for photographic light-sensitive materials or a rigid support such as glass, earthenware or metal. It is coated on a support.
What is useful as the flexible support is a film made of a semi-synthetic or synthetic polymer such as cellulose nitrate, cellulose acetate, cellulose acetate acetate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, a baryter layer or an α-olefin polymer. Examples include paper coated or laminated with (for example, polyethylene, polypropylene, ethylene / butene copolymer). The support may be colored with a dye or pigment. For coating silver halide photographic emulsion layers and other hydrophilic colloid layers,
For example, various known methods such as a dip coating method, a roller coating method, a curtain coating method and an extrusion coating method can be used. Also, if necessary, US Pat.
No. 1294, No. 2761791, No. 352652
No. 8, No. 3508947, etc. may be used to simultaneously apply multiple layers.

The invention of a color image forming method using the direct positive color photographic light-sensitive material will be described below. The direct positive color photographic light-sensitive material of the present invention can be subjected to development processing by a conventionally known development processing method after imagewise exposure, but it is preferable to perform development processing by another color image forming method of the present invention. The color image forming method of the present invention is characterized in that after the above direct positive color photographic light-sensitive material is imagewise exposed, it is processed with a developing solution containing a color developing agent represented by the formula (D) to obtain a positive color image. ..

Various exposing means can be used for exposing the light-sensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination light source or the writing light source. Flashlight sources such as natural light (sunlight), incandescent lamps, halogen atom filled lamps, mercury lamps, fluorescent lamps and strobes or metal burning flash bulbs are common. A gas, a dye solution or a semiconductor laser, a light emitting diode, or a plasma light source that emits light in a wavelength range from ultraviolet to infrared can also be used as the recording light source. In addition, a linear or planar shape of a micro-shutter array using a phosphor screen (CRT, etc.) emitted from a phosphor excited by an electron beam, liquid crystal (LCD), lanthanum-doped lead titan zirconate (PLZT), or the like. It is also possible to use an exposure means combining the above light sources. If necessary, the spectral distribution used for exposure can be adjusted with a color filter. In particular, by using high-density beam light such as gas lasers (He-Ne laser, Ar laser, He-Cd laser) and various lasers such as semiconductor lasers as a light source and moving it relative to the photosensitive material. An exposure means of so-called scanning exposure system (scanner system) for imagewise exposure is preferable for exposing the direct positive color photographic light-sensitive material of the present invention. As the scanning exposure device, for example, a color copying machine AP-5000 manufactured by Fuji Photo Film Co., Ltd. can be used. In the case of exposure by the scanning exposure system, the time for exposing silver halide is the time required for exposing a certain minute area. As this minute area, the minimum unit for controlling the light quantity from digital data is generally used and is called a pixel. Therefore, the exposure time per pixel varies depending on the size of the pixel. The size of this pixel depends on the pixel density and is in a practical range of 50 to 2000 dpi. In the direct positive color photographic light-sensitive material of the present invention,
When the pixel density is 400 dpi, the pixel size is set to 1 pixel, and scanning exposure is performed under the condition that the exposure time per pixel is 10 ^-3 seconds or less (preferably 10 ^-6 to 10 ^-4 seconds). preferable.

In the general formula (D) showing the developing agent used in the present invention, R ^D1 preferably has 1 to 1 carbon atoms.
The alkyl group of 8 is particularly preferable, and a methyl group, an ethyl group, a butyl group, a methoxymethyl group and the like are preferable. R ^D2 is preferably an alkylene group having 2 to 6 carbon atoms, and particularly preferable ones are an ethylene group and a trimethylene group. Preferred specific examples of the developing agent represented by formula (D) are shown below.

[0249]

[Chemical 103]

[0250]

[Chemical 104]

The amount of the developing agent represented by formula (D) to be used is preferably about 0.1 g to about 20 g, and more preferably about 0.5 g to about 10 g per liter of the developing solution. An aromatic primary amine type color developing agent other than the above may be used in combination, but it is preferable that the developing solution contains the developing agent represented by the general formula (D) in an amount of 50 mol% or more. The developing solution used in the development processing method of the present invention is the same as the conventional color developing solution except that the developing agent is the above specific compound. Further, the development processing method is the same as the development processing method known per se, except that the above-mentioned developing solution is used. The photographic light-sensitive material after the above color development processing is generally subjected to desilvering treatment including bleaching and fixing treatment, and further, after desilvering treatment, washing and / or stabilization treatment is generally performed. Regarding the above-mentioned series of processing steps, JP-A-3
The method described on pages 380 to 381 of JP-A-120537 can be preferably used.

The direct positive color photographic light-sensitive material of the present invention comprises
There are various uses, but color printing, color copying,
Suitable for making color proofs. The method for producing a color proof of the present invention is a method for producing a color proof by using a conventional method for producing a color proof, in addition to using the direct positive color photographic light-sensitive material of the present invention as described above. That is, the method for producing a color proof of the present invention comprises a cyan plate halftone dot image film, a magenta halftone dot image film, and a yellow halftone dot image film obtained by subjecting the direct positive color photographic light-sensitive material of the present invention to color separation and halftone image conversion. And a black halftone dot image film, which is sequentially exposed to red light, green light and blue light, and then subjected to color development processing as described above to form a color image. This method is, for example, a fine checker F manufactured by Fuji Photo Film Co., Ltd.
It can be easily performed by using C850H (exposure time: about 0.02 to 0.3 seconds).

[0253]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. However, the present invention is not limited to these examples.

Example 1 Preparation of Photosensitive Material (Sample 101 = Comparative Example) Paper support laminated on both sides with polyethylene (thickness: 100 μm)
, The following 1st to 14th layers on the front side and the 15th layer on the back side.
The 16th to 16th layers were multilayer-coated to directly produce a positive color photographic light-sensitive material. The polyethylene on the side coated with the first layer contains titanium oxide (4 g / m ² ) as a white pigment and a trace amount (0.003 g / m ² ) of ultramarine as a bluing dye (the chromaticity of the surface of the support is , L *, a *, b * system 8
It was 8.0, -0.20, -0.75). (Composition of photosensitive layer) Components and coating amount (g / m ² unit) below
Indicates. However, the addition amount of the sensitizing dye is shown in mol per mol of silver. For silver halide, the coating amount in terms of silver is shown. The emulsion used for each layer is the emulsion EM- which will be described later.
It was made according to the manufacturing method of 1. However, as the emulsion for the 14th layer, a Lippmann emulsion not surface-sensitized was used.

First Layer (Antihalation Layer) Black Colloidal Silver 0.10 Color Mixing Inhibitor (Cpd-7) 0.05 Gelatin 0.70 Second Layer (Intermediate Layer) Gelatin 0.70 Third Layer (Low Sensitivity Red) Sensitive layer) Silver bromide (average grain size: 0.25 μm, grain size distribution) spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3, each equivalence meter 3.8 × 10 ⁻⁴ ). [Variation coefficient] 8%, octahedron) 0.04 Silver chlorobromide (chloride) spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3, each equivalence meter 3.8 × 10 ⁻⁴ ). Silver 5 mol%, average particle size: 0.40 μm, particle size distribution: [variation coefficient] 10%, octahedron) 0.08 gelatin 1.00 cyan coupler (ExC-1) 0.30 anti-fading agent (Cpd-) Equal amounts of 1, 2, 3, 4, and 30) 0.18 Anti-staining agent (Cpd-5) 0 0.003 Coupler dispersion medium (Cpd-6) 0.03 Coupler solvent (Equivalent amounts of Solv-1, 2, and 3) 0.12 Fourth layer (high-sensitivity red-sensitive layer) Red sensitizing dye (ExS-1, 2,3, silver bromide spectrally sensitized with each equivalence meter 3.8 × 10 ⁻⁴ (average grain size: 0.6 μm, grain size distribution: [variation coefficient] 15%, octahedron) 0 .14 Gelatin 1.00 Cyan coupler (ExC-1) 0.30 Anti-fading agent (Equivalent amounts of Cpd-1, 2, 3, 4, 30) 0.18 Coupler dispersion medium (Cpd-6) 0.03 Coupler solvent (Equivalent amounts of Solv-1, 2, and 3) 0.12 Fifth layer (intermediate layer) Gelatin 1.00 Color mixing inhibitor (Cpd-7) 0.08 Color mixing inhibitor solvent (Solv-4, 5) 0.16 Polymer latex (Cpd-8) 0.10

Sixth Layer (Low Sensitivity Green Sensitive Layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS- ^4, 2.6 × 10 ⁻⁴ ) (average grain size: 0.25 μm, grain Size distribution: [variation coefficient] 8%, octahedron) 0.04 Silver chlorobromide spectrally sensitized with a green sensitizing dye (ExS- ^4, 2.6 × 10 ⁻⁴ ) (silver chloride 5 mol%, Average particle size: 0.40 μm, particle size distribution: [variation coefficient] 10%, octahedron) 0.06 gelatin 0.80 magenta coupler (ExM-1) 0.11 anti-fading agent (Cpd-9, 26 for each) 0.15 Anti-staining agent (Cpd-10, 11, 12, 13 in a ratio of 10: 7: 7: 1) 0.025 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv- Equal amounts of 4 and 6) 0.15 7th layer (high-sensitivity green-sensitive layer) Green sensitizing dye (Ex -4,2.6 × 10 ^-4) in spectrally sensitized silver bromide (average grain size: 0.65 .mu.m, particle size distribution: [variation coefficient] 16%, octahedral) 0.10 Gelatin 0. 80 Magenta coupler (ExM-1) 0.11 Anti-fading agent (equal amounts of Cpd-9, 26) 0.15 Anti-staining agent (Cpd-10, 11, 12, 13 of 10: 7: 7: 1) 0.025 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Equivalent amounts of Solv-4 and 6) 0.15 8th layer (intermediate layer) Same as 5th layer 9th layer (yellow) Filter layer) Yellow colloidal silver (particle size 100Å) 0.12 Gelatin 0.70 Color-mixing inhibitor (Cpd-7) 0.03 Color-mixing inhibitor solvent (Solv-4, 5 and each equivalent) 0.10 Polymer latex ( Cpd-8) 0.07 10th layer Intermediate layer) The same as the fifth layer

Eleventh Layer (Low Sensitivity Blue Sensitive Layer) Silver bromide (average grain) spectrally sensitized with a blue sensitizing dye (equal amounts of ExS-5 and ExS-5, total 3.5 × 10 ⁻⁴ ). Size: 0.40 μm, particle size distribution: [variation coefficient] 8%, octahedron) 0.07 Spectral sensitization with blue sensitizing dye (ExS-5, 6 in equal amounts, total 3.5 × 10 ⁻⁴ ). Sensitive silver chlorobromide (silver chloride 8 mol%, average particle size: 0.60 μm, particle size distribution: [variation coefficient] 11%, octahedron) 0.14 gelatin 0.80 yellow coupler (ExY- Equal amounts of 1, 2, and 3) 0.35 Antifade agent (Cpd-14) 0.10 Antifade agent (Cpd-30) 0.05 Stain inhibitor (Cpd-5, 15 ratio 1: 5) 0.007 coupler dispersion medium (Cpd-6) 0.05 coupler solvent (Solv-2) 0.10 12th layer (High-sensitivity blue-sensitive layer) Silver bromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6 in equal amounts, 3.5 × 10 ⁻⁴ in total) (average grain size: 0.85 μm, Particle size distribution: [variation coefficient] 18%, octahedron) 0.15 gelatin 0.60 yellow coupler (Equivalent of ExY-1, 2, 3) 0.30 anti-fading agent (Cpd-14) 0. 10 Anti-fading agent (Cpd-30) 0.05 Anti-staining agent (Cpd-5, 15 in a ratio of 1: 5) 0.007 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-2) 0.10 Thirteenth layer (ultraviolet absorbing layer) Gelatin 1.00 Ultraviolet absorber (Equivalent amounts of Cpd-2, 4, 16) 0.50 Color mixing inhibitor (Equivalent amount of Cpd-7, 17) 03 Dispersion medium (Cpd-6) 0.02 UV absorber solvent (Solv-2, 7 Equal amount) 0.08 Anti-irradiation dye (Cpd-18, 19, 20, 21, 27 in the ratio of 10: 10: 13: 15: 20) 0.05 14th layer (protective layer) Fine particle chlorobromide Silver (97 mol% of silver chloride, average size 0.1 μm) 0.03 Acrylic modified copolymer of polyvinyl alcohol (molecular weight: 50,000) 0.01 Polymethylmethacrylate particles (average particle size: 2.4 μm) and silicon oxide (Average particle size: 5 μm) each equivalent 0.05 Gelatin 1.80 Gelatin hardening agent (Equivalent each H-1 and H-2) 0.18

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

Preparation of Silver Halide Emulsion (Preparation of Emulsion EM-1) An aqueous solution of potassium bromide and silver nitrate was stirred vigorously in an aqueous gelatin solution at 75 ° C. at 15 ° C.
At the same time, the components were added in a timely manner to obtain a silver halide solution containing octahedral silver bromide grains having an average grain size of 0.35 μm. At this time, 0.3 g of 3,4-dimethyl-1,
3-Thiazolin-2-thione was added. To this emulsion, 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) were sequentially added per 1 mol of silver, and the mixture was heated at 75 ° C. for 80 minutes for chemical sensitization. Using the grains thus obtained as a core, silver halide grains were further grown in the same precipitation environment as in the first time, and finally an octahedral monodisperse core / shell silver bromide having an average grain size of 0.7 μm. An emulsion was obtained. The coefficient of variation of particle size was about 10%. To this emulsion were added 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mol of silver, and the mixture was added at 60 ° C. for 6 hours.
Chemical sensitization was performed by heating for 0 minutes to obtain an internal latent image type silver halide emulsion. ExZ is used as a nucleating agent in each photosensitive layer.
1 for K-1 and 1 for ExZK-2 for silver halide
0 ^-3 wt%, ^10-2% by weight, as a nucleation accelerator Cpd-
22, 28 and 29 were used at 10 ^-2 wt% each. Further, alkanol XC (Du Po
nt) and sodium alkylbenzene sulfonate as coating aids and succinate and Magefa
cF-120 (manufactured by Dainippon Ink and Chemicals, Inc.) was used. Equal amounts of Cpd-23, 24 and 25 were used as stabilizers in the silver halide and colloidal silver containing layers.
This sample was designated as sample (101). The compounds used in the above sample preparation are shown below.

[0260]

[Chemical 105]

[0261]

[Chemical formula 106]

[0262]

[Chemical formula 107]

[0263]

[Chemical 108]

[0264]

[Chemical 109]

[0265]

[Chemical 110]

[0266]

[Chemical 111]

[0267]

[Chemical 112]

[0268]

[Chemical 113]

[0269]

[Chemical 114]

[0270]

[Chemical 115]

[0271]

[Chemical formula 116]

Solv-1 di (2-ethylhexyl)
Sebacate Solv-2 Trinonyl Phosphate Solv-3 Di (3-methylhexyl) Phthalate Solv-4 Tricresyl Phosphate Solv-5 Dibutyl Phthalate Solv-6 Trioctyl Phosphate Solv-7 Di (2-ethylhexyl) Phthalate H-11 , 2-Bis (vinylsulfonylacetamide) ethane H-2 4,6-dichloro-2-hydroxy-1,3,5-triazine / Na salt

ExZK-17- (3-ethoxythiocarbonylaminobenzamido) -9-methyl-10-propargyl-1,2,3,3
4-Tetrahydroacridinium trifluoromethanesulfonate ExZK-2 2- [4- {3- [3- {3- [5- {3- [2-chloro-5- (1-dodecyloxycarbonylethoxycarbonyl) phenyl) Carbamoyl] -4-hydroxy-1
-Naphthylthio} tetrazol-1-yl] phenyl}
Ureido] benzenesulfonamide} phenyl] -1-
Formyl hydrazine

(Preparation of Photosensitive Material (Sample 102 = Comparative Example)) In the preparation of Sample 101, the third layer and the fourth layer were prepared.
Sample 102 was prepared in the same manner as in Sample 101, except that the cyan coupler (ExC-1) contained in the layer was replaced with an equimolar amount of the cyan coupler (ExC-2) shown below. ..

[0275]

[Chemical 117]

(Preparation of Light-Sensitive Material (Sample 103 to Sample 107 = Invention))
Cyan coupler (ExC-) contained in the fourth layer and the fourth layer
1) is an equimolar amount of the cyan coupler (CaII
I-3), (CaIII-10), (CaIV-6), (C
aVII-1) or (CbVIII-18), respectively, in the same manner as in the preparation of Sample 101, Sample 103 which is a direct positive color photographic light-sensitive material of the present invention,
Sample 104, sample 105, sample 106 and sample 107 were created.

[0277]

[Chemical 118]

[0278]

[Chemical 119]

(Photosensitive Material (Sample 108 and Sample 109 =
Preparation of the present invention) In preparation of Sample 103 above, the magenta coupler (ExM) contained in the sixth and seventh layers was used.
-1) is an equimolar amount of a magenta coupler (M
-36) or (M-41), respectively,
In the same manner as in the preparation of Sample 103, Sample 108 and Sample 10 which are direct positive color photographic light-sensitive materials of the present invention.
9 was created.

[0280]

[Chemical 120]

(Photosensitive Material (Sample 110 and Sample 111 =
Preparation of the present invention)) In preparation of the above-mentioned sample 108, the cyan coupler contained in the third layer and the fourth layer was 5
Sample 110, which is a direct positive color photographic light-sensitive material of the present invention, was prepared in the same manner as in the preparation of Sample 108, except that the following hydroquinone derivative (HQ1-1) or (HQ1-2) of mol% was further added. Sample 111 was created.

[0282]

[Chemical 121]

(Photosensitive Material (Sample 112 and Sample 113 =
Preparation of the present invention) In preparation of the above sample 108, the cyan coupler contained in the third and fourth layers was 3
Sample 112, which is the direct positive color photographic light-sensitive material of the present invention, was prepared in the same manner as in the preparation of Sample 108 except that the following hydroquinone derivative (HQ2-4) or (HQ2-5) was further added. Sample 113 was created.

[0284]

[Chemical formula 122]

(Photosensitive Material (Sample 114 and Sample 115 =
Preparation of the present invention) In the preparation of Sample 109, 5 mol% of the hydroquinone derivative (HQ1-1) or (HQ1-2) with respect to the color mixing inhibitor contained in the fifth layer.
Sample 114 and Sample 115 which are the direct positive color photographic light-sensitive materials of the present invention were prepared in the same manner as in the preparation of Sample 109 except that the above was added.

[Evaluation as direct positive color photographic light-sensitive material] Samples 101 to 115 obtained above were evaluated for color reproducibility and color developability according to the following evaluation methods. An image was formed by the following processing step A. (Evaluation of color reproducibility) A general subject is printed using a reversal film, printed, and the image on each sample obtained by image formation is observed under the light for color evaluation to confirm color reproducibility. evaluated. The evaluation results are categorized and represented as follows based on the image obtained in Sample 101. A: It is much better than the image obtained with sample 101. B: Better than the image obtained with sample 101. C: It is equivalent to the image obtained with the sample 101. (Evaluation of color forming property) After each sample was formed into a single color in each hue of cyan or magenta to form a color forming image (dye image),
Densitometer (X-Rite310RT, X-Rite)
Was used to measure the maximum image density and the minimum image density to evaluate the color developability. The evaluation results were classified and expressed as follows based on the maximum image density and the minimum image density obtained for Sample 101. A: The maximum image density is higher and the minimum image density is lower than the image obtained with Sample 101, which is very excellent. B: The maximum image density is high and excellent as compared with the image obtained with the sample 101. C: The maximum image density and the minimum image density are equivalent to the image obtained with the sample 101. Table 27 shows the evaluation results based on the above.

(Processing Step A) The exposed sample was continuously processed using the automatic processor until the cumulative replenishment amount of the solution became 3 times the tank capacity in the following processing steps. ──────────────────────────────────── Treatment process time Temperature Tank capacity Replenishment amount ─────── ────────────────────────────── color development 135 sec 38 ° C. 11 liters 350 ml / m ² bleach-fixing 40 seconds 34 ° C. 3 liters 300 ml / m ² water washing (1) 40 seconds 32 ° C 3 liters-water washing (2) 40 seconds 32 ° C 3 liters 350 ml / m ² drying 30 seconds 80 ° C ───────────────── ──────────────────── The replenishment amount indicates the replenishment amount per 1 m ² of the sample. The replenishing system for the washing water was a countercurrent replenishing system for guiding the overflow solution of the washing bath (2) to the washing bath (1). At this time, the carry-out amount of each processing solution by the light-sensitive material was 35 ml / m ² .

The composition of each processing liquid is as follows. ──────────────────────────────────── Color developer Mother solution Replenisher ───────── ───────────────────────────── D-sorbit 0.15g 0.20g sodium naphthalenesulfonate ・ 0.15g 0.20g formalin condensation Product Nitrilotris (methylenephosphonic acid) 1.8 g 1.8 g pentasodium salt diethylenetriaminepentaacetic acid 0.5 g 0.5 g 1-hydroxyethylidene-1,1-0.15 g 0.15 g diphosphonic acid diethylene glycol 12.0 ml 16.0 ml Benzyl alcohol 13.5 ml 18.0 ml Potassium bromide 0.70 g --- Benzotriazole 0.003 g 0.004 g Sodium sulfite 2.4 g 3.2 g Disodium N, N-bis (sulfo 8.0 g 10.6 g natoethyl) hydroxylamine triethanolamine 6.0 g 8.0 g N-ethyl-N- (β-methanesul 6.0 g 8.0 g phonamidoethyl) -3-methyl − 4-Aminoaniline / 3/2 sulfuric acid monohydrate Potassium carbonate 30.0 g 25.0 g Optical brightener (diaminostilbene type) 1.3 g 1.7 g Water is added 1000 ml 1000 ml ─────── ───────────────────────────── pH (25 ℃) 10.30 10.79 (pH adjustment with KOH or sulfuric acid) ── ──────────────────────────────────

──────────────────────────────────── Bleach-fixing solution Mother solution Replenishing solution ───── ──────────────────────────────── ethylenediaminetetraacetic acid ・ 4.0g Same as mother liquor disodium ・ dihydrate ethylenediaminetetraacetic acid -Fe (III) -55.0 g ammonium dihydrate ammonium thiosulfate (750 g / l) 168 ml sodium p-toluenesulfinate 30.0 g ammonium sulfite 35.0 g 5-mercapto-1,3,4-triazole 0.5 g Ammonium nitrate 10.0g Add water 1000ml ──────────────────────────────────── pH (25 ℃) 6.20 (pH adjustment with ammonia water or acetic acid ────────────────────────────────────

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

[0291]

[Table 27] Table 27 ──────────────────────────────── Sample No. Color reproducibility Chromogenic cyan Magenta ─── ───────────────────────────── 101 (Comparative example) Evaluation standard Evaluation standard Evaluation standard 102 (Comparative example) C CC 103 ( The present invention B B C 104 (the present invention) B B C 105 (the present invention) B B C 106 (the present invention) B B C 107 (the present invention) B B C 108 (the present invention) A B B 109 (the present invention) ) A B B 110 (the present invention) A A B 111 (the present invention) A A B 112 (the present invention) A A B 113 (the present invention) A A B 114 (the present invention) A A A 115 (the present invention) A A A ──────────────────────────────── Clear from the results shown in Table 27. As such, positive color photographic light-sensitive material directly containing specific cyan couplers of the present invention, (a high maximum image density) which is excellent in color developing property is excellent in color reproducibility. Further, the direct positive color photographic light-sensitive material of the present invention containing a specific magenta coupler together with a specific cyan coupler is further excellent in color reproducibility and color developability. Further, the direct positive color photographic light-sensitive material of the present invention to which a specific hydroquinone derivative is added has a lower minimum image density and is more preferable.

[Example 2] Of the samples obtained in Example 1, samples 101 to 104 and samples 108 to 11
3 is used to develop a color developing agent (N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate) in the color developing solution used in Example 1.
Or (D-3) (composition in treatment liquid; mother liquor: 4.3 g, replenisher: 5.6 g) or (D-3) (composition in treatment liquid; mother liquor: 4.6 g). Replenisher: An image was formed in the same manner as in Example 1 except that the color developing solution was changed to 6.1 g), and the obtained image was evaluated in the same manner as in Example 1. .. As a result, the image obtained by using the compound (D-2) or (D-3) as the color developing agent was preferable because the maximum image density was high and the minimum image density was low.

[0293]

[Chemical 123]

[Example 3] Of the samples obtained in Example 1, sample 101, sample 103, sample 108, sample 11
No. 0, Sample 112 and Sample 114 were used, and a plate-making film having a halftone image was adhered using a fine checker FC850H manufactured by Fuji Photo Film Co., Ltd.
Red exposure (SC-60 filter manufactured by Fuji Photo Film Co., Ltd.), green exposure (BP manufactured by Fuji Photo Film Co., Ltd.)
B-53 filter) and blue exposure (SC-42 filter manufactured by Fuji Photo Film Co., Ltd.), respectively. At that time, a plate-making film for cyan image and black image was overlapped at the time of red exposure, a plate-making film for magenta image and black image at the time of green exposure, and a plate-making film for yellow image and black image at the time of blue exposure. The image formation in this case is performed in the following processing step B.
Went according to.

[Processing Step B] The exposed sample is
The cumulative replenishment amount of the liquid in the process below is 3 of the tank capacity.
It processed continuously until it doubled. ──────────────────────────────────── Treatment process time Temperature Tank capacity Replenishment amount ─────── ────────────────────────────── color development 135 sec 38 ° C. 28 liters 240 ml / m ² bleach-fixing 40 seconds 35 ° C. 11 liters 320 ml / m ² water washing (1) 40 seconds 35 ° C 7 liters-water washing (2) 40 seconds 35 ° C 7 liters 320 ml / m ² drying 30 seconds 80 ° C ───────────────── ──────────────────── The replenishment amount indicates the replenishment amount per 1 m ² of the sample. The replenishing system for the washing water was a countercurrent replenishing system for guiding the overflow solution of the washing bath (2) to the washing bath (1). At this time, the carry-out amount of each processing solution by the light-sensitive material was 35 ml / m ² .

The composition of each processing solution is as follows. ──────────────────────────────────── Color developer Mother solution Replenisher ───────── ───────────────────────────── D-sorbit 0.15g 0.20g sodium naphthalenesulfonate ・ 0.15g 0.20g formalin condensation Product Nitrilotris (methylenephosphonic acid) 1.8 g 1.8 g pentasodium salt diethylenetriaminepentaacetic acid 0.5 g 0.5 g 1-hydroxyethylidene-1,1-0.15 g 0.15 g diphosphonic acid diethylene glycol 12.0 ml 16.0 ml Benzyl alcohol 13.5 ml 18.0 ml Potassium bromide 0.70 g --- Benzotriazole 0.003 g 0.004 g Sodium sulfite 2.8 g 3.7 g Hydroxyl Min. 1/2 sulfate 3.0 g 4.0 g triethanolamine 6.0 g 8.0 g 4- [N-ethyl-N-([beta] -hydro 4.2 g 5.6 g xyethyl) amino] aniline sulfuric acid 1 / Dihydrate Potassium carbonate 30.0 g 25.0 g Optical brightener (diaminostilbene type) 1.3 g 1.7 g Water added 1000 ml 1000 ml ────────────────── ────────────────── pH (25 ℃) 10.35 10.93 (pH adjustment with KOH or sulfuric acid) ───────────── ───────────────────────

──────────────────────────────────── bleach-fixing solution mother liquor replenisher ───── ──────────────────────────────── ethylenediaminetetraacetic acid ・ 4.0g Same as mother liquor disodium ・ dihydrate ethylenediaminetetraacetic acid -Fe (III) -55.0 g ammonium dihydrate ammonium thiosulfate (750 g / l) 168 ml sodium p-toluenesulfinate 30.0 g ammonium sulfite 35.0 g 5-mercapto-1,3,4-triazole 0.5 g Ammonium nitrate 10.0g Add water 1000ml ──────────────────────────────────── pH (25 ℃) 6.20 (pH adjustment with ammonia water or acetic acid ────────────────────────────────────

──────────────────────────────────── [Washing water] (Same as mother liquor and replenisher) ) ──────────────────────────────────── Sodium chlorinated isocyanurate 0.02g Deionized water ( Conductivity 5μs / cm or less) 1000ml pH 6.5 ──────────────────────────────────── This result The images obtained by using the sample 103, sample 108, sample 110, sample 112 and sample 114 of the direct positive color photographic light-sensitive material of the present invention are the sample 101 of the comparative example.
The halftone image was better than the image obtained using

[Example 4] As a light source, a helium-neon gas laser (wavelengths: 633 nm and 543 nm) was used.
Using an argon gas laser (wavelength: 458 nm), a luminous flux with a diameter of 80 μm is 1.6 m at a pitch of 100 μm.
Sequential scanning exposure on the sample (substantial exposure time: about 5 × 10
^-5 seconds) assembled a device that can. Using this apparatus, Sample 101 (Comparative Example) and Sample 114 obtained in Example 1
The reproducibility of the halftone image obtained by exposing (invention) and forming an image according to the processing step B used in Example 3 was evaluated. Sample 101 was able to reproduce only a halftone dot area ratio of 4%, but sample 114 was good at being able to reproduce a halftone dot area ratio of 2%.

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

[Procedure amendment]

[Submission date] February 1, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0244

[Correction method] Change

[Correction content]

Known photographic additives that can be used in the present invention are described in Research Disclosure No. 17643
(December 1978) and the same No. I8716 (19
(November 1979), and the relevant parts are summarized in the table below. Additive type RD17643 RD18716 ────────────────────────────── 1 Chemical sensitizer page 23, page 648, right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, pages 23 to 24, page 648, right column to supersensitizer, page 649, right column 4, whitening agent, page 24 5, antifoggant, pages 24 to 25, page 649, right column, stabilizer, page 650, right Column 6 Light absorber, Page 25 Right column, Page 649 Right column, Filter dye, Page 650, Left column UV absorber 7 Stain inhibitor, Page 25 Right column 8, Dye image stabilizer, Page 25 9 Hardener, Page 26, 651 Left column 10 Binder page 26 Same as above ────────────────────────────── In addition to the above UV absorbers, triazine compounds (for example,
Kai 46-3335, European Published Patent No. 520,938
No. A), benzophenone compounds (European publication)
The one described in Japanese Patent No. 521,823A) is preferably used.
it can.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0257

[Correction method] Change

[Correction content]

Eleventh Layer (Low Sensitivity Blue Sensitive Layer) Silver bromide (average grain size) spectrally sensitized with a blue sensitizing dye (equal amounts of ExS-5 and ExS-5, total 3.5 × 10 ⁻⁴ ). : 0.40 μm, particle size distribution: [variation coefficient] 8%, octahedron) 0.07 Spectral sensitization with blue sensitizing dyes (EXS-5, 6 in equal amounts, total 3.5 × 10 ⁻⁴ ). Silver chlorobromide (silver chloride 8 mol%, average grain size: 0.60 μm, grain size distribution: [variation coefficient] 11%, octahedron) 0.14 gelatin 0.80 yellow coupler (ExY-1, 2) 3 is an equal amount) 0.35 Anti-fading agent (Cpd-14) 0.10 Anti-fading agent (Cpd-30) 0.05 Anti-staining agent (Cpd-5, 15 in a ratio of 1: 5) 0 0.007 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (So1V-2) 0.10 Two layers (sensitive肯感layer) Blue sensitizing dye (ExS-5, 6 each equal amounts, total 3.5 × ^{10 -4)} in spectrally sensitized silver bromide (average grain size: 0.85 .mu.m , Particle size distribution: [variation coefficient] 18%, octahedron) 0.15 gelatin 0.60 yellow coupler (equal amounts of ExY-1, 2, and 3) 0.30 antifading agent (Cpd-14) 0. 10 Anti-fading agent (Cpd-30) 0.05 Anti-staining agent (Cpd-5, 15 in a ratio of 1: 5) 0.007 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-2) 0.10 Thirteenth layer (ultraviolet absorbing layer) Gelatin 1.00 Ultraviolet absorber (Equivalent amounts of Cpd-2 , 4 , 16 , 30, 31 ) 0.50 Anti-color mixing agent (Cpd-7, 17) Amount) 0.03 Dispersion medium (Cpd-6) 0.02 UV absorber solvent Solv-2, 7 in each equivalent amount) 0.08 Anti-irradiation dye (Cpd-18, 19, 20, 21, 27 in a ratio of 10: 10: 13: 15: 20) 0.05 14th layer ( Protective layer) Fine particle silver chlorobromide (97 mol% silver chloride, average size 0.1 μm) 0.03 Acrylic modified copolymer of polyvinyl alcohol (molecular weight: 50000) 0.01 Polymethylmethacrylate particles (average particle size: 2 .4 .mu.m) and silicon oxide (average particle size: 5 .mu.m) are each equivalent 0.05 Gelatin 1.80 Gelatin hardening agent (Equivalent amounts of H-1 and H-2) 0.18

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0269

[Correction method] Change

[Correction content]

[0269]

[Chemical 114]

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0270

[Correction method] Change

[Correction content]

[0270]

[Chemical 115]

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

Claims (6)

[Claims] 1. A blue-sensitive layer, a green-sensitive layer and a red-sensitive layer containing an internal latent image type silver halide grain not previously fogged and a color image-forming coupler on a support, and a non-photosensitive layer adjacent thereto. In a direct positive color photographic light-sensitive material having at least one of each of the following, the color image-forming coupler of the red-sensitive layer is represented by the following formula (Ca
I) or (CbI): [In the formula, R ^C11 and R ^C12 each independently represent an electron-withdrawing group having a Hammett's substituent constant σ _P value of 0.2 or more. However, the sum of the sigma _P value of sigma _P value and R ^C12 of R ^C11 is 0.65 or more. Z ^C11 is -NH- or -C.
H (R ^C13 ) ^-is represented. Z ^C12 represents -C (R ^C14 ) = or -N =. Z ^C13 represents -C (R ^C15 ) = or -N =. R ^C13 has a Hammett's substituent constant σ _P value of 0.
Represents two or more electron withdrawing groups. R ^C14 and R ^C15 each independently represent a hydrogen atom or a substituent. X ^C11 is
Represents a group capable of splitting off by a coupling reaction with a hydrogen atom or an oxidant of an aromatic primary amine color developing agent] [In the formula, R ^C21 represents a hydrogen atom or a substituent. R ^C22
Represents a substituent. Z ^{C2 1} represents a non-metal atom group necessary for forming a nitrogen-containing 6-membered heterocycle. However, the heterocycle is
It has at least one dissociative group. X ^C21 represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidation product of an aromatic primary amine color developing agent]. Photographic material. 2. The color image-forming coupler of the green-sensitive layer is represented by the following formula (M): [In the formula, R ^M represents a hydrogen atom or a substituent, and Z ^M represents a non-metal necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, together with the carbon atom and the nitrogen atom to which they are bonded. Represents a group of atoms, the azole ring is a substituent (including fused rings)
X ^M represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent.
The direct positive color photographic light-sensitive material according to claim 1, which is a magenta coupler represented by 3. At least one of the blue-sensitive layer, the green-sensitive layer, the red-sensitive layer and the non-photosensitive layer has the following formula (HQ1) or (HQ
2): [Wherein, R ^Q1 and R ^Q2 each independently represent a hydrogen atom or a group that releases a hydroxyl group by breaking a bond with an oxygen atom during development processing, and R ^Q3 , R ^Q4 and R ^Q6 each independently represent, Hydrogen atom, halogen atom, sulfo group, carboxyl group, cyano group, alkyl group, alkenyl group, aryl group, acylamino group, sulfonamide group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, acyloxy group, A sulfonyl group, a carbamoyl group, an alkoxycarbonyl group, a sulfamoyl group, a ureido group, a urethane group or a carbonic acid ester group is represented, and R ^Q5 is an aryl group which is bonded through the same group or a linking group as the group represented by R ^Q3. the representative, however, the R ^Q5, when the same groups as those represented by the R ^Q3, also the R ^Q3 and R ^Q4 R ^Q5 and R ^Q6 may together form a carbocycle or a heterocycle, and at least one of the above R ^{Q3 to} R ^Q6 is not a hydrogen atom, and R ^{Q3 to} R ^Q6 is a hydrogen atom. And an alkyl group alone, at least one of the alkyl groups has 6 or more carbon atoms, and R ^Q3
The total number of carbon atoms in R ^Q6 is 15 or less. ] [Chemical 5] [In the formula, R ^{Q11 to} R ^Q16 are each independently a hydrogen atom,
Halogen atom, sulfo group, carboxyl group, cyano group,
An alkyl group, an alkenyl group, an aryl group, an acylamino group, a sulfonamide group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, an acyloxy group, a sulfonyl group, a carbamoyl group, an alkoxycarbonyl group or a sulfamoyl group, R ^Q11 and R ^Q12 or R ^Q14 and R ^Q15 may together form a carbocycle or a heterocycle; R ^Q17 and R ^Q18 are each independently a hydrogen atom, an alkyl group, an aryl group or a heterocycle. Represents a group, and R ^Q17 and R ^Q18 described above may together form a carbocycle or a heterocycle. ] The direct positive color photographic light-sensitive material according to claim 1, containing at least one hydroquinone derivative represented by the formula [1]. 4. A color photographic light-sensitive material according to any one of claims 1, 2 and 3, after imagewise exposure, the following formula (D): [In the formula, R ^D1 represents an alkyl group and R ^D2 represents an alkylene group, provided that R ^D1 and R ^D2 may be linked to each other to form a ring. ] The development processing using the developing agent shown by these, The color image forming method characterized by the above-mentioned. 5. A cyan plate halftone dot image film or a magenta plate halftone dot obtained by color separation and halftone dot image conversion of the color photographic light-sensitive material according to any one of claims 1, 2 and 3. A method for producing a color proof, characterized in that an image film, a halftone dot image film for a yellow plate and a halftone dot image film for a black plate are sequentially exposed to red light, green light and blue light, and then color development processing is performed. 6. The color photographic light-sensitive material according to claim 1, 10 or 10
A color image forming method characterized by performing color development processing after scanning exposure for an exposure time of ^-3 seconds or less.