JP2860924B2 - Direct positive color photographic light-sensitive material, color image forming method, and color proof forming method - Google Patents

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, and a method for forming a color image and a color proof using the same. About the method.

[0002]

BACKGROUND OF THE INVENTION Photographic methods for obtaining a positive image directly without the need for a reversal step or a negative film are well known.
As a conventionally known method for producing a positive image using a direct positive color silver halide photographic light-sensitive material, there is a method using an internal latent image type silver halide emulsion which is not fogged in advance. In this method, a photographic light-sensitive material is subjected to surface development after image exposure, fogging, or fogging, thereby directly obtaining a positive color image. The non-pre-fogged internal latent image type silver halide photographic emulsion is a type of halide having a photosensitive nucleus mainly inside silver halide grains and forming a latent image mainly inside the grains by exposure. Silver photographic emulsion. Various techniques are known in the art. For example, US Pat. No. 2,592,250
Nos. 2,466,957, 2,497,875 and 25
Nos. 88982, 3317322, and 3761266
No. 3,761,276, No. 3,796,577 and British Patent Nos. 1,115,363, 1,115,553 and 10,
What is described in each specification etc. of No. 11062 is the main thing. The mechanism of forming a direct positive image is described as follows. That is, a so-called internal latent image is formed on the silver halide upon imagewise exposure, and then a fogging process is performed, whereby a surface desensitizing effect caused by the internal latent image works (that is, the halogen in the exposed area). Development nuclei (fog nuclei) are not generated on the surface of silver halide), and development nuclei are selectively generated only on the unexposed portions of the silver halide surface.
Thereafter, a normal surface development treatment is performed to form a photographic image (positive image) on the unexposed portions. As the fogging method, there are a so-called "optical fogging method" for exposing the entire surface of the photosensitive layer and a "chemical fogging method" using a nucleating agent. Direct positive color silver halide photographic materials using an internal latent image type silver halide emulsion that has not been previously fogged as described above have recently been accepted for the simplicity of the processing steps, and color copying, color plate making, It has been used for plate inspection of prints and creation of color proofs for inspection.

[0003] The operation process of a color print includes a process of separating a color original into colors and converting the color original into a halftone image to produce a transmission halftone image. A printing plate is made from the obtained transmission type halftone image, but prior to this, the final printed matter (final printing)
There is a step of inspecting the state, characteristics, etc. of the device and performing necessary calibration (color calibration). Conventionally, as a method of color proofing, a method of preparing a printing plate and performing trial printing has been used. However, recently, various color proofs have been created for the purpose of speeding up the proofing process and reducing costs.
As a method for producing a color proof, a surprint method and an overlay method using a photopolymer, a diazo method, a photo-adhesive polymer and the like are known (for example, US Pat. No. 3,582,327, JP-A-56-50121).
No. 7, No. 59-97140). However, all of these methods require superimposing or transferring images, and also require superimposing or transferring a plurality of figures, and require a lot of time and cost due to complicated processes. . JP-A-56-104335 discloses that
A method for producing a color proof using a color photographic light-sensitive material has been disclosed. This method has great advantages in terms of simplicity of the process and low cost, and has features such as 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 color developing method having a continuous tone, and the magenta (M), cyan (C), and yellow ( This is a method in which each plate of Y) color and black (B) color is successively contact-exposed so as to print a color negative on a color paper, and then a specified color development process is performed to obtain a color proof. This method has features that the process is simple and easy to automate as compared with the various methods described above. There are several silver halide color photographic light-sensitive materials that can be used for such a color proof. Among them, the transmission type black and white halftone dot image used in the above-described color print production process is often a positive type especially in Japan and Europe, and therefore, as a silver halide color photographic light-sensitive material for color proofing, Positive-positive photosensitive materials are often used. Among them, the direct positive type color photographic light-sensitive material, which has been rapidly advanced in recent years, has been attracting attention as being most suitable for color proof applications because of its simplicity of processing.

A positive color image can be obtained by subjecting a photosensitive material containing yellow, magenta and cyan color image forming couplers to photosensitive layers having different color sensitivities as described above to image development and then performing color development processing. it can.
The color development processing causes a coupling reaction between the oxidized form of the developing agent and the coupler to generate a coloring dye, which forms a positive color image. In this case, the coupler to be used is desired to have a coupling speed as high as possible and to provide a high color density in a limited time and a good color developing property. It is desired that the generated coloring dyes are yellow, magenta, and cyan dyes having little side absorption and give color images having good color reproducibility. Also, from the viewpoint of color reproducibility, it is important to realize a high whiteness by lowering the minimum image density. Conventionally,
As color image forming couplers used in direct positive color photographic light-sensitive materials, acylacetanilide yellow couplers, 2,5-diacylaminophenol cyan couplers and pyrazoloazole magenta couplers are known. For example, JP-A-2-220049 discloses that an acyl group has a pivaloyl type [(CH ₃ ) ₃ CC
A direct positive photographic light-sensitive material containing an acylacetanilide-based yellow coupler and a 2,5-diacylaminophenol-based cyan coupler as an O-] in a photosensitive layer is disclosed. The above publication describes an example in which a pyrazoloazole-based magenta coupler is used together with the yellow coupler and the cyan coupler. The above-mentioned publication describes that a highly active hydroquinone compound is added to the emulsion layer.

[0005]

However, according to the study of the present inventors, the use of the coupler and the hydroquinone-based compound disclosed in the above-mentioned publications revealed that the coloring hue,
Both color developability and whiteness are not satisfactory enough,
Further improvements are desired. Accordingly, an object of the present invention is to provide a direct positive color photographic light-sensitive material having good color hue (good color reproducibility), excellent color developability, and low minimum density (good whiteness). Another object of the present invention is to provide a method for forming a color image and a method for forming a color proof using the above-mentioned direct positive color photographic light-sensitive material.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies for cyan couplers suitable for the above-mentioned purpose, and as a result, selectively use a specific cyan coupler represented by the above formula. By using the cyan coupler in combination with a specific compound, it is further found that the object can be achieved by using the cyan coupler in combination with a specific developing agent, thereby completing the present invention. did. The present invention relates to a blue-sensitive layer (blue-sensitive emulsion layer) and a green-sensitive layer (green-sensitive emulsion layer) containing an internal latent image type silver halide grain and a color image-forming coupler which have not been previously fogged on a support. And a red-sensitive layer (red-sensitive emulsion layer) and at least one non-photosensitive layer adjacent thereto are provided in a direct positive color photographic light-sensitive material. CaI) or (CbI):

[0007]

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[Wherein, 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 -N =. R ^C13 is Hammett's substituent constant σ
_P value represents an electron-withdrawing group 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 which can be removed by a coupling reaction with an oxidized form of an aromatic primary amine color developing agent]

[0009]

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Wherein R ^C21 represents a hydrogen atom or a substituent. R ^C22 represents a substituent. Z ^{C2 1} represents a nonmetallic atom group necessary for forming a 6-membered heterocyclic nitrogen-containing. However, the heterocycle has at least one dissociating group. X
^C21 represents a hydrogen atom or a group capable of being removed by a coupling reaction with an oxidized form of an aromatic primary amine color developing agent], and at least one cyan coupler represented by the formula: It is a photosensitive material.

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

[0012]

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[Wherein, R ^M represents a hydrogen atom or a substituent, and Z ^M together with the bonding carbon atom and nitrogen atom are necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms. Wherein the azole ring may have a substituent (including a condensed ring), and X ^M represents a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized developing agent. Is a direct positive color photographic light-sensitive material which is a magenta coupler represented by the following formula:

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

[0015]

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[In the formula, R ^Q1 and R ^Q2 each independently represent a hydrogen atom or a group which breaks a bond with an oxygen atom during development to release a hydroxyl group, and R ^Q3 , R ^Q4 and R ^Q6 each represent 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 carbonate group, and R ^Q5 represents an aryl group bonded through the same group as the group represented by R ^Q3 or a linking group, provided that R ^Q5 is 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
That at least one hydrogen atom of the to R ^Q6, and if R ^Q3 to R ^Q6 consists only hydrogen atom and an alkyl group, at least one of the alkyl groups are at least 6 carbon atoms, and R ^Q3 To R ^{Q6 has} a total carbon number of 15 or less. ]

[0017]

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Wherein R ^{Q11 to} R ^Q16 each independently represent 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 , 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, wherein R ^Q11 and R ^Q12 or R ^Q14 and R
^Q15 may together form a carbocyclic or heterocyclic ring; R ^Q17 and R ^Q18 each independently represent a hydrogen atom,
It represents an alkyl group, an aryl group or a heterocyclic group, and the above R ^Q17 and R ^Q18 may form a carbocyclic or heterocyclic ring together. The above direct positive color photographic light-sensitive material comprises at least one hydroquinone derivative represented by the formula:

In still another embodiment of the present invention, the above-mentioned direct positive color photographic light-sensitive material is exposed to an image, and then subjected to the following formula (D):

[0020]

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[0021] In the formulas, R ^D1 is an alkyl group, R ^D2
Represents an alkylene group, provided that R ^D1 and R ^D2 may be linked to each other to form a ring. And a developing process using a developing agent represented by formula (1).

Still another aspect of the present invention is a cyan halftone dot image film, a magenta halftone dot image film, a yellow halftone dot image film, and a black plate obtained by subjecting the above color photographic light-sensitive material to color separation and halftone image conversion. This 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 color development processing.

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

[0024]

By using the direct positive color photographic light-sensitive material of the present invention containing the cyan coupler represented by the formula (CaI) or (CbI), the color hue is good (good color reproducibility), and A cyan image with good coloring can be obtained. Further, the cyan coupler and the formula (M)
When the magenta coupler is used in combination, the unnecessary absorption density of each of the cyan image and the magenta image decreases, and the color density also increases, so that an excellent color image satisfying both the color 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 density is reduced and high whiteness is obtained. Further, when forming a color image, if the color developing solution containing the specific developing agent represented by the formula (D) is used, the above-mentioned 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. The direct positive color photographic light-sensitive material of the present invention is provided with 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 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 are not previously fogged. As described above, the red-sensitive layer contains a cyan coupler represented by the formula (CaI) or (CbI).
Further, it is preferable that the green-sensitive layer contains the magenta coupler represented by the formula (M).

Hereinafter, 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. First, a cyan coupler represented by the following formula (CaI) will be described.

[0027]

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In the above formula (CaI), R ^C11 and R ^C12 each independently represent a Hammett's substituent constant σ _P
The value represents an electron-withdrawing group of 0.2 or more. Where 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 leaving by a coupling reaction with an oxidized form 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]

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

In the present invention, the formulas (CaII), (CaII)
A cyan coupler represented by formula (III) or (CaIV) is preferred, and a cyan coupler represented by formula (CaIII) is particularly preferred.

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, the σ _p values are each 0.3
It is an electron-withdrawing group having 5 or more, 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. 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.

The Hammett's rule was introduced in 1935 in L.L. in 1935 in order to discuss quantitatively the effect of a substituent on the reaction or balance of a benzene derivative. P. A rule of thumb proposed by Hammett, which is widely accepted today. Σ _p value and σ _m
There are values, and these values are described in many common books. For example, A. Dean (Lange's Hand book of che)
mistry "12th edition, 1979 (Mc Graw-Hill) and" Chemical Area Special Edition ", No. 122, pp. 96-103, 1979
Know more about the year (Nankodo). In the present invention, R ^C11 , R ^C12
And R ^C13 are limited by the Hammett's substituent constant σ _p value, but this does not mean that it is limited to only those substituents having known values in the literature described in these books, and the values are unknown in the literature. Of course, when measured based on the Hammett's rule, it is of course included as long as it is included in the range.

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 include:
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 include an aryl group, a heterocyclic group, a halogen atom, an azo group, or a selenocyanate group substituted with another electron-withdrawing group having a σ _p value of 0.20 or more. Among these substituents, a group which may further have a substituent is represented by R
^It may further have a substituent as ^exemplified for ^C14 .

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

Examples of the alkoxycarbonyl group include, for example, methoxycarbonyl, ethoxycarbonyl, 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.
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.

As the alkylsulfonyl group, for example,
Methanesulfonyl and octanesulfonyl can be mentioned. Examples of the arylsulfonyl group include benzenesulfonyl and toluenesulfonyl. Examples of the sulfonyloxy group include methanesulfonyloxy and toluenesulfonyloxy. Acylthio groups include, for example, acetylthio, and benzoylthio.

Examples of the sulfamoyl group include N-
Ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, and N, N-diethylsulfamoyl can be mentioned. . Examples of the thiocarbonyl group include methylthiocarbonyl and phenylthiocarbonyl.

Examples of the halogenated alkyl group include, for example,
Trifluoromethyl and heptafluoropropyl can be mentioned. Examples of the halogenated alkoxy group include trifluoromethyloxy. Examples of the halogenated aryloxy group include, for example, pentafluorophenyloxy. Examples of the halogenated alkylamino group include N, N-di- (trifluoromethyl) amino. Examples of the halogenated alkylthio group include difluoromethylthio,
1,1,2,2-tetrafluoroethylthio can be mentioned.

Examples of the aryl group substituted with another electron-withdrawing group having a σ _p value of 0.20 or more include the following.
Examples thereof include 2,4-dinitrophenyl, 2,4,6-trichlorophenyl, and pentachlorophenyl.
Examples of the heterocyclic group include 2-benzoxazolyl,
Examples thereof include 2-benzothiazolyl, 1-phenyl-2-benzimitazolyl, 5-chloro-1-tetrazolyl, and 1-pyrrolyl. 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 the electron-withdrawing group include a cyano group (0.66), a nitro group (0.78), a trifluoromethyl group (0.54), and an 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 include acyl, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, cyano, nitro, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, sulfamoyl, and halogenated alkyl A halogenated alkyloxy group, a halogenated alkylthio group, a halogenated aryloxy group, a halogenated aryl group, an aryl group substituted with two or more nitro groups, and a heterocyclic group. Among them, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, and a halogenated alkyl group are preferable, and a cyano group, an unsubstituted or substituted alkoxycarbonyl group substituted with a fluorine atom, an alkoxycarbonyl group or a carbamoyl group, an unsubstituted or an alkyl group, An aryloxycarbonyl group substituted with an alkoxy group is more preferred.

In the present invention, more preferably, R ^C11 ,
At least one of R ^C12 and R ^C13 has a σ _p value of 0.60.
These are the 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. R ^C11 is particularly preferably a cyano group.

R ^C14 and R ^C15 each independently represent a hydrogen atom or a substituent (including an atom). 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, aryl or heterocyclic thio group, an acyloxy group, a carbamoyloxy group, and 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, imide group, azolyl group, hydroxy group, cyano group,
Examples 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 a substituent as 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 include methyl, ethyl, propyl, isopropyl, tert-butyl, tridecyl, 2-methanesulfonylethyl, 3- (3-pentadecylphenoxy) propyl, 3- {4-} 2- [4-
(4-hydroxyphenylsulfonyl) phenoxy] dodecanamido {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, such as phenyl, naphthyl, 4-hexadecyloxyphenyl, 4-tert-butylphenyl, 2,4-di-tert-amylphenyl, 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,
-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.

As the acylamino group, for example, acetamido, benzamido, tetradecaneamido, 2-
(2,4-tert-amylphenoxyacetamide, 2-
[4- (4-hydroxyphenylsulfonyl) phenoxy)] decanamide, isopentadecaneamide, 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) dodecanamido] anilino, and 2-chloro-5-dodecyloxycarbonylanilino. Examples of the ureido group include methyl ureide, phenyl ureide, N,
N-dibutylureide and dimethylureide.

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,
Phenylpropanoyl, and 4-dodecyloxybenzoyl. Examples of the alkyl, aryl or heterocyclic sulfonyl group include, for example, methanesulfonyl,
Octanesulfonyl, benzenesulfonyl, and toluenesulfonyl.

The sulfinyl group includes, for example, octanesulfinyl, dodecylsulfinyl, dodecanesulfinyl, phenylsulfinyl, 3-pendadecylphenylsulfinyl, 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.

Examples of the sulfonamide group include methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, and 2-methoxy-5-
tert-butylbenzenesulfonamide. Examples of the carbamoyl group include N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, and N- [3- (2,4- Di-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.

Examples of the phosphonyl group include phenoxyphosphonyl, octyloxyphosphonyl, and phenylphosphonyl. Imide groups include, for example, 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.

Further preferred are an alkyl group and an aryl group, and more preferred are an alkyl group and an aryl group having at least one of an alkoxy group, a sulfonyl group, a sulfamoyl group, a carbamoyl group, an acylamide group or a 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 capable of leaving when a coupler reacts with an oxidized form of an aromatic primary amine color developing agent (hereinafter, simply referred to as a “leaving group”). The leaving group may be a halogen atom, an aromatic azo group, or an alkyl, aryl, or 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. , An alkyl, aryl or heterocyclic carbonyl group, and a heterocyclic group bonded to the coupling position at a nitrogen atom. Examples of these include a halogen atom, an alkoxy group, an aryloxy group,
Acyloxy group, alkyl or arylsulfonyloxy group, acylamino group, alkyl or arylsulfonamide group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl, aryl or heterocyclic thio group, carbamoylamino group, arylsulfinyl group, arylsulfonyl And a 5- 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 for R ^C14 , and when two or more of these substituents are present, they are the same. Or different. Further, these substituents may further have the substituents described for R ^C14 above.

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 the aryloxy group,
For example, 4-methylphenoxy, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarboxyphenoxy, 3-acetylaminophenoxy, and 2-carboxyphenoxy. Acyloxy groups include, for example, acetoxy, tetradecanoyloxy, and benzoyloxy.

Examples of the alkyl or arylsulfonyloxy group include methanesulfonyloxy and toluenesulfonyloxy. Acylamino groups include, for example, 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. Can be As the arylsulfonyl group, for example, 2-butoxy-5-te
rt-octylphenylsulfonyl. As the arylsulfinyl group, for example, 2-butoxy-5
-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 imido group include succinimide and hydantoinyl. As the arylazo group, for example, phenylazo,
And 4-methoxyphenylazo.

The above groups may be further substituted with the groups mentioned as the substituents for R ^C14 . Further, as a leaving group that is bonded to the coupling position via a carbon atom, there is a bis-type coupler obtained by bonding a four-equivalent coupler with an aldehyde or a ketone. 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 includes a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, an arylsulfonyl group, an arylsulfinyl group,
A 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active site 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]

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In the above formula (CbI), R ^C21 represents a hydrogen atom or a substituent. R ^C22 represents a substituent. Z
^C21 represents a nonmetallic atom group necessary for forming a nitrogen-containing 6-membered heterocyclic ring. However, the heterocycle has at least one dissociating group. X ^C21 represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized form of an aromatic primary amine color developing agent.

As the substituents for R ^C21 and R ^C22 , there can be mentioned the substituents mentioned for R ^C14 above. 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 a σ _p value of 0.35 or more. These are more preferably 0.60 or more electron-withdrawing groups. Particularly preferably, R ^C21 , 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 in R ^C11 above.

The above Z ^C21 represents a nonmetallic atom group necessary for forming a nitrogen-containing 6-membered heterocyclic ring. Provided that the heterocyclic ring has at least one dissociating group. Examples of the four divalent linking groups constituting such a nitrogen-containing 6-membered heterocyclic ring include -NH-, -N (R)-, -N =, -CH (R)-,-
CH =, -C (R) =, -CO-, -S-, -SO-,
-SO ₂ - and the like (R is a substituent, wherein R
^And the substituents mentioned for ^C14 ). Examples of the dissociating group include those having an acidic proton, such as -NH- and -CH (R)-. Preferably, the pKa in water is 3-1.
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 preferred, and couplers represented by the formulas (CbII), (CbIII) or (CbVIII) are more preferred.

[0072]

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[0073]

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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
The substituents of ^{C 27} and R ^C28 are the same as those described for R ^C14 above. The electron-withdrawing group represented by EWG is the same as that described 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)
It contains a cyan coupler skeleton represented by (I) or (CbI) and forms a dimer or higher multimer, or contains a polymer chain and forms a homopolymer or a copolymer. You may. The homopolymer or copolymer containing a polymer chain is an addition polymer having a cyan coupler residue represented by the formula (CaI) or (CbI), a homopolymer or a copolymer of an ethylenically unsaturated compound. Is a typical example.
In this case, the polymer may contain one or more cyan-color-forming repeating units having a cyan coupler residue represented by the formula (CaI) or (CbI). Copolymers containing one or more non-color-forming ethylene type monomers which do not couple with the oxidation products of aromatic primary amine color developing agents, such as methacrylates and maleates. Good.

Hereinafter, specific examples of the coupler represented by the formula (CaI) will be described. The substituents used in these specific examples are as follows.

[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

[Table 1] Table 1 II CaII R ^C11 R ^C12 R ^C14 R ^C15 X ^C11 １ 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]

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[0085]

[Table 2] Table 2 IIICaIII 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]

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[0087]

[Table 3] Table 3 IV 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) ───────── ───────────────────────────

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[0089]

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

[0090]

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[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]

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[0093]

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

[0094]

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[0095]

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

[0096]

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[0097]

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

Hereinafter, specific examples of the coupler represented by the formula (CbI) will be shown. The substituents used in these specific examples are as follows.

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[0103]

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[0104]

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[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]

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[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) ) ────────────────────────────────────

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[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) ─────────── ─────────────────────────

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

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

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[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) ─────────── ─────────────────────────

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[0119]

[Table 15] Table 15 ──────────────────────────────────── CbVIII R ^C21 R ^C22 R ^C25 X ^C21 １ 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]

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[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]

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[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]

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[0125]

[Table 18] Table 18 ──────────────────────────────────── CbXI R ^C21 R ^C22 R ^C23 R ^C26 EWG X ^C21 １ 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]

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[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]

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[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]

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[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]

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[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]

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[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]

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[0137]

[Table 24] Table 24 ──────────────────────────────────── CbXVII R ^C21 R ^C22 R ^C27 R ^C28 EWG X ^C21 １ 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]

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[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]

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[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 compounds of the present invention and their intermediates can be synthesized by known methods. 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., No. 27, 2301 (1988), Rec. Trav. chim., 80, 1075
(1961), 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]

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

The compound (3a) obtained above (101.1)
g, 0.3 mol) in dimethylformamide (200 ml) solution was added with potassium hydroxide (252 g, 4.5 mol) powder at room temperature and stirred well. To this, under water cooling, hydroxylamine-0-sulfonic acid (237 g,
2.1 mol), so that the temperature does not rise rapidly,
The mixture was added little by little, and stirred for 30 minutes after the addition. 0.1N more
A hydrochloric acid aqueous solution was added dropwise, and the mixture was neutralized while looking at the pH test paper.
The obtained solution was extracted three times with ethyl acetate, and 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 the residue was purified by column chromatography (developing solvent; hexane: ethyl acetate = 2: 1) to obtain compound (4a) (9.50 g, 9%).

The compound (4a) (7.04 g, 2
(0 mmol) in acetonitrile (30 ml) was added carbon tetrachloride (9 cc) at room temperature, followed by triphenylphosphine (5.76 g, 22 mmol) and refluxed for 8 hours. After cooling, water was added, and the mixture was extracted three 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) provided compound (5a) (1.13 g, 17%).

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

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

[0151]

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2-amino-3-cyano-4-phenylpyrrole (compound a) 1 obtained by condensation of 2-aminoacetophenone hydrochloride and malononitrile in the presence of an alkali
8.3 g and diethyl ethoxyethylidenemalonate 2
5.3 g were dispersed in 300 ml of ethanol, and 22.0 ml of a 28% methanol solution of sodium methylate was added thereto, followed by heating under reflux for 5 hours. After cooling, ethyl acetate was added, and 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. Next, 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 ° C to 140 ° C for 6 hours. After cooling, the residue was purified by silica gel chromatography (developing solvent; hexane: ethyl acetate = 1: 1) to obtain 14.7 g of the desired exemplified compound (CbIII-3) as a pale yellow oil.

The cyan couplers described above may be used alone or in combination of two or more. Moreover, you may use together with another well-known coupler. The above formula (CaI)
Alternatively, the amount of the cyan coupler represented by (CbI) in the light-sensitive material is 1 × 10 ⁻⁵ per m ² of the light-sensitive material.
Mol to 1 × 10 ^-2 mol, preferably 1 × 10 ⁻² mol.
In the range of 10 ^-4 mol to 5 × 10 ^-2 mol, more preferably,
The range is from 2 × 10 ⁻⁴ mol to 1 × 10 ⁻³ mol.

Next, a magenta coupler which is preferable as a 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. This magenta coupler is a magenta coupler represented by the following formula (M).

[0155]

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[Wherein, R ^M represents a hydrogen atom or a substituent, and Z ^M together with the bonding carbon atom and nitrogen atom are necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms. Wherein the azole ring may have a substituent (including a condensed ring), and X ^M is a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized developing agent. Represents]. Among the magenta couplers represented by the formula (M), a particularly preferred 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):
Having an H -pyrazolo [1,5- b ] [1,2,4] triazole skeleton, 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)
Those having a -pyrazolo [1,5- d ] tetrazole skeleton and those having a 1H -pyrazolo [1,5- a ] benzimidazole skeleton represented by the following formula (MV).

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The formulas (MI), (M-II) and (M-II)
I), R ^{M1 in} each of the formulas (M-IV) and (MV),
R ^M2, R ^M3, the R ^M4, n ^M and X ^M will be described in detail. R ^M1 is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, a sulfo group, an amino group, an alkoxy group, an aryloxy group, an acylamino group, an alkylamino 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 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 (for example, a chlorine atom or a bromine atom), an alkyl group (for example, a linear or branched alkyl group having 1 to 32 carbon atoms, an aralkyl group, an alkenyl group). Group, alkynyl group, cycloalkyl group, cycloalkenyl group, specifically, for example, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3-
(3-pentadecylphenoxy) propyl, 3- {4-
{2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecanamido} phenyl} propyl, 2-
Ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl); aryl group (for example, 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, -Methanesulfonylethoxy); aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3
-Methoxycarbamoyl); acylamino group (for example,
Acetamide, benzamide, tetradecaneamide, 2
-(2,4-di-t-amylphenoxy) butanamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decaneamide; alkylamino group (For example, methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino); anilino group (for example, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino,
-Chloro-5-dodecyloxycarbonylanilino, N
-Acetylanilino, 2-chloro-5- {2- (3-t
-Butyl-4-hydroxyphenoxy) dodecaneamide {anilino); ureido group (eg, phenylureido, methylureide, N, N-dibutylureido); sulfamoylamino group (eg, N, N-dipropylsulfamoylamino) , N-methyl-N-decylsulfamoylamino); alkylthio groups (for example, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3- (4-
t-butylphenoxy) propylthio); arylthio groups (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); carbamoyl group (eg, 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); a heterocyclic oxy group (eg, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy); an azo group (eg, phenylazo, 4-methoxyphenylazo, 4-pi Baroylaminophenylazo,
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 (for example, N
-Succinimide, N-phthalimide, 3-octadecenylsuccinimide); a 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) Aryloxycarbonyl group (for example, phenoxycarbonyl); acyl group (for example, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl); or azolyl group (for example, imidazolyl, pyrazolyl, 3). -Chloropyrazol-1-yl, triazolyl).

Among these substituents, the group which can have a substituent further includes an organic substituent linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom, or a halogen 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 include a urethane group and an acylamino group.

R ^M2 is the same group as the substituent exemplified for R ^M1 , and is 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, An acyl group, a cyano group and the like can be mentioned. R ^M3 is R ^M1
Are the same as the substituents exemplified for, preferably, a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group,
Examples include an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, a carbamoyl group, and an acyl group.
Examples thereof include an alkyl group, an aryl group, a heterocyclic group, an alkylthio group, and an arylthio group. Also, R
^M4 is the same group as the substituent exemplified for R ^M1 ,
Preferably, a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an acyl group, an acylamino group, an alkoxycarbonylamino group, and a sulfonamide group , A sulfamoylamino group, a cyano group, and the like.

N represents an integer of 1 to 4, preferably an integer of 1 to 3. X ^M represents a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized developing agent (particularly, an aromatic primary amine color developing agent). Examples of the removable group include a halogen atom and an alkoxy group. An aryloxy group, an acyloxy group, an alkyl or arylsulfonyloxy group, an acylamino group, an alkyl or arylsulfonamide group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkyl, aryl or heterocyclic thio group, a carbamoylamino group, membered or 6-membered nitrogen-containing heterocyclic group, an imido group, and a arylazo group, these groups may be further substituted with the groups exemplified as the substituent of R ^M1. More specifically, the group capable of leaving in the reaction with the oxidized form of the developing agent represented by X ^M includes a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom); an alkoxy group (for example, 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 group (eg, acetoxy, tetradecanoyloxy, benzoyloxy); alkyl or arylsulfonyloxy Acyl groups (eg, methanesulfonyloxy, toluenesulfonyloxy); acylamino groups (eg, dichloroacetylamino, heptafluorobutyrylamino); alkyl or arylsulfonamide groups (eg, 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 group (eg, succinimide, hydantoinyl); arylazo group (eg, phenylazo, 4-methoxyphenylazo).

X ^M is, in addition to the above, an aldehyde or ketone as a leaving group bonded through a carbon atom.
It may take the form of a bis-type coupler obtained by condensing equivalent couplers. X ^M may contain a photographically useful group such as a development inhibitor or 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- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active site with a nitrogen atom. , A halogen atom, a substituted aryloxy group, a substituted arylthio group,
Or a substituted 1-pyrazolyl group.

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

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The magenta coupler represented by the formula (M) is
It can be synthesized by a synthesis method described in the following literature. For example, the compound represented by the formula (MI) is disclosed 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;
JP-A-61-65245, JP-A-62-209457 and JP-A-62-249155 disclose the compound represented by the formula (M-III) in
-27411, U.S. Pat. No. 3,725,067 and the like, the formula (M-
The compound represented by IV) can be synthesized by the synthesis methods described in JP-A-60-33552 and the like.

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

The non-preliminarily fogged internal latent image type silver halide emulsion of the present invention is an emulsion containing silver halide grains whose surface is not fogged and whose latent image is mainly formed inside the grains. More specifically, a silver halide emulsion is coated on a transparent support in a fixed amount (0.5 to 0.5).
-3 g / m ² ), exposed to the solution for a fixed time of 0.01 to 10 seconds, and developed in the following developer (internal developer) at 20 ° C. for 5 minutes. The maximum density measured by the measuring method is the maximum value obtained when the same amount of the above-mentioned silver halide emulsion coated and exposed in the same manner is developed in the following developer (surface type developer) at 18 ° C. for 6 minutes. Those having a concentration at least 5 times greater than the concentration are preferred, and more preferably those having a concentration at least 10 times greater.

Internal developer Metol 2.0 g Sodium sulfite (anhydride) 90.0 g Hydroquinone 8.0 g Sodium carbonate (monohydrate) 52.8 g KBr 5.0 g KI 0.5 g Add water 1000 ml Surface developer Metol 2.5 g L-ascorbic acid 10.0 g NaBO ₂ .4H ₂ O 35.0 g KBr 1.0 g Water was added and 1000 ml

Specific examples of the internal latent image type silver halide emulsion include, for example, a conversion type silver halide emulsion described in US Pat. No. 2,592,250; and US Pat. No. 3,761,276, US Pat. No. 4035185, No. 43954
Nos. 78 and 4504570;
156614, 55-127549, 53-6
Nos. 0222, 56-22681, 59-2085
No. 40, No. 60-107641, No. 61-3137
No. 62-215272, German Patent No. 2332802c2, Research Disclosure Magazine No. No. 23510 (November 1983), page 236; furthermore, a specification of U.S. Pat. No. 4,789,627 having a silver chloride shell; JP-A-63-10160 concerning a silver chlorobromide core-shell emulsion;
JP-A-63-47766 and Japanese Patent Application No. 1-24.
No. 67, JP-A-63-191145 and JP-A-1-5214 concerning emulsions doped with metal ions.
No. 6, core / shell type silver halide emulsions described in each publication. The internal latent image type silver halide grains not fogged in advance used in the present invention are preferably of a core / shell type. The molar ratio of the core and shell silver halide in the internal latent image type core / shell silver halide emulsion is not more than 20/1 and 1/10.
0 or more is particularly preferred.

The internal latent image type silver halide grains not fogged in advance 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, and 10
^-7 to 10 ^-3 mol is more preferred. Among the above metals, P
The use of b (lead), Ir (iridium), Bi (bismuth) and Rh (rhodium) is preferred. When forming silver halide grains while mixing and stirring a silver ion solution and an aqueous halogen solution, these metals are mixed with each other in the form of a solution in which the metal (metal ion) is dissolved in an aqueous solution or an organic solvent. By adding it to the silver halide grains (or coexisting in an aqueous halogen solution), it can be incorporated in the silver halide grains. Further, after the silver halide grains are formed, the above-mentioned metals can be incorporated in the grains by adding them to the emulsion in the form of an aqueous solution of the above-mentioned metal or a solution 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 metal complex salt (complex) or a metal compound such as an oxyacid salt or an organic acid salt of the metal. The methods for incorporating these metals are described in U.S. Pat.
395478 and JP-A-59-216136.
No., etc.

The shape of the silver halide grains used in the present invention may be cubic, octahedral, dodecahedral, or tetradecahedral (see JP-A-2-22).
No. 3948), an irregular crystal form such as a sphere, etc .;
And emulsions in which tabular grains having a length / thickness ratio of 5 or more, particularly 8 or more, occupying 50% or more of the total projected area of the grains described in JP-A No. 1-158429 may be used. . Emulsions having a complex form of these various crystal systems or a mixture thereof may be used. The composition of silver halide includes silver chloride, silver bromide, and mixed silver halide. The silver halide preferably used in the present invention contains no silver iodide, or contains silver iodide. 3 mol%
The following are silver (iodo) bromide, silver (iodo) chloride or silver (iodo) bromide. The average grain size of silver halide grains (in the case of spherical or nearly spherical grains, the grain diameter, in the case of cubic grains, the vertical length, each of which is the grain size and is represented by an average based on the projected surface) is 1.5 μm. Hereinafter, it is preferably at least 0.1 μm, particularly preferably at most 1.2 μm,
It is 0.2 μm or more. The particle size distribution may be narrow or wide, but may be within ± 40%, preferably within 30%, and most preferably ± 30% of the average particle size in terms of the number or weight of the particles in order to improve graininess and sharpness. It is preferred to use so-called "monodisperse" silver halide emulsions having a narrow grain size distribution such that 90% or more, particularly 95% or more of all grains fall within 20%.

In order to satisfy the desired gradation of the light-sensitive material, two or more kinds of monodispersed silver halide emulsions having different grain sizes or substantially the same size in an emulsion layer having substantially the same color sensitivity. Can be mixed in the same layer or multi-layer coated in another layer. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be used as a mixture or as a mixture.

The silver halide emulsion used in the present invention is preferably chemically sensitized inside or on the surface of the grain by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization alone or in combination. JP-A-2-199450 and JP-A-2-199449 disclose a method for chemically sensitizing core particles.
Can be used. JP 1
As described in 197742, in the presence of a mercapto compound;
As described in JP-A-9738 and JP-A-2-273735, thiosulfinic acid, sulfinic acid and sulfite may be added. Detailed examples are described in, for example, Research Disclosure Magazine No. 17643-III (published December 1978), p. 23 and the like.

The photographic emulsion used in the present invention is spectrally sensitized by a conventional method using a photographic sensitizing dye. Particularly useful dyes are those belonging to cyanine dyes, merocyanine dyes and complex merocyanine dyes, and these dyes can be used alone or in combination. Further, the above dyes and supersensitizers may be used in combination. For detailed examples, see Research
Disclosure Magazine No. 17643-IV (197
(Issued in December 2008) on pages 23 to 24 and the like. The photographic emulsion used in the present invention may contain an antifoggant or a stabilizer for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. For a detailed example,
For example, Research Disclosure Magazine No. 1764
3-VI (issued December 1978) and E.C. J. B
irr "Stabiliaution of Photographic Silver Hai
lde Emulsion "(Focal Press), 1974.

In the present invention, the above-mentioned formula (CaI)
Or a cyan coupler represented by (CbI) and a formula (M)
Various color couplers may be used in addition to the magenta coupler represented by. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolone or birazoloazole 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 (issued in December 1978), 25 pages, VI
No. ID, the same No. 18717 (issued in November 1979) and the compounds described in JP-A-62-215272 and the patents cited therein. Examples of the yellow coupler preferably used in the present invention include, for example, US Pat. Nos. 3,933,501 and 402,262.
Nos. 0, 432,024 and 4,401,752, Japanese Patent Publication No. 58-10739, and British Patent No. 14
Those described in JP-A Nos. 25020 and 1476760 are preferable.

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

First, the compound represented by formula (HQ1) will be described in detail. In the above formula (HQ1), examples of the group represented by R ^Q1 and R ^Q2 , in which the bond with an oxygen atom is released during development to release a hydroxyl group, include an acyl group, an alkoxycarbonyl group, an aminocarbonyl group, or Further, there may be mentioned groups described in JP-A-59-97037 and JP-A-59-201057. 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 groups represented by R ^Q1 and R ^Q2, which are capable of releasing a hydroxyl group by breaking a bond with an oxygen atom during development processing, are linking groups bonded to R ^Q3 , R ^Q4 and R ^Q6 , or R ^Q5. And may form a 5- to 7-membered ring. Such examples include * -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-**, * -CONHNH-**
Can be mentioned. Here, * bonds to an oxygen atom of hydroquinone, and ** denotes 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 Preferably, R ^Q1 and R ^Q2 are 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
^{As the} alkyl group represented by ^Q3 , ^RQ4 and ^RQ6 , 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, for example, groups 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. As the sulfonamide group represented by R ^Q3 , R ^Q4 and R ^Q6 ,
Examples include 30 (preferably 1 to 15) sulfonamide groups, for example, groups such as methanesulfonamide and benzenesulfonamide. Examples of the alkoxy group represented by R ^Q3 , R ^Q4 and R ^Q6 include alkoxy groups having 1 to 30 (preferably 1 to 15) carbon atoms, for example, groups such as methoxy, butoxy, benzyloxy and dodecyloxy. it can.

The aryloxy groups represented by R ^Q3 , R ^Q4 and R ^Q6 each have 6 to 30 carbon atoms (preferably 6 to 1 carbon atoms).
5) Aryloxy groups, for example, groups such as phenoxy and p-methoxyphenoxy. R ^Q3 ,
Examples of the alkylthio group represented by R ^Q4 and R ^Q6 include an alkylthio group having 1 to 30 (preferably 1 to 15) carbon atoms,
For example, groups such as butylthio and decylthio can be exemplified. The arylthio groups represented by R ^Q3 , R ^Q4 and R ^Q6 include arylthio groups having 6 to 30 (preferably 6 to 15) carbon atoms, for example, groups such as phenylthio and p-hexyloxyphenylthio. . R ^Q3 ,
The acyl group represented by R ^Q4 and R ^Q6 has 2 to 2 carbon atoms.
Examples include 30 (preferably 2 to 15) acyl groups such as acetyl, benzoyl, and hexanoyl. 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 such as methanesulfonyl and benzenesulfonyl. 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 such as N, N-diethylcarbamoyl and N-phenylcarbamoyl. The alkoxycarbonyl group represented by R ^Q3 , R ^Q4 and R ^Q6 has 2 to 30 carbon atoms.
(Preferably 2 to 15) alkoxycarbonyl groups, for example, groups such as methoxycarbonyl and butoxycarbonyl.

As the sulfamoyl group represented by R ^Q3 , R ^Q4 and R ^Q6 , a sulfamoyl group having no substituent or a substituent having 1 to 30 (preferably 1 to 15) carbon atoms, for example, N, N-dipropyls Groups such as rufamoyl and N-phenylsphamoyl can be used. R ^Q3 , R ^Q4
And the ureido group represented by R ^Q6 has 1 to 2 carbon atoms.
A ureido group having 0 (preferably 1 to 15) substituents, for example, groups such as 3-methylureide, 3-isopropylureide, 3-cyclohexylureide, 3-hexadecylureide, and 3-phenylureide may be mentioned. it can. Examples of the urethane group represented by R ^Q3 , R ^Q4 and R ^Q6 include urethane groups having 2 to 20 (preferably 2 to 15) carbon atoms, for example, methoxycarbonylamino, t-butyloxycarbonylamino, dodecyloxydicarboniamino And phenoxycarbonylamino. The carbonate groups represented by R ^Q3 , R ^Q4 and R ^Q6 have 2 to 20 carbon atoms (preferably 2 to 20 carbon atoms).
15) Carbonic ester groups, for example, groups such as ethoxycarbonyloxy and phenoxycarbonyloxy. R ^Q5 represents the same group as the group represented by R ^Q3 or an aryl group bonded via 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 substituted for R ^Q8 described below. However, R ^Q5 is ^equal to R ^Q3 above.
When the same group as the group represented by is represented, the above R ^Q3 and R ^Q4
And R ^Q5 and R ^Q6 may together form a carbocyclic or heterocyclic ring. 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 consist only of a hydrogen atom and an alkyl group, at least one of the alkyl groups has 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 equation (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,
It is preferably a halogen atom, an alkyl group, an aryl group, an alkoxy group, a cyano group, an acylamino group or an alkylthio group, and more preferably a hydrogen atom, an alkyl group, an alkoxy group or an acylamino group.

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

[0213]

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[Wherein, R ^Q7 represents a group which can be substituted 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. And p represents an integer of 1 to 3, and m represents an integer of 0 to 4 wherein m is 2
In the above case, the plurality of R ^Q7s may be the same or different. As the group which can be substituted on the benzene ring represented by R ^Q7 , the same group as the group represented by R ^Q3 can be exemplified. 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, and a sulfamoyl group are more preferable. Or an acylamino group. In the present invention, m
Is preferably 0 or 1. R ^Q3 , R
The total carbon number of ^Q4 and R ^Q6 and the above R ^Q7 is preferably 50 or less, more preferably 35 or less, and particularly preferably 20 or less.
It is as follows.

As the divalent linking group represented by L,
It is an atom or an atomic group containing at least one of C, N, S and O. Specifically, (1) an alkylene group (preferably having 1 to 12 carbon atoms, for example, methylene, ethylene, trimethylene and the like), (2) an alkenylene group (preferably having 2 to 12 carbon atoms, for example, vinylene , Butylene, etc.), (3) alkynylene group (preferably having 2 to 2 carbon atoms)
12 things, eg, ethinylene, butynylene etc.),
(4) an arylene group (preferably one having 6 to 10 carbon atoms, for example, phenylene, naphthylene and the like), (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. As a specific example of the above combination, 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.). In the present invention, L
Is an alkylene (in _{particular, -CH 2 -), - NHCO-} ,
_{-NHSO 2 -, - NHCONH-, NHSO} 2 NH-
And -NHCO- (alkylene)-;
CO- is particularly preferred. p is preferably 1 to 2, especially 1
It is.

As the alkyl group represented by R ^Q8 ,
Examples thereof include an alkyl group having 1 to 30 carbon atoms, for example, methyl, ethyl, butyl, isopropyl, t-butyl, cyclohexyl, octyl, and hexadecyl.
The alkenyl group represented by R ^Q8 has 2 to 2 carbon atoms.
There may be mentioned 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.
Zero aryl groups may be mentioned, for example, phenyl and naphthyl. The heterocyclic group represented by R ^Q8 is a 3- to 12-membered heterocyclic ring containing at least one heteroatom selected from a nitrogen atom, an oxygen atom, a sulfur atom and selenium. Examples of such include pyridyl, triazinyl, uracil, pyrrolyl, thienyl, furanyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl, pyrrolidinyl and morpholinyl. R ^Q8 may have a substituent (including an atom). Examples of the substituent include an alkyl group (1 to 18 carbon atoms) and an alkenyl group (2 to 1 carbon atoms).
8), alkynyl group (2-18 carbon atoms), aralkyl group (7-20 carbon atoms), aryl group (6-20 carbon atoms),
A hydroxyl group, an alkoxy group (1 to 18 carbon atoms), an aryloxy group (6 to 20 carbon atoms), a halogen atom, an amino group, an alkylthio group (1 to 18 carbon atoms), an arylthio group (6 to 20 carbon atoms), Acyloxy group (C 1
To 18), a sulfonyloxy group (1 to 18 carbon atoms), an acylamino group (1 to 18 carbon atoms), a sulfonamide group (1 to 18 carbon atoms), a carboxyl group, an alkoxycarbonyl group (2 to 18 carbon atoms), Aryloxycarbonyl group (C7-20), acyl group (C1-2)
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) ), A urethane group (2 to 20 carbon atoms), and a carbonate group (2 to 2 carbon atoms)
0). R ^Q8 is preferably an alkyl group (1 to 16 carbon atoms (preferably 1 to 10, more preferably 8 to 10)) or an aryl group (phenyl).

Hereinafter, specific examples of the compound represented by the formula (HQ1) will be shown.

[0218]

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[0219]

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[0220]

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[0221]

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[0222]

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[0223]

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Examples of the synthesis of the compound represented by the above formula (HQ1) are shown below. Synthesis of Compound (HQ1-2) To 100 ml of acetonitrile, 15.3 g of 2,5-dimethoxyaniline and 10.1 g of triethylamine were added, and 37 g of 2-dodecanesulfonamidobenzoyl 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
g was added and reacted at 120 ° C. for 5 hours. The obtained reaction product was added little by little to ice water, extracted with ethyl acetate, washed with water three times, and then the organic layer was concentrated under reduced pressure.
The residue was dissolved in isopropyl alcohol (150 ml), n-hexane (500 ml) was added, and the precipitated crystals were collected by filtration to obtain 39 g (yield: 82%) of the desired product.

Next, the compound represented by the following formula (HQ2) will be described in detail. In the formula (HQ2), the groups represented by R ^{Q11 to} R ^Q16 are the same as the groups represented by R ^Q3 described above. The R ^Q11 and R ^Q12 and R ^Q14 and R ^{Q1 5} may form a carbocyclic or heterocyclic ring in cooperation, further R ^Q11 to R ^{Q1 6,} said R
^It may be substituted with the substituents ^listed as substituents for ^Q3 . As the alkyl group represented by R ^Q17 and R ^Q18 , an alkyl group having 1 to 40 carbon atoms, for example, methyl,
Groups such as i-propyl, undecyl, benzyl and the like can be mentioned. As the aryl group represented by R ^Q17 and R ^Q18 , an aryl group having 6 to 40 carbon atoms, for example,
Examples include groups such as phenyl and p-tolyl.
As the heterocyclic group represented by R ^Q17 and R ^Q18 ,
Examples thereof include a heterocyclic group having 1 to 40 carbon atoms, for example, a pyridin-2-yl group. R ^Q17 and R ^Q18 may form a carbocyclic or heterocyclic ring together. 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. Further, the compound of the formula (HQ2) may form a bis-form (tetrakis-form as the hydroquinone moiety) at R ^Q17 and / or R ^Q18 . In the above formula (HQ2), R ^{Q1 to} R ^Q16 are preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an acylamino group or an alkylthio group. More preferably, they are 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 carbocyclic ring. 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, and more preferably 10 to 30.

Hereinafter, specific examples of the compound represented by the formula (HQ2) will be shown.

[0227]

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[0228]

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[0229]

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[0230]

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[0231]

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[0232]

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[0233]

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The compounds represented by the above formulas (HQ1) and (HQ2) may be used alone or in combination of two or more. 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
In general, 1 × 10 ⁻⁸ mol / m ² per 1 m ^{2 of} photosensitive 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 ⁻³ mol / m ^2
-6 it is used in the range of mole / m ² ~1 × 10 ^-4 mol / m ^2.

Colored couplers for correcting unnecessary absorption in the short wavelength region of the resulting dyes, couplers in which the color forming dyes have an appropriate diffusivity, colorless couplers, and development inhibitors are released with the coupling reaction DIR couplers and polymerized couplers can also be used. Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are available from Research Disclosure N
o. 17643, Patents described in VII to F, JP-A-57-151944, JP-A-57-154234, and JP-A-60
-184248, U.S. Pat. No. 4,248,962 and JP-A-63-146035.
What is described in the gazette is preferable. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2097140 and 2131188.
Nos., JP-A Nos. 59-157638 and 59-1.
No. 70840, International Publication (WO) 88/01
No. 402 is preferred. The standard amount of the color coupler is in the range of 0.001 to 1 mol per mol of the light-sensitive 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, the amount is 0.02 to 1.0 mol.

Gelatin is advantageously used as a binder or protective colloid which can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, but other hydrophilic colloids can also be used. In the photosensitive material of the present invention,
Color fog inhibitors or color mixture inhibitors can also be used. Representative examples thereof are described in JP-A-62-215272, 185
To 193 pages. Compounds that release a photographically useful group include those described in
Nos. 3-153540 and 63-259555,
JP-A-2-61636, JP-A-2-244401, JP-A-2-24441
And the compounds described in each publication of JP-A-308240. In the present invention, a coloring enhancer can be used for the purpose of improving the coloring property of the coupler. Representative examples of the compounds include those described in JP-A-62-215272, pp. 121-125. Dyes for preventing irradiation and halation (for example, compounds described in JP-A-2-85850 and JP-A-2-89047) may be used in the light-sensitive material of the present invention. A solid microcrystal dispersion method may be used.), An ultraviolet absorber, a plasticizer, a fluorescent brightener, a matting agent, an air fog inhibitor, a coating aid, a hardener, an antistatic agent, a slipperiness improver, and the like. Can be added. Typical examples of these additives are research and
Disclosure Magazine No. 17643VII-XII
Section I (published December 1978), pp. 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, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as needed. The preferred order of the layer arrangement is red sensitivity, green sensitivity, blue sensitivity or green sensitivity, red sensitivity, and blue sensitivity from the support side. Each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, or a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. . Normally, the cyan-sensitive coupler is contained in the red-sensitive emulsion layer, the magenta-forming coupler is contained in the green-sensitive emulsion layer, and the yellow-forming coupler is contained in the blue-sensitive emulsion layer. Different combinations, such as mixing, can also be used. In the light-sensitive material of the present invention, in addition to the silver halide emulsion layer, an auxiliary layer such as a protective layer, an intermediate layer, a filter layer, an antihalation layer, a back layer, and a white reflective layer, which are non-photosensitive layers, may be appropriately provided. preferable.

The fogging treatment of the photographic light-sensitive material of the present invention is carried out by the following “light fogging method” and / or “chemical fogging method”. The entire surface exposure in the “light fogging method”, that is, the fogging exposure is performed after the imagewise exposure, before the color development processing, or during the color development processing. That is, an imagewise exposed light-sensitive material is immersed in a color developing solution or a pre-bath of the color developing solution, or is exposed before being taken out of these solutions and dried, but is exposed in the color developing solution. Is most preferred. As a light source for fogging exposure, for example, JP-A-56-137350 and JP-A-58-70223
Light sources having high color rendering properties (close to white as possible) as described in the above publications are preferred. Light illuminance is 0.01-20
00 lux, preferably 0.05 to 30 lux, more preferably 0.05 to 5 lux is suitable. A light-sensitive material using a higher-sensitivity emulsion preferably has a lower illuminance. The adjustment of the illuminance may be performed by changing the luminous intensity of the light source, by changing the light sensitivity by various filters, the distance between the light-sensitive material and the light source, or the angle between the light-sensitive material and the light source. Further, the illuminance of the fogging light may be increased continuously from low illuminance to high illuminance or stepwise. The light-sensitive material is preferably immersed in a color developing solution or a solution in a pre-bath thereof, and the light is preferably irradiated after the solution has sufficiently penetrated the emulsion layer of the light-sensitive material. The time from the penetration of the liquid to the light fogging and exposure is generally 2 seconds to 2 minutes, preferably 5 seconds to 1 minute, more preferably 10 seconds to 30 seconds. The exposure time for fogging is generally 0.01 seconds to 2 minutes, preferably 0.1 second.
It is from 1 second to 1 minute, more preferably from 1 second to 40 seconds.

In the present invention, the nucleating agent used for performing the so-called “chemical fogging method” can be contained in the photosensitive material or in the processing solution of the photosensitive material. A preferred method is to use it by incorporating it in a photosensitive material. Here, the nucleating agent is a substance which acts upon directly developing a latent image type silver halide emulsion which has not been previously fogged to form a positive image. In the present invention, the fogging treatment is preferably performed using a nucleating agent. When it is contained in the light-sensitive material, it is preferable to add it to the internal latent image type silver halide emulsion layer, but as long as it diffuses during coating or processing and the nucleating agent is adsorbed on the silver halide, other components are added. 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; 15162 (November 1976) 76-77
Page, the same magazine No. 23510 (November 1983) 346
To 352 pages, hydrazine compounds and the like. Two or more of these nucleating agents may be used in combination.

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

In the present invention, the quaternary heterocyclic compound and the hydrazine compound are preferably used 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 a nucleating agent is added to the processing solution, the amount used is 10 ^-8 to 10 ^-1 per liter.
Mol is preferable, 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 addition amount may vary over a wide range because it varies depending on the characteristics of the silver halide emulsion actually used, the chemical structure of the nucleating agent and the development conditions, but about 1 × per mole of silver in the silver halide emulsion. A range from 10 ^-8 moles to about 1 x 10 ^-2 moles is practically useful, preferably from about 1 x 10 ^-5 moles to about 1 x 10 ^-3 moles per mole of silver.

When a nucleating agent is used, it is preferable to use a nucleating agent for promoting the action of the nucleating agent. A nucleation accelerator has substantially no 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 speeds up the development time required to obtain a certain maximum density of a direct positive image. Examples of such a nucleation accelerator include thiadiazoles, oxadiazoles, benzotriazoles, tetrazaindenes having at least one mercapto group optionally substituted with an alkali metal atom or an ammonium group, Triazaindenes and pentazaindenes and compounds described in JP-A-63-106656, pages 5 to 16 can be mentioned. Also, JP-A-63-
No. 226652, No. 63-106656, No. 63-8
No. 740.

[0243] Two or more 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. Among the light-sensitive materials, it is contained in the internal latent image type silver halide emulsion and other hydrophilic colloid layers (intermediate layer, protective layer, etc.). Is preferably contained. Particularly preferred is a layer in or adjacent to a silver halide emulsion. The addition amount of the nucleation accelerator is preferably from 10 ^-6 to 10 ^-2 mol, more preferably from 10 ^-5 to 10 ^-2 mol, per mol of silver halide. When the nucleation accelerator is added to a processing solution, that is, a developing solution or a prebath thereof, it is preferably 10 ^-8 to 10 ^-3 mol, more preferably 10 ^-7 to 10 ^-4 mol per liter. is there.

Known photographic additives which 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 locations are summarized in the following table. Additive type RD17643 RD18716 １ 1 Chemical sensitizer page 23 648 right column 2 sensitivity enhancer Same as above 3 Spectral sensitizer, page 23-24 page 648 right column-supersensitizer 649 page right column 4 Brightener 24 page 5 Antifoggant 24-25 page 649 right column-stabilizer 650 right Column 6 Light absorber, page 25 right column Page 649 right column to filter dye, page 650 left column UV absorber 7 Stain inhibitor 25 page right column 8 Dye image stabilizer 25 page 9 Hardener 26 page 651 left column 10 Binder page 26 Same as above ──────────────────────────────In addition to the above- mentioned ultraviolet absorber, triazine-based compounds (for example,
No. 46-3335, EP-A-520,938
A), benzophenone compounds (European publication)
Patent No. 521,823A) is preferably used.
it can.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers may be formed of a flexible support such as a plastic film, paper, cloth or the like, or a rigid support such as glass, pottery, metal or the like, which is usually used for the photographic light-sensitive material. Coated on a support.
Useful as flexible supports are films, semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc., baryta layer or α-olefin polymer. (Eg, polyethylene, polypropylene, ethylene / butene copolymer) or the like, which is coated or laminated. The support may be colored using a dye or a pigment. For the application of 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 and No. 352652
No. 8, No. 3508947, etc., multiple layers may be applied simultaneously.

Next, the invention of a color image forming method using the above direct positive color photographic light-sensitive material will be described. After the image exposure, the direct positive color photographic light-sensitive material of the present invention can be developed by a conventionally known developing method, but is preferably developed by another color image forming method of the present invention. The color image forming method of the present invention is characterized in that after directly exposing the above positive color photographic light-sensitive material, it is processed with a developing solution containing a color developing agent represented by the formula (D) to obtain a positive color image. .

For the exposure of the light-sensitive material of the present invention, various exposure means can be used. 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. Flash light sources such as natural light (sunlight), incandescent lamps, halogen-filled lamps, mercury lamps, fluorescent lamps, and strobe or metal-burning flash bulbs are common. Gas, dye solution or semiconductor lasers, light emitting diodes, and plasma light sources that emit light in a wavelength range from ultraviolet to infrared can also be used as the recording light source. In addition, a phosphor screen (CRT, etc.) emitted from a phosphor excited by an electron beam or the like, a liquid crystal (LCD) or a micro-shutter array using lanthanum-doped lead zirconate titanate (PLZT) or the like has a linear or planar shape. Exposure means combining the above light sources can also be used. If necessary, the spectral distribution used for exposure can be adjusted with a color filter. In particular, by using a high-density beam light such as a gas laser (He-Ne laser, Ar laser, He-Cd laser) or various lasers such as a semiconductor laser as a light source, and moving the light relatively to the photosensitive material. Exposure means using a so-called scanning exposure method (scanner method) for exposing an image is preferable for directly exposing the positive color photographic light-sensitive material of the present invention. As the scanning exposure apparatus, for example, a color copier AP-5000 manufactured by Fuji Photo Film Co., Ltd. can be used. In the case of exposure by the scanning exposure method, the time required for exposing the silver halide is the time required for exposing a small area. As the minute area, a minimum unit for controlling the light amount from digital data is generally used, and is called a pixel. Therefore, the exposure time per pixel changes depending on the size of the pixel. The size of this pixel depends on the pixel density, and is 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 one pixel, and scanning exposure is performed under the condition that the exposure time for one pixel is 10 ⁻³ seconds or less (preferably, 10 ⁻⁶ to 10 ⁻⁴ seconds). preferable.

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

[0249]

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[0250]

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The amount of the developing agent represented by the general formula (D) 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. In addition, an aromatic primary amine-based 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 developing method of the present invention is the same as the conventional color developing solution except that the developing agent is the above specific compound. The developing method is the same as the well-known developing method except that the above-described developer is used. The photographic light-sensitive material after the color developing process is generally subjected to a desilvering process including bleaching and fixing processes, and is generally subjected to a washing and / or stabilizing process after the desilvering process. The above series of processing steps are described in
The method described on pages 380 to 381 of JP-A-2020537 can be preferably used.

The direct positive color photographic light-sensitive material of the present invention comprises
There are various uses, color print, color copy,
It is suitable for producing a color proof. The method for producing a color proof according to the present invention is a method for producing a color proof using a conventional method for producing a color proof, except for 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 according to the present invention comprises the steps of: producing a direct positive color photographic light-sensitive material of the present invention by color separation and halftone image conversion; And sequentially exposing with red light, green light, and blue light using a black dot image film to form a color image by color development as described above. This method can be performed, for example, using a Fine Checker F manufactured by Fuji Photo Film Co., Ltd.
It can be easily performed using C850H (exposure time: about 0.02 to 0.3 seconds).

[0253]

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

[Example 1] (Preparation of photosensitive material (sample 101 = comparative example)) A paper support laminated on both sides with polyethylene (thickness: 100 µm)
Of the following first to fourteenth layers on the front side and fifteenth layer on the back side.
A positive color photographic light-sensitive material was prepared directly by coating the 16th layer from the layers. 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 blue as a bluing dye (the chromaticity of the surface of the support is , L *, a *, b * 8
8.0, -0.20, and -0.75). (Composition of photosensitive layer) The following components and coating amount (g / m ² unit)
Is shown. However, the amount of the sensitizing dye added is represented by mol per mol of silver. For silver halide, the coating amount is shown in terms of silver. The emulsion used for each layer was emulsion EM-
It was made according to 1. However, a Lippmann emulsion which had not been chemically sensitized on the surface was used as the emulsion of the 14th layer.

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 isotometer 3.8 × 10 ^-4 ). [Coefficient of variation] 8%, octahedron) 0.04 Silver chlorobromide (chlorinated) spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3, each equivalent 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-) 1,2,3,4,30 are each equivalent) 0.18 Stain inhibitor (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 equivalent 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, and 30) 0.18 coupler dispersion medium (Cpd-6) 0.03 Coupler solvent (Equivalent amounts of Solv-1, 2, 3) 0.12 Fifth layer (intermediate layer) Gelatin 1.00 Color mixture inhibitor (Cpd-7) 0.08 Color mixture inhibitor solvent (Solv-4, 5) 0.16 Polymer latex (Cpd-8) 0.10

Sixth Layer (Low-Sensitivity Green Sensitive Layer) Silver bromide (average grain size: 0.25 μm, grain sensitized with a green sensitizing dye (ExS- ^4, 2.6 × 10 ⁻⁴ )) Size distribution: [variation coefficient] 8%, octahedral) 0.04 Silver chlorobromide (5 mol% of silver chloride) spectrally sensitized with a green sensitizing dye (ExS- ^4, 2.6 × 10 ^-4 ) Average particle size: 0.40 μm, particle size distribution: [variation coefficient] 10%, octahedron) 0.06 gelatin 0.80 magenta coupler (ExM-1) 0.11 anti-fading agent (Cpd-9, 26 each) 0.15 Stain inhibitor (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- 0.15 7th layer (highly sensitive 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 (Equivalent amounts of Cpd-9 and 26) 0.15 Stain inhibitor (Cpd-10, 11, 12, and 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 100 mm) 0.12 Gelatin 0.70 Color-mixing inhibitor (Cpd-7) 0.03 Color-mixing inhibitor solvent (Equivalents of Solv-4 and 5, respectively) 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 spectrally sensitized with a blue sensitizing dye (equivalent amounts of ExS-5 and ExS-6, 3.5 × 10 ⁻⁴ in total) (average grain size) : 0.40 µm, particle size distribution: [variation coefficient] 8%, octahedron) 0.07 Spectral sensitization with blue sensitizing dye (equal amounts of EXS-5 and 6; total 3.5 x 10 ^-4 ) 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-1,2 0.3, each equivalent) 0.35 Anti-fading agent (Cpd-14) 0.10 Anti-fading agent (Cpd-30) 0.05 Anti-stain agent (Cpd-5, 15 in a ratio of 1: 5) 0 .007 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (So1V-2) 0.10 No. 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 (Equivalent to ExY-1, 2, 3) 0.30 Anti-fading agent (Cpd-14) 10 Anti-fading agent (Cpd-30) 0.05 Stain inhibitor (Cpd-5, 15 in a ratio of 1: 5) 0.007 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-2) 0.10 13th layer (ultraviolet absorbing layer) Gelatin 1.00 Ultraviolet absorbing agent (Equivalent amounts of Cpd-2 , 4 , 16 , 30 , and 31 ) 0.50 Anti-color mixing agent (Equivalent to Cpd-7, 17) Amount) 0.03 Dispersion medium (Cpd-6) 0.02 Ultraviolet absorber solvent Solv-2, 7 are each equivalent) 0.08 Anti-irradiation dye (Cpd-18, 19, 20, 21, 27 in a ratio of 10: 10: 13: 15: 20) 0.05 Fourteenth layer ( (Protective layer) Fine particle silver chlorobromide (silver chloride: 97 mol%, average size: 0.1 μm) 0.03 Acrylic-modified copolymer of polyvinyl alcohol (molecular weight: 50,000) 0.01 Polymethyl methacrylate particles (average particle size: 2) 0.4 μm) and silicon oxide (average particle size: 5 μm) in equivalent amounts 0.05 gelatin 1.80 Gelatin hardener (Equivalent amounts of H-1 and H-2) 0.18

Fifteenth layer (back layer) Gelatin 2.50 UV absorber (Equivalent amounts of Cpd-2, 4, 16) 0.50 Dye (Equivalent amounts of Cpd-18, 19, 20, 21, and 27) 0.06 Sixteenth layer (back layer protective layer) Equivalent amounts of polymethyl methacrylate particles (average particle size: 2.4 μm) and silicon oxide (average particle size: 5 μm) 0.05 gelatin 2.00 gelatin hardening Agent (Equal 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 added to an aqueous gelatin solution at 75 ° C. while stirring vigorously.
The silver halide solution containing octahedral silver bromide grains having an average grain size of 0.35 μm was obtained. At this time, 0.3 g of 3,4-dimethyl-1,1 per mole of silver was used.
3-Thiazoline-2-thione was added. The emulsion was chemically sensitized by sequentially adding 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) per mol of silver and heating at 75 ° C. for 80 minutes. Using the grains thus obtained as a core, silver halide grains are further grown in the same precipitation environment as in the first time, and finally an octahedral monodispersed core / shell silver bromide having an average grain size of 0.7 μm. An emulsion was obtained. The coefficient of variation of the particle size was about 10%. 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mole of silver were added to this emulsion,
The mixture was heated for 0 minutes to perform a chemical sensitization treatment to obtain an internal latent image type silver halide emulsion. Each photosensitive layer has ExZ as a nucleating agent.
K-1 and ExZK-2 were added to silver halide in an amount of 1
0 ^-3 wt%, ^10-2% by weight, as a nucleation accelerator Cpd-
22, 28 and 29 were each used in an amount of 10 ^-2 % by weight. Furthermore, alkanol XC (Du Po
nt) and sodium alkylbenzenesulfonate as succinic acid esters and Magefa as coating aids.
c F-120 (manufactured by Dainippon Ink and Chemicals, Inc.) was used. In the layer containing silver halide and colloidal silver, equivalent amounts of Cpd-23, 24 and 25 were used as stabilizers.
This sample was designated as Sample (101). The compounds used in the above sample preparation are shown below.

[0260]

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[0261]

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[0262]

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[0263]

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[0264]

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[0265]

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[0266]

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[0267]

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[0268]

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[0269]

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[0270]

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[0271]

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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 (vinylsulfonylacetamido) ethane H-2 4,6-dichloro-2-hydroxy-1,3,5-triazine.Na salt

ExZK-1 7- (3-ethoxythiocarbonylaminobenzamide) -9-methyl-10-propargyl-1,2,3
4-tetrahydroacridinium trifluoromethanesulfonate ExZK-2 2- [4- {3- [3-} 3- [5-} 3- [2-chloro-5- (1-dodecyloxycarbonylethoxycarbonyl) phenyl Carbamoyl] -4-hydroxy-1
-Naphthylthio {tetrazol-1-yl] phenyl}
Ureido] benzenesulfonamide @ phenyl] -1-
Formylhydrazine

(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 by an equimolar amount of the following cyan coupler (ExC-2). .

[0275]

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(Preparation of photosensitive material (samples 103 to 107 = the present invention))
Cyan coupler (ExC-
1) was converted to an equimolar amount of a cyan coupler (CaII
I-3), (CaIII-10), (CaIV-6), (C
aVII-1) or (CbVIII-18), except that Sample 103, 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 101.
Samples 104, 105, 106, and 107 were formed.

[0277]

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[0278]

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(Photosensitive material (Sample 108 and Sample 109 =
Preparation of the present invention) In the preparation of the above sample 103, the magenta coupler (ExM) contained in the sixth and seventh layers was used.
-1) is converted to an equimolar amount of a magenta coupler (M
-36) or (M-41), respectively,
Samples 108 and 10 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 103.
9 was created.

[0280]

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(Photosensitive material (Sample 110 and Sample 111 =
(Preparation of the present invention)) In the preparation of the above sample 108, the third layer and the fourth layer contained 5% of the cyan coupler contained therein.
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, Samples 110 and 110 which are the direct positive color photographic light-sensitive material of the present invention were prepared. Sample 111 was prepared.

[0282]

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

[0284]

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(Photosensitive material (Sample 114 and Sample 115 =
Preparation of the present invention) In the preparation of the above sample 109, 5 mol% of the hydroquinone derivative (HQ1-1) or (HQ1-2) based on the color mixture inhibitor contained in the fifth layer was used.
Samples 114 and 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 was added.

[Evaluation as Direct Positive Color Photographic Material] Samples 101 to 115 obtained above were evaluated for color reproducibility and color developability according to the following evaluation methods. Note that an image was formed by the following processing step A. (Evaluation of color reproducibility) The image on each sample obtained by printing using a reversal film taken of a general subject and forming an image is observed under a light beam for color evaluation to evaluate the color reproducibility. evaluated. The evaluation results were classified and expressed as follows based on the image obtained from the sample 101. A: Very superior to the image obtained with sample 101. B: Superior to the image obtained with sample 101. C: Equivalent to the image obtained with sample 101. (Evaluation of Chromogenic Property) After each sample was single-colored to each hue of cyan or magenta to form a colored image (dye image),
Densitometer (X-Rite310RT, manufactured by X-Rite)
Was used to measure the maximum image density and the minimum image density, and the color development was evaluated. The evaluation results were classified and expressed as follows based on the maximum image density and the minimum image density obtained from the sample 101. A: The maximum image density is higher and the minimum image density is lower than the image obtained from the sample 101, which is excellent. B: The maximum image density is higher and better than the image obtained from the sample 101. C: The maximum image density and the minimum image density are equivalent to the image obtained by the sample 101. Table 27 shows the results of the evaluation.

(Processing Step A) The exposed samples were continuously processed using an automatic developing machine in the following processing steps until the cumulative replenishment amount of the liquid became three times the tank capacity. ──────────────────────────────────── Processing time Time Temperature Tank capacity Refill ──────色 Color development 135 seconds 38 ° C 11 liters 350 ml / m ² Bleaching and 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 replenishment method of the washing water was a countercurrent replenishment method in which the overflow solution of the washing bath (2) was led to the washing bath (1). At this time, the carry-out amount of each processing solution by the photosensitive material was 35 ml / m ² .

The composition of each processing solution is as follows.色 Color developing solution Mother liquor 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 Diethylene glycol diphosphonic acid 12.0 ml 16.0 ml Benzyl alcohol 13.5ml 18.0ml Potassium bromide 0.70g --- Benzotriazole 0.003g 0.004g Sodium sulfite 2.4g 3.2g Disodium N, N-bis (sulfo 8.0 g 10.6 g natoethyl) hydroxylamine triethanolamine 6.0 g 8.0 g N-ethyl-N- (β-methanesulf 6.0 g 8.0 g honamidoethyl) -3-methyl -4-aminoaniline / 3/2 sulfuric acid monohydrate potassium carbonate 30.0 g 25.0 g Fluorescent whitening agent (diaminostilbene type) 1.3 g 1.7 g Water was added to add 1000 ml 1000 ml ───────────────────────────── pH (25 ° C) 10.30 10.79 (pH adjustment with KOH or sulfuric acid) ── ──────────────────────────────────

──────────────────────────────────── Bleaching-fixing solution Mother liquor replenisher ───── ─────────────────────────────── Ethylenediaminetetraacetic acid 4.0 g 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 for mother liquor and replenisher) ) ──────────────────────────────────── 0.020 g of chlorinated sodium isocyanurate Deionized water ( (Conductivity 5 μs / cm or less) 1000 ml pH 6.5

[0291]

[Table 27] Table 27 試 料 Sample No. Color reproducibility Chromogenic cyan magenta ─── １０１ 101 (Comparative Example) Evaluation Criteria Evaluation Criteria Evaluation Criteria 102 (Comparative Example) C C C 103 ( The present invention) BBC 104 (the present invention) BBC 105 (the present invention) BBC 106 (the present invention) BBC 107 (the present invention) BBC 108 (the present invention) ABB 109 (the present invention) ) ABB110 (present invention) AAB111 (present invention) AAB112 (present invention) AAB113 (present invention) AAB114 (present invention) AAA115 (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 has further excellent color reproducibility and color developing property. 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, the color developing agent (N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate) in the color developing solution used in Example 1
With the following compound (D-2) (composition in the treatment solution; mother liquor: 4.3 g, replenisher: 5.6 g) or (D-3) (composition in the treatment solution; 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, an image obtained by using the compound (D-2) or (D-3) as a color developing agent was preferable because the maximum image density was high and the minimum image density was low.

[0293]

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Example 3 Of the samples obtained in Example 1, Samples 101, 103, 108, and 11
0, using a sample checker FC850H manufactured by Fuji Photo Film Co., Ltd. to adhere a plate making film having a halftone dot image using the sample 112 and the sample 114,
Red exposure (Fuji Photo Film Co., Ltd. SC-60 filter), green exposure (Fuji Photo Film Co., Ltd. BP)
B-53 filter) and blue exposure (SC-42 filter manufactured by Fuji Photo Film Co., Ltd.). At this time, a plate making film of a cyan image and a black image was exposed during red exposure, a plate making film of a magenta image and a black image was exposed at the time of green exposure, and a plate making film of a yellow image and a black image were further adhered at the time of blue exposure. The image formation in this case is performed in the following processing step B.
Was performed according to

[Processing Step B] The exposed sample was
In the following processing steps, the cumulative replenishment amount of the liquid is 3 times the tank capacity.
Continuous processing was performed until the number became double. ──────────────────────────────────── Processing time Time Temperature Tank capacity Refill ──────色 Color development 135 seconds 38 ° C 28 liters 240ml / m ² Bleaching and 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 replenishment method of the washing water was a countercurrent replenishment method in which the overflow solution of the washing bath (2) was led to the washing bath (1). At this time, the carry-out amount of each processing solution by the photosensitive material was 35 ml / m ² .

The composition of each processing solution is as follows.色 Color developing solution Mother liquor 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 Diethylene glycol diphosphonic acid 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- (β-hydro 4.2 g 5.6 g xylethyl) amino] aniline sulfuric acid / 1 Dihydrate Potassium carbonate 30.0 g 25.0 g Fluorescent whitening agent (diaminostilbene) 1.3 g 1.7 g Add water 1000 ml 1000 ml ＰＨ pH (25 ° C) 10.35 10.93 (pH adjustment with KOH or sulfuric acid) ───────────── ───────────────────────

──────────────────────────────────── Bleaching-fixing solution Mother liquor replenisher ───── ─────────────────────────────── Ethylenediaminetetraacetic acid 4.0 g 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) ) ──────────────────────────────────── chlorinated sodium isocyanurate 0.02g deionized water ( (Electric conductivity 5 μs / cm or less) 1000 ml pH 6.5 The images obtained using Samples 103, 108, 110, 112 and 114 of the direct positive color photographic light-sensitive material of the present invention correspond to Sample 101 of the comparative example.
The dot image was good as compared with the image obtained using.

Example 4 As a light source, a helium-neon gas laser (wavelength: 633 nm and 543 nm)
Using an argon gas laser (wavelength: 458 nm) and a light beam having a diameter of 80 μm at a pitch of 100 μm and a diameter of 1.6 m.
/ Scanning speed on the sample at a scanning speed of / sec while moving vertically to the scanning direction (effective exposure time: about 5 × 10
^-5 seconds). Using this apparatus, the sample 101 (comparative example) and the sample 114 obtained in Example 1 were used.
The present invention was exposed to light, and the reproducibility of a halftone image obtained by forming an image according to the processing step B used in Example 3 was evaluated. Sample 101 could reproduce only up to a dot area ratio of 4%, while sample 114 could reproduce up to a dot area ratio of 2%, which was good.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI G03C 7/413 G03C 7/413 (56) References JP-A-4-174429 (JP, A) JP-A-4-204730 (JP) JP-A-2-90154 (JP, A) JP-A-63-286848 (JP, A) JP-A-2-51148 (JP, A) JP-A-3-51846 (JP, A) 3-92851 (JP, A) JP-A-2-212835 (JP, A) JP-A-3-230160 (JP, A) JP-A-4-30159 (JP, A) (58) Fields investigated (Int. Cl. ^6, DB name) G03C 7/38 G03C 1/485 G03C 7/00 540 G03C 7/00 550 G03C 7/392 G03C 7/413

Claims (6)

(57) [Claims] 1. A blue-sensitive layer, a green-sensitive layer and a red-sensitive layer containing an internal latent image type silver halide grain and a color image-forming coupler which have not been previously fogged on a support, and a non-light-sensitive layer adjacent thereto. Is provided in at least one layer, wherein the color image forming coupler of the red-sensitive layer is represented by the following formula (Ca)
I) or (CbI): [Wherein, 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 represents —NH— or —C
H (R ^C13 )-. 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 hydrogen atom or a group which can be removed by a coupling reaction with an oxidized form 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 nonmetallic atom group necessary for forming a 6-membered heterocyclic nitrogen-containing. Where the heterocyclic ring is
It has at least one dissociating group. X ^C21 represents a hydrogen atom or a group which can be removed by a coupling reaction with an oxidized form of an aromatic primary amine color developing agent]. Photosensitive material. 2. The color image forming coupler of the green sensitive layer is represented by the following formula (M): [Wherein, R ^M represents a hydrogen atom or a substituent, and Z ^M is a nonmetallic element necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms together with a bonding carbon atom and nitrogen atom. Represents an atomic group, and the azole ring has a substituent (including a condensed ring)
And X ^M represents a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of a developing agent]
The direct positive color photographic light-sensitive material according to claim 1, which is a magenta coupler represented by the following formula: 3. The following formula (HQ1) or (HQ) is added to at least one of the blue-sensitive layer, green-sensitive layer, red-sensitive layer and non-photosensitive layer.
2): embedded image [In the formula, R ^Q1 and R ^Q2 each independently represent a hydrogen atom or a group which is bonded to an oxygen atom during development to release a hydroxyl group, 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, Represents a sulfonyl group, a carbamoyl group, an alkoxycarbonyl group, a sulfamoyl group, a ureido group, a urethane group or a carbonate group, and R ^Q5 is the same as the group represented by R ^Q3 or an aryl group bonded via a linking group. the representative, however, the R ^Q5, when the same groups as those represented by the R ^Q3, also the R ^Q3 and R ^Q4 May form a carbocyclic or heterocyclic ring R ^Q5 and R ^Q6 taken together may also at least one is not hydrogen atom, and R ^Q3 to R ^Q6 are hydrogen atoms of the above R ^Q3 to R ^Q6 And only an alkyl group, at least one of the alkyl groups has 6 or more carbon atoms and R ^Q3
The total carbon number of R ^Q6 is 15 or less. ] [Wherein, R ^{Q11 to} R ^Q16 each independently represent a hydrogen atom,
Halogen atom, sulfo group, carboxyl group, cyano group,
Represents 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 carbocyclic or heterocyclic ring; R ^Q17 and R ^Q18 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic ring. R ^Q17 and R ^Q18 may together form a carbocyclic or heterocyclic ring. The direct positive color photographic light-sensitive material according to claim 1, comprising at least one hydroquinone derivative represented by the following formula: 4. The image of the color photographic light-sensitive material according to claim 1, after exposure of the color photographic light-sensitive material according to claim 1, to the following formula (D): [Wherein, R ^D1 represents an alkyl group, R ^D2 represents an alkylene group, provided that R ^D1 and R ^D2 may be linked to each other to form a ring. And a developing process using a developing agent represented by the formula: 5. A cyan halftone dot image film and a magenta halftone dot obtained by subjecting the color photographic light-sensitive material according to any one of claims 1, 2 and 3 to color separation and halftone image conversion. A method for producing a color proof, comprising successively exposing to red light, green light and blue light using an image film, a yellow halftone dot image film and a black halftone dot image film, followed by color development. 6. The color photographic light-sensitive material according to claim 1, wherein the color photographic light-sensitive material according to any one of claims 1, 2 and 3 is 10 pixels per pixel.
A color image forming method, comprising performing a color development process after scanning exposure for an exposure time of ^-3 seconds or less.