JP2000171950A - Silver halide photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material capable of forming a black-and-white image with color developing dyes and forming a black-and-white image stabilized in color tone in the case of fluctuated processing and capable of maintaining its improved effects even in the case of storing those images for a long period, and further, to provide a stable and high-quality image so as to decrease color tone fluctuation in the storage of the images. SOLUTION: The silver halide emulsion layers formed on a support contain yellow, magenta, and cyan couplers, and a ratio of the CRR value of the yellow coupler to that of the cyan coupler [CRR(Y)/CRR(C)] is controlled to >=1.07, and likewisse [CRR(M)/CRR(C)] is controlled to >=0.85, and [CRR(Y)/CRR(M)] is controlled to >=1.00.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material which forms a black-and-white image by using a dye image. More specifically, the present invention can form a black-and-white image having a stable hue by improving processing variability, The present invention relates to a silver halide photographic material capable of providing a stable and high-quality image with a small fluctuation after long-term storage and a small change in hue even during image storage, and an image forming method.

[0002]

2. Description of the Related Art In general, a black-and-white photographic image is formed by developing silver halide with a black-and-white developer to form a silver image. In this black-and-white developer, a reducing agent such as hydroquinone or ascorbic acid is used to reduce the exposed silver halide to metallic silver. In order to develop color prints and monochrome prints in a development lab, different developers and processing machines are required for color and black and white, which degrades the profitability of the lab and raises the problem of securing installation space. Will occur.

In order to solve such a problem, it is desired to propose a black-and-white light-sensitive material capable of color processing. To meet such a demand, Japanese Patent Application Laid-Open No. 6-505580 discloses a color developing method using a silver halide photosensitive material having a layer containing a balanced yellow coupler, a magenta coupler and a cyan coupler and an emulsion. It is disclosed that development is possible even in a process and a desired black and white image can be formed. JP-A-10-10661, 10
No.-10662, No.10-20428 and No.10-2
No. 0432 discloses a silver halide containing a yellow coupler, a magenta coupler, a cyan coupler, and a high silver chloride emulsion having a silver chloride content of 95 mol% or more, and the silver chloride is spectrally sensitized with various cyanine dyes. It is disclosed that a photographic photosensitive material can form a well-balanced black and white image from a low density portion to a high density portion even in a color development process.

However, in the above-mentioned technology, as is clear from the description, there is no change in hue and contrast due to a change in the processing solution, and there is no change in hue even when stored for a long period of time. Is not sufficient to form a black and white image having Furthermore, it is still insufficient to form a black-and-white image having excellent image storability without color balance collapse.

As a result of investigations by the present inventors, it has been found that, in the above-mentioned technology, that is, in the case of a photosensitive material which generally forms a black-forming coupler capable of being color-processed by mixing a yellow coupler, a magenta coupler and a cyan coupler, the fluctuation of the processing solution level In some cases, it was found that the hue of the image fluctuated easily and was unstable because of the variation. And this is because the hue of the image from the highlight part to the shadow part is not stable,
Hue and contrast were not stable depending on the scene. In particular, it has been found that when the pH of the color developing solution changes, the hue of the black and white image changes.

Therefore, in a photographic printing paper for forming a black-and-white image which is managed, stored and used by a wide range of users, the change in hue due to the fluctuation of the developing solution is fatal and may not be practical. Did not.

In the case of black-and-white light-sensitive materials, in order to match the memorized lightness of the visual perception with the lightness reproduction of a black-and-white image, the light-sensitive materials are blue-sensitive, green-sensitive, and red-sensitive as in the case of the naked eye. It is important to have

[0008] On the other hand, in the photographic industry, black and white prints in a photo lab are less consumed than color prints.
When a color and black-and-white system is used for development as described above, the processing of the black-and-white light-sensitive material tends to be postponed and the color light-sensitive material is often stored for a longer period of time.

The present inventors have studied various black-and-white light-sensitive materials capable of color processing. As a result, the light-sensitive material using a black-forming coupler capable of color processing shows a change in hue and a decrease in whiteness of a white portion during long-term storage. New problem that is likely to occur. In particular, it has been found that deterioration caused by a blue-sensitive silver halide emulsion necessary for a black-and-white light-sensitive material is large. However, when the blue-sensitive silver halide emulsion was deleted, the lightness reproducibility of a black-and-white image was deteriorated as described above.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and a first object of the present invention is to provide a system for forming a black-and-white image by a color developing process, which is stable from a low density portion to a high density portion. Another object of the present invention is to provide a silver halide photographic light-sensitive material having an improved hue. A second object of the present invention is to provide a silver halide photographic material which forms a black-and-white image having a stable hue even when processing fluctuations occur and has a stable hue and white background even when stored for a long period of time. Is to do. A third object of the present invention is to provide a silver halide photographic material having a small change in hue even when an image is stored.

[0011]

The object of the present invention is to provide a stable hue from a low-density portion to a high-density portion, and to reduce processing fluctuations.
A silver halide photographic material capable of stably obtaining a high-quality image without depending on aging is achieved by the following constitution. 1) In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer contains a yellow coupler, a magenta coupler and a cyan coupler, and the yellow coupler C
Ratio of RR value (CRR (Y)) to CRR value of cyan coupler (CRR (C)) (CRR (Y) / CRR (C))
Is not less than 1.07. 2) In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer is represented by at least one type of yellow coupler, magenta coupler and the following general formula (C-I). A silver halide photographic light-sensitive material comprising a cyan coupler to be used.

[0012]

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In the formula, R1 represents an alkyl group or an aryl group. R2 represents a fluorinated alkyl group or a fluorinated aryl group. R3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. R3 may form a ring together with R1. Z represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of an aromatic primary amine color developing agent. 3) The silver halide photographic material as described in 2) above, wherein the yellow coupler is a compound represented by the following general formula [Y-I].

[0014]

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In the formula, R21 represents an alkyl group or a cycloalkyl group, R22 represents an alkyl group, a cycloalkyl group or an aryl group, and R23 represents a substituent. X1 represents a group or an atom which is released by a reaction with an oxidized form of the color developing agent. 4) In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer comprises two of three couplers of a yellow coupler, a magenta coupler and a cyan coupler. 1. A silver halide photographic light-sensitive material comprising: an oil-in-water dispersion containing an oil-in-water dispersion; 5) a silver halide emulsion layer containing a cyan coupler, a magenta coupler and a yellow coupler, and a black dye-forming coupler optionally added, and a blue-sensitive silver halide emulsion layer; The silver halide photographic light-sensitive material according to 1), 2), 3) or 4), wherein the blue-sensitive silver halide emulsion layer is formed so as not to be adjacent to a support. 6) having a silver halide-containing layer and a blue-sensitive silver halide emulsion layer containing three types of couplers of a cyan coupler, a magenta coupler and a yellow coupler, and a black dye-forming coupler optionally added, and A non-photosensitive hydrophilic layer between the silver halide emulsion-containing layer formed closest to the support and the support;
The silver halide photographic light-sensitive material according to 2), 3) or 4). 7) The image forming method of 1), 2), 3), 4), 5) or 6), wherein the silver halide photographic light-sensitive material is exposed and color-developed, and the color development time is from 5 seconds to 40 seconds. An image forming method, comprising:

That is, the present inventors have conducted intensive studies on various problems in a system for forming a black-and-white image by a conventional color developing process depending on process fluctuations. Ratio of CRR value of cyan coupler (CRR (Y) / CRR
(C)) and paying attention to a specific ratio (1.0
7 or more), it has been found that the hue which has been dependent on the processing variation can be improved and a high-quality image can be formed stably, which has led to the present invention, which is completely unexpected and surprising. It should have been a result. This configuration is based on the C, C, and C couplers.
Simply adjusting the RR values to the same value may not sufficiently improve the problem in a system for forming a black-and-white image by color development processing, and has been found as a result of further studies.

Further, a cyan coupler having a specific structure is adopted, or two kinds are selected from three kinds of couplers, separated from the remaining one to form an oil-in-water dispersion and added. It has also been found that the same effect can be sufficiently exerted and good image storability and stable storability with time can be imparted to the present invention, thereby leading to the present invention, which is a surprising result which cannot be expected at all. Was.

[0018] Further, with respect to the problems that the hue change and the whiteness of the white portion are liable to occur during long-term storage in a system for forming a black-and-white image by a color development process, a layer containing a blue-sensitive silver halide emulsion is formed. This was improved by specifying the order of execution.

Hereinafter, the present invention will be described in detail.

The silver halide photographic light-sensitive material of the present invention (hereinafter simply referred to as "light-sensitive material") has at least one silver halide emulsion layer on a support.
The silver halide emulsion layer contains a yellow coupler, a magenta coupler and a cyan coupler, and the ratio (CRR (Y)) of the CRR value (CRR (Y)) of the yellow coupler to the CRR value (CRR (C)) of the cyan coupler. / CRR
(C)) is 1.07 or more,
(Claim 2) wherein the silver halide emulsion layer contains at least one kind of yellow coupler, magenta coupler and cyan coupler represented by the general formula (CI). Item 4) An oil-in-water dispersion in which the silver halide emulsion layer contains two of three couplers of a yellow coupler, a magenta coupler, and a cyan coupler, and an oil-in-water dispersion containing the remaining one coupler. It is characterized by containing three aspects.

With respect to claim 2, it is preferable to use at least one of the compounds represented by the above general formula [YI] as the yellow coupler.

The light-sensitive material of the present invention comprises a silver halide emulsion layer containing three couplers of a cyan coupler, a magenta coupler and a yellow coupler and optionally a black dye-forming coupler, and a blue-sensitive halide. A layer having a silver emulsion layer, wherein the blue-sensitive silver halide emulsion layer is formed so as not to be adjacent to the support, or between the silver halide emulsion-containing layer formed closest to the support and the support Preferably has a non-photosensitive hydrophilic layer.

First, the CRR value of the first invention will be described.

Regarding the CRR values of the yellow coupler, magenta coupler and cyan coupler used in the present invention, the ratio (CRR (C)) of the CRR value (CRR (Y)) of the yellow coupler to the CRR value (CRR (C)) of the cyan coupler is used. CR
R (Y) / CRR (C)) is 1.07 or more. When this value is 1.07 or more, the change in the hue of the image due to the change in the level of the processing solution is suppressed,
The effects of the present invention, such as stable image formation, are sufficiently achieved. In particular, a hue change of a black-and-white image when the pH of the color developing solution changes is also prevented. Preferably, CRR (Y) / CRR (C) is 1.2 or more, particularly preferably 1.5 or more.

In a preferred embodiment, the CRR value (CRR (M)) of the magenta coupler and the CR
R value (CRR (C)) ratio (CRR (M) / CRR)
(C)) is 1.0 or more, more preferably CRR
(M) / CRR (C) is 1.2 or more.
In addition, CRR (Y) / CRR (C) is preferably 2.2 or less. Of the above, CRR (Y)> CRR (M)> CRR
(C) is preferred. Also, the present invention provides a CRR
It is more effective when (Y), CRR (M) and CRR (C) are large values, and it is more preferable when CRR (M) is 1.25 or more.

The CRR value (Citraz-in)
ic acid RelativeRatio)
The Journal of Photographic Science (J. Photogr. Sci.) 3 utilizing a competitive reaction using a water-soluble external coupler, citrazic acid.
6, 14 (1988). The closer the CRR value is to 1.0, the faster the coupling speed of the coupler can be interpreted.

Next, the compound represented by formula (CI) of the second invention will be described.

[0028]

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In the formula, R1 represents an alkyl group or an aryl group. R2 represents a fluorinated alkyl group or a fluorinated aryl group. R3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. R3 may form a ring together with R1. Z represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of an aromatic primary amine color developing agent.

The alkyl group represented by R1 in the formula (C-I) is preferably an alkyl group having 1 to 32 carbon atoms, which may be linear or branched, and include those having a substituent. The aryl group is preferably a phenyl group, including those having a substituent. The fluorinated alkyl group represented by R2 preferably has 1 to 12 carbon atoms, and includes those having a substituent. R3 is a hydrogen atom,
Represents a halogen atom, an alkyl group or an alkoxy group, and the alkyl group and the alkoxy group include those having a substituent, and R3 is preferably a hydrogen atom. R3 is preferably a 5- or 6-membered ring as a ring formed in cooperation with R1. Examples of the group capable of leaving by the reaction with an oxidized aromatic primary amine color developing agent represented by Z include a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a sulfonyloxy group, an acylamino group, Examples thereof include a sulfonylamino group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, and an imide group (including those each having a substituent), preferably a halogen atom, an aryloxy group, or an alkoxy group.

The following are typical examples of the cyan coupler represented by the general formula (CI).

[0032]

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In the second invention, the yellow coupler is preferably a compound represented by the general formula [YI].

The yellow coupler represented by the general formula [Y-I] will be described in detail.

[0035]

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In the formula, R21 represents an alkyl group or a cycloalkyl group, R22 represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group;
R23 represents a substituent. X1 represents a group or an atom which is released by a reaction with an oxidized form of the color developing agent.

As the alkyl group represented by R21, a linear or branched alkyl group such as methyl, ethyl, i-
Groups such as propyl, t-butyl, dodecyl, 1-hexylnonyl and the like. Also, as a cycloalkyl group,
Groups such as cyclopropyl, cyclohexyl and adamantyl.

The alkyl group and the cycloalkyl group represented by R21 may further have a substituent. Examples of the substituent include a halogen atom (chlorine, bromine, etc.), a cyano group,
Nitro group, aryl group (phenyl, pt-octylphenyl, 2,4-di-t-amylphenyl, etc.), hydroxyl group, alkoxy group (methoxy, 2-ethoxyethoxy, etc.), aryloxy group (phenoxy, , 4-di-t-amylphenoxy, 4- (4-hydroxyphenylsulfonyl) phenoxy, etc.), a heterocyclic oxy group (4-
Pyridyloxy, 2-hexahydropyranyloxy, etc.), carbonyloxy group (alkyloxyoxy group such as acetyloxy, pivaloyloxy, aryloxy group such as benzoyloxy), sulfonyloxy group (methanesulfonyloxy, trifluoromethanesulfonyloxy) , An alkylsulfonyloxy group such as dodecanesulfonyloxy, an arylsulfonyloxy group such as benzenesulfonyloxy and p-toluenesulfonyloxy), a carbonyl group (an alkylcarbonyl group such as acetyl and pivaloyl), benzoyl, 3,5-di-t- Arylcarbonyl groups such as butyl-4-hydroxybenzoyl, etc.) and oxycarbonyl groups (alkoxycarboxyls such as methoxycarbonyl, cyclohexyloxycarbonyl, dodecyloxycarbonyl, etc.) An aryloxycarbonyl group such as 2,4-di-t-amylphenoxycarbonyl, a heterocyclic oxycarbonyl group such as 2-pyridyloxycarbonyl, 1-phenylpyrazolyl-5-oxycarbonyl, etc.), a carbamoyl group (dimethyl Alkylcarbamoyl groups such as carbamoyl, 4- (2,4-di-t-amylphenoxy) butylaminocarbonyl, arylcarbamoyl groups such as phenylcarbamoyl and 1-naphthylcarbamoyl), and sulfonyl groups (such as methanesulfonyl and trifluoromethanesulfonyl); An alkylsulfonyl group, an arylsulfonyl group such as p-toluenesulfonyl), a sulfamoyl group (dimethylsulfamoyl,
Alkylsulfamoyl groups such as 4- (2,4-di-t-amylphenoxy) butylaminosulfonyl; arylsulfamoyl groups such as phenylsulfamoyl; and acylsulfates such as acetylsulfamoyl and ethylcarbonylaminosulfonyl. Famoyl group), amino group (alkylamino group such as dimethylamino, cyclohexylamino, dodecylamino, arylamino group such as anilino, pt-octylanilino, etc.), sulfonamide group (methanesulfonamide, heptafluoropropane) Alkylsulfonamide groups such as sulfonamide and hexadecylsulfonamide; arylsulfonamide groups such as p-toluenesulfonamide and pentafluorobenzenesulfonamide; and acylamino groups (alkoxy such as acetylamino and myristoylamino). A carbonylamino group, an arylcarbonylamino group such as benzoylamino, an alkylthio group (methylthio, t-octylthio, etc.), an arylthio group (phenylthio, p-tolylthio, etc.) and a heterocyclic thio group (1-phenyltetrazole-5-thio, 5-methyl-1,3,4-oxadiazole-2-thio) and the like.

R21 is preferably an alkyl group, more preferably a branched alkyl group, and particularly preferably a t-butyl group.

Examples of the alkyl group and cycloalkyl group represented by R22 include groups having the same meaning as the alkyl group and cycloalkyl group represented by R21. Examples of the aryl group represented by R22 include a phenyl group and a 1-naphthyl group. The alkyl group, cycloalkyl group and aryl group represented by R22 may have a substituent. Examples of the substituent include groups represented by the same meaning as the alkyl group and cycloalkyl group represented by R21 and R1. And the groups defined as the substituents of the alkyl group and the cycloalkyl group. R22 is preferably an alkyl group, more preferably an unsubstituted alkyl group, and particularly preferably a methyl group.

Examples of the group or atom capable of leaving by reaction with the oxidized form of the developing agent represented by X1 include a nitrogen-containing heterocyclic group, an aryloxy group, and a nitrogen atom bonded to the coupling position.
Arylthio group, heterocyclic oxy group, heterocyclic thio group, acyloxy group, carbamoyloxy group, alkylthio group,
Examples include a hydrogen atom or a halogen atom.

When X1 represents a nitrogen-containing heterocyclic group bonded to the coupling position with a nitrogen atom, this nitrogen-containing heterocyclic group has 1 to 15, preferably 1 to 10 carbon atoms. It is preferably a 5- or 6-membered substituted or unsubstituted, saturated or unsaturated, monocyclic or condensed heterocyclic group. The hetero atom may include an oxygen atom or a sulfur atom in addition to the nitrogen atom. Preferred specific examples of the heterocyclic group include 1-pyrazolyl, 1-imidazolyl, pyrrino,
1,2,3-triazol-2-yl, 1,2,3-triazol-1-yl, benzotriazolyl, benzimidazolyl, imidazolidine-2,4-dione-3-yl, oxazolidine-2,4 -Dion-3-yl, 1,
2,4-triazolidine-3,5-dione-4-yl,
Imidazolidine-2,4,5-trion-3-yl, 2
-Imidazolinone-1-yl, 3,5-dioxomorpholino or 1-indazolyl. When these heterocyclic groups have a substituent, the substituent is not particularly limited. Preferred examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, and an aryloxycarbonyl group. , An alkylthio group, an acylamino group, a sulfonamide group, an aryl group,
A nitro group, a carbamoyl group, a cyano group or a sulfonyl group.

When X1 represents an aryloxy group, it is preferably a substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms. Particularly preferred is a substituted or unsubstituted phenoxy group. When the aryloxy group has a substituent, a preferred substituent is a case where at least one substituent is an electron-withdrawing group, and examples thereof include a sulfonyl group, an alkoxycarbonyl group, a sulfamoyl group, a halogen atom, Examples include a carbamoyl group, a nitro group, a cyano group, and an acyl group.

When X1 represents an arylthio group, it is preferably a substituted or unsubstituted arylthio group having 6 to 10 carbon atoms. Particularly preferred is a substituted or unsubstituted phenylthio group. When having a substituent, preferred substituents include
At least one substituent is an alkyl group, an alkoxy group, a sulfonyl group, an alkoxycarbonyl group, a sulfamoyl group, a halogen atom, a carbamoyl group or a nitro group.

When X1 represents a heterocyclic oxy group, the part of the heterocyclic group has 1 to 20, preferably 1 to 10 carbon atoms and has at least one nitrogen atom, oxygen atom or sulfur atom as a hetero atom. A substituted or unsubstituted, saturated or unsaturated, monocyclic or condensed heterocyclic group having 3 to 12, preferably 5 to 6 membered rings. Examples of heterocyclic oxy groups include pyridyloxy, pyrazolyloxy or furyloxy groups. When the heterocyclic oxy group has a substituent, preferred substituents include one substituent such as an alkyl group, an aryl group, a carboxyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group,
An aryloxycarbonyl group, an alkylthio group, an acylamino group, a sulfonamide group, a nitro group, a carbamoyl group or a sulfonyl group.

When X1 represents a heterocyclic thio group, the part of the heterocyclic group has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and has at least one nitrogen atom, oxygen atom or sulfur atom as a hetero atom. A substituted or unsubstituted, saturated or unsaturated, monocyclic or condensed heterocyclic group having 3 to 12, preferably 5 to 6 membered rings. Examples of heterocyclic thio groups include tetrazolylthio, 1,3,4
-Thiadiazolylthio, 1,3,4-oxadiazolylthio, 1,3,4-triazolylthio, benzimidazolylthio, benzothiazolylthio or 2-pyridylthio groups. When the heterocyclic thio group has a substituent, preferred substituents are those in which at least one of the substituents is an alkyl group, an aryl group, a carboxyl group, an alkoxy group,
A halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an acylamino group, a sulfonamide group, a nitro group, a carbamoyl group, a heterocyclic group or a sulfonyl group.

When X1 represents an acyloxy group, this acyloxy group preferably has 6 to 10 carbon atoms and is a monocyclic or condensed ring. A substituted or unsubstituted aromatic acyloxy group or a group having 2 to 30, preferably 2 carbon atoms
Or a substituted or unsubstituted aliphatic acyloxy group of -20. These may further have a substituent.

When X1 represents a carbamoyloxy group, this carbamoyloxy group is an aliphatic, aromatic, heterocyclic, substituted or unsubstituted carbamoyloxy group having 1 to 30, preferably 1 to 20 carbon atoms. . For example, N, N-
Diethylcarbamoyloxy, N-phenylcarbamoyloxy, 1-imidazolylcarbonyloxy or 1-
And a pyrrolocarbonyloxy group.

When X1 represents an alkylthio group, this alkylthio group is a linear, branched, saturated or unsaturated, substituted or unsubstituted alkylthio group having 1 to 30, preferably 1 to 20 carbon atoms. These may further have a substituent.

Among X1, preferred are groups represented by the following formulas (I), (II) and (III).

Formula (I) -OR24 Formula (II) -OCOR24

[0052]

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In the above general formulas (I) and (II), R
24 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. An alkyl group represented by R24,
Examples of the cycloalkyl group and the aryl group include, for example, an alkyl group represented by R22 in the general formula [Y-I],
Examples include groups having the same meaning as the cycloalkyl group and the aryl group. Further, as the heterocyclic group represented by R24,
Examples include groups such as 4-pyridyl and 2-hexahydropyranyl. The alkyl group, cycloalkyl group, aryl group and heterocyclic group represented by R24 may have a substituent, and examples of the substituent include, for example, those represented by the aforementioned general formula [Y-
In I], the same groups as the substituents for the alkyl group, cycloalkyl group and aryl group represented by R22 can be exemplified.

Among the alkyl, cycloalkyl, aryl and heterocyclic groups represented by R24, an aryl group is preferred. Examples of the substituent of R24 include an electron-withdrawing group (an oxycarbonyl group such as carboxyl, methoxycarbonyl or i-propyloxycarbonyl, an acyl group such as acetyl or benzoyl, a trifluoromethanesulfonyl group, and a 4-hydroxyphenylsulfonyl group). Sulfonyl group, nitro group, cyano group, halogen atom,
Sulfamoyl groups such as dimethylsulfamoyl, acylamino groups such as acetylamino or pentafluorobenzoylamino, and sulfonamide groups such as methanesulfonamide are preferred.

In the above formula (III), Z21 represents a nonmetallic atom group necessary for forming a 5- or 6-membered ring in cooperation with a nitrogen atom. Here, the atomic group necessary for forming the nonmetallic atomic group includes, for example, methylene, methine, substituted methine, -CO-, -N (R25)-(R25 is a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic ring. Represents a group),
-N =, -O- and -S (O) u- (u represents an integer of 0 to 2) and the like.

X 1 is particularly preferably a group represented by the following formula (IV).

[0057]

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In the above general formula (IV), Y1 is -N
(R26)-(R26 is a group represented by the general formula (III)
25 represents a group having the same meaning as the group represented by 25), -O- and -S
(O) a heteroatom represented by r- (r represents an integer of 0 to 2), or -CO-, -C (R27) (R28)-
(R27 and R28 represent a hydrogen atom or the above-mentioned general formula (I)
And -C (R29)-(where R29 is a hydrogen atom or a group represented by the aforementioned general formula [Y-I]), which represents the same groups as the substituents of the alkyl group, cycloalkyl group and aryl group represented by R24. Represents a group having the same meaning as the groups exemplified as the substituents of the alkyl group, cycloalkyl group and aryl group represented by R22).

Z22 represents a nonmetallic atom group necessary for forming a 5- or 6-membered ring in cooperation with -Y1-N-CO-. Here, examples of the atom group necessary for forming the nonmetal atom group include an atom group having the same meaning as the atom group represented by Z21 in the general formula (III).

[0060] Preferably the substituent represented by R ₂ 3 is an unsubstituted alkyl group having 11 to 21 carbon atoms, straight-chain alkyl group is more preferable.

The 2-equivalent yellow coupler represented by the general formula [Y-I] may be bonded at any substituent to form a bis-form, a tris-form, a tetrakis-form or a polymer-form.

The yellow coupler represented by the general formula [Y-I] is prepared by using a commercially available compound as a starting material, and by a conventionally known method, for example, JP-A-63-1230.
No. 47, JP-A-4-9051, JP-A-4-124661, and the like, and can be easily synthesized.

Specific examples of the yellow coupler represented by the general formula [YI] are shown below, but the yellow coupler of the present invention is not limited to these.

[0064]

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[0065]

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[0066]

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The yellow coupler in the present invention may be used in combination with two or more different yellow couplers.

In the second invention, the cyan coupler to be additionally used in combination is represented by the following general formula [C-II]
It is more preferable to include at least one compound represented by the formula:

[0069]

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In the formula, R31 represents an alkyl group having 2 to 6 carbon atoms. R32 represents a ballast group. X21 represents a group or an atom which is released by a reaction with an oxidized form of the color developing agent.

In the formula [C-II], the alkyl group having 2 to 6 carbon atoms represented by R31 may be linear or branched, and includes those having a substituent. R31 is preferably an ethyl group.

The ballast group represented by R32 is an organic group having a size and shape that gives the coupler molecule sufficient bulk to prevent the coupler from substantially diffusing from the layer to which the coupler is applied to another layer. It is. Preferred as the ballast group are those represented by -CH (R33) -O-Ar.

R33 represents an alkyl group having 1 to 12 carbon atoms, Ar represents an aryl group such as a phenyl group, and the aryl groups include those having a substituent.

Examples of the atom or group capable of leaving by reaction with the oxidized form of the color developing agent represented by X21 include a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a sulfonyloxy group, an acylamino group, Examples thereof include a sulfonylamino group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, and an imide group (including those each having a substituent), preferably a halogen atom, an aryloxy group, or an alkoxy group.

Next, specific examples of the coupler represented by the general formula [C-II] are shown, but it should not be construed that the invention is limited thereto.

[0076]

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The coupler used in the present invention may be 340 nm by a coupling reaction with an oxidized form of a color developing agent.
Any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a longer wavelength range can be used, but a typical example is a wavelength range of 350 to 50.
Yellow dye-forming coupler having a spectral absorption maximum wavelength at 0 nm, magenta dye-forming coupler having a spectral absorption maximum wavelength at a wavelength range of 500 to 600 nm, wavelength range of 600 to 7
Typical are cyan dye-forming couplers having a spectral absorption maximum wavelength at 50 nm.

Examples of the magenta coupler which can be used in the light-sensitive material according to the present invention include 5-pyrazolone type magenta couplers and general formulas (MI) and (M) described in JP-A-4-114154, page 4, upper right column. -II) pyrazolotriazole type magenta couplers. Specific compounds are shown in the lower left column of the same page to the upper right column of the same page.
Those described as C-1 to MC-11 can be exemplified. In the pyrazolotriazole type magenta coupler, among the couplers represented by the general formula (M-1) described in the upper right column on page 4, couplers in which the RM of the general formula (M-1) is a tertiary alkyl group are exemplified. Excellent in light fastness and preferable. MC-8 to MC-11 described in the upper column on page 5 are preferable because they are excellent in reproducing colors from blue to purple and red, and are also excellent in detail description.

Next, the oil-in-water dispersion of the third invention will be described.

In the third invention, a yellow coupler, a magenta coupler and a cyan coupler are added to a silver halide emulsion layer.
The oil-in-water dispersion containing two of the couplers and the oil-in-water dispersion containing the remaining one are separated and contained. As a result, even when processing fluctuations occur, a black-and-white image with stable hue and contrast can be formed,
Also, there is an effect that there is no deterioration after long-term storage. Furthermore,
Even when the image is stored, a change in hue is small, and a high-quality image can be stably formed.

According to the present invention, in preparing a silver halide emulsion, an oil-in-water type dispersion containing two types of couplers is used, unlike the conventional case where an oil-in-water type type dispersion containing three types of couplers is added. And the remaining oil-in-water type dispersion containing one type are separated and contained, and the configuration has an advantage unique to the present invention. Specifically, for example, when an oil-in-water dispersion containing a magenta coupler and a cyan coupler and an oil-in-water dispersion containing a yellow coupler are each prepared and added separately, very good results are obtained. Obtained and preferred.

When an oil-in-water type emulsification dispersion method is used to add a coupler or other organic compound, a low-boiling point and / or a low boiling point and / or Alternatively, they are dissolved together with a water-soluble organic solvent, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. After or simultaneously with the dispersion, a step of removing the low boiling organic solvent may be added. Examples of high boiling organic solvents that can be used to dissolve and disperse the coupler include dioctyl phthalate, diisodecyl phthalate, phthalic acid esters such as dibutyl phthalate, tricresyl phosphate, and phosphoric acid esters such as trioctyl phosphate;
Is preferably used. The high-boiling organic solvent preferably has a dielectric constant of 3.5 to 7.0. Two or more high-boiling organic solvents can be used in combination.

In place of the method using a high-boiling organic solvent or in combination with a high-boiling organic solvent, a water-insoluble and organic solvent-soluble polymer compound may be added, if necessary, to a low-boiling and / or water-soluble organic solvent. In a hydrophilic binder such as an aqueous gelatin solution by using a surfactant and emulsifying and dispersing by various dispersing means. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

As a preferred compound used as a surfactant for dispersing a photographic additive or adjusting the surface tension at the time of coating, a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule are preferable. Containing. Specifically, A-1 described in JP-A-64-26854 is described.
To A-11. Also, a surfactant in which a fluorine atom is substituted for an alkyl group is preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, and the time until the addition to the coating solution after the dispersion and the time from the addition to the coating solution after the addition are preferably 10 hours each. Preferably within 3 hours, more preferably within 20 minutes.

It is preferable to use an anti-fading agent in combination with each of the above couplers in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds include phenyl ether compounds represented by general formulas I and II described on page 3 of JP-A-2-66541,
A phenolic compound represented by the general formula IIIB described in JP-A-3-174150, an amine-based compound represented by the general formula A described in JP-A-64-90445, and a phenolic compound described in JP-A-6-182741. Formulas XII, XIII, XI
Metal complexes represented by V and XV are particularly preferred for magenta dyes. Compounds represented by the general formula I 'described in JP-A-1-19649 and compounds represented by the general formula II described in JP-A-5-11417 are particularly preferred for yellow and cyan dyes.

For the purpose of shifting the absorption wavelength of the coloring dye, compound (d-11) described in the lower left column of page 9 of JP-A-4-114154 and compound described in the lower left column of page 10 of the same specification Compounds such as (A'-1) can be used. In addition, US Pat.
187 can also be used.

In the first to third inventions, a blue-sensitive silver halide emulsion layer (hereinafter referred to as a blue-sensitive layer) is provided so that the blue-sensitive layer is not adjacent to the support. It is preferred to have a non-photosensitive hydrophilic layer between the silver halide emulsion layer formed or formed closest to the support and the support. Hue fluctuation during long-term storage of photosensitive material using a black-forming coupler capable of color processing,
It is possible to form a stable high-quality image by suppressing a decrease in whiteness of a white portion.

The blue-sensitive layer preferably contains a polymer latex and / or a dispersion oil of a water-insoluble organic compound.

The latex may be any generally known polymer latex, and the polymer may be a homopolymer of an alkyl ester of acrylic acid or a copolymer with acrylic acid or styrene, a styrene-butadiene copolymer, an active methylene group, a water-soluble polymer. A polymer or copolymer comprising a monomer having a functional group or a crosslinkable group with gelatin can be preferably used. In particular,
In order to increase affinity with gelatin which is a binder,
Most preferably, a copolymer with a monomer having a water-soluble group or a crosslinkable group with gelatin mainly containing a hydrophobic monomer such as an alkyl ester of acrylic acid or styrene is used.

Preferred examples of the monomer having a water-soluble group include acrylic acid, methacrylic acid, maleic acid and 2-
Desirable examples of monomers having a crosslinkable group with gelatin, such as acrylamide-2-methylpropanesulfonic acid and styrenesulfonic acid, include glycidyl acrylate, glycidyl methacrylate, and N-methylolacrylamide.

The polymer latex and its synthesis method are described in detail in JP-A-2-41, US Pat.
2,386, 2,853,457, 3,41
1,911, 3,411,912, 4,19
7,127, JP-B-45-5331, JP-A-60-
No. 18,540, etc., for example, an emulsion polymerization method, a method of redispersing a polymer obtained by solution polymerization, and the like.

As an example, in the emulsion polymerization method, water is used as a dispersion medium, 10 to 50% by weight of a monomer based on water and 0.05 to 5% by weight of a polymerization initiator based on the monomer. Using 1 to 20% by weight of a dispersant, about 30 to 100 ° C, preferably 6
It is obtained by polymerizing under stirring at 0 to 90 ° C. for 3 to 8 hours.

Examples of the polymerization initiator include water-soluble peroxides and water-soluble azo compounds. Examples of the dispersant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant in addition to the water-soluble polymer. These may be used alone or in combination.

The following are specific examples of the polymer latex preferably used in the present invention, but the present invention is not limited to these.

[0095]

Embedded image

The Tg (glass transition temperature) of the polymer forming the polymer latex used in the present invention is preferably 40 ° C. or less. Tg of polymer is "Polymer Handbook (1966, Wiley &Sons)"
The Tg of the copolymer (°
K) is represented by the following equation.

Tg (copolymer) = v1Tg1 + v2T
+ vWTgW In the formula, v1, v2... vW represent the weight fraction of the monomers in the copolymer, and Tg1, Tg2. ° K). Tg calculated according to the above equation has an accuracy of ± 5 ° C.

The average particle size of the polymer latex is 0.5
Any of those having a thickness of up to 300 nm can be preferably used. The average particle size of the polymer latex is
It can be measured by an electron micrograph, a soap titration method, a light scattering method, or a centrifugal sedimentation method described in "Chemistry of Polymer Latex (1973, Polymer Publishing Association)", but the light scattering method is preferably used.

The molecular weight of the polymer is not particularly limited, but is preferably 1,000 to 1,000,000 in total molecular weight.
00.

Examples of the water-insoluble organic compound dispersion oil include phthalic acid esters, phosphoric acid esters, fatty acid esters, organic acid amides, ketones, and hydrocarbon compounds. In addition, hydroquinones, phenols, benzotriazoles and the like generally contained in photographic light-sensitive materials can also be mentioned. Preferably, it is an organic compound having 15 or more carbon atoms.

The composition of the silver halide photographic emulsion according to the present invention has an arbitrary halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and silver chloroiodide. However, silver chlorobromide containing 95 mol% or more of silver chloride and containing substantially no silver iodide is preferred. Quick processing,
From the standpoint of processing stability, a silver halide emulsion containing preferably 97 mol% or more, more preferably 98 to 99.9 mol%, of silver chloride is preferred.

For obtaining the silver halide emulsion according to the present invention, a silver halide emulsion having a portion containing silver bromide at a high concentration is particularly preferably used. In this case, the portion containing a high concentration of silver bromide may be epitaxy-bonded to silver halide emulsion grains, a so-called core-shell emulsion, or may be formed only partially without forming a complete layer. May simply have regions with different compositions. Further, the composition may be changed continuously or discontinuously.
It is particularly preferable that the portion where silver bromide exists at a high concentration is the top of crystal grains on the surface of silver halide grains.

In order to obtain the silver halide emulsion according to the present invention, it is advantageous to include heavy metal ions. Heavy metal ions that can be used for such purposes include iron,
Iridium, platinum, palladium, nickel, rhodium,
Examples include Group 8 to 10 metals such as osmium, ruthenium, and cobalt; Group 12 transition metals such as cadmium, zinc, and mercury; and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium. Among them, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferred.

These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt.

When the heavy metal ion forms a complex, the ligand or ion may be a cyanide ion,
Examples include thiocyanate ion, cyanate ion, isothiocyanate ion, chloride ion, bromide ion, iodide ion, nitrate ion, carbonyl, ammonia and the like. Among them, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion and the like are preferable. In order to make the silver halide emulsion according to the present invention contain heavy metal ions, the heavy metal compound is subjected to physical ripening before formation of silver halide grains, during formation of silver halide grains, and during physical ripening after formation of silver halide grains. It may be added at any place in each step. In order to obtain a silver halide emulsion satisfying the above conditions, a heavy metal compound can be dissolved together with a halide salt and added continuously over the whole or a part of the grain forming step.

When the heavy metal ion is added to the silver halide emulsion, the amount is 1 × 10− per mole of silver halide.
It is more preferably from 9 mol to 1 × 10 −2 mol, particularly preferably from 1 × 10 −8 mol to 5 × 10 −5 mol.

The silver halide grains according to the present invention can have any shape. One preferred example is
It is a cube having a (100) plane as a crystal surface.
U.S. Pat. Nos. 4,183,756 and 4,225,6
No. 66, JP-A-55-26589, JP-B-55-42
No. 737 and The Journal of Photographic Science (J. Photogr. Sci.) 2
1, 39 (1973), etc., particles having an octahedral, tetradecahedral, dodecahedral or the like shape can be prepared and used. Further, particles having a twin plane may be used.

As the silver halide grains according to the present invention, grains having a single shape are preferably used, but it is particularly preferable to add two or more monodispersed silver halide emulsions to the same layer.

The grain size of the silver halide grains according to the present invention is not particularly limited, but is preferably 0.1 to 1.2 μm in consideration of other photographic properties such as rapid processing property and sensitivity.
m, more preferably in the range of 0.2 to 1.0 μm.

The particle size can be measured by using the projected area of the particle or an approximate value of the diameter. If the particles are substantially uniform in shape, the particle size distribution can represent this quite accurately as diameter or projected area.

The particle size distribution of the silver halide grains of the present invention is preferably a monodispersed silver halide grain having a variation coefficient of 0.22 or less, more preferably 0.15 or less, and particularly preferably a variation coefficient of 0 or less. .15 or less are added to the same layer. Here, the coefficient of variation is a coefficient representing the width of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R (where, S is the standard deviation of the particle size distribution, and R is the average particle size.) The particle size here is the diameter of a spherical silver halide particle. In the case of particles having a shape other than a cubic or a spherical shape, the diameter represents a diameter when the projected image is converted into a circular image having the same area.

As a device and method for preparing a silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion according to the present invention may be obtained by any of an acidic method, a neutral method, and an ammonia method. The particles may be grown at one time or may be grown after seed particles have been made. The method of producing the seed particles and the method of growing them may be the same or different.

The form in which the soluble silver salt and the soluble halide salt are reacted may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like. Is preferred. Further, as one type of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used.

Also, JP-A-57-92523, JP-A-57-92523.
No. 92524, etc., a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device disposed in a reaction mother liquor, and a water-soluble silver salt and a water-soluble halogen described in DE 292164, etc. Apparatus for continuously changing the concentration of a chloride salt aqueous solution, JP-B-56-501
No. 776, etc., a reaction mother liquor may be taken out of the reactor and concentrated by an ultrafiltration method to form grains while keeping the distance between silver halide grains constant.

If necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

The silver halide emulsion according to the present invention can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer.

As a chalcogen sensitizer applied to the silver halide emulsion according to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, etc. can be used, but a sulfur sensitizer is preferable. Thiosulfates as sulfur sensitizers,
Allyl thiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine, inorganic sulfur and the like can be mentioned.

The addition amount of the sulfur sensitizer according to the present invention is preferably changed depending on the kind of the silver halide emulsion to be applied and the size of the expected effect. The range is preferably -10 to 5 x 10-5 mol, more preferably 5 x 10-8 to 3 x 10-5 mol.

As the gold sensitizer according to the present invention, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. The amount of the gold compound used is not uniform depending on the type of the silver halide emulsion, the type of the compound used, the ripening conditions, etc., but usually from 1 × 10 −4 mol to 1 × 10 4 mol per mol of silver halide.
It is preferably -8 mol. More preferably, 1 × 1
It is from 0-5 mol to 1 × 10-8 mol.

The chemical sensitization of the silver halide emulsion according to the present invention may be a reduction sensitization.

The silver halide emulsion according to the present invention contains a known fog for the purpose of preventing fog occurring during the preparation step of the light-sensitive material, reducing performance fluctuation during storage, and preventing fog occurring during development. Inhibitors and stabilizers can be used. Examples of preferred compounds that can be used for such purposes include the compounds represented by the general formula (II) described in the lower section of page 7 of JP-A-2-14636, and more preferred specific examples Examples of such compounds include (IIa-1) to (IIa-1) described on page 8 of the publication.
(IIa-8), compounds of (IIb-1) to (IIb-7), 1- (3-methoxyphenyl) -5-mercaptotetrazole, 1- (4-ethoxyphenyl) -5-mercaptotetrazole and the like Compounds can be mentioned.
These compounds are added in a step of preparing silver halide emulsion grains, a step of chemical sensitization, at the end of the step of chemical sensitization, a step of preparing a coating solution or the like according to the purpose. When chemical sensitization is carried out in the presence of these compounds, it is preferably used in an amount of about 1 × 10 −5 mol to 5 × 10 −4 mol per mol of silver halide. When added at the end of chemical sensitization, 1 × 10 −6 mol / mol to 1 mol of silver halide is used.
The amount is preferably about 1 × 10 −2 mol, more preferably 1 × 10 −5 mol to 5 × 10 −3 mol. In the step of preparing a coating solution, when added to the silver halide emulsion layer, 1 × 10 −6 mol to 1 × 10 −1 per mol of silver halide is used.
The amount of about 1 mol is preferable, and 1 × 10 −5 mol to 1 × 10
-2 mol is more preferred. When it is added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 −9 mol to 1 × 10 −3 mol per m 2.

In the light-sensitive material according to the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any of the known compounds can be used. In particular, dyes having absorption in the visible region include those described in JP-A-3-2518.
The dyes of AI-1 to 11 described on page 308 of JP-A 40/40 and the dyes described in JP-A-6-3770 are preferably used.
The compounds represented by formulas (I), (II) and (III) described in the lower left column of page 2 of JP-A-80750 have preferable spectral characteristics and do not affect the photographic characteristics of silver halide photographic emulsions. It is also preferable because there is no contamination due to residual color. Specific examples of preferred compounds include Exemplified Compounds (1) to (45) listed on page 3, lower left column to page 5, lower left column of the same publication.

For the purpose of improving sharpness, the amount of these dyes added is 680 nm for an unprocessed sample of a light-sensitive material.
Is more preferably 0.7 or more, and even more preferably 0.8 or more.

It is preferable to add a fluorescent whitening agent to the light-sensitive material according to the present invention because whiteness can be improved. Preferred examples of the compound include a compound represented by the general formula II described in JP-A-2-232652.

When the light-sensitive material according to the present invention is used as a color photographic light-sensitive material, the light-sensitive material may be used in combination with a yellow coupler, a magenta coupler and a cyan coupler in a range of 400 to 90.
It has a layer containing a silver halide emulsion spectrally sensitized to a specific region in a wavelength range of 0 nm. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

As the spectral sensitizing dye used in the silver halide emulsion according to the present invention, any known compounds can be used.
BS-1 to 8 described in JP-A-251840, page 28, can be preferably used alone or in combination.
As the green photosensitive sensitizing dye, GS-1 to GS-5 described on page 28 of the same publication are preferably used. RS-1 to 8 described on page 29 of the same publication are preferably used as red-sensitive sensitizing dyes. When performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye. The dyes of IRS-1 to 11 described in JP-A No. 6-8 are preferably used. or,
These infrared, red, green and blue sensitizing dyes are disclosed in
Supersensitizer S described on pages 8 to 9 of 285950
S-1 to SS-9 and JP-A-5-66515, 15-
It is preferable to use compounds S-1 to S-17 described on page 17 in combination. These sensitizing dyes may be added at any time from the formation of silver halide grains to the end of chemical sensitization.

The sensitizing dye may be added by dissolving it in a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide or the like or water, or adding it as a solid dispersion. It may be added.

In the light-sensitive material according to the present invention, a compound which reacts with an oxidized developing agent is added to a layer between the light-sensitive layers to prevent color turbidity or added to a silver halide emulsion layer. It is preferable to improve fog and the like. The compound for this purpose is preferably a hydroquinone derivative, and more preferably a dialkylhydroquinone such as 2,5-di-t-octylhydroquinone. A particularly preferred compound is a compound represented by the general formula II described in JP-A-4-133056, and compounds II-1 to II-14 described on pages 13 to 14 and compound 1 described on page 17 of the same publication are described. No.

It is preferable to add an ultraviolet absorber to the light-sensitive material according to the present invention to prevent static fog or improve the light fastness of a dye image. Preferable ultraviolet absorbers include benzotriazoles. Particularly preferred compounds are compounds represented by the formula III-3 described in JP-A-1-250944, and JP-A-64-6664.
6, a compound represented by the general formula III,
UV-1L to UV-27 described in 3-187240
L, compounds represented by the general formula I described in JP-A-4-1633, and compounds represented by the general formulas (I) and (II) described in JP-A-5-165144.

It is advantageous to use gelatin as a binder in the light-sensitive material according to the present invention. If necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, A hydrophilic colloid such as a sugar derivative, a cellulose derivative, or a synthetic hydrophilic polymer such as a homopolymer or a copolymer can also be used.

As the hardener of these binders, it is preferable to use a vinyl sulfone hardener or a chlorotriazine hardener alone or in combination. JP-A-61-249
It is preferable to use the compounds described in JP-A Nos. 054 and 61-245153. Further, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 in the colloid layer in order to prevent the growth of mold and bacteria which adversely affect the photographic performance and image storability. Further, in order to improve the physical properties of the surface of the light-sensitive material or the sample after processing, a protective layer is disclosed in
It is preferable to add a slipping agent or matting agent described in JP 18543 or JP-A-2-73250.

As the support for use in the present invention, any material may be used, including paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, vinyl chloride sheet, and white pigment. For example, polypropylene, polyethylene terephthalate support, baryta paper, etc. may be used. Among them, a support having a water-resistant resin coating layer on both sides of the base paper is preferable. As the water-resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.

As the white pigment used for the support, inorganic and / or organic white pigments can be used, and preferably, inorganic white pigments are used. For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silica, silica such as synthetic silicate, calcium silicate, alumina, alumina hydrate, oxidation Examples include titanium, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide.

The amount of the white pigment contained in the water-resistant resin layer on the surface of the support was 13% by weight for improving sharpness.
The above is preferred, and more preferably 15% by weight.

The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, as the coefficient of variation described in the above-mentioned publication. In addition, the value of the center plane average roughness (SRa) of the support is 0.15 μm or less, and more preferably 0.12 μm or less.
It is more preferable that the particle size is not more than μm, because the effect that the glossiness is good can be obtained. In addition, a trace amount of ultramarine, oil-soluble dyes, etc. to adjust the spectral reflection density balance of the white background after treatment in the white pigment-containing water-resistant resin of the reflective support or in the applied hydrophilic colloid layer to improve the whiteness. It is preferable to add a bluing agent or a reddish agent.

The light-sensitive material according to the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support, if necessary, and then directly or undercoating (adhesion, antistatic properties of the support surface, It may be applied via one or more undercoat layers for improving dimensional stability, friction resistance, hardness, antihalation property, frictional properties and / or other properties.

In coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.

In order to form a photographic image using the photosensitive material according to the present invention, an image recorded on a negative may be optically formed on a photosensitive material to be printed and printed. After the image is once converted to digital information, the image may be formed on a CRT (cathode ray tube), and this image may be formed on a photosensitive material to be printed and printed. Printing may be performed by scanning while changing the intensity of the laser beam.

The present invention is preferably applied to a light-sensitive material in which the developing agent is not incorporated in the light-sensitive material, and particularly preferably applied to a light-sensitive material which directly forms an image for viewing. For example, color paper, color reversal paper, a photosensitive material for forming a positive image, a photosensitive material for a display, and a photosensitive material for a color proof can be used. It is particularly preferable to apply the invention to a photosensitive material having a reflective support.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. The following compounds can be mentioned as examples of these compounds. CD-1) N, N-diethyl-p-phenylenediamine CD-2) 2-amino-5-diethylaminotoluene CD-3) 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4 ) 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-5) 2-Methyl-4- (N-ethyl-N- (β
-Hydroxyethyl) amino) aniline CD-6) 4-Amino-3-methyl-N-ethyl-N
-([Beta]-(methanesulfonamido) ethyl) -aniline CD-7) N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide CD-8) N, N-dimethyl-p-phenylenediamine CD-9 ) 4-Amino-3-methyl-N-ethyl-N
-Methoxyethylaniline CD-10) 4-Amino-3-methyl-N-ethyl-
N- (β-ethoxyethyl) aniline CD-11) 4-amino-3-methyl-N-ethyl-
N- (γ-hydroxypropyl) aniline In the present invention, the above color developer can be used in an arbitrary pH range, but from the viewpoint of rapid processing, the pH is 9.5 to 13.0.
And more preferably pH 9.8-1.
It is used in the range of 2.0.

The processing temperature of color development according to the present invention is 35
The temperature is preferably from 70 ° C to 70 ° C. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing solution, the higher the temperature, the more preferable.

Conventionally, the color development time is generally about 3 minutes and 30 seconds, but in the present invention, it is preferably within 40 seconds, and more preferably within 25 seconds.

To the color developing solution, known developing component compounds can be added in addition to the above color developing agents. Usually, alkaline agents having a pH buffering action, chloride ions, development inhibitors such as benzotriazoles, preservatives,
A chelating agent or the like is used. The light-sensitive material of the present invention is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process,
Usually, a water washing process is performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed. The developing apparatus used for the development of the photosensitive material of the present invention may be a roller transport type in which the photosensitive material is transported between rollers arranged in a processing tank, or may be transported by fixing the photosensitive material to a belt. An endless belt method may be used, but a processing tank is formed in a slit shape, and a processing liquid is supplied to the processing tank and the photosensitive material is conveyed. A web system by contact with a carrier impregnated with, a system using a viscous treatment liquid, and the like can also be used. When processing in large quantities, it is usual to perform a running process using an automatic developing machine. At this time, the replenishment amount of the replenisher is preferably as small as possible. The addition of a treating agent in a form is disclosed in Published Technical Report 94-16.
935 is most preferred.

[0146]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 <Preparation of a silver halide photographic light-sensitive material> A basis weight of 180 g / m
High-density polyethylene was laminated on both sides of the paper pulp No. 2 to prepare a paper support. However, on the side to be coated with the emulsion layer, a molten polyethylene containing surface-treated anatase-type titanium oxide dispersed at a content of 15% by weight was laminated to produce a reflective support. After the reflective support was subjected to corona discharge treatment, a gelatin undercoat layer was provided thereon, and each layer having the following constitution was further provided thereon to prepare a silver halide photographic light-sensitive material. The coating solution was prepared as described below. (First layer coating solution) Yellow coupler (YA) 14.3
g, magenta coupler (MA) 4.9 g, cyan coupler (CA) 13.6 g, dye image stabilizer (ST-
1) 60 ml of ethyl acetate was added to and dissolved in 1.30 g, 0.65 g of (ST-2) and 23.1 g of a high boiling point organic solvent (DBP), and this solution was treated with a 10% surfactant (SU-1) 36.
The mixture was emulsified and dispersed in 420 ml of a 10% aqueous gelatin solution using an ultrasonic homogenizer to prepare a mixed dispersion of a yellow coupler, a magenta coupler, and a cyan coupler. This dispersion was mixed with a blue-sensitive silver halide emulsion Em-B prepared under the following conditions to prepare a first layer coating solution. (Second layer coating solution) Prepared in the same manner as the first layer coating solution.
(H-1) and (H-2) were added to the second layer as a hardener. Surfactants (SU-1) as coating aids,
(SU-2) was added to adjust the surface tension. In addition, an anti-foaming agent (F-1) was added to each layer so that the total amount was 0.04 g / m2. This dispersion was mixed with a green-sensitive silver halide emulsion Em-G prepared under the following conditions to prepare a second layer coating solution. (Third layer coating solution) A third layer coating solution was prepared as shown in Table 1. This dispersion was mixed with a red-sensitive silver halide emulsion Em-R prepared under the following conditions to prepare a third layer coating solution. (Fourth layer coating solution) A fourth layer coating solution was prepared as shown in Table 1,
An ultraviolet absorber layer was formed. (Fifth layer coating solution) A fifth layer coating solution was prepared as shown in Table 1,
A protective layer was formed.

Using the coating solution prepared as described above,
A silver halide photographic light-sensitive material was prepared, and Sample 101 was obtained.
The layer structure is shown in Table 1 below. The amounts of silver halide emulsions are shown in terms of silver.

[0149]

[Table 1]

[0150]

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[0151]

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[0152]

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SU-1: di (2-ethylhexyl) sulfosuccinate sodium salt SU-2: di (2,2,3,3,4,4, sulfosuccinate)
5,5-octafluoropentyl) sodium salt DBP: dibutyl phthalate H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium HQ-1: 2 , 5-Di [(1,1-dimethyl-4-hexyloxycarbonyl) butyl] hydroquinone (Preparation of blue-sensitive silver halide emulsion (Em-B)) 40 ° C.
In a liter of a 2% aqueous gelatin solution kept warm in
Solution) and (solution B) were added simultaneously over 30 minutes while controlling pAg = 7.3 and pH = 3.0.
And (D solution) were simultaneously added over 180 minutes while controlling pAg = 8.0 and pH = 5.5. At this time, pAg was controlled by the method described in JP-A-59-45437.
H was controlled using sulfuric acid or an aqueous solution of sodium hydroxide. (Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Add water 200 ml (Solution B) Silver nitrate 10 g Add water 200 ml (Solution C1) Sodium chloride 102.7 g K2IrCl6 4 × 10-8 mol K4Fe (CN ) 6 2 × 10-5 mol Potassium bromide 1.0 g Water 600 ml (solution D) Silver nitrate 300 g Water 600 ml after addition After completion of addition, Kao Atlas 5% aqueous solution of Demol N and 20% magnesium sulfate After desalting using an aqueous solution, it was mixed with an aqueous gelatin solution to give an average particle size of 0.71 μm.
m, coefficient of variation (S / R) = 0.07, silver chloride content 9
A 9.5 mol% monodisperse cubic emulsion (EMP-1) was obtained.

Next, in the preparation of the above (EMP-1), except that the addition time of (solution A) and (solution B) and the addition time of (solution C1) and (solution D) were changed, Monodisperse cubic emulsion having an average particle size of 0.64 µm, a coefficient of variation in particle size distribution of 0.07, and a silver chloride content of 99.5 mol% (EMP-
1B) was obtained.

The above (EMP-1) was optimally chemically sensitized at 60 ° C. using the following compounds to obtain a blue-sensitive silver halide emulsion (Em-B1). Also, (EMP-1B)
Was similarly optimally chemically sensitized to obtain a blue-sensitive silver halide emulsion (Em-B1B). Sensitized (Em
-B1) and (Em-B1B) were mixed at a silver ratio of 1: 1 to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer (STAB-1) 3 × 10 −4 mol / mol AgX Sensitizing dye (BS-1) 4 × 10 −4 Mol / mol AgX sensitizing dye (BS-2) 1 × 10 −4 mol / mol AgX (Preparation of green-sensitive silver halide emulsion (Em-G)) (EM
In the preparation of P-1), the average particle diameter was 0.40 μm, and the variation coefficient was the same except that the addition time of (solution A) and (solution B) and the addition time of (solution C1) and (solution D) were changed. 0.0
8. Monodisperse cubic emulsion having a silver chloride content of 99.5% (EM
P-2) was obtained.

Next, the average particle diameter was 0.50 μm, and the variation coefficient was 0.1 mm, except that the addition time of (solution A) and (solution B) and the addition time of (solution C1) and (solution D) were changed. 08, a monodisperse cubic emulsion having a silver chloride content of 99.5% (EMP-2
B) was obtained.

The above (EMP-2) was optimally chemically sensitized at 55 ° C. using the following compounds to obtain a green light-sensitive silver halide emulsion (Em-G1). Also, (EMP-2B)
Was similarly optimally chemically sensitized to obtain a green-sensitive silver halide emulsion (Em-G1B). Sensitized (Em
-G1) and (Em-G1B) were mixed at a silver ratio of 1: 1 to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer (STAB-1) 3 × 10 −4 mol / mol AgX stabilizer (STAB-2) 3 × 10 −4 mol / Mol AgX stabilizer (STAB-3) 3 × 10 −4 mol / mol AgX sensitizing dye (GS-1) 4 × 10 −4 mol / mol AgX (Preparation of red-sensitive silver halide emulsion (Em-R)) ) (EM
In the preparation of P-1), the average particle diameter was 0.38 μm, and the variation coefficient was the same except that the addition time of (solution A) and (solution B) and the addition time of (solution C1) and (solution D) were changed. 0.0
8. Monodisperse cubic emulsion having a silver chloride content of 99.5% (EM
P-3) was obtained.

Next, the average particle diameter was 0.40 μm, and the variation coefficient was 0.1 mm, except that the addition time of (solution A) and (solution B) and the addition time of (solution C1) and (solution D) were changed. 08, a monodisperse cubic emulsion having a silver chloride content of 99.5% (EMP-3
B) was obtained.

The above (EMP-3) was optimally chemically sensitized at 60 ° C. using the following compounds to obtain a red-sensitive silver halide emulsion (Em-R1). Also, (EMP-3B)
Was similarly optimally chemically sensitized to obtain a red-sensitive silver halide emulsion (Em-R1B). Sensitized (Em
-R1) and (Em-R1B) were mixed at a silver ratio of 1: 1 to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX Chloroauric acid 2.0 mg / mol AgX Stabilizer STAB-1 3 × 10 −4 mol / mol AgX Stabilizer STAB-2 3 × 10 −4 mol / mol AgX Stable Agent STAB-3 3 × 10 −4 mol / mol AgX sensitizing dye RS-1 1 × 10 −4 mol / mol AgX sensitizing dye RS-2 1 × 10 −4 mol / mol AgX STAB-1: 1- ( 3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole 2.0 × 10 −3 mol of SS-1 was added per mol of silver halide.

[0163]

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[0164]

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Next, Samples 102 to 107 were prepared in the same manner as in Sample 101 except that the sample was changed as shown in Table 2. <Developing treatment> Each sample was exposed by a conventional method and subjected to a developing treatment in the following developing treatment step. (Processing step) The developing step is shown below.

Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C. 45 seconds 80 ml Bleaching and fixing 35.0 ± 0.5 ° C. 45 seconds 120 ml Stabilization 30-34 ° C. 60 seconds 150 ml Drying 60 to 80 ° C. for 30 seconds The composition of the developing solution is shown below. Color developing solution tank solution and replenisher tank solution Replenisher Pure water 800 ml 800 ml triethylenediamine 2 g 3 g diethylene glycol 10 g 10 g potassium bromide 0.01 g-potassium chloride 3.5 g-potassium sulfite 0.25 g 0.5 g N-ethyl-N- (Β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0 g 10.0 g N, N-diethylhydroxylamine 6.8 g 6.0 g triethanolamine 10.0 g 10.0 g sodium diethylenetriaminepentaacetate Salt 2.0 g 2.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Water was added to make a total volume of 1 liter, and the tank solution was pH = 1.
Adjust the replenisher to pH = 10.60 to 0.10. Bleaching-fixer tank solution and replenisher Ferric ammonium diethylenetriaminepentaacetate dihydrate 65 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4-thiadiazole 2.0 g Ammonium sulfate (40% aqueous solution) 27.5 ml Add water to make the total volume 1 liter, and adjust the pH to 5.0 with potassium carbonate or glacial acetic acid. Stabilizing liquid tank solution and replenisher o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g diethylene glycol 1. 0 g Optical brightener (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP (polyvinylpyrrolidone) 1.0 g ammonia water (25% ammonium hydroxide aqueous solution) 2.5 g nitrilotriacetic acid / trisodium salt 1.5 g water is added to make the total volume 1 liter, and the pH is adjusted to 7.5 with sulfuric acid or aqueous ammonia.

The neutrality characteristics of these treated samples were evaluated as follows. <Evaluation> (Neutrality) Perform development processing as described above,
The G density of status A of each sample on which an image is formed is 0.
The hue of each density portion of 3, 1.0, and 1.8 was measured using a Minolta colorimeter CM-2022 (standard light C / 2 ° field of view), and a metric chroma C ^* was obtained. As a guide. The results are shown in Table 2 below.

[0168]

[Table 2]

[0169]

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As can be seen from Table 2, CRR (Y) / CR
Samples 101 and 102 where R (C) is less than 1.07
As shown in (1), the neutrality is poor, which is not preferable as a photosensitive material for monochrome images. As can be seen from Samples 101 and 102 and Sample 103, the CRR value ratio of the three types of couplers, yellow coupler, magenta coupler, and cyan coupler, is important, but CRR (Y) / CRR
Those with (C) around 1.00 are rather poor, and CRR
(Y) / CRR (C) having a relatively large value of 1.170 to 1.626 had a smaller metric chroma C ^* in each concentration region, indicating better neutrality.

Further, when CRR (Y) / CRR (C) is 1.
It is apparent from the samples 104 to 106 of the present invention that are 07 or more that the effects of the present invention can be sufficiently obtained even if the type of the coupler is changed.

Further, in particular, CRR (Y) / CRR (C) C
RR (M) / CRR (C) CRR (Y) / CRR (M)
It can be seen that the sample 103 has good neutrality from the low density portion to the high density portion and can provide a photosensitive material capable of forming a black and white image with stable hue.

Example 2 The cyan coupler in Sample 103 of Example 1 was
Is changed to a compound represented by the general formula (C-I), and a compound represented by the general formula [C-I] is added to the compound represented by the general formula [C-I]
Samples 201 and 202 were produced in the same manner as shown in Table 3, except that the compound represented by I) was mixed and added at a ratio of 1: 1.

In the same manner as in Example 1, the hue of the portion where the G concentration of the status A of each sample was 1.0 was evaluated for neutrality, and the pH fluctuation resistance of the processing solution and the dark fading shown below were evaluated. Was done. <Evaluation> (Treatment liquid pH fluctuation resistance)
Prepare a sheet and p
After the same treatment was performed using the treatment liquid whose pH was adjusted to H9.7 and 10.5, (a ^* , b ^* ) when the G concentration of the status A of each sample was 1.0 was measured. Next, a color shift ΔE ^* (defined as a distance in the a ^* , b ^* plane of the CIELAB color space) under each processing condition with respect to the reference processing was calculated. (Dark Fading Property) The obtained sample was stored for one month under the conditions of 85 ° C. and 60% RH, and evaluated by obtaining the residual rate (%) of the dye image at an initial density of 1.0. The results are shown in Table 3 below.

[0175]

[Table 3]

As is clear from Table 3, the neutrality of sample 103 near the status density of 1.0 was good, but the hue variation was large from the evaluation of the pH fluctuation resistance of the processing solution, and the color was also reduced from dark fading. It can be seen that the balance is lost, which is not preferable as a photosensitive material for forming a black and white image. Further, as can be seen from Sample 201, when the compound represented by the general formula (C-I), which is the second invention of the present invention, is used, the hue fluctuation from the reference treatment also occurs when the pH of the treatment liquid varies. It can be seen that a black-and-white image that is small and has a more stable hue even under the influence of processing is formed. On the other hand, as can be seen from Sample 202, when the compound represented by the general formula [C-II] was used, dark fading was reduced, and it was found that the compound was more preferable in terms of color balance.

Example 3 Table 4 shows the yellow coupler in Sample 201 of Example 2.
A sample 301 was prepared in the same manner except that the temperature was changed as shown in FIG.

In the same manner as in Example 1, the hue of the portion where the G concentration of the status A of each sample was 1.0 was evaluated for neutrality, and the pH of the undertreatment solution was evaluated for pH fluctuation resistance. The results are shown in Table 4 below.

[0179]

[Table 4]

[0180]

Embedded image

As is clear from Table 4, in the sample 301, the neutrality of the status A at a G density of 1.0 is good, but the pH fluctuation resistance of the processing solution is large, the hue is largely changed, and a black and white image is formed. It turns out that it is not preferable as a photosensitive material. Also, as can be seen from Sample 201, the general formula [Y-
The use of the compound represented by the formula (I) is more preferable because the hue change from the standard treatment is small even when the pH of the processing solution changes, and a black-and-white image excellent in quality stability can be formed.

Example 4 Sample 401 was prepared in the same manner as in Sample 1 except that the dispersion form of the coupler in Sample 104 was changed as shown in Table 5.
402 was produced.

In the same manner as in Example 1, the hue of the portion where the G density of the status A of each sample was 1.0 was subjected to neutrality evaluation and dark fading evaluation. The bleaching property was evaluated. <Evaluation> (Hue variation ΔE ^* after storage over time)
・ Before and after preservation at 40% for 7 days, exposure by the usual method,
G of the status A of each sample formed by performing the development process
(A ^* , b ^* ) at a concentration of 1.0 was measured. Next, a color shift ΔE ^* (defined as a distance in the a ^* , b ^* plane of the CIELAB color space) under each processing condition with respect to the reference processing was calculated. (Blinking and fading) The obtained sample was stored outdoors under sunlight (exposure table) for 3 months, and evaluated by obtaining the residual ratio (%) of the dye image at an initial density of 1.0. The results are shown in Table 5 below.

[0184]

[Table 5]

As is clear from Table 5, in the sample 104, the neutrality of the status A at the G density of 1.0 is good, but the color balance is disturbed from dark fading and light fading, and the black-and-white image cannot be obtained. It turns out that it is not preferable as a photosensitive material to be formed. Particularly, when a yellow coupler, a magenta coupler, and a cyan coupler are mixed and added, the Y-density light-fading property is large, and the image becomes a blue-tone image. Further, it can be seen that hue changes occur after storage over time.

On the other hand, as can be seen from Sample 401, when the yellow coupler and cyan coupler according to the third invention of the present invention are mixed and dispersed and only the magenta coupler is dispersed alone, the neutrality is slightly inferior to that of Sample 104. No significant deterioration was observed, and it was found that the light-fading property, particularly the fading of yellow density, was reduced, which was favorable in terms of the fading level and the color balance. Even more surprisingly, it was found that the hue fluctuation after storage of the raw sample was small and an image having a stable color tone was formed.

As can be seen from Sample 402, when the magenta coupler and cyan coupler according to the third invention of the present invention were mixed and dispersed, and only the yellow coupler was dispersed alone, the neutrality was slightly increased as in Sample 401. Although inferior to Sample 105, it was found that light fading, especially fading of yellow density, was reduced, and not only the fading level and color balance were improved, but also the dark fading was improved, which was favorable.

Example 5 Samples 501 to 506 were prepared in the same manner as in Sample 201 except that Sample 201 of Example 1 was changed as shown in Table 6.
Was prepared.

In the same manner as in Example 4, the change in hue after storage with time was evaluated, and the change in density of the white portion after storage with time shown below was evaluated. <Evaluation> (Increase in density of white area after storage over time)
・ Before and after preservation at 40% for 7 days, exposure by the usual method,
After performing a development process, the reflection density of the white portion was measured, and the increase density of the white portion during storage with time was measured. The results are shown in Table 6 below.

[0190]

[Table 6]

(Layer A Coating Solution) Gelatin 0.60 g / m 2 PVP 0.01 g / m 2 Fluorescent Brightener W-1 0.02 g / m 2

[0192]

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As is clear from Table 6, the first to fifth embodiments of the present invention are described.
It can be seen that in the sample in which the application position of the blue-sensitive layer, which is a preferred embodiment of the third invention, is specified, an image with good hue fluctuation and whiteness can be obtained even after storage over time.

Example 6 In Examples 1 to 5, NPS-868J manufactured by Konica Corporation was used as an automatic developing machine, and ECO was used as a processing chemical.
Running processing was performed using JET-P according to the process name CPK-2-J1. As a result of evaluation in the same manner as in Example 1, it was confirmed that the effects of the present invention were sufficiently exhibited.

Example 7 In Examples 1 to 5, treatment was performed under the following processing conditions, and evaluation was performed in the same manner as in Examples 1 to 5. As a result, it was confirmed that the effects of the present invention were sufficiently exhibited.

The thickness of the section of the processing space of the processing apparatus is about 2.5
mm, and the following development processing steps were performed using a processing system designed so that the processing solution volume in the processing space was about 60% of the total volume of the processing solution used in this system. <Development> (Development processing step) Processing step Processing temperature Time Replenishment amount Color development 42.0 ± 0.3 ° C 18 seconds 65ml Bleaching and fixing 38.0 ± 0.5 ° C 19 seconds 60ml Stabilization 30-34 ° C 16 seconds 120 ml Drying 60-80 ° C. 27 seconds The composition of the developing solution is shown below. Color developer tank solution and replenisher tank solution Replenisher Pure water 800 ml 800 ml diethylene glycol 15 g 15 g potassium bromide 0.02 g 0.008 g potassium chloride 3 g 0.3 g potassium sulfite N-ethyl-N- (β-methanesulfonamidoethyl) -3-Methyl-4-aminoaniline sulfate 8.0 g 15.0 g N, N-bis (2-sulfoethyl) hydroxyamine 6.0 g 6.0 g diethylenetriaminepentaacetic acid sodium salt 5.0 g 7.5 g p-toluenesulfone Sodium acid 15.0 g 15.0 g Potassium carbonate 33 g 30 g Water is added to make the whole volume 1 liter, and the tank solution is adjusted to pH = 10.10 and the replenisher is adjusted to pH = 10.40. Bleach-fixer tank solution and replenisher tank solution Replenisher ammonium ferric ethylenediaminedisuccinate 0.20 mol 0.32 mol ethylenediaminedisuccinic acid 0.02 mol 0.032 mol ammonium thiosulfate 0.65 mol 1.04 Molar ammonium sulfite 0.12 mol 0.192 mol Water was added to make the total volume 1 liter, the pH of the tank solution was adjusted to 6.0 with potassium carbonate or glacial acetic acid, and the replenisher was adjusted to pH = 5.
Adjust to 0. Stabilizing solution tank solution and replenisher o-phenylphenol 0.1 g Optical brightener (Tinopearl SFP) 1.0 g Zinc sulfate 7H2O 0.1 g 1-hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 3 1.0 g Ethylenediaminetetraacetic acid 1.5 g Ammonium sulfite (40% aqueous solution) 5.0 ml Water is added to make the total volume 1 liter, and the pH is adjusted to 7.8 with sulfuric acid or aqueous ammonia.

Example 8 In Examples 1 to 5, processing was performed under the following processing conditions, and evaluation was performed in the same manner as in Examples 1 to 5. As a result, it was confirmed that the effects of the present invention were sufficiently exhibited.

As a processing apparatus, an apparatus of a coating and developing system is used. The first constituent liquid (a) is supplied to the emulsion surface of the photosensitive material heated by the heating means of the processing apparatus. In the same manner as in b), a color development step was carried out by supplying the emulsion to the emulsion surface of the light-sensitive material. After the supply of the first constituent liquid,
After 0.5 second, the second constituent liquid is supplied.

The processing steps including the color development step are described below.

Processing Step Processing Temperature Time Replenishment Color Development 80 ° C. 7 seconds 40 ml Bleaching and Fixing 38.0 ± 0.5 ° C. 7 seconds 60 ml Stabilization 30-34 ° C. 16 seconds 120 ml Drying 60-80 ° C. 15 seconds The composition is shown below. Color developing solution: first constituent solution (a) pure water 500 ml sodium sulfite 1.0 g diethylenetriaminepentaacetic acid pentasodium 3.0 g p-toluenesulfonic acid 20.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-Methyl-4-aminoaniline sulfate 43.0 g Water was added to make up to 1 liter, and potassium hydroxide or 50%
Adjust to pH 2.0 with sulfuric acid. Color developing solution: Second component solution (b) Pure water 500 ml Potassium chloride 10.0 g Diethylenetriaminepentaacetic acid pentasodium 3.0 g Potassium carbonate 82.0 g p-toluenesulfonic acid 15.0 g Water was added to make 1 liter, and water was added. Potassium oxide or 50%
Adjust to pH 13.5 with sulfuric acid. Bleaching-fixing, stabilizing process Same as in Example 7.

[0201]

According to the present invention, in a system for forming a black-and-white image with a coloring dye, that is, in a system for forming an image with a photosensitive material in a color development process, a black-and-white image with a stable hue is formed even when the process varies. However, even when stored for a long period of time, the improvement effect is not impaired, and the hue fluctuation is small even in image preservability, and a remarkably excellent effect that a high quality image can be stably provided can be provided. Play. In addition, the above-described method of processing the light-sensitive material by color development for a specific time can form an image in which the conventional problems are improved.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 7/388 G03C 7/388 7/407 7/407

Claims (7)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
The silver halide emulsion layer contains a yellow coupler, a magenta coupler and a cyan coupler, and the ratio (CRR (Y)) of the CRR value (CRR (Y)) of the yellow coupler to the CRR value (CRR (C)) of the cyan coupler. / CRR
(C)) is 1.07 or more. 2. A silver halide photographic material having at least one silver halide emulsion layer on a support,
A silver halide photographic light-sensitive material, wherein the silver halide emulsion layer contains at least one kind of yellow coupler, magenta coupler and cyan coupler represented by the following formula (CI). Embedded image In the formula, R1 represents an alkyl group or an aryl group. R2 represents a fluorinated alkyl group or a fluorinated aryl group. R3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. R3 may form a ring together with R1.
Z represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of an aromatic primary amine color developing agent. 3. The yellow coupler represented by the following general formula [Y
3. The silver halide photographic material according to claim 2, which is a compound represented by the formula (I). Embedded image In the formula, R21 represents an alkyl group or a cycloalkyl group, R22 represents a halogen atom, an alkyl group, a cycloalkyl group or an aryl group, and R23 represents a substituent. X
1 represents a group or an atom which is released by a reaction with an oxidized form of the color developing agent. 4. A silver halide photographic material having at least one silver halide emulsion layer on a support,
The silver halide emulsion layer is composed of two couplers of a yellow coupler, a magenta coupler and a cyan coupler.
A silver halide photographic light-sensitive material comprising an oil-in-water dispersion containing seeds and an oil-in-water dispersion containing the remaining one kind. 5. A silver halide emulsion layer containing a cyan coupler, a magenta coupler and a yellow coupler, and a black dye-forming coupler optionally added, and a blue-sensitive silver halide emulsion layer. 5. The silver halide photographic material according to claim 1, wherein said blue-sensitive silver halide emulsion layer is formed so as not to be adjacent to a support. 6. A silver halide emulsion layer and a blue-sensitive silver halide emulsion layer containing a cyan coupler, a magenta coupler and a yellow coupler, and optionally containing a black dye-forming coupler. And the silver halide emulsion layer formed closest to the support
5. The silver halide photographic light-sensitive material according to claim 1, further comprising a non-photosensitive hydrophilic layer between the supports. 7. An image forming method for exposing and developing a silver halide photographic light-sensitive material according to claim 1, wherein the color development time is 5 to 40 seconds. An image forming method comprising: