JP2876079B2 - Silver halide color photographic materials - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material, and more particularly, to a silver halide color having excellent spectral absorption characteristics and markedly improved light fastness. It relates to a photographic material.

(Prior art) Generally, a color image obtained by photographic processing of a silver halide color photographic light-sensitive material is obtained from an azomethine dye or an indoaniline dye formed by a reaction between an oxidized aromatic primary amine developing agent and a coupler. Become.

In order to obtain a color photographic image having good color reproducibility, a vivid dye having little side absorption is required. Particularly in the case of magenta dyes, U.S. Pat.Nos. 3,061,432 and 4,50 than 5-pyrazoloneazomethine dyes having side absorption around 400 to 450 nm.
No. 0,630, JP-B-47-27411, JP-A-59-171956,
Dyes obtained from pyrazoloazole-based magenta couplers described in Nos. 60-33552, 60-43659 and Research Disclosure No. 24626 are more advantageous.

However, when these pyrazoloazole-based magenta couplers are used in a silver halide color photographic light-sensitive material, the light fastness is remarkably poor as compared with a 5-pyrazolone-based magenta coupler.

The present inventors have found that a compound having a specific structure is effective in improving the light fastness of a magenta image obtained from a pyrazoloazole-based magenta coupler.
4,588,679, 4,735,893, EP 218,26
6, 298,321 and JP-A-62-92945.

However, of the color-developed areas generated by the development processing,
It was found that these compounds markedly improved the light fastness in the high color region where the dye concentration was high, but were insufficient and insufficient in the low color region. Moreover, in the low-density color region, the light fastness of magenta was inferior to that of yellow and cyan, and the color balance of these three colors changed over time, indicating that the fading of magenta was further enhanced visually.

On the other hand, use of a 2-acylamino or 2-sulfonamidophenol compound for preventing discoloration of a 5-pyrazolone-based magenta coupler is disclosed in EP-A-176845. In addition, EP-A-145342 discloses the use of a specific phenol having an electron-absorbing group for the purpose of improving the dispersion stability, coloring, hue or fastness of couplers including pyrazoloazole-based magenta couplers. No.60-262157, No.61-279855, No.61-286853, No.
62-25755, 62-27737, 62-27739, 62-1
No. 75748 has been proposed.

However, although the compounds specifically described in these patents show effects on dispersion stability, color development and hue, their effects on light fastness are insufficient. Particularly, the compound described in EP-A-176845 is excellent in improving the light fastness of yellow,
-For pyrazolone-based magenta couplers, yellow and cyan without an inhibitor were not improved to the level of cyan and insufficient. Moreover, the effect is even weaker for pyrazoloazole.

(Problem to be Solved by the Invention) A first object of the present invention is to provide a silver halide color photographic light-sensitive material having excellent spectral absorption characteristics, good color reproduction, and markedly improved light fastness of a dye image. It is in.

A second object of the present invention is to provide a silver halide color photographic light-sensitive material in which the fading speeds of the high color density region and the low color density region where the dye density is high are uniform, that is, the balance of fading does not change over the entire color density region. To provide.

A third object of the present invention is to provide a silver halide color photographic light-sensitive material in which the color balance does not change in the three colors of yellow, magenta and cyan.

A fourth object of the present invention is to provide a silver halide color photographic light-sensitive material in which yellow stain and colored stain on a white background are less generated with respect to light, heat and temperature.

(Means for Solving the Problems) The present inventors have conducted various studies more vigorously. As a result, when the compound represented by the general formula (II) is used in combination with a known phenol or hydroquinone-based discoloration inhibitor, the color development density range is compared with the case where the compound represented by the general formula (II) is used alone. The light fastness over the entire region is poor, or the light fastness is improved in the low color density range, but the light fastness is degraded in the high color density range. It has been found that the compound can greatly improve the fastness in the low color density range without deteriorating the light fastness in the high color density range, and completed the present invention. That is, the following general formula (I) A silver halide emulsion layer containing at least one coupler represented by the general formula (II) and at least one compound represented by the general formula (III). It has been found that the above-mentioned object is achieved.

General formula (I) In the formula, R represents a hydrogen atom or a substituent, and Za, Zb, and Zc represent methine, substituted methine, or any of ＝ N— and —HN—. Y represents a hydrogen atom, a group capable of leaving in a coupling reaction with an oxidized form of a developing agent, or a substituent. However, when Y is a substituent, any of Za, Zb, and Zc is a methine group or a substituted methine group substituted with a group capable of leaving in a coupling reaction with an oxidized developing agent. R, Y or Za, Zb or Zc may form a dimer or higher multimer.

General formula (II) In the formula, X ₁ and X ₂ may be the same or different, and Represents -SO ₂ -or a single bond. However, X ₁ and X ₂ are not a single bond at the same time. R ₁ represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an alkenoxy group, an aryloxy group, a heterocyclic oxy group, an amino group or a substituted amino group. R ₂ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group or a sulfonyl group. R ₃ is an alkyl group, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group or Represents R ₄ represents a halogen atom, a heterocyclic group or a group defined for R ₃ . n represents an integer of 0 to 3. n is 2
In the case of ３3, a plurality of R ₄ may be the same or different. Here, R ₁ and R ₂ , R ₁ and R ₄ , R ₂ and R ₄ , R ₃ and R ₄ , among a plurality of R ₄ , groups at the ortho position are bonded to each other to form a 5- to 7-membered ring. It may be formed.

General formula (III) In the formula, R ₁₁ and R ₁₂ represent an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. X is -O- or Represents R ₁₄ represents a hydrogen atom or a group defined for R ₁₁ . R ₁₃ represents an alkylthio group, an arylthio group, a group defined for R ₁₁ or —XR ₁₂ . m represents an integer of 0 to 4. When m is 2 or more, a plurality of R ₁₃ may be the same or different from each other. R ₁₁ and R ₁₂ , R ₁₁ and R ₁₄ , R ₁₁ and R ₁₃ , R ₁₂
And R _14, R ₁₂ and R _13, R ₁₃ and R _14,. 5 to be what R ₁₃ in the ortho position to each other among the plurality of R ₁₃ are bonded to each other
A 7-membered ring may be formed.

Among the couplers represented by formula (I), preferred couplers are represented by formulas (Ia), (Ib), (Ic), (Id) and (Ie).

The substituents in the general formulas (Ia) to (Ie) will be described in detail. R, R ′ and R ″ represent an aliphatic group, an aromatic group, a heterocyclic group or a coupling-off group, and these groups further include an alkyl group, an aryl group, a heterocyclic group,
An alkoxy group (eg, methoxy, 2-methoxyethoxy), an aryloxy group (eg, 2,4-di-tert-amylphenoxy, 2-chlorophenoxy, 4-cyanophenoxy), an alkenyloxy group (eg, 2-propenyloxy) ), Acyl groups (eg, acetyl, benzoyl), ester groups (eg, butoxycarbonyl, phenoxycarbonyl, acetoxy, benzoyloxy, butoxysulfonyl, toluenesulfonyloxy), amide groups (eg, acetylamino, methanesulfonamide, Propylsulfamoylamino), carbamoyl group (eg, dimethylcarbamoyl, ethylcarbamoyl), sulfamoyl group (eg, butylsulfamoyl), imide group (eg, succinimide, hydantoinyl), ureido group (eg, For example, phenylureido, dimethylureido), an aliphatic or aromatic sulfonyl group (eg, methanesulfonyl, phenylsulfonyl),
It may be substituted with a group selected from an aliphatic or aromatic thio group (eg, ethylthio, phenylthio), a hydroxy group, a cyano group, a carboxy group, a nitro group, a sulfo group, a halogen atom, and the like. R, R 'and R "further represent RO-, _{RS-, RSO-, RSO 2 -,} RSO 2 NH-, RNH-, It may be a hydrogen atom, a halogen atom, a cyano group, or an imide group. (R represents an alkyl group, an aryl group and a heterocyclic group).

R, R 'and R "may further be a carbamoyl group, a sulfamoyl group, a ureido group or a sulfamoylamino group, and the nitrogen atom of these groups is a substituent allowed for R to R". It may be substituted. Of these, alkyl groups, branched alkyl groups, aryl groups,
Preferred are an alkoxy group, an aryloxy group, a ureido group and the like.

Y represents a group defined by the general formula (I), and the substituent represented by Y has the same meaning as R, R 'or R ".

When Y represents a group capable of leaving in a coupling reaction with an oxidized form of a developing agent (hereinafter, referred to as a coupling-off group), the coupling-off group is a coupling activated carbon atom and an aliphatic group via an oxygen, nitrogen or sulfur atom. Group,
An aromatic group, a heterocyclic group, an aliphatic / aromatic or heterocyclic sulfonyl group, a group bonding to an aliphatic / aromatic or heterocyclic carbonyl group, a halogen atom, an aromatic azo group, etc. The aliphatic group, aromatic group or heterocyclic group contained in the coupling-off group may be substituted with a substituent permitted by R to R ″.

Specific examples of the coupling-off group include a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom), an alkoxy group (for example, ethoxy, dodecyloxy, methoxyethoxy, methoxyethylcarbamoyl, carboxypropyloxy, methylsulfonylethoxy). ), Aryloxy groups (for example, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy), acyloxy groups (for example, acetoxy, tetradecanoyloxy, benzoyloxy), aliphatic or aromatic A sulfonyloxy group (eg, methanesulfonyloxy, toluenesulfonyloxy), an acylamino group (eg, dichloroacetylamino, heptafluorobutylamino), an aliphatic or aromatic sulfonamide group (eg, methanesulfonamide) p-toluenesulfonamide), alkoxycarbonyloxy group (for example, ethoxycarbonyloxy, benzyloxycarbonyloxy), aryloxycarbonyloxy group (for example, phenoxycarbonyloxy), aliphatic / aromatic or heterocyclic thio group (Eg, ethylthio, phenylthio, tetrazolylthio), carbamoylamino group (eg, N
-Methylcarbamoylamino, N-phenylcarbamoylamino), a 5- or 6-membered nitrogen-containing heterocyclic group (eg, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,2-dihydro-2-oxo-1-pyridyl), Examples include an imide group (eg, succinimide, hydantoinyl) and an aromatic azo group (eg, phenylazo). The coupling-off group of the present invention may contain a photographically useful group such as a development inhibitor, a development accelerator and a desilvering accelerator. Of these, halogen atoms and arylthio groups are particularly preferred.

Among the couplers represented by the general formulas (Ia) to (Ie),
From the viewpoint of the effects of the present invention, those represented by the general formulas (Ic) and (Id) are preferable.

Hereinafter, specific examples of the coupler represented by Formula (I) are shown.

Specific examples of the pyrazoloazole-based magenta coupler represented by formula (I) used in the present invention and the synthesis method thereof are described in JP-A Nos. 59-1625485, 60-43659, and 59-1719.
No. 56, No. 60-33552, No. 60-177292, No. 61-292143
No. 63-231341, No. 63-291058, U.S. Pat.
Nos. 1,432 and 4,728,598.

The compound represented by formula (II) will be described in more detail.

In the general formula (II), X ₁ and X ₂ may be the same or different. Represents -SO ₂ -or a single bond. However, X ₁ and X ₂ are not a single bond at the same time. R ₁ is an alkyl group (a linear, branched or cyclic substituted or unsubstituted alkyl group;
For example, methyl, ethyl, isopropyl, tert-butyl,
Octyl, decyl, octadecyl, cyclohexyl, benzyl), alkenyl group (eg, vinyl, allyl, oleyl, cyclohexenyl), aryl group (eg, phenyl, naphthyl), heterocyclic group (oxygen atom, nitrogen atom, sulfur atom, phosphorus atom) A 5- to 7-membered heterocyclic group in which at least one atom is incorporated as a ring-constituting atom, for example, piperazyl, piperidyl, morpholinyl, thienyl, furyl, pyridyl, pyrazolyl, triazinyl, chromanyl, azepinyl), an alkoxy group (for example, Methoxy, ethoxy, isoamyloxy, cyclohexyloxy, octyloxy, dodecyloxy, hexadecyloxy, octadecyloxy, benzyloxy),
An alkenyloxy group (eg, vinyloxy, allyloxy, cyclohexenyloxy), an aryloxy (eg, phenoxy, naphthoxy), a heterocyclic oxy group (at least one of an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom is incorporated as a ring-constituting atom) A 5- to 7-membered heterocyclic oxy group such as tetrahydrofuranyloxy, tetrahydropyran-2-yloxy, pyrazinyloxy, triazinyloxy, chroman-6-yloxy), an amino group or a substituted amino group (as a substituent) For example, it represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group). R ₂ is a hydrogen atom, an alkyl group (linear, branched or cyclic alkyl group such as methyl, ethyl, isopropyl, tert-butyl, hexyl, octyl, decyl, tridecyl, cyclohexyl, octadecyl, benzyl), alkenyl group (for example, 5 to 7 in which at least one atom of vinyl, allyl, oleyl, cyclohexenyl), an aryl group (for example, phenyl, naphthyl), a heterocyclic group (an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom is incorporated as a ring-constituting atom) Membered heterocyclic group, for example, piperazyl,
Piperidyl, morpholinyl, thienyl, furyl, pyridyl, pyrazolyl, triazinyl, chromanyl, azepinyl), acyl groups (eg, acetyl, myristoyl, stearoyl, acryloyl, benzoyl) or sulfonyl groups (eg, methanesulfonyl, octanesulfonyl,
Benzenesulfonyl, toluenesulfonyl).
R ₃ represents an alkyl group (linear, branched or cyclic alkyl group such as methyl, ethyl, isopropyl, tert-butyl,
-Octyl, sec-decyl, pentadecyl, octadecyl, cyclohexyl, benzyl), an aryl group (eg, phenyl, naphthyl), an alkoxycarbonyl group (eg, methoxycarbonyl, butoxycarbonyl, isoamyloxycarbonyl, cyclohexyloxycarbonyl, oleyloxycarbonyl, hexadecyl) Oxycarbonyl), an aryloxycarbonyl group (eg, phenyloxycarbonyl, 2,4-di-tert-amylphenoxycarbonyl, naphthyloxycarbonyl) or Represents R ₄ is a 5- to 7-membered member in which at least one atom of a halogen atom (for example, a fluorine atom, a chloro atom, a bromo atom), a heterocyclic group (an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom is incorporated as a ring atom) cyclic heterocyclic group, for example piperazyl, piperidyl, morpholinyl, thienyl, furyl, pyridyl, pyrazolyl, triazinyl, chromanyl, a group as defined azepinyl) or R _3. n represents an integer of 0 to 3. When n is 2 to 3, a plurality of R ₄ may be the same or different. Where R ₁
R ₂ , R ₁ and R ₄ , R ₂ and R ₄ , R ₃ and R ₄ , and a plurality of R ₄ 's may be mutually bonded to form a 5- to 7-membered ring.

Among the compounds represented by the general formula (II), a compound represented by the following general formula (II-a) is preferable from the viewpoint of the effect of the present invention.

General formula (II-a) In the formula, R ₁ , R ₂ and n represent the meaning defined in the general formula (II). X ₃ Or -SO _2- . R ′ ₃ represents an alkyl group, an aryl group or And R ′ ₄ represents the group defined for R ′ ₃ .

Among the compounds represented by the general formula (II-a), X ₃
But Is preferred.

The compound represented by formula (III) will be described in more detail.

In the general formula (III), R ₁₁ and R ₁₂ represent the general formula (II)
Alkyl group with the same meaning as R _11, an alkenyl group, an aryl group, a heterocyclic group. X is -O- or Represents R ₁₄ represents a hydrogen atom or a group defined for R ₁ . R ₁₃ represents an alkylthio group (eg, methylthio, ethylthio, isoamylthio, cyclohexylthio, octylthio, hexadecylthio, octadecylthio, benzylthio), an arylthio group (eg, phenylthio, naphthylthio), the group defined for R ₁₁ , or —XR ₁₂ . m
Represents an integer of 0 to 4. When m is 2 or more, a plurality of R ₁₃
May be the same or different. R ₁₁ and R ₁₂ , R ₁₁
And R _14, R ₁₁ and R _13, R ₁₂ and R _14, R ₁₂ and R _13, R ₁₃ and R _14,. 5 to be what R ₁₃ in the ortho position to each other among the plurality of R ₁₃ are bonded to each other A 7-membered ring may be formed.

Among the compounds represented by the general formula (III), a compound in which -XR ₁₂ is in the ortho position or the para position with respect to -OR ₁₁ is preferable from the viewpoint of the effect of the present invention.

More preferably, the following general formulas (III-a) to (III-
This is a compound represented by e).

In the general formulas (III-a) to (III-e), R ′ ₁₁ , R ″
₁₁ , R ₁₈ and R ₁₉ may be the same or different and each represents an alkyl group, an alkenyl group or an aryl group, and R ₁₈ further represents a hydrogen atom. R ₅ , R ₆ and R ₇
May be the same or different, and each represents a hydrogen atom, an alkyl group or an aryl group. A is 5-6
Represents a group of non-metallic atoms forming a member ring. R ₁₃ and m have the same meaning as defined in formula (III). m ₁ is 0
Represents an integer of 0 to 3, and 1 represents an integer of 0 to 2. m,
When each of m ₁ and l is 2 or more, a plurality of R ₁₃ may be the same or different.

In the general formula (III-b), R ′ ₁₁ and R ₁₃ may be bonded to each other to form a 5- or 6-membered ring;
In (III-e), R ₁₈ and R ₁₉ , or R ₁₉ and R ₁₃ may be bonded to each other to form a 5- to 6-membered ring.

Among the compounds represented by formulas (III-a) to (III-e), more preferred compounds are those represented by formulas (III-a) to (III-a).
It is a compound represented by (III-c).

Of the groups defined in general formulas (II) and (III),
The group having an alkyl, aryl, or heterocyclic moiety may be further substituted with a substituent. Examples of these substituents include an alkyl group, an alkenyl group, an alkynyl group,
Aryl group, heterocyclic group, alkoxy group, alkenoxy group, aryloxy group, heterocyclic oxy group, alkylthio group, alkenylthio group, arylthio group, heterocyclic thio group, hydroxy group, amino group, substituted amino group, halogen atom, Nitro group, cyano group, acyl group, sulfonyl group, carbamoyl group, sulfamoyl group, acyloxy group, silyloxy group, phosphonyl group, sulfinyl group,
Examples include a sulfo group, a carboxyl group, and an ester group.

Hereinafter, specific examples of the compound represented by the general formula (II) are shown, but the invention is not limited thereto.

The compound represented by formula (II) of the present invention can be synthesized by the method described in EP-A-176845 or a method analogous thereto.

Hereinafter, specific examples of the compound represented by formula (III) are shown, but the invention is not limited thereto.

The compounds represented by the general formula (III) of the present invention are described in U.S. Pat. Nos. 4,360,589, 4,332,836 and 4,155,765.
No. 4,483,918, or a method analogous thereto can be easily synthesized.

The amount of the compounds represented by formulas (II) and (III) of the present invention is 1 × 10 ^-2 to 1 mol per coupler.
It is preferably 10 mol, more preferably 3 × 10 ^{-2 to} 5 mol. If the amount is less than this, the effect of the present invention is not easily exerted. The ratio (general formula (II) / general formula (III)) used in combination of the compounds represented by the general formulas (II) and (III) is 1 × 10 ⁻² to 1 × 10
^-2 is preferred, and more preferably 0.1 to 10.

In the present invention, the effect of the present invention can be further enhanced by using it in combination with at least one kind of ultraviolet absorber.

An ultraviolet absorber can be added to any layer. Preferably, an ultraviolet absorber is contained in or adjacent to the cyan coupler-containing layer used in the present invention. The ultraviolet absorbers that can be used in the present invention are the compounds listed in Section VIIIC of Research Disclosure No. 17643, but are preferably benzoates represented by the following general formula (UV). It is a triazole derivative.

In the formula, R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ may be the same or different and represent a hydrogen atom or a substituent. Examples of the substituent include R and R 'described in the general formulas [Ia to Ie].
And the substituents defined for R ″ apply. R ₂₄ and R ₂₅ may be closed to form a 5- or 6-membered aromatic ring composed of carbon atoms. May be further substituted with a group.

The compounds represented by the above general formula (UV) can be used alone or in combination of two or more. Hereinafter, typical examples of the ultraviolet absorbent which can be used in the present invention will be described. In these chemical structural formulas, A method for synthesizing the compound represented by the general formula (UV) or other compound examples is described in JP-B-44-29620,
No. 151149, JP-A-54-95233, U.S. Pat.
No., EP0057160, Research Disclosure Magazine No.
22519 (1983). In addition,
-111942, 58-178351 (UK Patent 2118315A), U.S. Patent 4,455,368, JP-A-59-19945 and JP-A-59-19945
No. 23344 (British Patent No. 2127569A) can also be used.
-6. Low-molecular and high-molecular ultraviolet absorbers can be used in combination.

The coating amount of the ultraviolet absorber may be an amount sufficient to impart light stability to the dye image, but if used in an excessively large amount, the unexposed portion (white background portion) of the color photographic light-sensitive material may cause yellowing. Therefore, it is usually preferably 1 × 10 ⁻⁴ mol / m ² to
2 × 10 ⁻³ mol / m ² , particularly preferably 5 × 10 ⁻⁴ mol / m ²
It is set in the range of 1.5 × 10 ⁻³ mol / m ² .

Due to the processing solution components remaining in the film of the color photographic light-sensitive material after the development processing, in particular, an aromatic amine-based developer generates colored stains during storage after the processing. In the present invention, it is preferable to use the compound defined by (1) or (2) alone or in combination thereof in order to prevent the generation of the colored stain. The general formulas (I) to (II) of the present invention
When combined with the compound represented by I), the storage stability improving effect is further improved.

(1) a compound which chemically bonds to an aromatic amine-based color developing agent remaining in the color photographic light-sensitive material after the color developing process to form a chemically inert and substantially colorless compound; (2) after the color developing process Compounds that form a chemically inert and substantially colorless compound by chemically bonding with an oxidized form of an aromatic amine color developing agent remaining in a color photographic light-sensitive material. Preferred compounds have a second-order rate constant k ₂ (80 ° C. in trioctyl phosphate) of p-anisidine of 1.0 l / mol · sec. To 1 × 10 ⁻⁵ l /
mol · sec. This rate constant can be measured by the method described in EP-A-258662. More preferred such compounds can be represented by the following general formula (EI) or (E-II).

General formula ( _EI ) R _{e1 An} X General formula (E-II) In the formula, R _e1 and R _e2 each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0. A
Represents a group that forms a chemical bond by reacting with an aromatic amine-based developing agent, and X represents a group that is released by reacting with an aromatic amine-based developing agent. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group or a sulfonyl group. Y represents a group which promotes the addition of the aromatic amine-based developing agent to the compound represented by formula (E-II). Here, R _e1 and X, Y and R _e2 or B may be bonded to each other to form a cyclic structure.

Representative methods of chemically bonding with the remaining aromatic amine-based developing agent are a substitution reaction and an addition reaction.

Preferred compounds among the compounds defined in (2) can be represented by the general formula (F).

Formula (F) RZ In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group. Z represents a nucleophilic group or a group which decomposes in the light-sensitive material to release a nucleophilic group.

In the compound represented by the general formula (F), Z is a nucleophilic ⁿ CH ₃ I value of Pearson (RGPearson, et al., J. Amer. Chem. Soc., 9
0, 319 (1968)) is ⁿ CH ₃ I value decompose at 5 or more groups or light-sensitive material is preferably a group which releases 5 or more groups.

The typical examples of the compounds defined in the above (1) or (2) are shown below, but the compounds used in the present invention are not limited thereto.

Other preferred compound examples and synthetic methods of the compounds defined in (1) or (2) above are described in US Pat. No. 4,704,350.
No. 4,770,987, European Patent No. 230,048, No. 25
No. 5,722, No. 258,662, No. 277,589, No. 298,321
No. etc.

The compounds defined in the above (1) or (2) may be used alone, however, it is preferable to use them in combination because the effect is enhanced.

Of the compounds defined in the above (1) or (2), those having a low molecular weight or those which easily dissolve in water may be added to the processing bath in the development step and incorporated into the photosensitive material. A preferred method is to add it to the photosensitive material at the stage of producing the photosensitive material.

The addition amount of the compound defined by the above (1) or (2) is preferably 1 × 10 ^-2 to 10 mol per 1 mol of the coupler,
It is more preferably 3 × 10 ^{-2 to} 5 mol.

The color photographic light-sensitive material of the present invention can be constituted by coating at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer and one red-sensitive silver halide emulsion layer on a support. In general, color printing paper is usually coated on a support in the order described above, but may be performed in a different order. Further, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned emulsion layers. In these light-sensitive emulsion layers, a silver halide emulsion having a sensitivity in each wavelength region and a dye having a complementary color with the light to be exposed, that is, yellow for blue, magenta for green, and cyan for red are formed. By incorporating a so-called color coupler, the color reproduction by the subtractive color method can be performed. However, the photosensitive layer and the color hue of the coupler may not have the above correspondence.

As the silver halide emulsion used in the present invention, an emulsion composed of silver chlorobromide or silver chloride containing substantially no silver iodide can be preferably used. Here, "contains substantially no silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. The halogen composition of the emulsion may be different or the same between grains. However, when an emulsion having the same halogen composition between grains is used, it is easy to make the properties of each grain uniform. Regarding the distribution of the halogen composition inside the silver halide emulsion grains, a so-called uniform type grain having the same composition at any part of the silver halide grains, and a core (core) inside the silver halide grains and the same. A so-called laminated type particle having a different halogen composition from the surrounding shell (one or more layers) or
Particles having a structure having a different halogen composition in a non-layered manner inside or on the surface of the particles (edges of the particles when they are on the surface of the particles, structures where different composition portions are bonded on corners or surfaces) are appropriately selected and used. be able to. In order to obtain high sensitivity, it is advantageous to use one of the latter two particles rather than particles having a uniform structure, and this is also preferable from the viewpoint of pressure resistance. In the case where the silver halide grains have the above-described structure, the boundary between different portions in the halogen composition may be a clear boundary or an unclear boundary due to the formation of a mixed crystal due to a composition difference. It is also possible to employ a structure in which a continuous structural change is positively provided.

Regarding the halogen composition of these silver chlorobromide emulsions, those having an arbitrary silver bromide / silver chloride ratio can be used. Although this ratio can take a wide range according to the purpose, a silver chloride ratio of 2% or more can be preferably used.

Further, a so-called high silver chloride emulsion having a high silver chloride content is preferably used as a photosensitive material suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably at least 90 mol%,
95 mol% or more is more preferable.

Such high silver chloride emulsions preferably have a structure in which a silver bromide localized layer is formed in a layered or non-layered form as described above on the inside and / or on the surface of silver halide grains.
The halogen composition of the localized phase is preferably at least 10 mol% in terms of silver bromide content, and more preferably more than 20 mol%. These localized layers can be on the inside of the particle, on the edge, on the corner or on the surface of the particle. One preferable example is a layer grown epitaxially on the corner of the particle.

On the other hand, in order to minimize the decrease in sensitivity when the photosensitive material is subjected to pressure, even in a high silver chloride emulsion having a silver chloride content of 90 mol% or more, grains having a uniform distribution of the halogen composition in the grains are used. It is also preferably used.

It is also effective to further increase the silver chloride content of the silver halide emulsion in order to reduce the replenishment amount of the developing solution. In such a case, the silver chloride content is 98 mol% to 10 mol%.
Emulsions of substantially pure silver chloride, such as 0 mol%, are also preferably used.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0.1 μm to 2 μm. preferable.

In addition, their particle size distribution has a coefficient of variation (standard deviation of particle size distribution divided by average particle size) of 20%
In the following, a so-called monodispersed one of desirably 15% or less is preferable. At this time, for the purpose of obtaining a wide latitude, it is preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multilayer coating.

Silver halide grains contained in photographic emulsions have a regular (regular, cubic, tetradecahedral or octahedral) shape.
r) Those having a crystal form, those having an irregular crystal form such as a sphere, a plate, or the like, or those having a composite form thereof can be used. Further, it may be composed of a mixture of those having various crystal forms. In the present invention, 50% or more, preferably 70% or more of the particles having the regular crystal form among these,
More preferably, the content is 90% or more.

In addition, emulsions in which tabular grains having an average aspect ratio (diameter / circle diameter in circle) of 5 or more, preferably 8 or more, as projected area exceeds 50% of all grains can be preferably used.

The silver chlorobromide emulsion used in the present invention is described in Chimi by P. Glafkides.
e et Phisique Photograhique (Paul Montel, 19
67), Photograhic Emulsion Chemistry by GFDuffin
(Focal Press, 1966), M by VLZelikman et al
aking and Coating Photograhic Emuldion (Focal Pres
s company, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halide, any method such as a one-side mixing method, a simultaneous mixing method, and a combination thereof may be used. May be used. A method of forming particles in an atmosphere containing excess silver ions (a so-called reverse mixing method) can also be used. As one form of the double jet method, a method of generating silver halide, that is, a method of keeping pAg in a liquid phase constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

In the silver halide emulsion used in the present invention, various polyvalent metal ion impurities can be introduced during the process of forming emulsion grains or physical ripening. Examples of the compound to be used include salts of cadmium, zinc, lead, copper, thallium and the like, or salts or complex salts of Group VIII element iron, ruthenium, rhodium, palladium, osmium, iridium and platinum. it can. Especially above VI
Group II elements can be preferably used. The addition amount of these compounds is preferably 10 ^{< -9>} to 10 ^<-2> mol with respect to silver halide over a wide range depending on the purpose.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization and spectral sensitization.

As the chemical sensitization method, sulfur sensitization represented by addition of an unstable sulfur compound, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compounds used for chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used.

Spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye that absorbs light in a wavelength range corresponding to the intended spectral sensitivity—a spectral sensitizing dye. As the spectral sensitizing dye used at this time, for example, Heterocyclic compo by FM Harmar
unds-Cyanine dyes and related compounds (John Wil
ey & Sons [New York, London], 1964). As specific examples of the compounds, those described in the above-mentioned JP-A-62-215272, page 22, upper right column to page 38, are preferably used.

To the silver halide emulsion used in the present invention, various compounds or their precursors are added for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. be able to. As specific examples of these compounds, those described on page 39 to page 72 of JP-A-62-215272 described above are preferably used.

The emulsion used in the present invention is either a so-called surface latent image type emulsion in which a latent image is mainly formed on the surface of a grain, or a so-called internal latent image type emulsion in which a latent image is mainly formed inside a grain. Is also good.

The cyan coupler and yellow coupler used in the present invention may be any coupler having any structure as long as it couples with an oxidized aromatic amine-based color developing agent to form cyan and yellow colors. From the viewpoint of the effects of the present invention, it is preferable to use the following cyan and yellow couplers.

The cyan coupler contained in the cyan dye image forming layer includes the following general formulas [C-I], [C-II] and [C-III].
And [C-IV].

General formula [C-I] General formula [C-II] General formula [C-III] General formula [C-IV] In the formula, Z represents a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of a developing agent.

R ¹⁰ is -NHSO ₂ -R ¹⁴ , Or it represents a -SO ₂ -R ^16. Where R ¹³ , R ¹⁴ , R ¹⁵ and R
¹⁶ represents an aliphatic group, an aromatic group, a heterocyclic group, or an amino group which may have a substituent. R ¹³ and R ¹⁵ further represent an aliphatic oxy group, an aromatic oxy group, or a heterocyclic oxy group. R ¹¹
Represents a group as defined hydrogen atom, an aliphatic group, or R ^10. R ¹² represents a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an aliphatic oxy group, or a group defined for R ¹⁰ . X ¹⁰ represents = CH- or = N-. R ¹¹ and R
¹² may combine with each other to form a 5- to 7-membered ring. R ²¹
And R ²² may be the same and different, all of which are aromatic groups,
Represents a substituent which is a heterocyclic group or at least one of which is an electron withdrawing group. Q ³⁰ represents a group of non-metallic atoms necessary for forming a nitrogen-containing heterocyclic ring. R ³¹ , R ³² and R ³³ may be the same or different and each represents a hydrogen atom or a substituent. At least one of R ³² and R ³³ are further R ³² and R ³³ represents a group as defined Z. n represents 1 or 2.
n is two R ³² when 2 connexion be different even in the same. However, at least one of R ³¹ , R ³² and R ³³ is an electron withdrawing group. Q ⁴⁰ represents> = (X ⁴⁰ -Y ⁴⁰ ) _m = <a non-metal atom group necessary for forming a heterocyclic ring or an aromatic group together with the residue. X ⁴⁰ and Y ⁴⁰ represent a nitrogen atom or a methine group which may have a substituent, and m represents 1 or 2. R ⁴⁰ and R ⁴¹ represent a substituent. However, at least one of R ⁴⁰ and R ⁴¹ represents an electron withdrawing group. When m is 2,
Two X ⁴⁰ and two Y ⁴⁰ may be the same or different from each other.

The electron-withdrawing group in the general formulas [C-III] and [C-IV] represents a substituent in which the value of Hammett's substituent constant σ is larger than 0.

General formula (Y) In the formula, R ₁₁ represents a halogen atom, an alkoxy group, a trifluoromethyl group or an aryl group, and R ₁₂ represents a hydrogen atom, a halogen atom or an alkoxy group. A is -NHC
OR ₁₃ , -NHSO ₂ -R ₁₃ , -SO ₂ NHR ₁₃ , -COOR ₁₃ , Represents Here, R ₁₃ and R ₁₄ each represent an alkyl group, an aryl group or an acyl group. Y ₁ represents a leaving group. R ₁₂
And the substituents of R ₁₃ and R ₁₄ include R and R of the general formulas (Ia to Ie)
Represents a substituent defined by R ′ and R ″, and the leaving group Y ₁ is preferably of a type capable of leaving with either an oxygen atom or a nitrogen atom, and a leaving type of nitrogen atom is particularly preferred.

Typical compounds as a cyan coupler and a yellow coupler are shown below.

These cyan couplers are described in U.S. Pat.
4,511,647, 2,772,162, 4,500,653, 4,5
No. 64,586, European Patent Application Publication EP0.249,453A2,
The compound can be synthesized by the methods described in 1-390441, 61-153640, 62-257158, and the like, and a method analogous thereto.

On the other hand, yellow couplers are described, for example, in JP-B-51-10783.
No. 51-33410, No. 52-25733, JP-A-47-26133
Nos. 48-73147, 51-102636, 50-130442
No. 50-6341, No. 50-123342, No. 51-21827,
No. 50-87650, No. 52-82424, No. 52-115219, British Patent No. 1425020, West German Patent No. 1547868, West German Application Publication 2219
No. 917, No. 2261361, No. 2414006, European Patent 272041
249473, JP-A-63-43144, and the like, and can be synthesized according to them.

The couplers represented by the above general formulas (C-I) to (Y) are usually added in the silver halide emulsion layer constituting the photosensitive layer in an amount of 0.1 to 1.0 mol, preferably 0.1 to 1.0 mol per mol of silver halide.
0.50.5 mol.

In the present invention, various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by an oil-in-water dispersion method known as an oil protection method, and after being dissolved in a solvent, it is emulsified and dispersed in an aqueous gelatin solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water dispersion with phase inversion. The alkali-soluble coupler can also be dispersed by a so-called fish dispersion method. After removing the low-boiling organic solvent from the coupler dispersion by a method such as distillation, noodle washing or ultrafiltration, it may be mixed with a photographic emulsion.

Dielectric constant (25 ° C) as a dispersion medium for such couplers
It is preferable to use a high-boiling organic solvent having a refractive index of 2 to 20 and a refractive index (25 ° C.) of 1.5 to 1.7 and / or a water-insoluble polymer compound. Particularly preferred are high boiling organic solvents having a dielectric constant of 6.5 or less.

As the high boiling point organic solvent, preferably, the following general formula (A)
The high-boiling organic solvent represented by (E) is used.

General formula (A) General formula (B) W ₁ -COO-W ₂ General formula (C) General formula (D) Formula (E) W ₁ -OW ₂ (wherein W ₁ , W ₂ and W ₃ each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group, and W ₄ the W _1, OW ₁ or SW
_And n is an integer of 1 to 5, and when n is 2 or more, W ₄ may be the same or different, and in the general formula (E), W ₁ and W ₂ are a condensed ring May be formed).

The high-boiling organic solvent that can be used in the present invention is a compound that is not miscible with water having a melting point of 100 ° C. or less and a boiling point of 140 ° C. or more other than the general formulas (A) to (E). Can be used. The high boiling point organic solvent preferably has a melting point of 80 ° C. or lower. The boiling point of the high boiling organic solvent is preferably 160 ° C.
And more preferably 170 ° C. or higher.

Details of these high-boiling organic solvents are described in
Compounds described in the lower right column on page 137 to the upper right column on page 144 of JP-A-215272 are particularly preferred.

These couplers may be impregnated with a loadable latex polymer (for example, U.S. Pat. No. 4,203,716) in the presence or absence of the high boiling organic solvent, or dissolved in a water-insoluble and organic solvent-soluble polymer. And emulsified and dispersed in a hydrophilic colloid aqueous solution.

Preferably, pages 12 to 30 of WO 88/00723
The homopolymers or copolymers described on the page are used, and the use of an acrylamide polymer is particularly preferred for stabilizing a color image.

The light-sensitive material prepared by using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, and the like as a color fogging inhibitor.

In the light-sensitive material of the present invention, the compounds represented by formulas (II) and (III) and various known anti-fading agents can be used in combination. That is, hydroquinones as organic anti-fading agents for cyan, magenta and / or yellow images,
6-hydroxychromans, 5-hydroxychromans, spirochromans, p-alkoxyphenols,
Representative examples are hindered phenols, mainly bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives in which the phenolic hydroxyl group of each of these compounds is silylated or alkylated. It is listed as. Further, a metal complex represented by a (bissalicylaldoximato) nickel complex and a (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Specific examples of the organic anti-fading agent are described in the specifications of the following patents.

Hydroquinones are disclosed in U.S. Pat.Nos. 2,360,290 and 2,4
No. 18,613, No. 2,700,453, No. 2,701,197, No. 2,
No. 728,659, No. 2,732,300, No. 2,735,765, No.
No. 3,982,944, No. 4,430,425, UK Patent No. 1,363,921
No., U.S. Pat.Nos. 2,710,801 and 2,816,028,
6-Hydroxychromans, 5-hydroxycoumarins, and spirochromans are described in U.S. Pat.
No. 3,573,050, No. 3,574,627, No. 3,698,909, No. 3,764,337, JP 52-152225, etc. UK Patent 2,0
No. 66,975, JP-A-59-10539, JP-B-57-19765, and the like, hindered phenols are disclosed in U.S. Pat.
No., JP-A-52-72224, U.S. Pat.
No. 52-6623, gallic acid derivatives, methylenedioxybenzenes and aminophenols are described in U.S. Pat.
No. 3,457,079, No. 4,332,886, JP-B-56-21144, etc., hindered amines are U.S. Pat.
No. 4,268,593, British Patent No. 1,326,889, No. 1,354,
No. 313, No. 1,410,846, JP-B-51-1420, JP-A-58
Nos. 1-114036, 59-53846 and 59-78344, metal complexes are disclosed in U.S. Pat.Nos. 4,050,938 and 4,241,155.
And British Patent No. 2,027,731 (A). These compounds can achieve the object by adding usually 5 to 100% by weight of the corresponding color coupler to the photosensitive layer after co-emulsification with the coupler. In order to prevent the deterioration of the cyan dye image due to heat and particularly to light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent thereto.

As the ultraviolet absorber, a compound represented by the general formula (UV) is preferable.

The photosensitive material prepared according to the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, gelatin is lime-treated,
Either one treated with an acid may be used. The details of the method for producing gelatin are described in The Macromolecule Chemistry of Gelatin (Academic Press, 1964), by Arthur Wuice.

As the support used in the present invention, a transparent film such as a cellulose nitrate film or a polyethylene terephthalate, which is usually used for a photographic material, or a reflective support can be used. For the purposes of the present invention, the use of a reflective support is more preferred.

The term "reflective support" used in the present invention refers to a material which enhances reflectivity and sharpens a dye image formed in a silver halide emulsion layer. Examples include those coated with a hydrophobic resin dispersedly containing a light reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin dispersedly containing a light reflecting substance as a support. For example, baryta paper, polyethylene-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer or combined with a reflective substance, such as a glass plate, polyethylene terephthalate, a polyester film such as cellulose triacetate or cellulose nitrate, Examples include a polyamide film, a polycarbonate film, a polystyrene film, and a vinyl chloride resin.

Other reflective supports include specular or secondary
A support having a seed diffuse reflective metal surface can be used. The metal surface has a spectral reflectance of 0.5 in the visible wavelength range.
The above materials are preferred, and the metal surface is preferably roughened or diffusely reflective using metal powder. As the metal, aluminum, tin, silver, magnesium or an alloy thereof is used, and the surface may be a metal plate, a metal foil, or a thin metal layer obtained by rolling, vapor deposition, plating, or the like. Above all, it is preferable to obtain a metal by vapor deposition on another substrate. It is preferable to provide a water-resistant resin, especially a thermoplastic resin layer, on the metal surface. An antistatic layer is preferably provided on the side of the support of the present invention opposite to the side having the metal surface. For details of such a support, see, for example, JP-A-61-21.
0346, 63-24247, 63-24251 and 63-24255
No. etc.

 These supports can be appropriately selected depending on the purpose of the specification.

As the light-reflective substance, it is preferable to sufficiently knead a white pigment in the presence of a surfactant.
It is preferable to use those treated with a to tetravalent alcohol.

The occupied area ratio (%) per defined unit area of the white pigment fine particles is most typically obtained by dividing the observed area into adjacent 6 μm × 6 μm unit areas and projecting the unit area. It can be obtained by measuring the occupied area ratio (%) (R _i ) of the fine particles. Variation coefficient of the occupied area ratio (%) is the ratio of the standard deviation s of R _i to the average value of R _i () s /
Can be obtained by The number (n) of the target unit areas is preferably 6 or more. Therefore the coefficient of variation s / Can be obtained by

In the present invention, the occupied area ratio of the pigment fine particles (%)
Is preferably 0.15 or less, particularly preferably 0.12 or less. 0.08
In the following cases, it can be said that the dispersibility of the particles is substantially “uniform”.

The color developer used in the development of the photosensitive material of the present invention is
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as the color developing agent.
Phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N-ethyl-N
-Β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-Β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof.
These compounds can be used in combination of two or more depending on the purpose.

The color developing solution includes a pH buffer such as an alkali metal carbonate or phosphate, a development inhibitor such as a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound or an antifoggant. It is common to include. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, N, N-
Hydrazines such as biscarboxymethylhydrazine,
Various preservatives such as phenylsemicarbazides, triethanolamine, catecholsulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, and dye formation Couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, various chelating agents represented by aminopolycarboxylic acids, aminopolyphosphonic acids, alkylsulfonic acids, and phosphonocarboxylic acids ,
For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N-trimethylenephosphonic acid, ethylenediamine N, N, N ', N'
-Tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as typical examples.

When the reversal processing is performed, color development is usually performed after black-and-white development and reversal processing are performed. In this black and white developer,
Known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone and aminophenols such as N-methyl-p-aminophenol can be used alone or in combination. .

The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the light-sensitive material. By reducing the bromide ion concentration in the replenishing solution, 500 ml
It can also be: When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The contact area between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below. That is, the aperture ratio = the contact area between the treatment liquid and the air (cm ² ) / the volume of the treatment liquid (cm ³ ). The above-mentioned aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05.

As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in Japanese Patent Application No. 62-241342, Examples of the method include a slit developing method described in JP-A-63-216050.

The reduction of the aperture ratio is preferably applied not only to both the color development and black-and-white development steps but also to the following various steps, for example, all the steps such as bleaching, bleach-fixing, fixing, washing and stabilization.

Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time for the color development processing is usually set between 2 and 5 minutes, but the processing time can be further reduced by using a high temperature, a high pH and using a high concentration of the color developing agent.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further processing in two successive bleach-fix baths,
Fixing before bleach-fixing or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, for example, a compound of a polyvalent metal such as iron (III) is used. A typical bleach is iron (II
Organic complex salts of I), for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol ether diaminetetraacetic acid, or citric acid and tartaric acid And complex salts such as malic acid. Of these, aminopolycarboxylate iron (III) complex salts such as ethylenediaminetetraacetate iron (III) complex salt are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually
4.0 to 8.0, but lower for faster processing
It can be treated at pH.

A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their prebaths, if necessary. Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent 1,290,812, JP-A-53-812.
No. 95630, Research Disclosure No. 17,129 (July, 1978), etc .; compounds having a mercapto group or disulfide bond; thiazolidine derivatives described in JP-A-50-140129; described in US Pat. No. 3,706,561 Thiourea derivatives; iodide salts described in JP-A-58-16235; polyoxyethylene compounds described in West German Patent No. 2,748,430; polyamine compounds described in JP-B-45-8836; Can be used. Among them, a compound having a mercapto group or a disulfide group is preferable in view of a large accelerating effect, and in particular, U.S. Patent No. 3,893,858,
Compounds described in West German Patent No. 1,290,812 and JP-A-53-95630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether-based compounds, thioureas, and a large amount of iodide.The use of thiosulfates is common,
In particular, ammonium thiosulfate can be used most widely. Preservatives for the bleach-fix solution include sulfites and bisulfites, p
-Sulfinic acids such as toluenesulfinic acid or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the aqueous process depends on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the use, the rinsing water temperature,
It can be set in a wide range depending on the number of washing tanks (number of stages), a replenishment method such as countercurrent flow, forward flow, and other various conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the Society of Motion Picture and T
It can be determined by the method described in elevision Engineers, Vol. 64, pp. 248-253 (May, 1955).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, the method of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively as a solution to such a problem. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., written by Hiroshi Horiguchi, "Bactericidal and antifungal chemistry" (19
1986) Sankyo Publishing, Sanitary Technology Society, “Sterilization and sterilization of microorganisms,
A fungicide described in "Encyclopedia of Fungicides" (1986), "Encyclopedia of Fungicides and Antifungal Agents" (1986) edited by the Industrial Technology Association and the Japan Society of Antifungals and Fungi can also be used.

In the processing of the light-sensitive material of the present invention, the pH of the washing water is from 4 to
9, preferably 5 to 8. Washing water temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the use, etc., but in general, 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of 30 seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization process, Japanese Unexamined Patent Application Publication No.
Known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can all be used.

Further, after the above-mentioned water washing treatment, a stabilization treatment may be further carried out. For example, a stabilizing bath containing formalin and a surfactant used as a final bath of a color light-sensitive material for photography can be mentioned. . Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.
In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline compounds described in U.S. Pat.No. 3,342,599, 3,342,599, Schiff base type compounds described in Research Disclosure 14,850 and 15,159, aldol compounds described in 13,924, U.S. Pat. Metal complex, JP 53
-135628 can be mentioned.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-1444547, and JP-A-58-144547.
No. 15438.

The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to. Further, in order to save silver of the light-sensitive material, a process using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

(Examples) Hereinafter, the present invention will be described specifically with reference to Examples.
The present invention is not limited to this.

Example 1 A multilayer color photographic paper having the following layer constitution was produced on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

Preparation of first layer coating solution 19.1 g of yellow coupler (ExY) and color image stabilizer (Cp
d-1) 27.2 cc of ethyl acetate in 4.4 g and (Cpd-7) 1.8 g
Then, 4.1 g of each of the solvents (Solv-3) and (Solv-6) were added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. On the other hand, a silver chlorobromide emulsion (silver bromide 80.0 mol%, cubic; one having an average grain size of 0.85 μm and a variation coefficient of 0.08;
A mixture of 80.0% silver bromide, cubic; one having an average grain size of 0.62 μm and a variation coefficient of 0.07, mixed at a ratio of 1: 3 (Ag molar ratio) with sulfur was sensitized with a blue-sensitive sensitizing dye shown below. To silver 1
A solution prepared by adding 5.0 × 10 ⁻⁴ mol per mol was prepared. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the following composition.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

 The following were used as spectral sensitizing dyes for each layer.

Blue-sensitive emulsion layer (5.0 × 10 ^-4 mol per mol of silver halide) Green-sensitive emulsion layer (4.0 × 10 ^-4 mol per mol of silver halide) and (7.0 × 10 ^-5 mol per mol of silver halide) Red-sensitive emulsion layer (0.9 × 10 ⁻⁴ mol per mol of silver halide) The following compounds were added to the red-sensitive emulsion layer at 2.6 × 10 ⁻³ mol per mol of silver halide.

Also, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mole of silver halide.
4.0 × 10 ^-6 mol, 3.0 × 10 ^-5 mol, 1.0 × 10 ^-5 mol or 2
- methyl -5-t-octyl hydroquinone 8 × 10 ^-3 mol per mol of silver halide, respectively, 2 × 10 ^-2 mol, was added 2 × 10 ^-2 mol.

Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1.2 × 10 ^-2 mol, 1.1 ×
10 ^-2 mol was added.

Further, to the red-sensitive emulsion layer, the following mercaptoimidazoles were added in an amount of 2 × 10 ^-4 mol per mol of silver halide and the following mercaptothiadiazoles were added in an amount of 4 × 10 ^-4 mol per mol of silver halide.

The following dyes were added to the emulsion layer to prevent irradiation.

and (Layer Configuration) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [The first layer of polyethylene contains white pigment (TiO ₂ ) and blue dye (ultramarine)] First layer (blue-sensitive layer) The above-mentioned silver chlorobromide emulsion (AgBr: 80 mol%) 0.26 gelatin 1.83 yellow coupler (ExY) 0.83 color image stabilizer (Cpd-1) 0.19 color image stabilizer (Cpd-7) 0.08 solvent (Solv-3) 0.18 solvent (Solv-6) 0.18 second layer (color mixing prevention) Layer) Gelatin 0.99 Color mixing inhibitor (Cpd-5) 0.08 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (green sensitive layer) Silver chlorobromide emulsion (AgBr 90 mol%, cube, average particle size)
0.47μm, coefficient of variation 0.12, AgBr90mol%, cube, average particle size 0.36μm, coefficient of variation 0.09
0.16 Gelatin 1.79 Magenta coupler (ExM) 0.32 Color image stabilizer (Cpd-4) 0.01 Color image stabilizer (Cpd-8) 0.03 Color image stabilizer (Cpd-9) 0.04 Solvent (Solv-2) 0.65 Fourth layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixture inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24 Fifth layer (red Layer) Silver chlorobromide emulsion (AgBr 70 mol%, cubic, average grain size
0.49 μm, variation coefficient 0.08 and AgBr 70 mol%, cubic, average particle size 0.34 μm, variation coefficient 0.10
0.23 gelatin 1.34 cyan coupler (ExC) 0.30 color image stabilizer (Cpd-6) 0.17 color image stabilizer (Cpd-7) 0.40 solvent (Solv-6) 0.20 Six layers (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol Merging (degree of denaturation
17%) 0.17 Liquid paraffin 0.03 The multilayer color photographic light-sensitive material thus produced was used as a sample A. As shown in Table 2, the magenta coupler in the third layer was changed or the compound represented by the general formula (II) or (III) of the present invention was used. Other samples were prepared in the same manner as Sample A except that the comparative compound was further added. In addition,
During the production of sample A ₄₈ to A _59, and multiplied using the amount of silver chlorobromide emulsion of the third layer.

A sensitometer (Fuji Photo Film Co., Ltd., FWH
Using a mold and a color temperature of a light source of 3200 ° K), a gradation exposure of a three-color separation filter for sensitometry was given. The exposure at this time was performed so that the exposure amount was 250 CMS with an exposure time of 0.1 second.

The sample after the exposure was processed using an automatic developing machine using a solution having the following processing step and processing solution composition. Processing temperature / time Color development 37 ° C 3 minutes 30 seconds Bleaching and fixing 33 ° C 1 minute 30 seconds Washing 24-34 ° C 3 minutes Drying 70-80 ° C 1 minute The composition of each processing solution is as follows.

Color developer Water 800 ml Diethylenetriamine 1.0 g Nitrilotriacetic acid 2.0 g Benzyl alcohol 15 ml Diethylene glycol 10 ml Sodium sulfite 2.0 g Potassium bromide 1.0 g Potassium carbonate 30 g N-ethyl-N- (β-methanesulfonamidoethyl)
-3-Methyl-4- aminoaniline sulfate 4.5g Hydroxylamine sulfate 3.0g Fluorescent brightener (WHITEX 4B, manufactured by Sumitomo Chemical) 1.0g Add water 1000ml pH (25 ° C) 10.25 Bleaching fixer Water 400ml Thio Ammonium sulfate (70%) 150 ml Sodium sulfite 18 g Iron (III) ethylenediaminetetraacetate 55 g Addition of 5 g of disodium ethylenediaminetetraacetate 5 g water 1000 ml pH (25 ° C) 6.70 The sample thus obtained was subjected to a xenon bleach tester (10 The residual dye rate after irradiation for 3 weeks at 10,000 lux was evaluated at initial densities of 1.5 and 0.5. Table 1 shows the results.

The compound represented by the general formula (II) alone is not sufficient for improving the light fastness, and the compound represented by the general formula (III) alone is largely light-fast at an initial concentration of 1.5 or less, but has an initial concentration of 0.5. It can be seen that the light fastness of the sample is extremely insufficient.

On the other hand, when the compound represented by the general formula (II) and the compound represented by the general formula (III) of the present invention are used in combination, the light fastness of not only the high concentration part but also the low concentration part is remarkably improved. . This degree of improvement is a very surprising effect which cannot be predicted from the degree of improvement alone or from the 5-pyrazolone magenta coupler.

Example 2 A multilayer color photographic paper having the following layer constitution was produced on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

Preparation of first layer coating solution 19.1 g of yellow coupler (ExY) and color image stabilizer (Cp
d-1) 27.2 cc of ethyl acetate and 8.2 g of a solvent (Solv-1) were added to 4.4 g of the color image stabilizer (Cpd-7) and 0.7 g of the color image stabilizer (Cpd-7) and dissolved, and the resulting solution was dissolved in 10% sodium dodecylbenzenesulfonate 8c.
It was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution containing c. On the other hand, a silver chlorobromide emulsion (cubic, 3: 7 mixture (average grain size) of 0.88 μm and 0.70 μm) (silver molar ratio) The coefficient of variation of the grain size distribution is 0.80 and 0.10, and each emulsion is silver bromide
The following blue-sensitive sensitizing dyes are added to the large-sized emulsion in an amount of 2.0 × 10 ⁻⁴ mol per mol of silver, and the small-sized emulsion is added to the small-sized emulsion. , Each of which was subjected to sulfur sensitization after addition of 2.5 × 10 ^-4 mol. The above-mentioned emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the following composition.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardener for each layer, 1-
Oxy-3,5-dichloro-s-triazine sodium salt was used.

 The following were used as spectral sensitizing dyes for each layer.

(Per mole of silver halide, 2.0 × 10 ^-4 mole for large-size emulsion and 2.5 × ^10-4 mole for small-size emulsion, respectively)
10 ^-4 mol) (Per mole of silver halide, for large emulsions
4.0 × 10 ^-4 mol, 5.6 × 10 ^-4 mol for small size emulsion) and (Per mole of silver halide, for large emulsions
7.0 × 10 ^-5 mol, and 1.0 × 10 ^-5 for small size emulsions
Mole) (Per mole of silver halide, for large emulsions
0.9 × 10 ^-4 mol, and 1.1 × 10 ^-4 for small size emulsions
The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Also, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mole of silver halide.
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added.

Also, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 × 10 ^-4 mol and 2 × 10 mol, respectively, per mol of silver halide. ×
10 ^-4 mol was added.

The following dyes were added to the emulsion layer to prevent irradiation.

and (Layer Configuration) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [The first layer of polyethylene contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (blue-sensitive layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35 Color image stabilizer (Cpd-7) 0.06 Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture inhibitor (Cpd-5) 0.08 Solvent ( Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (green sensitive layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of 0.55 μm average and 0.39 μm emulsion (Ag mole) The coefficient of variation of the grain size distribution is 0.10 and 0.08, and each emulsion has AgBr0.
0.12 gelatin 1.24 Magenta coupler (ExM) 0.20 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-4) 0.02 Solvent (Solv-2) 0.40 Gelatin 1.58 UV absorber (UV-1) 0.47 Color mixture inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture (Ag molar ratio) of 0.58 µm and 0.45 µm in average grain size, variation coefficient of grain size distribution is 0.09 and 0.11, AgBr for each emulsion
0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cpd-7) 0.40 Color image stabilizer ( Cpd-8) 0.04 Solvent (Solv-6) 0.15 Sixth layer (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (Protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree
17%) 0.17 Liquid paraffin 0.03 The thus prepared multilayer color photographic light-sensitive material was
In the same manner as in Example B except that the magenta coupler in the third layer was changed as shown in Table 2, or the compounds represented by formulas (II) and (III) of the present invention and a comparative compound were further added. To make other samples. It should be noted that the sample B ₂₆ ~B
₂₉ is a yellow coupler of the first layer at Y-9, and a cyan coupler of the fifth layer is C-2 / C-14 / C-18 (1/1/1/1 by weight).
Was subjected to substitution equimolar to ExY and ExC, respectively.

First, each sample was exposed according to the method described in Example 1. The exposed sample was subjected to continuous processing (running test) using a paper processor until the replenishment was twice the tank capacity for color development in the next processing step.

Step Temperature Time Replenisher ^* Tank capacity Color development 35 ° C. 45 seconds 161 ml 17l blix 30 to 35 ° C. 45 seconds 215 ml 17l Rinse 30 to 35 ° C. 20 seconds - 10l Rinse 30 to 35 ° C. 20 seconds - 10l Rinse 30 to 35 ° C. 20 sec 350 ml 10l drying 70 to 80 ° C. 60 seconds * replenishment rate is composition (3 and a tank countercurrent system. to rinse →) each processing solution per photosensitive material 1 m ² is as follows.

Bleach-fix solution (same as tank solution and replenisher) Water 400ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 17g Ammonium iron (III) ethylenediaminetetraacetate 55g Disodium ethylenediaminetetraacetate 5g Ammonium bromide 40g Add water 1000ml pH ( 6.0 rinsing solution (same as tank solution and replenisher) Ion-exchanged water (3 ppm or less for calcium and magnesium, respectively) Each of the samples thus obtained was subjected to light emission of a magenta color image in the same manner as in Example 1. A fading test was performed. Table 2 shows the results.

From Table 2, the compound represented by the general formula (III) is used in combination with other known compounds, the compounds represented by the general formula (II) and the compounds represented by the general formula (III) are obtained in combination. The effect of improving the light fastness is insufficient, and the compound represented by the general formula (II) and the compound represented by the general formula (III)
It can be seen that remarkable light fastness can be achieved only by combining the compounds represented by the following formulas. It was found that the level of lightfastness obtained at this time was almost comparable to the level of lightfastness of the yellow and fifth layers of the first and fifth layers performed simultaneously.

Example 3 A multi-layer color photographic paper having the following layer constitution was produced on a paper support which was laminated on both sides with polyethylene and the surface of which was subjected to a corona discharge treatment. The coating solution was prepared as follows.

Preparation of first layer coating solution 60.0 g of yellow coupler (ExY) and anti-fading agent (Cp
d-1) In 28.0 g, 150 cc of ethyl acetate and a solvent (Solv-
3) Add 1.0 cc and 3.0 cc of a solvent (Solv-4) to dissolve the solution, and add this solution containing sodium dodecylbenzenesulfonate to 10%.
% Gelatin aqueous solution, and dispersed with an ultrasonic homogenizer. The resulting dispersion was treated with 420 g of a silver chlorobromide emulsion (0.7 mol% of silver bromide) containing the following blue-sensitive sensitizing dye.
To prepare a coating solution for the first layer.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1,2-
Bis (vinylsulfonyl) ethane was used. The following were used as spectral sensitizing dyes for each layer.

Blue-sensitive emulsion layer; anhydro-5,5'-dichloro-3,3'-
Disulfoethyl thiacyanine hydroxide Green-sensitive emulsion layer; anhydro-9-ethyl-5,5'-diphenyl-3,3'-disulfoethyloxacarbocyanine hydroxide Red-sensitive emulsion layer; 3,3'-diethyl- 5-methoxy-9,11-
Neopentylthiadicarbocyanine iodide The followings were used as stabilizers for each emulsion layer.

Further, the following substances were used as the irradiation preventing dye.

[3-carboxy-5-hydroxy-4- (3- (3
-Carboxy-5-oxo-1- (2,5-bisulfonatophenyl) -2-pyrazolin-4-ylidene) -1-propenyl) -1-pyrazolyl] benzene-2,5-disulfonate-disodium salt N, N '-(4,8-dihydroxy-9,10-dioxo-3,7
-Disulfonatoanthracene-1,5-diyl) bis (aminomethanesulfonate) -tetrasodium salt [3-cyano-5-hydroxy-4- (3- (3-cyano-5-oxo-1- ( 4-sulfonatophenyl)
-2-pyrazolin-4-ylidene) -1-bentanyl)
-1-Pyrazolyl] benzene-4-sulfonate-sodium salt (Layer composition) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Paper support laminated on both sides with polyethylene and corona discharge treated on the surface First layer (blue-sensitive layer) Silver chlorobromide emulsion (AgBr 0.7 mol%, cubic, average particle size 0.9 μm) 0.29 Gelatin 1.80 Yellow coupler (ExY) 0.60 Anti-fading agent (Cpd-1) 0.28 Solvent (Solv-3) 0.01 Solvent (Solv-4) 0.03 Second layer (color mixture prevention layer) Gelatin 0.80 Color mixture inhibitor (Cpd-2) 0.055 Solvent ( Solv-1) 0.03 Solvent (Solv-2) 0.15 Third layer (green-sensitive layer) Silver chlorobromide emulsion described above (AgBr 0.7 mol%, cubic, average particle size 0.45 μm) 0.18 Gelatin 1.86 Magenta coupler (ExM) 0.27 Solvent (Solv-1) 0.2 Solvent (Solv-2) 0.03 Fourth layer (color mixture prevention layer) Gelatin 1.70 Color mixture prevention agent (Cpd-2) 0.065 UV absorber (UV-1) 0.45 UV absorber (UV-2) 0.23 Solvent (Solv-1) 0.05 Solvent (Solv-2) 0.05 Fifth layer (red sensitive layer) Silver chlorobromide emulsion described above (AgBr 4 mol%, cubic, average particle size 0.5 μm) 0.21 Gelatin 1.80 Cyan coupler (ExC-1) 0.26 Cyan coupler (ExC-2) 0.12 Anti-fading agent (Cpd-1) 0.20 Solvent ( Solv-1) 0.16 Solvent (Solv-2) 0.09 Color development accelerator (Cpd-5) 0.15 Sixth layer (UV absorbing layer) Gelatin 0.70 UV absorbing agent (UV-1) 0.26 UV absorbing agent (UV-2) 0.07 Solvent (Solv-1) 0.30 Solvent (Solv-2) 0.09 Seventh layer (protective layer) Gelatin 1.07 (ExY) yellow coupler α-bivalyl-α- (3-benzyl-1-hydantoinyl) -2-chloro-5- [ β- (dodecylsulfonyl) butylamide] acetanilide (ExM) magenta coupler 7-chloro-6-isopropyl-3- {3-[(2-
Butoxy-5-tert-octyl) benzenesulfonyl
Propyl-1H-pyrazolo [5,1- C ] -1,2,4-triazole (ExC-1) cyan coupler 2-pentafluorobenzamide-4-chloro-5
[2- (2,4-di-tert-amylphenoxy) -3-methylbutyramide phenol (ExC-2) cyan coupler 2,4-dichloro-3-methyl-6- [α- (2,4-di −
tert-Amylphenoxy) butyramide] phenol (Cpd-1) Anti-fading agent (Cpd-2) Color-mixing inhibitor 2,5-di-tert-octylhydroquinone (Cpd-5) Color-promoting agent p- (p-toluenesulfonamido) phenyl-dodecane (Solv-1) solvent di (2-ethylhexyl) Phthalate (Solv-2) solvent Dibutyl phthalate (Solv-3) solvent Di (i-nonyl) phthalate (Solv-4) solvent N, N-diethylcarbonamide-methoxy-2,4-di-
t-Amylbenzene (UV-1) UV absorber 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole (UV-2) UV absorber 2- (2-hydroxy-3,5) -Di-tert-butylphenyl) benzotriazole [5,1- C ] -1,2,4-triazole (ExC-1) cyan coupler 2-pentafluorobenzamide-4-chloro-5
[2- (2,4-di-tert-amylphenoxy) -3-methylbutyramidophenol (ExC-2) cyan coupler 2,4-dichloro-3-methyl-6- [α- (2,4-di −
tert-Amylphenoxy) butyramide] phenol (Cpd-1) Anti-fading agent (Cpd-2) Color mixing inhibitor 2,5-di-tert-octylhydroquinone The sample thus prepared was designated as C, and 50 mol% of (II-1) and 50 mol% of (III- 1), (III-
3), (III-15), (III-18), (III-32), (III
-34), (III-35) or (III-39) were prepared in the same manner as Sample C, except that they were added in combination.

These samples were exposed by the method described in Example 1, and the samples which were separately subjected to imagewise exposure to the above-mentioned photosensitive material were replenished with a paper processing machine in the following processing step to double the tank capacity of color development. A continuous process (running test) was performed until the color image was obtained.

Processing process temperature time replenisher ^* tank capacity Color development 35 ° C 45 seconds 161ml 17l Bleaching and fixing 30-36 ° C 45 seconds 215ml 17l Stable 30-37 ° C 20 seconds −10l Stable 30-37 ° C 20 seconds −10l Stable 30-37 ° C 20 seconds - 10l stable 30 to 37 ° C. 30 seconds 248 ml 10l drying 70 to 85 ° C. 60 seconds * replenishment rate per photosensitive material 1 m ² (. was a four-tank counter-current system to a stable →) the composition of each processing solution It is as follows.

Bleach-fix solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (70%) 100 ml The sample thus obtained was subjected to a photobleaching test of a magenta color image in the same manner as in Example 1. In the same manner as in Examples 1 and 2, the samples in which the compound represented by the general formula (II) and the compound represented by the general formula (III) of the present invention were used together showed almost no residual dye at the initial concentrations of 1.5 and 0.5. Equally, it has been found that the addition of these compounds significantly improves the light fastness.

The present invention is also preferably applied to various color photosensitive materials such as reversal color paper and reversal color film. The following is a specific example of the embodiment.

Example 4 A color photographic light-sensitive material (reversal color paper) described in Example 2 of JP-A-1-158431 was prepared. However, the sixth
Each of the layer (low-sensitivity green-sensitive layer) and the seventh layer (high-sensitivity green-sensitive layer) contains 0.10 g / m ^{2 of} another compound (III-18). Of Cpd-25 was added in an amount of 0.01 g / m ² .

The sample thus prepared was designated as D, and the sixth layer and the seventh layer each contained 50 mol% of the general formula (I) based on the magenta coupler.
Samples of combinations shown in Table 3 to which the compound represented by I) was added were prepared.

These samples were exposed using a continuous wedge for sensitometry, and then developed by the following developing process.

Processing step First development (black and white development) 38 ° C 75 seconds Rinse 38 ° C 90 seconds Reverse exposure 100 lux or more 60 seconds or more Color development 38 ° C 135 seconds Rinse 38 ° C 45 seconds Bleach-fix 38 ° C 120 seconds Rinse 38 ° C 135 seconds Drying Processing solution composition (First developer) Nitrilo-N, N, N-trimethylenephosphonic acid / pentasodium 0.6 g Diethylenetriaminepentaacetic acid / pentasodium 4.0 g Potassium sulfite 30.0 g Potassium thiocyanate 1.2 g Potassium carbonate 35.0 g Hydroquinone Monosulfonate potassium salt 25.0 g Diethylene glycol 15.0 ml 1-phenyl-4-hydroxymethyl-4-methyl-3
-Pyrazolidone 2.0 g Potassium bromide 0.5 g Potassium iodide 5.0 mg Add water 1 (pH 9.70) (Color developer) Benzyl alcohol 15.0 ml Diethylene glycol 12.0 ml 3,6-Dithia-1,8-octanediol 0.2 g Nitrilo -N, N, N-trimeletin phosphonic acid / pentasodium salt 0.5 g diethylenetriaminepentaacetic acid / pentasodium salt 2.0 g sodium sulfite 2.0 g potassium carbonate 25.0 g hydroxylamine sulfate 3.0 g N-ethyl-N- (β-methane Sulfonamidoethyl)
-3-Methyl-4-aminoaniline sulfate 5.0 g Potassium bromide 0.5 g Potassium iodide 1.0 mg Add water to add 1 (pH 10.40) (bleach-fix solution) 2-mercapto-1,3,4-triazole 1.0 g Ethylenediaminetetraacetic acid, disodium, dihydrate 5.0 g Ethylenediaminetetraacetic acid, Fe (III), ammonium monohydrate 80.0 g Sodium sulfite 15.0 g Sodium thiosulfate (700 g / l solution) 160.0 ml Glacial acetic acid 5.0 ml Add water 1 (pH 6.50) Each sample thus obtained was evaluated with a xenon tester (Xe) [illuminance: 20,000 Lux] for 10 days after exposure to magenta dyes at initial densities of 1.5 and 0.5.

 Table 3 shows the results.

As is clear from Table 3, the samples which are the combination of the present invention
D ₁ to D ₅ are high concentration, is excellent in light fastness improving effect at a low concentration both.

Example 5 A color light-sensitive material (reversed color film) was prepared according to Sample 101 of Example 1 of JP-A-2-854. However, the seventh
The compound (III-18) of the present invention is contained in a layer (first green-sensitive emulsion layer).
0.03 g / m ² , 0.08 g / m ² of the compound (III-18) of the present invention in the eighth layer (second green-sensitive emulsion layer), and 0.03 g / m ² in the ninth layer (third green-sensitive emulsion layer). 0.08 g / m of the compound (III-18) of the present invention
^2, further addition of each of these layers, the following instead of the magenta coupler magenta coupler ^{M-33 (0.10g / m 2} ), was further added Cpd-26 below (0.05g / m ^2).

In this way, the sample that was created and E _0.

Further, the compound of the general formula (II) of the present invention is represented by the seventh, eighth, and ninth compounds.
It was added as Table 4 respectively in the layer, creating the samples E ₁ to E _5.

After exposing these samples through a continuous wedge for sensitometry, they were developed by the developing process described in Example 1 of JP-A-2-854.

Each of the samples thus obtained was evaluated for the residual ratio of the magenta dye after exposure for 4 days with a xenon tester (Xe) [illuminance 200,000 Lux] at initial densities of 1.5 and 0.5.

 Table 4 shows the results.

As is clear from Table 4, the samples which are the combination of the present invention
E ₁ to E ₅ is a high density, and excellent light fastness improving effect at a low concentration both.

(Effect of the Invention) By using the compounds of formulas (I), (II) and (III) according to the present invention in combination, good color reproducibility is obtained, and all color development from a high color density portion to a low color density portion is achieved. A color photograph having excellent light fastness in the density range and less generation of stain can be obtained.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-64-2042 (JP, A) JP-A-59-125732 (JP, A) JP-A-62-239150 (JP, A) JP-A 59-125 222836 (JP, A) JP-B 62-30619 (JP, B2) JP-B-59-37497 (JP, B2)

Claims (1)

(57) [Claims] 1. A silver halide emulsion layer containing at least one coupler represented by the following general formula (I), wherein at least one compound represented by the general formula (II) and a compound represented by the general formula (III) A silver halide color photographic light-sensitive material comprising at least one kind. General formula (I) In the formula, R represents a hydrogen atom or a substituent, and Za, Zb, and Zc represent methine, substituted methine, or any of ＝ N— and —HN—. Y represents a hydrogen atom, a group capable of leaving in a coupling reaction with an oxidized form of a developing agent, or a substituent. However, when Y is a substituent, Za, Zb, or
Any of Zc is a substituted methine group substituted by a methine group or a group capable of leaving in a coupling reaction with an oxidized form of the developing agent. R, Y or Za, Zb or Zc may form a dimer or higher multimer. General formula (II) In the formula, X ₁ and X ₂ may be the same or different, and Represents -SO ₂ -or a single bond. However, X ₁ and X ₂ are not a single bond at the same time. R ₁ represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an alkenoxy group, an aryloxy group, a heterocyclic oxy group, an amino group or a substituted amino group. R ₂ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group or a sulfonyl group. R ₃ is an alkyl group, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group or Represents R ₄ represents a halogen atom, a heterocyclic group or a group defined for R ₃ . n represents an integer of 0 to 3. n is 2
In the case of ３3, a plurality of R ₄ may be the same or different. Here, R ₁ and R ₂ , R ₁ and R ₄ , R ₂ and R ₄ , R ₃ and R ₄ , among a plurality of R ₄ , groups at the ortho position are bonded to each other to form a 5- to 7-membered ring. It may be formed. General formula (III) In the formula, R ₁₁ and R ₁₂ represent an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. X is -O- or Represents R ₁₄ represents a hydrogen atom or a group defined for R ₁₁ . R ₁₃ represents an alkylthio group, an arylthio group, a group defined for R ₁₁ or —XR ₁₂ . m represents an integer of 0 to 4. When m is 2 or more, a plurality of R ₁₃ may be the same or different from each other. R ₁₁ and R ₁₂ , R ₁₁ and R ₁₄ , R ₁₁ and R ₁₃ , R ₁₂
And R _14, R ₁₂ and R _13, R ₁₃ and R _14,. 5 to be what R ₁₃ in the ortho position to each other among the plurality of R ₁₃ are bonded to each other
A 7-membered ring may be formed.