JPH09114062A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a sensitive material capable of processing under low replenishment and low discharge, excellent in sharpness, causing no unevenness in processing and less liable to the lowering of color density even in color development after storage in an unexposed state in an environment at high humidity by incorporating a specified compd. into a photographic constituent layer. SOLUTION: This sensitive material contains a reducing agent for coloring or its precursor and a coupler in one of the photographic constituent layers and contains at least one kind of compd. represented by formula I and/or at least one kind of compd. represented by formula II in one of the layers. In the formula I, each of R<1> and R<3> is an electron withdrawing group having a Hammett's substituent constant σp of >=0.3, each of R<2> and R<4> is alkyl or aryl, each of L<1> -L<5> is methine and M<1> is H or an atomic group or a metallic atom which turns into a monovalent cation. In the formula II, each of R1 -R4 is H or a substituent, the total atomic weight of one of (R1 +R3 ) and (R2 +R4 ) is <=160, (n) is 0-2 and M is H, an atomic group which turns into a monovalent cation or an alkali metal.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, which is particularly excellent in environmental protection and sharpness, has no unevenness in processing, and has an unexposed light-sensitive material in a high humidity environment. The present invention relates to a silver halide color photographic light-sensitive material and a color image forming method in which a reduction in color density is small even in a color development process after storage.

[0002]

2. Description of the Related Art In a conventional color developing process for a silver halide color photographic light-sensitive material, an exposed light-sensitive material is dipped in a basic aqueous solution (color-developing solution) in which a p-phenylenediamine derivative is dissolved. On the surface of the silver halide grain having a latent image in the light-sensitive material, the oxidized p-phenylenediamine derivative reacts with the coupler to form an image. However, the p-phenylenediamine derivative made into a basic aqueous solution is unstable and easily deteriorates with time, and more frequent replenishment is required to maintain stable development performance. As a result, there is a problem that a large amount of an aqueous solution that requires a complicated disposal process is generated, and there has been a strong demand for achieving low replenishment and low discharge of the color developing solution in photographic processing. As one of effective means for achieving low replenishment and low discharge of the color developing solution, there is a method of incorporating an aromatic primary amine or a precursor thereof as a color-forming reducing agent in a hydrophilic colloid layer. Possible aromatic primary amine developing agents or precursors thereof include, for example, US Pat.
Examples thereof include compounds described in No. 060418. Also,
The method of incorporating the sulfone hydrazide type compound described in European Patent Nos. 545491A1 and 565165A1 into the hydrophilic colloid layer is also an effective means.

On the other hand, under the present circumstances where the high image quality of an image using a photographic light-sensitive material is considered not only as a photographic print material but also as a hard copy material for an electronic image, the characteristics of the silver halide photographic light-sensitive material are more characteristic. In order to make the image stand out, research is being actively conducted to improve sharpness and color reproducibility and to achieve higher image quality. Various methods have heretofore been developed as means for improving the sharpness of a silver halide photographic light-sensitive material having a reflective support. As the method, 1) prevention of irradiation by using a water-soluble dye. 2) Prevent halation by using colloidal silver, mordant dye, solid fine particle dye, etc. 3) To increase the filling rate of the white pigment in the laminating resin on the paper support, or to newly coat the support with the white pigment as a gelatin dispersion to prevent the penetration of light into the support. The method 1) or 2) has a large residual color at the time of processing, and further has an adverse effect on the photosensitive layer during storage of the light-sensitive material. Among the methods of 3), the method of coating a white pigment as a gelatin dispersion on a support can improve the sharpness, but it is a new method due to the deterioration of the storage stability of the light-sensitive material and the increase of the total film thickness. However, it is not suitable for practical use due to various problems (deterioration of process fluctuation, delay in drying, increase in cost, etc.). Further, the sharpness can be improved by a method of increasing the white pigment in the polyolefin laminate on the support, but the increase in the content ratio of the white pigment in the polyolefin increases the cost, which is an obstacle to practical use. . Therefore, as a means for improving the sharpness, the water-soluble dye, which is most advantageous in terms of cost and has a small harmful effect, is generally used. As the water-soluble dye, there are 27th European Patent EP 0337490A2 specifications.
The dyes described on pages 76 to 76 are commonly used. Of these, oxonol dyes and cyanine dyes are most often used because they have less residual color after treatment.

However, in a light-sensitive material containing the color-forming reducing agent, if the amount of the water-soluble dye used is increased in order to improve the sharpness, processing unevenness occurs and the sharpness is satisfactory. It is the current situation that the amount of usage cannot be increased to the level. Further, when the amount of these oxonol dyes used is increased, there arises a problem that the color density is lowered in the color development processing after the unexposed light-sensitive material is stored in a high humidity environment. Assuming areas where color papers are commonly used,
This decrease in color density has been a serious problem to be solved in practical use. Moreover, it has been found that these problems become more serious when a rapid processing is carried out by incorporating an auxiliary developing agent in the light-sensitive material in addition to the color-forming reducing agent.

[0005]

Therefore, an object of the present invention is to provide an unexposed light-sensitive material which enables low replenishment and low discharge processing, is excellent in sharpness, has no processing unevenness, and has no processing unevenness. It is an object of the present invention to provide a silver halide color photographic light-sensitive material in which the reduction in color density is small even in the color development processing after storage in a high humidity environment.

[0006]

As a result of various studies conducted by the present inventor to solve the above problems of the conventional silver halide color photographic light-sensitive material, the occurrence of processing unevenness is known as a water-soluble dye. We have found that the inclusion of one type of oxonol compound in a silver halide photographic light-sensitive material significantly suppresses it. In the color development processing, there has been a problem that the color density is lowered. Therefore, as a result of further diligent study on this problem, as a result of using a specific compound among the oxonol compounds and further using a specific color-forming reducing agent in combination therewith, the above-mentioned decrease in color density is remarkable. It was found that they were suppressed, and the present invention was completed. The above objects of the present invention have been achieved by the following silver halide color photographic light-sensitive materials. That is, (1) in a silver halide color photographic light-sensitive material obtained by coating a support with a photographic constituent layer containing at least one photosensitive silver halide emulsion layer, a reducing agent for color formation in any of the photographic constituent layers. Or a precursor thereof, and a color-forming coupler which forms a dye by a coupling reaction with an oxidant of the color-forming reducing agent, and a compound represented by the following general formula (I) in any of the photographic constituent layers And / or at least one compound represented by the following general formula (II). General formula (I)

[0007]

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In the general formula (I), R ¹ and R ³ each represent an electron-withdrawing group having a Hammett substituent constant σ _p of 0.3 or more, and R ² and R ⁴ each represent an alkyl group or an aryl group. Represents a group, L ^{1 to} L ⁵ represent a methine group, and M ¹ represents a hydrogen atom or an atomic group or a metal atom which becomes a monovalent cation. Here, at least one of L ^{1 to} L ⁵
One has a substituent. General formula (II)

[0009]

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In the general formula (II), R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a substituent. However, the sum of the atomic weights of at least one of (R ₁ + R ₃ ) and (R ₂ + R ₄ ) is 160 or less. n is 0, 1,
2 is represented. M represents a hydrogen atom, an atomic group that becomes a monovalent cation, or an alkali metal. (2) The silver halide color photographic light-sensitive material according to item (1), wherein the color-forming reducing agent is a compound represented by the following general formula (III). General formula (III)

[0011]

[Chemical 6]

In the general formula (III), R ¹¹ is an aryl group or a heterocyclic group which may have a substituent, and R ¹² is an alkyl group, an alkenyl group, an alkynyl group or an aryl which may have a substituent. It is a group or a heterocyclic group. Χ is -SO
_2- , -CO-, -COCO-, -CO-O-, -CO
^{-N (R 13) -, -} COCO-O -, - COCO-N
(R ¹³ ) — or —SO ₂ —N (R ¹³ ) —. Here, R ¹³ is a hydrogen atom or a group described for R ¹² . (3) In the general formula (III), X is -CONH-,
The silver halide color photographic light-sensitive material according to the item (2).

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The compound represented by formula (I) of the present invention is described below. Examples of the electron-withdrawing group represented by R ¹ and R ³ having a Hammett's substituent constant σp of 0.3 or more (preferably 0.8 or less) include, for example, a carbamoyl group (0.36) and a methylcarbamoyl group (0 .3
6), carboxyl group (0.45), methoxycarbonyl group (0.45), ethoxycarbonyl group (0.4
5), methylsulfinyl group (0.49), methylsulfonyl group (0.72), sulfamoyl group (0.6
0), benzoyl group (0.43), acetyl group (0.5
0), trifluoromethyl group (0.54), diethylphosphono group (0.60), cyano group (0.66), nitro group (0.78) and the like. Where σp
, Chemical Reviews, 17: 125-136 (1
935). R ¹ and R ³ are preferably a carboxyl group, an alkoxycarbonyl group (eg methoxycarbonyl, ethoxycarbonyl), an acyl group (eg acetyl, henzoyl), a carbamoyl group (eg carbamoyl, methylcarbamoyl, morpholinocarbamoyl), and an alkoxycarbonyl group. Alternatively, a carbamoyl group is particularly preferable. Further, R ¹ and R ³ are preferably the same group.

At least one of R ² and R ⁴ is preferably an alkyl group having 1 to 8 carbon atoms substituted with at least one sulfo group, and specific examples thereof include a sulfomethyl group, a 2-sulfoethyl group, 3-sulfopropyl group, 4
Examples thereof include -sulfobutyl group and o-sulfobenzyl group, which may further have a substituent. Preferred substituents are a halogen atom (eg fluorine, chlorine, bromine), a hydroxyl group, a carbonyl group, a cyano group, an aryl group having 6 to 7 carbon atoms (eg phenyl, p-tolyl), an alkoxy group having 1 to 7 carbon atoms. (Eg methoxy,
(Ethoxy, butoxy), an acyl group having 2 to 7 carbon atoms (eg, acetyl, benzoyl), an alkoxycarbonyl group having 2 to 7 carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl), an amino group having 0 to 7 carbon atoms (eg, amino,
Dimethylamino, diethylamino) and the like.

Further, at least one of R ² and R ⁴ is preferably an aryl group having 6 to 10 carbon atoms which is substituted with at least one sulfo group, and specific examples thereof include an o-sulfophenyl group and m-. Examples thereof include a sulfophenyl group, a p-sulfophenyl group, a 2,5-disulfophenyl group, a 3,5-disulfophenyl group, and a 4,8-disulfo-2-naphthyl group, and further have a substituent. You may have.
A preferred substituent is a halogen atom (eg, fluorine,
Chlorine, bromine), hydroxyl group, carboxyl group, cyano group, alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl, butyl), alkoxy group having 1 to 4 carbon atoms (eg, methoxy, ethoxy, butoxy), carbon number An acyl group having 2 to 4 (eg acetyl), an alkoxycarbonyl group having 2 to 4 carbon atoms (eg methoxycarbonyl, ethoxycarbonyl), an amino group having 0 to 4 carbon atoms (eg amino, dimethylamino, diethylamino) and the like can be mentioned. . R ² ,
R ⁴ is more preferably a phenyl group substituted with at least one sulfo group, and more preferably it is substituted with two or more sulfo groups. Further, R ² and R ⁴ are preferably the same group.

At least one of the methine groups represented by L ¹ , L ² , L ³ , L ⁴ and L ⁵ has a substituent. L ¹
As the substituent of the methine group of L ⁵ to L ⁵ , an alkyl group having 1 to 8 carbon atoms which may have a substituent, an aryl group having 6 to 10 carbon atoms which may have a substituent, and a substituent. Optionally substituted C1-6 alkoxy group (methoxy, ethoxy, etc.), optionally substituted C1-6 alkylthio group (methylthio, etc.), optionally substituted carbon number 6-10 arylthio groups (phenylthio, etc.), optionally substituted C0-8 amino groups (amino, dimethylamino, etc.), optionally substituted heterocyclic groups (4-pyridyl) , 1-pyrrolidinyl), halogen (chlorine, bromine, etc.), hydroxyl group, carbonyl group,
Examples thereof include a sulfo group and a cyano group. Further, specific examples of the substituents on the above groups include those which may be present on the specific examples of the alkyl group or aryl group mentioned as the preferred substituents of L ^{1 to} L ^5. In addition to the specific substituents described below, a heterocyclic group (4-pyridyl and the like) can be mentioned. Preferred examples of the substituent of the methine group of L ^{1 to} L ⁵ include an alkyl group having 1 to 8 carbon atoms and an aryl group having 6 to 10 carbon atoms. Preferred alkyl groups having 1 to 8 carbon atoms are methyl, ethyl, propyl, isopropyl, butyl, t-butyl, hexyl, octyl and the like, which may further have a substituent. Preferred substituents are halogen atoms (eg fluorine, chlorine, bromine), hydroxyl groups, carboxyl groups,
Sulfo group, cyano group, aryl group having 6 to 7 carbon atoms (eg phenyl, p-tolyl), alkoxy group having 1 to 7 carbon atoms (eg methoxy, ethoxy, butoxy), 2 carbon atoms
To an acyl group having 7 to 7 (eg acetyl, benzoyl), an alkoxycarbonyl group having 2 to 7 carbon atoms (eg methoxycarbonyl, ethoxycarbonyl), an amino group having 0 to 7 carbon atoms (eg amino, dimethylamino, diethylamino) and the like. To be Preferable examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like, which may further have a substituent. Preferred substituents are a halogen atom (eg, fluorine, chlorine, bromine), a hydroxyl group, a carboxyl group, a sulfo group, a cyano group, an alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl, butyl), 1 to 1 carbon atoms.
4 alkoxy groups (eg methoxy, ethoxy, butoxy), C 2-4 acyl groups (eg acetyl), C 2-4 alkoxycarbonyl groups (eg methoxycarbonyl, ethoxycarbonyl), C 0-4 An amino group (for example, amino, dimethylamino, diethylamino) and the like can be mentioned.

M ¹ represents a hydrogen atom or an atomic group which becomes a monovalent cation (eg ammonium, triethylammonium, pyridinium) or a metal atom (eg lithium, sodium, potassium), preferably a hydrogen atom, sodium or potassium. is there. The compound represented by the general formula (I) of the present invention is preferably a compound represented by the general formula (IV).

[0018]

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R ⁵ and R ⁶ are electron withdrawing groups having a Hammett's substituent constant σp of 0.3 or more and 0.6 or less, and specific examples thereof are R ¹ and R ³ of the general formula (I). Examples include each group (excluding methylsulfonyl group, cyano group and nitro group), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group)
Alternatively, a carbamoyl group (eg, carbamoyl group, methylcarbamoyl group) is particularly preferable. Further, R ⁵ and R ⁶ are preferably the same group. R ⁷ and R ⁸ represent a hydrogen atom, a halogen atom, a hydroxyl group, a methyl group or a methoxy group, preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

A is an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, and preferable examples thereof include L ¹ , L ² , L ³ , L ⁴ of the general formula (I),
It includes the same as those described as substituents of L ^5. Preferred is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl, sulfoethyl, etc.). Particularly preferred is a methyl group. M ² ,
M ³ has the same meaning as M ¹ . p and q are 2 respectively
It represents an integer of 5 or less, preferably 2 or 3, and more preferably 2. Especially on SO ₃ M on phenyl group
^At least one substituent of the ² (M ³ ) group is preferably at the 2-position (ortho-position) with respect to the pyrazolone. The general formula (I) or the general formula (I
Specific examples of the pyrazolone-pentamethineoxonol compound of V) are shown below, but the present invention is not limited thereto.

[0021]

[Table 1]

[0022]

[Table 2]

[0023]

[Table 3]

[0024]

[Table 4]

[0025]

[Table 5]

The compound represented by the general formula (I) or (IV) can be synthesized by a method known to those skilled in the art. For example, a symmetrical oxonol compound (R ¹ = R ³ ,
In the case of R ² = R ⁴ ), the compound (A) and the compound (B) are mixed with a suitable solvent (for example, methanol, ethanol, N, N-dimethylformamide, N,
N-dimethylacetamide, dimethyl sulfoxide,
A salt is formed by reacting with water or a mixed solvent thereof in the presence of a base (eg, pyridine, γ-picoline, triethylamine, etc.), and further with potassium acetate, sodium acetate, potassium iodide, etc., if necessary. It can be synthesized by

[0027]

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In the reaction formula, R ¹ , R ² , M ¹ , L ¹ ,
L ² , L ³ , L ⁴ , and L ⁵ have the same meanings as those described for the general formula (I), and Y is an atom (eg, chlorine, bromine, iodine) or an atomic group (eg, Perk) which becomes a monovalent anion. Lorate, p-toluenesulfonate).

Further, the compound (A) and the compound (B) are in a one-to-one relationship.
After reacting (molar ratio), another asymmetrical oxonol compound (R ¹
It is also possible to synthesize ≠ R ³ and / or R ² ≠ R ⁴ ).

The compound represented by the general formula (I) of the present invention can be added to the photosensitive layer and / or the non-photosensitive layer by various known methods. That is, to add, the compound is directly dispersed in the photosensitive layer or the non-photosensitive layer, or a suitable solvent (for example, methyl alcohol, ethyl alcohol, propyl alcohol, methyl cellosolve, JP-A-48-9715 or US Pat. Patent No. 3,7
No. 56,830, a method in which it is dissolved in a halogenated alcohol, acetone, water, pyridine, etc., or a mixed solvent thereof) and the like and added in the form of a solution. This compound, when added to both the light-sensitive layer and the non-light-sensitive layer, diffuses almost uniformly throughout the photographic constituent layers during coating. The amount of this compound used is not particularly limited, but is 0.1 mg / m ² ~
It is preferably used in the range of 200 mg / m ^2, particularly preferably from ^{1mg / m 2 ~100mg / m 2} .

Next, the dye compound of the general formula (II) will be described in detail. In the general formula (II), (R ₁ + R ₃ )
The sum of the atomic weights of at least one of (R ₂ + R ₄ ) must be 160 or less, and both should be 160 or less.
The following is preferred. n is particularly preferably 1. The substituents R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom,
Alkyl group, -COOR ₅ ,, CONR ₆ R ₇ ,, CONHR ₈ ,, NR ₉ COR ₁₀ ,, NR
₁₁ R ₁₂ ,, CN, -OR ₁₃ ,, NR ₁₄ CONR ₁₅ R ₁₆ (R _{5 to} R ₁₆ represent a hydrogen atom or an optionally substituted alkyl group, and R ₆ and R ₇ or R ₁₁ and R ₁₂ or R ₁₅ and R ₁₆ may form a ring). Furthermore, it is more preferable that none of the substituents R ₁ , R ₂ , R ₃ and R ₄ has a dissociative group. A dissociative group is 25
It is a substituent that is substantially dissociated in water at 0 ° C, and more specifically, a dissociative group having a pKa of 12 or less. Specific examples of such a dissociative group include a sulfonic acid group, a carboxyl group and a phosphoric acid group. Further, R ₁ and R ₂ are more preferably a hydrogen atom or an alkyl group, and the alkyl group is preferably an alkyl group having a carbon number of 3 or less such as a methyl group, an ethyl group and a propyl group and having a substituent. You may. Such a substituent is preferably a substituent having an unshared electron pair such as a hydroxyl group, an ether group, an ester group, a carbamoyl group, a sulfonyl group, a sulfamoyl group, and a cyano group. A hydroxyl group and an ether group are particularly preferable.

Alkali metals represented by M are Li, Na,
K and Cs are preferred. When the substituents R ₃ and / or R ₄ are alkyl groups, preferred alkyl groups are lower alkyl groups such as methyl group, ethyl group, propyl group and butyl group, which may have a substituent. Of these, a methyl group and an ethyl group are particularly preferable. When the substituents R ₃ and / or R ₄ are represented by —COOR ₅ , the alkyl group of R ₅ is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, and has a substituent. Good. Of these, a methyl group and an ethyl group are particularly preferable.

The substituents R ₃ and / or R ₄ are -CONR ₆ R ₇
When represented by, R ₆ and R ₇ may be hydrogen atoms or alkyl groups, but at least one is preferably an alkyl group. The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group and propyl group, which may have a substituent. As the substituent, a hydroxyl group or an ether group is preferable. Further, R ₆ and R ₇ may be connected to each other to form a ring. In that case, the ring formed is preferably a 5- or 6-membered nitrogen-containing heterocycle, and particularly preferably a morpholine ring. When the substituent R ₃ and / or R ₄ is represented by —CONHR ₈ and R ₈ is an alkyl group, the alkyl group has the same meaning as R ₆ and R ₇ . Substituent R ₃ and / or R
_{When 4} is represented by -NR ₉ COR ₁₀ , R ₉ and R ₁₀ may be a hydrogen atom or an alkyl group. As the alkyl group, a lower alkyl group such as a methyl group, an ethyl group and a propyl group is preferable, and a methyl group is particularly preferable. Further, it may have a substituent. As the substituent, a hydroxyl group or an ether group is preferable.

The substituents R ₃ and / or R ₄ are —NR ₁₁ R ₁₂
Alternatively, when represented by —OR ₁₃ , R ₁₁ , R ₁₂ and R ₁₃ may be a hydrogen atom or an alkyl group. As the alkyl group, a methyl group, an ethyl group, a propyl group and the like are preferable, and the alkyl group may have a substituent. A hydroxyl group or an ether group is preferable as the substituent. Further, R ₁₁ and R ₁₂ may be connected to each other to form a ring. The above-mentioned ring is, for example, a 5- or 6-membered saturated or unsaturated ring. Substituent R ₃ and / or R ₄
Is represented by -NR ₁₄ CONR ₁₅ R ₁₆ , R ₁₄ , R ₁₅ and R ₁₆ may be a hydrogen atom or an alkyl group. As the alkyl group, a lower alkyl group such as a methyl group, an ethyl group and a propyl group is preferable, and a methyl group is particularly preferable. Further, it may have a substituent. As the substituent, a hydroxyl group or an ether group is preferable. R ₁₅ and R ₁₆ may combine with each other to form a ring as described above.

As the substituents R ₃ and R ₄ , among others, -CON
R ₆ R ₇ is particularly preferred. The dye in the present invention is preferably present in the coating film in a molecularly dispersed state such as a single molecule or a dimer. The molecular dispersion state is represented by the general formula (I)
It means that the compound represented by is almost uniformly diffused in the emulsion layer and other hydrophilic colloid layers and does not exist substantially in a solid state. Preferably, it is in a single molecule or dimer state. Next, specific examples of the compound represented by the general formula (II) used in the present invention will be shown, but the present invention is not limited to these specific examples.

[0036]

[Table 6]

[0037]

[Table 7]

[0038]

[Table 8]

[0039]

[Table 9]

[0040]

[Table 10]

[0041]

[Table 11]

[0042]

[Table 12]

[0043]

[Table 13]

[0044]

[Table 14]

[0045]

[Table 15]

[0046]

[Table 16]

[0047]

[Table 17]

[0048]

[Table 18]

[0049]

[Table 19]

These compounds can be synthesized according to the method described in JP-A-7-82251 and according to this method. The compound of the general formula (II) of the present invention can be molecularly dispersed in the photosensitive layer or the non-photosensitive layer in the same manner as the compound of the general formula (I). The compound of the general formula (II) of the present invention, when added to either the light-sensitive layer or the non-light-sensitive layer, diffuses almost uniformly throughout the photographic constituent layers during coating. The amount of the compound of the present invention used is not particularly limited, but is 0.1 mg / m ² to 200
Use in the range of mg / m ² is preferred, particularly preferred is 1 mg / m ^2.
It is in the range of m ^{2 to} 100 mg / m ² .

By adjusting the coating pH of the silver halide photographic light-sensitive material of the present invention to 6.5 or less, the object of the present invention can be achieved more effectively. Here, the coating pH is the pH of all photographic constituent layers obtained by coating the coating solution on a support, and the p of the coating solution is
H does not always match. The coating pH is JP-A-61.
-245135 can be measured by the following method. That is, (1) 0.05 cc of pure water is dropped on the surface of the photosensitive material on the side coated with the silver halide emulsion. Next, (2) After leaving for 3 minutes, the film pH measuring electrode (Gr.
S-165F) measures the film pH. The photosensitive material of the present invention preferably has a coating pH of 6.5 or less obtained by such a measuring method, more preferably 4.0 to 6.
0. If the pH exceeds 6.5, fog, which is considered to be due to changes in the dye or the silver halide emulsion itself, tends to occur during long-term storage. The coating pH can be adjusted with acids (eg sulfuric acid, citric acid) or alkalis (eg sodium hydroxide, potassium hydroxide).

The color-forming reducing agent used in the present invention is described in detail below. The color-forming reducing agent used in the present invention causes a rapid redox reaction with the exposed silver halide by an oxidation-reduction reaction directly or with an oxidation product of an auxiliary developing agent generated by a development reaction of an auxiliary developing agent described later. The compound is characterized by producing an oxidant and then forming a color image by a coupling reaction between the oxidant and a coexisting dye-forming coupler. Specific examples of the color-forming reducing agent include aromatic primary amines represented by phenylenediamines and their precursors (for example, US Pat. Nos. 3,342,597 and 3,719,492).
No. 1, British Patent No. 1,138,762) and hydrazine compounds (particularly preferred are compounds represented by the general formula (III)). The general formula (I
The structure of the color-forming reducing agent represented by II) will be described in detail. The aryl group or heterocycle represented by R ¹¹ may have a substituent. The aryl group of R ¹¹ is preferably one having 6 to 14 carbon atoms, for example,
Examples include phenyl and naphthyl. The heterocyclic group represented by R ¹¹ is preferably a saturated or unsaturated 5-membered ring containing at least one of nitrogen, oxygen, sulfur and selenium;
It is a membered or seven-membered ring. These may be condensed with a benzene ring or a hetero ring. Examples of the hetero ring of R ¹¹ include furanyl, thienyl, oxazolyl, thiazolyl, imidazolyl, triazolyl, pyrrolidinyl,
Benzoxazolyl, benzothiazolyl, pyridyl, pyridazyl, pyrimidinyl, pyrazinyl, triazinyl,
Examples include quinolinyl, isoquinolinyl, phthalazinyl, quinoxalinyl, quinazolinyl, prenyl, pteridinyl, azepinyl, benzooxepinyl and the like.

Examples of the above-mentioned substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group and an acyloxy group. Group, acylthio group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, amino group, alkylamino group, arylamino group, amide group, alkoxycarbonylamino group, aryl Oxycarbonylamino group, ureido group,
Sulfonamide group, sulfamoylamino group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, acylcarbamoyl group, carbamoylcarbamoyl group, sulfonylcarbamoyl group, sulfamoylcarbamoyl group, alkylsulfonyl group,
Arylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, alkoxysulfonyl group, aryloxysulfonyl group, sulfamoyl group, acylsulfamoyl group, carbamoylsulfamoyl group, halogen atom, nitro group, cyano group, carboxy group, sulfo group , Phosphono group, hydroxy group, mercapto group, imide group, azo group and the like. The alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group of R ¹² may have a substituent.

The alkyl group of R ¹² is preferably a linear, branched or cyclic group having 1 to 16 carbon atoms, such as methyl, ethyl, hexyl, dodecyl, 2-octyl, t-butyl, cyclopentyl, cyclooctyl and the like. Is mentioned. The alkenyl group for R ¹² is preferably a chain or cyclic group having 2 to 16 carbon atoms, and examples thereof include vinyl, 1-octenyl and cyclohexenyl.

The alkynyl group for R ¹² preferably has 2 to 16 carbon atoms, and examples thereof include 1-butynyl and phenylethynyl. As the aryl group and heterocyclic group for R ¹² , those described for R ¹¹ can be mentioned.
As the above-mentioned substituents, the substituents exemplified for R ¹¹ are applied. Preferably as X include -SO ₂ -, - CO-,
-COCO -, - CO-N is <, more _preferably, -SO 2 -, - is a CO-N <. Particularly preferred is -CO-NH-.

Specific compound examples of the general formula (III) are shown below.

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A part of the compound represented by the general formula (III) of the present invention is described in, for example, US Pat. Nos. 2,424,256, 4,481,268 and European Patent 0565165A.
No. 1, JP-A No. 61-259249, etc., and other compounds can be synthesized by the methods described therein.

These color-forming reducing agents are contained in the light-sensitive material in the same manner as in the dye-forming coupler described later.
The reducing agent for color formation may be contained in a layer adjacent to the photosensitive layer, but it is preferable to contain it in the photosensitive layer (silver halide emulsion layer) because the color forming efficiency is high. It is also preferable to use different kinds of color-forming reducing agents for adjusting the activity of each photosensitive layer. The content of these compounds is preferably 1 × 10 ⁻⁵ mol to 1.0 × 10 ³ per 1 m ^{2 in} each layer.
^-2 mol, more preferably 1 x 10 ^-4 mol to 1 x
It is 10 ^-3 mol. The content of the dye-forming coupler described below is preferably 0.05 to 10 times, and more preferably 0.2 to 10 times the molar amount of the color-forming reducing agent.
5 times the amount.

The auxiliary developing agent and its precursor used in the light-sensitive material of the present invention will be described below. The auxiliary developing agent used in the present invention is a compound capable of developing exposed silver halide grains and oxidizing the same to oxidize a color-forming reducing agent (hereinafter referred to as cross-oxidation). As the auxiliary developing agent used in the present invention, pyrazolidones, dihydroxybenzenes, reductones or aminophenols are preferably used, and pyrazolidones are particularly preferably used. It is preferable that the diffusivity in the hydrophilic colloid layer is low, and for example, the solubility in water (25
C.) is preferably 0.1% or less, more preferably 0.05% or less, and particularly preferably 0.01% or less. The precursor of the auxiliary developing agent used in the present invention is a compound which is stably present in the light-sensitive material, but rapidly releases the above-mentioned auxiliary developing agent once processed with a processing solution. It is also preferable that the diffusivity in the hydrophilic colloid layer is low. Solubility in water (25
C.) is preferably 0.1% or less, more preferably 0.
It is 05% or less, particularly preferably 0.01% or less. The solubility of the auxiliary developing agent released from the precursor is not particularly limited, but the auxiliary developing agent itself preferably has low solubility. The auxiliary developing agent precursor of the present invention is preferably represented by the general formula (A), and the auxiliary developing agent is preferably represented by the general formulas (B-1) and (B-2) described below. General formula (A) A- (L) _n -PUG A represents a blocking group in which the bond with (L) _n -PUG is cleaved during development, and L is L and A in general formula (A).
Represents a linking group in which the bond between L and PUG is cleaved after the bond with is cleaved, n represents an integer of 0 to 3, and PUG represents an auxiliary developing agent.

The group represented by the general formula (A) will be described below. As the block group represented by A, the following known ones can be applied. That is, JP-B-48-9968, JP-A-52-8828, and
No. 7-82834, U.S. Pat. No. 3,311,476,
And JP-B-47-44805 (U.S. Pat.
5,617) and other blocking groups such as acyl groups and sulfonyl groups; JP-B-55-17369 (US Pat. Nos. 3,888,677) and 55-9696 (US Pat. 791,830), ibid. 55-349.
No. 27 (U.S. Pat. No. 4,009,029);
6-77842 (U.S. Pat. No. 4,307,175)
No.), 59-105640, 59-105564
And blocking groups utilizing reverse Michael reaction described in JP-A No. 59-105642;
No. 9727, U.S. Pat. Nos. 3,674,478;
Nos. 932,480 and 3,993,661;
7-135944, 57-135945 (U.S. Pat. No. 4,420,554), 57-136640.
Nos. 61-196239 and 61-196240 (U.S. Pat. No. 4,702,999) and 61-185.
Nos. 743 and 61-124941 (U.S. Pat.
39, 408) and JP-A-2-280140, and the like, block groups utilizing the formation of quinone methide or a compound similar to quinone methide by intramolecular electron transfer;

US Pat. Nos. 4,358,525 and 4,358
No. 330,617, JP-A-55-53330 (U.S. Pat. No. 4,310,612), and JP-A-59-121328.
Nos. 59-218439 and 63-3185
55 (European Patent Publication No. 0,295,729) and other block groups utilizing an intramolecular nucleophilic substitution reaction; JP-A-57-76541 (US Pat. No. 4,33.
5,200), 57-135949 (U.S. Pat. Nos. 4,350,752), 57-179842, 59-137945, 59-140445 and 5).
9-219741, 59-202459, 60
-41034 (U.S. Pat. No. 4,618,563),
62-59945 (U.S. Pat. No. 4,888,268).
No. 62-65039 (US Pat. No. 4,772,
No. 537), No. 62-80647, and JP-A-3-236.
No. 047 and 3-238445, etc., a block group utilizing ring cleavage of a 5- or 6-membered ring; JP-A-59-201057 (US Pat. No. 4,518,6).
85) and 61-95346 (US Pat. No. 4,69).
0,885), 61-95347 (US Pat. No. 4,892,811), JP-A-64-7035 and JP-A-64-42650 (US Pat. No. 5,066,57).
No. 3), JP-A-1-245255 and JP-A-2-20724.
Nos. 9 and 2-35055 (U.S. Pat.
596) and 4-186344 and the like, a blocking group utilizing an addition reaction of a nucleophile to a conjugated unsaturated bond;

JP-A-59-93442 and 61-32.
Nos. 839 and 62-163051 and 5-3
7299 and the like utilizing a .beta.-elimination reaction; the blocking group utilizing the nucleophilic substitution reaction of diarylmethanes described in JP-A-61-188540; Block group utilizing the Rossen rearrangement reaction described in 187850;
Nos. 80646, 62-144163 and 62-
Block groups utilizing the reaction of N-acyl derivative of thiazolidine-2-thione with amines described in 147457; JP-A-2-296240 (US Pat.
No. 19,492), No. 4-177243, No. 4-17
No. 7244, No. 4-177245, No. 4-177724
No. 6, 4-177247, 4-177248,
4-177249, 4-179948, 4-
184337, 4-184338, WO92 / 21064, JP-A-4-330438, WO93 / 03419 and JP-A-5-4581.
No. 6, a block group having two electrophilic groups and reacting with a dinucleophile; mention is made of the block groups described in JP-A-3-236047 and JP-A-3-238445. You can

In the compound represented by the general formula (A), the group represented by L is a linking group capable of cleaving (L) _n-1 -PUG after leaving from the group represented by A during development processing. Anything will do as long as it is available. For example, U.S. Patent Nos. 4,146,396 and 4,652,51
No. 6,4,698,297, a group utilizing cleavage of a hemiacetyl tar ring, US Pat.
48,962, 4,847,185 or 4,857,440, a timing group for causing an intramolecular nucleophilic substitution reaction, US Pat. No. 4,409,3.
No. 23 or 4,421,845, a timing group for causing a cleavage reaction utilizing an electron transfer reaction, and the hydrolysis reaction of an imino ketal described in US Pat. No. 4,546,073. To cause a cleavage reaction, a group to cause a cleavage reaction by utilizing a hydrolysis reaction of an ester described in West German Published Patent No. 2,626,317, or European Patent 0,572,084. Examples thereof include groups that cause a cleavage reaction by utilizing the reaction with the sulfite ion described. Next, P in the general formula (A)
The UG will be described. The auxiliary developing agent means a substance having an action of promoting the transfer of electrons from the color-forming reducing agent to the silver halide in the development process of silver halide development, and the auxiliary developing agent in the present invention is preferably represented by the general formula ( B-1) or an electron-emitting compound represented by the general formula (B-2) according to the Kendall-Pertz rule. Among them, those represented by (B-1) are particularly preferred.

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In the general formulas (B-1) and (B-2),
R ^{51 to} R ⁵⁴ each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group.

R ^{55 to} R ⁵⁹ are each a hydrogen atom, a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, a cycloalkyloxy group, an aryloxy group or a hetero group. Ring oxy group, silyloxy group, acyloxy group, amino group, anilino group, heterocyclic amino group, alkylthio group, arylthio group, heterocyclic thio group, silyl group, hydroxyl group, nitro group, alkoxycarbonyloxy group, cycloalkyloxycarbonyl Oxy group, aryloxycarbonyloxy group, carbamoyloxy group, sulfamoyloxy group, alkanesulfonyloxy group, arenesulfonyloxy group, acyl group, alkoxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, Luvamoyl group, carbonamido group,
Ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, sulfamoylamino group, alkylsulfinyl group, arenesulfinyl group, alkanesulfonyl group,
Arenesulfonyl group, sulfamoyl group, sulfo group,
It represents a phosphinoyl group or a phosphinoylamino group.

Q represents an integer of 0 to 5, and when q is 2 or more, R ⁵⁵ may be different from each other. R ⁶⁰ represents an alkyl group or an aryl group. General formula (B-1),
A or L in the auxiliary developing agent represented by (B-2)
The bonding position with is the oxygen atom or nitrogen atom of the auxiliary developing agent. The compounds represented by formula (A), (B-1) or (B-2) are specifically shown, but the auxiliary developing agent and its precursor used in the present invention are limited to these specific examples. is not.

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These compounds may be added to any of the photosensitive layer, the intermediate layer, the undercoat layer and the protective layer, but when an auxiliary developing agent is contained, they are preferably added to the non-photosensitive layer for use. As a method of incorporating these compounds into the photosensitive material, in the coating liquid for the hydrophilic colloid layer, a method of dissolving in a water-miscible organic solvent such as methanol and directly adding this solution, in the presence of a surfactant, A method of adding as an aqueous solution or colloidal dispersion, a method of dissolving in a solvent or oil substantially immiscible with water and then adding a dispersion in water or a hydrophilic colloid, or adding in the state of solid fine particle dispersion Methods and the like can be adopted, and conventionally known methods can be applied alone or in combination. The amount added to the light-sensitive material is 1 mol% to 200 mol%, preferably 5 mol% to 100 mol%, and more preferably 10 mol% to the color-forming reducing agent.
50 mol%.

The dye-forming coupler used in the present invention is a compound which forms a dye by reaction with the oxidant of the above-mentioned color-forming reducing agent. This coupler may be a 4-equivalent coupler or a 2-equivalent coupler and is appropriately selected depending on the kind of the color-forming reducing agent used. For example, when a sulfonylhydrazine compound is used, the amino group that is the coupling site is protected by sulfonyl, and if there is a substituent at the coupling site on the coupler side during coupling, the reaction will be hindered by steric hindrance. Four equivalent couplers are preferred. When using a carbamoylhydrazine (semicarbazide) compound,
Particularly, the use of a 2-equivalent coupler is preferable because it improves the coupling activity. Specific examples of the coupler include the theory of the photography process (TH James, Theory of Th) in both 4 equivalent and 2 equivalent.
e Photographic Process Editing
Macmillan, 4th edition, 1977) 291-33.
Page 4, and pages 354 to 361, JP-A-58-123.
No. 53, No. 58-149046, No. 58-14904
No. 7, No. 59-11114, No. 59-124399.
Nos. 59-174835 and 59-231439
No. 59-231540, No. 60-2951, No. 60-14242, No. 60-23474, No. 60-
No. 66249 and the like. Examples of couplers preferably used in the present invention are listed below. The couplers preferably used in the present invention include compounds having the structures represented by the following general formulas (1) to (12). These are compounds generally called active methylene-based, pyrazolone-based, pyrazoloazole-based, phenol-based, naphthol-based, and pyrrolotriazole-based compounds, which are known compounds in the art.

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The general formulas (1) to (4) represent couplers called active methylene couplers, in which R ₁₄ is an optionally substituted acyl group, cyano group, nitro group or aryl. A group, a heterocyclic group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group or an arylsulfonyl group.

In the general formulas (1) to (3), R ₁₅ is an alkyl group which may have a substituent, an aryl group,
Alternatively, it is a heterocyclic group. In the general formula (4), R ₁₆
Are each an aryl group or a heterocyclic group which may have a substituent. Examples of the substituent that R ₁₄ , R ₁₅ and R ₁₆ may have include, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a cyano group, a halogen atom and an acylamino. Examples thereof include various substituents such as a group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylamino group, an arylamino group, a hydroxyl group, and a sulfo group.
Preferred examples of R ₁₄ include an acyl group, a cyano group, a carbamoyl group and an alkoxycarbonyl group.

In the general formulas (1) to (4), Y is a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized product of a developing agent. Examples of Y which can be released are a carboxy group, a formyl group, a halogen atom (for example, bromine and iodine), a carbamoyl group, and a methylene group having a substituent (the substituent is an aryl group, a sulfamoyl group, a carbamoyl group, an alkoxy group, Amino group, hydroxy group, etc.), acyl group, sulfo group and the like. In the general formulas (1) to (4), R ₁₄ and R ₁₅ , and R ₁₄ and R ₁₆ may combine with each other to form a ring.

The general formula (5) represents a coupler called a 5-pyrazolone type magenta coupler, wherein R ₁₇ is an optionally substituted alkyl group, aryl group,
It represents an acyl group or a carbamoyl group. R ₁₈ represents a phenyl group or a phenyl group substituted with one or more halogen atoms, an alkyl group, a cyano group, an alkoxy group, an alkoxycarbonyl group, or an acylamino group. Y has the same meaning as that of the general formulas (1) to (4). Among the 5-pyrazolone-based magenta couplers represented by the general formula (5), R ₁₇ is an aryl group or an acyl group, and R _{18 is}
Is preferably a phenyl group substituted with one or more halogen atoms.

Describing in detail about these preferable groups, R ₁₇ is phenyl, 2-chlorophenyl, 2-methoxyphenyl, 2-chloro-5-tetradecanamidophenyl, 2-chloro-5- (3-octadecenyl-1-succinimide. ) Phenyl, 2-chloro-5-octadecylsulfonamidophenyl or 2-chloro-5- [2
-(4-hydroxy-3-t-butylphenoxy) tetradecanamido] aryl group such as phenyl, acetyl, pivaloyl, tetradecanoyl, 2- (2,4-
Di-t-pentylphenoxy) acetyl, 2- (2,4
Acyl group such as -di-t-pentylphenoxy) butanoyl, benzoyl, 3- (2,4-di-t-amylphenoxyacetoazide) benzoyl, and these groups may further have a substituent; They are organic substituents or halogen atoms connected by carbon, oxygen, nitrogen or sulfur atoms.

R ₁₈ is 2,4,6-trichlorophenyl,
Substituted phenyl groups such as 2,5-dichlorophenyl and 2-chlorophenyl groups are preferred. The general formula (6) represents a coupler called a pyrazoloazole coupler, and in the formula,
R ₁₉ represents a hydrogen atom or a substituent. Z represents a group of non-metal atoms necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). For Y, the general formula (1) to
It is synonymous with that of (4). Among the pyrazoloazole couplers represented by the general formula (6), the imidazo [1,2-b] pyrazoles described in U.S. Pat. No. 4,500,630 and U.S. Pat. Fourth,
Pyrazolo [1,5-b] described in 540,654
[1,2,4] triazoles, US Pat. No. 3,72
Pyrazolo [5,1-c] [1, described in 5,067
2,4] triazoles are preferable, and in terms of light fastness,
Of these, pyrazolo [1,5-b] [1,2,4] triazoles are preferable.

For details of the substituents on the azole ring represented by the substituents R ₁₉ , Y and Z, see, for example, US Pat. No. 4,540,654, column 2, line 41 to column 8, line 27. It is described in. Pyrazoloazole couplers having a branched alkyl group directly bonded to the 2, 3 or 6-position of a pyrazolotriazole group, as described in JP-A-61-65245, JP-A-61-652.
No. 45, a pyrazoloazole coupler containing a sulfonamide group in the molecule, JP-A-61-1472.
Pyrazoloazole couplers having an alkoxyphenyl sulfonamide ballast group described in JP-A-54-54, JP
2-209457 or 63-307453, and pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position, and JP-A No. 2-294539.
It is a pyrazolotriazole coupler having a carbonamide group in the molecule described in JP-A-201443.

The general formulas (7) and (8) are couplers called phenol couplers and naphthol couplers, respectively, wherein R ₂₀ is a hydrogen atom or --SO ₂ NR _{22.
R 23, -NHSO 2 R 22,} -NHCOR 22, -NHCO
NR ₂₂ R _23, and represents a group selected from -NHSO ₂ NR ₂₂ R _23. R ₂₂ and R ₂₃ represent a hydrogen atom or a substituent. In the general formulas (7) and (8), R ₂₁ represents a substituent, 1 represents an integer selected from 0 to 2, and m represents an integer selected from 0 to 4. For Y, the general formula (1) to
It is synonymous with (4). Specific examples of R _{21 to} R ₂₃ include those mentioned as the substituents of R _{14 to} R ₁₆ . Preferable examples of the phenol-based coupler represented by the general formula (7) include U.S. Pat. Nos. 2,369,929, 2,801,171, 2,772,162, and 2,895. , 826, 3,772,002 and the like, 2-alkylamino-5-alkylphenol couplers, US Pat. Nos. 2,772,162, 3,758,308 and 4, 126,396, 4,334,011, 4,327,173,
West German Patent Publication No. 3,329,729, JP-A-59-1
2,6-diacylaminophenol couplers described in US Pat. No. 6,695,6, U.S. Pat. Nos. 3,446,622, 4,333,999, 4,451,559,
Examples thereof include 2-phenylureido-5-acylaminophenol-based couplers described in No. 4,427,767 and the like.

Preferred examples of the naphthol type coupler represented by the general formula (8) include US Pat. No. 2,474,474.
293, 4,052,212 and 4,14
No. 6,396, No. 4,228,233, No. 4,2
2-carbamoyl-1-naphthol type couplers described in US Pat. No. 4,690,889 and the like, and 2-carbamoyl-5-amido-1-naphthol type couplers described in US Pat.

The general formulas (9) to (12) are couplers called pyrrolotriazole couplers, and R ₃₂ ,
R ₃₃ and R ₃₄ represent a hydrogen atom or a substituent. Y has the same meaning as in formulas (1) to (4). R ₃₂ , R ₃₃ ,
_Examples of the substituent of R ₃₄ include those mentioned as the substituents of R _{14 to} R ₁₆ . Preferred examples of the pyrrolotriazole-based couplers represented by the general formulas (9) to (12) include European Patents 488, 248A1 and 49.
1,197A1 and 545,300, at least one of R ₃₂ and R ₃₃ is an electron-withdrawing group.

In addition, condensed ring phenol, imidazole,
A coupler having a structure such as pyrrole, 3-hydroxypyridine, active methylene, methine, 5,5-condensed heterocycle, or 5,6-condensed heterocycle can be used. Examples of the condensed ring phenol-based coupler include US Pat. No. 4,327,173.
No. 4,564,586 and 4,904,57
The couplers described in No. 5 and the like can be used. U.S. Pat. No. 4,818,672, as imidazole couplers,
The couplers described in JP-A-5,051,347 and the like can be used. Japanese Patent Application Laid-Open No. 4-1881 as a pyrrole coupler
The couplers described in No. 37, No. 4-190347, etc. can be used. As the 3-hydroxypyridine-based coupler, couplers described in JP-A-1-315736 and the like can be used.

Examples of active methylene-based or methine-based couplers are US Pat. Nos. 5,104,783 and 5,162.
The couplers described in No. 196 and the like can be used. Examples of 5,5-fused heterocyclic couplers include US Pat.
The pyrrolopyrazole couplers described in JP-A No. 289, the pyrroloimidazole couplers described in JP-A-4-174429 and the like can be used.

As the 5,6-fused heterocyclic coupler,
Pyrazolopyrimidine couplers described in U.S. Pat. No. 4,950,585, pyrrolotriazine couplers described in JP-A-4-204730, EP 556,70.
The couplers described in No. 0 can be used.

In the present invention, in addition to the couplers described above, West German Patent Nos. 3,819,051A and 3,823,049.
No. 4,840,883, US Pat.
No. 4,930, No. 5,051,347, No. 4,4
No. 81,268, European Patent Nos. 304,856A2, 329,036, 354,549A2, 374,781A2, 379,110A2, 386,930A1, 63-141055
Nos. 64-32260, 64-32261, JP-A-2-29747, JP-A-2-44340, and 2-
No. 110555, No. 3-7938, No. 3-16044
No. 0, No. 3-172839, No. 4-17247,
No. 4-179949, No. 4-182645, No. 4-
Nos. 184437, 4-188138, 4-188
No. 139, No. 4-194847, No. 4-204532
The couplers described in JP-A No. 4-204731, JP-A No. 4-204732, and the like can also be used.

Specific examples of the coupler which can be used in the present invention are shown below, but the present invention is not limited thereto.

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The color-forming reducing agent and coupler of the present invention can be introduced into a light-sensitive material by various known dispersion methods, dissolved in a high-boiling organic solvent (if necessary, a low-boiling organic solvent is also used), and emulsified in a gelatin aqueous solution. An oil-in-water dispersion method of dispersing and adding to a silver halide emulsion is preferred. The high boiling organic solvent used in the present invention has a melting point of 100 ° C. or lower and a boiling point of 140 ° C.
The above-mentioned water-immiscible compound can be used as long as it is a color-forming reducing agent and a good solvent for the coupler. The melting point of the high boiling organic solvent is preferably 80 ° C. or lower. The boiling point of the high boiling organic solvent is preferably 160 ° C. or higher, more preferably 170 ° C. or higher. Details of these high-boiling organic solvents are described in JP-A-62-215272, page 137, lower right column to page 144, upper right column.
In the present invention, the amount of the high-boiling organic solvent used may be any amount, but preferably with respect to the color-forming reducing agent,
The weight ratio of the high boiling point organic solvent / coloring reducing agent is preferably 20 or less, more preferably 0.02 to 5. In the present invention, a known polymer dispersion method may be used. The steps and effects of the latex dispersion method as one of the polymer dispersion methods, and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
No. 63, West German Patent Application No. (OLS) 2,541,274
No. 2,541,230, JP-B-53-4109
No. 1 and European Patent Publication No. 029,104, etc., and a dispersion method using an organic solvent-soluble polymer is described in PCT International Publication No. WO88 / 00723.

The average particle size of the lipophilic fine particles containing the reducing agent for color development of the present invention is not particularly limited, but it is preferably 0.05 μm to 0.3 μm from the viewpoint of color developability,
0.05 μm to 0.2 μm is more preferable.

Generally, in order to reduce the average particle size of the lipophilic fine particles, the type of surfactant is selected, the amount of surfactant used is increased, the viscosity of the hydrophilic colloid solution is increased, and the lipophilicity is increased. This can be achieved by lowering the viscosity of the organic layer by using a low-boiling point organic solvent in combination, or by increasing the shearing force such as increasing the rotation of the stirring blade of the emulsifying device or increasing the emulsification time. The particle size of the lipophilic fine particles can be measured, for example, by a device such as Nanosizer manufactured by Coulter Co. of England. The color light-sensitive material of the present invention is
Basically, it has a photosensitive silver halide, a dye-forming coupler, a color-forming reducing agent and a binder on a support. These components are often added to the same layer,
If it can react, it can be added by dividing into separate layers.

In order to obtain a wide range of colors on the chromaticity diagram by using the three primary colors of yellow, magenta and cyan, at least three silver halide emulsion layers having photosensitivity in different spectral regions are used in combination. . For example, there are three layers of a blue sensitive layer, a green sensitive layer, and a red sensitive layer, and a combination of a green sensitive layer, a red sensitive layer, and an infrared sensitive layer. Each photosensitive layer can adopt various arrangement orders known for ordinary color photosensitive materials. Each of these photosensitive layers may be divided into two or more layers as necessary. The photosensitive material may be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, an antihalation layer and a back layer. Further, various filter dyes can be added to improve color separation.

The color light-sensitive material used in the present invention has at least one yellow color-forming silver halide emulsion layer, magenta color-forming silver halide emulsion layer and cyan color-forming silver halide emulsion layer coated on a reflective support. It is preferable to install and configure. In general color photographic paper, color reproduction by the subtractive method can be performed by including a color coupler which forms a dye having a complementary color relationship with the light to which the silver halide emulsion is exposed. In general color photographic paper, silver halide emulsion grains are spectrally sensitized by blue-sensitive, green-sensitive, and red-sensitive spectral sensitizing dyes in the order of the above-described color-forming layers, respectively, and on a support in the order described above. It can be formed by coating.
However, the order may be different. In other words, from the viewpoint of rapid processing, it is preferable that the photosensitive layer containing the largest silver halide grains having the average grain size comes to the uppermost layer, or from the viewpoint of storage stability under light irradiation, the lowermost layer is the magenta color photosensitive layer. In some cases it may be preferable to do so. The photosensitive layer and the color hue may not have the above correspondence, and at least one infrared-sensitive silver halide emulsion layer may be used.

The support used in the present invention includes glass,
Any support can be used as long as it can be coated with a photographic emulsion layer such as paper and plastic film. The plastic film used in the present invention includes polyethylene terephthalate, polyethylene naphthalate, polyester films such as cellulose triacetate or cellulose nitrate, polyamide films, polycarbonate films,
A polystyrene film or the like can be used. The term "reflective support" used in the present invention refers to a support which enhances reflectivity to sharpen a dye image formed in a silver halide emulsion layer. Such a reflective support includes a support. One coated with a hydrophobic resin dispersedly containing a light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, calcium sulfate, etc., or one that uses the hydrophobic resin itself dispersedly containing a light-reflecting substance as a support Is included. For example, polyethylene-coated paper, polyester-coated paper, polypropylene-based synthetic paper, a support provided with a reflective layer, or together with a reflective material, such as a glass plate, polyethylene terephthalate, polyester film of cellulose triacetate or cellulose nitrate, polyamide film , Polycarbonate film, polystyrene film, vinyl chloride resin, etc. As the polyester-coated paper, the polyester-coated paper containing polyethylene terephthalate as a main component described in EP 0,507,489 is preferably used.

The reflective support used in the present invention is preferably a paper support whose both surfaces are coated with a water resistant resin layer, in which at least one of the water resistant resins contains white pigment fine particles. The white pigment particles are preferably contained at a density of 12% by weight or more, more preferably 14% by weight or more. As the light-reflective white pigment, it is preferable to sufficiently knead the white pigment in the presence of a surfactant, and it is preferable that the surface of the pigment particles is treated with a divalent to tetravalent alcohol. Further, it is preferable that the water resistant resin layer on the emulsion layer coating side comprises a plurality of layers, and that the resin layer on the side relatively far from the support substrate such as paper contains a large amount of white pigment. In the present invention, a support having a surface of diffuse reflection of the second kind is preferably used. The second-class diffuse reflectivity was obtained by giving unevenness to a surface having a mirror surface and dividing it into fine mirror surfaces facing different directions, and dispersing the directions of the divided fine surfaces (mirror surface). Refers to diffuse reflectivity. The unevenness of the surface of the second-class diffuse reflection has a three-dimensional average roughness of 0.1 to 2 μm, preferably 0.1 to 1.2 μm with respect to the center plane. For details of such a support, see JP-A-2-
239244.

In the silver halide photographic light-sensitive material of the present invention, the silver halide grains are 80 mol% to 100%.
Silver chloride, silver chlorobromide or silver chloroiodobromide grains in which silver chloride accounts for mol%, preferably 85 mol% or more, more preferably 95 mol% or more are used. In particular, in order to shorten the development processing time, the silver chloride content is substantially 9% without containing silver iodide.
It is preferably composed of 8 mol% or more of silver chlorobromide or silver chloride. Here, "contains substantially no silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. On the other hand, for the purpose of enhancing high illuminance sensitivity, spectral sensitization sensitivity, or improving stability over time of a light-sensitive material, 0.01% on an emulsion grain surface as described in JP-A-3-84545. In some cases, high silver chloride grains containing up to 3 mol% of silver iodide are preferably used.

The silver halide emulsion of the present invention preferably has a distribution or structure in terms of halogen composition in its grains. A typical example is JP-B-43-131.
No. 62, JP-A-61-215540 and JP-A-60-2
No. 22845, JP-A-60-143331, JP-A-6-143331
It is a core-shell type or double structure type grain having a halogen composition in which the inside and the surface layer of the grain are different as disclosed in, for example, 1-75337. In addition to a simple structure, a triple structure as disclosed in Japanese Patent Application Laid-Open No. 60-222844, or a multilayer structure of more than that, or a different composition on the surface of a core-shell double structure particle Or a thin silver halide having the following formula:

In order to give a structure to the inside of the particles, not only the wrapping structure as described above but also a so-called junction structure can be formed. Examples of these are JP-A-59
-133540, JP-A-58-108526, European Patent No. 199,290A2, JP-B-58-24772.
And JP-A-59-16254.
It is preferable that the crystal to be bonded has a halogen composition different from that of the crystal serving as the host and is bonded to the edge, corner, or surface of the host crystal. Such a junction crystal can be formed on the host crystal even if the host crystal has a uniform halogen composition or has a core-shell type structure. Among them, the bonding particles in which the silver bromide-rich phase is localized at the corners of the cubic silver chloride host particles are preferable. These particles have excellent photographic properties such as low fog and high sensitivity.

In the case of a joint structure, it is naturally possible to combine silver halides with each other, but a silver salt compound not having a rock salt structure such as silver rhodan or silver carbonate may be combined with silver halide to form a joint structure. Further, a non-silver salt compound such as lead oxide may be used as long as the bonding structure is possible. In the case of grains such as silver chlorobromide having these structures, it is a preferred embodiment that the core portion has a higher silver bromide content than the shell portion. On the contrary, in some cases, grains having a low silver bromide content in the core portion and a high shell portion are preferable. Similarly, for grains having a bonding structure, the silver bromide content of the host crystal is high, and even if the silver bromide content of the bonding crystal is relatively low,
Particles of the opposite may also be used. Further, the boundary portions having different halogen compositions of the grains having these structures may be clear boundaries or unclear boundaries. In addition, a configuration in which the composition is positively and continuously changed is also a preferable embodiment.

In the case of silver halide grains in which two or more silver halides exist as a mixed crystal or with a structure, it is important to control the halogen composition distribution between grains. The method for measuring the halogen composition distribution between grains is described in JP-A-60-254032. Uniform halogen distribution between grains is a desirable property. In particular, a highly uniform emulsion having a coefficient of variation of 20% or less is preferable.
Another preferred form is an emulsion where there is a correlation between grain size and halogen composition. It is important to control the halogen composition near the surface of the grains. Increasing the silver chloride content means
It can be selected according to the purpose because it changes the adsorbability of the dye and the developing speed. When changing the halogen composition in the vicinity of the surface, either a structure that wraps the entire grain or a structure that adheres only to a part of the grain can be selected. For example, the halogen composition may be changed only on one surface of the tetrahedral grain composed of the (100) plane and the (111) plane, or on one of the main plane and the side surface of the tabular grain.

The grain size distribution of the silver halide used in the present invention has a coefficient of variation (standard deviation of grain size distribution divided by average grain size) of 20% or less, preferably 15% or less, particularly preferably 10% or less. Some are so-called monodisperse particles. The lower limit is not particularly limited, but is usually 1% or more. In order to obtain the required gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes are coated in multiple layers in an emulsion layer having substantially the same color sensitivity, or the same layer is coated. It is also preferable to use by blending. The grain size of the silver halide emulsion is measured by a projection method using an electron microscope (diameter equivalent to the circle of the projected area). The photosensitive silver halide emulsion used in the present invention preferably has an average grain size (number average of circle equivalent diameters) of 0.05 μm to 1.0 μm. The coating amount of the silver halide emulsion used in the present invention is preferably 600 mg / m ² or less as the total coating amount of silver of all coating layers, and more preferably 30 mg / m ² or less 1 mg in view of omitting desilvering treatment. /
m ² or more.

The shape of silver halide grains is preferably cubic or tabular grains. In particular tabular grains are described in detail in U.S. Pat. No. 4,434,226,
It is also preferable in view of advantages such as improvement in covering power and improvement in color sensitization rate by the sensitizing dye. Tabular grains are described in "Theory and Practice of Photography " by Cleeve (Cleve, Photography).
Theory and Practice (193
0)), p. 131; Gatov, "Photographic Science and Engineering" (Gutof).
f, Photographic Science an
d Engineering ), Volume 14, 248-2
57 (1970); U.S. Pat. No. 4,434,226.
Nos. 4,414,310 and 4,433,048
No. 4,439,520, British Patent No. 2,112,
157 and JP-A-6-301128. That is, the use of tabular grain emulsions is demanded when the main planes (surfaces which are parallel to each other and have the largest area among the planes constituting tabular grains) facing each other are either {111} or {100} crystal faces. Be satisfied. However, tabular grains having a {100} crystal plane as the principal plane are more preferable because of the advantage of having intrinsic grain shape stability. In particular, when the halogen composition is set to a silver chloride content of 85 mol% or more, {100} tabular grains can be easily obtained stably. In the emulsion used in the present invention, tabular grains preferably account for more than 30% of the total grain projected area. The tabular emulsion grains have an average aspect ratio (average value of the diameter of the circle equivalent to the projected area of the main plane of each tabular grain divided by the thickness of the grain) of 2 or more, preferably 5 or more. The upper limit is not particularly limited, but is preferably 30 or less. Further, the particle thickness is preferably less than 0.3 μm, more preferably less than 0.1 μm. The lower limit is not particularly limited, but preferably 0.01
μm or more. Further, an emulsion having a high uniformity of thickness with a variation coefficient of grain thickness of 30% or less is also preferable.

In the case of tabular grains, dislocation lines can be observed with a transmission electron microscope. It is preferable to select a particle containing no dislocation line, a particle containing several dislocations, or a particle containing many dislocations according to the purpose. It is also possible to select a dislocation or a dislocation that is introduced linearly with respect to a specific direction of the crystal orientation of the grain, or to introduce the entire grain, or to introduce only a specific portion of the grain, for example. Dislocations can be introduced only in the fringe portion of the particles. The introduction of dislocation lines is preferable not only in the case of tabular grains but also in the case of regular grains or amorphous grains typified by potato grains. Also in this case, limiting to specific portions such as the vertices and edges of the particles is a preferable form for improving photographic properties.

The silver halide emulsion used in the present invention is a treatment for rounding grains as disclosed in European Patent Nos. 96,727B1 and 64412B1, or West German Patent No. 2,306,447C2. , JP Sho 60
The surface may be modified as disclosed in JP-A-221320. Although a structure having a flat particle surface is generally used, it is sometimes preferable to form irregularities intentionally. JP-A-58-106532, JP-A-60-221
For example, a method of making a hole in a part of a crystal described in No. 320, for example, a vertex or a center of a plane, or a raffle particle described in US Pat. No. 4,643,966.

During preparation of the emulsion of the present invention, for example, during grain formation,
In the desalting step, at the time of chemical sensitization, the presence of a metal ion salt before coating is preferable depending on the purpose. In the case of doping the grains, it is preferable to add them at the time of grain formation, when modifying the grain surface or when using as a chemical sensitizer, after grain formation and before the end of chemical sensitization. A method of doping the entire grain, a method of doping only the core portion of the grain, only the shell portion, only the epitaxial portion, or only the base grain can be selected. Ag, Ca, Sr, Ba, Al, Sc,
Y, LaCr, Mn, Fe, Co, Ni, Cu, Zn,
Ga, Ru, Rh, Pd, Re, Os, Ir, Pt, A
u, Cd, Hg, Tl, In, Sn, Pb, Bi and the like can be used. These metals are ammonium salts,
It can be added in the form of a salt that can be dissolved at the time of grain formation, such as an acetate, a nitrate, a sulfate, a phosphate, a hydroxide or a hexacoordinated complex salt and a tetracoordinated complex salt. For example, CdBr ₂ ,
CdCl ₂ , Cd (NO ₃ ) ₂ , Pb (NO ₃ ) ₂ , P
b (CH ₃ COO) ₂ , K ₃ [Fe (CN) ₆ ], (N
H ₄ ) ₄ [Fe (CN) ₆ ], K ₃ IrCl ₆ , (NH
₄ ) ₃ RhCl ₆ , K ₄ Ru (CN) _{6 and the} like. The ligand of the coordination compound can be selected from halogen, H ₂ O, cyano group, cyanate group, thiocyanate group, nitrosyl group, thionitrosyl group, oxo group and carbonyl group. These metal compounds may be used alone or in combination of two or more. The method of adding a chalcogen compound as described in U.S. Pat. No. 3,772,031 during emulsion preparation may be useful. In addition to S, Se, and Te, cyanide, thiocyanate, selenocyanic acid, carbonate, phosphate, and acetate may be present.

The silver halide grain of the present invention has at least one of sulfur sensitization, selenium sensitization, tellurium sensitization (these three types are collectively referred to as chalcogen sensitization), noble metal sensitization, or reduction sensitization. It can be applied at any step of the manufacturing process of the silver halide emulsion. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which chemically sensitized nuclei are embedded inside a grain, a type in which a chemical sensitized nucleus is embedded at a shallow position from the grain surface, and a type in which a chemically sensitized nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemically sensitized nucleus can be selected according to the purpose, but it is generally preferable that at least one type of chemically sensitized nucleus is formed near the surface.

The chemical sensitization which can be preferably carried out in the present invention is a chalcogen sensitization and a noble metal sensitization, alone or in combination thereof, and described by TH James, The Photographic Process, 4th Edition. , Published by Macmillan,
1977 (TH James, The Theor
y of the Photographic Pro
cess, 4th ed, Macmillan, 197
7) It can be carried out using active gelatin as described on pages 67-76, and Research Disclosure Item 12008 (April 1974); Item 13452 (June 1975);
307105 (November 1989); U.S. Pat.
642, 361, 3,297,446, 3,7
72,031, 3,857,711, 3,90
Nos. 1,714, 4,266,018, and 3,
No. 904,415 and British Patent 1,315,75.
As described in No. 5, sulfur, selenium, tellurium at pAg 5-10, pH 5-8 and temperature 30-80 ° C.
It can be performed with gold, platinum, palladium, iridium or a plurality of combinations of sensitizers containing these.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. . That is, thiazoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole,
1- (5-methylureidophenyl) -5-mercaptotetrazole, 1- (5-acetylaminophenyl)-
5-mercaptotetrazole) and the like; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes such as triazaindenes and tetraazaindenes (especially 4-hydroxy-6-methyl (1 , 3, 3a, 7)
Many compounds known as antifoggants or stabilizers, such as tetraazaindenes, pentaazaindenes and the like can be added. For example, US Pat.
No. 954,474, No. 3,982,947, Japanese Patent Publication No. 5
What was described in 2-28660 can be used. One of the preferable compounds is JP-A-63-212932.
There are compounds described in No. The antifogging agent and the stabilizer are used before the particle formation, during the particle formation, after the particle formation, in the water washing step,
It can be added according to the purpose during dispersion after washing with water, before chemical sensitization, during chemical sensitization, after chemical sensitization, and at various times before coating. In addition to exhibiting the original antifogging and stabilizing effects by adding during emulsion preparation, control the crystal habit of the grains, reduce the grain size, reduce the solubility of the grains, control the chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

The photographic emulsion used in the present invention is preferably spectrally sensitized with a methine dye or the like in order to exert the effects of the present invention. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc .; A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of
That is, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxadol nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, and a thiazolidine-2,4-
A 5- to 6-membered heterocyclic nucleus such as a dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied. In particular, as the red-sensitive spectral sensitizing dye for silver halide emulsion grains having a high silver chloride content, spectral sensitizing dyes described in JP-A-3-123340 are useful in terms of stability, adsorption strength, and exposure temperature. It is very preferable from the viewpoint of dependence and the like. In the case of efficiently spectrally sensitizing the infrared region in the light-sensitive material of the present invention, it is disclosed in
15049, page 12, upper left column to page 21, lower left column, or JP-A-3-20730, page 4, lower left column to page 15, lower left column, EP 0,420,011, page 4, line 21 to page 6, line 54,
EP 0,420,012, page 4, line 12 to page 10, 3
The sensitizing dyes described in Line 3, European Patent No. 0,443,466 and US Pat. No. 4,975,362 are preferably used.

The timing at which the sensitizing dye is added to the emulsion may be at any stage in the emulsion preparation which has heretofore been known to be useful. Most commonly, it is carried out after the completion of chemical sensitization and before coating, but it is described in US Pat. No. 3,62.
As described in JP-A-8-969 and JP-A-4,225,666, spectral sensitization can be carried out simultaneously with chemical sensitization by simultaneous addition with a chemical sensitizer.
It can be carried out prior to chemical sensitization as described in US Pat. No. 928, or it can be added before the completion of silver halide grain precipitation to initiate spectral sensitization. Furthermore, the addition of these said compounds separately as taught in U.S. Pat. No. 4,225,666, i.e. adding some of these compounds prior to chemical sensitization,
The balance can be added after chemical sensitization and can be at any time during silver halide grain formation including the method disclosed in US Pat. No. 4,183,756.

In the present invention, a colored layer which can be decolorized by treatment is used in combination with a water-soluble dye. The coloring layer that can be decolorized by the treatment used may be in direct contact with the emulsion layer,
They may be arranged so as to be in contact with each other via an intermediate layer containing a processing color mixture inhibitor such as gelatin or hydroquinone. This colored layer is preferably provided below the emulsion layer (on the side of the support) that develops the same primary color as the colored color. It is also possible to install all the colored layers corresponding to each primary color individually.
It is also possible to arbitrarily select and install only a part of them. It is also possible to provide a colored layer which is colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is the wavelength with the highest optical density in the wavelength range used for exposure (visible light range of 400 nm to 700 nm in normal printer exposure, wavelength of scanning exposure light source used in scanning exposure). The optical density value in is preferably 0.2 or more and 3.0 or less. More preferably, it is 0.5 or more and 2.5 or less, particularly preferably 0.8 or more and 2.0 or less.

In order to form the colored layer, conventionally known methods can be used in combination. For example, JP-A-2-2822
A hydrophilic colloid layer in the form of a solid fine particle dispersion such as the dyes described in No. 44, page 3, upper right column to page 8 and the dyes described in JP-A-3-7931, page 3, upper right column to page 11, lower left column. , A method of mordanting an anionic dye with a cationic polymer, a method of adsorbing the dye to fine particles such as silver halide and fixing it in the layer, JP-A-1-23954.
No. 4, using colloidal silver, and the like. As a method for dispersing a fine powder of a pigment in a solid state, for example, a method of containing a fine powder dye that is substantially water-insoluble at a pH of 6 or less but is substantially water-soluble at a pH of 8 or more is disclosed. 2-3
08244, pp. 4-13. Also,
For example, as a method of mordanting an anionic dye onto a cationic polymer, there are disclosed Nos. 18 to 26 of JP-A-2-84637.
Page. A method for preparing colloidal silver as a light absorber is shown in US Pat. Nos. 2,688,601 and 3,459,563. Among these methods, a method of incorporating a fine powder dye, a method of using colloidal silver, and the like are preferable.

As the binder or protective colloid that can be used in the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. Preferred gelatin has a calcium content of 800 p.
It is preferable to use low calcium gelatin of pm or less, more preferably 200 ppm or less. In order to prevent various fungi and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image, it is preferable to add a fungicide as described in JP-A-63-271247. When exposing the light-sensitive material of the present invention to a printer, US Pat. No. 4,880,7
It is preferable to use the band stop filter described in No. 26. As a result, light color mixing is removed, and color reproducibility is significantly improved.

Although the above-mentioned various additives are used in the light-sensitive material relating to the present technology, various additives other than the above can be used according to the purpose. These additives are described in more detail in Research Disclosure Item 1
7643 (December 1978), Item 1871
6 (November 1979) and Item 30710.
5 (November 1989), and the corresponding parts are summarized in the table below.

[0147]

[Table 20]

The light-sensitive material of the present invention is used not only in a printing system using an ordinary negative printer but also in a solid state laser using a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a semiconductor laser as an excitation light source, and a nonlinear laser. It is preferably used for digital scanning exposure using monochromatic high-density light such as a second harmonic generation light source (SHG) combined with an optical crystal. Compact system,
In order to make it inexpensive, it is preferable to use a semiconductor laser, or a second harmonic generation light source (SHG) that is a combination of a semiconductor laser or a solid-state laser and a nonlinear optical crystal. In particular, in order to design an apparatus that is compact, inexpensive, has a long life, and has high stability, it is preferable to use a semiconductor laser, and it is desirable to use a semiconductor laser as at least one of the exposure light sources.

When using such a scanning exposure light source,
The spectral sensitivity maximum of the light-sensitive material of the present invention can be arbitrarily set depending on the wavelength of the scanning exposure light source used. Solid-state laser using a semiconductor laser as an excitation light source or SHG obtained by combining a semiconductor laser with a nonlinear optical crystal
In the light source, the oscillation wavelength of the laser can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be provided in the usual three regions of blue, green and red. In order to use a semiconductor laser as a light source in order to make the device inexpensive, highly stable, and compact, at least two layers preferably have a spectral sensitivity maximum at 670 nm or more. This is because currently available inexpensive and stable III-V semiconductor lasers have emission wavelengths only in the red to infrared regions. However, at the laboratory level, oscillations of II-VI group semiconductor lasers in the green and blue regions have been confirmed, and if semiconductor laser manufacturing technology develops, these semiconductor lasers can be used stably at low cost. It is fully anticipated. In such a case, at least two layers have a thickness of 670 nm.
As described above, the necessity of having the maximum spectral sensitivity is reduced.

In such scanning exposure, the time during which the silver halide in the photosensitive material is exposed is the time required to expose a certain minute area. As the minute area, a minimum unit for controlling the amount of light from each digital data is generally used and is called a pixel. Therefore, the exposure time per pixel changes depending on the size of the pixel. The size of this pixel depends on the pixel density, and is a practical range of 50 to 2000 dpi. When the exposure time is defined as the time for exposing the pixel size when the pixel density is 400 dpi, the preferable exposure time is 10 ^-4 seconds or less, more preferably 10 ^-6 seconds or less. The processing material and processing method used in the present invention will be described. In the present invention, the light-sensitive material is subjected to development (silver development / cross oxidation of built-in reducing agent), (desilvering) and washing or stabilization treatment. Also, after washing or stabilizing treatment,
In some cases, a treatment for enhancing color development such as application of alkali is also performed. When developing a light-sensitive material according to the present invention, a developing solution functions as an auxiliary developing agent for silver halide and / or an oxidation product of the auxiliary developing agent generated by silver development is incorporated in the light-sensitive material. A compound having a function of cross-oxidizing the agent may be used. The above-mentioned pyrazolidones, dihydroxybenzenes, reductones and aminophenols are preferably used, and pyrazolidones are particularly preferably used.

Pyrazolidones include 1-phenyl-3
-Pyrazolidones are preferred, and 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4 , 4-Dihydroxymethyl-3-pyrazolidone, 1-phenyl-
5-methyl-3-pyrazolidone, 1-phenyl-5-phenyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-p
-Chlorophenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-2-hydroxymethyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-2-acetyl-3-pyrazolidone, 1-phenyl -2-hydroxymethyl-5-phenyl-3-pyrazolidone and the like. Examples of dihydroxybenzenes include hydroquinone, chlorohydroquinone, bromhydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,5-dimethylhydroquinone and potassium hydroquinone monosulfonate.

As the reductone, ascorbic acid or a derivative thereof is preferable, and the compounds described on pages 3 to 10 of JP-A-6-148822 can be used. Particularly, sodium L-ascorbate and sodium erythorbate are preferred. As p-aminophenols, N-methyl-p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol, and so on. These compounds are usually used alone,
It is also preferable to use two or more kinds in combination in order to enhance the developing and cross-oxidizing activities. The amount of these compounds used in the developer is 2.5 × 10 ⁻⁴ mol / liter to 0.2 mol / liter, preferably 0.0025 mol / liter to 0.1 mol / liter, and more preferably 0. .001
It is mol / liter-0.05 mol / liter. The pH of the developer used in the present invention is preferably 8 to 13, and more preferably 9 to 12. In order to maintain the above pH, it is preferable to use various buffer solutions. Further, conventionally known organic preservatives, development accelerators, anti-settling agents, optical brighteners and the like can be added to the developer.

The processing temperature of the developing solution applied to the present invention is 2
The temperature is 0 to 50 ° C, preferably 30 to 45 ° C. The processing time is 5 seconds to 90 seconds, preferably 10 seconds to 1 minute. Replenishment rate is desirably small, but the photosensitive material 1 m ² per 15
~ 600 ml, preferably 25-200 ml, more preferably 35-100 ml. After the development, desilvering is generally performed. The desilvering process includes a fixing process and a bleaching and fixing process. When the bleaching and fixing treatments are carried out, the bleaching treatment and the fixing treatment may be carried out individually or simultaneously (bleach-fixing treatment). Furthermore, processing in two continuous bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching bath and fixing bath, those conventionally known can be used. In addition, after development, desilvering is not applied, stabilization is performed,
It is also preferable to stabilize the silver salt or the color image.

The processing temperature in the desilvering step is 20 to 50 ° C, preferably 30 to 45 ° C. The processing time is 5 seconds to 2 minutes, preferably 10 seconds to 1 minute. The smaller the replenishing amount, the more preferable, but 15 to 600 ml, preferably 25 to 200 ml, and more preferably 35 to 10 ml per 1 m ^{2 of} the light-sensitive material.
0 ml. It is also preferable to perform the treatment without replenishment, to the extent that the evaporation amount is supplemented with water. The light-sensitive material of the present invention generally undergoes a washing step after desilvering. When the stabilization treatment is performed, the washing step may be omitted. The pH of the washing or stabilizing solution is 4 to 9, preferably 5 to 8. The treatment temperature is 15 to 45 ° C, preferably 25 ° C to 40
° C. The processing time is 5 seconds to 2 minutes, preferably 10 seconds to
40 seconds. The overflow solution accompanying the washing and / or replenishment of the stabilizing solution can be reused in other steps such as a desilvering step.

The amount of washing water and / or the stabilizing solution can be set within a wide range depending on various conditions, but the replenishing amount is preferably 15 to 360 ml per 1 m ² of the light-sensitive material, and 25 to 12
0 ml is more preferred. The processing time of each processing step in the present invention means the time required from the start of the processing of the photosensitive material in one step to the start of the processing in the next step. The actual processing time in an automatic developing machine is usually determined by the linear velocity and the capacity of the processing bath. In the present invention, the standard of the linear velocity is 500 to 4000 mm / min. In particular, in the case of a small developing machine, it is preferably 500 to 2500 mm / min. The total processing step, that is, the processing time from the developing step to the drying step is preferably 360 seconds or less, more preferably 120 seconds or less, and particularly preferably 90 to 30 seconds. Here, the processing time is the time from when the photosensitive material is immersed in the developing solution to when it comes out of the drying unit of the processor.

[0156]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

(Preparation of Silver Halide Emulsion A) 32 g of lime-processed gelatin was added to 800 cc of distilled water and dissolved at 40 ° C., then 5.8 g of sodium chloride and N, N′-dimethylimidazolidine-2-thione ( 1% aqueous solution) 1.9
cc was added and the temperature was raised to 72 ° C. Subsequently, a liquid obtained by dissolving 80 g of silver nitrate in 480 cc of distilled water and a liquid obtained by dissolving 27.6 g of sodium chloride in 480 cc of distilled water,
While maintaining the temperature at 72 ° C., the above liquid was added and mixed for 60 minutes. Next, a solution prepared by dissolving 80 g of silver nitrate in 300 cc of distilled water and a solution prepared by dissolving 24.3 g of sodium chloride and 4 mg of potassium hexacyanoferrate (II) trihydrate in 300 cc of distilled water was added to the solution over 20 minutes while maintaining the temperature at 72 ° C. Add and mix. After desalting and washing with water at 40 ° C., 90 g of lime-processed gelatin was added, and pAg was adjusted to 7.4 with sodium chloride and sodium hydroxide and pH was adjusted to 6.4.
Was adjusted. After the temperature was raised to 58 ° C., the blue-sensitive sensitizing dyes shown below were added in an amount of 1.4 × per mol of silver halide.
Spectral sensitization was carried out by adding 10 ⁻⁴ mol. Next, an ultrafine silver bromide emulsion (grain size: 0.05 μm) was added in an amount to give a silver bromide content of 0.4 mol% with respect to silver chloride, and a silver bromide localized phase was formed on the silver chloride surface. Formed. Further, triethylthiourea was added in an amount of 1 × 10 ⁻⁵ mol per mol of silver halide, and then tetrachloroauric (III) acid tetrahydrate was added to optimally perform gold sulfur sensitization. The silver chloride emulsion thus obtained was named Emulsion A.

From the electron micrograph of Emulsion A, the shape of grains,
The particle size and particle size distribution were determined. The particle size is represented by the average value of the diameter of the circle equivalent to the projected area of the particle, and the particle size distribution is the coefficient of variation, which is the standard deviation of the particle size divided by the average particle size. Emulsion A was cubic grains having sharp edges and an average grain size of 0.87 μm and a coefficient of variation of 8%. The X-ray diffraction of Emulsion A showed weak diffraction in a portion corresponding to a silver bromide content of 10 mol% to 40 mol%. Therefore, in Emulsion A-1, the silver bromide content was 10 mol% to the corner portions of the cubic silver chloride grains.
It can be said that 40 mol% of the localized phase is epitaxially grown.

(Preparation of Photosensitive Material 101) After corona discharge treatment was applied to the surface of a paper support laminated with polyethylene on both sides, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further formed. By coating, a multi-layer color photographic paper having the following layer constitution was produced. This is designated as a sample (101).

The coating liquid was prepared as follows. Preparation of first layer coating liquid 17 g of yellow coupler (ExY), reducing agent for color development (I
-49) 20 g and solvent (Solv-1) 80 g are dissolved in ethyl acetate 100 cc, and this solution is 10% sodium dodecylbenzenesulfonate 16 cc and citric acid 0.4 g.
Was added to 270 g of a 16% gelatin aqueous solution containing, and then emulsified and dispersed by an ultrasonic homogenizer. The resulting dispersion was mixed and dissolved with the silver chloride emulsion A to prepare a first layer coating solution.

The 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. In addition, Cdp-2 and Cd are added to each layer.
p-3, Cdp-4 and Cdp-5 the total amount respectively ^{15.0mg / m 2, 60.0mg / m} 2, 5.0mg /
m ² and 10.0 mg / m ² were added.

The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each photosensitive emulsion layer. Blue photosensitive emulsion layer

[0163]

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(1.4 × 10 ^-4 mol per mol of silver halide was used with respect to Emulsion A.) Green-sensitive emulsion layer

[0165]

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(The green light-sensitive sensitizing dyes D, E, and F were 3.0 × 10 ⁻⁴ mol and 4.0 × 10 mol, respectively, per mol of silver halide for the large-sized emulsion B-1. ^-5 mol,
2.0 × 10 ⁻⁴ mol was added, and for small size emulsion B-2, 3.6 × 1 per mol of silver halide, respectively.
0 ⁻⁴ mol, 7.0 × 10 ⁻⁵ mol and 2.8 × 10 ⁻⁴ mol were added. ) Red photosensitive emulsion layer

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(The red light-sensitive sensitizing dye G was used in an amount of 4.0 × 1 per mol of silver halide for the large-sized emulsion C-1.
0 ^-5 mol, to the small size emulsion C-2, 5.0 × 1
0 ^-5 mol, per mol of the silver halide red-sensitive sensitizing dye H, to the large size emulsion C-1, 5.0 × 10 ^-5
Mole, and for small size emulsion C-2, 6.0 × 1
0 ^-5 mol was added. The following compounds were further added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ⁻³ mol per mol of silver halide.

[0169]

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Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer in an amount of 8.5 × per mol of silver halide. 10 ^-4 mol, 3.0 x 10 ^-3
Mol, 2.5 × 10 ^-4 mol. Further, 4-hydroxy-6-methyl-1,3a, 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 ×, respectively, per mol of silver halide. ^10-4 mol was added.

[0171]

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[0172]

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[0173]

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(Layer Structure) 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 [White pigment (TiO ₂ 14
wt%) and bluish dye (ultra-blue)]

First Layer (Blue Sensitive Emulsion Layer) Silver Chloride Emulsion A 0.20 Gelatin 1.50 Yellow-Coupler (ExY-1) 0.17 Coloring Reducing Agent (I-49) 0.20 Solvent (Solv- 1) 0.80

Second Layer (Color Mixing Prevention Layer) Gelatin 1.09 1,5-Diphenyl-3-pyrazolidone 0.03 Color mixing inhibitor (Cpd-6) 0.11 Solvent (Solv-1) 0.19 Solvent (Solv -3) 0.07 Solvent (Solv-4) 0.25 Solvent (Solv-5) 0.09

Third Layer (Green Sensitive Emulsion Layer) Silver Chlorobromide Emulsion B Cube, large size emulsion B-1 with average grain size 0.55 μm, and small size emulsion B-2 with average grain size 0.39 μm 1: 3 mixture (silver molar ratio). The variation coefficient of grain size distribution was 8% and 6%, respectively, and 0.8 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride in each size emulsion. Further, 0.1 mg of potassium hexachloroiridium (IV) ate was added per mol of silver to the inside of the grain and the silver bromide localized phase, and 1 mg of potassium ferrocyanide was added in total. 0.13 Gelatin 1.50 Magenta coupler (ExM) 0.24 Coloring reducing agent (I-49) 0.20 Solvent (Solv-2) 0.80

Fourth Layer (Color Mixing Prevention Layer) Gelatin 0.77 1,5-diphenyl-3-pyrazolidone 0.03 Color mixing inhibitor (Cpd-6) 0.08 Solvent (Solv-1) 0.14 Solvent (Solv -3) 0.05 Solvent (Solv-4) 0.14 Solvent (Solv-5) 0.06 Fifth Layer (Red Sensitive Emulsion Layer) Silver Chlorobromide Emulsion C Cube, Large Size with Average Grain Size 0.50 μm A 1: 4 mixture (silver molar ratio) of emulsion C-1 and small size emulsion C-2 having an average grain size of 0.41 μm. Coefficients of variation of grain size distribution were 9% and 11%, respectively, and in each size emulsion, 0.8 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride. Furthermore, 0.3 mg of potassium hexachloroiridium (IV) ate was added per mol of silver and 1.5 mg of potassium ferrocyanide was added inside the grains and in the silver bromide localized phase. ) 0.18 gelatin 1.50 cyan coupler (ExC) 0.20 color-forming reducing agent (I-49) 0.20 solvent (Solv-1) 0.80

Sixth Layer (UV Absorbing Layer) Gelatin 0.64 UV Absorbing Agent (UV-1) 0.39 Color Image Stabilizer (Cpd-7) 0.05 Solvent (Solv-6) 0.05

Seventh Layer (Protective Layer) Gelatin 1.01 Acrylic Modified Copolymer of Polyvinyl Alcohol (Modification Degree 17%) 0.04 Liquid Paraffin 0.02 Surfactant (Cpd-1) 0.01

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The following compounds were added to the sixth layer as the irradiation preventing water-soluble dye (the amount in parentheses represents the coating amount).

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An equivalent sample to the sample (101) prepared as described above except that the compound of the present invention (oxonol compound of the general formula (I) or (II)) shown in Table 21 was added to the sixth layer. (121 to 151) were prepared (the compound added here is not only limited to the added layer but is almost uniformly diffused in all layers during coating). Also, samples (152 to 156) were prepared in exactly the same manner as the preparation of sample (151) except that the color-forming reducing agent (I-49) in the first layer was replaced with the compounds shown in Table 21 in equimolar amounts. . However, (15
In the samples of 2) and (155), (ExYY
(ExY-2) was used in an equimolar amount instead of -1). Further, samples (161) and (162) were prepared in exactly the same manner as the sample (151) except that the oxonol compound in the sixth layer was an equimolar mixture of the comparative compound and the compound of the present invention.

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[0187]

[Table 21]

For the evaluation of the prepared light-sensitive material, a sample for which the hardening reaction was completed was used. Each sample was stored in the dark for 1 month. Storage conditions are temperature 40 ℃ -humidity 40% and temperature 40
There are two types, ℃ -humidity 80%. After storage, FWH type sensitometer (manufactured by Fuji Photo Film Co., Ltd., color temperature 320 of light source)
A sample (40 ° C-40%) for evaluating the processing unevenness at 0K
(Only the sample stored in) was subjected to uniform exposure by adjusting the exposure amount so that the reflection density was 0.8, and the sample for evaluating the change in color density was exposed through a gradation wedge, and The following development processing was performed. Treatment process Temperature Time Image 40 ° C 40 seconds Bleaching and fixing 40 ° C 45 seconds Rinse chamber temperature 45 seconds Alkaline treatment chamber temperature 30 seconds

Developer water 600 cc Potassium phosphate 40 g KCl 5 g Hydroxyethylidene-1,1-diphosphonic acid (30%) 4 cc Water was added to 1000 cc pH (at 25 ° C./potassium hydroxide) 12

Bleach-fixing solution Water 600 cc Ammonium thiosulfate (700 g / l) 93 cc Ammonium sulfite 40 cc Ethylenediaminetetraacetic acid (III) ammonium 55 g Ethylenediaminetetraacetic acid 2 g Nitric acid (67%) 30 g Water is added 1000 cc pH (25 ° C / acetic acid and ammonia) (With water) 5.8

Rinsing solution Sodium isocyanurate chlorate 0.02 g Deionized water (conductivity 5 μS / cm or less) 1000 cc pH 6.5

Alkaline treatment liquid 800 cc 0.1N sodium hydroxide K ₂ CO ₃ 30 g Water was added to give 1000 cc pH (at 25 ° C./sulfuric acid) 10

In order to evaluate the processing unevenness, the reflection densities of yellow, magenta, and cyan of the sample to which uniform exposure was applied were taken as X.
-Measured by X-RITE310 manufactured by RITE. The measurement was performed at 20 points on the same sample. From the difference between the maximum density and the minimum density of each color, the average value of the density differences of the three colors was determined and summarized in Table 22 as a measure of processing unevenness. A characteristic curve was obtained from the sample subjected to gradation exposure by measuring the yellow reflection density. Difference in maximum color density between characteristic curves of samples stored at 40 ° C.-40% and samples stored at 40 ° C.-80% (ΔD _max = D _max (80%)-D
_max (40%)) was determined and summarized in Table 22. The larger this value is negative, the greater the decrease in concentration during high humidity storage. Further, for the purpose of evaluating the sharpness of the light-sensitive material, the above-mentioned light-sensitive material was exposed by using a negative film on which landscapes of buildings and distant mountains were photographed, and the above-mentioned processing was performed to form a color print. 20 color prints obtained
The sharpness was visually evaluated by a person. The obtained results are ⊚: very good; ∘: good; Δ: a little bad;
X: Bad; XX: Very bad.

[0194]

[Table 22]

As shown in Table 22, unless the oxonol compound is used, the unevenness in processing and the change in density are small, but the sharpness is poor and it is not preferable [Sample (101)]. When only the comparative compound is used as the oxonol compound, the sharpness is improved, but both the process unevenness and the density change are large, which is not preferable [Samples (111) and (112)]. On the other hand, the use of the oxonol compound of the present invention [Samples (121) to (156)] and the combined use of the oxonol compound of the present invention [Samples (161) and (162)] cause little unevenness in processing and decrease in density. It can be seen that a photosensitive material is obtained.

[0196]

By containing the oxonol compound of the present invention in the photographic constituent layer, even in a photographic light-sensitive material containing a color-forming reducing agent, development processing unevenness does not occur, and the unexposed light-sensitive material has a high humidity environment. Good images can be obtained even after storage in.

Claims (3)

[Claims] 1. A silver halide color photographic light-sensitive material comprising a support and a photographic constituent layer containing at least one light-sensitive silver halide emulsion layer coated on the support, and a reducing agent for color formation in any of the photographic constituent layers. Or a precursor thereof, and a color-forming coupler which forms a dye by a coupling reaction with an oxidant of the color-forming reducing agent, and a compound represented by the following general formula (I) in any of the photographic constituent layers And / or at least one compound represented by the following general formula (II). General formula (I) In the general formula (I), R ¹ and R ³ each represent an electron-withdrawing group having a Hammett substituent constant σ _p of 0.3 or more;
² , R ⁴ each represents an alkyl group or an aryl group, L ^{1 to} L ⁵ each represent a methine group, and M ¹ represents a hydrogen atom, or an atomic group or a metal atom which becomes a monovalent cation. Here, at least one of L ^{1 to} L ⁵ has a substituent. General formula (II) In formula (II), R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a substituent. However, (R ₁ + R
₃ ) and the sum of the atomic weights of at least one of (R ₂ + R ₄ ) is 160 or less. n represents 0, 1, or 2. M represents a hydrogen atom, an atomic group that becomes a monovalent cation, or an alkali metal. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the color-forming reducing agent is a compound represented by the following general formula (III). General formula (III) In the general formula (III), R ¹¹ is an aryl group or a heterocyclic group which may have a substituent, and R ¹² is an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a hetero group which may have a substituent. It is a cyclic group. Χ is -SO _2- , -CO
-, - COCO -, - CO -O -, - CO-N (R 13)
—, —COCO—O—, —COCO—N (R ¹³ ) — or —SO ₂ —N (R ¹³ ) —. Here, R ¹³ is a hydrogen atom or a group described for R ¹² . 3. The silver halide color photographic light-sensitive material according to claim 2, wherein X in the general formula (III) is —CONH—.