JPS5811616B2 - Silver halide color photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material which can improve the gradation and color haze of dye images obtained by processing.

In a silver halide color photographic light-sensitive material (hereinafter referred to as a color light-sensitive material), exposed silver halide grains are developed using an aromatic primary amine compound, and the resulting aromatic primary amine compound is oxidized. It is known that a dye image is formed by reaction of a product with a coupler.

This method typically uses phenolic or naphthol couplers such as 5-pyrazolone, pyrazolinobenzimidazole, pyrazolotriazole, indacylon or cyanoacetyl couplers to form cyan, magenta and yellow dye images, respectively; Acetamide or dibenzoylmethane couplers are used.

There are two known methods of adding these couplers into a silver halide emulsion layer and a method of adding them into a developer.

These methods tend to cause color capri, color discoloration, or staining when developing color photosensitive materials.

This is a place where the color developing agent is oxidized under the influence of oxygen in the air, and this oxidized developing agent is not exposed to light.
Non-selective coupling with the coupler causes color capri and contamination, and when the developing agent oxidized by the exposed silver halide migrates to other layers, color stain appears.

It has been known to add a diffusion-resistant hydroquinone derivative to color photosensitive materials in order to prevent color fogging, color smearing, and staining as described above.

However, hydroquinone derivatives, which are effective in preventing color fogging, color discoloration, and staining, have the following two major drawbacks.

The first disadvantage is that the gradation of the dye image obtained by processing is increased.

In particular, it makes the tone of the legs, which is important in terms of tone reproduction, hard-toned.

This particularly affects the tone reproduction of highlight areas on prints, and if there is a certain degree of high contrast on the base, the tone will not be consistent, and pigment will not be generated in the highlight areas, resulting in a finish that is extremely worthless as a color photographic material. It becomes something.

This is especially a problem in photographs of brides wearing pure white or light-colored costumes, because it becomes impossible to reproduce subtle tones and white is no longer white.

As a solution to the first drawback, (1-1): Reduce the amount of hydroquinone derivative used.

(1-2): A silver halide emulsion is prepared depending on the amount of hydroquinone derivative used.

However, with method (1-1), one must be prepared for a certain degree of color discoloration, color fogging, and contamination.

In method (1-2), the gradation of the silver halide emulsion must be constantly adjusted depending on the amount of hydroquinone derivative used, which is undesirable because it is very complicated in production.

As a method other than the above-mentioned method for adjusting the toe gradation, it is known to add a compound having a gradation adjusting effect to the color developing solution or the silver halide emulsion layer.

For example, when added to a color developing solution, a compound such as 1-amino-8-naphthol-3,6-disulfonic acid is an effective compound for controlling gradation.

However, since these compounds have a fast reaction rate with the developing agent oxide, they have the disadvantage of narrowing the gradation range.

Compounds such as 2,6-cyhydroxyisonicotinic acid have fewer of these drawbacks, but are expensive and are not industrially satisfactory.

When added to a color developer or silver halide emulsion, .beta.-naphthols also exhibit a fairly excellent gradation control effect, but they have a practical problem because they have absorption in the visible region.

Second drawback: The above-mentioned diffusion-resistant hydroquinone derivatives are not only oxidized during the process of preparing the dispersion, the coating process, or the process after the coating process and reduce their original functions, but also become uncolored due to coloring by oxidation products. The problem is that some parts become discolored.

This, as in the case of the first drawback mentioned above, significantly reduces the quality of the finished photographic material.

Catechol, pyrogallol, ascorbic acid, gallic acid, etc. are known to prevent oxidation of these hydroquinone derivatives.

It is true that the above-mentioned compounds are effective as antioxidants, but because of their diffusivity, they gradually accumulate in the developer during the development process, which affects the sensitivity and gradation of color photographic materials, which is not preferable.

A first object of the present invention is to provide a color photosensitive material in which the gradations of the legs of the resulting image are softened.

A second object of the present invention is to provide a color photosensitive material in which uncolored areas are not colored by oxidation products of hydroquinone derivatives.

A third object of the present invention is to provide a color photosensitive material that does not cause color capri, color smearing, or staining.

As a result of intensive studies, the present inventors found that the above object can be solved by using a combination of at least one compound represented by general formula [I] and a compound represented by general formula (II) (i.e., a hydroquinone derivative). I found out.

General formula [I] [wherein R1 and R2 are alkyl groups (e.g. methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-amyl group, i- amyl group,
Among the n-octyl group, n-dodecyl group, n-octadecyl group, etc., alkyl groups having 1 to 32 carbon atoms are particularly preferred.

), alkenyl groups (for example, allyl group, octenyl group, oleyl group, etc., particularly preferably alkenyl groups having 2 to 32 carbon atoms).

) A cycloalkyl group (for example, a cyclohexyl group, a cyclopentyl group, etc., and a 5- to 7-membered cycloalkyl group is particularly preferred).

), aryl groups (e.g. phenyl group, naphthyl group, etc.),
Heterocyclic groups (e.g. imidazolyl, furyl, pyridyl).

A heterocyclic group containing a 5- to 6-membered nitrogen atom, oxygen atom, and/or sulfur atom, such as a triazinyl group or a thiazolyl group, is preferable.

), and R3, R4R5 and R6 represent a hydrogen atom, a halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.), an alkyl group (e.g. methyl group, ethyl group, n-propyl group, 1-propyl group, n- Among the butyl group, i-butyl group, n-octyl group, n-dodecyl group, etc., alkyl groups having 1 to 32 carbon atoms are particularly preferred.

), alkenyl groups (for example, allyl group, octenyl group, etc., particularly preferably alkenyl groups having 2 to 32 carbon atoms).

), alkoxy groups (e.g. methoxy, ethoxy, methoxy, dodecyloxy, etc.), cycloalkyl groups (
For example, cyclopentyl group, cyclohexyl group, etc., especially 5
~7-membered cycloalkyl groups are preferred.

) Aryl group (e.g. phenyl group, naphthyl group, etc.), aryloxy group (e.g. phenoxy group), alkenoxy group (e.g. allyloxy group, oleyloxy group, etc.), carbamoyl group (e.g. methylcarbamoyl, dibutylcarbamoyl, octadecylcarbamoyl, phenylcarbamoyl) etc.), sulfamoyl groups (e.g. methylsulfamoyl, octadecylsulfamoyl etc.), acyl groups (e.g. acetyl, octanoyl, lauroyl etc.), alkoxycarbonyl groups (e.g. methoxycarbonyl, dodecyloxycarbonyl etc.) or aryloxycarbonyl groups ( For example, phenyloxycarbonyl, etc.), alkylthio groups (for example, methylthio group, n-butylthio group,
n-dodecylthio group, etc.), heterocyclic thio groups (e.g., tetrazolyl group, thiadiazolyl group, etc.) and heterocyclic groups containing a 5- to 6-membered nitrogen atom, oxygen atom, and/or sulfur atom are preferred.

), arylthio group (e.g. phenylthio group), alkylamino group (e.g. methylamine group, diethylamine group, n-octylamino group, di-n-decylamino group, etc.)
, acylamino groups (e.g. acetylamino group, octanoylamino group, benzoylamino group, etc.), their alkyl groups, alkenyl groups, aryl groups, alkoxy groups, alkenoxy groups, aryl groups, aryloxy groups, cycloalkyl groups and heterocycles The groups include halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom, etc.), alkyl groups (e.g. methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, 1-octyl group). base, n
-dodecyl group and the like, particularly preferably an alkyl group having 1 to 32 carbon atoms.

), aryl group (e.g. phenyl group), aryloxy group, alkylthio group, cyan group, acyloxy group, alkoxycarbonyl group, acyl group, sulfamoyl group, hydroxy group, nitro group, amine group, nitrogen atom, oxygen atom and/or 5- to 6-membered heterocyclic group containing a sulfur atom (
For example, morpholino group, pyranyl group, imidazolyl group, etc.)
It may be substituted with any substituent such as.

In general formula CI), preferably R1 and R2 are each a substituted or unsubstituted straight chain or branched alkyl group or alkenyl group, and R3, R4, R5 and R6 are each a hydrogen atom, a substituted or unsubstituted straight chain or It is a branched alkyl group or alkenyl group.

Furthermore, R1 and R2 are preferably unsubstituted alkyl groups, particularly preferably those having an alkyl group having 8 to 20 carbon atoms.

In particular, it is preferable that two of R3, R4, R5 and R6 are hydrogen atoms, and the others are alkyl groups having 1 to 8 carbon atoms.

Typical specific examples of these compounds are shown below, but the compounds of the present invention are not limited thereto.

The compound represented by general formula (I) is described in the Journal of
The Chemical Society (Journalof T)
he Chemical 5ociety) 2904
~2914 pages (1965) and The Journal of Organic Chemistry
of Organic Chemistry) 23
As described in Vol. 75-76, substituted or unsubstituted hydroquinone is reacted with an etherifying agent such as alkylbymite using a dehydrohalogenating agent such as sodium hydroxide in a suitable solvent such as alcohol. Although it can be easily synthesized by methods such as, specific representative synthesis examples are shown below.

Synthesis Example 1 [Synthesis of Exemplified Compound 4)] Potassium hydroxide 27,1, p was added to ethanol 50 Qm
50 g of 2-methyl-5-sec-dodecylhydroquinone and 56 g of butyl bromide were dissolved therein and heated under reflux while stirring.

After 2 hours, the inorganic substances are separated and the solvent is distilled off.

The residue was distilled under reduced pressure to obtain the desired product.

Boiling point 158-162°C/0.02 mmHg (but is a mixture of several isomers).

It was confirmed that it was the desired product by IR, NMR, mass, and elemental analysis results.

Elemental analysis value (C2□H4802) Calculated value C: 80.14 H: 11.96 Actual value C
:80.40 H:12.23 Synthesis Example 2 [Synthesis of Exemplary Compound vA7)] 843 g of potassium hydroxide was dissolved in 151 g of ethanol, and 2,000 g of 2-methyl-5-sec-octadecylhydroquinone was added thereto. ! li' and octyl bromide 2
Add 460 g and heat under reflux for 3.5 hours while stirring.

After the reaction, the inorganic substances are separated from each other and the solvent is concentrated and then distilled under reduced pressure to obtain the desired product.

Boiling point: 205-210°C, 10.2 mmHg NMR elemental analysis and IR confirmed that the product was the desired product.

Elemental analysis value (C4□H7602) Theoretical value C: 81.93 H: 12.75 Actual value C
:82.08 H:12.91 Synthesis Example 3 [Synthesis of Exemplified Compound (8)] 168.6 g of potassium hydroxide was dissolved in 500 d of ethanol, and 400 g of 2-methyl-5-sec-octadecylhydroquinone and octyl Bromide 49
2 g was dissolved and heated under reflux for 4 hours while stirring.

The reaction wave inorganic material was collected from door to door, and the solvent was concentrated and then distilled under reduced pressure to obtain a candy-like target product.

Boiling point 199-206°C/0.05 mm Hg, N
The product was confirmed to be the desired product by MR, IR and elemental analysis results.

Elemental analysis value (C41H7602) Theoretical value C: 81.93 H: 12.75 Actual value C
:82.11 H:12.92 Synthesis Example 4 [Synthesis of Exemplary Compound (11)] 2,300 g of 2.5-di-dodecyloxytoluene is dissolved in 2,000 ml of n-hexane, and 100 ml of concentrated sulfuric acid is added.

Stir and soak at 50°C to inhale isobutine.

After the reaction has stopped, n-hexane is distilled off under reduced pressure and the residue is washed with methanol to obtain a sleeve.

Cool to crystallize, and recrystallize from acetone to obtain the desired product as white needle-like crystals.

m, p, 40-41.5°C Infrared spectrum (IR), nuclear magnetic resonance spectrum (N
It was confirmed that it was the desired product based on the MR) mass spectrum (Mass) and elemental analysis results.

Elemental analysis value (C35H6402) Unit % Theoretical value
C: 81.33 H: 12.48 Actual value C: 81.
51 H:12.14 Synthesis Example 5 [Exemplary Compound (16
) Synthesis] 27.1 g of potassium hydroxide was added to 5 g of ethanol
007711 and 2-methyl-5-sec
- Add 50 g of dodecyl hydroquinone and 125 g of hexadecyl bromide and heat under reflux while stirring.

After 2 hours, the solvent is distilled off, the salt is dissolved in ligroin, and the ligroin is distilled off.

The resulting black residue is purified by column chromatography (silica gel 200 mesh inversion solvent: n-hexane) to obtain a pale yellow liquid (however, it is a mixture of several isomers).

The product was confirmed to be the desired product by IR, NMR and elemental analysis results.

Elemental analysis value (C51H9□02) Calculated value C: 82.63 H: 13.05 Actual value C
:82.89 H:13.27 Synthesis Example 6 [Synthesis of Exemplified Compound (17)] 480 g of potassium hydroxide was dissolved in 101 ethanol, and 5 ml of trimethylhydroquinone was dissolved in it.
00 g and 1410 g of octyl bromide were added, and the mixture was heated under reflux for 3.5 hours while stirring.

After the reaction, ethanol is distilled off, water is added to the residue, and n-hexane is extracted.

The n-hexane layer is washed with about 10 parts sodium hydroxide, then water, and concentrated under reduced pressure.

The residue is distilled under reduced pressure to obtain a yellow candy-like substance.

Boiling point 213-218°C/3mmHg, NMR, IR.

It was confirmed that it was the desired product based on mass and elemental analysis results.

Elemental analysis value (C25H4402) Theoretical value C near 9.73 H: 11.78 Actual value C
Near 9.93 H: 11.87 Synthesis Example 7 [Synthesis of Exemplified Compound (23)] 320g of potassium hydroxide was dissolved in 81g of ethanol, and 640g of 2,5-di-morpholinomethylhydroquinone and 960g of octadecyl bromide were dissolved therein. Add and heat to reflux for 4 hours while stirring.

Reaction Wave Crystals are obtained by cooling the inorganic material from door to door.

This is recrystallized from acetone to obtain the desired product as white crystals.

Melting point 66-8°C. The product was confirmed to be the desired product by NMR, IR, and elemental analysis results.

. Elemental analysis value (C5□H96N204) Theoretical value C near 6.79 H: 11.9 ON: 3.4
4 Actual value C near 6.94 H: 11.99 N: 3.4
7 Synthesis Example 8 [Synthesis of Exemplified Compound (51)] 182 g of potassium hydroxide was dissolved in 2,000 ml of ethanol, and 2,5-di-tert-butylhydroquinone 27
7.5 g of lauryl bromide and 810 g of lauryl bromide were dissolved and heated under reflux for 3 hours while stirring.

After the reaction, the acidified inorganic substance is cooled separately to obtain crystals.

Recrystallize from ethanol to obtain white crystals.

The melting point was 72.5-74°C, and the results of NMR, IR, and elemental analysis confirmed that it was the desired product.

Elemental analysis value (C38H7002) unit: % theoretical value C:
81.65 H: 12.62 Actual value C: 81.52
H: 12.80 Synthesis Example 9 [Synthesis of Exemplified Compound (52)] 664 g of hydroquinone-di-ethyl ether is dissolved in 1500 ml of ethyl acetate, and 600 ml of concentrated sulfuric acid is slowly added thereto.

Furthermore, 740 g of 2-methyl-1-pentene was added, and the mixture was heated and reacted under reflux while stirring.

After 7 hours, the solvent was distilled off and the remaining liquid was diluted with 250 methanol.
Addition of 0TLl gives white crystals.

The obtained crystals were recrystallized from methanol to a melting point of 76-7.
Obtain white needle-like crystals at °C.

It was confirmed to be the desired product by NMR, IR elemental analysis, and mass spectroscopy.

Elemental analysis value (C2□H3802) Theoretical value C near 8.98 H: 11.45 Actual value C
:89.21 H:11.48 Synthesis Example 10 [Synthesis of Exemplary Compound (56)] 50 g of hydroquinone-di-decyl ether was dissolved in 300 ml of nitrobenzene.

To this are added 14.9 g of aluminum chloride and 22.9 g of lauroyl chloride.

Stir and let stand at room temperature overnight.

After the reaction, nitrobenzene is distilled off by steam distillation, and the residue is cooled to obtain crystals.

This was subjected to column chromatography (silica case'/L'2
00 mesh, developing solvent: n-hexane-benzene) to obtain the desired product as white crystals.

It was confirmed that it was the desired product by melting point 61-62°C11R, NMR and elemental analysis results.

Elemental analysis value (C42N760a) Unit coefficient theoretical value C:
80.19 H: 12.18 Actual value C: 80.25
H: 12.28 Synthesis Example 11 [Exemplary Compound (59)
Synthesis] 75g of potassium hydroxide and 800ml of ethanol
110 g of 2,5-di-tert-butylhydroquinone and 265 g of 2-ethyl-hexyl bromide were dissolved therein, and heated under reflux for 2 hours while stirring.

After the reaction, the produced inorganic substances are separated in a furnace and the solvent is distilled off.

The residue is recrystallized from ethanol to obtain the desired product as white crystals.

The melting point was 34°C11R, and the results of NMR and elemental analysis confirmed that it was the desired product.

Elemental analysis value (C30H540□) Unit coefficient theoretical value C: 80.65 H: 12.18 Actual value C
:80.71 H:12.26 Synthesis Example 12 [Synthesis of Exemplified Compound (64)] 75 g of potassium hydroxide was dissolved in 8077 Il of ethanol, and 2,5-di-tert was added to the solution.
-125 g of amylhydroquinone and 265 g of n-octyl bromide were dissolved and heated under reflux for 2 hours while stirring.

After the reaction, the resulting crystals are cooled, separated from the furnace, washed with water, and then washed with methanol to obtain white crystals.

Recrystallize from ethanol to obtain the desired product as white needle-like crystals.

Melting point (myp): 43°C, IR, NMR, and elemental analysis results confirmed that the product was the desired product.

Elemental analysis value (C2□H3802) Unit: Theoretical value C: 80.95 H: 12.31 Actual value C
:81.05 H:12.38 Synthesis Example 13 [Synthesis of Exemplary Compound (66)] 4.69 methylhydroquinone-didodecyl ether was dissolved in 50 ml of tetrachloroethane, and 0.6 ji of aluminum chloride and 1 cyclohexene were dissolved therein. .0g was added and stirred at room temperature for 2.5 hours.

After the reaction, the solution was poured into 50 g of dilute hydrochloric acid (4%) and the organic layer was separated.

This is washed with dilute caustic soda water to neutralize it, and then steam distilled to remove tetrachloroethane.

The residue was purified by column chromatography (200 mesh of silica gel, developing temperature: n-hexane), and the resulting white crystals were recrystallized with acetone to obtain a crystalline product.

Melting point 53-54°C, NMR. The IR and elemental analysis results confirmed that the product was the desired product.

Elemental analysis value (C3, H6602) Unit % Theoretical value
C: 81.85 H: 12.25 Actual value C: 8
1.62 H:12.37 General formula in the present invention [
The compound represented by [I] is an excellent dye fading preventive agent, and it is surprising that this dye fading preventive agent exhibits better effects for the purpose of the present invention than known dye fading preventive agents. [■] In the formula, R7, R8, R9 and R10 have the same meaning as R3, R4, R5 and R6 in the general formula [■].

Specific examples of the compound represented by the general formula [''] according to the present invention include, for example, U.S. Pat.
, No. 290, No. 2,384,658, No. 2.403,
No. 721, No. 2,418,613, No. 2.675, 3
No. 14, No. 2,701,197, No. 2.704,71
No. 3, No. 2,710,801, No. 2,722,556
No. 2,728,659, No. 2.732,300, No. 2,735,765, No. 2.816.028,
No. 3,062,884, No. 3,236.893, British Patent No. 557,750, Specification of British Patent No. 557.802,
West German Patent Publication No. 2,149,789
No. 116, Japanese Unexamined Patent Publication No. 46-2128, Journal
Of Organic “Chemistry” (Journal
of Organic Chemistry) Volume 22, pages 772-774.

Among the compounds represented by the general formula [■] according to the present invention, substituents on the hydroquinone nucleus (i.e. R7゜R8, R9
and R10) having a total number of carbon atoms of 8 or more have low diffusivity and are suitable for being selectively present in a specific hydrophilic layer of a color photosensitive material.

Among the compounds represented by the general formula (IT) used in the present invention, those in which the substituent on the nucleus is a substituted or unsubstituted alkyl group are particularly useful; is particularly useful.

Specific examples of the hydroquinone derivatives used in the present invention are shown below, but the invention is not limited thereto.

(Hq-1) 2.5-di-tert-octylhydroquinone (Hq
-2) 2-1-octyl-5-methylhydroquinone (Hq-
3) 2.6-di-n-dodecyl-hydroquinone (Hq-4
) 2-n-dodecylhydroquinone (Hq-5) 2.2/-methylenebis-5,5'-di-t-butylhydroquinone (Hq-6) 2.5-di-n-octyl-hydroquinone (Hq-7
) 2-dodecylcarbamoylmethylhydroquinone (HC
I-8) 2-(β-n-dodecyloxycarbonyl)ethyl-hydroquinone (Hq-9) 2-(N,N-dibutylcarbamoyl)hydroquinone (Hq-10) 2-n-dodecyl-5-chloro Rhohydroquinone (Hq-11) 2-(2-octadecyl)-5-methylhydroquinone (Hq-12) 2.5-C(p-methoxyphenyl)hydroquinone (Hq-13) 2-t-Octylhydroquinone (Hq- i4) 2-[β-(3-(3-sulfonebenzamidebenzamide)ethylhydroquinone (Hq-15) 2.5-dichloro-3,6-siphenylbideroquinone (Hq-16) 2.6-simethyl-3- 1-octylhydroquinone (Hq-17) 2.3-dimethyl-5-t-octylhydroquinone (Hq-18) 2-(β-(dodecanoyloxy)ethyl)carbamoylhydroquinone (I-Iq-19) 2-do Decyloxycarbonylhydroquinone (Hq
-20) 2-(β-(4-#'7tanamidophenyl)ethyl)
Hydroquinone (Hq-21) 2-Methyl-5-dodecylhydroquinone (Hq-22
) 2.5-di-t-butylhydroquinone (Hq, -23) 2.5-di-t-amylhydroquinone (Hq -24) 2.5-di-t-amylhydroquinone The color photosensitive material according to the present invention is A hydrophilic colloid layer containing at least one silver halide emulsion layer is coated on a support, and the silver halide emulsion layer may have not only one layer but two or more layers.

In the present invention, the color photosensitive material preferably consists of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer, and these emulsion layers are coated with a subbing layer, an intermediate layer, etc. as necessary. It is.

The compound represented by the general formula [I] according to the present invention may be contained in any layer constituting the color light-sensitive material, or preferably contained in the silver halide emulsion layer, but may be contained in other layers such as the silver halide emulsion layer. It may be contained in an adjacent layer.

As the silver halide emulsion layer, a green-sensitive emulsion layer is particularly preferred.

In addition, the compound represented by the general formula [formula] according to the present invention may be contained in any layer constituting the color photosensitive material, or
It is preferably contained in the same layer as the compound represented by general formula [I], and may be contained in a layer adjacent to this layer.

The compounds represented by the general formulas CI) and CI) according to the present invention are generally oil-soluble and are generally used in high boiling point solvents (hereinafter referred to as H
(hereinafter referred to as BS), a low boiling point solvent (hereinafter referred to as LB) as necessary.
It is preferable to dissolve, disperse, and add to a silver halide emulsion, etc., in combination with S. I can't help it.

Furthermore, to explain in detail the method of adding the compound according to the present invention, the compound according to the present invention is added to organic acid amides, carbamates, esters, etc. at the same time as couplers, ultraviolet absorbers, or known antistatic agents, etc., as necessary. , ketones, urea derivatives, etc., especially di-octyl phthalate, triresyl phosphate, di-yne octyl azelate, di-n-butyl sebacate, t')-n-hexyl phosphate-1-
1N, N-di-ethyl-caprylamidobutyl, n-pentadecyl phenyl ether, triphenyl phosphate, di-octyl phthalate, n-nonylphenol,
N,N-diethyl laurylamide, 3-pentadecyl phenylethyl ether, 2,5-di-5ec-amylphenyl phthyl ether, monophenyl-di-0-chlorophenyl phosphate or fluoroparaffin, etc.
If necessary, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, cyclohexanetetrahydrofuran, methyl alcohol, ethyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, methyl isobutyl ketone, diethylene glycol, Monoacetate, acetylacetone, nitromecune, nitroethane, carbon tetrachloride, chloroform, etc. are soluble in LBS, and these HR8 and LBS may be used alone or in combination.

) mixed with an aqueous solution containing a hydrophilic binder such as gelatin containing anionic surfactants such as alkylbenzenesulfonic acids and alkylnaphthalenesulfonic acids and/or nonionic surfactants such as sorbitan sesquioleate and sorbitan monolaurate; It can be emulsified and dispersed using a high-speed rotating mixer, colloid mill, ultrasonic dispersion device, etc., and added to a hydrophilic colloid such as a silver halide emulsion.

The compound according to the present invention can also be easily dispersed according to a dispersion method using a latex solution.

Further, the compound according to the present invention may be separately dispersed by the above-mentioned method and added to the same layer.

A preferred addition method for the compound according to the present invention is the general formula CD
This is a method in which the compound represented by (■) and the coupler are dispersed and added together with other lipophilic additives (ultraviolet absorbers, etc.) using the method described above.

If the coupler used at this time is diffusive, the coupler may be added to a color developing solution to emulsify and disperse only the compound according to the present invention, and then added to a silver halide emulsion etc. for use. .

The amount of the compound according to the present invention to be added is not particularly limited since the compound is substantially colorless and therefore does not have any adverse effects such as coloring contamination by itself. However, the compound represented by the general formula [I] The material contains 0.1X10-1 mole per mole of silver halide, especially 2X10"-2 to 3X
Preferably it is added to 10-'mol.

The amount added is the same whether it is used alone or in combination with two or more types.

Further, the compound represented by the general formula [■] may be used alone or in combination of two or more, and the amount added is usually 0.01 to 10 mol per 1 mol of the coupler in a color photosensitive material containing a coupler. Preferably, 0.1 to 3 mol is particularly preferable.

In the case of a color light-sensitive material containing no coupler, the amount is preferably 0.01 to 1.0 mol, particularly preferably 0.02 to 0.6 mol, per 1 mol of silver halide.

Typical dye image-forming couplers that can be used in the color light-sensitive material according to the present invention include the following compounds.

Among these, the yellow dye image-forming couplers are benzoylacetanilide type, pivaloylacetanilide type, dibenzoylmethane type, or a substituent whose carbon atom at the coupling position can be separated during the coupling reaction (so-called split-off group). It is a substituted two-equivalent yellow dye image-forming coupler.

The magenta dye image-forming coupler is a 5-pyrazolone type, pyrazolotriazole type, pyrazolinobenzimidazole type, indashilon type, cyanoacetyl type or a two-equivalent type magenta dye image-forming coupler having a split-off type.

As the magenta coupler, 5-pyrazolone couplers are preferred, and 3-anilino-5-pyrazolone couplers are particularly preferred.

It is particularly preferable that the anilino group is substituted with a chlorine atom at the 2-position and an alkyl- or alkenyl-substituted succinimide group at the 5-1 position.

The cyan dye image-forming coupler is a phenol-based, naphthol-based, or equivalent type cyan dye image-forming coupler having a split-off group.

Specific representative examples of dye image-forming couplers used in the present invention are shown below.

(Y-1) α-(4-carboxyphenoxy)-α-pivalyl 2
-chloro5-[γ-(2,4-di-monoamylphenoxy)butyramide]acetanilide.

(Y-2) α-benzoyl-2-chloro-5-[γ-2゜4-di-
t-amylphenoxy)butyramide]acetanilide.

(Y-3) α-benzoyl-2-chloro-5-[α-(dodecyloxycarbonyl)ethoxycarbonyl]acetanilide.

(¥-4) α-(4-carboxyphenoxy)-α-pivalyl 2
-chloro5-[α-(3-pentadecylphenoxy)
butylamide] acetanilide.

(Y-5) α-(1-benzyl-2,4-dioxo-3-imitasolicinyl)-α-pivalyl-2-chloro5-[γ-(
2,4-di-t-amylphenoxy)butyramide]acetanilide.

(Y-6) α-(4-(1-benzyl-2-phenyl-3,5-dioxo-1,2,4-1 riazolidinyl)]-]]]α
-pivalyl-2-chloro-5-(2,4-di-t-amylphenoxy)butyramide]acetanilide.

(Y-7) α-acetoxy-α-(3-[α-(2,4-di-t-
amylphenoxy)butyramide]benzoyl)-2-
Methoxyacetanilide.

(Y-8) α-(3-[α-(2,4-di-t-amylphenoxy)butyramide]benzoyl)-2-methoxyacetanilide.

(Y-9) α-[4-(4-benzyloxyphenylsulfonyl)
phenoxy]-α-pivalyl-2-chloro-5-[γ-
(2,4-di-t-amylphenoxy)butyramide]
Acetanilide.

(Y-10) α-pivalyl α-(4,5-dichloro-3(2H-pyridazol-2-yl)-2-chloro-5-[(hexadecyloxycarbonyl)methoxycarbonyl]acetanilide.

(y-11) α-pivalyl α-(4-(p-'70lophenyl)-
5-oxo-Δ2-tetrazolin-1-yl-2-chloro-5-[α-(dodecyloxycarbonyl)ethoxycarbonyl]acetanilide.

(Y-12) α-(2,4-dioxo-5,5-dimethyloxazolidin-3-yl)-α-pivalyl-2-chloro-5-[
α-(2,4-di-t-amylphenoxy)butyramide]acetanilide.

(Y-13) α-hibivalyl-α-4-(1-methyl-2-phenyl-3,5-dioxo-1,2,4-triaziridinyl)
]-]]][2-chloro5-γ-,4-di-t-amylphenoxy)butyramide]acetanilide.

(Y-14) α-hihariru α-C4-(p-ethylphenyl)-5
-Oxo-Δ2-tetrasilyl-yl]-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)butyramide]acetanilide.

(M-1) ] -(2,4,6-trichlorophenyl)-3-(3
-(2,4-di-t-amylphenoxyacetamide)
Penzamide]-5-pyrazolone.

(M-2) ] -(2,4,6-trichlorophenyl)-3-(3
-dodecylsuccinimidobenzamide)-5-pyrazolone.

(M-3) 4.4'-methylenebis(1-(2,4,6-1-lichlorophenyl)-3-(3-(2,4-di-t-amylphenoxyacetamide)benzamide]-5 = pyrazolone) (M-4) 1-(2,4,6-dolichlorophenyl(2-chloro-5-octadecylsuccinimidoanilino)-5-pyrazolone.

(M-5) 1-(2-chloro-4,6-dimethylphenyl)-3-
(3-[:α-(3-pentadecylphenoxy)butyramide]penzamide)-5-pyrazolone.

(M-6) 1-(2,4,6-drichlorophenyl-4-5-occudecenylcarbamoylanilino)
-5-pyrazolone.

(M-7) 1-(2,4,6-drichlorophenylu-3-(4-[
α-(3-pentadecylphenoxy)butyramide]phenyl)-4-ethoxy-5-pyrazolone.

(M-8) 1-(2,46-trichlorophenyl)-3-(2-chloro-5-tetradecanamidoanilino)-5-pyrazolone.

(M-9) 1-(2,4,6-trichlorophenyl)-3-(2-
Chloro-5-[α-(3-t-butyl-4-hydroxyphenoxy)tetradecanamide anilino)-5-pyrazolone.

(M-10) 1-(2,4,6-trichlorophenyl)-3-(3-
(2,4-di-t-amylphenoxyacetamide)penzamide-4-acetoxy-5-pyrazodine.

(M-11) 1-(2,4,6-dolichlorophenyl(3-(2,
4-Ct-amylphenoxyacetamido)benzamide]-4-ethoxycarbonyloxy-5-pyrazolone.

(M-12) 1-(2,4,6-drichlorophenyl[3-(2,4-di-t-alumiphenoxyacetamido)penzamide)-4-(4-chlorocinnamoyloxy)-5-pyrazolone .

(M-13) 4,4'-Benzylidenebis(1-2,4,6-trichlorophenyl)-'312-ri-4-5-[γ-(2,
4-di-t-amylphenoxy)butyramide]anilino)-5-pyrazobutyramide].

(M-14) 4,4'-benzylidene bis(1-(2,3,4,5,
6-pentachlorophenyl)-3-(2-chloro-5-
[γ-(2,4-di-t-amylphenoxy)butyramide]anilino)-5-pyrazoylamide].

(M-15) 4,4'-(2-chloro)benzylidenebis[1-(2
,4,6-trichlorophenyl)-3-(2-ri40-
5-Dodecylsuccinimidoanilino-5-pyrazolone.

(M-16) 4,4'-methylenebis(1-(2,4,6-drichlorophenyl-amylphenoxy)butyramide]benzamide)-
5-pyrazoencephalon].

(M-17) 1-(2,6-cyclo-4-methoxyphenyl-3
-(2-methyl-5-acetamidoanilino-5-pyrazolone.

(M-18) 1-(2-di4-4,6-dimethylphenyl)-3-
(2-Methyl-5-chloroanilino)-5-pyrazo bleaching.

(M-19) 1-(2,4,6-1-lichlorophenyl)-3-(4
-nitroanilino)-5-pyrazobution.

(M-20) 1-(2,4,6-trichlorophenyl)-3-(2-
Chloro-5-octadecenylsuccini/imidoanilino)-5-pyrazolone.

(M-21) 1-(2,4,6-trichlorophenyl)-3=(ll
Rolow 5-tridecanamide anilino)-5-pyrazolone.

(C-1) 1-Hydroxy-N-Cδ-(2,4-di-t-amylphenoxy)butyl]-2-naphthamide.

(C-2) 2,4-dichloro-3-methyl-6-(2,4-di-t
-amylphenoxyacetamide)phenol.

(C-3) 2,4-dichloro-3-methyl-6-[α-(2,4-
di-t-amylphenoxy)butyramidophenol.

(C-4) 1-Hydroxy-4-(3-nitrophenylsulfonamide)-N-Cδ-(2,4-di-t-amylphenoxy)butyl-2-naphthamide.

(C-5) 1-Hydroxy-4-((β-methoxyethyl)carbamoyl]methoxy-N-[δ-(2,4-di-t-amylphenoxy)butyl-2-naphthamide.

(C-6) 1-Hydroxy-4-(isopropylcarbamoyl)methoxy-N-dodecyl-2-naphthamide.

(C-7) 2-perfluorobutyramide-5-[α-(2,4-
di-t-amylphenoxy)hexanamide]phenol.

(C-8) 1-Hydroxy-4-(4-nitrophenylcarbamoyl)oxy-N-[δ-(2,4-di-t-amylphenoxy)butyl-2-naphthamide.

(C-9) 2-(α, α, β, β-tetrafluoropropionamide)-5-(α-(2,4-di-t-amylphenoxy)butyramide diphenol.

(C-10) 1-Hydroxy-N-dodecyl-2-naphthamide.

(C-11) 1-hydroxy-4-nitrophenoxy-N-[δ-
(2,4-di-t-amylphenoxy)butylcou 2-
naphthamide.

(C-12) 1-Hydroxy-4-(1-phenyl-5-tetrazolyloxy)-N-(δ-(2,4-di-t-amylphenoxy)butyl]-2-naphthamide.

(C-13) 2-(α,α,β,β-tetrafluoropropionamide)-4-β-chloroethoxy-5-[α-(2,4-
di-t-aminophenoxy)butyramide diphenol.

(C-14) 2-chloro-3-methyl-4-ethylcarbamoylmethoxy-6-[α-(2,4-di-t-amylphenoxy)butyramide diphenol.

When the coupler used in the color photosensitive material according to the present invention is present in the color photosensitive material, it is generally 5 to 50 mol%, preferably 10 to 30 mol%, based on silver halide.
and when present in the developer, generally 0.5 to 3.0 g/l, preferably 1.0 to 2.0 u
used in

In this case, each of the yellow, magenta, and cyan couplers may be used alone or in combination of two or more kinds, and when two or more kinds are used in combination, the amounts mentioned above are sufficient.

The silver halide emulsion used in the color light-sensitive material according to the present invention is generally one in which silver halide grains are dispersed in a hydrophilic colloid, and the silver halide includes silver chloride, silver bromide, silver iodide, and chloride. These include silver halides, silver iodobromide, silver chloroiodobromide, and mixtures thereof, and these silver halides can be produced by various methods such as an ammonia method, a neutral method, a so-called conversion method, and a simultaneous mixing method.

In addition, gelatin and derivative gelatin such as phthalated gelatin and malonated gelatin are generally used as hydrophilic colloids for dispersing silver halide. Gum arabic, alginic acid, casein, partially hydrolyzed cellulose derivatives, partially hydrolyzed polyvinyl acetate, polyacrylamide, imidized polyacrylamide, polyvinylpyrrolidone, and copolymers of these vinyl compounds can also be used.

Furthermore, these silver halide emulsions can be optically sensitized using various sensitizing dyes in order to impart photosensitivity in the desired photosensitive wavelength range, and these sensitizing dyes can be cyanine dyes, merocyanine dyes or complex Cyanine dyes, etc., and these sensitizing dyes can be used alone or in a mixture of two or more, and if necessary, gold compounds, noble metal salts such as platinum, palladium, iridium, rhodium, and ruthenium, and sulfur compounds. , reducing substances or chemical sensitizers such as thioether compounds, quaternary ammonium salt compounds or polyalkylene oxide compounds; triazoles, imidazoles, azaindenes, benzothiazoliums, zinc compounds, cadmium compounds, mercapkuns, etc. Stabilizers such as chromium salt, zirconium salt, mucochloric acid, aldehyde type, vinyl sulfone type, polyepoxy compound, active halogen compound, ketone compound, acryloyl type, triethylenephosunamide type, ethyleneimine type hardening agent; glycerin , dihydroxyalkane plasticizers such as 1,5-bentanediol; fluorescent brighteners; antistatic agents; and coating aids. The resulting silver halide emulsion contains a dispersion of the compounds represented by the general formulas [■] and [formula] according to the present invention described above, and if necessary, an undercoat layer and a halation layer. A support such as a synthetic resin film such as cellulose acetate, cellulose nitrate, polycarbonate, polyethylene terephthalate, or polystyrene, baryta paper, polyethylene-coated paper, glass plate, etc., through a prevention layer, an intermediate layer, a yellow filter layer, a protective layer, etc. A color photosensitive material is obtained.

The silver halide emulsion layer constituting the color light-sensitive material according to the present invention is a red-sensitive silver halide emulsion layer that forms a cyan dye image, and a green-sensitive silver halide emulsion layer that forms a magenta dye image. and is a blue-sensitive silver halide emulsion layer forming a yellow dye image.

The color light-sensitive materials according to the present invention may have only one silver halide emulsion layer, or may have two or more layers, but in particular silver halide emulsions having three different color sensitivities may be used. Color photosensitive materials having layers are preferred.

Further, the number of silver halide emulsion layers having the same color sensitivity may be not limited to one, but may be two or more.

Although the color light-sensitive material according to the present invention can be applied to a coupler-containing inner-type color light-sensitive material or an outer-type color light-sensitive material containing a coupler in a developing solution, it is particularly advantageous to a coupler-containing inner-type color light-sensitive material, and is suitable for exposure to light. After that, it is advantageous to carry out color development using a color development method.

Furthermore, the coupler and the color developing agent are protected so that they do not come into contact with each other when unexposed and are present in the same layer, and the coupler is also included in a color photosensitive material that can come into contact with each other after exposure, or in a color photosensitive material that contains the coupler. It can be applied to color light-sensitive materials in which a color developing agent is contained in a layer that does not contain color, and the color developing agent is moved when an alkaline processing liquid is permeated therein, so that it can come into contact with a coupler. The compound according to the present invention can be added to the light-sensitive element and/or the image-receiving element of the photosensitive material, and it is particularly advantageous to have it present in the image-receiving element.

In the reversal process, the image is developed in a black and white negative developer, then exposed to white light or treated in a bath containing a fogging agent such as a boron compound, and then color developed in an alkaline developer containing a color developing agent.

At this time, there is no problem even if a fogging agent is included in an alkaline developer containing a color developing agent.

After color development, a silver image is obtained by bleaching with a bleaching solution containing ferricyanide or a ferric salt of aminopolycarboxylic acid as an oxidizing agent, and then fixing with a fixing solution containing a silver salt solvent such as thiosulfate. and residual silver halide,
Leaves a dye image.

Instead of using a bleaching solution and a fixing solution, bleach-fixing can also be carried out using a one-bath bleach-fixing solution containing an oxidizing agent such as a ferric salt of an aminopolycarboxylic acid and a silver salt solvent such as thiosulfate.

Further, in combination with color development, bleaching, fixing, or bleach-fixing, various treatments such as prehardening, neutralization, water washing, termination, and stabilization may be performed.

In particular, processing steps in which the color light-sensitive material according to the present invention is advantageously developed include, for example, color development, washing with water as necessary, bleach-fixing, washing with water, stabilization as necessary, and drying. This is carried out at a high temperature of, for example, 30° C. or higher and within an extremely short period of time.

Aromatic primary amine compounds which are particularly useful color developing agents used for color development of the color photographic material according to the present invention include primary phenylenediamines, aminophenols and derivatives thereof, such as the following: The following can be cited as a representative example.

N,N-dimethyl-p-phenylenediamine, N,N-
Diethyl-p-phenylenediamine, N-carbamidomethyl-N-methyl-p-phenylenediamine, N-carbamidomethyl-N-tetrahydrofurfuryl-2-methyl-p-phenylenediamine, N-ethyl-N-carboxymethyl- 2-methyl-p-phenylenediamine, N
-Carbamidomethyl-N-ethyl-2-methyl-p-phenylenediamine, N-ethyl-N-tetrahydrofurfuryl-2-methyl-p-aminephenol 3-acetylamino-4-aminodimethylaniline, N-ethyl-
N-β-methanesulfonamidoethyl-4-aminoaniline, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline, N-methyl-
N-β-sulfoethyl-p-phenylenediamine, 0-
Aminephenol, p-aminephenol, 5-amino-2-oxy-toluene N-ethyl-N-β-methoxyethyl-3-methyl-4-aminoaniline, N-ethyl-N-β-hydroxyethyl-3- Methyl-4-aminoaniline, N-ethyl-N-(2-(2-(2-methoxyethoxy)ethoxy]ethyl)-3-methyl-4-
Inorganic acids such as hydrochloric acid, sulfuric acid, or p-
Salts of organic acids such as toluenesulfonic acid.

These color developing agents may be used alone or in combination of two or more.

In addition to the above-mentioned color developing agent, various additives are added to the color developing solution as necessary.

Main examples include alkali agents such as alkali metal and amminilum hydroxides, carbonates, and phosphates, acetic acid,
Buffers such as boric acid, pH adjusters, development accelerators, antifoggants, stain or sludge inhibitors, interlayer effect accelerators,
Preservatives, etc.

Bleaching agents used for bleaching include ferricyanide such as red blood salt, dichromate, permanganate, hydrogen peroxide, mustard powder, and aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, and iminodiacetic acid. There are metal complex salts of polycarboxylic acids such as malonic acid, tartaric acid, malic acid, and diglycolic acid, ferric chloride, and the like, and these may be used alone or in combination as necessary.

Inoculum additives such as bleaching accelerators may be added to this bleaching solution as necessary.

Fixing agents used in the fixing process include thiosulfates such as sodium thiosulfate and ammonium thiosulfate, and cyanide urea derivatives, and various additives such as fixing accelerators may be added to this fixing process as necessary. can.

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

Example 1 The magenta coupler shown in Table 1-1 and the compound of the present invention were dissolved in the solvent shown in the same table, and then added to 500 cc of a 5% gelatin aqueous solution containing 2.5 g of sodium dodecylbenzenesulfonate, and then mixed with a homogenizer. The resulting dispersion was added to a green-sensitive silver chlorobromide (containing 80 mol% silver bromide) emulsion, and N, N', and N were added as hardeners.
2% of '-triacryloyl-6H-8-1-lyazine
Methanol solution 10ml 1. was coated on polyethylene coated paper and dried to obtain a silver halide photographic material.

After performing light wedge exposure on these samples, they were processed according to the processing method shown below.
Sensitome l-IJ- was carried out using Type-6 (manufactured by Konishiroku Photo Industry Co., Ltd.) and the results are shown in Table 1-2.

Processing process (30°C) Processing time Color development...3 minutes 30 seconds Bleaching and stabilization 0 seconds... Minutes 30 seconds Water washing...2 minutes stabilization... Dry for 1 minute. Composition of drying color developer: Benzyl alcohol 5. omeSodium hexametaphosphate 2.5g Anhydrous sodium sulfite 1.9g Sodium bromide
1.4g potassium bromide
0.5g boric acid (Na2 B4o□*
]0H20) 39.19N-ethyl-N-
β-Methanesulfonamidoethyl-4-aminoaniline sulfate 5.0g Add water to make 11, and adjust the pH to 1030G using sodium hydroxide.

Bleach-fix solution composition Ethylenediaminetetraacetate iron ammonium 61.0g Ethylenecyaminetetraacetate diammonium 5. OI Ammonium Thiosulfate 124.59 Sodium Metabisulfite 13. :1 Anhydrous sodium sulfite
Add 2.7 g of water to make the solution 11, and adjust the pH to 6.5 using aqueous ammonia.

Stabilizing liquid composition: Glacial acetic acid 20mg Water 80
After adding 0ml and adjusting the pH to 3.5 to 4.0 by adding sodium acetate, water was further added to make 11.

represents.

The same applies below.

Comparative samples include Comparative Sample-1: General formula (I) and C of the present invention from the sample.
Sample comparative sample-2 excluding the compound represented by II): Comparative sample-3 excluding the compound represented by the general formula of the present invention [IJ]; Comparative sample-4 excluding the compound: The following compound was used in place of the compound represented by the general formula [IJ] of the present invention.

(Described in U.S. Patent No. 3,432,300) No. 1-
From the results in Table 2, it is clear that the compounds of the present invention are excellent in controlling leg gradation and effectively preventing fogging.

Example-2 Samples-5 and 9 prepared in Example-1 were left at room temperature for two months, treated in the same manner as in Example-1, and subjected to sensitome l-IJ-. Shown in the table.

As is clear from Table 2-1, the combination of the compounds of the present invention is more effective in preventing fog during storage than other known combinations of compounds, and gamma does not change during storage.

Example-3 After dissolving the yellow coupler, cyan coupler and the compound of the present invention shown in Table 3-1 in the solvent shown in the same table, the solution was dissolved in sodium dodecylbenzenesulfonate 3.
After adding 0g of gelatin to 500cc of 5% gelatin aqueous solution, the dispersion was dispersed with a homogenizer, and the resulting dispersion was mixed with blue-sensitive silver chlorobromide (containing 90 mol% silver bromide) and red-sensitive salt, respectively. silver bromide (containing 87 mol% silver bromide) and 5% of triethylenephosphonamide as a hardening agent.
After adding 10 ml of % methanol solution, the mixture was coated on polyethylene coated paper and dried to obtain a silver halide photographic light-sensitive material.

This was photographically processed and subjected to sensitometry in the same manner as in Example 1. The results are shown in Table 3-2.

As shown above, it can be seen that the use of the compound of the present invention is effective in adjusting leg gamma and preventing fog.

Note that the comparative sample is the same as in Example-1.

Example-4 Samples-1 and 7 prepared in Example-3 were left at room temperature for two months, treated in the same manner as in Example-1, and sensitometrically performed. The results are shown in Table 4-1. .

As shown in the table above, it can be seen that the combination of the compounds of the present invention is more effective in preventing fogging during storage than other known combinations of compounds, and gamma does not change during storage.

Example 5 A silver halide color photographic material was prepared by sequentially coating the following layers on polyethylene coated paper from the support side.

The polyethylene coated paper has an average molecular weight of 100.
000, 200 parts by weight of polyethylene with a density of 0.95,
Polyethylene 2 with average molecular weight 2,000 and density 0.80
0 parts by weight was mixed with 6.8% by weight of anatase-type titanium oxide, and a coating layer with a thickness of 0.35 mm was formed on the surface of high-quality paper with a basis weight of 1709/m by extrusion coating method, and the back side was coated with polyethylene. A coating layer having a thickness of 0.040 mm was made by chiseling and used as a support for the present invention.

The polyethylene-coated surface of this support was pretreated by corona discharge, and then each layer was sequentially applied.

First layer: A blue-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 95 mol % of silver bromide. Sensitized using 2.5 x 10 moles of sensitive dye (1
Silver amount: 350 mg/m Contains 2 x 10 moles of yellow coupler (Y-13) per mole of silver halide dissolved and dispersed in DBP (using so-propyl alcohol)
It is coated so that it becomes 2.

2nd layer: 300 mg/m of (Hq-1) dissolved and dispersed in DBP
2. 2-(2'-hydroxy-3') as an ultraviolet absorber
, 5'-di-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-butylphenyl)penztriazole, 2-(2'-hydroxy-3'
-t-phthyl-5'-methylphenyl)-5-chlorobenzotriazole and 2-(2'-hydroxy-3
' , 5' t-butylphenyl)-5-chloro-
A layer of gelatin containing 200 m9 /yj of a mixture of benzo) IJ azole is coated in a gelatin layer of 2ooTnv'm2.

Third layer: A green-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 85 mol % of silver bromide, the emulsion containing 450 g of gelatin per mol of silver halide and the following per mol of silver halide: DBP and TCP (
Mazenk Kavlar (M-6) dissolved and dispersed in mixed HBS with a mixing ratio of 2:1) was added at 1 mol per mole of silver halide.
° Contains 5X10' moles and has a silver content of 380 m9/m
”It is coated to make it look like this.

4th layer: (Hq-1,)30■/m' dissolved and dispersed in DBP
and 2-(2'-hydroxy-37
,5/-di-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-1-butylphenyl)benzotriazole, 2-(2'-hydrobutylphenyl)3'
-t-butyl-5'-methylphenyl)-5-chlorobensotriazur and 2-(2'-hydroxy-3
7,5'-t-butylphenyl) = 5-riyamashiichibenzo I-IJ azole mixture (2:1.5:1.5
: 2) A gelatin layer containing 500mg/m2 is coated to give a gelatin density of 2000μ/m2.

Fifth layer: A red-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 85 mol% of silver bromide. The cyan coupler (C-3) was sensitized using 2.5 x 10 mol of the sensitizing dye, dissolved in DBP and decomposed, containing 3.5 x 10 -1 mol per mol of silver halide, and the amount of silver was 27.
It is coated so that it is 0 ynti/m.

Sixth layer: Gelatin layer coated with gelatin at a concentration of 100 mg/m2.

Silver halide 1 used for each photosensitive layer (1st, 3rd, 5th layer)
They were prepared by the method described in Mol Patent Publication No. 46-7772, chemically sensitized using sodium thiosulfate pentahydrate, and 4-hydroxy-6-methyl-
1,3,3a,7-tetrazaindene, bis(vinylsulfonylmethyl)ether as a hardening agent and saponin as a coating aid.

Further, the compound according to the present invention was dispersed in the above sample according to the method shown in Example-1, and contained as shown in Table 5-1.

The samples prepared by the above method were subjected to photographic processing and sensitometry using the method of Example 1. The results are shown in Table 5-2.

Comparative samples include Comparative Sample-1: A sample prepared by excluding the compound represented by the general formula (1) of the present invention. Comparative Sample-2. Sample comparison prepared by excluding the compound represented by the general formula (10) of the present invention. Sample-32 A sample prepared using (described in U.S. Pat. No. 3,432,300) instead of the compound represented by the general formula 〇] of the present invention Comparative Sample-4 ] (described in JP-A-51-6024) instead of the compound shown in It can be seen that it is also effective in prevention.

Further, Table 5-3 shows the results when the above sample was treated with a processing solution having the color developing solution composition (B) shown below.

Color developer composition CB) The processing steps when a color developer having the composition CB) is used are as follows.

Color development 322°G 90 seconds Bleach fixing 50 seconds 〃 Wash with water for 30 seconds The bleach-fix solution used was the same as in Example-1.

As shown in the table above, it can be seen that even when the treatments are different, the combination of the compounds of the present invention exhibits excellent gradation adjustment effects and fog prevention effects.

Example-6 The sample prepared in Example-5 was left at room temperature for two months, then subjected to the same treatment (development treatment (Al)) as in Example-5, and sensitometry was performed. The results are shown in Table 6-1. show.

As shown in the results in the table above, it can be seen that the combination of compounds of the present invention effectively maintains the gradation adjustment effect and antifogging effect even when stored.

Example-7 The sample prepared in Example-5 was continuously processed into a 100 cm2 sample without replenishment using the treatment liquid 11 shown in Example-1 according to the treatment steps shown in Example-1. 5
The results after processing 0 sheets are shown in Table 7-1.

As shown in the results in the above table, even when the compound of the present invention is continuously processed, the sensitivity of the conventionally known comparative sample-4 is decreased and the tone is soft (
It can be seen that the compound of the present invention causes far less desensitization and softening of tone, whereas the gamma value decreases.

Example-8 Compound (34) 28 of the present invention? and (Hq-1
) 245g to DBP15cc and ethyl acetate 50cc
After adding it to 120 cc of a 5% aqueous gelatin solution containing sodium dodecylbenzenesulfonate, it was dispersed with a homogenizer, and the resulting dispersion was added to 300 cc of a green-sensitive silver chlorobromide emulsion (silver chloride 50 mol%). After adding
The mixture was coated on polyethylene coated paper and dried to obtain a silver halide photographic material.

This silver halide photographic light-sensitive material was subjected to light wedge exposure according to the sensitometric method, and then heated at 24°C according to the following order.
treated at a temperature of

Processing solutions having the following formulations were used as the first developer, color developing solution, bleaching solution, and fixing solution.

Color developer prescription Bleaching solution prescription Fixer prescription The obtained color photographic material was subjected to sensitometry according to the method of Example 1. The results are shown in Table 8-1.

The comparative sample was prepared in the same manner as shown in Example-5.

Claims (1)

[Claims] 1. At least one compound represented by the following general formula [1]
A silver halide color photographic light-sensitive material characterized by containing a combination of a species and at least one compound represented by the following general formula (II) [wherein R1 and R2 are each a substituted or unsubstituted alkyl group] , alkenyl group, cycloalkyl group. Aryl group or heterocyclic group; and R3゜R4
, R5 and R6 are hydrogen atoms, halogen atoms, substituted and unsubstituted alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, alkoxy groups, alkylthio groups,
heterocyclic thio group, aryloxy group, arylthio group,
An acyl group, an acylamino group, an alkylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, or a sulfamoyl group. [In the formula, R7, R8, R9 and R10 are hydrogen atoms,
Halogen atoms, substituted and unsubstituted alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, alkoxy groups, alkylthio groups, aryloxy groups, arylthio groups, acyl groups, acylamino groups, alkylamino groups,
Alfuxica/l/represents a carbonyl group, an aryloxycarbonyl group, a carbamoyl group, or a sulfamoyl group. ]