JPH06258799A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide photographic sensitive material superior in solubility of photographic reagents and dispersion stability, good in the color reproduction performance of a dye, free from discoloration, and superior in the color developing performance of a diffusion-resistant dye-forming coupler. CONSTITUTION:The silver halide photographic sensitive material is characterized by containing in at least one layer on a support, at least one of compounds represented by the general formula in which R<1> is an aliphatic or aryl group; X is a carbon atom group necessary to form a 5-, 6-, or 7-membered ring together with N atom; n is 1, 2, or 3; m is 0 or 1; when n is 2 or 3, plural X may be the same or different; and when n is 1, plural R<1> and n may be the same or different, respectively.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide light-sensitive material, and more specifically, a diffusion-resistant coupler for forming a diffusion-resistant dye is incorporated in a silver halide emulsion to form an aromatic primary amine. The present invention relates to a silver halide color photographic light-sensitive material which forms a color image by processing with a color developing solution containing a color developing agent and then with a processing solution having a bleaching ability.

[0002]

2. Description of the Related Art Conventionally, photographically useful reagents which are poorly soluble in water (eg, oil-soluble couplers, antioxidants used for preventing fading, color fog or color mixture (eg, alkylhydroquinones, alkylphenols, chromanes, coumarones). ), A hardener, an oil-soluble filter dye, an oil-soluble ultraviolet absorber, an oil-soluble optical brightener, a DIR compound (for example, DI
R hydroquinones, non-colored DIR couplers), developing agents, dye developing agents, DDR redox compounds, DDR couplers} are suitable oil formers, ie, soluble in high-boiling solvents, hydrophilic organic colloids, especially of gelatin. Used as a dispersion in the presence of a surfactant in a solution in a hydrophilic organic colloid layer (eg, photosensitive emulsion layer, filter layer, back layer, antihalation layer, intermediate layer, protective layer) To be As such a high boiling point organic solvent, a phthalic acid ester compound or a phosphoric acid ester compound is generally used.

The phthalic acid ester compounds and phosphoric acid ester compounds, which are high-boiling point organic solvents, have an affinity for colloids such as gelatin, dispersibility of couplers, influence on the stability of the color image, and color image formation. It has been widely used because of its excellent effects on hue, chemical stability in light-sensitive materials, low availability, and the like. However, these known high-boiling point organic solvents (for example, phthalic acid ester compounds and phosphoric acid ester compounds) are particularly suitable for the light-sensitive materials of recent years that are required to have high performance, especially for light, heat, and humidity of color images. It was still insufficient in terms of preventing the resulting discoloration and stain generation. As described above, various requirements are imposed on the high-boiling-point organic solvent used in recent light-sensitive materials. For example, it can be easily obtained or manufactured at low cost, it has excellent solubility and dispersion stability of photographic reagents, it does not adversely affect developability and photographic properties, it has excellent safety and no environmental impact. It is a general requirement that it has excellent chemical stability and, in the case of a color light-sensitive material, has an excellent effect of preventing fading of a color image.

In color light-sensitive materials, dyes formed from couplers, particularly pyrazoloazole-based magenta dyes and pyrroloazole-based cyan dyes, are easily associated with each other in the film film, and the maximum absorption wavelength of absorption by the associated product. Is different from that of the dye monomer, and as a result, too large absorption by the aggregate is not preferable for color reproduction. Further, if the maximum absorption wavelength of the dye can be adjusted to a longer wavelength or a shorter wavelength by an additive or the like used in the same layer as the dye without changing the structure of the dye itself, a color light-sensitive material with favorable color reproduction can be obtained at a low cost. It can be provided at the manufacturing cost.

In order to solve such a problem, the maximum absorption wavelengths of the yellow, magenta and cyan dyes are made shorter and longer in an organic solvent having a high boiling point which can serve as a dispersion medium such as a dye-forming diffusion resistant coupler. It has been found that some of them have the effect of suppressing or promoting the association of dyes and changing the absorption waveform, and thus, they are attracting attention. Examples thereof include phosphine oxide, phosphinic acid ester, and phosphonic acid ester described in JP-A-63-301941. However, in these compounds, it is often difficult to satisfy both the requirement of the hue of the dye and the improvement of the solubility and the dispersion stability of the materials required when used as a dispersion medium. In many cases, the resulting dye-forming diffusion-resistant coupler has a reduced coloring property. When the compound is used in the same layer as the dye-forming diffusion-resistant coupler, the heat and humidity of the dye formed by the coupler,
In many cases, fading due to light deteriorated.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide light-sensitive material excellent in solubility and dispersion stability of a photographic reagent. Furthermore, the object of the present invention is to have excellent solubility and dispersion stability of photographic reagents,
It is an object of the present invention to provide a silver halide color photographic light-sensitive material which has good color reproducibility of dyes, has no fading, and has excellent color forming properties of dye-forming diffusion resistant couplers.

[0007]

The above object of the present invention is characterized in that at least one layer on a support contains at least one compound represented by the following general formula (I). This is achieved by a photosensitive material (hereinafter referred to as a photosensitive material).

[0008]

[Chemical 3]

(Wherein R ¹ represents an aliphatic group or an aryl group, and X represents a carbon atom group necessary for forming a saturated or unsaturated 5- to 7-membered ring by linking with a nitrogen atom. .N
Represents an integer of 1 to 3, and m represents 0 or 1. n is 2
When X is 3, X may be the same or different, and when n is 1, R ¹ and m may be the same or different. )

The present inventor particularly processes the compound represented by the general formula (I) with a color developing solution containing an aromatic primary amine color developing agent and processing with a processing solution having a bleaching ability. By doing yellow coupler, magenta coupler,
Yellow dye formed from each cyan coupler,
The inventors have found that the association of magenta dye and cyan dye is prevented, the maximum absorption wavelength and absorption waveform are affected, and the color reproducibility, fastness, and hue are improved, and the present invention has been completed. It was also found that even if the compound represented by the general formula (I) is used as a dispersion medium, it has excellent solubility, dispersion stability and the like. The compound represented by formula (I) is described in detail below.

When the substituent in the present specification contains an aliphatic moiety, the aliphatic moiety may be linear, branched or cyclic (for example, cycloalkyl) unless otherwise specified, and is saturated. Or may be unsaturated (for example, alkenyl), and may be substituted or unsubstituted. Alkyl is preferred as the aliphatic moiety. When the substituent in the present specification includes an aryl moiety, the aryl moiety may be substituted or unsubstituted, and may be a single ring (eg, phenyl) or a condensed ring (eg,
Naphthyl). Phenyl is preferred as the aryl moiety. Further, when the substituent in the present specification includes a heterocyclic moiety, examples of the heteroatom forming the ring of the heterocyclic moiety include a nitrogen atom, an oxygen atom, and a sulfur atom, and the number of rings is 5 to 8 members. Preferably. The carbon atom or nitrogen atom on the ring may be substituted or unsubstituted, and may be a monocycle or a condensed ring.

The above-mentioned substituents on the aliphatic moiety, aryl moiety, and heterocyclic moiety are aliphatic group, aryl group, aliphatic oxy group, aryloxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, acylamino. Group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxysulfonyl group, heterocyclic group, acyl group,
Examples thereof include an acyloxy group, a sulfonyloxy group, a cyano group, a nitro group and a halogen atom. Moreover, the carbon number of the substituent in this specification is the total carbon number of the whole substituent.

In the general formula (I), R ¹ is an aliphatic group such as methyl, isopropyl, t-butyl, allyl, cyclohexyl, benzyl, 2-ethylhexyl, octyl,
It represents a 3,5,5-trimethylhexyl, dodecyl or aryl group, for example phenyl, 2-naphthyl, 2-chlorophenyl, 3-methylphenyl, 4-dodecylphenyl, 4-methoxyphenyl.

When R ¹ is an aliphatic group, it preferably has 3 to 30 carbon atoms, and particularly preferably 6 to 24 carbon atoms. R ¹ as an aliphatic group is preferably unsubstituted,
Moreover, a branched chain is preferable. When R ¹ is an aryl group, it preferably has 6 to 30 carbon atoms, and particularly 6 to 30 carbon atoms.
24 is preferred.

In the general formula (I), m is 0 or 1.
When m is 0, R ¹ is preferably an aryl group, and particularly preferably a phenyl group.

In the general formula (I), X represents a carbon atom group which is linked to a nitrogen atom to form a saturated or unsaturated 5- to 7-membered ring. Carbon atoms on the ring may be substituted and may be further fused with a saturated or unsaturated ring. The substituent of the carbon atom on the ring may be the same as those mentioned above as the substituent of the aliphatic moiety or the like. The saturated or unsaturated ring formed by X and a nitrogen atom preferably has 4 to 30 carbon atoms, and more preferably has 6 to 24 carbon atoms. Preferred examples of the saturated or unsaturated ring formed by X and a nitrogen atom are shown below.

[0017]

[Chemical 4]

The ring formed by X and the nitrogen atom is
A saturated 5- or 6-membered ring is particularly preferable.

In the general formula (I), n represents an integer of 1 to 3. When n is 2 or 3, X may be the same or different, but are preferably the same. n is 1
In this case, R ¹ and m may be the same or different, but it is preferable that R ¹ and m are the same. n is preferably 2 or 3, and particularly preferably 3.

Incidentally, no coupler residue is contained in R ¹ and X.

Specific examples of the compound represented by the general formula (I) used in the present invention are shown below, but the present invention is not limited to these and includes all compounds included in the general formula (I). Can be used.

[0022]

[Chemical 5]

[0023]

[Chemical 6]

[0024]

[Chemical 7]

[0025]

[Chemical 8]

The synthetic examples of the compound (I) represented by the general formula (I) and used in the present invention are shown below, but the invention is not particularly limited thereto, and the compound (I) can be synthesized by various methods. obtain.

Synthesis of compound S-3

[0028]

[Chemical 9]

93.7 g (1.1 mol) of piperidine (2)
Was dissolved in 300 ml of tetrahydrofuran, and the mixture was stirred under ice-water cooling, and then dichlorophenyl phosphate (1) 4 was added thereto.
8.8 g (0.25 mol) was added dropwise over 30 minutes. After stirring at room temperature for 30 minutes, the mixture was refluxed for 1 hour. After cooling, ethyl acetate and water were added, the organic layer was separated and extracted, and washed with water. The extract was dried over magnesium sulfate, concentrated, and purified by silica gel column chromatography (developing solvent ethyl acetate: hexane = 1: 1 column) to obtain a compound represented by S-3. The yield was 59.5 g (81.0%).
It was confirmed by NMR and MS spectra that it had the structure of S-3.

Synthesis of Compound S-36

[0031]

[Chemical 10]

1,2,3,4-tetrahydroisoquinoline (4) 40.4 g (0.3 mol) and 1,8-diazabicyclo [5,4,0] -7-undecene (5) 50.2 g
(0.33 mol) was dissolved in 100 ml of dimethylacetamide and stirred, and phosphorus (3) 1
5.8 g (0.1 mol) was added dropwise over 30 minutes, and the mixture was further heated with stirring at 100 ° C. for 4 hours. After cooling, ethyl acetate and water were added to separate and extract the organic layer, which was washed with water. After drying over magnesium sulfate, the mixture was concentrated and purified by silica gel column chromatography (developing solvent; ethyl acetate) to obtain a white solid. Yield 17.1 g (38.5
%) And the melting point was 125 ° C. NMR and MS
It was confirmed by the spectrum that it had a structure represented by S-36.

The compound represented by the general formula (I) of the present invention is contained in at least one layer on a support, but it may be a hydrophilic colloid layer and at least one dye-forming diffusion-resistant coupler. It can be preferably contained in the contained silver halide emulsion layer.

The compound represented by the general formula (I) of the present invention is a non-color-forming compound which does not form a dye by a coupling reaction with an oxidized product of a developing agent, and therefore,
It has no coupler residue in the molecular structure. The compound represented by the general formula (I) of the present invention mainly functions as a high boiling point organic solvent. Here, the high boiling point means a boiling point of 175 ° C. or higher under normal pressure. The amount of the compound represented by the general formula (I) used can be changed according to the purpose and is not particularly limited. The usage amount is 1 m of light-sensitive material
0.0002 g to 20 g per ² is preferable, 0.0
The range of 0.1 to 5 g is more preferable, and the range of 0.1 to 4 is generally preferable, and the range of 0.1 to 2 is preferable, with respect to the photographically useful reagent such as a coupler.

The amount of the dispersion of the compound represented by the general formula (I) of the present invention and the photographically useful reagent such as a coupler to be used in the dispersion medium is 2 to the dispersion medium 1 in a weight ratio.
The range is 0.1, preferably 1.0 to 0.2. Here, as the dispersion medium, for example, gelatin is representative, and hydrophilic polymers such as polyvinyl alcohol can be mentioned. The dispersion of the present invention may contain various compounds according to the purpose in addition to the compound of the present invention and a photographically useful reagent. The compound represented by the general formula (I) of the present invention can be used in combination with a conventionally known high-boiling point organic solvent. When these known high-boiling organic solvents are used in combination, the compound of the present invention is preferably used in a weight ratio of 10 to the total amount of the high-boiling organic solvents.
% Or more, more preferably 30% or more.

Examples of the high boiling point solvent which can be used in combination with the compound of the present invention are described in US Pat. No. 2,322,027 and the like. Specific examples of the high boiling point organic solvent having a boiling point of 175 ° C. or higher at normal pressure include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-diphenyl phthalate). −
tert-amylphenyl) phthalate, bis (2,4-di-te
rt-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), esters of phosphoric acid or phosphonic acid (for example, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, Tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate), benzoic acid esters (for example, 2
-Ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (e.g. N, N-diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone), sulfonamides (e.g. , N-butylbenzenesulfonamide), alcohols or phenols (isostearyl alcohol, 2,4-di-tert.
-Amylphenol), aliphatic carboxylic acid esters (for example, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate),
Aniline derivative (N, N-dibutyl-2-butoxy-5
-Tert-octylaniline, etc.), hydrocarbons (for example,
Paraffin, dodecylbenzene, diisopropylnaphthalene), chlorinated paraffins, and the like. The auxiliary solvent has a boiling point of 30 ° C or higher, preferably 50 ° C.
Organic solvents having a temperature above 160 ° C. can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, and 2
-Ethoxyethyl acetate, dimethylformamide.

The photographically useful reagents which can be used in the present invention include dye-forming diffusion-resistant couplers (yellow couplers, cyan couplers, magenta couplers), as well as antioxidants used for preventing fading, color fog or color mixture (for example, Alkylhydroquinones, alkylphenols, chromanes, coumarones), hardeners, oil-soluble filter dyes, oil-soluble UV absorbers, oil-soluble fluorescent whitening agents, D
Examples thereof include IR compounds (for example, DIR hydroquinones, non-coloring DIR couplers), developers, dye developers, DDR redox compounds, DDR couplers and the like.

Examples of yellow couplers include US Pat. Nos. 3,933,501, 4,022,620, 4,326,024,
No. 4,401,752, No. 4,248,961, JP-B-58-10739
U.S. Pat.Nos. 1,425,020, 1,476,760, U.S. Patents 3,973,968, 4,314,023, 4,511,649,
European Patent Nos. 249473A, 446863A, 447969, JP-A-63-23145, JP-A-63-123047 and JP-A-1-250944.
No. 1-213648, No. 2-139544, No. 3-179042
And No. 3-203545.

Examples of magenta couplers include 5-pyrazolone compounds and pyrazoloazole compounds, and US Pat. Nos. 4,310,619, 4,351,897 and European Patent 736
36, U.S. Pat. Nos. 3,061,432 and 3,725,067, Research Disclosure, No. 24220 (June 1984)
, JP 60-33552, Research Disclosure, No. 24230 (June 1984), JP 60-43659,
61-72238, 60-35730, 55-118034, and
60-185951, U.S. Pat.Nos. 4,500,630 and 4,540,654
No. 4,556,630, International Publication No. WO88 / 04795, and the like.

Examples of cyan couplers include phenol type and naphthol type couplers, and US Pat.
2,212, 4,146,396, 4,228,233, 4,296,
No. 200, No. 2,369,929, No. 2,801,171, No. 2,772,16
No. 2, No. 2,895,826, No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,173, West German Patent Publication No.
3329729, European Patents 121365A, 249453A, U.S. Patents 3,446,622, 4,333,999, 4,775,616
No. 4,451,559, 4,427,767, 4,690,889
No. 4,254,212, 4,296,199, JP-A-61-2265
Those described in No. 8 and the like are preferable. Furthermore, JP-A-64-553
Nos. 64-554, 64-555, 64-556, 3-280964 and 3-335916, and azole couplers described in U.S. Pat. −33144
Imidazole couplers described in JP-A-64-3226
Imidazole couplers described in No. 0 or JP-A-64
The cyclic active methylene type cyan coupler described in -32260 can also be used.

In the present invention, the compound represented by the general formula (I) is the same as the cyan coupler represented by the following general formula (II) or the magenta coupler represented by the following general formula (III) among the couplers. When it is used in a single layer, it greatly affects the position of the maximum absorption wavelength of the dye and the size of the association peak, and is therefore more preferable.

[0042]

[Chemical 11]

(In the formula, Z ¹ and Z ² represent a group of nonmetallic atoms necessary for forming an azole ring in which a hetero atom is a nitrogen atom. R ² and R ³ are Hammett's substituent constant σ, respectively. Represents an electron-withdrawing group having _ap value of 0.30 or more R ⁴
Represents a hydrogen atom or a substituent. X ¹ and X ² represent a hydrogen atom or a group which is released by a coupling reaction with an oxidation product of an aromatic primary amine type color developing agent. ) Examples of the azole ring formed by Z ¹ and Z ² include the following.

[0044]

[Chemical 12]

In the formula, R ⁶ , R ⁷ and R ⁸ represent a hydrogen atom or a substituent. Z ¹ and Z ² are the above Z-2, Z-
3 is preferable, and Z-2 is particularly preferable. R ² and R ³ are electron-withdrawing groups having a Hammett's substituent constant σ _p value of 0.30 or more. The upper limit is an electron-withdrawing group having a σ _p value of 1.0 or less. Hammett's rule is to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives.
An empirical rule proposed by LP Hammett in 935, which is widely accepted today. There are σ _p and σ _m values for the substituent constants obtained by the Hammett's rule, and these values are described in many general textbooks. For example, see JA Dean's “Lange's Handbook of Chem”.
istry "12th edition, 1979 (McGraw-Hill) and" Special Issue on Chemistry ", No. 122, pages 96-103, 1979.
Detailed in the year (Nankodo). In the present invention, R ² and R ³ are defined by Hammett's substituent constant σ _p value, but it does not mean that the values known from the literatures described in these publications are limited to certain substituents, and their values It is a matter of course that even if is unknown in the literature, as long as it is included in the range when measured based on Hammett's rule.

R ² and R ³ will be described in detail. Examples of the electron withdrawing group having a σ _p value of 0.30 or more include an acyl group (eg, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl). A carbamoyl group (eg, carbamoyl, N-ethylcarbamoyl, N
-Phenylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl,
N- (4-n-pentadecanamide) phenylcarbamoyl, N-methyl-N-dodecylcarbamoyl, N-
{3- (2,4-di-t-amylphenoxy) propyl} carbamoyl), an alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl, tert-butyloxycarbonyl, isobutyloxycarbonyl, butyloxycarbonyl, Dodecyloxycarbonyl, octadecyloxycarbonyl), aryloxycarbonyl groups (eg,
Phenoxycarbonyl), cyano group, nitro group, sulfinyl group (eg, 3-phenoxypropylsulfinyl, 3-pentadecylphenylsulfinyl), sulfonyl group (eg, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), sulfonyloxy group (Methanesulfonyloxy, toluenesulfonyloxy), sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfate. Famoyl, N, N
-Diethylsulfamoyl), an alkyl group substituted with at least three or more fluorine atoms (eg, trifluoromethane, heptafluoropropane), a perfluoroaryl group (eg, pentafluorophenyl), and the like.

[0047] When the typical sigma _p value is listed sigma _p value of 0.30 or more electron-withdrawing group, a cyano group (0.66), nitro group (0.78), trifluoromethyl group (0. 5
4), carboxyl group (0.45), acetyl group (0.
50), benzoyl group (0.43), trifluoromethanesulfonyl group (0.92), methanesulfonyl group (0.72), benzenesulfonyl group (0.70), methanesulfinyl group (0.49), carbamoyl group (0.36), methoxycarbonyl group (0.45), ethoxycarbonyl group (0.45), phenoxycarbonyl group (0.44), pyrazolyl group (0.37), methanesulfonyloxy group (0.36) , A dimethoxyphosphoryl group (0.60), a sulfamoyl group (0.57), a pentafluorophenyl group (0.41), and the like.

In the general formula (II), R ² and R ³ are each preferably a cyano group, an acyl group, a carbamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, R ² is a cyano group and R ³ is-. CO ₂ -R
Further preferably, it is a group represented by ⁹ (R ⁹ represents an alkyl group or an aryl group). R ⁹ is particularly preferably a branched alkyl group.

R ⁴ , R ⁶ , R ⁷ and R ⁸ represent a hydrogen atom or a substituent, and the substituent is an aryl group (preferably having a carbon number of 6 to 30, for example, phenyl, m-acetylaminophenyl, p-). Methoxyphenyl), an alkyl group (preferably having 1 to 30 carbon atoms, for example, methyl, trifluoromethyl, ethyl, isopropyl, heptafluoropropyl, t-butyl, n-octyl, n-dodecyl), a cyano group, a formyl group, Acyl group (preferably having a carbon number of 1 to
30, for example, acetyl, pivaloyl, benzoyl, furoyl, 2-pyridinecarbonyl), a carbamoyl group (preferably having 1 to 30 carbon atoms, for example, methylcarbamoyl, ethylcarbamoyl, dimethylcarbamoyl, n).
-Octylcarbamoyl), an alkoxycarbonyl group (preferably having 1 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, diphenylmethylcarbonyl), an aryloxycarbonyl group (preferably having 7 to 30 carbon atoms, for example, phenoxy). Carbonyl, p-methoxyphenoxycarbonyl, m-chlorophenoxycarbonyl, o-methoxyphenoxycarbonyl), formylamino group, acylamino group [preferably an alkylcarbonylamino group having 1 to 30 carbon atoms (for example, acetylamino, propionylamino, Cyanoacetylamino), preferably 7 to 7 carbon atoms
A 30 arylcarbonylamino group, (for example, benzoylamino, p-trailamino, pentafluorobenzoylamino, m-methoxybenzoylamino), preferably a C4-30 hetarylcarbonylamino group,
(For example, 2-pyridylcarbonylamino, 3-pyridylcarbonylamino, furoylamino)], an alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, methoxyethoxycarbonylamino), aryloxy Carbonylamino group (preferably having 7 to 3 carbon atoms)
0, for example, phenoxycarbonylamino, p-methoxyphenoxycarbonylamino, p-methylphenoxycarbonylamino, m-chlorophenoxycarbonylamino), sulfonamide group, sulfonamide group (preferably having 1 to 30 carbon atoms, for example, metasulfone). Amide, benzenesulfonamide, p-toluenesulfonamide), ureido group (preferably having 1 to 30 carbon atoms, for example, methylureido, dimethylureido, p-cyanophenylureido), sulfamoylamino group (preferably having 1 carbon atom). To 30, for example, methylaminosulfonylamino, ethylaminosulfonylamino, anilinosphonylamino), an unsubstituted amino group, an alkylamino group (preferably having 1 to 30 carbon atoms, for example, methylamino, dimethylamino, ethylamino). Diethylamino, n- butylamino), an arylamino group (preferably 6 carbon atoms
30, for example, anilino), an alkoxy group (preferably having 1 to 30 carbon atoms, for example, methoxy, ethoxy, isopropoxy, n-butoxy, methoxyethoxy, n-dodecyloxy), an aryloxy group (preferably having 6 carbon atoms).
~ 30, for example, phenoxy, m-chlorophenoxy,
p-methoxyphenoxy, o-methoxyphenoxy),
Heteryloxy group (preferably having 3 to 30 carbon atoms, for example, tetrahydropyranyloxy, 3-pyridyloxy, 2- (1,3-benzimidazolyl) oxy), alkylthio group (preferably having 1 to 30 carbon atoms, for example, methylthio, ethylthio , N-butylthio, t-butylthio), an arylthio group (preferably having 6 to 30 carbon atoms, for example, phenylthio), a heterylthio group (preferably having 3 to 30 carbon atoms, for example, 2-pyridylthio, 2- (1,
3-benzimidazolyl) thio, 1-hexadecyl-
1,2,3,4-tetrazolyl-5-thio, 1- (3-
N-octadecylcarbamoyl) phenyl-1,2,
3,4-tetrazolyl-5-thio), a heterocyclic group (preferably having 3 to 30 carbon atoms, for example, 2-benzoxazolyl, 2-benzothiazolyl, 1-phenyl-2-benzimidazolyl, 5-chloro-1. -Tetrazolyl, 1-pyrrolyl, 2-furanyl, 2-pyridyl, 3-pyridyl), halogen atom (fluorine, chlorine, bromine), hydroxy group, nitro group, sulfamoyl group (preferably having 0 to 30 carbon atoms, for example, methyl Sulfamoyl, dimethylsulfamoyl, ethylsulfamoyl, N, N-dipropylsulfamoyl), sulfonyl group (preferably having 1 to 30 carbon atoms, for example, methanesulfonyl, benzenesulfonyl, toluenesulfonyl, trifluoromethanesulfonyl, Difluoromethanesulfonyl), alkyloxy group (preferably carbon 1-30, for example, formyloxy, acetyloxy, benzoyloxy), a carbamoyloxy group (preferably having 1 to 30 carbon atoms, for example, methylcarbamoyloxy, diethylcarbamoyloxy), an imide group (preferably having 4 to 30 carbon atoms, For example,
Succinimide, phthalimide), sulfinyl group (preferably having 1 to 30 carbon atoms, for example, diethylaminosulfinyl), phosphoryl group (preferably having 0 to 3 carbon atoms).
0, for example, dimethoxyphosphoryl, diphenylphosphoryl), a carboxyl group, a phosphono group, and an unsubstituted amino group. These groups may have the same substituents if possible. As R ⁴ , R ⁶ and R ⁷ , an alkyl group and an aryl group are preferable. In particular, R ⁴ is preferably a branched alkyl group. As R ⁶ and R ⁷ , an aryl group is more preferable, and an aryl group substituted with an alkoxy group, an acylamino group, a sulfonamide group, an alkyl group or the like is further preferable.

X ¹ and X ² are a hydrogen atom or an aromatic first group.
It represents a group (hereinafter referred to as "leaving group") which is released by a coupling reaction with an oxidized product of a primary amine color developing agent. Examples of the leaving group include a halogen atom (eg, fluorine, chlorine, bromine), an alkoxy group (eg, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy), an aryloxy group (eg, 4-chloro). Phenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy), acyloxy group (eg acetoxy, tetradecanoyloxy, benzoyloxy), sulfonyloxy group (eg methanesulfonyloxy, toluenesulfonyloxy), acylamino group (eg dichloro). Acetylamino, heptafluorobutyrylamino), sulfonamide group (eg, methanesulfonamide, p-toluenesulfonamide), alkoxycarbonyloxy group (eg, ethoxycarboxyl) Niruokishi, benzylcarbonyloxy), an aryloxycarbonyloxy group (e.g.,
Phenoxycarbonyloxy), alkylthio groups (eg carboxymethylthio), arylthio groups (eg 2-butoxy-5-tert-octylphenylthio), heterocyclic thio groups (eg terrarazolylthio), carbamoylamino groups (eg N- Methylcarbamoylamino, N-phenylcarbamoylamino), a 5- or 6-membered nitrogen-containing heterocyclic group (eg, imidazolyl,
Pyrazolyl, triazolyl, tetrazolyl, 1,2-dihydro-2-oxo-1-pyridyl), imide group (for example, succinimide, hydantoinyl), aromatic azo group (for example, phenylazo), sulfinyl group (for example,
2-butoxy-5-tert-octylphenylsulfinyl), sulfonyl group (for example, 2-butoxy-5-tert.
-Octylphenylsulfonyl) and the like. Particularly, X ¹ and X ² are preferably a halogen atom or an arylthio group.

The coupler represented by the general formula (II) or (III) is a coupler represented by the general formula (II) or (III) in the group of R ² , R ³ , R ⁴ , R ⁶ , R ⁷ or R ⁸ . It may have a coupler residue to form a dimer or higher multimer, and R ² , R ³ ,
The groups R ⁴ , R ⁶ , R ⁷ or R ⁸ may form a homopolymer or copolymer having a polymer chain. The homopolymer or copolymer bound to the polymer chain is represented by the general formula (II)
Alternatively, a typical example is an addition polymer having a coupler residue (III), a homopolymer or a copolymer of an ethylenically unsaturated compound. In this case, one or more kinds of color-forming repeating units having a coupler residue represented by the general formula (II) or (III) may be contained in the polymer, and acrylic acid ester, methacrylic acid ester, maleic acid as a copolymerization component may be contained. It may be a copolymer containing one or more non-color-forming ethylenic monomers such as acid esters. Formula (II) or
Specific examples of the compound represented by (III) are shown below, but the present invention is not limited thereto.

[0052]

[Chemical 13]

[0053]

[Chemical 14]

[0054]

[Chemical 15]

[0055]

[Chemical 16]

[0056]

[Chemical 17]

[0057]

[Chemical 18]

[0058]

[Chemical 19]

[0059]

[Chemical 20]

[0060]

[Chemical 21]

[0061]

[Chemical formula 22]

[0062]

[Chemical formula 23]

[0063]

[Chemical formula 24]

Compounds that release a photographically useful residue upon coupling can also be used in the present invention. DIR couplers releasing development inhibitors are described in Research Disclosure, No. 17643, Section VII-F, Patents,
JP-A-57-151944, 57-154234, 60-184248
No. 63-37346, U.S. Pat.Nos. 4,248,962, 4,7
Those described in No. 82,012 are preferable. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,097,140 and 2,131,188, JP-A No.
Those described in 59-157638 and 59-170840 are preferable.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,472 and 4,33.
Multi-equivalent couplers described in No. 8,393 and No. 4,310,618,
D described in JP-A-60-185950 and JP-A-62-24252
IR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 1
73302A coupler releasing a dye that recolors after withdrawal, Research Disclosure, No. 11449, N.
No. 24241, a bleaching accelerator releasing coupler described in JP-A-61-201247, a ligand-releasing coupler described in U.S. Pat. No. 4,553,477, and a coupler releasing a leuco dye described in JP-A-63-75747. , US Pat. No. 4,774,181, and the like, which release a fluorescent dye.

The standard amount of the color coupler used in the present invention is 0.0 per 1 mol of the photosensitive silver halide.
It is in the range of 0 to 1 mol, preferably 0.01 to 0.5 mol for the yellow coupler, 0.003 to 0.3 mol for the magenta coupler, and 0.003 to 0.3 mol for the cyan coupler.
It is 0.002-0.3 mol. The compound represented by formula (I) used in the present invention may be used in combination with a known anti-fading agent, in which case the anti-fading effect is further enhanced.
Further, two or more compounds represented by the general formula (I) may be used in combination. Cyan, magenta and // which can be used in combination
Alternatively, as an organic anti-fading agent for yellow images, hydroquinones, 6-hydroxychromans, 5-hydroxymalans, spirochromans, p-alkoxyphenols, hindered phenols centering on bisphenols, gallic acid derivatives Representative examples thereof include methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl groups of these compounds. Further, a metal complex represented by a (bissalicylaldoximato) nickel complex and a (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Specific examples of such organic anti-fading agents include US Pat. Nos. 2,360,290, 2,418,613 and 2,7.
00,453, 2,701,197, 2,728,659, 2,73
2,300, 2,735,765, 3,982,944, 4,430,
425, UK Patent 1363921, US Patent 2,710,801
No. 2,816,028, etc .; hydroquinones; US Pat. Nos. 3,432,300, 3,573,050, 3,574,627
No. 3,698,909, No. 3,764,337, JP-A-52-1522
6-hydroxychromans, 5-hydroxychromans, spirochromans described in US Pat. No. 4,36.
Spiroindans described in US Pat. No. 2,735,
765, British Patent No. 2066975, JP-A-59-10539,
P-Alkoxyphenols described in JP-B-57-19765 and the like; hindered phenols described in US Pat. Nos. 3,700,455 and 4,228,235, JP-A-52-72224, JP-B-52-6623 and the like; Gallic acid derivatives described in U.S. Pat. No. 3,457,079; methylenedioxybenzenes described in U.S. Pat. No. 4,332,886; aminophenols described in Japanese Patent Publication No. 56-21144; U.S. Pat. Nos. 3,336,135 and 4,268,593
No., British Patent Nos. 1326889, 1354313, 1410846
Japanese Patent Publication No. 51-1420, Japanese Patent Laid-Open No. 58-114036, 59-53.
Hindered amines described in 846 and 59-78344 and the like; metal complexes described in US Pat. Nos. 4,050,938 and 4,241,155, and British Patent 2027731 (A). These compounds can achieve the object by usually coemulsifying 5 to 100% by weight of the corresponding color coupler with the coupler and adding it to the photosensitive layer.

The silver halide color photographic light-sensitive material of the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant. Further, in order to prevent deterioration of the cyan dye image due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent thereto. Examples of the ultraviolet absorber include aryl group-substituted benzotriazole compounds (for example, those described in US Pat. No. 3,533,794), 4-thiazolidone compounds (for example, US Pat. No. 3,314,794 and the like).
3,352,681), benzophenone compounds (for example, those described in JP-A-46-2784), cinnamic acid ester compounds (for example, US Pat. No. 3,705,805, the same).
3,707,395), butadiene compounds (for example, those described in U.S. Pat.No. 4,045,229), benzoxazole compounds (for example, those described in U.S. Pat. Nos. 3,406,070 and 4,271,307) or triazine compounds (for example, Those described in JP-A-46-3335) can be used. UV absorbing couplers (eg, α-
A naphthol-based cyan dye-forming coupler), an ultraviolet absorbing polymer, or the like may be used. These UV absorbers may be mordanted in a specific layer. Among them, the benzotriazole compound substituted with the above aryl group is preferable.

The light-sensitive material of the present invention contains at least one compound represented by the general formula (I) of the present invention in at least one layer on its support. A color light-sensitive material is generally formed by coating at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer and at least one red-sensitive silver halide emulsion layer on a support in this order. However, the order may be different from this. Also, an infrared sensitive silver halide emulsion layer can be used in place of at least one of the above described photosensitive emulsion layers. Color reproduction of the subtractive method is performed by incorporating a silver halide emulsion having sensitivity in each wavelength range and a color coupler forming a dye having a complementary color relationship with the light to be exposed in these light-sensitive emulsion layers. be able to. That is,
A blue-sensitive silver halide emulsion layer contains a diffusion-resistant yellow coupler that forms a diffusion-resistant yellow dye, and a green-sensitive silver halide emulsion layer contains a diffusion-resistant magenta dye that forms a diffusion-resistant magenta dye. The silver halide emulsion layer contains a diffusion resistant cyan coupler which forms a diffusion resistant magenta dye. However, the hues of the light-sensitive emulsion layer and the color coupler may not have the above correspondence.

The light-sensitive material of the present invention can be applied to, for example, black-and-white film, color paper, color reversal paper, direct positive color light-sensitive material, color negative film, color positive film, color reversal film and the like. Of these, application to a color light-sensitive material having a reflective support (for example, color paper, color reversal paper) or a color light-sensitive material having a positive image (for example, direct positive color light-sensitive material, color positive film, color reversal film) is preferable,
In particular, it is preferably applied to a color light-sensitive material having a reflective support.

As the silver halide used in the present invention, silver chloride, silver bromide, silver chlorobromide, silver iodochlorobromide, silver iodobromide, silver iodochloride and the like can be mainly used. A color negative film for high sensitivity from the viewpoint of photography,
In the case of color reversal film or color reversal paper,
Silver iodochlorobromide, silver iodobromide or silver iodochloride emulsions containing 1 to 20 mol% of silver iodide, and silver bromide in the case of an internal latent image type direct positive color light-sensitive material which has not been fogged in advance. A silver chlorobromide or pure silver bromide emulsion having a content of 50 to 100 mol%, and particularly a color paper or the like intended for rapid processing, has a silver chloride content of 90 to 100 substantially free of silver iodide.
Mol%, more preferably 95 to 100 mol%, especially 98 to 10
Preference is given to using 0 mol% silver chlorobromide or pure silver chloride emulsion.

In the light-sensitive material of the present invention, for the purpose of improving the sharpness of an image, a hydrophilic colloid layer, a dye which can be decolorized by the treatment described in EP No. 0337490A2, pages 27 to 76, is used. Oxonol dye) so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more, or 2 to 2 is added to the water resistant resin layer of the support.
It is preferable to contain 12% by weight or more (more preferably 14% by weight or more) of titanium oxide surface-treated with a tetravalent alcohol (eg, trimethylolethane).

Further, in the light-sensitive material of the present invention, it is preferable to use a color image storability improving compound as described in EP 0277589A2 together with a coupler. In particular, it is preferably used in combination with the above-mentioned pyrazoloazole coupler or pyrroloazole coupler. That is, the compound (F) which chemically bonds with the aromatic amine developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound and / or the fragrance remaining after the color development processing. The use of a compound (G), which forms a chemically inactive and substantially colorless compound by chemically bonding with an oxidant of a group amine type color developing agent, simultaneously or solely, for example, in storage after processing. It is preferable in order to prevent stains and other side effects due to the formation of a coloring dye due to the reaction of the coupler with the color developing agent remaining in the film or its oxidant.

Further, the light-sensitive material of the present invention contains a mildew-proofing agent as described in JP-A-63-271247 in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image. Is preferably added. The support used in the light-sensitive material of the present invention may be a white polyester support for display or a support provided on a support having a silver halide emulsion layer on which a layer containing a white content is provided. You may use. Further, in order to improve the sharpness, it is preferable to apply an antihalation layer on the silver halide emulsion layer-coated side or the back side of the support. In particular, the transmission density of the support is preferably set in the range of 0.35 to 0.8 so that the display can be viewed with both reflected light and transmitted light.

The light-sensitive material according to the present invention is imagewise exposed to
After color development, it is processed with a processing solution having a bleaching ability (bleaching solution and bleach-fixing solution). These are described in Research Disclosure, No. 17643, pp. 28-29 and the same.
See page 615, left column to right column of No. 18716. For example, color development processing step, bleaching step, fixing step,
A water washing process step is performed. Instead of the bleaching step using a bleaching solution and the fixing step using a fixing solution, a bleach-fixing processing step using a bleaching-fixing solution can be performed, and a bleaching processing step, a fixing processing step, and a bleach-fixing step can be performed at any time. You may combine in order. The stabilizing process may be performed instead of the water washing process, or the stabilizing process may be performed after the water washing process. Further, in combination with these processing steps, a pre-hardening processing step, a neutralizing step thereof, a stop fixing processing step, a post-hardening processing step, an adjusting step, an intensifying step and the like may be performed. In order to obtain a color reversal image, after the image exposure, the first development, the reversal process, and the color development process and the subsequent steps are performed. In this case, an adjusting step is generally performed between the bleaching steps of the color developing step. An intermediate water washing step may be optionally provided between the above steps.

The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied in the present invention, and processing methods and processing additions applied for processing this light-sensitive material. As the agent, those described in the patent publications of Tables 1 to 5 and European Patent No. 0519190A2 are preferable,
Particularly, those described in European Patent No. 0355660A2 are preferably used.

[0077]

[Table 1]

[0078]

[Table 2]

[0079]

[Table 3]

[0080]

[Table 4]

[0081]

[Table 5]

[0082]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Example 1 (Preparation of Sample 101) The surface of a paper support laminated on both sides with polyethylene was subjected to corona discharge treatment, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated. A multilayer color photographic paper having the following layer structure was prepared. The coating liquid was prepared as follows.

Preparation of coating solution for fifth layer: 33 g of cyan coupler (C-7), ultraviolet absorber (UV
-2) 10 g, color image stabilizer (Cpd-9) 0.6 g, color image stabilizer (Cpd-10) 0.6 g, color image stabilizer (Cp
d-11) 0.6 g, color image stabilizer (Cpd-8) 0.6
g, color image stabilizer (Cpd-6) 0.6 g, color image stabilizer (Cpd-1) 18 g, high boiling point organic solvent (Solv-
3) 33 ml of ethyl acetate was added to and dissolved in 57 ml, and this solution was added to 270 ml of 20% gelatin aqueous solution containing 7.0 g of sodium dodecylbenzenesulfonate, and then emulsified and dispersed by a high-speed stirrer to prepare an emulsified dispersion. . On the other hand, silver chlorobromide emulsion (cube, average grain size 0.50μ
m large size emulsion C and 0.41 μm small size emulsion C 1: 4 mixture (Ag molar ratio). The coefficient of variation of the grain size distribution is 0.09 and 0.11, respectively, and in each size emulsion, 0.8 mol% of AgBr is localized on a part of the grain surface, and the rest is composed of silver halide grains of silver chloride). Was prepared. This emulsion contains the red-sensitive sensitizing dye E shown in Table 8 below.
Is 0.9 × 10 ⁻⁴ mol per mol of silver halide for large size emulsion and 1.
1 × 10 ⁻⁴ mol is added. Further, the compound F shown in Table 8 below is 2.6 × 10 ⁻³ per mol of silver halide.
Mol is added. The chemical ripening of this emulsion was carried out by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion and this red-sensitive silver chlorobromide emulsion were mixed and dissolved, and Table 11 below was used.
A fifth layer coating solution was prepared so as to have the composition shown in.

The coating solutions for the first to fourth layers, the sixth layer and the seventh layer were prepared in the same manner as the fifth layer coating solution. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. In addition, the total amount of Cpd-14 and Cpd-15 in each layer is 25.0.
It was added to a mg / m ² and 50.0 mg / m ^2. The spectral sensitizing dyes shown in Tables 6 to 8 below were used in the silver chlorobromide emulsions of the respective photosensitive emulsion layers.

[0085]

[Table 6]

[0086]

[Table 7]

[0087]

[Table 8]

Further, 1- (5-methylureidophenyl) is added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer.
-5-mercaptotetrazole was added to each of 8.5 x 10 ^-4 mol, 7.7 x 10 ^-4 mol, and 1 mol of silver halide.
2.5 × 10 ⁻⁴ mol was added. Further, 4-hydroxy-6-methyl-1, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer,
3,3a, 7-Tetrazaindene was added in an amount of 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol, respectively, per mol of silver halide. Further, the following dyes (the amount in parentheses represents the coating amount) were added to the emulsion layer to prevent irradiation.

[0089]

[Chemical 25]

(Layer Structure) Tables 9 to 11 below show the composition of each layer. The coating amount (g / m ² ) is shown in the left column. The silver halide emulsion is expressed as a coating amount in terms of silver.

[0091]

[Table 9]

[0092]

[Table 10]

[0093]

[Table 11]

[0094]

[Chemical formula 26]

[0095]

[Chemical 27]

[0096]

[Chemical 28]

[0097]

[Chemical 29]

[0098]

[Chemical 30]

[0099]

[Chemical 31]

(Production of Samples 102 to 124) Sample 102
In preparing an emulsified dispersion of the fifth layer coating liquid of
Instead of the combination of the coupler and the high boiling point organic solvent used in Sample 101, the combination of the coupler and the high boiling point organic solvent shown in Table 12 was used. Here, sample 1
For 02, a double amount of high boiling point organic solvent was used, and
3-115, 117, 118, 120, 121, 12
For 3 and 124, the additives shown in Table 12 were added in the same amount as the high boiling point organic solvent. Thereafter, a coating liquid was prepared and applied in the same manner as in Sample 101, to prepare Samples 102 to 124. At this time, the amount of coupler used was equimolar to C-7 in Sample 101. CS-1 to CS-8 were used as comparative compounds.

[0101]

[Chemical 32]

[0102]

[Chemical 33]

Incidentally, CS-1 and CS-3 are Japanese Patent Publication No. 52
Nos. 4182 and 39-8790 are disclosed respectively as a gelatin hardener, and CS-5 is disclosed as an anti-fading agent in JP-A-5-2248. Also, CS-2 is a British Patent No. 209112.
No. 4, CS-6 to 8 are disclosed as high boiling point organic solvents in JP-A-63-301941.

First, a sensitometer (manufactured by Fuji Photo Film Co., Ltd., FWH type, light source color temperature 3200K) was used for each sample, and gradation exposure of a red filter for sensitometry was performed. The exposure at this time is 25 seconds with the exposure time of 0.1 seconds.
The exposure amount was 0 CMS. The exposed sample was subjected to continuous processing (running test) using a test paper processor using a solution having the following process and processing solution composition until replenishment of twice the tank capacity for color development.

(Processing step) (Temperature) (Time) (Replenisher) * (Tank capacity) Color development 35 ° C. 45 seconds 161 ml 1 liter Bleach fixing 35 ° C. 45 seconds 215 ml 1 liter Stability (1) 35 ° C. 20 Second-0.6 liter Stability (2) 35 ° C 20 sec-0.6 liter Stability (3) 35 ° C 20 sec-0.6 liter Stability (4) 35 ° C 20 sec 248 ml 0.6 liter Dry Dry 80 ° C 60 seconds * Replenishment amount per 1 m ² of light-sensitive material. * The stable process is a 4-tank countercurrent system from (4) to (1)

The composition of each processing liquid is as follows. [Color developer] Tank liquid Replenisher Water 800 ml 800 ml 1-Hydroxyethylidene-1,1-diphosphonic acid (60%) 0.8 ml 0.8 ml Lithium sulfate (anhydrous) 2.7 g-triethanolamine 8 0.0 g 8.0 g Sodium chloride 1.4 g-Potassium bromide 0.03 g 0.025 g Diethylhydroxyamine 4.6 g 7.2 g Potassium carbonate 27 g 27 g Sodium sulfite 0.1 g 0.2 g N-ethyl-N- (β- Methanesulfonamidoethyl) -3-methyl-4-aminoaminoline / 3/2 sulfuric acid monohydrate 4.5 g 7.3 g Optical brightener (4,4′-diaminostilbene type) 2.0 g 3. 0g Add water 1000 ml 1000 ml pH (add potassium hydroxide) 10.2 10.80

[Bleach-fixing solution] (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetic acid disodium 5 g Glacial acetic acid 9 g Add water to add 1000 ml pH (25 ° C) 5.40 [Stabilizer] (same as tank liquid and replenisher) Benzisothiazolin-3-one 0.02 g Polyvinylpyrrolidone 0.05 g Add water to add 1000 ml pH (25 ℃) 7.40

(Evaluation of Sample) The absorption spectrum of each sample after the treatment was measured with a spectrophotometer (Shimadzu UV365). The absorption spectrum of the portion where the absorbance at the maximum absorption wavelength was 1.0 was measured. 600 of this spectrum
The magnitude of the absorbance in nm was set to D _600nm and used as a measure of the size of the association. The smaller the value of D _600nm, the smaller the association. The maximum color density (D _max ) of each sample after treatment was also measured using red light. Further, each sample after the treatment was subjected to a fading test for 3 weeks under the conditions of a temperature of 90 ° C. and a humidity of 60%, and the fading rate (%) of the cyan dye at an initial density of 1.0 was measured. The fading rate is the ratio of the density after fading to the initial density, and the smaller the fading rate, the smaller the fading. Table 12 shows the values of D _600nm , D _max and fading rate of each sample.

[0109]

[Table 12]

The results shown in Table 12 show the following. Sample 101 of a high-boiling-point organic solvent alone (Comparative Example), Samples 103 to 110 to which a phosphoric acid amide compound or the like was added (Comparative Example)
On the other hand, all of the samples 111 to 115, 117 and 118, 120 and 121, 123 and 124 to which the phosphoric acid amide-based compound or the like used in the present invention is added have a relatively D _{600 nm.}
Is small, in particular, samples 111 to 115, 120 and 12
1, 123 and 124 have small D _600nm , and it can be seen that the association is suppressed. Further, it can be seen that the sample to which the phosphoric acid amide-based compound or the like used in the present invention is added has a large D _{max and} high color developability. Further, it can be seen that the fading rate is small and the light fastness is excellent. On the other hand, the sample 103 containing CS-1 and the sample 105 containing CS-3 (comparative example) lacked the hydrophobicity of the additive, so that CS-1, CS-3, etc. flowed out into the developer. It seems that they have done it. From these, it is clear that the compound used in the present invention is excellent in hydrophobicity.

Example 2 (Preparation of Samples 201 to 215) When preparing an emulsified dispersion of the coating liquid for the third layer of Samples 201 to 215, in Sample 201, an organic solvent having a higher boiling point than that of Sample 101 was used. Is doubled, and in Sample 202, Sample 101
The amount of the high boiling point organic solvent used is halved compared to the case of, and Samples 203 to 215 are prepared in the same manner as in Sample 101 except that the additives shown in Table 13 are added in the same amount as the high boiling point organic solvent. Prepared and applied. Next, samples 201 to 21
In Example 5, the sensitometer used for preparing the sample 101 was used at the time of exposure, and gradation exposure of the green filter for sensitometry was performed. The exposure at that time is 25 with the exposure time of 0.1 seconds.
The exposure amount was set to 0 CMS. The exposed sample was developed similarly to Sample 101.

(Evaluation of Sample) The absorption spectrum of each sample after the treatment was measured with a spectrophotometer (Shimadzu UV365). The absorption spectrum of the portion where the absorbance at the maximum absorption wavelength was 1.0 was measured. 500 of this spectrum
The magnitude of the absorbance in nm was set to D _{500 nm} and used as a measure of the size of the association. The smaller the value of D _{500 nm,} the smaller the association. The maximum color density (D _max ) of each sample after treatment was also measured using green light. Furthermore, each sample after the treatment was subjected to a fading test for 3 weeks under the conditions of a temperature of 90 ° C. and a humidity of 60%, and the fading rate (%) of the magenta dye at an initial density of 1.0 was measured. The fading rate is the ratio of the density after fading to the initial density, and the smaller the fading rate, the smaller the fading. Table 13 shows D _500nm and D _max of each sample.
And the value of the fading rate are shown. The comparative compound is the same as each of Example 1.

[0113]

[Table 13]

The results shown in Table 13 show the following. Sample 202 of high boiling point organic solvent alone (comparative example), Samples 203 to 2 to which CS-1 to 8 such as phosphoramide compound was added
In contrast to 10 (Comparative Example), all samples 211 to 215 to which the phosphoric acid amide compound used in the present invention was added were D.
_It can be seen that the association was suppressed with a small value of _{500 nm} . Further, it can be seen that D _max is large and color development is excellent. Further, it can be seen that the fading rate is small and the light fastness is excellent.

Example 3 High boiling organic solvent oi of the ninth layer of the multilayer color reversal light-sensitive material sample 401 of Example 4 described in JP-A-4-359249.
Compound S using 1-1 (dibutyl phthalate) in the present invention
-1 (0.1 g), the compound S-10.05 g used in the present invention was added to the tenth layer, and the high boiling point organic solvent oil-1 (dibutyl phthalate) in the eleventh layer was used in the present invention. -1 (0.08 g), except that the sample 30 was prepared by the same method as described in the same issue
1 was slit into a width of 35 mm, perforated in the same format as a commercially available film, and then uniformly exposed. The sample thus obtained was treated with the treatment No. 1 described in Example 4 of the same item. When processing was carried out using a hanging type automatic developing machine in No. 11, excellent hue, color developability and fastness were confirmed.

[0116]

Since the silver halide photographic material of the present invention has the above-mentioned constitution, it has an effect of being excellent in solubility and dispersion stability of a photographic reagent. Further, since the silver halide light-sensitive material of the present invention has the above-mentioned constitution, when it is used as a light-sensitive material for color photography, it has excellent solubility and dispersion stability of a photographic reagent and good color reproducibility of a dye. Thus, there is no fading, and the effect of excellent color development of the dye diffusion resistant coupler is exhibited.

Claims (2)

[Claims] 1. A silver halide light-sensitive material characterized in that at least one layer on a support contains at least one compound represented by the following general formula (I). [Chemical 1] (In the formula, R ¹ represents an aliphatic group or an aryl group, and X represents a carbon atom group necessary for forming a saturated or unsaturated 5- to 7-membered ring by linking with a nitrogen atom. Represents an integer of 1 to 3, m represents 0 or 1. When n is 2 or 3, X may be the same or different, and when n is 1, R ¹ and m are the same or different. Good too.) 2. A layer containing at least one kind of the compound represented by the general formula (I) is at least one kind of cyan coupler represented by the following general formula (II) or the following general formula (II).
The silver halide light-sensitive material according to claim 1, containing at least one kind of magenta coupler represented by I). [Chemical 2] (In the formula, Z ¹ and Z ² represent a nonmetallic atom group necessary for forming an azole ring in which a hetero atom is a nitrogen atom.
R ² and R ³ each represent an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.30 or more. R ⁴ represents a hydrogen atom or a substituent. X ¹ and X ² represent a hydrogen atom or a group which is released by a coupling reaction with an oxidation product of an aromatic primary amine type color developing agent. )