JPH06258801A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve solubility, dispersion stability of photographic reagents, color reproduction performance, discoloration resistance, and color development performance. CONSTITUTION:The silver halide photographic sensitive material contains in at least one layer on a support at least one of color-nondeveloping compounds represented by the formula in which each of R<1> and R<2> is an aliphatic or aryl group; R<3> is a group substitutable on a benzene ring; n is an integer of 0-4; and the sum of the total carbon atoms of R<1>-R<3> is 2-50.

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 in particular, a diffusion-resistant coupler which forms a diffusion-resistant dye is incorporated in a silver halide emulsion to produce an aromatic primary amine color. 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 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 the 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 the effect of preventing 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,
Can be easily obtained or manufactured at low cost, has excellent solubility and dispersion stability of photographic reagents, has no adverse effect on developability and photographic properties, has excellent safety and has no environmental impact, and chemicals. It is a general requirement that the optical stability is excellent, and in the case of a color light-sensitive material, the effect of preventing fading of a color image is excellent.

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. For example, the urea compound of European Patent 0309158A1 and European Patent 030
Examples thereof include amide compounds of No. 9160A1. 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. Also,
When the compound was used in the same layer as the dye-forming diffusion-resistant coupler, the dye formed from the coupler often deteriorated in discoloration due to heat, humidity and light. In particular, deterioration of discoloration due to heat, humidity, and light of such dyes is caused by the above-mentioned European Patent No. 0309158A1 and European Patent No. 0309160A.
This was remarkable when the urea and amide compounds having a hydrogen atom on the nitrogen atom described in No. 1 etc. were used in the same layer as the dye-forming diffusion-resistant coupler. In addition, JP-A-5-22
Urethane compounds are listed as anti-fading agents in 48, but these do not make the hue of the dye preferable, and further, they have poor compatibility with couplers and the like, and therefore, are not suitable for use as a high boiling organic solvent. It wasn't right. On the other hand, JP-A-2-93639 discloses that a urethane compound and an anionic surfactant are used in combination to improve coatability, sensitivity and fog. Then, there is no effect of making the hue preferable, and the fading of the dye due to heat, humidity and light is 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. An object of the present invention is to provide a silver halide excellent in solubility and dispersion stability of a photographic reagent, good color reproducibility of a dye, no fading, and excellent color forming property of a dye-forming diffusion-resistant coupler. To provide a light-sensitive material.

[0007]

The object of the present invention is characterized in that at least one layer on a support contains at least one non-color-forming compound represented by the following general formula (I). This is achieved by a silver halide light-sensitive material (hereinafter referred to as a light-sensitive material).

[0008]

[Chemical 3]

(In the formula, R ¹ and R ² each represent an aliphatic group or an aryl group, R ³ represents a group capable of substituting for a benzene ring, and n represents an integer of 0 to 4, provided that R is R 4. ¹ , R
The total number of carbon atoms of ² and R ³ is 2 to 50. )

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 and R ² are aliphatic groups or aryl groups. As the carbon number of the aliphatic group of R ¹ and R ² , 1 to 30 is preferable, 2 to 20 is more preferable, and 4 to 18 is further preferable. Examples of the aliphatic group include methyl, ethyl, isopropyl, butyl,
Examples thereof include t-butyl, cyclohexyl, allyl, 2-ethylhexyl, octyl, isononyl, dodecyl, chloromethyl, trifluoromethyl, benzyl, 2-butoxymethoxy and the like. The aryl group of R ¹ and R ² preferably has 6 to 30 carbon atoms, more preferably has 6 to 20 carbon atoms, and further preferably has 6 to 18 carbon atoms. Examples of the aryl group include phenyl, 2-naphthyl, 4-methoxyphenyl, 2-methylphenyl and the like. R ¹ and R ²
Is preferably an unsubstituted aliphatic group, and more preferably an unsubstituted branched chain aliphatic group. Further, in the general formula (I), it is more preferable that R ¹ and R ² are the same. In the general formula (I), R ³ represents a group capable of substituting on the benzene ring, and preferably, for example, an aliphatic group (eg, methyl, 2-ethylhexyl, benzyl), an aryl group (eg, phenyl, 2-naphthyl), a fat Group oxy groups (eg methoxy, 2-ethylhexyloxy), aryloxy groups (eg phenoxy, 2-naphthoxy),
They are an aliphatic oxycarbonyl group (eg methoxycarbonyl, octyloxycarbonyl) and an aryloxycarbonyl group (eg phenoxycarbonyl). In the general formula (I), n is an integer of 0 to 4, preferably n is 0 or 1, and more preferably n is 0.
When n is 2 or more, R ^3's may be linked to each other to form a ring. In the general formula (I), R ¹ , R ² and R
The total number of carbon atoms of ³ is 2 to 50, preferably 4 to 40, and more preferably 8 to 36. Specific examples of R ¹ and R ² in the general formula (I) are shown below, but the present invention is not limited thereto.

[0014]

[Chemical 4] Specific examples of R ³ in the general formula (I) are shown below,
The present invention is not limited to this.

[0015]

[Chemical 5] Specific examples of the compound represented by formula (I) used in the present invention are shown below, but the present invention is not limited thereto.

[0016]

[Chemical 6]

[0017]

[Chemical 7] The synthesis examples of the compound represented by formula (I) used in the present invention are shown below, but the present invention is not limited thereto. Synthesis of S-5

[0018]

[Chemical 8]

Benzimidazolone (1) 40.5 g
(0.3 mol), sodium hydride 24.0 g (0.
6 mol) was dissolved in 500 ml of dimethylacetamide and stirred at 80 ° C. for 30 minutes, and then sodium iodide 8 was added.
9.9 g (0.6 mol) was added, and 11-5.7 g (0.6 mol) of 2-ethylhexyl bromide (2) was further added.
It was added dropwise over 0 minutes. Raise the temperature to 150 ° C, then 8
Stir for hours. After cooling, ethyl acetate and water were added for liquid separation, the organic layer was extracted, washed with water, dried over magnesium sulfate, and concentrated. The product was isolated and purified by silica gel column chromatography (developing solvent; ethyl acetate: hexane = 1: 10), and the oily S- was obtained in a yield of 65.1 g (60.5%).
Got 5. The structure was confirmed by NMR and MS spectra.

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 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 in the present invention may contain various compounds according to the purpose in addition to the compound used in the present invention and the 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 point organic solvents are used in combination, the compound used in the present invention is preferably used in a weight ratio of 10% or more, more preferably 30% or more, based on the total amount of the high-boiling point organic solvent.

Examples of the high boiling point solvent which can be used in combination with the compound used in 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 (eg, dibutyl phthalate, dicyclohexyl phthalate, di-2).
-Ethylhexyl phthalate, decyl phthalate, bis
(2,4-di-t-amylphenyl) phthalate, bis (2,4
-Di-t-amylphenyl) isophthalate, bis (1,1
-Diethylpropyl) phthalate), esters of phosphoric acid or phosphonic acid (eg triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxy) Ethyl phosphate,
Trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate), benzoic acid esters (for example, 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (for example, N, N-diethyldodecane amide) , N, N-diethyllaurylamide, N-tetradecylpyrrolidone), sulfonamides (eg, N
-Butylbenzenesulfonamide), alcohols or phenols (isostearyl alcohol, 2,4-di-
t-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
-T-octylaniline and the like), hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene), chlorinated paraffins and the like. As the auxiliary solvent, an organic solvent having a boiling point of 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone. , 2-
Examples include ethoxyethyl acetate and 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 mixing (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 and 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.

[0029]

[Chemical 9]

(In the formula, Z ¹ and Z ² represent a group of non-metal atoms necessary for forming an azole ring in which a hetero atom is a nitrogen atom. R ¹¹ and R ¹² are Hammett's substituent constant σ, respectively. Represents an electron-withdrawing group having _ap value of 0.30 or more R ¹³
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.

[0031]

[Chemical 10]

In the formula, R ¹⁴ , R ¹⁵ and R ¹⁶ 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 ¹¹ and R ¹² 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 used to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives.
A rule of thumb advocated by LP Hammett in '35, 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, "De Lange's Handbook of Chemist" edited by JA Dean
ry "12th edition, 1979 (McGraw-Hill) and" Chemistry special issue ", No. 122, pp. 96-103, 1979 (Nankodo). In the present invention, R ¹¹ and R ¹² are defined by the 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 are not limited. 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 ¹¹ and R ¹² 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, t-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.

A typical electron withdrawing group having a σ _p value of 0.30 or more and its σ _p value are cyano groups (0.6
6), nitro group (0.78), trifluoromethyl group (0.54), carboxyl group (0.45), acetyl group (0.50), benzoyl group (0.43), trifluoromethanesulfonyl group ( 0.92), methanesulfonyl group (0.72), benzenesulfonyl group (0.7
0), methanesulfinyl group (0.49), carbamoyl group (0.36), methoxycarbonyl group (0.4
5), ethoxycarbonyl group (0.45), phenoxycarbonyl group (0.44), pyrazolyl group (0.3
7), methanesulfonyloxy group (0.36), dimethoxyphosphoryl group (0.60), sulfamoyl group (0.57), pentafluorophenyl group (0.41)
Etc.

In the general formula (II), R ¹¹ and R ¹² are each preferably a cyano group, an acyl group, a carbamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, R ¹¹ is a cyano group and R ¹² is-. CO ₂ -R
More preferably, it is a group represented by ¹⁷ (R ¹⁷ represents an alkyl group or an aryl group). R ¹⁷ is particularly preferably a branched alkyl group.

R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ represent a hydrogen atom or a substituent, and the substituent is an aryl group (preferably having 6 to 30 carbon atoms, 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 1 to 1 carbon atoms)
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 ¹³ , R ¹⁴ and R ¹⁵ , an alkyl group and an aryl group are preferable. A branched alkyl group is particularly preferable as R ¹³ . As R ¹⁴ and R ¹⁵ , 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-t-octylphenylsulfinyl), sulfonyl group (for example, 2-butoxy-5-t-
Octylphenylsulfonyl) and the like. As X ¹ and X ² , a halogen atom and an arylthio group are preferable.

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 ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ or R ¹⁶ . It may have a coupler residue to form a dimer or higher multimer, and R ¹¹ , R ¹² ,
The groups of R ¹³ , R ¹⁴ , R ¹⁵ or R ¹⁶ may form a homopolymer or a 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.

[0039]

[Chemical 11]

[0040]

[Chemical 12]

[0041]

[Chemical 13]

[0042]

[Chemical 14]

[0043]

[Chemical 15]

[0044]

[Chemical 16]

[0045]

[Chemical 17]

[0046]

[Chemical 18]

[0047]

[Chemical 19]

[0048]

[Chemical 20]

[0049]

[Chemical 21]

[0050]

[Chemical formula 22]

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 use amount of these color couplers in the present invention is 0.0 per mol of light-sensitive 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 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. Examples of the organic anti-fading agent for cyan, magenta and / or yellow images that can be used in combination include hydroquinones,
6-hydroxychromans, 5-hydroxymalans,
Spirochromans, p-alkoxyphenols, hindered phenols centering on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and the phenolic hydroxyl groups of these compounds are silylated and alkylated. The ether or ester derivative is a typical example.
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 photographic material of the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative and the like as a color fog inhibitor. 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. As the ultraviolet absorber, a benzotriazole compound substituted with an aryl group (for example, those described in US Pat. No. 3,533,794), a 4-thiazolidone compound (for example, those described in US Pat. Nos. 3,314,794 and 3,352,681) , Benzophenone compounds (for example, those described in JP-A-46-2784), cinnamic acid ester compounds (for example, those described in US Pat. Nos. 3,705,805 and 3,707,395), butadiene compounds (for example, US Pat.
4,045,229), a benzoxazole compound (for example, those described in U.S. Pat.Nos. 3,406,070 and 4,271,307) or a triazine compound (for example, those described in JP-A-46-3335). it can.
An ultraviolet absorbing coupler (for example, an α-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 of the general formula (I) of the present invention in at least one layer on the support. In a color light-sensitive material, generally, 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 are coated 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 compound used in the present invention can be applied to, for example, black-and-white film, color paper, color reversal paper, direct positive color photographic 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, and particularly, 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 is provided with a dye which can be decolorized by the treatment described in EP No. 0337490A2, pages 27-76. 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. As the support used in the light-sensitive material of the present invention, a white polyester-based support for a display or a support provided on the support on the side having a silver halide emulsion layer containing a white content is used. May be. 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 set to 0. so that the display can be viewed with both reflected light and transmitted light.
It is preferably set in the range of 35 to 0.8.

The light-sensitive material of the present invention is imagewise exposed, color-developed, and then processed with a processing solution having a bleaching ability (bleaching solution and bleach-fixing solution). These are described in Research Disclosure, No. 17643, pages 28-29 and No. 187.
See page 16, left column to right column, page 615. For example, a color development processing step, a bleaching step, a fixing step, and a water washing processing step are 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 the processing method and processing addition 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.

[0064]

[Table 1]

[0065]

[Table 2]

[0066]

[Table 3]

[0067]

[Table 4]

[0068]

[Table 5]

[0069]

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) After the surface of a paper support laminated with polyethylene on both sides was subjected to corona discharge treatment, 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 5th layer coating solution 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. In this emulsion, the red-sensitizing dye E shown in Table 8 below was added to the emulsion of large size per mol of silver halide in an amount of 0.2.
9 × 10 ^-4 mol, or 1.1 × for small emulsions
10 ⁻⁴ mol is added. Further, compound F shown in Table 8 below was added in an amount of 2.6 × 10 ⁻³ mol per mol of silver halide. 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 to prepare a coating solution for the fifth layer having the composition shown in Table 11 below.

The coating solutions for the first to fourth layers, the sixth layer and the seventh layer were prepared in the same manner as the coating solution for the fifth layer. 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.

[0072]

[Table 6]

[0073]

[Table 7]

[0074]

[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.

[0076]

[Chemical formula 23]

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

[0078]

[Table 9]

[0079]

[Table 10]

[0080]

[Table 11]

[0081]

[Chemical formula 24]

[0082]

[Chemical 25]

[0083]

[Chemical formula 26]

[0084]

[Chemical 27]

[0085]

[Chemical 28]

[0086]

[Chemical 29]

(Preparation of Samples 102 to 121) When preparing the emulsified dispersion of the fifth layer coating liquid, the coupler and high boiling point organic solvent in Sample 101 were used as the coupler and high boiling point organic solvent shown in Table 12. . Further, for the sample 102, double the amount of the high boiling point organic solvent was used, and the samples 103 to 11 were used.
2, 114, 115, 117, 118, 120, 121
For, the additives shown in Table 12 were added in the same amount as the high boiling point organic solvent. Hereinafter, a coating solution is prepared in the same manner as in Sample 101,
Application was performed to prepare samples 102 to 121. At this time, the amount of coupler used was equimolar to C-7 in Sample 101. As comparative compounds, CS-1, CS-2, CS-
3, CS-4, CS-5, CS-6 were used.

[0088]

[Chemical 30]

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 Samples) The absorption spectrum of each processed sample 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.

[0094]

[Table 12]

The results shown in Table 12 show the following. Sample 101 of high boiling point organic solvent alone, urea-based, amide-based, urethane-based compounds CS-1, CS-2, CS- other than the present invention
Sample 10 containing 3, CS-4, CS-5, CS-6
Sample 10 in which the compound of the present invention was added to 3 to 108
All of 9 to 112 and the like show a small value of D _600nm , the association is suppressed, a large value of D _max , a high color developing property, a low fading ratio, and excellent light fastness. ing.

Example 2 (Preparation of Samples 201 to 212) When preparing an emulsified dispersion of the third layer coating solution of Sample 101, in Sample 202, the amount of the high-boiling organic solvent used was halved to prepare Sample 203. ~
For 212, a coating liquid was prepared and coated in the same manner as in Sample 101, except that the additives shown in Table 13 were added in the same amount as the high boiling point organic solvent. Next, in each of Samples 201 to 212, the sensitometer used to prepare 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 250 CM with the exposure time of 0.1 seconds.
The exposure amount was set to S. 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.

[0098]

[Table 13]

The results shown in Table 13 show the following. Sample 202 of high boiling point organic solvent alone, urea-based, amide-based, urethane-based compounds CS-1, CS-2, CS- other than the present invention
Sample 20 to which 3, CS-4, CS-5, CS-6 was added
Sample 20 in which the compound of the present invention was added to 3 to 208
9 to 212 all show a small value of D _{500 nm} ,
The association is suppressed, the D _max has a large value, the color developability is high, and the fading rate is small, and the light fastness is excellent.

Example 3 High boiling organic solvent o of the ninth layer of the multilayer color reversal light-sensitive material sample 401 in Example 4 of JP-A-4-359249
replaced il-1 compounds in the present invention (dibutyl phthalate) S-5 (0.1g / m 2), the compound S-5 in the present invention 0.05 g / m ² was added to the tenth layer, the first
One layer of high boiling organic solvent oil-1 (dibutyl phthalate)
Was replaced with the compound S-5 (0.08 g / m ² ) of the present invention, and a sample 301 produced in the same manner as in Example 4 of 4-359249 was slit to a width of 35 mm to obtain a commercially available film. After performing perforation processing in the same format as above, give a uniform exposure.
No. 9249, process No. 4 of the fourth embodiment. When the processing was carried out using the hanging type automatic developing machine in 11, excellent hue,
Color development and fastness were confirmed.

Example 4 In the third layer of the sample 103 of Example 1 of JP-A-4-359249, 3% of the high boiling organic solvent Solv-1 (tricresyl phosphate) 7.0 × 10 ⁻³ g / m ² was added. 0.5 × 10 ^-3 g /
m ² and the compound S-5 in the present invention was added to 3.5 × 10 ⁻³
g / m ² was further added, in the fourth layer, the same Solv-1 of 0.1 g / m ² to 0.05 g / m ^2, the compound S-5 in the present invention 0.05 g / m ² In addition, also, In the fifth layer, the same Solv-2 (dibutyl phthalate) 0.0
A sample prepared in the same manner as in Example 1 of JP-A-4-359249 except that 8 g / m ² was replaced with the compound S-5 of the present invention in the same weight, and after the imagewise exposure, the sample
No. 59249, the processing No. 1 of the first embodiment. When the treatment was performed at 18, the increase in the minimum density due to the residual color of the sensitizing dye was suppressed.

[0102]

Since the silver halide light-sensitive material of the present invention has the above constitution, it exhibits 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 for color photography, it is excellent in solubility and dispersion stability of the photographic reagent, and the color reproducibility of the dye is good, There is no fading, and the dye-diffusion-resistant coupler is excellent in color development.

Claims (2)

[Claims] 1. A silver halide light-sensitive material characterized in that at least one layer of a non-color forming compound represented by the following formula (I) is contained on a support. [Chemical 1] (In the formula, R ¹ and R ² each represent an aliphatic group or an aryl group, and R ³ represents a group capable of substituting on the benzene ring.
Represents an integer of 0 to 4. However, the total number of carbon atoms of R ¹ , R ² and R ³ is 2 to 50. ) 2. A layer containing at least one compound represented by the general formula (I) is at least one cyan coupler represented by the following general formula (II) or the following general formula (III).
2. The silver halide light-sensitive material according to claim 1, containing at least one kind of magenta coupler represented by [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 ¹¹ and R ¹² each represent an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.30 or more. R ¹³ 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. )