JPH0693084B2 - Silver halide photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material, and in particular, a photograph of tricyclo [5.2.1.0 ^2,6 ] decanedicarboxylic acid ester which is hardly soluble in water. The present invention relates to a silver halide photographic light-sensitive material in which a useful reagent is dispersed and contained in a hydrophilic organic colloid layer.

(Prior Art) Conventionally, a photographically useful reagent which is sparingly soluble in water {for example, an oil-soluble coupler, an antioxidant 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, DIR compounds (eg DIR hydroquinones, non-colored DIR compounds), developers, dye developers, DDR redox compounds , DDR couplers} are dissolved in a suitable oil former, ie a high boiling solvent, and dispersed in the solution of a hydrophilic organic colloid, especially gelatin in the presence of a surfactant,
It is used by being contained in a hydrophilic organic colloid layer (for example, a photosensitive emulsion layer, a filter layer, a back layer, an antihalation layer, an intermediate layer, a protective layer). As the high boiling point organic solvent, a phthalic acid ester compound or a phosphoric acid ester compound is particularly used.

The phthalic acid ester compounds and phosphoric acid ester compounds, which are high boiling point organic solvents, affect the dispersibility of couplers, the affinity with colloid layers such as gelatin, and the stability of the color image.
It has been widely used because it is excellent in that it affects the hue of the color-developed color image, is chemically stable in the light-sensitive material, and can be obtained at low cost.

However, these known high-boiling point organic solvents (for example, phthalic acid ester compounds and phosphoric acid ester compounds) are caused by light, heat, and humidity of a color image for a recent photosensitive material that is required to have high performance. It was still insufficient in terms of the effect of preventing discoloration and generation of stain. In addition, these high-boiling point organic solvents may not always be appropriate in order to obtain a desired hue in the color-developed color image, and a new high-boiling point organic solvent has been demanded.

In addition, in the situation where the simplification and speeding-up of the developing process is remarkably progressed as typified by the recent two-bath process consisting of color developing process and bleach tightening process and reduction of washing water, stain after the process is The issue of (ground color pollution) is being highlighted.

It is considered that the developing agent (paraphenylenediamine derivative) remaining in the light-sensitive material after color development becomes an oxidant due to air oxidation or oxidation during bleach-fixing processing, and this reacts with the remaining coupler to produce stain. As a countermeasure against this, a means for reducing the amount of the developing agent remaining in the light-sensitive material has been proposed.

For example, JP-A-54-118246 discloses a high boiling point organic solvent having a low dielectric constant (for example, n-butyl adipate, di- (2-ethylhexyl) adipate, di- (2-ethylhexyl) azelate, di- (2-ethylhexyl)). Sebacate}, and these compounds were indeed effective in preventing stain after treatment. However, these dibasic acid esters do not have sufficient dispersion stability for photographic reagents,
Further, the stability of the color image against heat and light has been desired to be improved one step further. Incidentally, phosphoric acid esters and phthalic acid esters which have been generally used conventionally have a high dielectric constant and have already been unsuitable from the viewpoint of the effect of preventing stain after treatment.

In addition, the tricyclo [5.2.1.0 described in JP-A-58-130337]
^Although the diesters of ^2,6 ] decane dimethanol are improved in comparison with the dibasic acid esters in terms of dispersion stability of photographically useful reagents and stability of color image against heat and light, The performance was still insufficient to materialize the light-sensitive material.

(Problems to be Solved by the Invention) The first object of the present invention is to provide a novel high-boiling-point organic solvent excellent in solubility and dispersion stability of a photographically useful reagent and a silver halide photographic light-sensitive material using the same. To provide.

The second object of the present invention is to provide a silver halide photographic light-sensitive material having a reduced stain after processing by using a novel high boiling point organic solvent.

Thirdly, an object of the present invention is to provide a silver halide photographic light-sensitive material in which the fastness of a color image to light and heat is improved by using a novel high boiling point organic solvent.

(Means for Solving the Problems) These objects of the present invention include halogenation in which a poorly water-soluble photographic reagent is dispersed in a hydrophilic colloid composition in the presence of at least one high-boiling organic solvent. In the silver photographic light-sensitive material, at least one of the high-boiling organic solvents is tricyclo [5.2.1.0 ^2,6 ] decanedicarboxylic acid ester represented by the following general formula (I). Achieved in material.

General formula (I) In formula (I), R ₁ and R ₂ are each independently an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group, and R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom or Represents an alkyl group.

The compound represented by formula (I) is described in detail below.

The compound represented by the general formula (I) is represented by the following general formula (I
-1), (I-2) and (I-3) are preferably used, and these have an isomer relationship, and are used alone or as a mixture when obtained as a mixture depending on the production method. You can

General formula (I-1) General formula (I-2) General formula (I-3) In the general formulas (I-1), (I-2) and (I-3)
R ₃ and R ₄ are bonded to carbon atoms at positions 1, 7, 8, 9 and 10 in the case of an alkyl group, and R ₅ and R ₆ are 2, 3, 4, 5 and 6 in the case of an alkyl group. attached to any carbon atom positions, further _{COOR 1, COOR 2, R 3} , R 4, R 5 and any substituent tricyclo [5.2.1.0 ^{2, 6]} of R ₆ decane for endo or exo Can be substituted at any position of.

Further, the compounds represented by formulas (I-1), (I-2) and (I-3) all exist as a mixture of enantiomers.

In formula (I), R ₁ and R ₂ are preferably alkyl groups having 1 to 24 carbon atoms, alkenyl groups having 2 to 24 carbon atoms, aralkyl groups having 7 to 30 carbon atoms, and 6 carbon atoms.
~ 30 aryl group or a heterocyclic group having 2 to 30 carbon atoms, and these groups further include a halogen atom (fluorine atom, chlorine atom, bromine atom and iodine atom), a hydroxyl group, a hydroxyl group, Alkyl group, alkenyl group,
It may be substituted with an aryl group, a heterocyclic group, an alkoxycarbonyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, a sulfonyl group or an epoxy group. Examples of R ₁ and R ₂ are alkyl groups (for example, methyl, ethyl, butyl, isobutyl, n-hexyl, 2-ethylhexyl, n-decyl, 3,5,5-trimethylhexyl, n-hexadecyl, 2-chloroethyl, cyclohexyl. , 1-methylcyclohexyl, 1,
1-diethylpropyl, 1-ethyl-1,5-dimethylhexyl, menthyl, bornyl, methoxyethyl, butoxyethyl, phenoxyethyl, 5-methylhexyl, 3
-Methylhexyl, 2,4-dimethylpentyl, 2-hexyldecyl, 3-dodecyloxypropyl), alkenyl groups (e.g. vinyl, allyl, hexenyl, undecenyl, cyclohexenyl, oleyl), aralkyl groups (e.g. benzyl, α-phenethyl) , Β-phenethyl, 3-phenylpropyl, 1-naphthylmethyl, 4-methoxybenzyl), aryl groups (eg phenyl, 4-methoxyphenyl, 4-t-butylphenyl, 2,4-di-t-pentylphenyl, 4 -Methoxycarbonylphenyl, 4
-(1,3,3-Tetramethylbutyl) phenyl, p-tolyl, 2-chlorophenyl} or a heterocyclic group (for example, furyl, thienyl, pyridyl, N-methylpyrrolyl, tetrahydrofuryl, pyranyl, N-methylimidazolyl, quinolyl) There is.

In the general formula (I), R ₃ , R ₄ , R ₅ and R ₆ are preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl). , Isopentyl, hexyl)
Represents

Next, among the compounds represented by formula (I), the compounds particularly preferably used in the present invention will be explained.

In formula (I), R ₁ and R ₂ are preferably an alkyl group or an aryl group, and a substituent of these groups is preferably a halogen atom, an alkyl group (in the case of an aryl group), an alkoxy group or an alkoxycarbonyl group. In the case of an alkyl group, it preferably has 2 to 18 carbon atoms, and particularly preferably 4 to 12 carbon atoms. In the case of an aryl group, it preferably has 6 to 24 carbon atoms, and particularly preferably 6 to 18 carbon atoms. Further, it is most preferable that both R ₁ and R ₂ are alkyl groups, and the total number of carbon atoms of R ₁ and R ₂ is preferably 3 or more, more preferably 6 or more, in order to prevent diffusion and evaporation in the light-sensitive material. , 8 or more are particularly preferable.

In formula (I), R ₃ , R ₄ , R ₅ and R ₆ are preferably hydrogen atoms or methyl groups, and particularly preferably hydrogen atoms.

Specific examples of the compound represented by formula (I) are shown below, but the invention is not limited thereto.

Compounds (I-1) to (I-43) These compounds represented by the general formula (I) are derived from tricyclo [5.2.1.0 ^2,6 ] decanedicarboxylic acid or tricyclo [5.2.1.0 ^2,6 ] decanedicarboxylic acid dimethyl ester as follows.

(However, R represents R ₁ or R _2. ) In the reaction a, chlorinating agents such as thionyl chloride, phosphorus trichloride, phosphorus pentachloride, carbon tetrachloride, phosphorus oxychloride are added to dicarboxylic acids without solvent or benzene, toluene, The acid chlorides can be obtained by acting in a solvent such as xylene, methylene chloride, chloroform, dichloroethane, carbon tetrachloride and the like. Preferred reaction conditions are 2 to 10 mol (preferably 3 to 6 mol) of thionyl chloride to 1 mol of dicarboxylic acid from room temperature to 100 ° C (preferably 50 to 8 mol).
The reaction is carried out at 0 ° C for 10 minutes to 10 hours (preferably 30 minutes to 3 hours), and unreacted thionyl chloride is heated to 100 ° C or less (preferably 8 minutes).
There is a method of distilling off at 5 ° C or less) to obtain as a residue or by vacuum distillation.

In the reaction b, acid chlorides and alcohols (ROH) are used without base or with bases (for example, pyridine, triethylamine, DBU, DBN, tetramethylguanidine, picoline, lutidine, sodium carbonate, potassium carbonate, sodium hydride, t-butoxy). (Potassium) without solvent or in the presence of a solvent such as benzene, toluene, xylene, methylene chloride, chloroform, dichloroethane, carbon tetrachloride, acetonitrile, tetrahydrofuran, dimethylformamide, dimethylacetamide, etc. A compound of formula (I) can be obtained. As a preferable reaction condition, ROH 1 to 5 mol (preferably 1.5 to 2.5 mol) is used without solvent or in the presence of a solvent such as benzene, toluene, xylene, methylene chloride, chloroform, dichloroethane to ROH 1 to 5 mol per mol of acid chloride at room temperature to 120 mol. C. (preferably 40.degree. C. to 85.degree. C.) for 30 minutes to 3 hours or in the presence of 1 to 10 mol (preferably 2 to 3 mol) of a base such as pyridine or triethylamine.
There is a method of reacting at 85 ° C (preferably 0 ° C to 50 ° C) in a solvent such as methylene chloride, chloroform, dichloroethane, toluene and tetrahydrofuran.

In reaction c, alcohols (ROH) are used in an amount of 1 to 10 mol (preferably 1.5 to 3 mol) per mol of dicarboxylic acid,
In the presence of no solvent or a solvent such as benzene, toluene, xylene, chloroform, dichloroethane, etc., a dehydrating agent such as sulfuric acid, paratoluenesulfonic acid, hydrogen chloride or polyphosphoric acid at room temperature to 120 ° C (preferably 50 ° C to 120 ° C). The desired compound represented by the general formula (I) can be obtained by the action. Preferable reaction conditions include using 2 to 3 moles of ROH to 1 mole of dicarboxylic acids, using toluene or xylene as a solvent, and adding sulfuric acid or paratoluenesulfonic acid as a catalyst to 0.01 to 1 mole while distilling off the produced water. There is a method of heating under reflux.

In the reaction d, an aqueous solution of 2 to 20 mol of sodium hydroxide or potassium hydroxide is allowed to act at room temperature to 100 ° C (preferably 50 to 80 ° C) with respect to 1 mol of dimethyl esters, and then neutralized to dicarboxylic acid. Can be obtained.

In reaction e, dimethyl esters can be obtained by adding a large excess of methanol to dicarboxylic acids and reacting sulfuric acid or hydrogen chloride at room temperature to reflux temperature.

In the reaction f, 1 to 10 mol (preferably 2 to 3 mol) of alcohols (ROH) is used for 1 mol of dimethyl ester, and 0.01 to 0.1 mol of titanium tetrabutoxide or titanium tetraisopropoxide is used as a catalyst without solvent. Alternatively, the desired compound represented by the general formula (I) can be obtained by reacting with a solvent such as benzene, toluene or xylene at 50 ° C to 200 ° C (preferably 80 ° C to 160 ° C).

Tricyclo [5.2.1.0 ^{2, 6]} decane dicarboxylic acids other by the reaction d, tricyclo obtained by oxo synthesis of dicyclopentadiene [5.2.1.0 ^{2, 6]} de cyclopentadienyl shown in oxidation or below Kanji aldehyde It is obtained by carbonation of anions and then catalytic hydrogenation.

The latter reaction conditions are CJ Bouboulis, J.Org.Chem., 32 (1
Details on 1), 3540-3 (1967).

Tricyclo [5.2.1.0 ^2,6 ] decanedicarboxylic acid dimethyl esters are obtained by methoxycarbonylation of dicyclopentadienes with dicobalt octacarbonyl. Details of this reaction are described in JP-A-58-110538.
No.

The synthesis examples of the compound of the present invention are shown below.

(Synthesis Example 1) Synthesis of Exemplified Compound (I-19) 126 g (0.5 mol) of tricyclo [5.2.1.0 ^2,6 ] decanedicarboxylic acid dimethyl ester and 2-ethylhexanol 1
5 g of titanium tetrabutoxide was added to 43 g (1.1 mol), and the mixture was heated and stirred. While distilling off the produced methanol, the temperature was raised from 100 ° C to 160 ° C in about 5 hours. After cooling the reaction solution
200 ml of 1N hydrochloric acid was added and stirred for about 1 hour. 200 ml of ethyl acetate
Was added to separate the layers, and the ethyl acetate layer was washed with an aqueous sodium hydrogen carbonate solution and water and then concentrated. The concentrate was distilled under reduced pressure to obtain 188 g of the desired Exemplified Compound (I-19). yield
84%, boiling point 205-215 ° C / 0.4 mmHg, IR spectrum is shown in Fig. 1.

(Synthesis Example 2) Synthesis of Exemplified Compound (I-7) In place of 2-ethylhexanol in Synthesis Example 1, n
In the same manner as in Example 1 except that 148 g (2 mol) of butanol was used and the reaction temperature was changed from 80 ° C to 140 ° C, 131 g of the desired exemplified compound (I-7) was obtained. Yield 78%, boiling point 192
Fig. 2 shows the IR spectrum at ° C / 0.25 mmHg.

(Synthesis Example 3) Synthesis of Exemplified Compound (I-10) Instead of 2-ethylhexanol in Synthesis Example 1, n
-159 g of the desired exemplary compound (I-10) was prepared in the same manner as in Synthesis Example 1 except that 123 g (1.2 mol) of hexanol was used.
Obtained. The yield is 81%, the boiling point is 213 to 215 ° C./0.3 to 0.35 mmHg, and the IR spectrum is shown in FIG.

The amount of the compound represented by the general formula (I) used in the present invention is
Depends on the type of photographically useful reagent to be coexisted and its physicochemical properties, but in most cases 1 for the amount of photographically useful reagent
It can be arbitrarily changed within the range of up to 200% by weight. Preferably,
The compound represented by the general formula and the photographically useful reagent are used under the condition that they are uniformly coexisting and dispersed in a compatible state. The compound represented by formula (I) of the present invention can be added to the hydrophilic organic colloid layer of the photographic light-sensitive material together with a photographically useful reagent by an oil-in-water dispersion method or the like. In this method, a low boiling auxiliary solvent is optionally used in combination with oil to obtain a solution of a photographically useful reagent, and then finely dispersed in an aqueous medium such as water or an aqueous gelatin solution in the presence of a surfactant. The dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, rinsing with water, ultrafiltration or the like before being used for coating.

The compound represented by the general formula (I) of the present invention may be used alone or as a mixture of two kinds, and a photographically useful reagent which is hardly soluble in water may be dissolved in water as a high boiling point organic solvent, and other compounds may be used if necessary. You may use together with a well-known high boiling point organic solvent.

The photographically useful reagents which are sparingly soluble in water in the present invention include all the photographically useful reagents which have been dispersed in a hydrophilic organic colloid layer using a conventionally known high boiling point organic solvent.

Representative water-insoluble photouseful reagents include photographic couplers (for example, yellow couplers, magenta couplers,
Cyan coupler, black coupler, non-color coupler),
Antioxidants and anti-fading agents (for example, alkylhydroquinones and their mono- or dialkyl ethers, alkylphenols, chromanes, coumarans, hindered amines, transition metal complexes) that prevent color fog and discoloration of color images. Membrane agents, oil-soluble filter dyes, oil-soluble antihalation dyes, oil-soluble UV absorbers, optical brighteners, DIR compounds (eg DIR couplers, DIR hydroquinone), developers, DDR couplers, DRR compounds, dye developers, developers Inhibitors and their precursors, development accelerators and their precursors and the like can be mentioned.

The compound represented by the general formula (I) of the present invention can be dispersed in such water as a poorly soluble photographically useful reagent and can be contained in the hydrophilic organic colloid layer. It is extremely advantageously used when it is incorporated in a functional silver halide emulsion layer.

The photographic coupler applicable to the present invention means a compound capable of causing a coupling reaction with an oxidized product of an aromatic primary amine developing agent (for example, a phenylenediamine derivative or an aminophenol derivative) in color development processing. However, for example, magenta couplers include 5-pyrazolone couplers, pyrazolotriazole couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and the like, and yellow couplers include acylacetamide couplers (for example, benzoylacetanilide couplers, Pivaloylacetanilide couplers, malondiamide couplers, etc.), and naphthol couplers and phenol couplers can be mainly mentioned as cyan couplers.

Specific examples of the cyan, magenta and yellow couplers used in the present invention are described in RD17643 (December 1978) Item VII-D.
18717 (November 1979).

These couplers preferably have ballast groups or are polymerized and are diffusion resistant. The coupling position is preferably substituted with a leaving group rather than a hydrogen atom. It is also possible to use couplers, colored couplers, colorless couplers or couplers which release a development inhibitor or a development accelerator upon a coupling reaction so that the color forming dye has an appropriate diffusibility.

A typical example of the yellow coupler that can be used in the present invention is an oil protect type acylacetamide coupler. A specific example is U.S. Pat. No. 2,407,21.
No. 0, No. 2,875,057 and No. 3,265,506. A 2-equivalent yellow coupler can be preferably used in the present invention, and US Pat. Nos. 3,408,194 and 3,447,9 can be used.
No. 28, No. 3,933,501 and No. 4,401,752 oxygen atom desorption type yellow couplers described in JP-B-58-10739, U.S. Pat.
No. 24, RD18053 (April 1979), British Patent No. 1,425,020
Representative examples thereof include nitrogen atom-releasing yellow couplers described in West German Application Publication Nos. 2,219,917, 2,261,361, 2,329,587, and 2,433,812. The α-pivaloyl acetanilide type coupler is characterized by the fastness of the color forming dye, while the α-benzoyl acetanilide type coupler is characterized by good color forming property.

Examples of magenta couplers that can be used in the present invention include oil protector type indazolone type or cyanoacetyl type couplers, preferably 5-pyrazolone type and pyrazoloazole type couplers such as pyrazolotriazoles. The 5-pyrazolone-based coupler is preferably one in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and coloring speed of the coloring dye, and typical examples thereof are U.S. Pat. , The second,
No. 600,788, No. 2,908,573, No. 3,062,653, No.
No. 3,152,896 and No. 3,936,015. A 2-equivalent 5-pyrazolone-based coupler is preferable, and the leaving group is preferably a nitrogen atom leaving group described in US Pat. No. 4,310,619 or an arylthio group described in US Pat. No. 4,351,897. Further, the 5-pyrazolone type coupler having a ballast group described in EP 73,636 has a high color developing reactivity.

As a pyrazoloazole-based coupler, European Published Patent 11
Pyrazolo [1,5, -b] [1,2,4] triazoles described in 9860, pyrazolobenzimidazoles described in US Pat. No. 3,369,897, preferably RD24220 (June 1984)
Pyrazolotetrazole and RD24230 (1984
Pyrazolopyrazoles described in (June, 2014).
The imidazopyrazoles and the pyrazolo [1,5, -b] [1,2,4] triazoles described in Japanese Patent Application No. 58-23434 have low yellow sub-absorption of a coloring dye and light fastness. Most preferred are those used in combination.

Cyan couplers that can be used in the present invention include oil-protection type naphthol-based and phenol-based couplers, naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.No. 4,052,212.
No. 4,146,396, No. 4,228,233 and No. 4,296,20
A representative example is the oxygen atom-dissociation type highly active 2-equivalent naphthol coupler described in No. 0. Specific examples of phenol-based couplers include U.S. Pat.
2,423,730, 2,772,162, 2,801,171 and 2,895,826.

Cyan couplers that are fast against heat, humidity and temperature are preferably used in the present invention, and typical examples thereof include a phenolic cyan coupler described in U.S. Pat.No. 3,772,002,
U.S. Pat.Nos. 2,772,162, 3,758,308, 4,126,
Nos. 396, 4,334,011, 4,327,173, 2,5-Diacylamino-substituted phenol couplers described in West German Patent Publication No. 3,329,729 and Japanese Patent Application No. 58-42671, and U.S. Pat. No. 4,333,999, same
2, described in 4,451,559 and 4,427,767
Examples thereof include a phenolic coupler having a phenylureido group at the -position and an acylamino group at the 5-position.

In order to correct unnecessary absorption in the short wavelength region which the coloring dyes of magenta and cyan couplers have, it is preferable to use a colored coupler in combination with the color photographic material for photographing. Yellow colored magenta couplers described in U.S. Pat.No. 4,163,670 and JP-B-57-39413 or U.S. Pat.
004,929, 4,138,258 and British Patent 1,146,36
Typical examples include magenta colored cyan couplers described in No. 8 and the like.

These color couplers may form a dimer or higher polymer. Typical examples of polymerized couplers are described in US Pat.
No. 3,451,820 and No. 4,080,211.
Specific examples of polymerized magenta couplers are described in British Patent 2,10
2,173 and U.S. Pat. No. 4,367,282.

Further, a color forming dye diffusion type coupler can be used in combination to improve the graininess, and such a coupler is described in U.S. Pat.
Examples of magenta couplers are described in 237 and British Patent 2,125,570, and examples of yellow, magenta and cyan are described in EP 96,873 and West German Patent Publication (OLS) 3,324,533.

These couplers may be used in combination of two or more kinds in the same layer in order to satisfy the characteristics required for the light-sensitive material, and it is of course possible to add the same compound to two or more different kinds.

These couplers may be dispersed by using the compound represented by the general formula (I) of the present invention. May be. Further, it may be separately emulsified using a known high boiling point organic solvent and used in combination with the present invention.

Specific examples of the high boiling point organic solvent that can be used in combination with the compound represented by the general formula (I) of the present invention include phthalic acid esters (dibutyl phthalate, dixylhexyl phthalate, di-2-ethylhexyl phthalate, dodecyl phthalate. Etc.), esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate) , Di-2-ethylhexylphenyl phosphate, etc., benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylexyl-p-hydroxy) Benzoate), amides (diethyldodecane amide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (dioctyl) Azelates, dioctyl sebacates, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffins) , Chlorinated paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like.

The coupler which is particularly preferably used in combination with the compound represented by formula (I) of the present invention is described in detail below. That is, the following general formulas (II), (III), (IV), (V), (VI)
Most preferably, the compound represented by formula (I) of the present invention is used for dispersing the coupler represented by (VII).

General formula (II) In the general formula (II), R ₁₁ is a tertiary alkyl group or an aryl group, R ₁₂ is a hydrogen atom, a halogen atom, an amino group,
An alkoxy group or an alkyl group, R ₁₃ represents a halogen atom, an alkoxy group, an alkyl group, a carbonamido group, a sulfonamide group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group or a cyano group. m represents an integer of 0 to 4, and when m is plural, plural R ₁₃ may be the same or different. X ₁₁ represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developer (for example, a halogen atom, an acyloxy group, an aryloxy group, a heterocyclic oxy group, an arylthio group, a heterocyclic thio group). , A monocyclic or condensed ring heterocyclic group bonded to the coupling active position with a nitrogen atom). Examples of R ₁₁ include t-butyl group and 1-ethyl-1
-Methylpropyl group, 2-chloro-1,1-dimethylethyl, adamantyl group, phenyl group, 4-methoxyphenyl group, 2-methylphenyl group and the like, as an example of R ₁₂ , chlorine atom, bromine atom, fluorine atom, Methoxy group, methyl group,
A dimethylamino group or the like, a chlorine atom as an example of R ₁₃ , a methoxy group, a dodecyloxycarbonyl group, a hexadecanesulfonamide group, a 2- (2,4-di-tert-amylphenoxy) butanamide group, a 4- (2,4 -Di-tert-amylphenoxy) butanamide group, tetradecyloxy group, etc., examples of X ₁₁ include acetyloxy group, 4-dodecyloxycarbonylphenoxy group, 4- (4-benzyloxyphenylsulfonyl) phenoxy group, 4- ( 4-hydroxyphenylsulfonyl) phenoxy group, pyrazolyl group, imidazolyl group, chlorotriazolyl group, 2-pyridyloxy group, 1-benzyl-3-hydantoinyl group,
1-benzyl-5-ethoxy-3-hydantoinyl group,
1-benzyl-2-phenylurazol-3-yl group,
Examples thereof include a 4,5-dimethoxycarbonylimidazol-1-yl group and a 4-carboxyphenoxy group. The coupler represented by the general formula (II) is R ₁₁ , R
They may be linked together at ₁₂ , R ₁₃ or X ₁₁ to form a multimeric or polymeric coupler.

General formula (III) In the general formula (III), R ₂₁ is a carbonamido group, anilino group or ureido group, R ₂₂ is a phenyl group, and X ₂₁ is removable by a coupling reaction with an oxidized aromatic primary amine developer. Represents a group (hereinafter referred to as a leaving group).

X ₂₁ is a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom or a carbon atom and is coupled to activated carbon and an aliphatic group, an aromatic group, a heterocyclic group, an aliphatic / aromatic or heterocyclic sulfonyl group, an aliphatic group. -Aromatic or heterocyclic carbonyl group, a carbamoyl group, an alkoxycarbonyl group, a group capable of binding to an aryloxycarbonyl group, a halogen atom, an aromatic azo group, a heterocyclic group, and the like. Aliphatic, aromatic or heterocyclic group contained in X ₂₁ , R ₂₁ and R ₂₂
May be further substituted, and examples thereof include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an alkyl group (eg, methyl, t-octyl, dodecyl, trifluoromethyl), an alkenyl group (eg, allyl, octadecenyl). ), Aryl groups (eg phenyl, p-tolyl, naphthyl), alkoxy groups (eg methoxy, benzyloxy, methoxyethoxy), aryloxy groups (eg phenoxy, 2,4-di-tert-amylphenoxy, 3-tert-). Butyl-4-hydroxyphenoxy),
Acyl group (eg acetyl, benzoyl), sulfonyl group (eg methanesulfonyl, toluenesulfonyl),
Carboxy group, sulfo group, cyano group, hydroxy group, amino group (eg amino, dimethylamino), carbonamide group (eg acetamide, trifluoroacetamide, tetradecane amide, benzamide), sulfonamide group (eg methanesulfonamide, hexadecane sulfone) Amide, p-toluenesulfonamide), acyloxy group (eg acetoxy), sulfonyloxy group (eg methanesulfonyloxy), alkoxycarbonyl group (eg dodecyloxycarbonyl), aryloxycarbonyl group (eg phenoxycarbonyl),
Carbamoyl group (eg dimethylcarbamoyl, tetradecylcarbamoyl), sulfamoyl group (eg methylsulfamoyl, hexadecylsulfamoyl), imide group (eg succinimide, phthalimide, octadecenylsuccinimide), heterocyclic group (eg 2- Pyridyl, 2-furyl, 2-thienyl), an alkylthio group (for example, methylthio), and an arylthio group (for example, phenylthio) can be mentioned. Specific examples of X ₂₁ include halogen atom (for example, fluorine atom, chlorine atom, bromine atom), alkoxy group (for example, benzyloxy), aryloxy group (for example, 4-chlorophenoxy, 4-methoxy), acyloxy group (for example, Acetoxy, tetradecanoyloxy, benzoyloxy), aliphatic or aromatic sulfonyloxy groups (eg methanesulfonyloxy, toluenesulfonyloxy), carbonamide groups (eg dichloroacetamide, trifluoroacetamide), aliphatic or aromatic sulfonamides Groups (eg methanesulfonamide, p-toluenesulfonamide), alkoxycarbonyloxy groups (eg ethoxycarbonyloxy, benzyloxycarbonyloxy), aryloxycarbonyloxy groups (eg phenoxy). Cycarbonyloxy), aliphatic / aromatic or heterocyclic thio groups (eg ethylthio, hexadecylthio, 4
-Dodecylphenylthio, pyridylthio), a ureido group (for example, methylureido, phenylureido), a 5- or 6-membered nitrogen-containing heterocyclic group (for example, imidazolyl,
Examples include pyrazolyl, triazolyl, tetrazolyl, 1,2-dihydro-2-oxo-1-pyridyl), imide groups (eg succinimide, phthalimide, hydantoinyl), aromatic azo groups (eg phenylazo) and the like. Further, there is a so-called bis-type coupler obtained by binding a 4-equivalent coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom.

R ₂₁ , R ₂₂ or X ₂₁ may be a divalent or higher polyvalent group to form a multimer such as a dimer,
Further, the polymer main chain may be connected to the coupler mother nucleus to form a polymer coupler.

The coupler represented by the general formula (III) has the following keto-
It is known in the art to have enol tautomerism.

Examples of compounds represented by the general formula (III), synthetic methods, and the like are described in, for example, JP-A-49-111631, JP-A-54-48540, and JP-A-55-485.
62454, 55-118034, 56-38045, 56-80045
No. 56, No. 56-126833, No. 57-4044, No. 57-35858, No. 57
-94752, 58-17440, 58-50537, 58-85432
Issue 58-117546, Issue 58-126530, Issue 58-145944,
58-205151, JP-A-54-170, 54-10491, 54-
21258, 53-46452, 53-46453, 57-36577
No. 58-110596, No. 58-132134, No. 59-26729
U.S. Pat.Nos. 3,227,554, 3,432,521, and 4,
No. 310,618 and No. 4,351,897.

General formula (IV) In formula (IV), R ₃₁ represents a hydrogen atom or a substituent, and X ₃₁ represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. Za, Zb and Zc represent methine, substituted methine, = N- or -NH-.

The compound represented by the general formula (IV) is a 5-membered to 5-membered fused nitrogen heterocyclic coupler, and its coloring mother nucleus shows isoelectronic aromaticity with naphthalene, and is a chemical structure generally called azapentalene. Has become. Among the couplers represented by formula (IV), preferred compounds are 1H-imidazo [1,2-b] pyrazoles, 1H-pyrazolo [1,5-b] pyrazoles, 1H-pyrazolo [5,1- c] [1,2,4] triazoles, 1H-pyrazolo [1,5-b] [1,2,4] triazoles and 1H-pyrazolo [1,5-b] tetrazoles, each having the general formula (IVa), (IVb), (IVc), (I
It is represented by Vd) and (IVe).

The substituents R ₃₂ , R ₃₃ and R _{34 in the} general formulas (IVa) to (IVe) will be described in detail. R ₃₂ , R ₃₃ and R ₃₄ represent an aliphatic group, an aromatic group or a heterocyclic group, and these are substituents which are usually used for these substituents (for example, a halogen atom, an alkyl group, an alkynyl group and an aryl group). , Heterocyclic group, alkoxy group, aryloxy group, acyloxy group, sulfonyloxy group, acyl group, sulfonyl group, carboxy group, sulfo group, hydroxy group, amino group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group , An alkoxycarbonyl group, an aryloxycarbonyl group, a ureido group, a sulfinyl group, an alkylthio group, an arylthio group, a cyano group). R ₃₂ , R ₃₃ and R ₃₄ may further be a hydrogen atom or a substituent having a halogen atom or less in the above ().
X ₃₁ represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized product of the aromatic primary amine developing agent (hereinafter referred to as a leaving group). When X ₃₁ represents a leaving group, X ₃₁ represents an activated carbon and an aliphatic group, an aromatic group, a heterocyclic group, an aliphatic group, an aromatic group or a coupling active carbon through an oxygen atom, a nitrogen atom, a sulfur atom or a carbon atom. A heterocyclic sulfonyl group, a group that bonds with an aliphatic, aromatic or heterocyclic carbonyl group, a halogen atom, an aromatic azo group, etc., and an aliphatic, aromatic or heterocyclic group contained in these leaving groups. May be substituted with the substituents allowable for R ₃₂ , R ₃₃ and R ₃₄ , and when two or more of these substituents are present, they may be the same or different. If the specific example of a substituent is given,
Halogen atom (eg fluorine atom, chlorine atom, bromine atom), alkoxy group (eg ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methanesulfonylethoxy), aryloxy group (eg 4-chlorophenoxy, 4-methoxy) Phenoxy, 4-carboxyphenoxy), an acyloxy group (eg acetoxy, tetradecanoyloxy,
Benzoyloxy), aliphatic or aromatic sulfonyloxy groups (eg methanesulfonyloxy, toluenesulfonyloxy), acylamino groups (eg dichloroacetylamino, trifluoroacetylamino, heptafluorobutyrylamino), aliphatic or aromatic sulfonamides Groups (eg methanesulfonamide, p-toluenesulfonamide), alkoxycarbonyloxy groups (eg ethoxycarbonyloxy, benzyloxycarbonyloxy), aryloxycarbonyloxy groups (eg phenoxycarbonyloxy), aliphatic, aromatic or heterocycles A thio group (eg ethylthio, phenylthio), a carbamoylamino group (eg N-methylcarbamoylamino, N-phenylcarbamoylamino),
5- or 6-membered nitrogen-containing heterocyclic group (eg imidazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,2
- dihydro-2-oxo-1-pyridyl), an imido group (e.g. succinimido, hydantoinyl), there is such an aromatic azo group (e.g. phenylazo), as these groups further substituents R _32, R ₃₃ and R ₃₄ It may be substituted with an acceptable substituent. Further, there is a bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom.

Any of R ₃₂ , R ₃₃ , R _34, or X ₃₁ may be a divalent or higher polyvalent group to form a dimer or a multimer, or linked to the polymer main chain to form a polymer. Couplers may be formed.

Examples of compounds of the couplers represented by the general formulas (IVa) to (IVe), synthetic methods, and the like are described in the following documents. The compound of general formula (IVa) is described in Japanese Patent Application No. 58-23434, and the compound of general formula (IVb) is described in Japanese Patent Application No. 58-15134.
The compound of the general formula (IVc) is described in Japanese Patent Publication No. 47-27411, and the compound of the general formula (IVd) is disclosed in Japanese Patent Application Nos. 58-45512 and 59-27745.
No. 58-142801 and the compounds of general formula (IVe)
No., etc., respectively.

Further, JP-A-58-42045, Japanese Patent Application Nos. 58-88940 and 58-52923.
No. 58-52924 and No. 58-52927, the highly chromogenic ballast group can be applied to any of the compounds of the general formulas (IVa) to (IVe).

General formula (V) In the general formula (V), R ₄₁ is an alkyl group, an aryl group or a heterocyclic group, R ₄₂ is a hydrogen atom, a halogen atom or an alkyl group, and R ₄₃ is an alkyl group, an aryl group, an anilino group or a heterocyclic group. , X ₄₁ is a group capable of splitting off upon reaction with hydrogen or an oxidized aromatic primary amine developing agent (for example, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a carbamoyloxy group, a sulfonamide group, And a heterocyclic oxy group and a heterocyclic thio group). Of the groups mentioned for R ₄₁ , R ₄₂ , R ₄₃ and X ₄₁ , the substitutable group is a substituent usually used for these groups (for example, a halogen atom, a hydroxy group, a carboxy group, a cyano group, a nitro group, an alkyl group). Group, aryl group, heterocyclic group, alkoxy group, aryloxy group, heterocyclic oxy group, alkylthio group group, arylthio group,
Alkylsulfonyl group, arylsulfonyl group, acyl group, carbamoyl group, sulfamoyl group, ureido group,
It may be substituted with an alkoxycarbonyl group, a carbonamido group, a sulfonamide group, a sulfamoylamino group). R ₄₁ and R ₄₂ may combine with each other to form a 5- to 7-membered ring.

Examples of R ₄₁ are t-butyl group, 1- (2,4-di-tert-amylphenoxy) propyl group, 1- (2,4-di-tert-
Amylphenoxy) amyl group, 1- (3-tert-butyl-4-hydroxyphenoxy) tridecyl group, 1- (4
-Tert-amyl-2-chlorophenoxy) heptyl group and the like, a fluorine atom, a chlorine atom, a methyl group and the like as an example of R _42, a trifluoromethyl group, a heptafluoropropyl group, 1,1, as an example of R ₄₃ 2,2-tetrafluoroethyl group,
Phenyl group, 2-chlorophenyl group, 2-methanesulfonamidophenyl group, 2,4-dichlorophenyl group, 4-
Cyanophenyl group, 2-chloro-4-cyanophenyl group, pentafluorophenyl group, 2-butanesulfonamidophenyl group, 4-cyanoanilino group, 4-methanesulfonylanilino group, 4-butanesulfonylanilino group, 4- N, N-diethylsulfamoylphenyl group, 3,4
- dichloro anilino group, 3-methanesulfonamide anilino group, a 2-chloro-3-Shianoanirino group, X ₄₁
Examples of fluorine atom, chlorine atom, bromine atom, methoxy group, methoxyethoxy group, 2-hydroxyethoxy group,
Carboxymethoxy group, N- (2-methoxyethyl) carbamoylmethoxy group, 3-carboxypropyloxy group, 2-carboxymethylthioethoxy group, phenoxy group, 4-methoxyphenoxy group, 4-chlorophenoxy group, 4-tert-octyl Examples thereof include a phenoxy group and a 3-pentadecylphenoxy group.

General formula (VI) In formula (VI), R ₅₁ is an alkyl group or an alkoxy group, R ₅₂ is a halogen atom or an alkyl group, R ₅₃ is an alkyl group, an aryl group or a heterocyclic group, and X ₅₁ is a hydrogen atom or an aromatic first group. A group capable of splitting off upon coupling reaction with an oxidized product of a primary amine developing agent (for example, halogen atom, alkoxy group, aryloxy group, alkylthio group, arylthio group, carbamoyloxy group, sulfonamide group, heterocyclic oxy group, heterocyclic thio group). Group).

Methyl group Examples of R _51, ethyl group, propyl group, isopropyl group, n- butyl group, t- butyl group, a pentadecyl group, a methoxy group, an ethoxy group, a butoxy group, R ₅₂
As an example of, a fluorine atom, a chlorine atom, a methyl group, an ethyl group and the like, as an example of R _53, a 1- (2,4-di-tert-amylphenoxy) propyl group, 1- (2,4-di-tert- Amylphenoxy) amyl group, 1- (2,4-di-tert-amylphenoxy) heptyl group, 1- (4-tert-amyl-2-
A chlorophenoxy) heptyl group, a tridecyl group, a pentadecyl group, a 1- (2-tert-amyl-4-chlorophenoxy) heptyl group, etc. as an example of X ₅₁ , X in the general formula (V)
Each of the substituents listed in ₄₁ can be mentioned.

The couplers represented by formulas (V) and (VI) may be used in combination.

General formula (VII) In the general formula (VII), R ₆₁ is a hydrogen atom, a hydroxy group,
Amino group, carbonamido group, sulfonamide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group or alkoxysulfonylamino group, R
₆₂ represents an alkyl group, an aryl group or a heterocyclic group, X ₆₁
Is a group capable of splitting off by a coupling reaction with a hydrogen atom or an aromatic primary amine developer oxidant (for example, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a carbamoyloxy group, a sulfonamide group, And a heterocyclic oxy group and a heterocyclic thio group).

Examples of R ₆₁ are hydroxy group, amino group, ethylamino group, anilino group, acetamide group, trifluoroacetamide group, methanesulfonamide group, toluenesulfonamide group, ethoxycarbonylamino group, isobutoxycarbonylamino group, 3-phenyl. Ureido group, R
Examples of ₆₂ are n-dodecyl group, n-hexadecyl group, n
-Dodecyloxypropyl group, 3- (2,4-di-tert-
Amylphenoxy) propyl group, 4- (2,4-di-tert
-Amylphenoxy) butyl group, 2-tetradecyloxyphenyl group, 2-chloro-5-dodecyloxycarbonylphenoxy group and the like, as an example of X ₆₁ , X in the general formula (V).
Each of the substituents listed in ₄₁ can be mentioned.

The couplers represented by the general formulas (V), (VI) and (VII) are R ₄₁ , R ₄₂ , R ₄₃ or X _{41 of} the general formula (V), R ₅₁ , R ₅₂ and R of the general formula (VI), respectively. ₅₃ or X _{51 of} the general formula (VII)
Any of R ₆₁ , R ₆₂ or X ₆₁ may be a divalent or higher polyvalent group to form a dimer or higher polymer, and the polymer main chain and the coupler mother The core may be linked to form a polymeric coupler.

Examples of couplers preferably used in the present invention are shown below.

Specific examples of the magenta dye-forming coupler represented by the general formula (IV) used in the present invention other than the above and the synthesis method of these compounds are described in, for example, International Patent Publication Nos. WO86 / 01915 and 86/0.
2467, European Patent Publication (EP) 182617, US Pat. No. 3,06
1,432, 3,705,896, 3,725,067, 4,500,630
Issue 4,540,654, 4,548,899, 4,581,326,
4,607,002, 4,621,046, 4,675,280, JP-A-59-228252, 60-33552, 60-43659, 60-55.
No. 343, No. 60-57838, No. 60-98434, No. 60-107032,
61-53644, 61-65243, 61-65245, 61-652
No. 46, No. 61-65247, No. 61-120146, No. 61-120147,
61-120148, 61-120149, 61-120150, 61-
No. 120151, No. 61-120152, No. 61-120153, No. 61-12015
No. 4, No. 61-141446, No. 61-144647, No. 61-147254,
61-151648, 61-180243, 61-228444, 61-
230146, 61-230147, 61-292143, etc.

The compound represented by the general formula (V) of the present invention can be used as a photographically useful reagent for emulsifying and dispersing an ultraviolet absorber. For example, U.S. Patent Nos. 3,553,794 and 4,236,013,
Benzotriazoles substituted with an aryl group described in JP-B-51-6540 and European Patent No. 57,160,
The butadienes described in U.S. Pat. Nos. 4,450,229 and 4,195,999, U.S. Pat. Nos. 3,705,805 and
Cinnamic acid esters described in 3,707,375, U.S. Pat.No. 3,215,530 and benzophenones described in British Patent 1,321,335, U.S. Pat.
A polymer compound having an ultraviolet absorbing residue as described in 4,431,726 can be dispersed. U.S. Pat.No. 3,49
UV-absorbing optical brighteners described in 9,762 and 3,700,455 may be used. Typical examples of the ultraviolet absorber are described in RD24239 (June 1984) and the like.

Specific examples of the ultraviolet absorber used in the present invention are shown below.

Improvement of storability of color dye image, stain on white background (stain)
The present invention can be applied to organic type and metal complex type anti-fading agents and anti-color mixing agents in order to prevent the above-mentioned phenomenon and color mixing between layers. Hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, spiroindans, p-alkoxyphenols, hindered phenols centering on bisphenols, gallic acid derivatives,
Typical examples are methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating, acylating or alkylating the phenolic hydroxyl groups of these compounds, and metal complexes are also known.

Specific examples of these compounds are described in the specifications of the following patents.

Hydroquinones are US Patents 2,360,290 and 2,418,613
No., No. 2,700,453, No. 2,701,197, No. 2,728,659,
2,732,300, 2,735,765, 3,982,944, 4,4
30,425, British Patent 1,363,921, U.S. Patent 2,710,801
No. 2,816,028, and the like, 6-hydroxychromans, 5-hydroxycoumarans, and spirochromans are US Patents 3,432,300, 3,573,050, 3,574,627,
No. 3,698,909, No. 3,764,337, and JP-A No. 52-152225. Spiroindanes are described in US Pat. No. 4,360,589, p.
-Alkoxyphenols include U.S. Pat. No. 2,735,765, British Patent 2,066,975 (B), JP-A-59-10539, and JP-B-5.
Hindered phenols are US patents such as 7-19764
3,700,455, JP-A-52-72225, U.S. Pat.
And Japanese Patent Publication No. 52-6623, gallic acid derivatives, methylenedioxybenzenes and aminophenols are described in U.S. Patent Nos. 3,457,079, 4,332,886 and Japanese Patent Publication No. 56-21144, respectively.
Hindered amines have been described in U.S. Pat.
No. 4,268,593, British Patent 1,326,889, 1,354,31
No. 3, 1,410,846, Japanese Patent Publication No. 51-1420, JP-A-58-1140
No. 36, No. 59-53846, No. 59-78344, etc., ether and ester derivatives of phenolic hydroxyl groups are disclosed in US Pat.
No. 5, No. 4,174,220, No. 4,254,216, No. 4,264,720,
JP-A Nos. 54-145530, 55-6321, 58-105147 and 5
9-10539, Japanese Patent Publication No. 57-37856, U.S. Pat.No. 4,279,990,
In Japanese Patent Publication No. 53-5263, metal complexes are disclosed in U.S. Pat.
No. 4,241,155, British Patent 2,027,731 (A), etc., respectively.

Examples of these anti-fading agents and anti-color mixing agents are shown below.

The light-sensitive material of the present invention may have at least one silver halide emulsion layer of a blue color-sensitive layer, a green color-sensitive layer and a red color-sensitive layer provided on a support. The number of layers and the non-photosensitive layer and the order of the layers are not particularly limited. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, it is generally a unit photosensitive layer. The arrangement is such that the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer are arranged in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

A non-photosensitive layer such as various intermediate layers may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748, 59-113438 and 5
No. 9-113440, No. 61-20037, No. 61-20038 may contain a coupler as described in the specification, DIR compounds and the like, it may also contain a color mixing inhibitor as commonly used Good.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,470 or British Patent No. 923,045.
No. 2 of high-speed emulsion layer and low-speed emulsion layer as described in No.
A layer structure can be preferably used. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. In addition, JP-A-57-112751 and 62-20
No. 0350, No. 62-206541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support. .

As a specific example, from the side farthest from the support, low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL), or BH / BL / GL
It can be installed in the order of / GH / RH / RL or BH / BL / GH / GL / RL / RH.

Further, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. In addition, JP-A-56-25738 and 62-6
As described in 3936, the blue-sensitive layer / GL / RL / GH / RH may be arranged in this order from the side farthest from the support.

Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. A silver halide emulsion layer having a low degree of sensitivity is arranged, and the sensitivities are gradually lowered toward the support.
An example is an array composed of layers. Even in the case of being composed of three layers having different sensitivities as described above, JP-A-59-20246
As described in No. 4, the medium-speed emulsion layer / high-speed emulsion layer / low-speed emulsion layer may be arranged in this order from the side distant from the support in the same color-sensitive layer.

As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.

When the photographic light-sensitive material of the present invention is a color negative film or a color reversal film, the preferred silver halide contained in the photographic emulsion layer is about 30 mol% or less of silver iodide. It is silver chloride or silver iodochlorobromide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 25% mol silver iodide.

When the photographic light-sensitive material of the present invention is a color photographic paper, the silver halide contained in the photographic emulsion layer is a silver chlorobromide or silver chloride containing substantially no silver iodide. It can be preferably used. The phrase "substantially free of silver iodide" as used herein means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide /
Silver chloride can be used. This ratio can take a wide range depending on the purpose, but a silver chloride ratio of 2 mol% or more can be preferably used. A so-called high silver chloride emulsion having a high silver chloride content is preferably used for a light-sensitive material suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more, more preferably 95 mol% or more. For the purpose of reducing the replenishment amount of the developing solution,
An almost pure silver chloride emulsion having a silver chloride content of 98 to 100 mol% is also preferably used.

The silver halide grains in a photographic emulsion are those having regular crystals such as cubes, octahedra and tetradecahedrons, those having irregular crystal shapes such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof.

The grain size of silver halide may be fine grains of about 0.2 μm or less, or large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No. 17643 (December 1978).
Mon., pp. 22-23, "I. Emulsion preparation
and types) ”, and No. 18716 (November 1979), 648.
P.Glafkides, Chemic et Phisique Photographi, "Physics and Chemistry of Photography" by Graphide
que, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographi
c Emulsion Chemistry (Focal Press, 1966)), "Production and Coating of Photographic Emulsions" by Zelikmann et al., published by Focal Press (VLZelikman et al., Making and Coating Photo
It can be prepared using the method described in Graphic Emulsion, Focal Press, 1964) and the like.

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineerin.
g), 14: 248-257 (1970); U.S. Pat. No. 4,434,2
No. 26, No. 4,414,310, No. 4,433,048, No. 4,439,520, and British Patent No. 2,112,157, and the like can be easily prepared.

The crystal structure may be uniform, may have different halogen compositions in the inside and the outside, may have a layered structure, and may have a different composition by epitaxial bonding. Alternatively, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide.

Also, a mixture of particles having various crystal forms may be used.

As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. Additives used in such processes are Research Disclosure No.176.
43 and No. 18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is preferable to add to the light-sensitive material a compound capable of reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is 28 μm or less, and the film swelling speed T _1/2 is preferably 30 seconds or less. Film thickness is 25 ° C relative humidity
Means the film thickness measured under 55% humidity control (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, A.Gree
n) et al., Photographic Science and Engineering (Photogr.Sci.Eng), Volume 19, Issue 2, 1.
It can be measured by using a swellometer (swelling meter) of the type described on pages 24 to 129, and T _1/2 is 30 in a color developer.
90% of the maximum swollen film thickness reached when treated at 3 ℃ for 15 minutes
Is defined as the saturated film thickness, and is defined as the time until the film thickness of T _1/2 is reached.

The film swelling rate T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is 150
~ 400% is preferred. The swelling rate is calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness) /
It can be calculated according to the film thickness.

The color photographic light-sensitive material according to the present invention has the above-mentioned RD.
Development can be carried out by a usual method described on pages 28 to 29 of 643 and 615, left column to right column of No. 18716.

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N diethylaniline and 3-methyl. -4-amino-N-ethyl-N-β
-Hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and sulfates thereof, Hydrochloride or p-toluene sulfonic acid salt etc. are mentioned. Two or more of these compounds can be used in combination depending on the purpose.

The color developer contains a pH buffer such as an alkali metal carbonate, borate or phosphate, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound or a development inhibitor or a fog. Generally, it contains an inhibitor and the like. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, and coupler agents such as sodium boron hydride. , 1-
Auxiliary developing agents such as phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethyleneazimine-N, Representative examples are N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.

When the reversal process is performed, black and white development is usually performed before color development. The black-and-white developing solution may be a known black-and-white developing agent such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishment amount of these developers is
Although it depends on the color photographic light-sensitive material to be processed, it is generally 3 l or less per 1 m 2 of the light-sensitive material, and can be reduced to 500 ml or less by reducing the bromide ion concentration in the replenisher. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution.

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

The photographic emulsion layer of the color developer is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further processing with two continuous bleach-fix baths,
The fixing treatment before the bleach-fixing treatment or the bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose.
Examples of bleaching agents include iron (III), cobalt (III),
Compounds of polyvalent metals such as chromium (IV) and copper (II), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are ferricyanide; dichromate; iron (II
I) or cobalt (III) organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3
-Aminopolycarboxylic acids such as diaminopropane tetraacetic acid and glycol ether diamine tetraacetic acid, or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. it can. Of these, aminopolycarboxylic acid iron (II) including ethylenediaminetetraacetic acid iron (III) complex salts
I) Complex salts and persulfates are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Further aminopolycarboxylic acid iron (III)
Complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. Specific examples of useful bleach accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988.
No. 53-32736, No. 54-57831, No. 53-37418,
53-72623, 53-95630, 53-95631, 53-104
No. 232, No. 53-124424, No. 53-141623, No. 53-28426
No. 17129 (July 1978) and the like, compounds having a mercapto group or a disulfide group; thiazolidine derivatives described in JP-A-50-140129; JP-B-45-8506; Sho 52-20832, 5
3-32735, thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent 1,127,715, iodide salts described in JP-A-58-16,235; Poly German compounds described in West German Patents 966,410 and 2,748,430. Oxyethylene compounds; polyamine compounds described in JP-B-45-8836; other JP-A-49-42,434,
49-59,644, 53-94,927, 54-35,727, 55-
Compounds described in Nos. 26,506 and 58-163,940; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, U.S. Pat. No. 3,893,858, West patent 1,290,812
And the compounds described in JP-A-53-95,630 are preferred. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are generally used, and ammonium thiosulfate is the most widely used. Can be used for As a preservative for the bleach-fix solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering process.
The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions. It can be set in a wide range. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in Jour.
nal of the Society of Motion Picture and Televisio
n Engineers, Volume 64, P.248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, such a problem is a solution,
The method of reducing calcium and magnesium ions described in JP-A-62-288,838 can be used very effectively. Also, isothiazolone compounds and siabendazoles, chlorinated germicides such as chlorinated sodium isocyanuric acid, etc., which have been transferred to JP-A-57-8,542, and other benzotriazoles, etc. It is also possible to use the fungicides described in "Technology for Sterilization, Sterilization, and Antifungal of Microorganisms" edited by Hygiene Technology Society, "Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society for Antibacterial and Antifungal Agents.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9
And preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, application, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, Japanese Patent Laid-Open No.
All known methods described in Nos. -8543, 58-14834, and 60-220345 can be used.

Further, there is a case where a stabilizing treatment is further performed after the water washing treatment, and an example thereof is a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. . Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution can be reused in other steps such as the desilvering step as the washing and / or the stabilizing solution is replenished.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in U.S. Pat. Salt complex, JP-A-5
The urethane compounds described in 3-135628 can be mentioned.

The silver halide color light-sensitive material of the present invention contains various 1-phenyl-containing compounds, if necessary, for the purpose of promoting color development.
You may incorporate 3-pyrazolidones. Typical compounds are JP-A-56-643339, JP-A-57-144547, and JP-A-58-115.
No. 438, etc.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to. Further, in order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

The present invention can be applied to various color and black and white light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers, color diffusion transfer type photosensitive materials and heat developable color photosensitive materials. it can. RG17123 (July 1978) and the like by utilizing a three color coupler mixture, or US Pat. No. 4,126,46
The present invention can be applied to a black-and-white light-sensitive material for X-ray and the like by utilizing the black color coupler described in No. 1 and British Patent No. 2,102,136. Plate-making film such as lith film or scanner film, X-ray film for straight line / indirect medical treatment or industry, negative black-and-white film for photography, black-and-white printing paper, COM or normal micro film, silver salt diffusion transfer type photosensitive material and print The present invention can be applied to an out type photosensitive material.

Further, the high-boiling organic solvent of the present invention, U.S. Patent No. 4,500,62
6, JP-A-60-133449, JP-A-59-218443, JP-A-61-25
It can also be applied to the photothermographic materials described in 8056 and European Patent No. 210,660A2.

(Effect of the Invention) The silver halide photographic light-sensitive material of the present invention has a remarkable effect of having excellent solubility and dispersion stability of a photographically useful reagent. Further, in the silver halide photographic light-sensitive material of the present invention, the generation of stain after photographic processing is significantly reduced. Further, according to the silver halide photographic light-sensitive material of the present invention, a color image having remarkably improved fastness to light and heat can be formed.

(Example) The following invention will be described in more detail based on examples.

Example 1 19.3 g of a yellow coupler having the following structure and 27.2 cc of ethyl acetate
And a high-boiling organic solvent (see Table 1) were added to the coupler at a weight ratio of 0.3 and dissolved, and this solution was dissolved in 10
10% including 8% sodium dodecylbenzene sulfonate
% Gelatin aqueous solution was emulsified and dispersed in 185 cc.

The above emulsion was allowed to stand at 10 ° C. for 4 weeks and then coated on a glass with a spin coat, and the presence or absence of crystallization of the coupler was observed with a polarizing microscope. The results are shown in Table 1.

As is clear from Table 1, crystallization over time was not observed in the emulsion-dispersed product of the compound of the present invention.

The structures of the high boiling point organic solvents used for comparison are as follows.

R-1 Tricresyl phosphate R-2 Dibutyl phthalate Example 2 On a paper support laminated on both sides with polyethylene, a multi-layer silver halide light-sensitive material A having the following layer constitution was prepared. The coating liquid was prepared as follows. Raw materials such as couplers and color image stabilizers used are shown later.

(Preparation of coating solution) Yellow couplers (ExY-1) and (ExY-2) 1 each
0.2g, 9.1g and 4.4g of color image stabilizer (Cpd-1) to 27.2cc of ethyl acetate and 7.7cc (8.0cc of high boiling solvent (Solv-1))
g) was added and dissolved, and this solution was added with 185 cc of 10% gelatin aqueous solution containing 10 cc of 10% sodium dodecylbenzenesulfonate.
Emulsified and dispersed. This emulsified dispersion and emulsions EM1 and EM2 were mixed and dissolved, and the gelatin concentration was adjusted to give the following composition to prepare the coating solution for the first layer.

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

Moreover, (Cpd-2) was used as a thickener.

(Layer constitution) The composition of each layer is shown below. Numbers represent coating weight (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support Polyethylene laminated paper (Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye) First layer (blue sensitive layer) Single layer spectrally sensitized with sensitizing dye (ExS-1) Dispersed silver chlorobromide emulsion (EM1) 0.13 Monodispersed silver chlorobromide emulsion (EM2) spectrally sensitized with sensitizing dye (ExS-1) 0.13 Gelatin 1.86 Yellow coupler (ExY-1) 0.44 Yellow Coupler (ExY-2) 0.39 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35 Second layer (color mixing inhibitor) Gelatin 0.99 Color mixing inhibitor (Cpd-3) 0.08 Third Layer (green-sensitive layer) Monodisperse silver chlorobromide emulsion (EM3) spectrally sensitized with sensitizing dye (ExS-2,3) ... 0.05 Spectral sensitizing with sensitizing dye (ExS-2,3) Monodisperse silver chlorobromide emulsion (EM4) 0.11 Gelatin 1.80 Magenta coupler (ExM-1) 0.39 Color image stabilizer (Cpd-4) 0.20 Solvent (Solv-2) 0.12 Solvent Solv-3) 0.25 4th layer (ultraviolet absorbing layer) Gelatin 1.60 Ultraviolet absorber (Cpd-7 / Cpd-8 / Cpd-9 = 3/2/6: weight ratio) 0.70 Color mixture inhibitor (Cpd- 10)… 0.05 Solvent (Solv-4)… 0.27 Fifth layer (red sensitive layer) Monodispersed silver chlorobromide emulsion (EM6)… 0.07 sensitized by spectral sensitization with sensitizing dye (ExS-4,5) Monodisperse silver chlorobromide emulsion spectrally sensitized with dyes (ExS-4,5) 0.16 Gelatin 0.92 Cyan coupler (ExC-1) 0.32 Color image stabilizer (Cpd-8 / Cpd-9 / Cpd- 12 = 3/4/2: weight ratio)
... 0.17 Solvent (Solv-1) 0.20 Sixth layer (UV absorbing layer) Gelatin ... 0.54 UV absorber (Cpd-7 / Cpd-9 / Cpd-12 = 1/5/3: weight ratio) 0.21 Solvent ( Solv-2) 0.08 7th layer (protective layer) Gelatin 1.33 Polyvinyl alcohol acrylic modified copolymer (degree of modification
17%) 0.17 Fluctuating paraffin 0.03 At this time, Cp is used as an anti-irradiation dye.
d-13 and Cpd-14 were used. Alkanol XC (trade name, manufactured by Dupont), sodium alkylbenzenesulfonate, succinic acid ester, and Magefacxf-120 (trade name, manufactured by Dainippon Ink and Chemicals) were used for each layer as an emulsifying dispersant coating aid. Cpd as a stabilizer of silver halide
-16 was used.

Details of the emulsion used are as follows.

The compounds used are as follows.

Solv-1 Dibutyl phthalate Solv-2 Tricresyl phosphate Solv-3 Trioctyl phosphate Solv-4 Trinonyl phosphate Next, a light-sensitive material B was prepared in exactly the same manner as the light-sensitive material A except that the same amount of Solv-1 was used instead of the solvent for the third and fifth layers of the light-sensitive material A. Similarly, as shown in Table 2, the solvent of the photosensitive material A was changed to the same amount of a known solvent to prepare photosensitive materials C and D.

On the other hand, the solvent in the first, third, and fifth layers of the photosensitive material A is changed to the second solvent.
Photosensitive materials E to K were prepared in the same manner as photosensitive material A except that the same amount of the compound of the present invention was used as shown in the table.

The above light-sensitive material was exposed through an optical wedge and then processed in the next step. Processing process temperature Time Color development 38 ℃ 1 minute 40 seconds Bleach fixing 30-34 ℃ 1 minute 00 seconds Rinse 30-34 ℃ 20 seconds Rinse 30-34 ℃ 20 seconds Rinse 30-34 ℃ 20 seconds Dry 70-80 ℃ 50 seconds (A three-tank countercurrent flow system from rinse to → was used.) The composition of each processing solution is as follows. Color developer water 800 ml Diethylenetriaminepentaacetic acid 1.0 g 1-Hydroxyethylidene 1,1-diphosphonic acid (60%)
2.0g Nitrilotriacetic acid 2.0g Benzyl alcohol 16ml Diethylene glycol 10ml Sodium sulfite 2.0g Potassium bromide 0.5g Potassium carbonate 30g N-ethyl-N- (β-methanesulfonamidoethyl)
-3-Methyl-4-aminoaniline sulphate 5.5g Hydroxylamine sulphate 3.0g Fluorescent whitening agent (WHITEX4B, Sumitomo Chemical Co., Ltd.) 1.5g Add water 1000ml pH (25 ℃) 10.25 Bleach fixer water 400ml Ammonium thiosulfate (70%) 200 ml Sodium sulfite 20 g Ethylenediaminetetraacetic acid iron (III) ammonium 60 g Ethylenediaminetetraacetic acid disodium 10 g Water was added to 1000 ml pH (25 ℃) 7.00 Rinsing solution Benzotriazole 1.0 g Ethylenediamine-N, N, N ', N '-Tetramethylenephosphonic acid 0.3 g Water was added to 1000 ml pH (25 ° C) 7.50 Immediately after the treatment, the magenta and cyan reflection densities (stain) of the non-image area were measured, and then the mixture was allowed to stand at 80 ° C-15% RH for 7 days. Then, the reflection density of the non-image area was measured again. The increase in stain immediately after the treatment is shown in Table 2.

As is clear from Table 2, in the light-sensitive material of the present invention, the increase in stain after processing is remarkably suppressed.

Using the samples (light-sensitive materials A to K) prepared above, the same processing as described above was performed, and then the light resistance and thermal fading tests were performed.

The light resistance was measured by measuring the color density with blue light, and when the density before the light resistance test was 2.0, a xenon fade meter (9.5
(10,000 lux) and the decrease concentration after irradiation for 150 hours is expressed as a percentage of the original concentration.

The thermal bleaching property was measured by measuring the color density before the thermal bleaching test with red light, and was shown as a percentage of the original density after the thermal bleaching test at a density of 2.0.

The results are shown in Table 3.

From Table 3, it can be seen that in the light-sensitive material of the present invention, the effect of improving the light resistance of yellow and the dark heat fading of cyan are recognized.

Example 3 On a paper support laminated on both sides with polyethylene, a multilayer silver halide light-sensitive material L having the following layer constitution was prepared. The coating liquid was prepared as follows. Raw materials such as couplers and color image stabilizers used are shown later.

(Preparation of coating solution) To 27.1 g of yellow coupler (ExY-2) and 4.4 g of color image stabilizer (Cpd-1), 27.2 cc of ethyl acetate and 7.7 cc (8.0 g) of high boiling point solvent (Solv-1) were added and dissolved. , This solution 1
10% containing 8% sodium dodecylbenzene sulfonate 10
% Gelatin aqueous solution was emulsified and dispersed in 185 cc. This emulsified dispersion and emulsions EM7 and EM8 were mixed and dissolved, and the gelatin concentration was adjusted so that the following composition was obtained to prepare the coating solution for the first layer.
The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer.

Moreover, (Cpd-2) was used as a thickener.

(Layer constitution) The composition of each layer is shown below. Numbers represent coating weight (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support Polyethylene laminated paper (Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye) First layer (blue sensitive layer) Single layer spectrally sensitized with sensitizing dye (ExS-1) Dispersed silver chlorobromide emulsion (EM7) 0.15 Monodispersed silver chlorobromide emulsion (EM8) spectrally sensitized with sensitizing dye (ExS-1) 0.15 Gelatin 1.86 Yellow coupler (ExY-2) 0.82 colors Image stabilizer (Cpd-2) 0.19 Solvent (Solv-1) 0.35 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing inhibitor (Cpd-3) 0.08 Third layer (green sensitive layer) Sensitizing dye Monodisperse silver chlorobromide emulsion (EM9) spectrally sensitized with (ExS-2,3) 0.12 Monodisperse silver chlorobromide emulsion (EM10 spectrally sensitized with sensitizing dye (ExS-2,3) ) 0.24 Gelatin 1.24 Magenta coupler (ExM-2) 0.39 Color image stabilizer (Cpd-4) 0.25 Color image stabilizer (Cpd-5) 0.12 Solvent (Solv-2) 0.25 Fourth layer (purple) Line absorbing layer) Gelatin 1.60 UV absorber (Cpd-6 / Cpd-7 / Cpd-8 = 3/2/6: weight ratio) 0.70 Color mixture inhibitor (Cpd-9) 0.05 Solvent (Solv-3) … 0.42 Fifth layer (red sensitive layer) Monodispersed silver chlorobromide emulsion (EM11) spectrally sensitized with sensitizing dye (ExS-4,5)… 0.07 Spectral with sensitizing dye (ExS-4,5) Sensitized monodisperse silver chlorobromide emulsion (EM12) 0.16 Gelatin 0.92 Cyan coupler ExC-2 0.146 Cyan coupler ExC-3 0.184 Color image stabilizer Cpd-7 / Cpd-8 / (Cpd-10 = 3/4/2: weight ratio)
... 0.17 Dispersing polymer (Cpd-11) ... 0.14 Solvent (Solv-1) ... 0.20 Sixth layer (UV absorbing layer) Gelatin ... 0.54 UV absorbing agent (Cpd-6 / Cpd-8 / Cpd-10 = 1/5) / 3: Weight ratio) 0.21 Solvent (Solv-4) 0.08 7th layer (protective layer) Gelatin 1.33 Polyvinyl alcohol acrylic modified copolymer (degree of modification
17%)… 0.17 Liquid paraffin… 0.03 At this time, Cp is used as an anti-irradiation dye.
d-12 and Cpd-13 were used. Alkanol XC (trade name, manufactured by Dupont), sodium alkylbenzene sulfonate, succinic acid ester and Magefacx F-120 (trade name, manufactured by Dainippon Ink and Chemicals) were used for each layer as an emulsion dispersion coating aid. Cpd as a stabilizer of silver halide
-14 and Cpd-15 were used.

Details of the emulsion used are as follows.

The structural formulas of the compounds used are as follows.

Solv-1 Dibutyl phthalate Solv-2 Tricresyl phosphate Solv-3 Trioctyl phosphate Solv-4 Trinonyl phosphate Next, the solvent Solv-1 for the first and fifth layers of the light-sensitive material L
A light-sensitive material M was prepared in the same manner as the light-sensitive material L except that the same amount of Solv-2 was used. Similarly, as shown in Table 4, photosensitive materials N and O were prepared by replacing the solvents of the first, third and fifth layers with the same amount of a known solvent.

On the other hand, the solvent in the first, third, and fifth layers of the light-sensitive material L is changed to the fourth solvent.
Photosensitive materials P to U were prepared in the same manner as photosensitive material L except that the same amount of the compound of the present invention was substituted as shown in the table.

The light-sensitive material was exposed through an optical wedge and then processed in a process. Step Temperature Time Color developing 35 ° C. 45 seconds blix 30 to 35 ° C. 45 sec Rinse 30 to 35 ° C. 20 sec Rinse 30 to 35 ° C. 20 sec Rinse 30 to 35 ° C. 20 sec Rinse 30 to 35 ° C. 30 seconds Drying 70-80 ℃ 60 seconds (Rinse → 3 tank countercurrent system.) The composition of each processing solution is as follows. Color developer water 800ml Ethylenediamine-N, N, H ', N'-tetramethylenephosphonic acid 1.5g Triethylenediamine (1,4-diazabicyclo (2,2,2)
Octane 5.0g Octane 5.0g Sodium chloride 1.4g Potassium carbonate 25g N-ethyl-N- (β-methanesulfonamidoethyl)
-3-Methyl-4-aminoaniline sulfate 5.0g N, N-diethylhydroxylamine 4.2g Optical brightener (UVITEX CK Ciba-Geigy Co., Ltd.) 2.0g Water is added 1000ml pH (25 ° C) 10.10 Bleach-fixer water 400ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 18g Ethylenediaminetetraacetic acid iron (III) ammonium 55g Ethylenediaminetetraacetate disodium 3g Ammonium bromide 40g Glacial acetic acid 8g Water added 1000ml pH (25 ℃) 5.5 Rinse liquid Ion-exchanged water (calcium Immediately after the treatment, the reflection density (stain) of the non-image area was measured with blue light immediately after the treatment, then left under 80-80% RH for 2 weeks, and again measured with blue light.

Table 4 shows the increase in stain immediately after the treatment.

As is clear from Table 4, in the light-sensitive material of the present invention, stains with the passage of time after processing are significantly suppressed.

Example 4 On a subbed cellulose triacetate film support,
A multi-layer color light-sensitive material having the following composition was prepared.

(Composition of photosensitive layer) The coating amount of silver halide and colloidal silver is silver.
The amount expressed in units of g / m ^2, also couplers, additives and moles per mole of silver halide in the same layer for amounts and sensitizing dyes represented by the unit of g / m ² for gelatin Indicated by.

1st layer (antihalation layer) Black Croyde silver 0.2 Gelatin 1.3 ExM-9 0.06 UV-1 0.03 UV-2 0.06 UV-3 0.06 Solv-1 0.15 Solv-2 0.15 Solv-3 0.05 Second layer (intermediate layer) Gelatin ... 1.0 UV-1 ... 0.03 ExC-4 ... 0.02 ExF-1 ... 0.004 Solv-1 ... 0.1 Solv-2 ... 0.1 Third layer (low-sensitivity red-sensitive emulsion layer) Iodobromide Silver emulsion (AgI 4 mol%, uniform AgI type, sphere equivalent diameter 0.5
μ, coefficient of variation of equivalent spherical diameter 20%, plate-like particles, diameter / thickness ratio
3.0) Silver coating amount 1.2 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, spherical equivalent diameter 0.3
μ, coefficient of variation of equivalent spherical diameter 15%, spherical particles, diameter / thickness ratio
1.0) Coating silver amount ... 0.6 Gelatin ... 1.0 ExS-1 ... 4 × 10 ^-4 ExS-2 ・ ・ ・ 5 × 10 ^-5 ExC-1 ・ ・ ・ 0.05 ExC-2 ・ ・ ・ 0.50 ExC-3 ・ ・ ・ 0.03 ExC-4 ・ ・ ・ 0.12 ExC- 5 ... 0.01 4th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, core-shell ratio of 1: 1)
AgI type, equivalent sphere diameter 0.7μ, variation coefficient of equivalent sphere diameter 15%, plate-like particles, diameter / thickness ratio 5.0) Coating silver amount ... 0.7 Gelatin ... 1.0 ExS-1 ... 3 × 10 ^-4 ExS-2 ... 2.3 × 10 ^-5 ExC-6 ... 0.11 ExC-7 ... 0.05 ExC-4 ... 0.05 Compound (I-10) of the present invention ... 0.10 Fifth layer (intermediate layer) Gelatin ... 0.5 Cpd-1 ... 0.1 Solv-1 ... 0.05 6th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, surface height of 1: 1 core-shell ratio)
AgI type, equivalent sphere diameter 0.5μ, variation coefficient of equivalent sphere diameter 15%, plate-shaped particles, diameter / thickness ratio 4.0) Coating silver amount ... 0.35 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent to sphere) Diameter 0.3
μ, coefficient of variation of equivalent spherical diameter 25%, spherical particles, diameter / thickness ratio
1.0) coating silver amount ... 0.20 Gelatin ... 1.0 ExS-3 ... 5 × 10 -4 ExS-4 ... 3 × 10 -4 ExS-5 ... 1 × 10 -4 ExM-8 ... 0.4 ExM-9 ... 0.07 ExM-10 ... 0.02 ExY-11 ... 0.03 Compound (I-10) of the present invention ... 0.35 Seventh layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, core-shell ratio of 1: 3)
AgI type, sphere equivalent diameter 0.7μ, variation coefficient of sphere equivalent diameter 20%, plate-like particles, diameter / thickness ratio 5.0) Coating silver amount ... 0.8 Gelatin ... 0.5 ExS-3 ... 5 × 10 ^-4 ExS-4 ... 3 × 10 ^-4 ExS-5 ... 1 × 10 ^-4 ExM-8 ... 0.1 ExM-9 ... 0.02 ExY-11 ... 0.03 ExC-2 ... 0.03 ExM-14 ... 0.01 Compound (I-10) of the present invention ... 0.21 No. Eight layers (intermediate layer) Gelatin ... 0.5 Cpd-1 ... 0.05 Solv-1 ... 0.02 Ninth layer (donor layer having a multilayer effect for the red-sensitive layer) Silver iodobromide emulsion (AgI 2 mol%, core-shell ratio 2: 1) Internal height
AgI type, equivalent sphere diameter 1.0μ, variation coefficient of equivalent sphere diameter 15%, plate-shaped particles, diameter / thickness ratio 6.0) coated silver amount ... 0.35 silver iodobromide emulsion (AgI 2 mol%, core-shell ratio 1: 1) Internal height
AgI type, equivalent sphere diameter 0.4μ, variation coefficient of equivalent sphere diameter 20%, plate-like particles, diameter / thickness ratio 6.0) Silver coating amount 0.20 Gelatin 0.5 ExS-3 8x10 ^-4 ExY-13 0.11 ExM-12 ... 0.03 ExM-14 ... 0.10 Compound (I-10) of the present invention ... 0.20 Layer 10 (yellow filter layer) Yellow colloidal silver ... 0.05 Gelatin ... 0.5 Cpd-2 ... 0.13 Solv-1 ... 0.13 Cpd-1 … 0.10 11th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4.5 mol%, uniform AgI type, spherical equivalent diameter 0.
7μ, coefficient of variation of equivalent sphere diameter 15%, tabular grains, diameter / thickness ratio 7.0) Coating silver amount ... 0.3 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent sphere diameter 0.3)
μ, coefficient of variation of equivalent spherical diameter 25%, plate-shaped particles, diameter / thickness ratio
7.0) Coating silver amount ... 0.15 Gelatin ... 1.6 ExS-6 ... 2 * ^10-4 ExC-16 ... 0.05 ExC-2 ... 0.10 ExC-3 ... 0.02 ExY-13 ... 0.07 ExY-15 ... 1.0 Compound of the present invention (I -10) 0.20 12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, equivalent spherical diameter)
1.0μ, 25% variation coefficient of equivalent spherical diameter, multiple twin plate-like particles,
Diameter / thickness ratio 2.0) Coating silver amount ... 0.5 Gelatin ... 0.5 ExS-6 ... 1 * ^10-4 ExY-15 ... 0.20 ExY-13 ... 0.01 Compound (I-10) of the present invention ... 0.10 13th layer (1st layer) Protective layer) Gelatin ... 0.8 UV-4 ... 0.1 UV-5 ... 0.15 Solv-1 ... 0.01 Solv-2 ... 0.01 14th layer (second protective layer) Fine grain silver bromide emulsion (AgI 2 mol%, uniform AgI type, Equivalent diameter
0.07 μ) 0.5 Gelatin 0.45 Polymethylmethacrylate particle diameter 1.5 μ 0.2 H-1 0.4 Cpd-5 0.5 Cpd-6 0.5 In addition to the above components, each layer contains emulsion stabilizer Cpd-3 ( 0.0
4 g / m ² ) Surfactant Cpd-4 (0.02 g / m ² ) was added as a coating aid.

Solv-1 Tricresyl Phosphate Solv-2 Dibutyl Phthalate After exposing the color photographic light-sensitive material as described above, it was processed by the method described below.

Processing method Process processing time Processing temperature Color development 3 minutes 15 seconds 38 ℃ Bleach 1 minute 00 seconds 38 ℃ Bleach fixing 3 minutes 15 seconds 38 ℃ Water wash (1) 40 seconds 38 ℃ Water wash (2) 1 minute 00 seconds 38 ℃ Stable 40 Second 38 ° C drying 1 minute 15 seconds 55 ° C (3 tank countercurrent system from rinse to) The composition of the treatment liquid is shown below.

(Color developer) Diethylenetriamine pentaacetic acid 1.0 g 1-Hydroxyethylidene 1,1-diphosphonic acid 3.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 g 4- (N -Ethyl-N-β-hydroxyethylamino)
2-Methylaniline sulfate 4.5g Water was added to 1.0l pH 10.05 (bleaching solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 120.
0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium bromide 100.0g Ammonium nitrate 10.0g Bleach accelerator 0.005mol Ammonia water (27%) 15.0ml Add water 1.0l pH 6.3 (bleach-fixing solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 50.0
g Ethylenediaminetetraacetic acid disodium salt 5.0g Sodium sulfite 12.0g Ammonium thiosulfate aqueous solution (70%) 240.0ml Ammonia water (27%) 6.0ml Water is added to 1.0l pH 7.2 (Washing solution) Tap water is H type strong acidic cation Exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type anion exchange resin (Amberlite IR-400) were passed through a mixed bed column to obtain calcium and magnesium ion concentration of 3 mg / l. The following treatment was followed by the addition of 20 mg / l sodium isocyanurate dichloride and 150 mg / l sodium sulfate. The pH of this solution is in the range 6.5-7.5.

(Stabilizer) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g Ethylenediaminetetraacetic acid disodium salt 0.05 g Water was added to 1.0 l pH 5.0 to 8.0 When tested in the same manner as in Example 2, it showed a remarkable effect of suppressing stain with time after treatment and an excellent effect of improving yellow photofading.

[Brief description of drawings]

1 to 3 show tricyclo [5.2.
1 shows an infrared spectrum of 1.0 ^2,6 ] decanedicarboxylic acid ester.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material comprising a hydrophilic colloid in which a photographically useful reagent which is sparingly soluble in water is dispersed in the presence of at least one high-boiling organic solvent. At least one is represented by the following general formula (I)
A silver halide photographic light-sensitive material, which is a tricyclo [5.2.1.0 ^2,6 ] decanedicarboxylic acid ester represented by General formula (I) In the general formula (I), R ₁ and R ₂ are each independently an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group, and R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom or Represents an alkyl group.