JP3086347B2 - Silver halide photographic material, developer and image forming method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material, a developer and an image forming method.

[0002]

2. Description of the Related Art A phenomenon in which the image density of an unexposed portion of a silver halide photographic light-sensitive material increases in a developing process is called "development fog". Generally, development fog is more likely to occur as the photosensitive material has higher sensitivity. It is also likely to occur when the photosensitive material is stored for a long period of time or when stored under high temperature and high humidity conditions. Furthermore, to reduce processing time,
Even when high-temperature processing or high-activity processing is performed, development fog is extremely likely to occur. Development fog causes deterioration of photographic performance such as reduction of image contrast, and thus it is necessary to suppress the occurrence of development fog as much as possible.

[0003] In order to suppress development fogging, a method of adding an additive called an antifoggant to a photosensitive material or a developing solution has conventionally been adopted. For antifoggants, see Stabilization of Photographic Silver Halide Emulsions (Birr, "Stabi
lization of Photographic Silver Halide Emulsions '' F
ocal Press, 1974). Many compounds, mainly nitrogen-containing heterocyclic compounds, have already been proposed as antifoggants. However, compounds having a strong antifogging effect have problems such as lowering the sensitivity of the photosensitive material, softening the gradation, or inhibiting the adsorption of the sensitizing dye to lower the spectral sensitivity. I have. For this reason, development of a strong antifoggant which has less of these problems is desired.

[0004] Most of the conventional antifoggants are nitrogen-containing heterocyclic compounds. However, the existence of compounds having an antifogging action other than the nitrogen-containing heterocyclic compound has been reported. For example, British Patent 1308138 describes that
An antifoggant effect of a selenium compound having the following formula is described.

[0005]

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In the formula, R is an alkyl group, an aralkyl group, an alkaryl group, an aryl group or a heterocyclic group. Q
Is halogen, cyano or the following formula:

[0007]

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In the formula, R ₁ , R ₂ and R ₃ are each an alkyl group, an aralkyl group or an aryl group. X is an anion, but does not exist when R itself has an anionic group.

Japanese Patent Publication No. 50-40665 describes an antifoggant effect of a phosphorus or nitrogen compound having the following formula.

[0010]

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Wherein Z is P or N. R ₁ , R
₂ , R ₃ and R ₄ are an alkyl group, an aryl group, an aralkyl group or an aryl group, respectively. R
_At least one of ₁ , R ₂ , R ₃ and R ₄ is an aryl group or an aralkyl group having an electron-withdrawing substituent. X ^- is an acid anion.

Each of the compounds described in British Patent No. 1308138 and Japanese Patent Publication No. 50-40665 is
Even though it has an antifogging action, its action is poor, and practically it is not possible to sufficiently prevent development fog. For this reason, practically used antifoggants are substantially limited to nitrogen-containing heterocyclic compounds.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic material, a developing solution and an image forming method in which the occurrence of fog is prevented without causing a problem such as a decrease in sensitivity. is there.

[0014]

This object is achieved by the following (1)
(3) was achieved. (1) A silver halide photographic light-sensitive material having a silver halide emulsion layer on a support, comprising a compound represented by the following formula (I):

[0015]

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Wherein R ¹ is an alkyl group, an alkenyl group,
It is an aralkyl group, an aryl group or a heterocyclic group. R
² , R ³ and R ⁴ are each an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, an amino group, —SR ⁵ , —OR ⁶ or —SeR ⁷ . R
⁵ , R ⁶ and R ⁷ are an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group, respectively. Each of the above groups may further have a substituent.
X is a counter anion. X may be included in the above substituent to form an inner salt.

(2) A developer for a silver halide photographic light-sensitive material, comprising a compound represented by the above formula (I). (3) A method in which a silver halide photographic light-sensitive material having a silver halide emulsion layer on a support is image-exposed, and an image is formed by a developing treatment using a developing solution. Or an image forming method, wherein the developer contains the compound represented by the formula (I).

[0018]

According to the study of the present inventors, it has been found that the compound represented by the above formula (I) has an excellent antifogging action. Its operation is the same as that of the aforementioned British Patent 130813.
Compared with the compounds described in JP-B No. 8 and JP-B-50-40665, the compound is much stronger and can sufficiently prevent development fog in practical use. Further, even when this compound is used as an antifoggant, problems such as a decrease in sensitivity, softening of gradation, and inhibition of adsorption of a sensitizing dye hardly occur. Therefore, when the photographic light-sensitive material, the developing solution or the image forming method of the present invention is employed, a clear image in which generation of fog is prevented can be formed without causing a problem such as a decrease in sensitivity.

[0019]

DETAILED DESCRIPTION OF THE INVENTION The present invention is characterized by using a compound represented by the following formula (I) as an antifoggant. The antifoggant can be added to the photographic material (the photographic material of the present invention). The antifoggant may be added to the developer (the developer of the present invention). Further, after the use of the photographic material is started (that is, after the image exposure is started), the antifoggant is included in the photographic material or the developer before the development process is completed, and the development process is performed in the presence of the antifoggant. Is also good. For example, after the image exposure, the photographic material may be immersed in a solution containing an antifoggant (pre-development bath), and then subjected to a development process. The image forming method of the present invention includes such an embodiment that the developing treatment is performed in the presence of the antifoggant.

[0020]

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R ¹ is an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group. Alkyl, alkenyl, aralkyl and aryl groups are preferred, alkyl, alkenyl and aralkyl groups are more preferred, and alkyl groups are most preferred. R ² ,
R ³ and R ⁴ are each an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, an amino group, -SR ^5, an -OR ⁶ or --SeR ^7. Alkyl, alkenyl, aralkyl, aryl and —SR ⁵ are preferred, alkyl, alkenyl, aralkyl and aryl are more preferred, and alkyl and aryl are most preferred. R ⁵ , R ⁶ and R ⁷ are an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group, respectively. Alkyl, alkenyl, aralkyl and aryl groups are preferred, alkyl, alkenyl and aralkyl groups are more preferred, and alkyl groups are most preferred.

Each of the above groups may further have a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, an amino group, a cyano, a nitro, a hydroxy, a halogen atom (eg,
Chlorine, bromine, fluorine), alkoxy groups (eg, methoxy,
Ethoxy), alkylthio groups (eg, methylthio, ethylthio), alkoxycarbonyl groups (eg, methoxycarbonyl), acyloxy groups (eg, acetoxy), carbamoyl, amide groups (eg, acetamido), ureido, thioureido, carboxyl, and sulfo be able to. Nitro, carboxyl and sulfo may form salts with anions. This anion may be a counter anion corresponding to X, in which case it forms an inner salt with phosphonium. The number of carbon atoms in each of the above groups is 3
It is preferably 0 or less, and more preferably 20 or less.

Examples of alkyl groups (including substituted alkyl groups) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, carboxymethyl, methoxyethyl, dimethylaminoethyl, n-
Hexyl, cyclohexyl, n-octyl, n-decyl and sulfoethyl can be mentioned. Examples of alkenyl groups include vinyl, allyl and butenyl. Examples of aralkyl groups include benzyl and phenethyl. Examples of aryl groups (including substituted aryl groups) include phenyl and 2-methylphenyl. Examples of heterocyclic groups include 2-thienyl and 2-pyridyl. Examples of the substituted amino group include dimethylamino.

X is a counter anion. As an example of X:
Examples thereof include trifluoromethanesulfonic acid ion, bromine ion, iodine ion, perchlorate ion, tetrafluoroborate ion and p-toluenesulfonic acid ion. X may be included in the above substituents to form an inner salt with phosphonium.

Examples of the compound represented by the formula (I) are shown below.

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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The chemical formula represented by the formula (I) used in the present invention is a compound represented by the following formula:
ron Lett. ) 16, 175 (1964); Journal of American Chemical Society (J. Am. Chem. Soc.) 21, 7297 (1)
979); Tetrahedron Letters
drone Lett. ) 28, 5821 (1987);
Chemical and Pharmaceutical Bulltin (Chem. Pharm. Bull.) 28 (3), 5
821 (1987); and ibid, 35 (11),
It can be synthesized according to the description of 4473 (1987). The following shows a synthesis example.

Synthesis Example 1 Synthesis of Exemplified Compound (1) Triphenylphosphine sulfide (8.83 g) was added to 150 ml of toluene, and the mixture was stirred and dissolved. Then, methyl trifluoromethanesulfonate (4.92 g) was added. 10
After stirring at 0 ° C. for 1 hour, the reaction solution was returned to room temperature, and the solvent was distilled off under reduced pressure. The obtained syrupy oil was crystallized by adding 100 ml of diethyl ether, and the obtained crystals were collected by filtration under reduced pressure and dried under reduced pressure to obtain the desired product 13.4.
g was obtained. The melting point is 89-91 ° C.

Synthesis Example 2 Synthesis of Exemplified Compound (8) To 50 ml of toluene, 1 g of tricyclohexylphosphine sulfide was added, and the mixture was stirred and dissolved. Then, 1.15 g of methyl trifluoromethanesulfonate was added. After heating under reflux for 2 hours, the reaction solution was returned to room temperature, and the solvent was distilled off under reduced pressure. To the obtained crystals, 50 ml of diethyl ether was added, filtered under reduced pressure, and dried under reduced pressure to obtain 1.35 g of the desired product.

Synthesis Example 3 Synthesis of Exemplified Compound (2) Tris (2,6-dimethoxyphenyl) obtained from elemental sulfur and tris (2,6-dimethoxyphenyl) phosphine
After dissolving the phosphine sulfide in 50 ml of toluene, 0.49 g of methyl trifluoromethanesulfonate is dissolved.
Was added. Crystals were precipitated by stirring at room temperature, and the obtained crystals were collected by filtration under reduced pressure and dried under reduced pressure to obtain 1.3 g of the desired product.
I got The melting point is 271-275 ° C.

In the present invention, development processing is performed in the presence of the compound represented by the formula (I). When the compound of the present invention is added to a photographic material,
It is preferably added to a silver halide emulsion layer or another hydrophilic colloid layer. Further, an embodiment in which the compound of the present invention is added to a developer and an embodiment in which the photographic material is immersed in a solution containing the compound of the present invention after image exposure (bath before development) are also preferable. The most preferred embodiment is that the compound of the present invention is added to a photographic light-sensitive material, particularly a silver halide emulsion layer. The compound of the present invention may be dissolved in an appropriate solvent and then added to a photographic material or a developer. The solvent is preferably water or an organic solvent miscible with water (eg, alcohols, ethers, glycols, ketones, esters, amides).
When the compound of the present invention is added to a photographic light-sensitive material, its amount is preferably from 10 ^{-7 to} 10 ^-2 / mol Ag, more preferably from 10 ^{-6 to} 10 ^-2 mol / mol Ag. . When the compound of the present invention is added to a developer or a pre-development bath, the amount of the compound used is 10 ^{-6 to} 10 ^-1 mol / mol.
Liter, preferably 10 ^{-5 to} 3 × 10 ^-2
More preferably, it is mol / liter.

The silver halide used in the photographic light-sensitive material is preferably silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride. The silver halide grains may have a regular crystal form such as cubic or octahedral,
It may have an irregular crystal form such as a sphere, a plate, or the like, or may have a complex form of these crystal forms. Also, a mixture of particles of various crystal forms can be used. Silver halide grains having a regular crystal form are particularly preferred.

The silver halide grains may have different phases between the inside and the surface layer or may consist of a uniform phase. Particles having two or more multi-structures having different iodine compositions between the inside of the particle and the surface layer (particularly, the iodine content inside is larger) are also preferred. Also, grains whose latent image is mainly formed on the surface (eg, a negative emulsion) may be formed, and grains whose main image is mainly formed inside the grains (eg, an internal latent image type emulsion, a directly fogged emulsion which has been previously fogged) It may be. Preferably, the particles are such that the latent image is mainly formed on the surface. The silver halide emulsion has a thickness of 0.5 micron or less, preferably 0.1 micron or less.
Tabular grain emulsions having a grain size of 3 microns or less, preferably 0.6 microns or more, and having an average aspect ratio of 3 or more occupy 50% or more of the total projected area are preferred. Further, a monodisperse emulsion having a statistical variation coefficient (a value S / d obtained by dividing a standard deviation S by a diameter d in a distribution expressed by a diameter when the projected area is approximated by a circle) of 20% or less is also preferable. Two or more tabular grain emulsions and monodispersed emulsions may be used as a mixture.

Silver halide emulsions are described in P. Glafkides, Chimie Physique Photographeque (Paul Montell, 1967), GF Duffin ( GFDuffin), Photographic Emulsion Chemistry
(Focal Press, 1966), VLZelikman et al., Making and
Coating Photographic Emulsion (Ma
king and Coating Photographic Emulsion) (Focal Press, 1964) and the like.

In forming the silver halide grains, a silver halide solvent may be used to control the growth of the grains. Examples of silver halide solvents include ammonia, rodancali, rodanammon, and thioether compounds (US Pat. Nos. 3,271,157, 3,574,628, 3,704,130, 4,297,439, and 4,2763).
No. 74), thione compounds (JP-A-53-1)
Nos. 44319, 53-82408, 55-777
No. 37) and amine compounds (Japanese Unexamined Patent Publication No.
No. 100717). Cadmium salts, zinc salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or iron complex salts may be coexistent during the formation or physical ripening of silver halide grains.

The silver halide emulsion is usually used after being chemically sensitized. However, a so-called unripened emulsion (brimitive emulsion) without chemical sensitization may be used. Chemical sensitization includes sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, and noble metal sensitization. These may be implemented in combination. In sulfur sensitization, a compound containing sulfur that can react with active gelatin or silver (eg, thiosulfate, thioureas, mercapto compounds, rhodanines) is used as a sulfur sensitizer. Examples of selenium compounds used for selenium sensitization include N, N-dimethylselenourea and triphenylphosphine selenide. Examples of reducing substances used for reduction sensitization include stannous salts, amines, hydrazines, formamidinesulfinic acid and silane compounds. In the noble metal sensitization, a complex salt of a metal of Group VIII of the periodic table, such as platinum, iridium, or palladium, is used in addition to the gold compound.

Gelatin is advantageously used as a protective colloid of the silver halide emulsion and a binder for the emulsion layer or the non-photosensitive layer. Gelatin derivatives, gelatin graft polymers and hydrophilic polymers other than gelatin can also be used as protective colloids and binders. Gelatin includes lime-treated gelatin, acid-treated gelatin, enzyme-treated gelatin (Bull. Soc. Sci. Phot. Japan, No. 16, 30)
P. 1966), gelatin hydrolysates and enzymatic degradation products. Hydrophilic polymers other than gelatin include proteins, polysaccharides and hydrophilic synthetic polymers. Examples of proteins include albumin and casein. Examples of polysaccharides include cellulose derivatives (eg, hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate), sodium alginate and starch derivatives. Examples of hydrophilic synthetic polymers include polyvinyl alcohol, polyvinyl alcohol partial acetal,
Mention may be made of poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole and copolymers thereof.

An inorganic or organic hardener may be added to any hydrophilic colloid layer including a silver halide emulsion layer or a back layer. Examples of hardeners include chromium salts;
Aldehyde salts (eg, formaldehyde, glyoxal, glutaraldehyde); N-methylol-based compounds (eg, dimethylol urea); active halogen compounds (eg,
2,4-dichloro-6-hydroxy-1,3,5-triazine and its sodium salt; active vinyl compounds (eg, 1,3-bisvinylsulfonyl-2-propanol, 1,2-bis (vinylsulfonylacetamide) ) Ethane, bis (vinylsulfonylmethyl) ether, vinyl-based polymers having a bitylsulfonyl group in the side chain);
Carbamoylpyridinium salts (eg, (1-morpholinocarbonyl-3-pyridinio) methanesulfonate); and haloamidinium salts (eg, 1- (1-chloro-1-pyridinomethylene) pyrrolidinium-2-naphthalenesulfate) Can be mentioned. Active halogen compounds, active vinyl compounds, N-carbamoylpyridinium salts and haloamidinium salts are preferred because the curing rate of a hydrophilic colloid such as gelatin is high. Active halogen compounds and active vinyl compounds are particularly preferred because they impart stable photographic properties to the photographic material.

The silver halide photographic emulsion may be spectrally sensitized using a sensitizing dye. Examples of sensitizing dyes include methine dyes, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Cyanine dyes, merocyanine dyes and complex merocyanine dyes are particularly useful. The sensitizing dye usually has a basic heterocyclic nucleus. The heterocyclic nucleus of the cyanine dye includes a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, and a pyridine nucleus. Condensed nuclei and nuclei obtained by condensing an aromatic hydrocarbon ring with these nuclei are included. Examples of the fused ring nucleus include an indolenine nucleus, a benzindolenin nucleus, an indole nucleus, a benzoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus and a quinoline nucleus. be able to. These nuclei may have a substituent on a carbon atom. Merocyanine dyes or complex merocyanine dyes are
It has a 5- or 6-membered heterocyclic nucleus having a ketomethylene structure. Examples of the heterocyclic nucleus having a ketomethylene structure include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and
-Thiooxazolidine-2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus.

Two or more sensitizing dyes may be used in combination. Combinations of sensitizing dyes are often used, especially for supersensitization. Along with the sensitizing dye, a dye that does not itself have a spectral sensitizing effect or a substance that does not substantially absorb visible light and that exhibits supersensitization (supersensitizer) is added to the silver halide emulsion. May be. Examples of supersensitizers include aminostilbenzene compounds substituted with a nitrogen-containing heterocyclic nucleus group (US Pat. Nos. 2,933,390 and 363).
5721), an aromatic organic acid formaldehyde condensate (described in US Pat. No. 3,743,510),
Cadmium salts and azaindene compounds are included. Combinations of sensitizing dyes and supersensitizers are disclosed in US Pat.
No. 613, No. 3615641, No. 3617295,
No. 3,635,721.

An antifoggant other than the compound of the present invention may be further added to the silver halide photographic emulsion. For the purpose of stabilizing photographic performance, a stabilizer may be added to the emulsion. Representative examples of antifoggants and stabilizers include azoles, mercaptopyrimidines, mercaptotriazines, thioketo compounds, azaindenes, benzenethiosulfonic acid, benzenesulfinic acid and benzenesulfonamide. Examples of azoles include benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptothiadiazoles , Aminotriazoles, benzotriazoles, nitrobenzotriazoles, and mercaptotetrazoles (eg, 1-phenyl-5-mercaptotetrazole). Oxadrinthione can be mentioned as an example of the thioketo compound. Examples of azaindenes include triazaindenes and tetraazaindenes (eg, 4-hydroxy-substituted (1,3,3a, 7)
Tetraazaindenes) and pentaazaindenes.

The light-sensitive material may contain a coating aid, a surfactant for improving antistatic properties, improving slipperiness, emulsifying and dispersing, preventing adhesion or improving photographic properties (for example, development acceleration, high contrast, sensitization). Any of a nonionic surfactant, an anionic surfactant, an amphoteric surfactant and a cationic surfactant can be used. Examples of nonionic surfactants include saponins (steroids); alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers, polyethylene glycol alkyl aryl ethers, polyethylene glycol esters) , Polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicone); glycidol derivatives (eg, alkenyl succinic acid polyglycerides, alkylphenol polyglycerides); fatty acid esters of polyhydric alcohols; And sugar alkyl esters. Examples of anionic surfactants include carboxylic acids (eg, alkyl carboxylic acids); sulfonic acids (eg, alkyl sulfonic acids, alkyl benzene sulfonic acids, alkyl naphthalene sulfonic acids); sulfate esters (eg, alkyl sulfate esters). Phosphoric esters (eg, alkyl phosphoric esters, polyoxyethylene alkyl phosphoric esters); N-acyl-N-alkyltaurines; sulfosuccinic esters; and sulfoalkylpolyoxyethylenalkylphenyl ethers Can be mentioned. Examples of amphoteric surfactants include amino acids; aminoalkyl sulfonic acids; aminoalkyl sulfates or phosphates; alkyl betaines; and amine oxides. Examples of the cationic surfactant include alkylamine salts; aliphatic or aromatic quaternary ammonium salts; heterocyclic quaternary ammonium salts (eg, pyridinium, imidazolium); and aliphatic or heterocyclic groups. Including phosphonium or sulfonium salts. When a surfactant is used as an antistatic agent, a fluorine-containing compound is particularly preferred.

A water-soluble dye may be added as a filter dye to the hydrophilic colloid layer of the light-sensitive material. Water-soluble dyes may be used for the purpose of preventing irradiation or halation. As water-soluble dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, azo dyes, cyanine dyes, azomethine dyes, triarylmethane dyes, and phthalocyanine dyes are useful. Oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes and azo dyes are preferred. The oil-soluble dye may be emulsified by an oil-in-water dispersion method and added to the hydrophilic colloid layer.

The present invention is applicable to multilayer multicolor photographic materials having at least two different spectral sensitivities on a support.
The multilayer natural color photographic material usually has at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. The order of arrangement of these layers can be arbitrarily selected as needed. The preferred layer arrangement is from the support side in the order of red-sensitive, green-sensitive and blue-sensitive layers, blue-sensitive layer, green-sensitive layer and red-sensitive layer or in order of blue-sensitive, red-sensitive and green-sensitive layers. The emulsion layer of any color sensitivity may be composed of two or more emulsion layers having different sensitivities to improve the sensitivity. Further, the graininess may be further improved as a three-layer structure. Further, a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. An emulsion layer having a different color sensitivity may be inserted between emulsion layers having the same color sensitivity. A reflective layer such as fine grain silver halide may be provided under the high-sensitivity layer, particularly under the high-sensitivity blue-sensitive layer to improve the sensitivity. Generally, the cyan-sensitive coupler is contained in the red-sensitive emulsion layer, the magenta-forming coupler is contained in the green-sensitive emulsion layer, and the yellow-forming coupler is contained in the blue-sensitive emulsion layer. For example, a combination of infrared-sensitive layers may be used for pseudo color photography or semiconductor laser exposure.

Various color couplers can be used in the photographic material. For couplers, see Research Disclosure (RD) No. 17643, VII-C ~
G.

For the yellow coupler, see US Pat.
No. 933501, No. 40222620, No. 43260
Nos. 24 and 441752, British Patent No. 14205020
Nos. 1476760 and JP-A-58-107.
No. 39 is described in each gazette.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred. For magenta couplers, see U.S. Pat.
No. 3725067, No. 4310619, No. 4351
Nos. 897, 4500630 and 4540654
No. 24220 (June 1984), Research Disclosure No. 24230 (June 1984), JP-A-60-33552 and JP-A-60-4365.
No. 9 is described in each gazette.

As the cyan coupler, a phenol type coupler and a naphthol type coupler are preferable. Cyan couplers are described in U.S. Pat. Nos. 2,369,929 and 280,117.
No. 1, 2772162, 2895826, 3
No. 446622, No. 3772002, No. 375830
No. 8, No. 4052212, No. 4146396, No. 4
No. 228233, No. 4296200, No. 432717
No. 3, No. 4333999, No. 4334011, No. 4
Nos. 427767 and 4455159, West German Patent Publication 3
329729, EP121365A and EP161626A.

A colored coupler for correcting unnecessary absorption of a coloring dye may be used. Regarding colored couplers, see Research Disclosure No. 1764
3, VII-G, U.S. Pat.
Nos. 8258 and 4163670, British Patent 11463
No. 68, each of which is described in JP-B-57-39413. A coupler in which the coloring dye has an appropriate diffusibility may be used. This coupler is described in US Pat.
No. 6237, British Patent No. 2125570, European Patent 96
570 and West German Patent (publication) 3234533.

Polymerized dye-forming couplers may be used. This coupler is described in U.S. Pat.
No. 820, No. 4080211, No. 4367282,
It is described in British Patent No. 2,102,173. Couplers that release a photographically useful residue upon coupling can also be used. DIR couplers releasing a development inhibitor are described in RD17643, VII-F, JP-A-57-151.
No. 944, No. 57-154234, No. 60-1842
No. 48, and US Pat. No. 4,248,962. Couplers which release a nucleating agent or a development accelerator imagewise during development can also be used. These couplers are described in British Patent Nos. 2097140 and 2131188, JP-A-59-157538 and JP-A-59-170.
No. 840, each publication.

Examples of other couplers include competing couplers (described in US Pat. No. 4,130,427) and multi-equivalent couplers (US Pat. Nos. 4,283,472 and 4,338,393).
And DIR redox compounds or DIR coupler-releasing couplers (described in JP-A-60-185950 and JP-A-62-24252), couplers that release a dye that recovers color after separation (Europe) Patent No. 173302A), bleach accelerator releasing couplers (RD Nos. 11449 and 24241, described in JP-A-61-201247), and ligand releasing couplers (described in US Pat. No. 4,553,477) Is included.

The coupler can be introduced into the light-sensitive material by various known dispersion methods. The high boiling point solvent used in the oil-in-water dispersion method is described in US Pat. No. 2,322,027. In the oil-in-water dispersion method, the boiling point at normal pressure is 175 ° C.
It is preferable to use the above high-boiling organic solvents. Examples of the organic solvent include phthalic acid esters (eg, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,
4-di-t-amylphenyl) phthalate, bis (2,
4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate); esters of phosphoric acid or phosphonic acid (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, Tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate and trichloropropyl phosphate, di-2-ethylhexylphenyl phosphate); benzoic acid esters (eg, 2-ethylhexyl benzoate, dodecyl benzoate, 2- Ethylhexyl-p-hydroxybenzoate); amides (eg, N, N-diethyldodecaneamide, N, N-diethyllauramide, N-tetradecylpyrrolidone); Alcohols or phenols (e.g., isostearyl alcohol, 2,4-di -tert-
Amylphenol); aliphatic carboxylic acid esters (eg, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate); aniline derivatives (eg, N, N-dibutyl) -2-butoxy-5
-Tert-octylaniline); and hydrocarbons (eg,
Paraffin, dodecylbenzene, diisopropylnaphthalene). As an auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or more, preferably 50 ° C. or more and about 160 ° C. or less may be used. Examples of co-solvents include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate and dimethylformamide.

For examples of latex dispersion process steps, effects and examples of impregnation latex, see US Pat.
No. 3, West German Patent Application (OLS) 2541274 and No. 2541230.

In the production of a photographic light-sensitive material, a silver halide emulsion layer and other layers are formed by coating on a support usually used for a photographic light-sensitive material. In addition to a flexible support such as a plastic film, paper, or cloth, a rigid material such as glass, pottery, and metal can be used for the support. Plastic film and baryta layer or α
-Paper coated or laminated with an olefin polymer is a preferred flexible support. Examples of the plastic include cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, and polycarbonate. Examples of the α-olefin polymer include polyethylene, polypropylene, and ethylene / butene copolymer. The support may be colored using a dye or a pigment. The support may be black for light blocking purposes. The surface of the support is generally subbed to improve adhesion with a hydrophilic colloid layer such as a silver halide emulsion layer. The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation or flame treatment before or after the undercoating treatment.

For coating the photographic emulsion layer and other hydrophilic colloid layers, various known coating methods such as dip coating, roller coating, curtain coating and extrusion coating can be used. Multiple layers may be applied simultaneously. No. 2,681,294 for multi-layer simultaneous coating.
Nos. 2,761,791, 3,526,528 and 3,508,947.

The present invention can be applied to various color and black-and-white photographic materials. Photographic materials 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 development type color photosensitive materials are included. The present invention can be applied to a black-and-white photographic material for X-rays by using a three-color coupler mixture or a black color coupler. Three color coupler mixing is described in Research Disclosure, No. 17123 (July 1978). U.S. Pat.
No. 26461 and British Patent No. 2102136. Further, a plate making film such as a lith film or a scanner film, a direct or indirect medical or industrial X-ray film, a negative black and white film for photography, a black and white photographic paper, a COM or ordinary micro film, a silver salt diffusion transfer type photosensitive material The present invention can also be applied to a printout type photosensitive material.

When the photographic element of the present invention is applied to the color diffusion transfer photographic method, a peeling (peel apartment) type and an integrated (integrated) type (JP-B-46-16356)
And JP-A-48-33697, JP-A-50-13040 and British Patent No. 1330524) or a film unit which does not require peeling (described in JP-A-57-119345). it can.

Various exposure means can be used for the light-sensitive material of the present invention. Any light source that emits a broad ray corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination light source or the writing light source. Flash light sources such as natural light (sunlight), incandescent lamps, halogen-filled lamps, mercury lamps, fluorescent lamps, and strobe or metal-burning flash bulbs are common. A gas, dye solution or semiconductor laser that emits light in the wavelength range from ultraviolet to infrared,
Light emitting diodes and plasma light sources can also be used as recording light sources. In addition, a phosphor screen (eg, CRT) emitted from a phosphor excited by an electron beam or the like, a liquid crystal (LC)
Exposure means in which a linear or planar light source is combined with a micro-shutter array using D) or lanthanum-doped lead titanium zirconate (PLZT) can also be used. If necessary, the spectral distribution used for exposure can be adjusted with a color filter.

The color developing solution used in the developing treatment is preferably an alkaline aqueous solution mainly containing an aromatic primary amine color developing agent. As the color developing agent, p
-A phenylenediamine compound is preferred. Aminophenol compounds are also useful. Examples of the p-phenylenediamine-based compound include 3-methyl-4-amino-N,
N-diethylaniline, 3-methyl-4-amino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-
Ethyl-N-β-methoxyethylaniline and the sulfates, hydrochlorides or p-toluenesulfonates thereof can be mentioned. These diamines are generally more stable in a salt than in a free state, and are preferably used.

The color developing solution is generally composed of a pH buffer (eg, an alkali metal carbonate, borate or phosphate) and a development inhibitor or an antifoggant (eg, bromide, iodide, benzimidazoles, benzoic acid). Thiazoles, mercapto compounds). If necessary, preservatives (eg, hydroxylamine, sulfite), organic solvents (eg, triethanolamine, diethylene glycol), development accelerators (eg, benzyl alcohol, polyethylene glycol,
Quaternary ammonium salts, amines, nucleating agents (eg, dye-forming couplers, competitive couplers, sodium boron hydride), auxiliary developing agents (eg, 1-phenyl-3-pyrazolidone), viscosity-imparting agents, chelating agents (examples) , Aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid,
A phosphonocarboxylic acid) or an antioxidant (described in the specification of West German Patent Application (OLS) 2622950) may be added to the color developer.

In the process of developing a reversal color photosensitive material, color development is usually performed after black-and-white development. This black-and-white developer contains a black-and-white developer. Examples of black-and-white developers include dihydroxybenzenes (eg, hydroquinone), 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone), and aminophenols (eg, N-methyl-p-aminophenol). be able to. Two or more black-and-white developers may be used in combination.

The silver halide emulsion layer after color development is usually subjected to bleaching. The bleaching process may be performed simultaneously with the fixing process, or may be performed individually. In order to speed up the processing, a processing method of performing a bleach-fixing process after the bleaching process may be used. The bleaching agents include compounds of polyvalent metals such as iron (III), cobalt (III), chromium (IV) and copper (II), peracids, quinones, and nitroso compounds. Examples of the bleaching agent include ferricyanide; dichromate; an organic complex of iron (III) or cobalt (III) (eg, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-acid) Aminopolycarboxylic acids such as propanoltetraacetic acid or complex salts of organic acids such as citric acid, tartaric acid and malic acid); persulfates; manganates; and nitrosophenols. Iron (III) ethylenediaminetetraacetate, iron (III) diethylenetriaminepentaacetate, and persulfate are preferable because they can speed up the treatment and have little effect on the environment. The iron (III) complex salt of ethylenediaminetetraacetate is particularly useful in both an independent bleaching solution and a single bath bleach-fixing solution.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Examples of the bleaching accelerator include compounds having a mercapto group or a disulfide group (U.S. Pat. No. 3,893,858, West German Patents 1,290,812 and 2,059,988), JP-A-53-32736 and JP-A-53-57831.
Nos. 37418, 53-65732, 53-
No. 72623, No. 53-95630, No. 53-956
No. 31, 53-104232, 53-12442
Nos. 4, 53-141623 and 53-28426, Research Disclosure No. 4; 17129
No. (July 1978)); thiazolidine derivatives (described in JP-A-50-140129); thiourea derivatives (JP-B-45-8506, JP-A-52-20832)
Nos. 53-32735 and U.S. Pat.
No. 61); iodide (West German Patent 1127715)
Nos., JP-A-58-16235); polyethylene oxides (West German Patent Nos. 966410 and 2)
748430); polyamine compounds (described in JP-B-45-8836); and iodine or bromine ions. Bleaching accelerators are described in JP-A-49-42434 and JP-A-49-59644.
And JP-A-53-94927, JP-A-54-35727, JP-A-55-26506 and JP-A-58-163940. A compound having a mercapto group or a disulfide group is preferable because of a large accelerating effect. A bleaching accelerator may be added to the light-sensitive material. When bleach-fixing a color photographic material for photography, these bleaching accelerators are particularly effective. Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and iodides (used in large amounts). Thiosulfate is typical. A preservative may be added to the bleach-fix solution or the fix solution. Examples of preservatives include sulfites, bisulfites and carbonyl bisulfite adducts.

After the bleach-fixing process or the fixing process, a washing process and a stabilizing process are usually performed. Various additives may be used in the washing step and the stabilizing step. In order to prevent precipitation, a water softener (eg, inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid, organic phosphoric acid) is used. A fungicide or a fungicide may be used to prevent the occurrence of various bacteria, algae and mold. A magnesium salt, an aluminum salt or a bismuth salt may be added. Surfactants can also be used to prevent drying load and unevenness. Further, a hardener may be added. The addition of a chelating agent or an anti-binder is particularly effective. These additives are described in Photographic Science and Engineering by West (LE West, Phot. Sci. Eng.), Volume 6,
Also described on pages 344 to 359 (1965).

In the water washing step, a general method is to use two or more tanks in countercurrent washing to save water. Instead of the water washing step, a multi-stage countercurrent stabilization step (Japanese Patent Laid-Open No.
May be implemented. In the case of a multi-stage countercurrent stabilization treatment step, 2 to 9 countercurrent baths are required. Various compounds are added to the stabilizing bath in addition to the above-mentioned additives for the purpose of stabilizing an image. Additives include various buffers (eg, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, potassium hydroxide, sodium hydroxide) for adjusting the membrane pH (for example, pH 3 to 9). Aqueous ammonia, monocarboxylic acids, dicarboxylic acids, polycarboxylic acids and combinations thereof) and aldehydes (eg, formalin). If necessary, a chelating agent (eg, inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid), a bactericide (eg,
(Benzoisothiazolinone, irithiazolone, 4-thiazoline benzimidazole, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactant, optical brightener or hardener may be used. Two or more compounds may be used in combination.

After the treatment, an ammonium salt may be added as a membrane pH adjuster. Examples of membrane pH adjusters include ammonium chloride, ammonium nitrate, ammonium sulfate,
Mention may be made of ammonium phosphate, ammonium sulfite and ammonium thiosulfate. In the color light-sensitive material for photography, the washing-stabilizing step after fixing can be changed to the above-mentioned stabilizing step and washing step (water saving processing). At this time, if the magenta coupler has 2 equivalents,
Formalin in the stabilizing bath may be removed. The time required for rinsing and stabilizing processing varies depending on the type of photosensitive material and processing conditions. The processing time is usually from 20 seconds to 10 minutes, preferably from 20 seconds to 5 minutes.

The silver halide color light-sensitive material may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. Examples of the precursor include an indoaniline-based compound (eg, US Pat.
No. 597); Schiff base-type compounds (described in US Pat. No. 3,342,599, Research Disclosure Nos. 14850 and 15159); aldol compounds (described in Research Disclosure No. 13924); metal salt complexes (described in US Pat. No. 3,719,492) Urethane compounds (JP-A-53-135628)
And a salt-type precursor (Japanese Unexamined Patent Publication No.
No. 6235, No. 56-16133, No. 56-5923
No. 2, 56-67842, 56-83734,
No. 56-83735, No. 56-83736, No. 56
-89735, 56-81837, 56-54
No. 430, No. 56-106241, No. 56-1072
No. 36, No. 57-97531, and No. 57-83565). The silver halide color light-sensitive material may contain 1-phenyl-3-pyrazolidones for the purpose of accelerating color development. For 1-phenyl-3-pyrazolidone analog, see JP-A-56-6
No. 4339, No. 57-144547, No. 57-211
No. 147, No. 58-50532, No. 58-50536
No. 58-50533, No. 58-50534, No. 58-50535 and No. 58-11543.

Various treatment liquids are used at 10 ° C. to 50 ° C. Temperatures between 33 ° C and 38 ° C are standard. The temperature may be further increased to accelerate the processing and shorten the processing time. Conversely, the temperature may be lowered to improve the image quality or the stability of the processing solution. Processing using cobalt intensification or hydrogen peroxide intensification to save silver in photosensitive materials (West German Patent 2
226770 or U.S. Pat. No. 3,674,499). If necessary, a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, and a squeegee may be provided in the various treatment baths. For continuous processing, use the replenisher of each processing solution,
A certain finish can be obtained by preventing the fluctuation of the liquid composition. The replenishment amount can be reduced to half or less than the standard replenishment amount for cost reduction and the like. When the light-sensitive material is color paper, bleach-fix processing can be performed very generally. Even when the light-sensitive material is a color photographic material for photography, it can be subjected to bleach-fixing if necessary.

[0094]

【Example】

[Example 1] A silver bromide gelatin emulsion comprising monodisperse tetrahedral grains (average grain size of silver halide grains: about 0.1 mm).
8 μm), diphenylthiourea, potassium chloroaurate and rhodan ammonium were added and the mixture was aged.
0.1 mol% of potassium iodide was added to the obtained emulsion. Further, 3,3′-disulfopropyl-5,5′-
After the addition of sodium dichloro-9-ethyloxacarbocyanine, the compound of the invention and the comparative compound are added first.
Added as shown in the table. Further, a coating aid (sodium dodecylbenzenesulfonate) and a hardener (2,4-
Dichloro-6-hydroxy-s-triazine),
Samples 101 to 109 were obtained by coating and drying on a cellulose triacetate support.

These samples were exposed using an optical wedge provided with a yellow filter using a sensitometer (1/20 second) and developed with a developer having the following composition at 35 ° C. for 35 seconds. After fixing, washing and drying by a usual method, photographic properties (sensitivity and fog) were measured, and the results shown in Table 1 were obtained.

組成 Developer composition 組成ナ ト リ ウ ム Sodium sulfite 40 g Hydroquinone 25 g Boric acid 10 g 1-Phenyl-3-pyrazolidone 1.5 g Potassium hydroxide 30 g 5 -Methylbenzotriazole 0.15 g Glutaraldehyde bisulfite 15 g Acetic acid 12 g Potassium bromide 10 g Add water and add 1 liter. ──────────

[0097]

[Table 1] Table 1 ──────────────────────────────────── Sample No. Compound addition amount Fog sensitivity ──────────────────────────────────── 101 (comparative example) None --- 0.27 100 102 (Comparative Example) (A) 1 × 10 ⁻³ 0.30 70 103 (Comparative Example) (A) 3 × 10 ⁻³ 0.33 35 104 (Comparative Example) (B) 3 × 10 ⁻³ 0.23 76 105 (comparative example) (C) 3 × 10 ⁻³ 0.25 83 106 (the present invention) (1) 3 × 10 ⁻³ 0.18 96 107 (the present invention) (5) 3 × 10 ⁻³ 0.16 89 108 (the present invention) (10) 3 × 10 ⁻³ 0.14 85 109 (the present invention) (22) 3 × 10 ⁻³ 0.20 96 ─────────────── ─────────── ──────────

The amounts of the compounds added are shown in moles per mole of silver halide. The photographic sensitivity is the fog value +0.
The reciprocal of the logarithm of the exposure amount required to obtain the optical density of 2 was determined, and the value of the sample 101 was set to 100, and the other values were relatively indicated.

[0099]

Embedded image

[0100]

Embedded image

As is evident from the results shown in Table 1, the compounds of the present invention were compared with Comparative Compounds A, B and C,
The decrease in relative sensitivity is small, and the fog density is reduced.

Example 2 A silver iodobromide gelatin emulsion (average grain size of silver halide grains: about 0.8 μm) containing 6 mol% of silver iodide was prepared by using sodium thiosulfate, potassium chloroaurate and rhodan ammonium. To obtain a high-sensitivity silver iodobromide emulsion. The compounds of the invention and comparative compounds were then added as shown in Table 2. Further, in the same manner as in Example 1, a coating aid and a hardener were added, and the mixture was applied and dried to obtain Samples 201 to 208.

One set of the obtained samples was allowed to stand at room temperature for 4 days, and the other two sets were allowed to stand at high temperature and low humidity and at high temperature and high humidity (conditions are shown in Table 2) for 4 days. These three
The sets of samples were exposed through an optical wedge in the usual manner and developed with Kodak D-72 developer for 4 minutes at 20 ° C. After fixing, washing and drying by a usual method, photographic properties (sensitivity and fog) were measured, and the results shown in Table 2 were obtained.

[0104]

[Table 2] Table 2 試 料 Sample number Compound addition amount Room temperature 4 day between 50 ° C. 20% 4 days 50 ° C. 80% 4 days fogging sensitivity fog sensitivity fog sensitivity ─────────────────────────────── ───── 201 (Comparative Example) None --- 0.10 100 0.28 141 0.26 78 202 (Comparative Example) (A) 2 × 10 ^-3 0.10 56 0.42 74 0.33 66 203 (Comparative Example) (D) 1 × 10 ^-3 0.08 52 0.18 87 0.18 87 204 (the present invention) (1) 0.3 × 10 ^-3 0.08 98 0.20 141 0.08 105 205 (the present invention) (1) 1 × 10 ^-3 0.07 93 0.15 107 0.08 100 206 (the present invention) ) (4) 1 × 10 ^-3 0.06 98 0.17 112 0.07 102 207 (present invention) (6) 1 × 10 ^-3 0.09 100 0.20 105 0.10 107 208 (present invention) (46) 1 × 10 ^-3 0.08 96 0.16 125 0.10 98 ────────────────────────────────────

The amounts of the compounds added are shown in moles per mole of silver halide. 20% and 80% indicate relative humidity. The photographic sensitivity was calculated by calculating the reciprocal of the logarithm of the amount of exposure required to obtain an optical density of fog value +0.2.
The value obtained by leaving 1 at room temperature was taken as 100, and the others were relatively shown.

[0106]

Embedded image

As is evident from the results shown in Table 2, even when the photographic material was left under severe storage conditions, the compounds of the present invention suppressed the occurrence of fog as compared with Comparative Compounds A and B. , With little change in sensitivity.

Example 3 Sodium thiosulfate was added to a silver iodobromide gelatin emulsion (average grain size of silver halide grains: about 0.8 μm) containing 5 mol% of silver iodide.
The mixture was heated at 60 ° C. for 60 minutes for aging. The compounds of the present invention and comparative compounds were added to the obtained emulsion as shown in Table 3. Further, the following couplers, sensitizing dyes, hardeners and coating aids were added, and coated and dried to obtain samples 301 to 301.
207 was obtained.

<< Additives of Silver Halide Emulsion >>カ プ ラ Coupler 1- (2,4,6-trichlorophenyl) -3- [3 -(2,4-di-t-aminophenoxy) acetamido] benzamide-5-pyrazolone {Sensitizing dye bis- [2- {1-ethyl-3- (3-sulfopropyl) -5,6-dichlorobenzimidazole}] trimethine cyanine sodium salt} ────────────────────────────── Hardener 2,4-dichloro-6-hydroxy-1,3,5-triazine Nato Salt 塩 Coating aid Sodium p-dodecylbenzenesulfonate and p -Sodium nonylphenoxypoly (ethyleneoxy) propanesulfonate

These samples were exposed to light through a yellow filter (1/20 second), and then subjected to color development processing as described below, followed by measurement of photographic properties. The results shown in Table 3 were obtained.

──────────────────────────────────── Processing Step Processing Time ─────── ───────────────────────────── 1. Color development 2 minutes 45 seconds (38 ° C.) Bleaching 6 minutes 30 seconds 3. 3 minutes and 15 seconds 4. Fixing 6 minutes 30 seconds 5. 3 minutes and 15 seconds 6. Stable 3 minutes 15 seconds 処理 Composition of processing solution used for each process Is as follows.

────────────────────────────────────Color developer 液ナ ト リ ウ ム Sodium nitrilotriacetate 1.0 g Sodium sulfite 4.0 g Sodium carbonate 30.0 g Potassium bromide 1. 4 g hydroxylamine sulfate 2.4 g 4- (N-ethyl-N-β-hydroxyethylamino-2-methylaniline sulfate 4.5 g 1 liter of water was added. ────────────────────────

────────────────────────────────────Bleaching solution─────────ア ン モ ニ ウ ム Ammonium bromide 160.0 g Ammonia water (28%) 25.0 ml Ethylenediaminetetraacetic acid / sodium iron salt 130 1.0 g Glacial acetic acid 14.0 ml Add water and add 1 liter.

──────────────────────────────────── Fixing solution ─────────ナ ト リ ウ ム Sodium tetrapolyphosphate 2.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (70%) 175.0 ml Bisulfite 4.6 g of sodium and 1 liter of water

────────────────────────────────────Stabilizing solution 安定ホ ル Formalin 8.0ml Add water 1 liter ───────────── ───────────────────────

[0116]

[Table 3] Table 3 ──────────────────────────────────── Sample No. Compound addition amount Fog sensitivity ──────────────────────────────────── 301 (comparative example) None --- 0.24 100 302 (Comparative Example) (A) 1 × 10 ⁻³ 0.26 74 303 (Comparative Example) (D) 1 × 10 ⁻³ 0.20 81 304 (Invention) (3) 1 × 10 ⁻³ 0.14 93 305 (the present invention) (4) 1 × 10 ⁻³ 0.12 91 306 (the present invention) (21) 1 × 10 ⁻³ 0.13 89 307 (the present invention) (46) 1 × 10 ⁻³ 0.13 98 ────────────────────────────────────

The amounts of the compounds added are shown in moles per mole of silver halide. The photographic sensitivity is the fog value +0.
The reciprocal of the logarithm of the exposure amount required to obtain the optical density of 2 was determined, and the value of the sample 301 was set to 100, and the other values were relatively indicated.

As is evident from the results shown in Table 3, the compounds of the present invention have a small decrease in relative sensitivity and effectively lower the fog density in comparison with Comparative Compounds A and D also in color development.

Example 4 A comparative experiment was conducted by adding the compound of the present invention to a developer. The sample 101 of Example 1 was exposed in the same manner as in Example 1. The same developer as in Example 1
Compounds of the invention and comparative compounds were added as shown in the table. Using these developing solutions, the exposed sample was heated to 35 ° C.
For 35 seconds, and the results shown in Table 4 were obtained in the same manner as in Example 1.

[0120]

[Table 4] Table ──────────────────────────────────── Sample No. Compound addition amount Fog sensitivity ──────────────────────────────────── 101 (comparative example) None --- 0.27 100 110 (The present invention) (1) 5.0 × 10 ⁻⁴ 0.14 90 111 (the present invention) (5) 5.0 × 10 ⁻⁴ 0.15 92 112 (the present invention) (10) 5.0 × 10 ^-4 0.13 84 113 (the present invention) (22) 5.0 × 10 ^-4 0.14 87 114 (comparative example) (A) 5.0 × 10 ^-4 0.26 65 115 (comparative example) ( B) 5.0 × 10 ^-4 0.28 75 116 (Comparative Example) (C) 5.0 × 10 ^-4 0.30 75 ────────────────── ─────────────────

The amounts of the compounds added are shown in terms of moles per liter of the developing solution. Photo sensitivity is fog value +0.2
The reciprocal of the logarithm of the amount of exposure required to obtain the optical density of the sample 101 was determined.

As is clear from the results shown in Table 4, even when the compound of the present invention was added to the developer, Comparative Compounds A and B
As compared with C and C, the decrease in relative sensitivity is small and the fog density is effectively reduced.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-49-73123 (JP, A) JP-A-4-62544 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03C 1/34 G03C 5/305

Claims (3)

(57) [Claims] 1. A silver halide photographic light-sensitive material having a silver halide emulsion layer on a support, comprising a compound represented by the following formula (I). Embedded image In the formula, R ¹ is an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group. R ² , R ³ and R ⁴ each represent an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, an amino group, -S
R ⁵ , —OR ⁶ or —SeR ⁷ . R ⁵ , R ⁶ and R ⁷ are an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group, respectively. Each of the above groups may further have a substituent. X is a counter anion. X may be included in the above substituent to form an inner salt. 2. A developing solution for a silver halide photographic light-sensitive material, comprising a compound represented by the following formula (I). Embedded image In the formula, R ¹ is an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group. R ² , R ³ and R ⁴ each represent an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, an amino group, -S
R ⁵ , —OR ⁶ or —SeR ⁷ . R ⁵ , R ⁶ and R ⁷ are an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group, respectively. Each of the above groups may further have a substituent. X is a counter anion. X may be included in the above substituent to form an inner salt. 3. A method in which a silver halide photographic material having a silver halide emulsion layer on a support is image-exposed and an image is formed by a developing process using a developing solution. An image forming method, wherein the photographic material or the developer contains a compound represented by the following formula (I). Embedded image In the formula, R ¹ is an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group. R ² , R ³ and R ⁴ each represent an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, an amino group, -S
R ⁵ , —OR ⁶ or —SeR ⁷ . R ⁵ , R ⁶ and R ⁷ are an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group, respectively. Each of the above groups may further have a substituent. X is a counter anion. X may be included in the above substituent to form an inner salt.