WO2004095129A1 - Silver halide photographic lightsensitive material and method of processing the same - Google Patents

Abstract

A silver halide photographic lightsensitive material and a method of processing the same. In particular, a silver halide photographic lightsensitive material that is excellent in stability of image density even when subjected to mass processing, and a method of processing the same. More particularly, a silver halide photographic lightsensitive material comprising a support and, superimposed thereon, at least one lightsensitive layer and at least one non-lightsensitive layer, characterized in that the lightsensitive layer or non-lightsensitive layer contains at least one member selected from among the compounds of the following general formulae (I) to (IV), that the lightsensitive material in its coating layers contains calcium whose total content is in the range of 10 to 0.01 mg/m2, and that the lightsensitive material contains gelatin whose total amount is in the range of 6.2 to 4.0 g/m2 .

Description

 Description Silver halide photographic light-sensitive material and processing method thereof

 The present invention relates to a silver halide photographic light-sensitive material and a method for processing the same, and more particularly, to a silver halide photographic light-sensitive material having excellent image density stability even when processed in a large amount, and a method for processing the same. Background art

 In recent years, the photographic industry has demanded a silver halide photographic light-sensitive material that can be rapidly processed, has high image quality, and can always maintain stable performance.

 In order to achieve rapid processing in response to the current situation and needs of such markets, approaches are being taken from two aspects: photosensitive materials and processing solutions. There have been many attempts to optimize the temperature and pH of processing solutions and to add additives such as development accelerators. However, these processes often involve performance degradation such as an increase in capri. On the other hand, the halogen composition of a silver halide emulsion used in a light-sensitive material affects the development speed, but it is known that a particularly high development speed is exhibited, particularly when high chloride silver halide is used. .

It is also necessary to improve not only the silver halide emulsion but also the color-forming component such as a coupler having a high coupling speed with an oxidized color developing agent. For this reason, it is necessary to adjust the addition of couplers, high-boiling organic solvents, color-mixing inhibitors, color fading inhibitors, etc. to be contained in the silver halide photographic material. However, when printing a large amount on a commercial basis, there is a problem that the image density tends to vary. In particular, it was found that in the reprocessing of the color developing solution in the rapid processing, variations in the image density tended to occur. Reuse of the color developer is an important technology from the viewpoint of cost reduction and environmental load reduction. As a result of various studies on the above problems, the present inventors have found that the problems can be solved by using a silver halide photosensitive material having a specific structure, and have reached the present invention.

 On the other hand, although the technology of the compound according to the present invention has already been disclosed (for example, see Patent Document 1), the constitution of the present invention is neither described nor suggested. Also, there is no description of stabilizing the image density in the reproduction processing of the color developing solution.

 Accordingly, it is an object of the present invention to provide a silver halide photographic light-sensitive material having a stable image density of a developed image and a processing method thereof.

(Patent Document 1)

 Japanese Patent Application Laid-Open No. 6-118585 / 1991 Disclosure of the Invention

 The above object of the present invention is achieved by each of the following constitutions.

(1) In a silver halide photographic material having at least one light-sensitive layer and at least one non-light-sensitive layer on a support, the light-sensitive layer or the non-light-sensitive layer is represented by the following general formula (I) ) To (IV), wherein the total calcium content in the coating layer of the light-sensitive material is from 10 mm ^{2 to} 0.001 mg / m ² . And the total amount of gelatin contained in the photosensitive material Silver halide photography characterized by being at 0 g / m ²

General formula (I)

O N-CHzCH-Ri

 \ _ / I

N0 ₂

(In the formula, Ri represents a hydrogen atom, a lower alkyl group, or an aryl group.) General formula (II)

(Wherein, R ₂ is a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, (R ₆ ) (R ₅ )> NC (= 0), (R 6) (R 5) > NC (= S) —, and R ₅ and R _e each represent a hydrogen atom, an alkyl group, an aryl group, a cyano group, a heterocyclic group, an alkylthio group, an arylthio group, an alkylsulfoxy group, or an alkylsulfonyl group. , R ₃ and R ₄ may combine with each other to form an aromatic ring, and R ₅ and R ₆ each represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.)

(式中、 Xはハロゲン原子、 ニトロ基、 ヒ ドロキシ基、 シァノ基、 低級アルキ ル基、 低級アルコキシ基、 ァリール基、 アルケニル基、 スルホニル基、 ァラル キル基、 一 COR₇、 -N< ( R₈)( R₉)、 一 S 0₃M²を表し、 R₇は水素原子、 一 OM²、 低級アルキル基、 ァリール基、 ァラルキル基、 低級アルコキシ基、 了 リールォキシ基、 ァラルキルォキシ基、 — Nく ( Rio) ( Rii ) を表す。 R₈、 R ₉は各々水素原子、 低級アルキル基、 ァリール基、 ァラルキル基、 一 COI^ ₂、 一S 0₂R₁₂を表し、 互いに同じであっても異なっていてもよく、 R₁₀、 R Hは各々水素原子、 低級アルキル基、 ァリール基、 ァラルキル基を表し、 互い に同じであっても異なっていてもよく、 R₁₂は低級アルキル基、 ァリール基、 ァラルキル基を表し、 M²は水素原子、 アルカリ金属原子及び 1価のカチ オンを形成するに必要な原子群を表し、 mは 0〜5の整数を表し、 mが 2〜5 の場合、 Xは同じ基であっても上記の基が複数組み合わされていても構わな い。） 一般式 (IV)

—General formula (ΙΠ)

(Wherein, X is a halogen atom, a nitro group, arsenate Dorokishi group, Shiano group, lower alkyl group, a lower alkoxy group, Ariru group, an alkenyl group, a sulfonyl group, Araru kill group, one COR _7, -N <(R ₈ ) (R ₉ ), represents one S 0 ₃ M ² , R ₇ is a hydrogen atom, one OM ² , a lower alkyl group, an aryl group, an aralkyl group, a lower alkoxy group, an aryloxy group, an aryloxy group, —N represents a (Rio) (Rii). R 8, R 9 are each a hydrogen atom, a lower alkyl group, Ariru group, Ararukiru group, one COI ^ _2, represents an S 0 ₂ R _12, different from be the same as each other R ₁₀ and RH each represent a hydrogen atom, a lower alkyl group, an aryl group or an aralkyl group, which may be the same or different, and R ₁₂ represents a lower alkyl group, an aryl group or an aralkyl group. M ² represents a hydrogen atom, Represents an alkali metal atom and a group of atoms necessary to form a monovalent cation, m represents an integer of 0 to 5, and when m is 2 to 5, X is the same group even if X is the same group. Multiple combinations may be used.) General formula (IV)

(In the formula, R ₁₃ represents an unsubstituted or substituted alkylene group, Y represents a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, a cyano group, a lower alkyl group, a lower alkoxy group, an aryl group, an alkenyl group, sulfonyl group, Ararukiru _{group, -COR 14, -N <(R} 15) (R 16), - represents S 0 ^₃ M _3, R "is hydrogen sheet one OM ^3, lower alkyl group, Ariru group, Ararukiru R ₁₅ , R _ie represents a lower alkoxy group, an aryloxy group, an aralkyloxy group, and 1 N (R ₁₇ ) (Ris). A hydrogen atom, a lower alkyl group, an aryl group, an aralkyl group, — COR ₁₉ , —SO ₂ R ₁₉ , which may be the same or different, and R ₁₇ and R ₁₈ are each a hydrogen atom or a lower alkyl R ₁₉ represents a lower alkyl group, an aryl group or an aralkyl group; R ³ represents a lower alkyl group, an aryl group or an aralkyl group; M ³ represents a hydrogen atom, an aralkyl metal atom and 1 Represents the group of atoms necessary to form a multivalent cation. n represents an integer of 0 or 1 to (6_p), and p represents an integer of 1 to 6. When n and p are 2 or more, a plurality of the above groups may be combined. )

 (2) The silver halide photographic material as described in (1), further comprising an anionic surfactant having a benzene ring or a naphthalene ring.

(3) The silver halide photographic light-sensitive material according to (1) or (2), wherein the support is a double-sided resin-coated paper, and the weight of the support is 2 17 g / m ² or less. material.

 (4) After the imagewise exposure of the silver halide photographic light-sensitive material according to any one of (1) to (3), an overflow of a color developing solution generated when the silver halide photographic material is continuously processed is regenerated. A method for processing a silver halide photographic material, wherein the material is recycled for processing the material. BEST MODE FOR CARRYING OUT THE INVENTION

The present invention provides a silver halide photographic material having at least one light-sensitive layer and at least one light-insensitive layer on a support, wherein the light-sensitive layer or the non-light-sensitive layer has the general formula It contains at least one compound selected from the compounds represented by (I) to (IV), and has a total calcium content of 10 m in the coating layer of the light-sensitive material. g / m ^{2 to} 0.01 mg / m ² , and the total amount of gelatin contained in the light-sensitive material is 6.2 g / m ² to 4.0 gZm ² .

 The compounds represented by the general formulas (I) to (IV) are compounds generally known as anti-bacterial agents. By combining with reducing the total calcium content, the coupler dispersion by bacteria and calcium can be achieved. It is estimated that destruction can be effectively suppressed and stabilized, and that the stabilization of image density, which is the object of the present invention, has been achieved.

 First, the compounds represented by the general formulas (I) to (IV) will be described. In the formula of the compound represented by the general formula (I), represents a hydrogen atom, a lower alkyl group (eg, a methyl group, an ethyl group, etc.) and an aryl group (eg, a phenyl group, a 4-chlorophenyl group, etc.).

In the formula of the compound represented by the general formula (11), R ₂ is a hydrogen atom, a linear or branched substituted or unsubstituted alkyl group (methyl, ethyl, tert-butyl, octadecyl, 2-hydroxyxethyl) , 2-carboxyethyl, 2-cyanoethyl, sulfoptyl, N, N-getylaminoethyl), substituted or unsubstituted cyclic alkyl groups (eg cyclohexyl, 3-methylcyclohexyl, 2-oxocyclopentyl) Substituted or unsubstituted alkenyl groups (aryl, methylaryl), substituted or unsubstituted aralkyl groups (eg, benzyl, p-methoxybenzyl, o-cyclobenzyl, p-iso-propylbenzyl), substituted or unsubstituted Aryl groups (phenyl, naphthyl, o-methylphenyl, m-2-trophenyl, 3,4-dichlorophenyl), heterocyclic groups 2 _ b imidazolyl, 2-off Lil, 2-thia Zoriru, _{2-pyridyl), (R 6) (R} 5)> N- C (= 0) _{one, (R 6) (R 5} )> N one C (= S), and R ₅ and R ₆ are each a hydrogen atom, a substituted or unsubstituted alkyl (Eg, methyl, ethyl, chloromethyl ヽ 2-hydroxyethyl, tert-butyl, octyl), substituted or unsubstituted cyclic alkyl groups (eg, cyclohexyl, 2-oxocyclopentyl), substituted or unsubstituted aryl. Groups (eg, phenyl, 2-methylphenyl, 3,4-dichlorophenyl, naphthyl, 4-nitrophenyl, 4-aminophenyl, 3-acetamidophenyl), cyano groups, heterocyclic groups (eg, 2-imidazolyl) , 2-thiazolyl, 2-pyridyl), substituted or unsubstituted alkylthio groups (eg, methylthio, 2-cyanoethylthio, 2-ethoxycarbonylthio), substituted or unsubstituted arylthio groups (eg, phenylthio, 2-carboxyphenylthio, p-methoxyphenylthio), substituted or unsubstituted alkyl Represents a sulfoxy group (eg, methylsulfoxy, 2-hydroxysulfyloxy), a substituted or unsubstituted alkylsulfonyl group (eg, methylsulfonyl, 2-bromoethylsulfonyl), and R ₃ and R ₄ are linked to each other To form an aromatic ring.

R ₅ and R ₆ are each a hydrogen atom, a substituted or unsubstituted alkyl group (eg, methyl, ethyl, iso-propyl, 2-cyanoethyl, 2-butoxycarboylethyl), a substituted or unsubstituted aryl group (Eg, phenyl, naphthyl, 2-methoxyphenyl, m-nitrophenyl, 3,5-dichlorophenyl-3-acetamidophenyl), substituted or unsubstituted aralkyl groups (eg, benzyl, phenol, p — Iso — propylbenzyl, 0 — black benzene, m-methoxybenzyl).

In the formula of the compound represented by the general formula (HI), X represents a halogen atom (eg, chlorine atom, bromine atom, fluorine atom), a nitro group, a hydroxy group, a cyano group, a lower alkyl group (eg, methyl, ethyl, is 0-propyl, tert-butyl), lower alcohol Xy groups (eg, methoxy, butoxy, 2-methoxetoxy), aryl groups (eg, phenyl, naphthyl, 2-methoxyphenyl, 3-acetamidophenyl), alkenyl groups (eg, aryl, 1-butenyl), a sulfonyl group (e.g. methylstyrene Ruhoniru, benzenesulfonyl), Ararukiru groups (e.g. benzyl, p-IS 0 - propyl base Njiru, O-methyl benzyl), one _{C OR 7, _N <(R} 8) (R 9), Represents S 0 ₃ M ² , R ₇ is a hydrogen atom, —OM ² , a lower alkyl group (eg, methyl, butyl), an aryl group (eg, phenyl, 4-chlorophenyl, 3-nitrophenyl), Aralkyl groups (eg, benzyl, P-iso-propylbenzyl, o_methylbenzyl), lower alkoxy groups (eg, methoxy, butoxy, 2-methoxyshethoxy), aryloxy groups Ruokishi group (e.g. Fuwenokishi naphthoquinone butoxy, representing four twelve Toro phenoxy :), Ararukiru old alkoxy group (e.g. Benjiruokishi, p- chloro downy Nji _{Ruokishi), -N <(R 10)} (Rii). R ₈ and R ₉ are each a hydrogen atom, a lower alkyl group (eg, methyl, ethyl, 2-ethylhexyl), an aryl group (eg, phenyl, naphthyl, 2-methoxyphenyl, 3-acetamide), aralkyl groups (e.g. benzyl, single black port base Njiru.), _C OR _12, - represents S 0 ₂ R _12, or different and the same as each other, Ri. And are respectively a hydrogen atom, a lower alkyl group (eg, methyl, iso-propyl, 2-cyanoethyl), an aryl group (eg, phenyl, 4-ethoxycarbonylphenyl, 3-nitrophenyl), an aralkyl group (eg, benzyl, p- R ₁₂ is a lower alkyl group (eg, ethyl, 2-methoxethyl, 2-hydroxyxethyl), an aryl group (eg, phenyl). , Naphthyl, 4-sulfophenyl, 4-carboxyphenyl) and aralkyl groups (eg, benzyl, phenethyl), MM ² is a hydrogen atom, an alkali metal Represents an atom and a group of atoms necessary to form a monovalent cation (eg, ammonium cation, phosphonium cation), m represents an integer of 0 to 5, and when m is 2 to 5, X represents the same group. In addition, a plurality of the above groups may be combined. In the formula of the compound represented by the general formula (IV), ₃ represents an unsubstituted or substituted alkylene group (for example, represents an ethylene group, a propylene group, a methylethylene group, etc., and the substituent is a halogen atom, a nitro group, a hydroxy group or the like). Group, a cyano group, a lower alkyl group, a lower alkoxy group, an aryl group, an alkenyl group, a sulfonyl group, an aralkyl group, etc., and an alkylene group having 1 to 6 carbon atoms is particularly preferable. Y is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, fluorine atom), nitro group, hydroxy group, cyano group, lower alkyl group (eg, methyl, ethyl, is. Propyl, tert-butyl), lower Alkoxy groups (eg, methoxy, butoxy, 2-methoxetoxy), aryl groups (eg, phenyl, naphthyl, 2-methoxyphenyl, 3-acetamidophenyl), alkenyl groups (eg, aryl, 1-butenyl), sulfonyl groups (e.g. methylsulfonyl, benzylsulfonyl), Ararukiru groups (e.g. benzylヽp-IS 0- propyl benzyl, o - methylbenzyl), one _{COR ", -N <(R 15} ) (R 16), one S 0 ₃ M ³ represents a hydrogen atom, _OM ³ , a lower alkyl group (eg, methyl, butyl), an aryl group (eg, phenyl, Phenyl, 3-nitrophenyl), aralkyl group (for example, benzyl, p-iso-propylbenzyl, 0-methylbenzyl), lower alkoxy group (for example, methoxy, butoxy, 2-methoxetoxy), aryloxy Group (for example, phenoxy, naphthoxy, 4-nitrophenoxy), aralkyloxy group (for example, benzyloxy, p-chlorobenzyloxy), and -N <(R17) (Ris). R ₁₅ and R 6 each represent a hydrogen atom or a lower alkyl group (eg, methyl Acetyl, 2-ethylhexyl), aryl group (eg, phenyl, naphthyl, 2-methoxyphenyl, 3-acetamidophenyl), aralkyl group (eg, benzyl, o-chlorobenzyl), one COR ₁₉ represents an S 0 ₂ R _19, or different and the same as each other, R _17, R ₁₈ are each a hydrogen atom, a lower alkyl group (e.g. methyl, iso _ propyl, 2-Shianoechiru), Ariru group (Eg, phenyl, 4-ethoxycarbonylphenyl, 3-nitrophenyl), an aralkyl group (eg, benzyl, p-chlorobenzyl), which may be the same or different, and R ₁₉ is Lower alkyl groups (eg, ethyl, 2-methoxyl, 2-hydroxyxethyl), aryl groups (eg, phenyl, naphthyl, 4_sulfophenyl, 4-carboxy) M ³ represents a hydrogen atom, an aralkyl metal atom (eg, sodium or potassium) and an atom group necessary to form a monovalent cation (eg, phenyl or aralkyl group). For example, an ammonium cation and a phosphonium cation. n represents an integer of 0 or 1 to (6-p), and p represents an integer of 1-6. When n and p are 2 or more, a plurality of the above groups may be combined.

 Next, specific examples of the compounds represented by the general formulas (I) to (IV) are shown, but the present invention is not limited thereto.

(1-1) (1-2) Γ ~ \

0 N-CH ₂ CH, Ο N-CH ₂ CC ₂ H ₅

 \ _ / I \ _ f I

N0 ₂ Ν0 ₂

( 一 II)

(I II)

0ΐ

 ττ

et C00Zdf / X3d OAV o

et

(S) II Ϊ> Ι— OH ox () 《》 (ΙΠ 4 says—

 () ((} m1mday2——

() () 1129Π301-

3OH CO MHCOCH

} () (>> 10ΠΙ11m12—Ι— 2SHONHC C xo》 (m9—

本発明の化合物の使用量は写真用コロイ ド組成物である水溶液、 その他の添 加すべき溶液に対して 0. 001〜0. 05質量％の範囲が好ましい。 しかし この範囲は感光材料の種類、 水溶液の種類、 保存状態等によって増減させても よいことは勿論である。 (IV -16) (IV -17)

The amount of the compound of the present invention to be used is preferably in the range of 0.001 to 0.05% by mass with respect to the aqueous solution of the photographic colloid composition and other solutions to be added. However, this range may of course be increased or decreased depending on the type of the photosensitive material, the type of the aqueous solution, the state of storage, and the like.

The compound of the present invention is dissolved in water or a solvent such as methanol, ethanol, isopropanol, acetone, ethylene dalicol or a mixed solvent thereof. It may be added as a liquid, or may be dissolved in a high-boiling solvent or a low-boiling solvent and then emulsified and dispersed using a surfactant.

 The compounds of the present invention are preferably used not alone but in combination of two or three.

 The compound of the present invention can be applied to each layer constituting a silver halide color photographic light-sensitive material, for example, any one of a silver halide emulsion layer, an undercoat layer, an intermediate layer, a filter, an anti-halation layer, a protective layer, and the like. It is preferably added to a hydrophilic colloid dispersion containing a color-forming coupler. It is also preferable to add to a plurality of layers from the same point.

The present invention, the calcium content in the coating設層silver halide photographic light-sensitive ^{material, 1 O m gZm 2 ~0.} 0 1 mg but be in the range of Zm ² is characterized, where words Cormorants calcium the content of calcium atoms contained in the photosensitive material 1 m ^2, Cal Shiumuion, calcium salts and the like, and the mass in terms of all compounds containing calcium Cal Shiumu atom, as the assay ICP (I nductive 1 y Conpied Plasma) Emission analysis is used.

 Details of this analytical method are described in “Chemistry, Special Issue No. 127” (Nankodo, published in 1980) and VA Fassel: Anal. Chem., 46, 1110A (1974). There is a description.

Gelatin, which is advantageously used as a binder for light-sensitive materials, usually contains several thousand ppm of calcium salts, calculated as calcium atoms, derived from raw materials and manufacturing processes. Specifically, for direct viewing photographic material in practical use, it contains usually 15 m gZm ² or more calcium. In the present invention, the calcium content contained in the coating設層of the photosensitive ^{material, 10 m gZm 2 ~0. O} lm gZm ² , but more preferably in the range of 8 mg / m ^{2 to} 0.01 mg / m ² .

 In order to reduce the calcium content in the light-sensitive material, a method using gelatin having a low calcium content as a binder, a coating solution applied to a support during the manufacture of the light-sensitive material, or a halogen contained in the coating solution are used. A method of desalting a dispersion containing a hydrophobic compound such as a silver halide emulsion or a coupler, or a gelatin-containing composition such as a gelatin solution by noodle washing, dialysis, ultrafiltration, etc., but gelatin having a low calcium content It is preferable to use

 In order to reduce the calcium content in gelatin, an ion exchange treatment is generally preferably used. As described in, for example, Japanese Patent Application Laid-Open No. 63-296035, the ion exchange treatment is performed by exchanging the gelatin solution during the production or use of the gelatin with a cation exchange resin to remove the cation exchange resin, especially calcium ion. A treatment for contacting with a resin is preferably used.

 Examples of gelatin having a low calcium content include acid-treated gelatin in which calcium is hardly mixed in the production process.

 The gelatin used in the present invention is preferably a lime-processed gelatin subjected to an ion exchange treatment in view of the effects of the present invention. In addition, an oxidation treatment with hydrogen peroxide or the like can be performed for the purpose of reducing photographic activity.

0 gZm²である。総ゼラチン塗設量としては、 6. 0 _g m²〜5. O gZm²で あることが好ましく、 5. 7〜5. 1 gZm²であることがより好ましい。 本発明に係るハロゲン化銀写真感光材料は、 ベンゼン環またはナフタレン環 を有するァニォン系界面活性剤を含有することが好ましいが、 該活性剤はべン ゼン環またはナフタレン環とァニオン基を有する界面活性剤であればいづれで もよいが、 ァニオン基としてスルホン酸基を有するものが好ましい。 Gelatin is preferred as the binder contained in the layer coated on the silver halide photographic light-sensitive material of the present invention, and the total coating amount of gelatin is 6.S

Is 0 gZm ^2. The total gelatin coating amount is preferably 6. is ^{_{0 g m 2 ~5. O gZm}} 2, 5. 7~5. More preferably 1 gZm ^2. The silver halide photographic light-sensitive material according to the present invention has a benzene ring or a naphthalene ring. The surfactant preferably contains an anionic surfactant having any of the following formulas. The surfactant may be any surfactant having a benzene ring or a naphthalene ring and an anion group, and a sulfonic acid group is used as the anion group. Are preferred.

 Further, a surfactant in which a sulfonic acid group is directly substituted on a benzene ring or a naphthalene ring is preferable. Addition of these compounds can contribute to stabilization of coupler dispersion.

 Preferred compounds include the following.

 S—1: sodium dodecylbenzenesulfonate

 S—2: sodium octadecylbenzenesulfonate

 S-3: isopropyl naphthalene sulfonic acid

 The surfactant may be added to any layer in the silver halide photographic light-sensitive material, and the amount added is appropriately determined according to the design of the light-sensitive material.

 The silver halide used in the silver halide emulsion layer according to the present invention includes any silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodide and the like. Is mentioned.

 The silver halide grains preferably used in the present invention have a silver chloride content of 95 mol% or more, a silver bromide content of 5 mol% or less, and a silver iodide content of 0.5 mol%. % Is preferable. More preferably, it is silver chlorobromide having a silver bromide content of 0.1 to 2 mol%. The silver halide grains may be used alone or as a mixture with other silver halide grains having different compositions. Further, it may be used by mixing with silver halide grains having a silver chloride content of 95 mol% or less.

In a silver halide layer containing silver halide grains having a silver chloride content of 95 mol% or more, all silver halide grains contained in the emulsion layer are occupied. The proportion of silver halide grains having a silver chloride content of at least 95 mol% is at least 60 mass%, preferably at least 80 mass%. The composition of the silver halide grains may be uniform from the inside to the outside of the grains, or the inside and outside compositions of the grains may be different. When the inside and outside compositions of the particles are different, the composition may change continuously or may be discontinuous.

 The silver halide grains according to the present invention may have any shape. One preferable example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756 and 4,225,666, JP-A-55-26589, JP-B-55-42737, and the "Journal" Photographic Science. ) Particles having shapes such as octahedron, tetradecahedron, and dodecahedron can be prepared and used by methods described in documents such as 21 and 39 (1973). Further, particles having twin planes may be used.

 As the silver halide grains according to the present invention, grains having a single shape may be used, or grains having various shapes may be mixed.

The particle size of the silver halide grains according to the present invention is not particularly limited, but is preferably 0.1 to 1.2 m, more preferably, in consideration of other photographic performances such as rapid processing and sensitivity. It is in the range of 0.2 to 1.0 m. The particle size can be measured by various methods generally used in the technical field. A typical method is Lapland's “Particle Size Analysis Method” (ASTM Symposium 'On-Light' Microscopy, pp. 94-122, 1955) or “Theory of Photographic Process, Third Edition” ( The method described in “Miss and James”, Chapter 2, published by Macmillan, 1966) can be mentioned. This particle size can be measured using the projected area of the particle or its approximate diameter. If the particles are substantially uniform in shape, the particle size distribution can represent this quite accurately as diameter or projected area.

 The size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse. Monodisperse silver halide grains having a coefficient of variation of preferably 0.22 or less, more preferably 0.15 or less are preferred. Here, the coefficient of variation is a coefficient representing the width of the particle size distribution, and is defined by the following equation.

 Coefficient of variation = S / R (where S is the standard deviation of the particle size distribution and R is the average particle size.) The particle size referred to here is the diameter of a spherical silver halide particle, In the case of particles having a shape other than a cube or a sphere, it represents the diameter when the projected image is converted into a circular image of the same area. Various methods known in the art can be used as an apparatus and a method for preparing a silver halide emulsion.

 The silver halide emulsion according to the present invention may be obtained by any of an acidic method, a neutral method, and an ammonia method. The particles may be grown at a time or may be grown after seed particles have been made. The method of making the seed particles and the method of growing them may be the same or different.

 The form of reacting the soluble silver salt with the soluble halide salt may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like, but a method obtained by the simultaneous mixing method is preferable. Further, as one form of the simultaneous mixing method, the pAg controlled double / double jet method described in JP-A-54-4852-1 can be used.

Further, an aqueous solution of a water-soluble silver salt and a water-soluble halide salt was added from an addition device arranged in a reaction mother liquor described in JP-A-57-92523 and JP-A-57-92524. Device for supplying a water-soluble silver salt and a water-soluble halide salt aqueous solution described in German Patent Publication No. 2,921,164, etc. Take out the reaction mother liquor out of the reactor as described in No. 501, 776, etc., and use an apparatus that forms particles while keeping the distance between silver halide grains constant by concentrating by ultrafiltration. You may.

 If necessary, a silver halide solvent such as polyester may be used. Further, a compound having a mercapto group, a compound such as a tetracyclic compound or a sensitizing dye may be added to the nitrogen-containing compound at the time of forming silver halide grains or after the completion of grain formation.

 For the reduction sensitization of the silver halide emulsion according to the present invention, a known method can be used. For example, a method of adding various reducing agents can be used, a method of ripening under a high silver ion concentration condition, or a method of ripening under a high pH condition can be used.

 Examples of the reducing agent used for reduction sensitization of the silver halide emulsion according to the present invention include stannous salts such as stannous chloride, borane such as tri-t-butylamborane, sodium sulfite, and sulfurous acid rim. Examples thereof include reductones such as sulfites and ascorbic acid, and thiourea dioxide. Of these, thiourea dioxide, ascorbic acid and its derivatives, and sulfites can be preferably used. The method using a reducing agent as described above is preferable because it is excellent in reproducibility, as compared with the case of performing a reduction sensation by controlling the silver concentration and pH during ripening.

These reducing agents may be dissolved in a solvent such as water or alcohol and added to a silver halide emulsion for ripening, or may be added during the formation of silver halide grains to form a grain. Reduction sensitization may be performed simultaneously with formation.

The amount of these reducing agents to be added must be adjusted according to the pH of the silver halide emulsion, silver ion concentration, etc. In general, the amount is preferably from 10 to ⁷ to 1 CI per mole of the silver halide emulsion. — ² moles is preferred.

 After reduction sensitization, a small amount of oxidizing agent may be used to modify the reduction sensitizing nucleus or deactivate the remaining reducing agent. Examples of the compound used for such a purpose include potassium hexacyanoferrate (111), bromosuccinimide, p-quinone, potassium perchlorate, aqueous hydrogen peroxide and the like.

 The silver halide emulsion according to the present invention is subjected to reduction sensitization, and can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer. As a chalcogen sensitizer applied to the silver halide emulsion according to the present invention, a silver sensitizer, a selenium sensitizer, a tellurium sensitizer, or the like can be used, and a silver sensitizer is preferable. . Examples of the sensitizer include thiosulfate, arylthiocarbamidothiourea, arylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine and the like.

As the gold sensitizer applied to the silver halide emulsion according to the present invention, various gold complexes such as chloroauric acid, gold sulfate, gold thiosulfate and the like can be added. Examples of the ligand compound to be used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazol, and mercaptotriazole. The amount of gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc., but usually 1 x 1 CT ⁴ mol to 1 x 1 per mol of silver halide It is preferably from 0 to ⁸ mol. More preferably, it is from 1 × 10 to ⁵ mol to 1 × ¹⁰ to ¹⁸ mol. The silver halide emulsion according to the present invention includes a known silver halide emulsion for the purpose of preventing capri generated during the process of preparing a silver halide photographic material, reducing performance fluctuation during storage, and preventing capri generated during development. Capri inhibitors and stabilizers can be used. Examples of the compound which can be used for such a purpose include a compound represented by the general formula (II) described in the lower section of page 7 of JP-A-2-14636, and specific examples thereof are given below. Examples of such compounds include compounds (IIa_1) to (IIa-8), (IIbl) to (IIb-7), and 1- (3-meth) described on page 8 of the publication. Toxifenyl) _5_mercaptotetrazole and the like. These compounds are added in the steps of preparing silver halide emulsion grains, the chemical sensitization step, the completion of the chemical sensitization step, and the step of preparing a coating solution, depending on the purpose. When performing chemical sensitization in the presence of these compounds are preferably used in an amount of 1 X 1 0- ⁵ mol ~ 5 X 1 0 mol per mol of silver halide. When added at the end of chemical sensitization, the amount is preferably about 1 × 10 to ⁶ mol to 1 × 10 to ¹² mol, and more preferably about 1 × 10 to ⁵ mol to 5 × 10 mol per mol of silver halide. — ³ moles is more preferred. In the step of preparing a coating solution, when it is added to the silver halide emulsion layer, the amount is preferably about 1 × ¹⁰ to ⁶ mol to 1 × ¹⁰ to 1 mol per mol of silver halide, and 1 × ^{10 to 1} mol. ⁵ mol ~ 1 X 1 0- ² moles is more preferable. When it is added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 to ⁹ mol to 1 × 10 to ³ mol.

When the silver halide photographic light-sensitive material according to the present invention is used as a color photographic light-sensitive material, it is spectrally sensitized to a specific region in a wavelength region of 400 to 900 nm in combination with a yellow coupler, a magenta cover, and a cyan coupler. And a layer containing a silver halide emulsion. The silver halide emulsion contains one or more dyes. Is contained in combination.

 As the spectral sensitizing dye for use in the silver halide emulsion according to the present invention, any of known compounds can be used. As the blue-sensitive sensitizing dye, Japanese Patent Application No. 2-511124 BS-1 to 8 described in the specification, pages 108 to 109, can be preferably used alone or in combination. As the green photosensitive dye, GS 11 to 5 described on page 110 of the same specification are preferably used. As the red photosensitive sensitizing dye, R S — 1 to 8 described in pages 11 to 11 of the same specification are preferably used. When the silver halide photographic light-sensitive material according to the present invention is exposed by a printer using a semiconductor laser, it is necessary to use a sensitizing dye having sensitivity to infrared light. The dyes of IRS_1 to 11 described in Japanese Patent Application No. 3-73619, pages 12 to 14 are preferably used. It is preferable to use the superchromic sensitizers SS-1 to SS-9 described on pages 14 to 15 in the same specification in combination with these dyes.

When exposing the silver halide photographic light-sensitive material according to the present invention using a laser, it is advantageous to use an exposure apparatus using a semiconductor laser in terms of miniaturization of the apparatus. In scanning exposure, the exposure time per pixel corresponds to the exposure time actually received by the silver halide emulsion, but the exposure time per pixel is defined as laser-light scanning exposure. In the spatial change in the intensity of the light beam, the point where the light intensity reaches the maximum value of 1 to 2 is defined as the outer edge of the light beam, and is parallel to the scanning line and passes through the point passing through the point where the light intensity is the maximum. When the distance between two points where the outer edges intersect is defined as the beam diameter (beam diameter) / (scanning speed), the exposure time per pixel can be considered. As the exposure time per pixel becomes shorter, the relationship between exposure time and color density tends to become more complex. The present invention is particularly effective when a short device is used.

 Examples of a laser printer device that can be applied to such a system include, for example, Japanese Patent Application Laid-Open Nos.

No. 7947, JP-A-2-74942, JP-A-2-236583, JP-B-56-14963, JP-A-56-40822, European wide-area patent 77, 410, Electronic and Telecommunications Department Technical Research Report 8◦Vol. 244 No. and the Journal of Motion Picture and Television Engineering 1984 6 (3

82), pages 34 to 36, and the like.

 In the silver halide photographic light-sensitive material according to the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any of the known compounds can be used. In particular, as dyes having absorption in the visible region, see Japanese Patent Application No. 2-511124, pages 117 to L; The dyes represented by A1-1-1-11 described above are preferably used. Examples of the infrared absorbing dyes include general formulas (I), (I1), and (I1) described in the lower left column of page 2 of JP-A-11-280750. The compound represented by 111) has preferable spectral characteristics, does not affect the photographic characteristics of the silver halide photographic emulsion, and is preferable without contamination by residual color. Specific examples of preferred compounds include the exemplified compounds (1) to (45) listed in the lower left column of page 3 to the lower left column of page 5 of the publication.

As the coupler used in the silver halide photographic light-sensitive material according to the present invention, a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a coupling reaction with an oxidized form of a color developing agent is used. Any compound that can be formed can be used, but a yellow coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, a wavelength range Cyan with a spectral absorption maximum wavelength between 600 and 750 nm What is known as a coupler is typical.

 Examples of the yellow coupler that can be preferably used for the silver halide photographic light-sensitive material according to the present invention include couplers represented by the general formula (Y-1) described in page 8 of JP-A-2-234208. Can be mentioned. Specific compounds include those described as YC-1 to YC-9 on pages 9 to 11 of the same specification. Among them, YC-8 and YC-9 described on page 11 of the same specification are preferable because they can reproduce yellow having a preferable color tone. Examples of the magenta coupler include couplers represented by general formulas (M-I) and (M-II) described in JP-A-2-234208, page 12. Specific compounds include those described as MC-1 to MC-11 on pages 13 to 16 of the same specification. Among them, MC-8 to MC-11 described in pages 15 to 16 of the same specification are excellent in reproducing colors from blue to violet and red, and are also excellent in detail depiction, which is preferable. .

 The silane couplers which can be preferably used in the silver halide photographic light-sensitive material according to the present invention include those represented by the general formulas (C-I) and (C-II) described in page 17 of Japanese Patent Application No. 234208/1990. Couplers to be used. Specific compounds include those described as CC-1 to CC-9 on pages 18 to 21 of the same specification.

When an oil-in-water type emulsion dispersion method is used to add the coupler used in the silver halide photographic light-sensitive material according to the present invention, a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C or more is usually used. If necessary, dissolve using a low boiling point or water-soluble organic solvent in combination, and emulsify and disperse in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. Dispersing means include stirrer, homogenizer, colloid mill, flow A jet mixer, an ultrasonic disperser or the like can be used. After the dispersion, or simultaneously with the dispersion, a step of removing the low boiling organic solvent may be added. As high-boiling organic solvents that can be used to dissolve and disperse the coupler, phthalic esters such as octyl phthalate and phosphoric esters such as tricresyl phosphite are preferably used.

 Alternatively, instead of using a high-boiling organic solvent, a coupler and a water-insoluble and organic solvent-soluble polymer compound may be dissolved in a low-boiling or water-soluble organic solvent if necessary, and a hydrophilic binder such as an aqueous gelatin solution may be used. A method of emulsifying and dispersing by a variety of dispersing means using a surfactant therein may be employed. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (N_t_butylacrylamide).

 For the purpose of shifting the absorption wavelength of the color-forming dye, the compound (d-11) described in Japanese Patent Application No. 2-232430, page 33, the compound described in page 35 of the same specification Compounds such as (A'-1) can be used. In addition, the fluorescent dye releasing compounds described in U.S. Pat. Nos. 4,774,187 can also be used.

The coating amount of the coupler is not particularly limited as long as a sufficiently high concentration can be obtained, but is preferably 1 × 10 to ^{3 to} 5 mol, more preferably 1 × 10 mol per mol of silver halide. As used 1 0 ² to 1 mols.

In the present invention, it is preferable to add an oil-soluble dye. An oil-soluble dye is an organic dye having a solubility in water at 20 ° C of 0.01 or less, and a molecular absorption coefficient of a maximum absorption wavelength at a wavelength of 400 nm or more of 2000 or more. Are preferred. Preferred compounds include the compounds shown on page 26 of Japanese Patent Application No. 64-1640. Specific examples of preferable compounds are described in the above specification, p. Compounds 1 to 27 on page 32 can be mentioned. Of these, compounds 4 and 9 are particularly preferred. Oil-soluble dye is preferably added to the non-photosensitive layer, 0.0 5-5 is preferably added in an amount of mg Z m ^2.

 It is advantageous to use gelatin as a binder in the silver halide photographic light-sensitive material according to the present invention, but if necessary, other gelatin, gelatin derivatives, gelatin and other high-molecular-weight graft polymers, other than gelatin A hydrophilic colloid such as a protein, a sugar derivative, a cellulose derivative, or a synthetic hydrophilic polymer such as a homopolymer or a copolymer can also be used.

 As the reflective support according to the present invention, any material may be used, such as a white pigment-containing polyethylene-coated paper, a baryta paper, a vinyl chloride sheet, a polypropylene containing a white pigment, and a polyethylene terephthalate support. Etc. can be used.

Above all, it is a support having a polyolefin resin layer on both sides, and the weight of the support is preferably ² 17 g / m ² or less, more preferably 2 15 g / m ² or less. Further, the polyolefin resin layer preferably contains a white pigment.

As the white pigment used in the reflective support according to the present invention, an inorganic or organic white pigment can be used, and an inorganic white pigment is preferably used. For example, sulfates of alkaline earth metals such as barium sulfate, carbonates of alkaline earth metals such as calcium carbonate, silicas such as finely divided gay acid and synthetic silicates, calcium calcium oxide, alumina, Alumina hydrate, titanium oxide, zinc oxide, talc, clay and the like. The white pigment is preferably barium sulfate or titanium oxide. The amount of the white pigment contained in the water-resistant resin layer on the surface of the reflective support according to the present invention is preferably 10% by mass or more in the water-resistant resin layer, and more preferably 1% by mass or more. The content is preferably 3% by mass or more, more preferably 15% by mass or more. The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, and preferably 0.10 or less, as the coefficient of variation described in the publication. More preferably, it is.

 The silver halide photographic light-sensitive material according to the present invention may be subjected to direct discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support, if necessary, and then directly or undercoating (adhesion of the surface of the support, charging). Or one or more subbing layers to improve antistatic, dimensional stability, rub resistance, hardness, anti-halation, friction or other properties) .

 When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. As a coating method, an extrusion coating and a force coating, which can simultaneously apply two or more kinds of layers, are particularly useful.

In general, in a silver halide photographic light-sensitive material, halide ions and organic compounds (for example, sensitizing dyes and inhibitors) are eluted from the light-sensitive material into a developing solution during the developing process, and the elution is accumulated in the developing solution. As a result, it is known that the development reaction is suppressed. Therefore, it is necessary to reduce the amount of eluted substances in the developer and to maintain the concentration constant. In a normal development processing method, halide ions and organic compounds are eluted from a photosensitive material into a developer, and further, a developing agent, a preservative, an alkaline agent and the like are consumed and reduced. Therefore, a replenisher is added to the developer in order to maintain these concentrations substantially constant and maintain the developing characteristics, and the added amount is used as an overflow liquid. Halogen ions and organic compounds that flow out of the developer tank system and accumulate in the developer are removed outside the system. In addition, the replenisher was used to replenish the deficient components, such as the consumed developing agent, to maintain the concentration of the developer constant.

 In the present invention, it is intended to regenerate an overflow solution of a color developing solution generated during continuous processing after imagewise exposure of a silver halide photographic light-sensitive material, and to reuse the overflow solution for processing the silver halide photographic light-sensitive material. O Recycling of the developing solution achieves cost reduction and environmental load reduction.

 As a method for regenerating the color developer, any known method may be used. For example, the ion-exchange resins described in JP-A-3-69936, JP-A-3-194552, JP-A-55-144240, JP-A-53-132343, JP-A-57-146249 and JP-A-61-95352 can be used. Japanese Unexamined Patent Application Publication No. Sho 51-85722 discloses a method of adding a deficient component as a regenerating agent without particularly removing components eluted in a developer described in JP-A-3-17154. No. 54-37731, No. 56-1049, No. 56-27 142, No. 56-33644, No. 56-149036, No. 61-10199, No. 61-52459 A method using electrodialysis is exemplified.

 Of these, a regeneration method using an ion exchange resin and a regeneration method using a regenerating agent are preferable from the viewpoints of maintainability, cost and ease of use.

 Known compounds can be used as the aromatic primary amine developing agent used in the present invention. The following compounds can be mentioned as examples of these compounds.

 CD-1) N, N—Jetil _ p—Fenylenediamine

CD-2) 2-Amino-5-Jetylamino Toluene CD-3) 2-Amino 5— (N-ethyl-N-laurylamino) Toluene CD—4)-(N-ethyl-1N — (— Hydroxyshetyl) amino) anilin

 CD-5) 2-Methyl-14- (N-Ethyl-1-N- (1-Hydroxyshetyl) Amino) Anilin

 CD-6) 4-Amino 3-Methyl _N— (β- (Methanesulfonamide) ethyl) monoaniline

 CD— 7) N— (2-amino-5-getylaminophenylethyl) methane sulfone amide

 CD-8) N, N-dimethyl_p-phenylenediamine

 CD— 9) 4—Amino 3-Methyl_N—Ethyru N—Methoxyschilananiline

 CD— 10) 4-amino-3—methyl-N-ethyl-N——ethoxyl) aniline

 CD-I 1) 4-amino-3 -methyl-N-ethyl-N-(^ 9-butoxyethyl) aniline

Color developing agent used in the present invention is usually Developer 1 used in liters per 1 X 1 0 one ² ~ 2 X 10- ¹ mols, from the viewpoint of rapid processing color developer 1 Li Tsu preferably used in torr per ^{1. 5 X 10- 2 ~2 X 1} 0- 1 mole range. The color developing agent used in the image forming method of the present invention may be used alone, or may be used in combination with other known p-phenylenediamine derivatives.

In the preferred developer of the present invention, it is preferable that benzyl alcohol is not substantially contained. Here, "substantially not contained" means that benzyl alcohol is less than 2 m1. The following is shown, and it is most preferable not to include it at all in the present invention.

 The color developer used in the present invention may contain the following components in addition to the above components. As the alkali agent, for example, sodium hydroxide, sodium hydroxide, sodium metaborate, sodium metaborate, sodium sodium phosphate, potassium triphosphate, borax, silicate, etc., alone or in combination Therefore, they can be used together within a range that does not cause precipitation and maintains the pH stabilizing effect. Furthermore, for the purpose of dispensing, or for the purpose of increasing ionic strength, etc., sodium hydrogen phosphate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, borane Various salts, such as acid salts, can be used.

 Further, in the color developing solution according to the present invention, JP-A-63-146043, JP-A-63-146042, JP-A-63-146041, JP-A-63-146041, and JP-A-63-146043 are used in place of hydroxyamine which has been conventionally used as a preservative. No. 63-146040, Nos. 63-135938, No. 63-118748, and hydroxamic acids and hydrazines described in JP-A Nos. 64-62639 and 1-303438. , Hydrazides, phenols, monohydroxyketones, monoaminoketones, saccharides, monoamines, diamines, quaternary ammonium salts, nitroxy radicals, alcohols, aldehydes, diamide compounds And condensed amines are preferably used as the organic preservative.

 These compounds can be used in combination with the conventionally used hydroxylamine and the above-mentioned organic preservative. However, it is more preferable not to use hydroxylamine from the viewpoint of developing characteristics.

Furthermore, if necessary, a development accelerator can be used. U.S. Pat. Nos. 2,648,604, 3,671,247, and Shoko 4 4-9503, various cationic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, US Pat. Nos. 2,533,990 and 2 , 531, 832, 2,950,970, 2,577,127 and JP-B-44-9504 described in Japanese Patent Publication No. Compounds, organic solvents and organic amines described in JP-B-44-9509, ethanolamine, ethylenediamine, diethanolamine, triethanolamine and the like are included. In addition, phenethyl alcohol described in U.S. Pat.No. 2,304,925 and others, acetylene glycol, methylethylketone, cyclohexanone, pyridine, ammonia, hydrazine, thioethers, amines and the like can be used. No.

 Further, the color developing solution used in the present invention may be, if necessary, ethylene glycol, methyl cellulose solvent, methanol, acetone, dimethylformamide, / 3-cyclodextrin, and other JP-B-47-33378. The compounds described in each of the publications can be used as an organic solvent for increasing the solubility of the developing agent.

Further, an auxiliary developer can be used together with the developing agent. These auxiliary developers include, for example, N-methyl-1-p-aminophenol sulfate, phenylidone, Ν, Ν'-Jetyl-1-ρ-aminophenol hydrochloride, Ν, Ν, Ν ', N'-tetramethyl-ρ _ Phenylenediamine hydrochloride and the like are known, and the amount of the phenylenediamine added is usually 0.01 to 1.0 Og per liter of developer. In addition, a competitor coupler, a fogging agent, a development inhibitor releasing type coupler (so-called DIR coupler), a development inhibitor releasing compound, etc. can be added as necessary. O

 Furthermore, various additives such as other anti-stin agents, anti-sludge agents, and layering effect promoters can be used.

 Each component of the color developing solution can be prepared by sequentially adding and stirring a certain amount of water. In this case, the component having low solubility in water can be added by mixing with the above-described organic solvent such as triethanolamine. More generally, a plurality of components, each of which can stably coexist, is added to a concentrated aqueous solution or a solution prepared in advance in a small container in a solid state in water, and used in the present invention by stirring. A color developing solution can also be prepared.

Sulfite concentration of the color developing solution according to the present invention is preferably not more than 1 X 1 0- ² mol ZL. Particularly good when the following 7 X 1 0 _ ³ moles ZL comprises 0, especially 0 to comprise 5 X 1 0 - preferably during the following ³ moles ZL. -In the present invention, the above color developer can be used in an arbitrary pH range, but from the viewpoint of rapid processing, the pH is preferably pH 9.5 to 13.0, and more preferably pH 9.5. Used in the range of 8-12.0.

 The processing temperature of color development used in the present invention is preferably 35 ° C. or more and 70 ° C. or less. The higher the temperature, the shorter the processing time is possible, which is preferable. However, it is preferable that the temperature is not too high from the viewpoint of the stability of the processing solution, and the processing is preferably performed at a temperature of 35 ° C or more and 6 (TC or less. In the present invention, the time is preferably within 45 seconds.

The processing step essentially comprises a color developing step, a bleach-fixing step, and a rinsing step (including a stabilizing treatment in place of rinsing), but steps with additional or equivalent meanings as long as the effects of the present invention are not impaired. Can be replaced by For example, the bleach-fixing process can be separated into a bleaching process and a fixing process, or a bleaching process before the bleach-fixing process. It is also possible to set a course. As a processing step used in the image forming method of the present invention, a bleach-fixing step is preferably provided immediately after the color developing step.

 The bleaching agent that can be used in the bleach-fixing solution used in the present invention is not limited, and is preferably a metal complex salt of an organic acid. The complex salt is obtained by coordinating an organic acid such as polycarboxylic acid, aminopolycarboxylic acid, or oxalic acid or citric acid with a metal ion such as iron, cobalt, or copper. The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

 Specific examples of these compounds include the compounds [2: !!] described in JP-A No. 1-205262, pages 58-59. To [20].

These bleaches are used in an amount of 5 to 450 g, preferably 20 to 250 g, per liter of the bleach-fix solution. The bleach-fixing solution contains a silver halide fixing agent in addition to the bleaching agent as described above, and if necessary, a solution having a composition containing a sulfite as a preservative is applied. A bleach-fixing solution having a composition in which a large amount of a halide such as ammonium bromide is added in addition to the ethylenediaminetetraacetate (III) bleach and the silver halide fixing agent, and furthermore, ethylenediaminetetraacetate (II) Ii) A special bleach-fixing solution having a composition comprising a combination of a bleaching agent and a large amount of a halide such as ammonium bromide can be used. As the halide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide and the like may be used in addition to ammonium bromide. it can. As the silver halide fixing agent contained in the bleach-fixing solution, a compound which reacts with silver halide to form a water-soluble complex salt as used in ordinary fixing processing, for example, potassium thiosulfate, titanium Representative examples include thiosulfates such as sodium sulfate and ammonium thiosulfate, potassium thiocyanate, potassium thiocyanate, thiocyanates such as sodium thiocyanate and ammonium thiocyanate, and the like. It is. These fixing agents are used in an amount of at least 5 g per liter of the bleach-fix solution and in a dissolvable range, but generally used in an amount of 70 to 250 g. In addition, boric acid, borax, sodium hydroxide, sodium hydroxide, sodium carbonate, sodium carbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, acetic acid, sodium acetate, Various pH buffers such as ammonium hydroxide can be used alone or in combination of two or more. Furthermore, various fluorescent whitening agents, antifoaming agents or surfactants can be contained. In addition, preservatives such as bisulfite adducts of hydroxylamine, hydrazine and aldehyde compounds, organic chelating agents such as aminopolycarboxylic acid or stabilizers such as nitroalcohol and nitrate, methanol, dimethylsulfonamide, and dimethyl An organic solvent such as sulfoxide can be appropriately contained. The bleach-fixing solution used in the present invention includes JP-B-46-280, JP-B-45-8506, JP-B-46-556, Belgian Patent No. 770910, JP-B-45-8836, and JP-B-53-9854. Various bleaching accelerators described in JP-A-54-71634 and JP-A-49-42349 can be added.

The pH of the bleach-fix solution is used at pH 4.0 or higher, but is generally used in the range of pH 4.0 to 9.5, preferably pH 4.5 to 8.5. Most preferably, it is used in the pH range of 5.0 to 8.5. Processing temperature is below 80 ° C, Desirably, use at 55 ° C or less with evaporation suppressed. The processing time for bleach-fixing is preferably 3 to 45 seconds. In the developing process used in the present invention, a water washing process is performed subsequent to the color developing and bleach-fixing steps. The pH of the washing water applicable to the present invention is in the range of 5.5-10.0. The treatment temperature of the water washing treatment is preferably 15 ° C. to 60 ° C., more preferably 20 ° C. (: more preferably 45 ° C .; and the water washing treatment time is preferably 5 to 90 seconds. When performing the water washing process in the tank, it is preferable that the treatment be performed in a shorter time in the front tank and the processing time be longer in the rear tank. Is preferred.

 As a development processing apparatus for the silver halide photographic light-sensitive material used in the image forming method of the present invention, any known apparatus may be used. Specifically, even with a transporter that transports photosensitive material across a mouthpiece placed in a processing tank, an endless belt that transports the photosensitive material fixed on a belt The processing tank may be formed in a slit shape, and a processing liquid may be supplied to this processing tank and the photosensitive material may be transported, a processing liquid may be sprayed, or a processing liquid may be sprayed. A web method by contact with the impregnated carrier, a method using a viscous treatment liquid, and the like can also be used. In the present invention, a large amount of photosensitive material is processed and run in these color development to drying steps, and elution of components from the photosensitive material into the processing solution and contamination between processing tanks ゃ evaporation of the processing solution are saturated and stabilized. This is especially effective when the treatment is performed later.

 In the present invention, the time from exposure to development may be any, but it is preferable that the time be short in order to shorten the overall processing time.

Next, the present invention will be described specifically with reference to examples, but embodiments of the present invention are not limited thereto. Example 1

 《Silver halide color photographic light-sensitive material: Preparation of sample 1◦1》

 (Preparation of silver halide emulsion)

 Each silver halide emulsion was prepared by the following method.

 (Preparation of red-sensitive silver halide emulsion)

 In 1 liter of 2% gelatin aqueous solution kept at 40 ° C, apply the following (Solution A) and (Solution B) for 30 minutes while controlling pAg to 7.3 and pH to 3.0. The following (Solution C) and (Solution D) were simultaneously added over 180 minutes while controlling the pAg at 8.0 and the pH at 5.5. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled using sulfuric acid or an aqueous sodium hydroxide solution.

 (A liquid)

 Sodium chloride 3.42 g bromide power 0.03 g Add water and 200 ml

(Solution B)

 Silver nitrate 10 g Add water 200 ml

(C solution)

Sodium chloride _{102. 7 g K 2 I r C} 16 X 10- 8 mol / mol _{A g K 4 F e (CN} ) 2 X 10- 5 mol / mol A g Nioikaryoku Riumu 1. 0 g 600 ml with water

(D solution)

 After adding 300 g of silver nitrate and 600 ml of water to complete the addition of each of the above solutions, desalting was carried out using a 5% aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate. After that, the emulsion is mixed with an aqueous gelatin solution to form a monodisperse cubic emulsion having an average particle size of 0.40π, a coefficient of variation of the particle size distribution of 0.07, and a silver chloride content of 99.5 mol%. I got EMP-1.

 Next, the average particle diameter was 0.38 in the same manner as in Emulsion EMP_1 except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. The emulsion EMP-1B was obtained as a monodisperse cubic emulsion having a m of 0.07, a coefficient of variation of the particle size distribution of 0.07, and a silver chloride content of 99.5 mol%.

 Emulsion EMP-1 was optimally chemically sensitized to 6 (TC using the following compound. Emulsion EMP-1B was also optimally chemically sensitized. The resulting emulsion EMP-1 and emulsion EMP-1B were mixed at a silver ratio of 1: 1 to obtain a red-sensitive silver halide emulsion (101R).

Chio sulfate Na preparative potassium 1 X 1 CT ⁴ mol Z moles A g X chloroauric acid] 2 X 1 0- ⁴ mol / mol A g X Stabilizer: STAB - 1 3 X 1 0 mol / mol A g X stabilizer : STAB- 2 3 X 1 0 ^_4 mol / mol A g X stabilizer: STAB- 3 3 X 1 0- ⁴ mol / mol A g X sensitizing dyes: RS- 1 1 X 1 0- ⁴ mol / mol A g X sensitizing dye: RS- 2 1 X 1 0- ⁴ mol / mol A g X S TAB—1: 1- (3-acetamidophenyl) 5-mercaptotetrazole

 S TAB-2: 1-phenyl-1-5-mercaptote tolazole

 S TAB—3: 1- (4-ethoxyphenyl) -1-5-mercaptote

Also the red-sensitive emulsion, and the SS _ 1 was added per mol of silver halide 2. 0 X 10 one ^3.

 (Preparation of green photosensitive silver halide emulsion)

 In the preparation of emulsion EMP-1 above, the average particle size was 0.40 m in the same manner except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. The emulsion EMP-2 was obtained as a monodisperse cubic emulsion having a coefficient of variation of 0.08 and a silver chloride content of 99.5%. Next, in the preparation of the emulsion EMP-1, the average particle size was adjusted in the same manner except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. Emulsion EMP-2B was obtained as a monodisperse cubic emulsion having a particle diameter of 50 m, a coefficient of variation of 0.08, and a silver chloride content of 99.5%.

 The emulsion EMP-2 prepared above was optimally chemically sensitized at 55 ° C using the following compounds. Similarly, after optimally chemical sensitizing the emulsion EMP_2B, the sensitized emulsion EMP-2 and emulsion EMP-2B were mixed at a silver ratio of 1: 1. After mixing, a green light-sensitive silver halide emulsion (101 G) was obtained.

Chio sodium sulfate 1 X 10- ⁴ mole _/ / mole A g X chloroauric acid 1. 2 X 10- ⁴ mol / mol A g X Stabilizer: S TAB- l 2. 5 X 10- 4 mol mol A g X stabilizers: S tAB- 2 3. 1 X 10- 4 mole mol A g X Stabilizer: STAB- 3 3. 1 X 1 0- 4 mol Z moles A g X增感Dye: GS- 1 ⁴ X 1 0- 4 mol Z moles A g X

(Preparation of blue-sensitive silver halide emulsion)

 In the preparation of Emulsion EMP-1, the average particle diameter was 0.7 m in the same manner except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. The emulsion EMP-3 was obtained as a monodisperse cubic emulsion having a coefficient of variation of 0.08 and a silver chloride content of 99.5%. Also, in the preparation of the emulsion EMP-1, the average particle size was adjusted in the same manner except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. Emulsion EMP-3B, which is a monodisperse cubic emulsion having a coefficient of variation of 0.08 and a silver chloride content of 99.5%, was obtained.

 The above emulsion EMP-3 was optimally chemically sensitized at 60 ° C using the following compounds. Similarly, after optimal chemical sensitization of emulsion EMP-3B, the sensitized emulsion EMP-3 and emulsion EMP-3B were mixed at a silver ratio of 1: 1. Thus, a blue-sensitive silver halide emulsion (101 B) was obtained.

Chio sulfate Na preparative potassium 1 X 1 CT ⁴ mol / mol A g X chloroauric acid 1. 2 X 1 0- ⁴ mol / mol A g Stabilizer: STAB- 1 2 X 1 0- ⁴ mol / mol A g X stabilizer: STAB _ 2 2. X 1 0- 4 mol / mol A g stabilizer: STAB - 3 2. 1 X 1 0- 4 mol / mol A g sensitizing dye: BS- 1 X 1 0 _ ⁴ mol / mol A gx增感dye: BS - 2 1 X 1 0- 4 mol mol A gx

 GS-1

₅)₃

₅ ) ₃

<< Production of silver halide photographic light-sensitive material >>

A reflective support was prepared by laminating high-density polyethylene on both sides of a paper pulp having a basis weight of 180 g / m ² . However, on the side to which the photosensitive layer was applied, molten polyethylene containing surface-treated anatase-type titanium oxide dispersed at a content of 15% by mass was laminated. The mass of the obtained support was 220 g Zm ² . After subjecting this reflective support to corona discharge treatment, a gelatin undercoat layer was provided, and each layer having the following constitution was further applied thereon, to prepare a silver halide color photographic material Sample 1 1. The coating solution was prepared as described below.

 (Preparation of first layer coating solution)

Yellow coupler (Y-1) 23.4 g, dye image stabilizer (ST-1) 3.34 g, (ST-2) 3.34 g, (ST-5) 3.34 g, stin inhibitor 0.34 g of (HQ-1), 5.0 g of image stabilizer A, 3.33 g of high-boiling organic solvent (DBP) and 1.67 g of high-boiling organic solvent (DNP) were mixed with ethyl acetate 6 Om 1. This solution was added and dissolved, and this solution was emulsified and dispersed in 220 ml of a 10% aqueous gelatin solution containing 7 ml of 20% surfactant (SU-1) using an ultrasonic homogenizer to prepare a yellow force blur dispersion liquid. . This yellow coupler dispersion was mixed with the blue-sensitive silver halide emulsion (101B) prepared above to prepare a first layer coating solution. (Preparation of coating solution for 2nd to 7th layers)

 The coating liquids for the second to seventh layers were prepared using the following additives in the same manner as in the method for preparing the one-layer coating liquid.

 (Configuration of sample 101)

 7th layer: protective layer> g / 'm gelatin 0.70 DID P 0.005 silicon dioxide 0.003

<Sixth layer: UV absorbing layer>

 Gelatin 0.3 0 UV absorber (UV-1) 0.12 UV absorber (UV-2) 0.04 UV absorber (UV-3) 0.16 Sting inhibitor (HQ-5) 0 0.4 PVP (polyvinylpyrrolidone) 0.03 Anti-irradiation dye (AI_1) 0.01 <5th layer: red-sensitive layer>

Gelatin 1.20 Red-sensitive silver halide emulsion (10 1 R) 0.21 Cyan coupler (C—1) 0.25 Cyan coupler (C — 2) 0.08 Dye image stabilizer (ST— 1) 0.10 Sting inhibitor (HQ-1) 0.04 DBP 0.10

D 0 P 0.20

<4th layer: UV absorbing layer>

Gelatin 0.90 UV absorber (UV-1) 0.28 UV absorber (UV-2) 0.09 UV absorber (UV-3) 0.38 Sting inhibitor (HQ-3) 0 . 10 Anti-irradiation dye (AI-1) 0.02

<3rd layer: green photosensitive layer>

Gelatin 1.20 Green light-sensitive silver halide emulsion (101 G) 0.14 Magenta coupler (M-1) 0.20 Dye image stabilizer (ST-3) 0.20 Dye image stability Agent (ST-4) 0.1 7

D I D P 0.1 3

D B P 0.13 Anti-irradiation dye (AI_2) 0.01

<Second layer: Middle layer>

Gelatin 1.10 Sting inhibitor (HQ-2) 0.03 Sting inhibitor (HQ-3) 0.03 Sting inhibitor (HQ-4) 0.05 Sting inhibitor (HQ-5) 0.23

D I D P 0.06 Fluorescent whitening agent (W-1) 0.10 Anti-irradiation dye (AI_3) 0.01 First layer: Blue-sensitive layer

Gelatin 1.10 Blue-sensitive silver halide silver halide emulsion (10 1 B) 0.26 Yellow coupler (Y-1) 0.70 Dye image stabilizer (ST-1) 0.10 Dye image stabilization Agent (ST-2) 0.10 Sting inhibitor (HQ-1) 0.01 Dye image stabilizer ( _ST- 15) 0.10 Image stabilizer A 0.15

DN P 0. 05

D B P 0.10 Support: Reflective support Polyethylene laminated paper (containing a trace amount of colorant) The amount of each of the above silver halide emulsions was expressed in terms of silver. In addition, (H-1) and (H-2) are added to each of the above coating solutions as a hardening agent, and the following surfactant (SC_1) is added as a coating aid, and The tension was adjusted.

 S U— 1: Tri-i-sodium propylnaphthalenesulfonate

 S C—1: sodium decyl sulfonate

 DBP: dibutyl phthalate

DN P: dinonyl phthalate DOP: Dioctyl phthalate

 D I D P: Di-i-decylphthalate

 H—1: Tetrakis (vinylsulfonylmethyl) methane

 H--22, -dichloro-1-hydroxystriazine '' 'sodium

H Q-1, 2, 5 — G

 H Q-2 2,5 —di-sec dodecyl didroquinone

 H Q-3 2, 5 — di secec

 H Q-42-s e c Dote sinore _ 5— s e c

H Q-52,5- -Di [(1,1_dimethyl-4_hexyloxycarbonyl) butyl] Hydroquinone

 Image stabilizer A: P-t-octylphenol

Y

C一 1

M-1

C-1

C-1 2

ST— 1

ST— 2

ST— 3

OSN— ( ⁷ ,> OC ₁₃ H ₂₇ (i)

ST— 4

UV-3

AI-2

AI-2

AI-3

次いで、 上記構成において、 一般式 （ I ) 〜 （ IV) で表される化合物 （添加 量は、 トータルで 0. 002 g/m ²を第 1層と第 6層に 1 ： 2の比率で添加し た。）、 全塗設層中のカルシウム含有量 （ゼラチンの種類を変化： イオン交換を 施した石灰処理骨ゼラチンを使用）、全層に使用されるゼラチンの総量（全層の 塗設ゼラチン量を、試料 10 1の各層の塗設量比率を保って変化）、及び支持体 質量 （中紙質量で調整） を下表に示すように変更した試料 1 02〜1 1 2を作 製した。 （表中、 C a ： カルシウム、 G e 1 ： ゼラチンを表す。） 試料 一般式 総 G e 1 支持体 備考

Next, in the above structure, the compounds represented by the general formulas (I) to (IV) (additional amount of 0.002 g / m ² was added to the first layer and the sixth layer in a ratio of 1: 2. ), Calcium content in all coated layers (change of gelatin type: use of lime-processed bone gelatin subjected to ion exchange), total amount of gelatin used in all layers (coated gelatin in all layers) Samples 102 to 112 were prepared in which the amount was changed while maintaining the coating amount ratio of each layer of Sample 101) and the weight of the support (adjusted by the weight of the inner paper) as shown in the table below. . (In the table, Ca: calcium, Ge1: gelatin) Sample General formula Total G e 1 Support Remarks

(I to (IV) Ca content / m ² mass

Compound mg / m 'g / m ²

10 1 None 2 10 6.5 5 220 Comparative example

102 None 2 10 6. 1 220 Comparative example

103 None 9 6. 1 220 Comparative example

104 II 1 1 9 6.1 220

105 I [1 1 9 6. 1 2 16 The present invention

106 II-1 9 6. 1 2 13 The present invention

107 II 1 1 9.5.7 2 13 The present invention

108 II- 1 7 5. 7 2 13 The present invention

109 I-4 7 5.7 2 13 The present invention

1 10 III 1 1 3 7 5. 7 2 13 The present invention

1 1 1 IV— 1 7 5. 7. 2 13 The present invention

1 1 2 IV- 1 7 5. 7. 2 13 The present invention Sample No. 112 was used as a surfactant, instead of (SC-1), di (2-ethylhexyl) sulfosuccinate. The sodium was used so as to have the same amount. Each of the obtained samples was subjected to white light exposure using a conventional method with an exposure time of 0.5 seconds, and then subjected to a development process in the following development process.

 Treatment process Treatment temperature Time Replenishment amount

Color development 35.0 ± 0.3 ° C 45 seconds 80m l Zm ² Bleach-fix 35.0 ± 0.5 ° C 4 5 seconds 2 15 ml / m ² Stabilization 30 0 3 4 ° C 60 seconds 2 48 ml / ra ² Dry 60 0 80 ° C 30 Second

 The composition of the developing solution is shown below.

 [Color developer tank solution and replenisher] Tank solution Replenisher Pure water 800 ml 180 ml Triethylenediamine 2 g 3 g Dethylene glycol 10 g 10 g Lithium bromide 0.0 1 g ― Potassium chloride 3.5 g ― Potassium sulfite 0.2 5 g 0.5 g

! ^ -Echiru! ^-(Β-methanesulfonamidoethyl) 1 3 —Methyl-4

—Aminoaniline sulfate 6.0 g 1 0.0 g

Ν, Ν-Jetylhydroxylamine 6.8 g 6.0 g Triethanolamine 10.0 g 10.0 g Gelatinent sodium pentaacetic acid pentasodium salt 2.0 g 2.0 g Fluorescent whitening agent (4,4'-Diaminostilbene disulfonic acid derivative)

 2.0 g 2.5 g Carbonated rim 30 g 30 g Add water to make 1 liter, tank liquid to ρ = 10.1 o, refill to pH = 10. Adjust to 60.

 (Bleach-fixer tank solution and replenisher)

Diethylene triammonium pentaacetate ammonium dihydrate 65 5 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml

2-amino-5-mercapto-1,3,4-thiadiazol 2.0 g ammonium sulfite (40% aqueous solution) 27.5 ml Add water to make 1 liter, carbon dioxide lime or glacial acetic acid Adjust to pH = 5.0.

 (Stabilizing solution tank solution and replenisher solution)

 0 _Phenylphenol l.O g 5-Methyl-1-2-Methyl 4-isothiazolin-3-one 0.02 g 2-Methyl-4-isothiazolin-1-3-one 0.02 g Diethylene glycol l.O g Optical brightener (Tinopearl SFP) 2.0 g

1-Hydroxyshethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate · 7-hydrate 0.2 g

PVP l. O g Ammonia water (25% aqueous solution of ammonium hydroxide) 2.5 g Trisodium triacetate 'trisodium salt 1.5 g Add water to make 1 liter, make sulfuric acid or ammonia water Adjust to pH = 7.5 with. The amount of overflow from the color developing solution at this time was 75 m 1 for processing the photosensitive material 1 m ^2.

Next, based on Japanese Patent Application No. 6-255481, a replenisher of the color developing solution was regenerated as shown below, and the regenerated replenisher was run at a replenishment amount of 40 m 1 Zm ² . [Regeneration method of color developer]

 When the overflow solution of the color developing solution was stocked (stock solution) and 16 L of replenisher was replenished, the stock volume became 9.8 L. Next, the following chemicals were added to 9.8 L of the stock solution, and water was added to make 16 L, which was reused as a replenisher.

 (Regeneration replenisher formulation)

 Stock solution 9.8 LN-Ethyl-1-N-(/ 3-Methanesulfonamidoethyl) -13-Methyl-14-aminoaniline sulfate 57 g N, N-Jetylhydroxylamine 56 g Triethanolamine 93 g Sodium diethylenetriaminepentaacetate 12 g Fluorescent whitening agent (4,4'-diaminostilbenesulfonic acid derivative) 16 g potassium carbonate 186 g Add water to make 16 liters. Adjust pH to 10.60 with KOH.

 The above regeneration was repeated 20 times for each of the samples 101 to 112. That is, the number of rounds is 40. The regeneration rate was set at 100%.

 《Evaluation》

In addition, each sample was processed by 500 m ² . Blue light reflection maximum density at this time of the neutral image (Dm a X) is measured, measuring the difference of the maximum reflection density in 500 m ^2, calculated and, to a concentration variation (Δ Dm a X).

The results obtained are shown in the table below. Sample No. Concentration variation Maximum concentration

 Δ D m a X D m a X

1 0 1 0. 0 2 5 2 .2 1 Comparative example

 1 0 2 0. 0 2 3 2 .2 4 Comparative example

 1 0 3 0. 0 2 1 2 .2 5 Comparative example

 1 0 4 0. 0 1 4 2 .3 5 The present invention

 1 0 5 0. 0 1 2 2 .3 5 The present invention

 1 0 6 0. 0 1 1 2 .3 6 The present invention

 1 0 7 0. 0 0 9 2 .1 The present invention

 1 0 8 0 .0 0 7 2 .3 The present invention

 1 0 9 0 .0 0 8 2.0 The present invention

 1 1 0 0 .0 0 6 2 .4 The present invention

 1 1 1 0 .0 0 6 2 .4 4 The present invention

 1 1 2 0. 0 0 0 9 2. 3 3 The present invention From the above table, in the sample according to the present invention, even when the regenerating solution was used, the density variation was small and a good image was obtained. This is an effect that was not expected in the prior art. Also, the maximum color density itself was larger than the comparative sample.

Furthermore, it was found that the use of the anionic surfactant (sc-1) according to the present invention as a surfactant further enhanced the effects of the present invention. Industrial potential T / JP2003 / 005149

56 As described above, according to the present invention, a silver halide photographic light-sensitive material excellent in image density stability even when processed in a large amount and a processing method thereof can be provided.

Claims

The scope of the claims 1. In a silver halide photographic light-sensitive material having at least one light-sensitive layer and at least one light-insensitive layer on a support, the light-sensitive layer or the light-insensitive layer is represented by the following general formula (I) And at least one compound selected from compounds represented by the formulas (IV) to (IV), wherein the total calcium content in the coating layer of the light-sensitive material is 10 mg, m ² to 0.1 mg Zm ² . There, and the total amount of gelatin contained in the photosensitive material, a silver halide photographic light-sensitive material comprising a 6. ² g / m 2 ~4. is 0 gZm ^2. General formula (I) ) I N-CHzCH- i N0 ₂ (In the formula, R, represents a hydrogen atom, a lower alkyl group, or an aryl group.) General formula (II)

(Wherein R ₂ is a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, (R ₆ ) (R ₅ )> N-C (= 0)-, (Re) (R ₅ )> NC (= S) —, where R ₅ and R ₆ are each a hydrogen atom, an alkyl group, an aryl group, a cyano group, It represents a heterocyclic group, an alkylthio group, an arylthio group, an alkylsulfoxy group, or an alkylsulfonyl group, and R ₃ and R ₄ may combine with each other to form an aromatic ring. R ₅ and R ₆ each represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. ) General formula (ΙΠ)

(Wherein X is a halogen atom, a nitro group, a hydroxy group, a cyano group, a lower alkyl group, a lower alkoxy group, an aryl group, an alkenyl group, a sulfonyl group, an aralkyl group, —COR ₇ , —N ₈ ) (R ₉ ), — SO ₃ M ² , where R ₇ is a hydrogen atom, _OM ² , lower alkyl group, aryl group, aralkyl group, lower alkoxy group, aryloxy group, aralkyloxy group, 1N R ₈ and R ₉ each represent a hydrogen atom, a lower alkyl group, an aryl group, an aralkyl group, —COF ^ ₂ , or S 0 ₂ R ₁₂ , and are the same as each other; R ₁₀ and R n each represent a hydrogen atom, a lower alkyl group, an aryl group or an aralkyl group, which may be the same or different from each other, and R ₁₂ is a lower alkyl group, Ariru group, a Ararukiru group, MM ² is hydrogen Represents an atomic group necessary to form a hydrogen atom, an alkali metal atom and a monovalent cation.m represents an integer of 0 to 5, and when m is 2 to 5, X is the same as above even if it is the same group. May be used in combination.) General formula (IV)

(In the formula, R ₁₃ represents an unsubstituted or substituted alkylene group, and Y represents a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, a cyano group, a lower alkyl group, a lower alkoxy group, an aryl group, an alkenyl group. , a sulfonyl group, Ararukiru _{group, - COR 14, -N <(} R 15) (R 16), - represents S 0 ^₃ M _3, RM is hydrogen sheet, - OM ^3, lower alkyl group, Ariru group, Ararukiru A lower alkoxy group, an aryloxy group, an aralkyloxy group, —N (R ₁₇ ) (R ₁₈ ), wherein R ₁₅ and R ₁₆ are each a hydrogen atom, a lower alkyl group, an aryl group, an aralkyl group, — COR ₁₉ , — SO ₂ R ₁₉ , which may be the same or different, and R ₁₇ , R ₁₈ each represent a hydrogen atom, a lower alkyl group, an aryl group, an aralkyl group, and shall apply also may be different, R ₁₉ Lower alkyl group, Ariru group, a Ararukiru group, M ³ is a hydrogen atom, is. N represent the atoms necessary to form Al force Li metal atom and a monovalent cation from 0 or 1 (6 _ p) And p represents an integer of 1 to 6. When n and p are 2 or more, a plurality of the above groups may be combined respectively.) 2. The silver halide photographic material according to claim 1, further comprising an anionic surfactant having a benzene ring or a naphthalene ring. 3. The silver halide photograph according to claim 1 or 2, wherein the support is a double-sided resin-coated paper, and the weight of the support is 2 17 g / m ² or less. Photosensitive material. 4. Reproduce the overflow of the color developing solution generated during continuous processing of the silver halide photographic light-sensitive material according to any one of claims 1 to 3 after imagewise exposure. A method for processing a silver halide photographic light-sensitive material, wherein the method is recycled for processing the light-sensitive material.