JP4079863B2 - Dye-forming coupler and silver halide color photographic material - Google Patents

Description

  The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material excellent in color reproducibility and image storage stability.

  In a silver halide photographic light-sensitive material obtained by the subtractive color method (hereinafter sometimes simply referred to as “photosensitive material”), a color image is formed by three primary color dyes of yellow, magenta, and cyan. In color photographic methods using current p-phenylenediamine color developing agents, acylacetanilide compounds are used as yellow couplers. However, the hue of yellow dyes obtained from these couplers is reddish due to poor absorption on the long wave side of absorption, and it is difficult to obtain a yellow hue with high purity. In order to obtain a desired color density, a large amount of coupler or silver halide is required, and the sharpness of a color image obtained by decreasing the film thickness of the photosensitive material may decrease. It was. Furthermore, the dye is easily decomposed under high-temperature and high-humidity conditions or light irradiation conditions, and there is a problem in image storability after development processing, and improvement is desired.

  In order to solve these problems, acyl groups and anilide groups have been improved. Recently, as couplers obtained by improving conventional acylacetate anilide systems, 1-alkylcyclopropanecarbonylacetate anilide compounds (Patent Document 1) are proposed. And cyclic malondiamide type couplers (see Patent Document 2), pyrrole-2 or 3-yl or indol-2 or 3-ylcarbonylacetate anilide couplers (see Patent Documents 3 to 4), and the like. It was. Dyes produced from these couplers are improved in hue and molecular extinction coefficient compared to the conventional ones, but are not yet sufficient in terms of image storage stability, and because the structure is complicated, the synthesis route is long, The coupler cost was high and there was a problem in practical use. In addition, acetate ester-type and acetic acid anilide-type couplers to which 1,2,4-benzothiadiazine-1,1-dioxide is bonded (for example, see Patent Documents 5 to 7) have been proposed. However, the long-wave side absorption of absorption is poor and these improvements have been desired.

Japanese Patent Laid-Open No. 4-218042 JP-A-5-11416 European Patent Application Publication No. 935870 European Patent Application No. 953871 US Pat. No. 3,841,880 JP 52-82423 A JP-A-2-28645

  Accordingly, an object of the present invention is to overcome the above-mentioned problems, provide a dye having good hue and storage stability, and provide a dye-forming coupler having a high color development property, and using this dye-forming coupler, An object of the present invention is to provide a silver halide photographic light-sensitive material which can form an image having a high degree of storage stability without causing discoloration or discoloration of a white background or a dye image for a long period of time. Another object of the present invention is a silver halide capable of forming an image having excellent hue and density, little fogging and color mixing, a dye image that does not change for a long period of time, and a low density drop even after storage for a long period of time. The object is to provide a photographic material. Furthermore, another object of the present invention is to provide a silver halide color photographic material excellent in hue and density, in which a dye image does not change color for a long period of time and has excellent development processing stability.

As a result of intensive studies, the present inventors have found that the above problem can be solved by a yellow dye-forming coupler represented by the following general formula (I). The present invention has been made based on this finding. That is, the present invention provides the following.
(1) A yellow dye-forming coupler represented by the following general formula (I).

Wherein, Q is -N = C-N ((CH 2) 3 O-R1) - represents a non-metallic atomic group forming a 5- to 7-membered ring together. R1 represents an alkyl group having 4 to 8 carbon atoms. R2 represents a substituent. R4 represents a primary alkyl group. m represents an integer of 0 or more and 4 or less. When m is 2 or more, a plurality of R2s may be the same or different from each other, and may be bonded to each other to form a ring. X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized developer.

(2) A silver halide color photographic light-sensitive material containing at least one kind of yellow dye-forming coupler represented by the general formula (I) described in the above item (1) in at least one layer on the support. material.
(3) the Q is -C in the general formula (I) (-R11) = C (-R12) -SO 2 - or -C (-R11) = C (-R12) -CO- group represented by (R11 And R12 are a group bonded to each other to form a 5- to 7-membered ring together with -C = C-, or each independently a hydrogen atom or a substituent). Silver color photographic light-sensitive material.
(4) The halogen described in (2) or (3) above, wherein the yellow dye-forming coupler represented by the general formula (I) is a yellow dye-forming coupler represented by the general formula (II) Silver halide color photographic material.

In the formula, R1 represents an alkyl group having 4 to 8 carbon atoms. R2 represents a substituent. R4 represents a primary alkyl group. m represents an integer of 0 or more and 4 or less. When m is 2 or more, a plurality of R2s may be the same or different from each other, and may be bonded to each other to form a ring. R3 represents a substituent. n represents an integer of 0 or more and 4 or less. When n is 2 or more, the plurality of R3 may be the same or different from each other, and may be bonded to each other to form a ring. X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized developer.
(5) In any one of the above items (2) to (4), in the general formula (I) or (II), m is an integer of 1 to 4, and R2 is a t-butyl group. 2. A silver halide color photographic light-sensitive material as described in 1 above.

  According to the present invention, it is possible to provide a silver halide color photographic light-sensitive material that is excellent in hue and density, does not discolor or fade for a long time on a white background or a dye image, and has a high degree of storage stability at a low cost. The silver halide photographic light-sensitive material of the present invention has little fogging and color mixing, little reduction in color density even when stored raw for a long time after coating, and excellent development processing stability.

The present invention is described in detail below.
In the present specification, aliphatic means that the aliphatic moiety is linear, branched or cyclic and may be saturated or unsaturated, such as an alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group. These may be unsubstituted or may have a substituent. Aryl may be a single ring or a condensed ring, and may be unsubstituted or have a substituent. In addition, the heterocyclic ring has a hetero atom (for example, nitrogen atom, sulfur atom, oxygen atom) in the ring, and may be a saturated ring or an unsaturated ring. They may be monocyclic or condensed, and may be unsubstituted or have a substituent.
Specific examples of the substituent in the present invention include an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aryloxy group, a heterocyclic oxy group, and an aliphatic group. Oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyloxy group, arylsulfonyloxy group, heterocyclic sulfonyloxy group, sulfamoyl Group, aliphatic sulfonamido group, aryl sulfonamido group, heterocyclic sulfonamido group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, hetero Ring oxycarbonyl amino Group, aliphatic sulfinyl group, arylsulfinyl group, aliphatic thio group, arylthio group, hydroxy group, cyano group, sulfo group, carboxyl group, aliphatic oxyamino group, aryloxyamino group, carbamoylamino group, sulfamoylamino Groups, halogen atoms, sulfamoylcarbamoyl groups, carbamoylsulfamoyl groups, dialiphatic oxyphosphinyl groups, diaryloxyphosphinyl groups, and the like.
First, the compound represented by the general formula (I) of the present invention (also referred to herein as a yellow dye-forming coupler) will be described in detail.

  In the formula, R1 represents a substituted or unsubstituted alkyl group having 4 to 8 carbon atoms. Examples of the substituent that R1 may have include, for example, a halogen atom, an alkyl group, a cycloalkyl group (including a bicycloalkyl group), an alkenyl group, a cycloalkenyl group (including a bicycloalkenyl group), an alkynyl group, and an aryl group. , Heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino Groups (including alkylamino groups and anilino groups), acylamino groups, aminocarbonylamino groups, alkoxycarbonylamino groups, aryloxycarbonylamino groups, sulfamoylamino groups, alkyl or arylsulfonylamino groups, mercapto groups, Alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group , Imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, and silyl group.

  In addition, the above-described substituent may be further substituted with a substituent, and examples of the substituent include the above-described groups.

  R1 is preferably an unsubstituted alkyl group having 4 to 6 carbon atoms, and more preferably an n-butyl group.

In the general formula (I), Q represents a nonmetallic atom group that forms a 5- to 7-membered ring with —N═C—N ((CH ₂ ) ₃ O—R 1) —. Preferably, the formed 5- to 7-membered ring is a substituted or unsubstituted, monocyclic or condensed heterocyclic ring, and more preferably, the ring constituent atoms are selected from a carbon atom, a nitrogen atom and a sulfur atom. More preferably Q is -C (-R11) = C (-R12 ) -SO 2 -, or in -C (-R11) = C represents a group represented by (-R12) -CO- (present invention, The representation of these groups does not limit the direction of bonding of the groups represented by these groups.) R11 and R12 are bonded to each other to form a 5- to 7-membered ring together with -C = C-, or each independently represents a hydrogen atom or a substituent. The formed 5- to 7-membered ring is a saturated or unsaturated ring, and the ring may be an alicyclic ring, an aromatic ring, or a heterocyclic ring. For example, a benzene ring, a furan ring, a thiophene ring, a cyclopentane ring And cyclohexane rings, and these rings may further have a substituent. Examples of the substituent include those exemplified as the substituent which the above-mentioned alkyl group of R1 may have (hereinafter also referred to as the substituent of R1).

  The ring formed by bonding each of these substituents or a plurality of substituents may be further substituted with a substituent (including the groups exemplified as the substituent for R1 described above).

In general formula (I), R2 represents a substituent other than a hydrogen atom. Examples of this substituent include those listed as examples of the substituent for R1 described above. Preferably R2 is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an alkyl group (eg, methyl, isopropyl, t-butyl), an aryl group (eg, phenyl, naphthyl), an alkoxy group (eg, methoxy, isopropyloxy), Aryloxy groups (eg phenoxy), alkylthio groups (eg methylthio, octylthio), arylthio groups (eg phenylthio, 2-methoxyphenylthio), acyloxy groups (eg acetyloxy), amino groups (eg dimethylamino, morpholino), acylamino Groups (eg acetamide), sulfonamido groups (eg methanesulfonamide, benzenesulfonamide), alkoxycarbonyl groups (eg methoxycarbonyl), aryloxycarbonyl groups (eg phenoxycarbox) Nyl), carbamoyl group (for example, N-methylcarbamoyl, N, N-diethylcarbamoyl), sulfamoyl group (for example, N-methylsulfamoyl, N, N-diethylsulfamoyl), alkylsulfonyl group (for example, methanesulfonyl) An arylsulfonyl group (for example, benzenesulfonyl), a cyano group, a carboxyl group, and a sulfo group. More preferable examples of the substituent include an alkyl group, an aryl group, an alkoxy group, and an aryloxy group.
The total carbon number of R2 is preferably from 0 to 60, more preferably from 0 to 50, and still more preferably from 0 to 40.
More preferably, R2 is a t-alkyl group, more preferably a t-butyl group, and most preferably R2 is a t-butyl group at the para position of -SR4.

In general formula (I), m represents an integer of 0 or more and 4 or less. When m is 2 or more, a plurality of R2s may be the same or different from each other, and may be bonded to each other to form a ring. In view of the effects of the present invention, m is preferably 0 or 1. In the general formula (I), R4 represents a primary alkyl group and may have a substituent. Examples of this substituent include those listed as examples of the substituent for R1 described above. Preferable carbon number of R4 including the substituent is 3 or more and 30 or less, more preferably 3 or more and 20 or less, and further preferably 6 or more and 12 or less. Preferred examples of the substituent include an alkyl group and an aryl group, and more preferred is an alkyl group. Most preferably R4 is a 2-ethylhexyl group.
In the present specification, the “primary alkyl group” means that when the carbon bonded to S in the formula (I) is a central carbon in the carbon skeleton of the alkyl group, the central carbon has at least two hydrogen atoms. It refers to what you have.

In the general formula (I), X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized developer. As an example of the case where X is a group that can be removed by a coupling reaction with oxidized developer, an atom (bonding atom) bonded to a carbon atom substituted by X is a nitrogen atom, an oxygen atom, or a sulfur atom. And a halogen atom (for example, a chlorine atom or a bromine atom).
The group in which the atom at the bonding position is a nitrogen atom includes a heterocyclic group (preferably a 5- to 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic (in this specification, 4n + 2 cyclic conjugated electrons). Or a non-aromatic, monocyclic or condensed heterocyclic group, more preferably a ring-constituting atom is selected from a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom, and a nitrogen atom, A 5- or 6-membered heterocyclic group having at least one hetero atom of oxygen and sulfur, such as succinimide, maleimide, phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4- Triazole, tetrazole, indole, benzopyrazole, benzimidazole, benzotriazole, imidazo Gin-2,4-dione, oxazolidine-2,4-dione, thiazolidine-2-one, benzimidazolin-2-one, benzoxazolin-2-one, benzothiazolin-2-one, 2-pyrrolin-5-one 2-imidazolin-5-one, indoline-2,3-dione, 2,6-dioxypurine, parabanic acid, 1,2,4-triazolidine-3,5-dione, 2-pyridone, 4-pyridone, 2- Pyrimidone, 6-pyridazone, 2-pyrazone, 2-amino-1,3,4-thiazolidin-4-one), carbonamide group (for example, acetamide, trifluoroacetamide), sulfonamide group (for example, methanesulfonamide, benzenesulfone) Amide), arylazo groups (eg phenylazo, naphthylazo), carbamoylamino groups (eg N Methylcarbamoylamino), and the like.

  Of the groups in which the atom at the bonding position is a nitrogen atom, preferred are heterocyclic groups, and more preferred are aromatic heterocyclic groups having 1, 2, 3 or 4 nitrogen atoms as ring-constituting atoms, or It is a heterocyclic group represented by the following general formula (L).

In the formula, L represents a residue that forms a 5- or 6-membered nitrogen-containing heterocycle together with -NC (= O)-.
These examples are given in the description of the heterocyclic group, and these are more preferable.
Among these, L is preferably a residue that forms a 5-membered nitrogen-containing heterocycle.

Examples of the group in which the atom at the bonding position is an oxygen atom include aryloxy groups (for example, phenoxy and 1-naphthoxy), heterocyclic oxy groups (for example, pyridyloxy and pyrazolyloxy), acyloxy groups (for example, acetoxy and benzoyloxy), alkoxy Groups (for example, methoxy, dodecyloxy), carbamoyloxy groups (for example, N, N-diethylcarbamoyloxy, morpholinocarbamoyloxy), aryloxycarbonyloxy groups (for example, phenoxycarbonyloxy), alkoxycarbonyloxy groups (for example, methoxycarbonyloxy, ethoxy) Carbonyloxy), alkylsulfonyloxy groups (eg methanesulfonyloxy), arylsulfonyloxy groups (eg benzenesulfonyloxy, toluenesulfonyloxy) And the like.
Of the groups in which the bonding atom is an oxygen atom, preferred are an aryloxy group, an acyloxy group, and a heterocyclic oxy group.

Examples of the group in which the atom at the bonding position is a sulfur atom include an arylthio group (for example, phenylthio, naphthylthio), a heterocyclic thio group (for example, tetrazolylthio, 1,3,4-thiadiazolylthio, 1,3,4-oxazolylthio). , Benzimidazolylthio), alkylthio groups (eg methylthio, octylthio, hexadecylthio), alkylsulfinyl groups (eg methanesulfinyl), arylsulfinyl groups (eg benzenesulfinyl), arylsulfonyl groups (eg benzenesulfonyl), alkylsulfonyl groups (eg methane) Sulfonyl) and the like.
Of the groups in which the bonding atom is a sulfur atom, preferred are an arylthio group and a heterocyclic thio group, and a heterocyclic thio group is more preferred.

X may be substituted with a substituent, and examples of the substituent substituted with X include those listed as examples of the substituent for R1 described above.
X is preferably a group in which the atom at the bonding position is a nitrogen atom, an oxygen atom or a sulfur atom, more preferably a group in which the atom at the bonding position is a nitrogen atom, and still more preferably, the atom at the bonding position is nitrogen. It is preferable in the order of the preferable groups described in the group which is an atom. Most preferably, X is a 5,5-dimethyloxazolidine-2,4-dione-3-yl group.

  X may be a photographically useful group. Examples of the photographically useful group include development inhibitors, desilvering accelerators, redox compounds, dyes, couplers, and the like, or precursors thereof.

  In order to immobilize the coupler in the light-sensitive material, it is preferable that at least one of Q, R 1, X, or R 2 has a total carbon number including a substituent of 8 or more and 60 or less, more preferably the total carbon number Is 8 or more and 50 or less.

  In view of the effect of the present invention, the compound represented by the general formula (I) (also referred to herein as a yellow dye-forming coupler) is a compound represented by the following general formula (II) (herein referred to as a yellow dye-forming coupler). (Also referred to as “also”). Hereinafter, the compound represented by formula (II) will be described in detail.

  In the general formula (II), R1, R2, R4, m, and X represent the same as those described in the general formula (I), and preferred ranges are also the same.

In general formula (II), R3 represents a substituent. Examples of this substituent include those listed as examples of the substituent for R1 described above. Preferably R3 is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), alkyl group (eg, methyl, isopropyl), aryl group (eg, phenyl, naphthyl), alkoxy group (eg, methoxy, isopropyloxy), aryloxy group ( For example, phenoxy), acyloxy group (eg acetyloxy), amino group (eg dimethylamino, morpholino), acylamino group (eg acetamido), sulfonamide group (eg methanesulfonamide, benzenesulfonamide), alkoxycarbonyl group (eg methoxycarbonyl) ), Aryloxycarbonyl group (for example, phenoxycarbonyl), carbamoyl group (for example, N-methylcarbamoyl, N, N-diethylcarbamoyl), sulfamoyl group (for example, N-methyls) Famoiru, N, N-diethyl-sulfamoyl), an alkylsulfonyl group (e.g. methanesulfonyl), an arylsulfonyl group (e.g., benzenesulfonyl), a cyano group, a carboxyl group, a sulfo group.
n represents an integer of 0 or more and 4 or less. When n is 2 or more, the plurality of R3 may be the same or different from each other, and may be bonded to each other to form a ring.
Preferred specific examples of the coupler represented by formula (I) or formula (II) of the present invention are shown below, but the present invention is not limited thereto. Note that a tautomer in which a hydrogen atom at a coupling position moves onto nitrogen at a C═N part bonded to the coupling position is also included in the present invention.

  In the following description, when referring to the exemplified compounds shown above, the number “x” in parentheses attached to each exemplified compound is used to indicate “coupler (x)”. .

  Specific synthesis examples of the compounds represented by the above general formula (I) or general formula (II) are shown below.

Synthesis Example 1: Synthesis of Coupler (2) Coupler (2) was synthesized by the route shown below.

  To a solution of 150 g of 3-butoxypropylamine, 192 ml of triethylamine, and 600 ml of acetonitrile, 253 g of orthonitrobenzenesulfonyl chloride was added little by little while stirring with ice cooling. The temperature of the reaction system was raised to room temperature and further stirred for 1 hour. Ethyl acetate and water were added for liquid separation, and the organic solvent layer was washed with dilute hydrochloric acid and saturated brine. The organic solvent layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain 362 g of a viscous oily compound (A-1).

  300.0 g of reduced iron and 30.0 g of ammonium chloride were dispersed in 1540 ml of isopropanol and 240 ml of water, and the mixture was stirred for 1 hour while heating under reflux. To this, 119 g of compound (A-1) was added little by little. The mixture was further stirred for 2 hours under reflux with heating, and then suction filtered through celite. Ethyl acetate and water were added to the filtrate for liquid separation, and the organic solvent layer was washed with saturated brine. The organic solvent layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain 327 g of an oily compound (A-2).

  A solution of 327 g of compound (A-2), 268.4 g of hydrochloride of iminoether (A-0) and 450 ml of ethyl alcohol was stirred with heating under reflux for 1 hour. After cooling, suction filtration was performed, 500 ml of p-xylene was added to the filtrate, and the mixture was heated to reflux for 4 hours while distilling off ethanol. The reaction solution was poured into 1000 ml of ice water, and extracted with 500 ml of ethyl acetate. The organic solvent layer was washed twice with saturated brine and dried over anhydrous magnesium sulfate. Magnesium sulfate was filtered off, and ethyl acetate and xylene were distilled off under reduced pressure. The obtained oil was crystallized from 1000 ml of n-hexane to obtain 370.1 g of compound (A-3).

  In a nitrogen atmosphere, 470 g of 4-t-butyl-2-nitrochlorobenzene was added to 343 g of 2-ethylhexanethiol, 800 ml of N, N-dimethylacetamide and 364 g of potassium carbonate, and the mixture was stirred with heating at 90 ° C. for 2 hours, and then 1000 ml of ice water. And extracted with 1000 ml of ethyl acetate. The organic solvent layer was washed twice with saturated brine and dried over anhydrous magnesium sulfate. Magnesium sulfate was filtered off, and the solvent was distilled off under reduced pressure to obtain 806 g of an oily compound (A-4).

  740 g of reduced iron and 74.0 g of ammonium chloride were dispersed in 2200 ml of isopropanol and 370 ml of water, and the mixture was stirred for 1 hour with heating under reflux. To this, 806 g of compound (A-4) was added little by little. The mixture was further stirred for 2 hours under reflux with heating, and then suction filtered through celite. Ethyl acetate and water were added to the filtrate for liquid separation, and the organic solvent layer was washed with saturated brine. The organic solvent layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain 671 g of an oily compound (A-5).

  110 g of compound (A-3) and 96.2 g of compound (A-5) were heated and stirred at 145 to 150 ° C. for 6 hours to obtain a crude product of compound (A-6). To this reaction crude product, 300 ml of ethyl acetate was added, and 31.2 g of N-chlorosuccinimide was added over 5 minutes with stirring under ice cooling. After stirring for 30 minutes under ice cooling, water was added for liquid separation, and the organic solvent layer was washed with saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain a crude product of compound (A-7).

  112 g of 5,5-dimethyloxazolidine-2,4-dione and 120 ml of triethylamine were dissolved in 100 ml of N, N-dimethylacetamide, and all of the crude product of the compound (A-7) synthesized above was dissolved in N, N with stirring at room temperature. What was melt | dissolved in N-dimethylacetamide 150ml was dripped in 10 minutes, and it heated up to 80 degreeC after that, and stirred for 3 hours. Ethyl acetate and ice water were added for liquid separation, and the organic solvent layer was washed with 0.1 N aqueous potassium hydroxide, dilute hydrochloric acid and saturated brine. The organic solvent layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure, followed by crystallization from an ethyl acetate / hexane mixed solvent to obtain 88.3 g of coupler (2). Melting point 124-125 ° C.

Synthesis Example 2: Synthesis of coupler (8) Coupler (8) was synthesized by the route shown below.

  To a solution of 120 g of 3-hexyloxypropylamine, 105 ml of triethylamine, and 500 ml of acetonitrile, 166 g of orthonitrobenzenesulfonyl chloride was added little by little while stirring with ice cooling. The temperature of the system was raised to room temperature and further stirred for 3 hours. Ethyl acetate and water were added for liquid separation, and the organic solvent layer was washed with dilute hydrochloric acid and saturated brine. The organic solvent layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain 252 g of a viscous oily compound (B-1).

  396 g of reduced iron and 40.0 g of ammonium chloride were dispersed in 2600 ml of isopropanol and 300 ml of water, and the mixture was stirred for 1 hour with heating under reflux. To this, 487 g of compound (B-1) was added little by little. The mixture was further stirred for 2 hours under reflux with heating, and then suction filtered through celite. Ethyl acetate and water were added to the filtrate for liquid separation, and the organic solvent layer was washed with saturated brine. The organic solvent layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain 418 g of an oily compound (B-2).

  A solution of 418 g of compound (B-2), 300 g of ethyl diethoxyacrylate (B-0), 2.5 g of p-toluenesulfonic acid monohydrate, and 980 ml of toluene was stirred for 1 hour while heating under reflux. Further, 14.9 g of potassium t-butoxy was added, and the mixture was heated to reflux for 5 hours while distilling off ethanol. The reaction solution was poured into 800 ml of ice water, and extracted with 800 ml of ethyl acetate and 20 ml of hydrochloric acid. The organic solvent layer was washed twice with saturated brine and dried over anhydrous magnesium sulfate. Magnesium sulfate was filtered off, and ethyl acetate and toluene were distilled off under reduced pressure. The obtained oil was crystallized from methanol and water to obtain 323 g of compound (B-3).

  Under a nitrogen stream, 50.1 g of 2-aminothiophenol was added dropwise over 30 minutes to a mixture of 77.2 g of 2-ethylhexyl bromide, 82.8 g of potassium carbonate and 200 ml of N, N-dimethylformamide under ice cooling. Then, it heated up to 40 degreeC and stirred for 2 hours. The reaction solution was poured into 500 ml of water and extracted with 500 ml of ethyl acetate. The organic solvent layer was washed with dilute hydrochloric acid and saturated brine, and dried over anhydrous magnesium sulfate. After magnesium sulfate was filtered off, the solvent was distilled off under reduced pressure to obtain 94.1 g of an oily compound (B-4).

  A mixture of 28.7 g of compound (B-3), 16.6 g of compound (B-4) and 20 ml of xylene was heated and stirred at 145 to 150 ° C. for 6 hours, and after xylene was distilled off, ethyl acetate, Purification was performed using n-hexane as an eluent, to obtain 29.8 g of an oily product of compound (B-5).

  To a solution of 28.9 g of compound (B-5) in 100 ml of ethyl acetate, 6.4 g of N-chlorosuccinimide was added over 5 minutes with stirring under ice cooling. After stirring for 30 minutes under ice cooling, water was added for liquid separation, and the organic layer was washed with saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain a crude product of compound (B-6).

  18.6 g of 5,5-dimethyloxazolidine-2,4-dione and 20 ml of triethylamine were dissolved in 100 ml of N, N-dimethylacetamide, and all of the crude product of the compound (B-6) synthesized above was dissolved therein at room temperature. A solution dissolved in 30 ml of N, N-dimethylacetamide was added dropwise over 10 minutes, and then the temperature was raised to 70 ° C. and stirred for 3 hours. Ethyl acetate and water were added for liquid separation, and the organic solvent layer was washed with 0.1 N aqueous potassium hydroxide, dilute hydrochloric acid and saturated brine. The organic solvent layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography using ethyl acetate and n-hexane as an eluent to obtain 18.1 g of an oily product of coupler (8).

Synthesis Example 3: Synthesis of Coupler (22) Coupler (22) was synthesized by the route shown below.

  In a nitrogen atmosphere, 47.5 g of 4-tert-butyl-2-nitrobromobenzene was added to 26.9 g of n-octanethiol, 120 ml of N, N-dimethylformamide, and 38 g of potassium carbonate, and the mixture was heated and stirred at 80 ° C. for 1 hour. Thereafter, the mixture was poured into 400 ml of ice water and extracted with 300 ml of ethyl acetate. The organic solvent layer was washed twice with saturated brine and dried over anhydrous magnesium sulfate. Magnesium sulfate was removed by filtration, and the solvent was distilled off under reduced pressure to obtain 58.0 g of an oily compound (C-1).

  84.0 g of reduced iron and 8.4 g of ammonium chloride were dispersed in 480 ml of isopropanol and 80 ml of water, and stirred for 1 hour while heating under reflux. To this, 58.0 g of compound (C-1) was added little by little. Further, 2 ml of acetic acid was added, and the mixture was stirred for 2 hours while heating under reflux, and then suction filtered through celite. Ethyl acetate and water were added to the filtrate for liquid separation, and the organic solvent layer was washed with saturated brine. The organic solvent layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography using ethyl acetate and n-hexane as an eluent to obtain 43.3 g of an oily compound (C-2). .

  A mixture of 53.6 g of compound (A-3), 43.0 g of compound (C-2) and 100 ml of xylene was heated and stirred at 145 to 150 ° C. for 6 hours. After distilling off xylene, the residue was purified by silica gel column chromatography using ethyl acetate and n-hexane as an eluent to obtain 59.5 g of an oily compound (C-3).

  To a solution of 59.2 g of compound (C-3) in 200 ml of ethyl acetate, 12.5 g of N-chlorosuccinimide was added over 25 minutes with stirring under ice cooling. After stirring for 30 minutes under ice cooling, water was added for liquid separation, and the organic solvent layer was washed with saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain a crude product of compound (C-4).

  36.4 g of 5,5-dimethyloxazolidine-2,4-dione and 39 ml of triethylamine were dissolved in 170 ml of N, N-dimethylacetamide, and all of the crude product of the compound (C-4) synthesized above was dissolved in this at room temperature. A solution dissolved in 30 ml of N, N-dimethylacetamide was added dropwise over 10 minutes, the temperature was raised to 70 ° C., and the mixture was stirred for 3 hours. Ethyl acetate and water were added for liquid separation, and the organic layer was washed with 0.1 N aqueous potassium hydroxide, dilute hydrochloric acid and saturated brine. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and crystallization was performed from a mixed solvent of isopropanol / hexane to obtain 59.8 g of coupler (22). Melting point 104-106 ° C

Synthesis Example 4: Synthesis of Coupler- (2) Coupler- (2) was synthesized by the route shown below in addition to Synthesis Example 1.

  To a solution of 181.2 g of 3-butoxypropylamine, 198.2 ml of triethylamine, and 840 ml of toluene, 300.0 g of orthonitrobenzenesulfonyl chloride was added little by little while stirring with ice cooling. The temperature of the reaction system was raised to 40 ° C. and further stirred for 1 hour. Hydrochloric acid (50 ml) and water (750 ml) were added for liquid separation, and the organic layer was washed with sodium bicarbonate water (750 ml) to obtain a reaction solution of compound (A-1).

  To the mixture of 8.5 g of 10% Pd / C and 50 ml of water, the reaction solution of the compound (A-1) and 100 ml of toluene were added, and at 40 ° C., 165 g of 80% hydrazine hydrate and 50 ml of water were added for 1 hour. The mixture was added dropwise and stirred at 45 ° C. for 1 hour. The mixture was washed with 350 ml of toluene, washed with 350 ml of toluene, 500 ml of isopropanol, and 1.5 l of water and then separated. The organic layer was washed twice with 500 ml of water to obtain a reaction solution of compound (A-2). After concentration under reduced pressure and distilling off 800 ml of the solvent, 400 ml of toluene, 305.7 g of ethyl 3,3-diethoxyacrylate, and 2.6 g of p-toluenesulfonic acid monohydrate were added and stirred at 85 ° C. for 30 minutes. . Further, 13.8 g of 90% sodium ethoxide was added, and the mixture was heated and stirred at 120 ° C. for 4 hours. After cooling, 25 ml of hydrochloric acid and 500 ml of water were added for liquid separation, and further 50 g of p-toluenesulfonic acid monohydrate and 500 ml of water were added for washing. After concentration under reduced pressure to distill off the solvent, 600 ml of methanol and 30 ml of water were added for crystallization, and 100 ml of methanol and 110 ml of water were further added dropwise to cool to 0 ° C. Suction filtration and washing with methanol-water gave 440.1 g of compound (A-3).

  A solution of 470 g of 4-t-butyl-2-nitrochlorobenzene and 14 g of tetrabutylammonium in 450 ml of toluene is added with a solution of 132 g of sodium hydroxide in 450 ml of water in a nitrogen atmosphere, and 330 g of 2-ethylhexanethiol is added at 70 ° C. for 1 hour and a half. Then, the mixture was further heated and stirred at 70 ° C. for 1 hour, and then 400 ml of toluene was added for liquid separation, and the organic solvent layer was washed twice with water to obtain a reaction solution of compound (A-4).

  All the reaction liquid of the compound (A-4), 10 g of Raney nickel, and 1500 ml of methanol were placed in an autoclave, pressurized through hydrogen, and stirred at 90 ° C. for 6 hours while replenishing. The catalyst was removed by suction filtration through Celite, and toluene and water were added to the filtrate for liquid separation, and the organic solvent layer was washed with water. The solvent was distilled off under reduced pressure to obtain 620 g of an oily product of compound (A-5).

  A mixture of 110 g of compound (A-3), 84.5 g of compound (A-5) and 200 ml of xylene was heated and stirred for 6 hours at 145 to 150 ° C. while occasionally removing the solvent under reduced pressure. A crude product was obtained. To this reaction crude product, 300 ml of toluene was added, and 43.6 g of 1,3-dibromo-5,5-dimethylhydantoin was added over 15 minutes with stirring under ice cooling. After stirring at room temperature for 1 hour, water was added for liquid separation, and the organic layer was washed with water to obtain a reaction solution of compound (A-8).

  All reaction liquids of the compound (A-8) synthesized previously in a mixture of 39.0 g of 5,5-dimethyloxazolidine-2,4-dione, 41.8 g of potassium carbonate, and 150 ml of N, N-dimethylacetamide at room temperature. Was added dropwise over 30 minutes, and then the temperature was raised to 50 ° C. and stirred for 2 hours. The organic layer was separated, and the organic layer was washed with 0.1 N aqueous potassium hydroxide, dilute hydrochloric acid and water. The solvent was distilled off under reduced pressure, and crystallization from a methanol solvent gave 172.0 g of coupler (2).

  In the present invention, a silver halide color photographic light-sensitive material (hereinafter sometimes simply referred to as “photosensitive material”) contains a silver halide emulsion layer containing a yellow dye-forming coupler and a magenta dye-forming coupler on a support. A silver halide color photographic material having at least one silver halide emulsion layer and a silver halide emulsion layer containing a cyan dye-forming coupler is preferably used.

  In the present invention, the silver halide emulsion layer containing the yellow dye-forming coupler contains a yellow coloring layer, and the silver halide emulsion layer containing the magenta dye-forming coupler contains a magenta coloring layer and the cyan dye-forming coupler. The silver halide emulsion layer functions as a cyan coloring layer. The silver halide emulsion contained in each of the yellow coloring layer, the magenta coloring layer, and the cyan coloring layer is sensitive to light in different wavelength regions (for example, light in the blue region, green region, and red region). It is preferable to have.

  The light-sensitive material of the present invention may have a hydrophilic colloid layer, an antihalation layer, an intermediate layer, and a colored layer, which will be described later, if desired, in addition to the yellow coloring layer, magenta coloring layer, and cyan coloring layer.

In the silver halide photographic light-sensitive material of the present invention, the yellow dye-forming coupler of the present invention is preferably added in an amount of 1 × 10 ⁻³ to 1 mol per mol of silver halide, and 2 × 10 ^{−3 to} 3 × 10. ^It is more preferable to add ^-1 mol.
The silver halide photographic light-sensitive material of the present invention preferably contains at least one yellow dye-forming coupler in at least one layer on the support.

The silver halide light-sensitive material preferably used in the present invention will be described in detail below.
The silver halide color photographic light-sensitive material preferably used in the present invention is applied to a light-sensitive material using a coupler. In particular, color negative film for general use or movie, color reversal film for slide or television, color paper (printing paper), color positive film for general use or movie, photosensitive material for display, color reversal paper, scanning exposure or surface exposure The present invention can be applied to various color light-sensitive materials such as color proof materials and monochrome light-sensitive materials using couplers. Further, the color negative film is suitable for the film unit with a lens described in Japanese Patent Publication No. 2-332615 and Japanese Utility Model Publication No. 3-39784.
Among these, a silver halide color photographic light-sensitive material that an observer directly observes, for example, a color reversal film for slide or television, a color paper (printing paper), a color positive film for general use or a movie, a light-sensitive material for display, Color reversal paper, color proof for scanning exposure or surface exposure is preferable, color paper (photographic paper), color positive film for general use or movie, photosensitive material for display, color reversal paper, color proof for scanning exposure or surface exposure Further preferred are color paper (photographic paper), photosensitive material for display, and color proof for scanning exposure.

  The silver halide grains in the silver halide emulsion used in the present invention are preferably substantially cubic or tetradecahedral crystal grains having {100} faces (these grains have rounded vertices and higher order faces. Or tabular grains having an aspect ratio of 2 or more in which 50% or more of the total projected area is composed of {100} faces or {111} faces. The aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of the particle. In the present invention, cubic particles, tabular grains having a {100} plane as a main plane, or tabular grains having a {111} plane as a main plane are preferably applied.

  As the silver halide emulsion used in the present invention, silver chloride, silver bromide, silver iodobromide, silver salt (iodo) bromide emulsion, etc. are used. From the viewpoint of rapid processability, the silver chloride content is low. Silver chloride, silver chlorobromide, silver chloroiodide, or silver chlorobromoiodide emulsions of 90 mol% or more are preferred, and silver chloride, silver chlorobromide, chloroiodination having a silver chloride content of 98 mol% or more Silver or silver chlorobromoiodide emulsions are preferred. Among such silver halide emulsions, 0.01 to 0.50 mol%, more preferably 0.05 to 0.40 mol% of silver iodide per mol of silver is contained in the shell portion of the silver halide grains. Thus, those having a silver chloroiodide phase are preferable because high sensitivity can be obtained and exposure to high illumination is excellent. Further, the silver halide grains having a silver bromide localized phase on the surface of the silver halide grains so that the silver bromide is 0.2 to 5 mol%, more preferably 0.5 to 3 mol% per mol of total silver, This is particularly preferable since high sensitivity can be obtained and photographic performance can be stabilized.

  The emulsion of the present invention preferably contains silver iodide. For the introduction of iodide ions, an iodide salt solution may be added alone, or an iodide salt solution may be added together with the addition of a silver salt solution and a high chloride salt solution. In the latter case, the iodide salt solution and the high chloride salt solution may be added separately or as a mixed solution of iodide salt and high chloride salt. The iodide salt is added in the form of a soluble salt such as an alkali or alkaline earth iodide salt. Alternatively, iodide can be introduced by cleaving iodide ions from organic molecules described in US Pat. No. 5,389,508. As another iodide ion source, fine silver iodide grains can be used.

  The addition of the iodide salt solution may be concentrated at one time of grain formation or may be performed over a certain period. The position of introduction of iodide ions into the high chloride emulsion is limited in obtaining an emulsion with high sensitivity and low covering. Iodide ions are introduced more into the emulsion grains and the increase in sensitivity is smaller. Therefore, the iodide salt solution is preferably added outside 50% of the grain volume, more preferably outside 70%, and most preferably outside 80%. The addition of the iodide salt solution is preferably completed within 98% of the grain volume, and most preferably within 96%. The addition of the iodide salt solution is completed slightly inside from the grain surface, so that an emulsion with higher sensitivity and lower covering can be obtained.

  For the distribution of iodide ion concentration in the depth direction within the grains, etching / TOF-SIMS (Time of Flight-Secondary Ion Mass Spectrometry) method is used, for example, TRIFT II type TOF-SIMS (trade name) manufactured by Phi Evans. Can be measured. The TOF-SIMS method is specifically described in “Surface Analysis Technology Selection, Secondary Ion Mass Spectrometry” Maruzen Co., Ltd. (1999), edited by the Surface Science Society of Japan. When the emulsion grains are analyzed by the etching / TOF-SIMS method, it is possible to analyze that iodide ions ooze out toward the grain surface even when the addition of the iodide salt solution is finished inside the grains. When the emulsion of the present invention contains silver iodide, the iodide ion has a concentration maximum on the grain surface and the iodide ion concentration is attenuated inward by analysis by etching / TOF-SIMS method. Is preferred.

The silver halide grains of the silver halide emulsion in the light-sensitive material of the present invention preferably have a silver bromide localized layer.
When the silver halide grains of the present invention contain a silver bromide localized phase, it is preferable that the silver bromide localized phase having a silver bromide content of at least 10 mol% is epitaxially grown on the grain surface. Moreover, it is preferable to have the outermost layer shell portion having a silver bromide content of 1 mol% or more in the vicinity of the surface layer.
The silver bromide content of the silver bromide localized phase is preferably in the range of 1 to 80 mol%, and most preferably in the range of 5 to 70 mol%. The silver bromide localized phase is preferably composed of 0.1 to 30 mol% of silver constituting the silver halide grains in the present invention, and is preferably composed of 0.3 to 20 mol% of silver. More preferably, it is configured. The silver bromide localized phase preferably contains a Group VIII metal complex ion such as an iridium ion. The amount of these compounds added varies widely depending on the purpose, but is preferably 10 ^-9 to 10 ^-2 mol per mol of silver halide.

In the present invention, it is preferable to add metal ions in the process of forming and / or growing silver halide grains to incorporate the metal ions into and / or on the surface of the silver halide grains. As the metal ion to be used, a transition metal ion is preferable, and iron, ruthenium, iridium, osmium, lead, cadmium, or zinc is particularly preferable. Further, these metal ions are more preferably used as a hexacoordinate octahedral complex with a ligand. When an inorganic compound is used as a ligand, cyanide ion, halide ion, thiocyan, hydroxide ion, peroxide ion, azide ion, nitrite ion, water, ammonia, nitrosyl ion, or thiol Nitrosyl ions are preferably used. These ligands are also preferably used by being coordinated to any of the above metal ions of iron, ruthenium, iridium, osmium, lead, cadmium, or zinc. It is also preferable to use it inside.
Among these, the silver halide grains of the silver halide emulsion of the present invention particularly preferably have iridium ions having at least one organic ligand for the purpose of improving high-illuminance reciprocity failure.
When an organic compound is used as the ligand, it is common to other transition metals, but preferred organic compounds include a chain compound having 5 or less carbon atoms in the main chain and / or a 5-membered ring or a 6-membered ring. The heterocyclic compound can be mentioned. More preferred organic compounds are compounds having a nitrogen atom, phosphorus atom, oxygen atom or sulfur atom in the molecule as a coordination atom to the metal, most preferably furan, thiophene, oxazole, isoxazole, thiazole, isothiazole. , Imidazole, pyrazole, triazole, furazane, pyran, pyridine, pyridazine, pyrimidine, and pyrazine, and compounds in which these compounds are used as a basic skeleton and substituents are introduced into them are also preferable.
Among these, a preferred ligand for iridium ions is particularly preferably 5-methylthiazole among thiazole ligands.

As a combination of a metal ion and a ligand, a combination of iron ion, ruthenium ion and cyanide ion is preferable. In these compounds, the cyanide ion preferably accounts for a majority of the coordination number to iron or ruthenium as the central metal, and the remaining coordination sites are thiocyan, ammonia, water, nitrosyl ion, dimethyl sulfoxide, pyridine, pyrazine. Or preferably 4,4′-bipyridine. Most preferably, all six coordination sites of the central metal are occupied by cyanide ions to form a hexacyanoiron complex or a hexacyanoruthenium complex. Complexes are preferably added 1 × 10 ^-8 mol to 1 × 10 ^-2 mol per mol of silver in the grain formation for these cyanide ion as a ligand, 1 × 10 ^-6 mol to 5 × 10 ^- It is most preferable to add ⁴ moles.
As the iridium ion, it is preferable to use not only an organic ligand but also a fluoride ion, a chloride ion, a bromide ion, and an iodide ion, and particularly a chloride ion or a bromide ion. As the iridium complex, the following specific compounds can be used in addition to those having the above-mentioned organic ligands. [IrCl ₆ ] ^3- , [IrCl ₆ ] ^2- , [IrCl ₅ (H ₂ O)] ^2- , [IrCl ₅ (H ₂ O)] ^- , [IrCl ₄ (H ₂ O) ₂ ] ^- , [ IrCl ₄ (H ₂ O) ₂ ] ⁰ , [IrCl ₃ (H ₂ O) ₃ ] ⁰ , [IrCl ₃ (H ₂ O) ₃ ] ⁺ , [IrBr ₆ ] ^3- , [IrBr ₆ ] ^2- , [ IrBr ₅ (H ₂ O)] ^2- , [IrBr ₅ (H ₂ O)] ^- , [IrBr ₄ (H ₂ O) ₂ ] ^- , [IrBr ₄ (H ₂ O) ₂ ] ⁰ , [IrBr ₃ ( H ₂ O) ₃ ] ⁰ , and [IrBr ₃ (H ₂ O) ₃ ] ⁺ . These iridium complexes are preferably added in an amount of 1 × 10 ⁻¹⁰ mol to 1 × 10 ⁻³ mol per mol of silver during grain formation, most preferably 1 × 10 ⁻⁸ mol to 1 × 10 ⁻⁵ mol. preferable.
When ruthenium and osmium are used as the central metals, it is also preferable to use nitrosyl ions, thionitrosyl ions, or water molecules and chloride ions as ligands. More preferably, a pentachloronitrosyl complex, a pentachlorothionitrosyl complex, or a pentachloroaqua complex is formed, and a hexachloro complex is also preferably formed. These complexes are preferably added in an amount of 1 × 10 ⁻¹⁰ mol to 1 × 10 ⁻⁶ mol, more preferably 1 × 10 ⁻⁹ mol to 1 × 10 ⁻⁶ mol, per mol of silver during grain formation. It is.

  In the present invention, the above complex is added directly to the reaction solution at the time of silver halide grain formation, added to an aqueous halide solution for forming silver halide grains, or added to other solutions to obtain a grain formation reaction. It is preferably incorporated into the silver halide grains by adding to the solution. Furthermore, it is also preferable that these methods are combined and contained in the silver halide grains.

  When these complexes are incorporated into silver halide grains, it is preferable that they be uniformly present inside the grains, but these are disclosed in JP-A-4-208936, JP-A-2-125245, and JP-A-3-188437. As described above, it is also preferable to make it exist only in the particle surface layer, and it is also preferable to add a layer containing no complex only on the particle surface and containing no complex on the particle surface. Further, as disclosed in US Pat. Nos. 5,252,451 and 5,256,530, physical ripening is performed with fine particles in which the complex is incorporated in the particles to modify the particle surface phase. It is also preferable. Furthermore, these methods can be used in combination, and a plurality of types of complexes may be incorporated in one silver halide grain. The halogen composition at the position where the above complex is contained is not particularly limited, and the silver chloride layer, the silver chlorobromide layer, the silver bromide layer, the silver iodochloride layer, and the silver iodobromide layer should each contain the complex. Is also preferable.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grains and the number average thereof) is 0.01 μm to 2 μm. Is preferred.
The particle size distribution is preferably a so-called monodispersed material having a coefficient of variation (the standard deviation of the particle size distribution divided by the average particle size) of 20% or less, desirably 15% or less, more preferably 10% or less. . At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above-mentioned monodispersed emulsions by blending them in the same layer or to coat them in multiple layers.

  Various compounds or precursors thereof are added to the silver halide emulsion used in the present invention for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing the photographic performance. be able to. Specific examples of these compounds are preferably those described in JP-A-62-215272, pages 39 to 72. Further, 5-arylamino-1,2,3,4-thiatriazole compounds described in EP 0447647 (the aryl residue has at least one electron-withdrawing group) are also preferably used.

  In the present invention, in order to improve the storage stability of the silver halide emulsion, the hydroxamic acid derivative described in JP-A No. 11-109576 and the carbonyl group described in JP-A No. 11-327094 are adjacent to both ends of an amino group. Alternatively, cyclic ketones having a double bond substituted with a hydroxyl group (particularly those represented by general formula (S1), paragraph numbers 0036 to 0071 can be incorporated in the present specification), JP-A-11- 143011-substituted sulfo-catechol and hydroquinones (for example, 4,5-dihydroxy-1,3-benzenedisulfonic acid, 2,5-dihydroxy-1,4-benzenedisulfonic acid, 3,4-dihydroxybenzenesulfone) Acid, 2,3-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzenesulfonic acid, 3,4,5 Such trihydroxybenzene acid and salts thereof), water-soluble reducing agents represented by the general formula of JP-A-11-102045 (I) ~ (III) is also preferably used in the present invention.

Spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength range for each layer of emulsion in the light-sensitive material of the present invention.
In the light-sensitive material of the present invention, examples of spectral sensitizing dyes used for spectral sensitization in the blue, green, and red regions include, for example, Heterocyclic compounds-Cyanine dyes and related compounds (John Wiley & Sons [New York, London] Published in 1964). As specific examples of compounds and spectral sensitization, those described in JP-A-62-215272, page 22, right upper column to page 38 are preferably used. In particular, as a red-sensitive spectral sensitizing dye for silver halide emulsion grains having a high silver chloride content, the spectral sensitizing dye described in JP-A-3-123340 is stable, the strength of adsorption, and the exposure temperature. This is very preferable from the viewpoint of dependency and the like.

The amount of these spectral sensitizing dyes to be added varies widely depending on the case, and is preferably in the range of 0.5 × 10 ⁻⁶ mol to 1.0 × 10 ⁻² mol per mol of silver halide. More preferably, it is in the range of 1.0 × 10 ⁻⁶ mol to 5.0 × 10 ⁻³ mol.

  The silver halide emulsion used in the present invention is usually subjected to chemical sensitization. Regarding chemical sensitization, sulfur sensitization represented by addition of unstable sulfur compounds, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As compounds used for chemical sensitization, those described in JP-A-62-215272, from page 18, right lower column to page 22, upper right column are preferably used. Of these, gold sensitization is particularly preferred. This is because by performing gold sensitization, fluctuations in photographic performance when scanning exposure is performed with laser light or the like can be further reduced.

  In order to perform gold sensitization on the silver halide emulsion used in the present invention, various inorganic gold compounds, gold (I) complexes having inorganic ligands, and gold (I) compounds having organic ligands are used. be able to. Examples of the inorganic gold compound include chloroauric acid or a salt thereof, and a gold (I) complex having an inorganic ligand, for example, a gold dithiocyanate such as gold (I) potassium dithiocyanate or gold (I) 3 dithiosulfate. It is preferable to use a compound such as a gold dithiosulfate compound such as sodium.

Examples of the gold (I) compound having an organic ligand include bisgold (I) mesoionic heterocycles described in JP-A-4-267249, such as gold (I) tetrafluoroborate bis (1,4,5- Trimethyl-1,2,4-triazolium-3-thiolate), organic mercaptogold (I) complexes described in JP-A-11-218870, such as potassium bis (1- [3- (2-sulfonatebenzamide) phenyl] -5-mercaptotetrazole potassium salt) Aurate (I) pentahydrate, gold (I) compound coordinated with nitrogen compound anion described in JP-A-4-268550, for example, bis (1-methylhydantoinato) Gold (I) sodium salt tetrahydrate can be used. Further, gold (I) thiolate compounds described in US Pat. No. 3,503,749, gold compounds described in JP-A-8-69074, JP-A-8-69075, and JP-A-9-269554, The compounds described in Patent Nos. 5,620,841, 5,912,112, 5,620,841, 5,939,245, and 5,912,111 are also used. be able to.
The amount of these compounds added may vary widely depending on the case, but is 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol per mol of silver halide. is there.

Colloidal gold sulfide can also be used, and the manufacturing method thereof is Research Disclosure (37154), Solid State Ionics 79, 60-66, 1995, Compt. Rend.Hebt.Seances Acad.Sci.Sect.B, 263, 1328, published in 1966. Various sizes of colloidal gold sulfide can be used, and those having a particle size of 50 nm or less can also be used. The addition amount can vary widely depending on the case, but is 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol as a gold atom per mol of silver halide. .
In the present invention, gold sensitization may be combined with other sensitization methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, or noble metal sensitization using other than gold compounds.

  In the light-sensitive material according to the present invention, a hydrophilic colloid layer is used for the purpose of preventing irradiation and halation, improving the safety light safety, etc., as described on pages 27 to 76 of European Patent 0337490A2, It is preferable to add a dye (in particular, an oxonol dye or a cyanine dye) that can be decolored by treatment. Furthermore, the dyes described in EP 0819977 are also preferably added to the present invention. Some of these water-soluble dyes degrade color separation and safelight safety when the amount used is increased. As the dye that can be used without deteriorating color separation, water-soluble dyes described in JP-A Nos. 5-127324, 5-127325, and 5-216185 are preferable.

  In the present invention, a colored layer that can be decolored by treatment is used in place of the water-soluble dye or in combination with the water-soluble dye. The colored layer that can be decolored by the treatment used may be in direct contact with the emulsion layer, or may be disposed so as to be in contact with an intermediate layer containing a treatment color mixing inhibitor such as gelatin or hydroquinone. This colored layer is preferably placed under the emulsion layer (support side) that develops the same primary color as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to select and install only some of them. It is also possible to install a colored layer that has been colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is the wavelength having the highest optical density in the wavelength range used for exposure (visible light range of 400 nm to 700 nm for normal printer exposure, wavelength of the scanning exposure light source used for scanning exposure). The optical density value at is preferably 0.2 or more and 3.0 or less. More preferably 0.5 or more and 2.5 or less, and particularly preferably 0.8 or more and 2.0 or less.

  In order to form the colored layer, a conventionally known method can be applied. For example, the dyes described in JP-A-2-282244, page 3, upper right column to page 8 and those described in JP-A-3-7931, page 3, upper right column to page 11, lower left column, can be used for solid fine particle dispersions. Described in JP-A-1-239544, a method of incorporating a hydrophilic colloid layer in a state, a method of mordanting an anionic dye into a cationic polymer, a method of adsorbing a dye to fine particles such as silver halide and fixing it in the layer Such as using colloidal silver. As a method of dispersing a fine powder of a pigment in a solid state, for example, a method of containing a fine powder dye which is substantially water-insoluble at least at pH 6 or less but is substantially water-soluble at least at pH 8 or more is disclosed in Japanese Patent Application Laid-Open No. Hei. 2-308244, pages 4-13. Further, for example, a method for mordanting an anionic dye into a cationic polymer is described on pages 18 to 26 of JP-A-2-84737. US Pat. Nos. 2,688,601 and 3,459,563 show methods for preparing colloidal silver as a light absorber. Among these methods, a method of containing a fine powder dye and a method of using colloidal silver are preferable.

  When the present invention is applied to color photographic paper, it may have at least one yellow color-developing silver halide emulsion layer, magenta color-developing silver halide emulsion layer, and cyan color-developing silver halide emulsion layer. In general, these silver halide emulsion layers are, in order from the support, a yellow color-forming silver halide emulsion layer, a magenta color-forming silver halide emulsion layer, and a cyan color-forming silver halide emulsion layer.

However, a different layer structure may be used.
In the light-sensitive material of the present invention, the silver halide emulsion layer containing a yellow coupler may be disposed at any position on the support, but when the yellow coupler-containing layer contains silver halide tabular grains. The magenta coupler-containing silver halide emulsion layer or the cyan coupler-containing silver halide emulsion layer is preferably coated at a position farther from the support than at least one layer. Further, from the viewpoints of accelerating color development, accelerating desilvering, and reducing residual color by sensitizing dye, the yellow coupler-containing silver halide emulsion layer is coated at a position farthest from the support than other silver halide emulsion layers. It is preferable to be provided. Further, from the viewpoint of reducing Blix fading, the cyan coupler-containing silver halide emulsion layer is preferably the center layer of other silver halide emulsion layers, and from the viewpoint of reducing photobleaching, the cyan coupler-containing silver halide emulsion layer is The lowest layer is preferred. Each of the color developing layers of yellow, magenta and cyan may be composed of two layers or three layers. For example, as described in JP-A-4-75055, 9-1114035, 10-246940, US Pat. No. 5,576,159, etc., a coupler layer containing no silver halide emulsion is used as a silver halide. It is also preferable to provide a color developing layer adjacent to the emulsion layer.

  Here, it is common to provide a hydrophilic colloid layer between each color-forming silver halide emulsion layer and on the opposite side to the support of the color-forming silver halide emulsion layer farthest from the support. It is also a preferred embodiment of the present invention to provide a hydrophilic colloid layer between the support and the color-forming silver halide emulsion layer closest to the support. These layers are described in US Pat. No. 5,393,571 and the like. It is preferable to apply simultaneously (preferably by a curtain coating method) by the method described.

  As silver halide emulsions and other materials (additives, etc.) and photographic composition layers (layer arrangement, etc.) applied in the present invention, and processing methods and processing additives applied to process this photosensitive material, And those described in JP-A-62-215272, JP-A-2-33144 and European Patent 0,355,660A2, particularly those described in European Patent 0,355,660A2. . Furthermore, JP-A-5-34889, JP-A-4-359249, JP-A-4-313733, JP-A-4-270344, JP-A-5-66527, JP-A-4-34548, JP-A-4-145433, JP-A-2-854. The silver halide color photographic light-sensitive materials and the processing methods thereof described in JP-A Nos. 1-158431, 2-90145, 3-194539, 2-93641, and European Patent Publication No. 0520457A2 are also preferable.

  In particular, in the present invention, a reflective support, a silver halide emulsion, a different metal ion species doped in the silver halide grains, a storage stabilizer or antifoggant for the silver halide emulsion, and a chemical sensitization method. (Sensitizer), spectral sensitization method (spectral sensitizer), cyan, magenta, yellow coupler and emulsifying dispersion method thereof, color image preservability improving agent (stain inhibitor and anti-fading agent), dye (colored layer) As for the gelatin type, the layer structure of the photosensitive material, the coating pH of the photosensitive material, and the like, those described in each part of the publications shown in the following table can be particularly preferably applied.

Other examples of the cyan, magenta and yellow couplers used in the present invention include those described in JP-A-62-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6; JP-A-2-33144, No. 3; Page 14 upper right column 14th line to 18th page upper left column last line, page 30 upper right column 6th line to page 35 lower right column 11th line, EP0355,660A2 page 4, 15th line to 27th line, 5th page Couplers described on page 30 to the end of page 28, page 45, line 29 to line 31, page 47, line 23 to page 63, line 50 are also useful.
In the present invention, compounds represented by general formulas (II) and (III) of WO98 / 33760 and general formula (D) of JP-A-10-221825 may be preferably added.

  As a cyan dye-forming coupler (sometimes simply referred to as “cyan coupler”) that can be used in the present invention, a pyrrolotriazole coupler is preferably used, and is represented by the general formula (I) or (II) of JP-A-5-313324. And couplers represented by general formula (I) of JP-A-6-347960 and the exemplified couplers described in these patents are particularly preferred. Phenol-based and naphthol-based cyan couplers are also preferable. For example, cyan couplers represented by the general formula (ADF) described in JP-A-10-333297 are preferable. Other cyan couplers include pyrroloazole type cyan couplers described in EP 0488248 and EP 0491197A1, 2,5-diacylaminophenol couplers described in US Pat. No. 5,888,716, US Pyrazoloazole type cyan couplers having an electron withdrawing group and a hydrogen bonding group at the 6-position described in Japanese Patent Nos. 4,873,183 and 4,916,051, particularly JP-A-8-171185, Pyrazoloazole type cyan couplers having a carbamoyl group at the 6-position described in JP-A Nos. 8-311360 and 8-339060 are also preferable.

  In addition to the diphenylimidazole cyan coupler described in JP-A-2-33144, 3-hydroxypyridine cyan couplers described in European Patent 0333185A2 (among others, couplers (42) listed as specific examples) And a cyclic active methylene-based cyan coupler described in JP-A No. 64-32260 or a coupler obtained by adding a chlorine leaving group to a 2-equivalent coupler (2), couplers (6) and (9) are particularly preferable) Among them, coupler examples 3, 8, and 34 listed as specific examples are particularly preferable), pyrrolopyrazole type cyan couplers described in EP 0456226A1 and pyrroloimidazole type cyan couplers described in EP 0484909 are used. You can also.

  Of these cyan couplers, pyrroloazole cyan couplers represented by the general formula (I) described in JP-A No. 11-282138 are particularly preferred. The couplers (1) to (47) are applied as they are to the present invention and are preferably incorporated as a part of the present specification.

  Examples of the magenta dye-forming coupler used in the present invention (sometimes simply referred to as “magenta coupler”) include 5-pyrazolone-based magenta couplers and pyrazoloazole-based magenta couplers described in the publicly known literatures in the above table. Among them, a secondary or tertiary alkyl group as described in JP-A-61-65245 is located at the 2, 3, or 6 position of the pyrazolotriazole ring, particularly in terms of hue, image stability, color developability and the like. Directly linked pyrazolotriazole couplers, pyrazoloazole couplers containing a sulfonamide group in the molecule as described in JP-A-61-65246, and alkoxyphenyl sulfones as described in JP-A-61-147254 Pyrazoloazole couplers having amide ballast groups and European Patent Nos. 226,849A and 294,785 Use of pyrazoloazole couplers having an alkoxy group or an aryloxy group at the 6-position as described in JP. In particular, the magenta coupler is preferably a pyrazoloazole coupler represented by the general formula (M-I) described in JP-A-8-122984. Paragraph Nos. 0009 to 0026 of the patent are directly applied to the present invention. Incorporated as part of the specification. In addition, pyrazoloazole couplers having sterically hindered groups at both the 3-position and the 6-position described in European Patent Nos. 854384 and 844640 are also preferably used.

  The yellow dye-forming coupler of the present invention may be used alone or in combination with other yellow dye-forming couplers. Examples of yellow dye-forming couplers that may be used in combination (in the present specification, sometimes simply referred to as “yellow couplers”) include the acyl groups described in EP 0447969A1 in addition to the compounds described in the above table. An acylacetamide type yellow coupler having a 3- to 5-membered cyclic structure, a malondianilide type yellow coupler having a cyclic structure described in European Patent No. 0482552A1, European Patent Nos. 935870A1, 953871A1, Pyrrole-2 or 3-yl or indole-2 or 3-ylcarbonylacetate anilide couplers described in US Pat. No. 5,118,599, U.S. Pat. No. 953872A1, 953873A1, 953874A1, and 953875A1. The dioxane structure described in the specification An acylacetamide type yellow coupler having is preferably used. Among them, the use of an acylacetamide type yellow coupler in which the acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide type yellow coupler in which one of the anilides constitutes an indoline ring is particularly preferred.

  Couplers for use in the present invention include loadable latex polymers (eg, US Pat. No. 4,203,716) in the presence (or absence) of high-boiling organic solvents described below, including the yellow dye-forming couplers of the present invention. It is preferably impregnated in a water-insoluble and organic solvent-soluble polymer and then emulsified and dispersed in a hydrophilic colloidal aqueous solution. Water-insoluble and organic solvent-soluble polymers that can be preferably used are described in U.S. Pat. No. 4,857,449, columns 7 to 15, and International Publication WO 88/00723, pages 12 to 30. The described homopolymers or copolymers are mentioned. More preferably, use of a methacrylate or acrylamide polymer, particularly an acrylamide polymer is preferred in view of color image stability.

  High-boiling organic solvents that can be used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, etc.), phosphoric acid or phosphonic acid esters (phosphoric acid). Triphenyl, tricresyl phosphate, tri-2-ethylhexyl phosphate, etc.), fatty acid esters (di-2-ethylhexyl succinate, tributyl citrate, etc.), benzoates (2-ethylhexyl benzoate, dodecyl benzoate, etc.) ), Amides (N, N-diethyldodecanamide, N, N-dimethyloleinamide, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), anilines (N, N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), salt Paraffins, hydrocarbons (dodecylbenzene, diisopropylnaphthalene, etc.), carboxylic acids (2- (2,4-di -tert- amylphenoxy) butyric acid and the like) and the like. Further, an organic solvent having a boiling point of 30 ° C. or higher and 160 ° C. or lower (ethyl acetate, butyl acetate, methyl ethyl ketone, cyclohexanone, methyl cellosolve acetate, dimethylformamide, etc.) may be used in combination as an auxiliary solvent. The high-boiling organic solvent is preferably used in an amount of 0 to 10 times, preferably 0 to 4 times the mass of the coupler.

From the viewpoint of improving stability over time during storage in the emulsion dispersion state, suppressing photographic performance changes in the final coating composition mixed with emulsion, and improving stability over time, the emulsion dispersion may be reduced in pressure as necessary. All or part of the auxiliary solvent can be removed by a method such as distillation, washing with noodles or ultrafiltration.
The average particle size of the lipophilic fine particle dispersion thus obtained is preferably 0.04 to 0.50 μm, more preferably 0.05 to 0.30 μm, and most preferably 0.08 to 0.20 μm. It is. The average particle size can be measured using a Coulter submicron particle analyzer model N4 (Coulter Electronics, trade name).

In the present invention, any color mixing inhibitor can be used, and among these, those described in the following publications are preferred.
For example, high molecular weight redox compounds described in JP-A-5-333501, phenidone and hydrazine compounds described in WO98 / 33760, U.S. Pat. No. 4,923,787, JP-A-5-249637, White couplers described in JP-A-10-282615 and German Patent No. 19629142A1 can be used. In particular, in the case of increasing the pH of the developer and speeding up development, German Patent No. 19618786A1, European Patent No. 839623A1, European Patent No. 842975A1, German Patent No. 19804646A1 and French Patent No. 2760460A1. It is also preferable to use the redox compound described in No. etc.

  In the present invention, a compound having a triazine skeleton with a high molar extinction coefficient is preferably used as the ultraviolet absorber, and for example, compounds described in the following patents can be used. These are preferably added to the photosensitive layer and / or non-photosensitive. For example, JP-A-46-3335, JP-A-55-15276, JP-A-5-197004, JP-A-5-232630, JP-A-5-307232, JP-A-6-21813, JP-A-8-53427, and 8- No. 234364, No. 8-239368, No. 9-31067, No. 10-115898, No. 10-147777, No. 10-182621, German Patent No. 19739797A, European Patent No. The compounds described in 501291 etc. can be used.

As the binder or protective colloid that can be used in the light-sensitive material according to the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. As a preferable gelatin, the heavy metal contained as impurities such as iron, copper, zinc and manganese is preferably 5 ppm or less, more preferably 3 ppm or less. The amount of calcium contained in the light-sensitive material is preferably 20 mg / m ² or less, more preferably 10 mg / m ² or less, and most preferably 5 mg / m ² or less.

  In the present invention, an antibacterial / antifungal agent as described in JP-A-63-271247 is added in order to prevent various wrinkles and bacteria that propagate in the hydrophilic colloid layer and degrade the image. Is preferred. Further, the film pH of the photosensitive material is preferably 4.0 to 7.0, more preferably 4.0 to 6.5.

In the present invention, a surfactant can be added to the photosensitive material from the viewpoints of improving the coating stability of the photosensitive material, preventing the generation of static electricity, and adjusting the charge amount. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a betaine surfactant, and a nonionic surfactant, and examples thereof include those described in JP-A-5-333492. The surfactant used in the present invention is preferably a fluorine atom-containing surfactant. In particular, a fluorine atom-containing surfactant can be preferably used. These fluorine atom-containing surfactants may be used alone or in combination with other conventionally known surfactants, but are preferably used in combination with other conventionally known surfactants. The amount of these surfactants added to the light-sensitive material is not particularly limited, but is generally 1 × 10 ^{−5 to} 1 g / m ² , preferably 1 × 10 ⁻⁴ to 1 × 10 ^{−. 1} g / m ² , more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² g / m ² .

  In the present invention, a transmissive support or a reflective support can be used as the photographic support. Transparent supports such as cellulose nitrate film and polyethylene terephthalate, as well as polyester of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG), and polyester of NDCA, terephthalic acid and EG For example, an information recording layer such as a magnetic layer is preferably used. As the reflective support, a reflective support that is laminated with a plurality of polyethylene layers or polyester layers and contains a white pigment such as titanium oxide in at least one of such a water-resistant resin layer (laminate layer) is preferable.

Furthermore, it is preferable to contain a fluorescent brightening agent in the water-resistant resin layer. Further, the fluorescent brightener may be dispersed in the hydrophilic colloid layer of the photosensitive material. As the optical brightener, benzoxazole-based, coumarin-based and pyrazoline-based compounds can be preferably used, and benzoxazolylnaphthalene-based and benzoxazolyl stilbene-based fluorescent whitening agents are more preferable. Although the usage-amount is not specifically limited, Preferably it is 1-100 mg / m < ² >. The mixing ratio in the case of mixing with a water resistant resin is preferably 0.0005 to 3% by mass, more preferably 0.001 to 0.5% by mass with respect to the resin.
The reflective support may be a transmissive support or a reflective colloid coated with a hydrophilic colloid layer containing a white pigment.
Further, the reflective support may be a support having a specular reflective or second-type diffuse reflective metallic surface.

  A more preferable reflective support in the present invention includes a polyolefin layer having fine pores on the paper substrate on the side on which the silver halide emulsion layer is provided. The polyolefin layer may consist of multiple layers, in which case the polyolefin layer adjacent to the gelatin layer on the silver halide emulsion layer side preferably has no micropores (eg polypropylene, polyethylene) and is close to the paper substrate More preferred is a polyolefin (for example, polypropylene or polyethylene) having micropores on the side. The density of the multi-layer or single-layer polyolefin layer located between the paper substrate and the photographic constituent layer is preferably 0.40 to 1.0 g / ml, more preferably 0.50 to 0.70 g / ml. In addition, the thickness of the multilayer or single polyolefin layer located between the paper substrate and the photographic constituent layer is preferably 10 to 100 μm, more preferably 15 to 70 μm. Further, the ratio of the thickness of the polyolefin layer to the paper substrate is preferably 0.05 to 0.5, and more preferably 0.1 to 0.2. In addition, it is also preferable to provide a polyolefin layer on the opposite side (back side) of the photographic constituent layer of the paper substrate from the viewpoint of increasing the rigidity of the reflective support, and in this case, the polyolefin layer on the back side has a matte surface. Polyethylene or polypropylene is preferred, and polypropylene is more preferred. The polyolefin layer on the back surface is preferably 5 to 50 μm, more preferably 10 to 30 μm, and further preferably the density is 0.7 to 1.1 g / ml. In the reflective support of the present invention, preferred embodiments relating to the polyolefin layer provided on the paper substrate are described in JP-A-10-333277, JP-A-10-333278, JP-A-11-52513, JP-A-11-65024, EP0880065. No. and examples described in EP 0880066.

The photosensitive material of the present invention can form an image by an exposure process in which light is irradiated according to image information and a development process in which the photosensitive material irradiated with light is developed.
The photosensitive material of the present invention is suitable for a scanning exposure system using a cathode ray (CRT) in addition to being used in a printing system using a normal negative printer. The cathode ray tube exposure apparatus is simpler and more compact and less expensive than an apparatus using a laser. Also, the adjustment of the optical axis and color is easy. As the cathode ray tube used for image exposure, various light emitters that emit light in the spectral region are used as necessary. For example, any one of red light emitters, green light emitters, and blue light emitters, or a mixture of two or more thereof may be used. The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in the yellow, orange, purple, or infrared region is also used. In particular, a cathode ray tube that emits white light by mixing these light emitters is often used.

  When the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions, and the cathode tube also has a phosphor exhibiting light emission in a plurality of spectral regions, a plurality of colors are exposed at the same time, that is, a plurality of colors are applied to the cathode ray tube. It is also possible to emit light from the tube surface by inputting a color image signal. A method of sequentially inputting image signals for each color to cause each color to emit light sequentially and exposing through a film that cuts the colors other than that color (surface sequential exposure) may be adopted. However, since a high-resolution cathode ray tube can be used, it is preferable for improving image quality.

  The photosensitive material of the present invention is a monochromatic high light source such as a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a second harmonic light source (SHG) using a combination of a solid state laser using a semiconductor laser and a nonlinear optical crystal. A digital scanning exposure method using density light is preferably used. In order to make the system compact and inexpensive, it is preferable to use a second harmonic generation light source (SHG) that combines a semiconductor laser, a semiconductor laser, or a solid-state laser and a nonlinear optical crystal. In particular, in order to design a compact, inexpensive, long-life and high-stability device, it is preferable to use a semiconductor laser, and at least one of the exposure light sources is preferably a semiconductor laser.

When such a scanning exposure light source is used, the spectral sensitivity maximum wavelength of the photosensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source to be used. In a solid laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal, the oscillation wavelength of the laser can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be given to the usual three wavelength regions of blue, green, and red. When the exposure time in such scanning exposure is defined as the exposure time of the pixel size when the pixel density is 400 dpi, the preferable exposure time is 10 ⁻⁴ seconds or less, more preferably 10 ⁻⁶ seconds or less.

  The silver halide color photographic light-sensitive material of the present invention can be preferably used in combination with the exposure and development system described in the following known documents. The developing system includes an automatic printing and developing system described in JP-A-10-333253, a photosensitive material conveying apparatus described in JP-A-2000-10206, and an image reading apparatus described in JP-A-11-215312. System, an exposure system comprising a color image recording system described in JP-A-11-88619 and JP-A-10-202950, a digital photo print system including a remote diagnosis system described in JP-A-10-210206, and Japanese Patent Application No. A photo print system including the image recording apparatus described in No. 10-159187 can be given.

  Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the table above.

When the light-sensitive material of the present invention is subjected to printer exposure, it is preferable to use a band stop filter described in US Pat. No. 4,880,726. This removes light color mixing and remarkably improves color reproducibility.
In the present invention, as described in European Patent Nos. 0789270A1 and 0789480A1, a yellow microdot pattern may be pre-exposed in advance and copy control may be performed before image information is given.

  In the processing of the photosensitive material of the present invention, JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-4-97355, page 5, upper left column, line 17 The processing materials and processing methods described in the 20th page, lower right column, line 20 are preferably applicable. Further, as the preservative used in the developer, compounds described in the patents listed in the above table are preferably used.

The present invention is preferably applied to a light-sensitive material having rapid processing suitability. In the case of rapid processing, the color development time is preferably 60 seconds or shorter, more preferably 50 seconds or shorter and 6 seconds or longer, more preferably 30 seconds or shorter and 6 seconds or longer. Similarly, the bleach-fixing time is preferably 60 seconds or shorter, more preferably 50 seconds or shorter and 6 seconds or longer, more preferably 30 seconds or shorter and 6 seconds or longer. Further, the washing time or stabilization time is preferably 150 seconds or shorter, more preferably 130 seconds or shorter and 6 seconds or longer.
The color development time refers to the time from when the photosensitive material enters the color developer until it enters the bleach-fixing solution in the next processing step. For example, in the case of processing with an automatic developing machine or the like, the time during which the photosensitive material is immersed in the color developer (so-called submerged time) and the photosensitive material leave the color developer and are bleached in the next processing step. The sum of both the time during which the toner is conveyed in the air toward the fixing bath (so-called air time) is referred to as color development time. Similarly, the bleach-fixing time refers to the time from when the photosensitive material enters the bleach-fixing solution until the next washing or stabilizing bath. The water washing or stabilization time refers to the time (so-called liquid time) that the photosensitive material is in the liquid for the drying process after entering the water washing or stabilizing liquid.

The light-sensitive material of the present invention can be developed after exposure using a conventional developing method containing an alkali agent and a developing agent, an activator such as an alkaline solution containing the developing agent in the photosensitive material and not containing the developing agent. In addition to a wet method such as a method of developing with a beta solution, a thermal development method that does not use a processing solution can be used. In particular, the activator method is a preferable method from the viewpoint of environmental protection because it does not contain a developing agent in the processing solution, so that the processing solution can be easily managed and handled, and the load during processing of the waste liquid is small.
In the activator method, examples of the developing agent incorporated in the light-sensitive material or a precursor thereof include, for example, JP-A-8-234388, JP-A-9-152686, JP-A-9-152893, JP-A-9-2111814, and JP-A-9-21814. The hydrazine type compound described in -160193 is preferable.

  Further, a developing method in which the amount of silver applied to the photosensitive material is reduced and image amplification processing (compensation processing) using hydrogen peroxide is preferably used. In particular, it is preferable to use this method for the activator method. Specifically, an image forming method using an activator solution containing hydrogen peroxide described in JP-A-8-297354 and 9-152695 is preferably used. In the activator method, after processing with an activator solution, desilvering is usually performed. However, in the image amplification processing method using a low silver amount of light-sensitive material, desilvering is omitted and washing or stabilization is simplified. Can be done. Further, in a method of reading image information from a photosensitive material with a scanner or the like, it is possible to adopt a processing form that does not require a desilvering process even when a high silver amount photosensitive material such as a photographic photosensitive material is used.

  For the activator solution, desilvering solution (bleaching / fixing solution), water washing and stabilizing solution used in the present invention, known processing materials and processing methods can be used. Preferably, those described in Research Disclosure Item 36544 (September 1994), pages 536 to 541 and JP-A-8-234388 can be used.

  When the configuration of the present invention is applied to color reversal, the contents described in the specification of JP-A-2001-142181 are preferably incorporated as part of the specification of the present invention.

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

[Example 1]
Preparation of sample 001 ( Preparation of blue-sensitive layer emulsion A)
Silver halide cubic grains having an average side length of 0.65 μm and a side length coefficient of variation of 8% and having a halogen composition of 98.9 mol% of silver chloride, 1 mol% of silver bromide, and 0.1 mol% of silver iodide were formed. . Spectral sensitizing dyes 1 and 2 were added at 2.5 × 10 ⁻⁴ mol / Ag mol and 2.0 × 10 ⁻⁴ mol / Ag mol, respectively.
In particle formation, K ₃ IrCl ₅ (H ₂ O), K ₄ Ru (CN) ₆ , K ₄ Fe (CN) ₆ , thiosulfonic acid compound-1, sodium thiosulfate, gold sensitizer-1, The optimum amount of mercapto compounds-1 and 2 was used.
In this way, high-sensitivity emulsion A-1 was prepared.
Similarly, cubic particles having an average side length of 0.50 μm and a side length variation coefficient of 9% were formed.
Spectral sensitization and chemical sensitization were carried out in amounts that were corrected to match the specific surface area (side length ratio 0.65 / 0.50 = 1.3 times) to produce low-sensitivity emulsion A-2.

(Preparation of emulsion C for green sensitive layer)
Except for lowering the temperature during grain formation and changing the type of sensitizing dye as described below, high-sensitivity emulsion C-1 for green-sensitive emulsion and low-sensitivity emulsion in the same manner as the preparation conditions of emulsions A-1 and A-2. C-2 was produced.

As for the particle size, the average side length is 0.40 μm on the sensitive side and the average side length is 0.30 μm on the low sensitive side. The coefficient of variation was 8% in all cases.
Sensitizing dye D per mole of silver halide is 3.0 × 10 ⁻⁴ mol for large size emulsions, 3.6 × 10 ⁻⁴ mol for small size emulsions, and sensitizing dye E Per mol of silver halide was added to 4.0 × 10 ⁻⁵ mol for large size emulsions and 7.0 × 10 ⁻⁵ mol for small size emulsions.

(Preparation of emulsion E for red-sensitive layer)
Except for lowering the temperature at the time of grain formation and changing the kind of sensitizing dye as follows, high-sensitivity emulsion E-1 for red-sensitive emulsion, low-sensitivity emulsion in the same manner as the preparation conditions of emulsions A-1 and A-2 E-2 was produced.

The particle size was 0.38 μm on the high sensitivity side and 0.32 μm on the low sensitivity side, and the coefficient of variation of the side length was 9% and 10%, respectively.
Sensitizing dyes G and H were added in an amount of 8.0 × 10 ⁻⁵ mol for a large emulsion and 10.7 × 10 ⁻⁵ mol for a small emulsion per mol of silver halide, respectively.
Further, the following compound I was added to the red-sensitive emulsion layer at 3.0 × 10 ⁻³ mol per mol of silver halide.

Preparation of first layer coating solution 57 g of yellow coupler (ExY), 7 g of color image stabilizer (Cpd-1), 4 g of color image stabilizer (Cpd-2), 7 g of color image stabilizer (Cpd-3), color image stabilizer 2 g of (Cpd-8) was dissolved in 21 g of a solvent (Solv-1) and 80 ml of ethyl acetate, and this solution was dissolved in 220 g of a 23.5% by weight gelatin aqueous solution containing 4 g of sodium dodecylbenzenesulfonate (dissolver). ), And water was added to prepare 900 g of emulsified dispersion A.
On the other hand, the emulsified dispersion A and the emulsions A-1 and A-2 were mixed and dissolved to prepare a first layer coating solution having a composition described later. The emulsion coating amount indicates the silver coating amount.

The coating solutions for the second to seventh layers were prepared in the same manner as the first layer coating solution. As the gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt (H-1), (H-2), (H-3) was used. In addition, (Ab-1), (Ab-2), (Ab-3), and (Ab-4) were added to each layer in a total amount of 15.0 mg / m ² , 60.0 mg / m ² , 5.0 mg / was added such that the m ² and 10.0 mg / ^{m 2.}

Also, 1- (3-methylureidophenyl) -5-mercaptotetrazole is added to the second layer, the fourth layer, the sixth layer, and the seventh layer, respectively, at 0.2 mg / m ² , 0.2 mg / m ² , 0.6 mg / m ² and 0.1 mg / m ² were added.
Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene is added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer, respectively at 1 × 10 ⁻⁴ mol per mol of silver halide, 2 × 10 ⁻⁴ mol was added.
Also, 0.05 g / m ^{2 of a} copolymer latex of methacrylic acid and butyl acrylate (mass ratio 1: 1, average molecular weight 200000-400000) was added to the red sensitive emulsion layer.
The second layer was added the fourth layer and the sixth layer in disodium catechol-3,5-disulfonate as respectively a ^{6mg / m 2, 6mg / m} 2, 18mg / m 2.
In order to prevent irradiation, the following dyes were added (the amount in parentheses represents the coating amount).

(Layer structure)
The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.
Support: Polyethylene resin laminated paper [white pigment (TiO ₂ ; content: 16% by mass, ZnO; content: 4% by mass) and polyethylene brightening agent (4,4′-bis (5- Methylbenzoxazolyl) stilbene, content 0.03% by mass), bluish dye (ultraviolet, content 0.33% by mass). The amount of polyethylene resin is 29.2 g / m ² ]
First layer (blue sensitive emulsion layer)
Silver chlorobromoiodide emulsion A (gold-sulfur sensitized cube, 3: 7 mixture of large size emulsion A-1 and small size emulsion A-2 (silver molar ratio)) 0.24
Gelatin 1.25
Yellow coupler (ExY) 0.57
Color image stabilizer (Cpd-1) 0.07
Color image stabilizer (Cpd-2) 0.04
Color image stabilizer (Cpd-3) 0.07
Color image stabilizer (Cpd-8) 0.02
Solvent (Solv-1) 0.21

Second layer (color mixing prevention layer)
Gelatin 1.15
Color mixing inhibitor (Cpd-4) 0.10
Color image stabilizer (Cpd-5) 0.018
Color image stabilizer (Cpd-6) 0.13
Color image stabilizer (Cpd-7) 0.07
Solvent (Solv-1) 0.04
Solvent (Solv-2) 0.12
Solvent (Solv-5) 0.11

Third layer (green sensitive emulsion layer)
Silver chlorobromoiodide emulsion C (gold-sulfur sensitized cube, 1: 3 mixture of large size emulsion C-1 and small size emulsion C-2 (silver molar ratio)) 0.14
Gelatin 1.21
Magenta coupler (ExM) 0.15
Ultraviolet absorber (UV-A) 0.14
Color image stabilizer (Cpd-2) 0.003
Color image stabilizer (Cpd-4) 0.002
Color image stabilizer (Cpd-6) 0.09
Color image stabilizer (Cpd-8) 0.02
Color image stabilizer (Cpd-9) 0.01
Color image stabilizer (Cpd-10) 0.01
Color image stabilizer (Cpd-11) 0.0001
Solvent (Solv-3) 0.09
Solvent (Solv-4) 0.18
Solvent (Solv-6) 0.07
Solvent (Solv-9) 0.10

Fourth layer (color mixing prevention layer)
Gelatin 0.68
Color mixing inhibitor (Cpd-4) 0.06
Color image stabilizer (Cpd-5) 0.011
Color image stabilizer (Cpd-6) 0.08
Color image stabilizer (Cpd-7) 0.04
Solvent (Solv-1) 0.02
Solvent (Solv-2) 0.07
Solvent (Solv-5) 0.065

5th layer (red-sensitive emulsion layer)
Silver chlorobromoiodide emulsion E (gold-sulfur sensitized cube, 5: 5 mixture of large size emulsion E-1 and small size emulsion E-2 (silver molar ratio)) 0.16
Gelatin 0.95
Cyan coupler (ExC-1) 0.023
Cyan coupler (ExC-2) 0.05
Cyan coupler (ExC-3) 0.17
Ultraviolet absorber (UV-A) 0.055
Color image stabilizer (Cpd-1) 0.22
Color image stabilizer (Cpd-7) 0.003
Color image stabilizer (Cpd-9) 0.01
Color image stabilizer (Cpd-12) 0.01
Solvent (Solv-8) 0.05

Sixth layer (UV absorbing layer)
Gelatin 0.46
Ultraviolet absorber (UV-B) 0.35
Compound (S1-4) 0.0015
Solvent (Solv-7) 0.18
Seventh layer (protective layer)
Gelatin 1.00
Acrylic-modified copolymer of polyvinyl alcohol (degree of modification 17%)
0.4
Liquid paraffin 0.02
Surfactant (Cpd-13) 0.02

Production of Samples 101 to 116 Samples 101 to 116 were produced in the same manner as the sample 001 except that the composition of the first layer of the sample 001 produced as described above was changed as follows.
First layer Blue-sensitive emulsion layer composition change sample 101:
Silver chlorobromoiodide emulsion A (gold-sulfur sensitized cube, 3: 7 mixture of large size emulsion A-1 and small size emulsion A-2 (silver molar ratio)) 0.24
Gelatin 1.20
Yellow coupler (comparative coupler Y1) 0.53
Color image stabilizer (Cpd-2) 0.05
Color image stabilizer (Cpd-8) 0.05
Color image stabilizer (Cpd-19) 0.04
Color image stabilizer (UV-3) 0.01
Solvent (Solv-4) 0.17
Solvent (Solv-9) 0.17
Solvent (Solv-6) 0.02
Sample 102 was prepared in the same manner as Sample 101 except that the yellow coupler in Sample 101 was changed to an equimolar comparison coupler Y2. Sample 116 was prepared in the same manner as Sample 101 except that the yellow coupler in Sample 101 was changed to an equimolar comparison coupler Y3. In preparing these samples, the amount of the solvent was adjusted so that the total of the yellow coupler, the color image stabilizer, and the solvent was constant. At that time, the composition of the three solvents was not changed.

Sample 103:
Silver chlorobromoiodide emulsion A (gold-sulfur sensitized cube, 3: 7 mixture of large size emulsion A-1 and small size emulsion A-2 (silver molar ratio)) 0.18
Gelatin 1.20
Yellow coupler (1) 0.33
Color image stabilizer (Cpd-2) 0.05
Color image stabilizer (Cpd-8) 0.05
Color image stabilizer (Cpd-19) 0.04
Color image stabilizer (UV-3) 0.01
Solvent (Solv-4) 0.26
Solvent (Solv-9) 0.26
Solvent (Solv-6) 0.04
In the sample 103, the silver halide emulsion coating amount is reduced to 75% and the yellow coupler coating amount is reduced to 67 mol% with respect to the sample 101, so that the total of the yellow coupler, the color image stabilizer and the solvent is constant. The amount of solvent was adjusted.
Samples 104 to 115 were prepared in the same manner as Sample 103 except that the yellow coupler in Sample 103 was changed to the equimolar yellow coupler of the present invention shown in Table 2. When the amount of the coupler varies depending on the molecular weight, the amount of the solvent is adjusted so that the sum of the yellow coupler, the color image stabilizer and the solvent becomes constant. At that time, the composition of the three solvents was not changed.

The light-sensitive material was evaluated by performing the following two processes with different processing solution compositions and process times.
Process A
Each of the above samples was processed into a 127 mm width roll, and a standard photographic image was exposed on the photosensitive material using a digital minilab frontier 330 (trade name, manufactured by Fuji Photo Film Co., Ltd.). Thereafter, continuous processing (running test) was performed until the volume of the color developer replenisher used in the following processing steps was twice that of the color developer tank.

  The treatment using this running treatment liquid was designated as treatment A.

Processing temperature Temperature Time Replenishment amount ^*
Color development 38.5 ° C 45 seconds 45 mL
Bleach fixing 38.0 ° C 45 seconds 35 mL
Rinse 1 ** 38.0 ° C 20 seconds-
Rinse 2 ** 38.0 ° C 20 seconds-
Rinse 3 ** 38.0 ° C 20 seconds-
Rinse 4 ** 38.0 ° C 20 seconds 121mL
Dry 80 ° C
(note)
* Replenishment amount per 1 m ^{2 of} photosensitive material ** Mounted with rinse screen RC50D (trade name) manufactured by Fuji Photo Film Co., Ltd., rinse solution is removed from rinse 3, and pumped to reverse osmosis module (RC50D) send. The permeated water sent in the tank is supplied to the rinse 4 and the concentrated solution is returned to the rinse 3. The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 mL / min, and the temperature was circulated for 10 hours a day. The rinsing was a 4-tank countercurrent system from rinse 1 to 4.

The composition of each treatment liquid is as follows.
[Color developer] [Tank solution] [Replenisher]
800 ml of water 800 ml
Optical brightener (FL-1) 2.2g 5.1g
Optical brightener (FL-2) 0.35 g 1.75 g
Triisopropanolamine 8.8g 8.8g
Polyethylene glycol (average molecular weight 300)
10.0g 10.0g
Ethylenediaminetetraacetic acid 4.0 g 4.0 g
Sodium sulfite 0.10g 0.20g
Potassium chloride 10.0 g −
Sodium 4,5-dihydroxybenzene-1,3-disulfonate
0.50g 0.50g
Disodium-N, N-bis (sulfonate ethyl) hydroxylamine
8.5g 14.0g
4-Amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline, 3/2 sulfate, monohydrate
4.8g 14.0g
Potassium carbonate 26.3g 26.3g
Add water for a total volume of 1000 mL 1000 mL
pH (adjusted with sulfuric acid and KOH at 25 ° C.) 10.15 12.5

[Bleaching Fixer] [Tank Solution] [Replenisher]
Water 800mL 600mL
Ammonium thiosulfate (750 g / L) 107 mL 214 mL
m-Carboxybenzenesulfinic acid 8.3 g 16.5 g
Ethylenediaminetetraacetic acid iron (III) ammonium
47.0g 94.0g
Ethylenediaminetetraacetic acid 1.4 g 2.8 g
Nitric acid (67%) 16.5g 33.0g
Imidazole 14.6g 29.2g
Ammonium sulfite 16.0 g 32.0 g
Potassium metabisulfite 23.1g 46.2g
Add water for a total volume of 1000 mL 1000 mL
pH (adjusted with nitric acid and ammonia water at 25 ° C)
6.5 6.5

[Rinse solution] [Tank solution] [Replenisher solution]
Chlorinated isocyanurate sodium 0.02g 0.02g
Deionized water (conductivity 5μS / cm or less) 1000mL 1000mL
pH (25 ° C.) 6.5 6.5

Process B
Each sample is processed into a 127 mm wide roll, and the average density of the photosensitive material is measured using an experimental processing device modified from Fuji Photo Film's Minilab Printer Processor PP350 (trade name) so that the processing time and processing temperature can be changed. The negative film was subjected to imagewise exposure, and continuous processing (running test) was performed until the volume of the color developer replenisher used in the following processing steps was twice the volume of the color developer tank. The treatment using this running treatment liquid was designated as treatment B.

Process temperature time replenishment amount ^*
Color development 45.0 ℃ 17 seconds 45mL
Bleach fixing 40.0 ℃ 17 seconds 35mL
Rinse 1 ** 40.0 ° C 8 seconds-
Rinse 2 ** 40.0 ° C 8 seconds-
Rinse 3 ** 40.0 ° C 8 seconds-
Rinse 4 ** 38.0 ° C 8 seconds 121mL
Drying 80 ° C 15 seconds (Note)
* Replenishment amount per 1 m ^{2 of} photosensitive material ** Mounted with rinse screen RC50D (trade name) manufactured by Fuji Photo Film Co., Ltd., rinse solution is removed from rinse 3, and pumped to reverse osmosis module (RC50D) send. The permeated water sent in the tank is supplied to the rinse 4 and the concentrated solution is returned to the rinse 3. The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 mL / min, and the temperature was circulated for 10 hours a day. The rinsing was a 4-tank countercurrent system from rinse 1 to 4.

The composition of each treatment liquid is as follows.
[Color developer] [Tank solution] [Replenisher]
800 ml of water 800 ml
Optical brightener (FL-3) 4.0g 8.0g
Residual color reducing agent (SR-1) 3.0 g 5.5 g
Triisopropanolamine 8.8g 8.8g
Sodium p-toluenesulfonate 10.0 g 10.0 g
Ethylenediaminetetraacetic acid 4.0 g 4.0 g
Sodium sulfite 0.10g 0.10g
Potassium chloride 10.0 g −
Sodium 4,5-dihydroxybenzene-1,3-disulfonate
0.50g 0.50g
Disodium-N, N-bis (sulfonate ethyl) hydroxylamine
8.5g 14.0g
4-Amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline, 3/2 sulfate, monohydrate
7.0g 19.0g
Potassium carbonate 26.3g 26.3g
Add water for a total volume of 1000 mL 1000 mL
pH (adjusted with sulfuric acid and KOH at 25 ° C.) 10.25 12.6

[Bleaching Fixer] [Tank Solution] [Replenisher]
Water 800mL 600mL
Ammonium thiosulfate (750 g / L) 107 mL 214 mL
Succinic acid 29.5g 59.0g
Ethylenediaminetetraacetic acid iron (III) ammonium
47.0g 94.0g
Ethylenediaminetetraacetic acid 1.4 g 2.8 g
Nitric acid (67%) 17.5g 35.0g
Imidazole 14.6g 29.2g
Ammonium sulfite 16.0 g 32.0 g
Potassium metabisulfite 23.1g 46.2g
Add water for a total volume of 1000 mL 1000 mL
pH (adjusted with nitric acid and ammonia water at 25 ° C)
6.00 6.00

[Rinse solution] [Tank solution] [Replenisher solution]
Chlorinated isocyanurate sodium 0.02g 0.02g
Deionized water (conductivity 5μS / cm or less) 1000mL 1000mL
pH (25 ° C.) 6.5 6.5

  Samples 101 to 116 were subjected to the following evaluation after storage for 10 days under the condition of 25 ° C. and 55% relative humidity after the photosensitive material was applied.

(Evaluation 1 color)
Each sample was subjected to three-color separation exposure, and color development processing was performed in the above-described processing step A to obtain single-color coloring samples of yellow, magenta, and cyan, respectively.
As a light source, a semiconductor laser light was used to obtain a 688 nm light source (R light), and by combining the semiconductor laser with SHG, a 532 nm light source (G light) and a 473 nm light source (B light) were obtained. The amount of R light was modulated using an external modulator, reflected by a rotating polyhedron, and subjected to scanning exposure on a sample moving perpendicular to the scanning direction. This scanning exposure was performed at 400 dpi, and the average exposure time per pixel was 8 × 10 ⁻⁸ seconds. The temperature of the semiconductor laser was made constant by using a Peltier element in order to suppress the change in light quantity due to temperature.
The density of the yellow coloring portion was measured using the obtained sample. The cyan density at a point giving a yellow density of 1.6 was measured to evaluate the color drift. The measurement was performed with status A using X-rite 310 (trade name, manufactured by X-rite).

(Evaluation 2: Light fastness)
Using the sample prepared in Evaluation 1, the concentration was measured before and after exposure to 100,000 lux Xe light for 14 days. The relative residual ratio after storage at an initial density of 0.5 of the yellow coloring portion was calculated.

(Evaluation 3 Fastness to wet heat)
Using the sample prepared in Evaluation 1, the concentration was measured before and after being stored for 21 days at 80 ° C. and 70% relative humidity. The relative residual ratio after storage at an initial density of 1.5 of the yellow coloring portion was calculated.

(Evaluation 4 Processing stability during rapid processing)
An exposure apparatus of evaluation 1 was used for each sample, and the exposure conditions were determined so as to give gray gradation in the processing step B. In processing step B, processing was carried out with the photosensitive material transport speed increased or decreased by 15%. The density fluctuation of the exposed portion that gave a density of 2.0 in the standard time processing of the processing step B was measured. As processing stability, (density fluctuation range) / (initial density 2.0) × 100 was calculated and evaluated.
The evaluation results are shown in Table 2.

  In the samples 103 to 115 of the present invention, the yellow coupler was reduced to 67%, but an equivalent color density was obtained as compared with the samples 101 and 102 using the comparative yellow coupler. Further, it was found that when the yellow coupler of the present invention is used, the color in the yellow is reduced, and the light fastness and wet heat fastness of the low density portion of the yellow dye image are excellent. Furthermore, a photosensitive material excellent in density stability during rapid processing was obtained.

[Example 2]
Samples 201 to 216 obtained by reversing the arrangement of the first layer and the fifth layer in the samples 101 to 116 of Example 1 were produced.
As a result of the evaluation in accordance with Example 1, the density of yellow and magenta was improved in comparison with the sample of Example 1 particularly in the gray image. Further, it has been found that when the coupler of the present invention is used, a light-sensitive material having little color blur, excellent light fastness and wet heat fastness, and excellent processing stability can be obtained.

[Example 3]
In the samples of Examples 1 and 2, samples in which the composition of the red photosensitive emulsion layer was changed as follows were prepared, and as a result of evaluation according to Examples 1 and 2, rapid processing was achieved in the configuration of the present invention. It was confirmed that the color reproducibility and the image fastness were excellent.

Red-sensitive emulsion layer composition Silver chlorobromoiodide emulsion E (gold-sulfur sensitized cube, 5: 5 mixture of large size emulsion E-1 and small size emulsion E-2 (silver molar ratio)) 0.10
Gelatin 1.11
Cyan coupler (ExC-1) 0.06
Cyan coupler (ExC-3) 0.02
Cyan coupler (ExC-4) 0.01
Cyan coupler (ExC-5) 0.06
Color image stabilizer (Cpd-1) 0.01
Color image stabilizer (Cpd-6) 0.05
Color image stabilizer (Cpd-7) 0.02
Color image stabilizer (Cpd-9) 0.04
Color image stabilizer (Cpd-10) 0.01
Color image stabilizer (Cpd-14) 0.01
Color image stabilizer (Cpd-15) 0.10
Color image stabilizer (Cpd-16) 0.01
Color image stabilizer (Cpd-17) 0.01
Color image stabilizer (Cpd-18) 0.07
Color image stabilizer (Cpd-19) 0.01
UV absorber (UV-5) 0.04
Solvent (Solv-5) 0.15

[Example 4]
Samples in which the silver halide emulsions were changed as follows in Examples 1 to 3 were prepared and evaluated according to Example 1. As a result, it was found that a silver halide color photographic material excellent in color reproducibility and rapid processability can be obtained according to the present invention.
First layer: 4 to 6 mixture of (emulsion BH) and (emulsion BL) (silver molar ratio)
Third layer: 5 to 5 mixture of (Emulsion GH) and (Emulsion GL) (silver molar ratio)
Fifth layer: 6 to 4 mixture of (emulsion RH) and (emulsion RL) (silver molar ratio)

(Preparation of emulsion BH)
A cubic high silver chloride emulsion having a sphere equivalent diameter of 0.55 μm and a coefficient of variation of 10% was prepared by a conventional method in which silver nitrate and sodium chloride were simultaneously added and mixed in a stirred gelatin aqueous solution. However, potassium bromide (3 mol% per mol of the finished silver halide) and K ₄ [Ru (CN) ₆ ] were added from the time when the addition of silver nitrate was 80% to 90%. When the addition of silver nitrate was completed 90%, potassium iodide (0.3 mol% per mol of the finished silver halide) was added. Further, K ₂ [Ir (5-methylthiazole) Cl ₅ ] and K ₂ [Ir (H ₂ O) Cl ₅ ] were added from the time point when the addition of silver nitrate was 92% to the time point of 98%. The obtained emulsion was desalted and then re-dispersed with gelatin. Sodium thiosulfonate, sensitizing dye A and sensitizing dye B were added to this emulsion, sodium thiosulfate pentahydrate as a sulfur sensitizer, and bis (1,4,5-trimethyl-1 as a gold sensitizer. , 2,4-Triazolium-3-thiolate) aurate (I) tetrafluoroborate was optimally aged. Further 1-phenyl-5-mercaptotetrazole and 1- (5-methylureidophenyl) -5-mercaptotetrazole were added. The emulsion thus obtained was named Emulsion BH.
(Preparation of emulsion B-L)
Emulsion B-H was prepared by changing only the addition rate of silver nitrate and sodium chloride to prepare a cubic high silver chloride emulsion having a sphere equivalent diameter of 0.45 μm and a coefficient of variation of 10%. The resulting emulsion was designated as Emulsion BL.

(Preparation of emulsion GH)
A cubic high silver chloride emulsion having a sphere equivalent diameter of 0.35 μm and a coefficient of variation of 10% was prepared by a conventional method in which silver nitrate and sodium chloride were simultaneously added and mixed in a stirred gelatin aqueous solution. However, K ₄ [Ru (CN) ₆ ] was added from the time when addition of silver nitrate was 80% to 90%. Potassium bromide (4 mol% per mol of finished silver halide) was added from the 80% to 100% addition of silver nitrate. When the addition of silver nitrate was completed 90%, potassium iodide (0.2 mol% per mol of finished silver halide) was added. K ₂ [Ir (5-methylthiazol) Cl ₅ ] was added from the time when the addition of silver nitrate was 92% to 95%. Further, K ₂ [Ir (H ₂ O) Cl ₅ ] was added from the time when the addition of silver nitrate was 92% to the time when it was 98%. The obtained emulsion was desalted and then re-dispersed with gelatin. Sodium thiosulfonate is added to this emulsion, sodium thiosulfate pentahydrate as a sulfur sensitizer, and bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate as a gold sensitizer. A) Orate (I) Tetrafluoroborate was used for aging. Further, sensitizing dye D, 1-phenyl-5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole and potassium bromide were added. The emulsion thus obtained was named Emulsion GH.
(Preparation of emulsion GL)
Emulsion GH was prepared by changing only the addition rate of silver nitrate and sodium chloride to prepare a cubic high silver chloride emulsion having a sphere equivalent diameter of 0.28 μm and a coefficient of variation of 10%. The resulting emulsion was designated as Emulsion GL.

(Preparation of emulsion RH)
A cubic high silver chloride emulsion having a sphere equivalent diameter of 0.35 μm and a coefficient of variation of 10% was prepared by a conventional method in which silver nitrate and sodium chloride were simultaneously added and mixed in a stirred gelatin aqueous solution. However, K ₄ [Ru (CN) ₆ ] was added from the time when addition of silver nitrate was 80% to 90%. Potassium bromide (4.3 mol% per mol of the finished silver halide) was added from the 80% to 100% addition of silver nitrate. When the addition of silver nitrate was completed 90%, potassium iodide (0.15 mol% per mol of the finished silver halide) was added. K ₂ [Ir (5-methylthiazol) Cl ₅ ] was added from the time when the addition of silver nitrate was 92% to 95%. Further, K ₂ [Ir (H ₂ O) Cl ₅ ] was added from the time when the addition of silver nitrate was 92% to the time when it was 98%. The obtained emulsion was desalted and then re-dispersed with gelatin. Sodium thiosulfonate is added to this emulsion, sodium thiosulfate pentahydrate as a sulfur sensitizer, and bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate as a gold sensitizer. A) Orate (I) Tetrafluoroborate was used for aging. Further, sensitizing dye H, 1-phenyl-5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound I and potassium bromide were added. The emulsion thus obtained was named Emulsion RH.
(Preparation of emulsion RL)
Emulsion RH was a cubic high silver chloride emulsion having a sphere equivalent diameter of 0.28 μm and a coefficient of variation of 10% by changing only the addition rate of silver nitrate and sodium chloride. The resulting emulsion was designated as Emulsion RL.

[Example 5]
The samples prepared in Examples 1 to 4 were subjected to scanning exposure using the apparatus shown below and evaluated according to Examples 1 to 4. As a result of using the sample of the configuration of the present invention, color reproducibility and rapidness were obtained. It has been found that the effect of the present invention that the processability is excellent can be obtained particularly remarkably.
Digital Minilab Frontier 330 (Fuji Photo Film, trade name), Lambda 130 (Durst, trade name), LIGHTJET 5000 (Gretag, trade name).

[Example 6]
A sample in which the coating amount (total coating amount in each layer) was changed as described below with respect to the sample of Example 1 was prepared.
240% of blue-sensitive silver halide emulsion layer
Coating amount of green photosensitive silver halide emulsion layer 250%
260% coating amount of red-sensitive silver halide emulsion layer
Support: Polyethylene terephthalate transparent support having a thickness of 180 μm These samples were processed by extending each processing step by 2.7 times in the processing step B of Example 1. As a result of evaluation according to Example 1, when the yellow coupler of the present invention was used, a light-sensitive material having less color dust and excellent image fastness was obtained.

[Example 7]
A sample 701 having the following layer structure was formed on the support of Example 1.
The gelatin hardener, preservative, antifogging agent, stabilizer, copolymer latex, and irradiation dye used in the second to seventh layers are the same as in Example 1, respectively. And in the same layer as in Example 1.

First layer (blue photosensitive emulsion layer)
Emulsion (5: 5 mixture of BH-1 and BL-1 (silver molar ratio)) 0.16
Gelatin 1.32
Example coupler (1) 0.34
Color image stabilizer (Cpd-1) 0.01
Color image stabilizer (Cpd-2) 0.01
Color image stabilizer (Cpd-8) 0.08
Color image stabilizer (Cpd-18) 0.01
Color image stabilizer (Cpd-19) 0.02
Color image stabilizer (Cpd-20) 0.15
Color image stabilizer (Cpd-21) 0.01
Color image stabilizer (Cpd-23) 0.15
Additive (ExC-1) 0.001
Color image stabilizer (UV-4) 0.01
Solvent (Solv-4) 0.23
Solvent (Solv-6) 0.04
Solvent (Solv-9) 0.23

Second layer (color mixing prevention layer)
Gelatin 0.78
Color mixing inhibitor (Cpd-4) 0.05
Color mixing inhibitor (Cpd-24) 0.01
Color image stabilizer (Cpd-5) 0.006
Color image stabilizer (Cpd-6) 0.05
Color image stabilizer (Cpd-7) 0.006
Color image stabilizer (Cpd-25) 0.006
Color image stabilizer (UV-C) 0.06
Solvent (Solv-1) 0.06
Solvent (Solv-2) 0.06
Solvent (Solv-5) 0.07
Solvent (Solv-11) 0.07

Third layer (green photosensitive emulsion layer)
Emulsion (1: 3 mixture of GH-1 and GL-1 (silver molar ratio)) 0.12
Gelatin 0.95
Magenta coupler (ExM) 0.12
UV absorber (UV-C) 0.03
Color image stabilizer (Cpd-2) 0.01
Color image stabilizer (Cpd-6) 0.08
Color image stabilizer (Cpd-7) 0.005
Color image stabilizer (Cpd-8) 0.01
Color image stabilizer (Cpd-9) 0.01
Color image stabilizer (Cpd-10) 0.005
Color image stabilizer (Cpd-11) 0.0001
Color image stabilizer (Cpd-20) 0.01
Solvent (Solv-3) 0.06
Solvent (Solv-4) 0.12
Solvent (Solv-6) 0.05
Solvent (Solv-9) 0.16

Fourth layer (color mixing prevention layer)
Gelatin 0.65
Color mixing inhibitor (Cpd-4) 0.04
Color mixing inhibitor (Cpd-24) 0.01
Color image stabilizer (Cpd-5) 0.005
Color image stabilizer (Cpd-6) 0.04
Color image stabilizer (Cpd-7) 0.005
Color image stabilizer (Cpd-25) 0.005
Color image stabilizer (UV-C) 0.05
Solvent (Solv-1) 0.05
Solvent (Solv-2) 0.05
Solvent (Solv-5) 0.06
Solvent (Solv-11) 0.06

5th layer (red photosensitive emulsion layer)
Emulsion (4: 6 mixture of RH-1 and RL-1 (silver molar ratio)) 0.10
Gelatin 1.11
Cyan coupler (ExC-5) 0.11
Cyan coupler (ExC-4) 0.01
Cyan coupler (ExC-3) 0.04
Color image stabilizer (Cpd-1) 0.03
Color image stabilizer (Cpd-7) 0.01
Color image stabilizer (Cpd-9) 0.04
Color image stabilizer (Cpd-10) 0.001
Color image stabilizer (Cpd-14) 0.001
Color image stabilizer (Cpd-15) 0.18
Color image stabilizer (Cpd-16) 0.002
Color image stabilizer (Cpd-17) 0.001
Color image stabilizer (Cpd-18) 0.05
Color image stabilizer (Cpd-19) 0.04
Color image stabilizer (UV-5) 0.10
Solvent (Solv-5) 0.19

Sixth layer (UV absorbing layer)
Gelatin 0.34
Ultraviolet absorber (UV-D) 0.24
Compound (S1-4) 0.0015
Solvent (Solv-10) 0.11

Seventh layer (protective layer)
Gelatin 0.82
Additive (Cpd-22) 0.03
Liquid paraffin 0.02
Surfactant (Cpd-13) 0.02

Each of the above emulsions was prepared as follows.
(Preparation of blue-sensitive layer emulsion BH-1)
High silver chloride cubic particles were prepared by simultaneously adding silver nitrate and sodium chloride to deionized distilled water containing deionized gelatin and mixing. In the course of this preparation, Cs ₂ [OsCl ₅ (NO)] was added from 60% to 80% addition of silver nitrate. From the 80% to 90% addition of silver nitrate, potassium bromide (1.5 mol% per mole of finished silver halide) and K ₄ [Fe (CN) ₆ ] were added. K ₂ [IrCl ₆ ] was added from 83% to 88% addition of silver nitrate. K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] were added from 92% to 98% addition of silver nitrate. When 94% of the addition of silver nitrate was completed, potassium iodide (0.27 mol% per mol of the finished silver halide) was added with vigorous stirring. The obtained emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.54 μm and a coefficient of variation of 8.5%. The emulsion was subjected to precipitation desalting treatment, and gelatin, preservatives Ab-1, Ab-2, Ab-3, and calcium nitrate were added and redispersed.

The redispersed emulsion was dissolved at 40 ° C., and spectral sensitizing dye I, spectral sensitizing dye J and spectral sensitizing dye-1 were added so as to optimize the spectral sensitization. Next, sodium benzenethiosulfate, triethylthiourea as a sulfur sensitizer, and compound-1 as a gold sensitizer were added and ripened so as to optimize chemical sensitization. Thereafter, a mixture of compounds represented by 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound-3, wherein n is 2 or 3 as a main component (terminal X ₁ and X ₂ are Hydroxyl group), compound-4 and potassium bromide were added to terminate the chemical sensitization. The emulsion thus obtained was designated as Emulsion BH-1.

(Preparation of blue-sensitive layer emulsion BL-1)
In the preparation of emulsion BH-1, except that the temperature and rate of addition of silver nitrate and sodium chloride were changed and mixed, and the amounts of various metal complexes added during the addition of silver nitrate and sodium chloride were changed. Emulsion grains were obtained in the same manner. The emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.44 μm and a coefficient of variation of 9.5%. After redispersing this emulsion, Emulsion BL-1 was prepared in the same manner except that the amount of various compounds added was changed from that of BH-1.

(Preparation of green sensitive layer emulsion GH-1)
High silver chloride cubic particles were prepared by simultaneously adding silver nitrate and sodium chloride to deionized distilled water containing deionized gelatin and mixing. In the course of this preparation, K ₄ [Ru (CN) ₆ ] was added from 80% to 90% addition of silver nitrate. Potassium bromide (2 mol% per mole of finished silver halide) was added from the point where the addition of silver nitrate was 80% to 100%. K ₂ [IrCl ₆ ] and K ₂ [RhBr ₅ (H ₂ O)] were added from 83% to 88% addition of silver nitrate. When 90% of the addition of silver nitrate was completed, potassium iodide (0.1 mol% per mol of the finished silver halide) was added with vigorous stirring. Further, K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] were added when the addition of silver nitrate was 92% to 98%. The obtained emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.42 μm and a coefficient of variation of 8.0%. This emulsion was subjected to precipitation desalting and redispersion in the same manner as described above.

  This emulsion was dissolved at 40 ° C. and sodium benzenethiosulfate, p-glutaramide phenyl disulfide, sodium thiosulfate pentahydrate as a sulfur sensitizer and (bis (1,4,5-trimethyl-1) as a gold sensitizer. , 2,4-triazolium-3-thiolate) orate (I) tetrafluoroborate) and ripened to optimize chemical sensitization. Thereafter, 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound-4 and potassium bromide were added. Further, spectral sensitization was performed by adding spectral sensitizing dye D, spectral sensitizing dye K, spectral sensitizing dye L, and spectral sensitizing dye M as sensitizing dyes during the emulsion preparation process. The emulsion thus obtained was designated as Emulsion GH-1.

(Preparation of green-sensitive layer emulsion GL-1)
In the preparation of emulsion GH-1, except that the temperature and rate of addition of silver nitrate and sodium chloride were changed and mixed, and the amounts of various metal complexes added during the addition of silver nitrate and sodium chloride were changed. Emulsion grains were obtained in the same manner. The emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.35 μm and a coefficient of variation of 9.8%. After redispersion of this emulsion, Emulsion GL-1 was prepared in the same manner except that the amount of various compounds added was changed from that of Emulsion GH-1.

(Preparation of emulsion RH-1 for red-sensitive layer)
High silver chloride cubic particles were prepared by simultaneously adding silver nitrate and sodium chloride to deionized distilled water containing deionized gelatin and mixing. In the course of this preparation, Cs ₂ [OsCl ₅ (NO)] was added from 60% to 80% addition of silver nitrate. K ₄ [Ru (CN) ₆ ] was added from the time point when the addition of silver nitrate was 80% to 90%. Potassium bromide (1.3 mol% per mol of finished silver halide) was added from the 80% to 100% addition of silver nitrate. K ₂ [IrCl ₅ (5-methylthiazole)] was added from 83% to 88% when silver nitrate was added. When the addition of silver nitrate was completed 88%, potassium iodide (amount of silver iodide to be 0.05 mol% per mol of finished silver halide) was added with vigorous stirring. Further, K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] were added when the addition of silver nitrate was 92% to 98%. The obtained emulsion grains were monodispersed cubic silver iodobromochloride emulsion grains having a cube side length of 0.39 μm and a coefficient of variation of 10%. The obtained emulsion was subjected to precipitation desalting and redispersion in the same manner as described above.

  This emulsion was dissolved at 40 ° C. and spectral sensitizing dye H, compound I, triethylthiourea as sulfur sensitizer and compound-1 as gold sensitizer were added, and ripened to optimize chemical sensitization. . Thereafter, 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound-4 and potassium bromide were added. The emulsion thus obtained was designated as Emulsion RH-1.

(Preparation of emulsion RL-1 for red-sensitive layer)
In the preparation of emulsion RH-1, except that the temperature and rate of addition of silver nitrate and sodium chloride were changed and mixed, and the amounts of various metal complexes added during the addition of silver nitrate and sodium chloride were changed. Emulsion grains were obtained in the same manner. The emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.29 μm and a coefficient of variation of 9.9%. This emulsion was subjected to precipitation desalting treatment and redispersion, and then emulsion RL-1 was prepared in the same manner except that the amount of various compounds added was changed from that of emulsion RH-1.

  Further, the exemplified coupler (1) in the first layer in the sample 701 is changed to the exemplified coupler (2), (3), (4), (6), (8), (9), (11), (17). , (21), (31), (33), and (39) were prepared as samples 702 to 713 which were different from each other only in equimolar amounts. Each of these samples was exposed and developed in the same manner as in Example 1 and evaluated in the same manner as in Example 1. As a result, the color was almost the same as in Example 1; It was confirmed that the concentration was excellent and the concentration stability during rapid processing was excellent.

[Example 8]
When preparing each sample of Examples 1 to 7, the position closest to the support on the support [the support and the first layer (in Example 2, the fifth layer of Example 1 is the first layer) ))], The coating solution having the following composition is applied by the following method, and one more layer is added. The viscosity of the coating solution of the additional layer and the remaining layer to be coated on the added layer is Each sample corresponding to each example was prepared in exactly the same manner except that the adjustment was made as described above. Of these samples, exposure, development processing and evaluation were performed in the same manner as in each of Examples 1 to 7, using each sample corresponding to each of Examples 1 to 7. As in Example 7, the excellent effect of the coupler of the present invention was confirmed.

  The coating solution for the added layer was prepared by adding a surfactant (Cpd-13) and a thickener used in the examples of US Pat. No. 5,393,571 to an aqueous solution containing 5% by weight of alkali-treated gelatin. About 0.1% by mass of each was added to adjust the viscosity to 140 mPa · s. The coating solution thus prepared and the remaining coating solution to be coated on the added layer were simultaneously coated by a curtain coating method in accordance with the method described in US Pat. No. 5,393,571. did. When applying, the viscosity of the coating solution in each layer is about 140 mPa · s (the added layer), 350 mPa · s (initial first layer), and about 120 mPa · s (initial second layer) in order from the support. The initial fifth layer) was adjusted to about 40 mPa · s (the ultraviolet absorption layer as the initial sixth layer and the protection increase as the initial seventh layer), and the coating was applied at a speed of 350 to 450 m / min.

Claims (2)

A yellow dye-forming coupler represented by the following general formula (I).

Wherein, Q is -N = C-N ((CH 2) 3 O-R1) - represents a non-metallic atomic group forming a 5- to 7-membered ring together. R1 represents an alkyl group having 4 to 8 carbon atoms. R2 represents a substituent. R4 represents a primary alkyl group. m represents an integer of 0 or more and 4 or less. When m is 2 or more, a plurality of R2s may be the same or different from each other, and may be bonded to each other to form a ring. X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized developer.   A silver halide color photographic material comprising at least one dye-forming coupler represented by formula (I) according to claim 1 in at least one layer on a support.