JPH06167773A - Silver halide color photographic sensitive material and color photographic image forming method - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material for a color print superior in processing speed and small in fluctuation of photographic performances against storage before and after exposure by specifying a support and a hardener for hardening hydrophilic colloidal layers to be formed on it by coating and incorporating a specified mercapto compound in the photosensitive material. CONSTITUTION:This reflective support is obtained by coating the surface of a paper base on the side of the photosensitive hydrophilic colloidal layers with a composition prepared by mixing and dispersing the white pigment into the polyester resin the polycondensation product of dicarboxylic acid and diol, and at least one of the hydrophilic colloidal layers contains the mercapto compound represented by formula I and silver halide emulsion grains having >=90mol% silver chloride content, and it is hardened with the carboxy-activation type hardener or the the compound represented by formula II. In formulae I and II, Q is an atomic group necessary to form a 5- or 6-membered hetero ring; M is H or a cation; each of X<1> and X<2> is -CH=CH2 or the like; and L is a divalent bonding group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, it has excellent rapidity of processing and has little fluctuation in photographic property with respect to storage of the light-sensitive material before exposure. The present invention relates to a silver halide color photographic light-sensitive material having little fluctuation in photographic property even after storage after exposure.

[0002]

2. Description of the Related Art With the spread of color photographic light-sensitive materials, the speed of color development processing has been required more and more.
Further, with the spread of minilabs and the like, the storage conditions of color photographic light-sensitive materials are not uniform, and there are severe conditions, and it is desired that the photographic properties do not change even under such conditions. There is. Further, in order to improve working conditions in the laboratory, it is desired to support exposure and development processing over holidays. In response to such demands, for speeding up the processing, for example, International Publication WO87 / 045
It is known that it is preferable to use a so-called high silver chloride emulsion having a high silver chloride content as the silver halide emulsion, as described in JP-A-34-34 and JP-A 64-26837. Further, various studies have been conducted on methods for improving fluctuations in photographic properties under severe conditions, and it is known that the effect is also obtained depending on the type of hardener used for hardening the photosensitive material. ing. As a hardener for photosensitive materials,
U.S. Pat. Nos. 3,325,287 and 3,645,74
The chlorotriazine-based hardeners described in JP-A No. 3-40244 and JP-A-57-40244 are known, and these hardeners can be used under high temperature or high humidity as described in JP-A-1-216340. If it is stored under such severe conditions as described above, the sensitivity will decrease. Meanwhile, U.S. Pat. No. 3,490,911
Nos. 2,749,260 and the vinyl sulfone type hardeners described in Japanese Patent No. 2,749,260 are disclosed in JP-A-1-216.
As described in Japanese Unexamined Patent Publication No. 176650 and Japanese Unexamined Patent Publication No. 2-176650,
It is known that the sensitivity does not easily decrease even under severe conditions such as high temperature or high humidity. However, when the present inventor prepared a light-sensitive material using a vinyl sulfone-based hardener and evaluated the change in photographic property under severe conditions such as high temperature or high humidity, the sensitivity after storage was Although the decrease was reduced, it was found that the sensitivity of the blue-sensitive layer remarkably fluctuated when the light-sensitive material after storage was exposed and stored at room temperature for several days.

[0003]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to provide excellent processing speed, small change in photographic property with respect to storage of a light-sensitive material before exposure, and photographic property for storage after exposure. To provide a silver halide color photographic light-sensitive material, especially a color print light-sensitive material.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventor has found that a support used for the above-mentioned purpose and a dura mater used for hardening a hydrophilic colloid layer coated thereon. It has been found that this can be effectively achieved by selecting the agent and incorporating the mercapto compound in the light-sensitive material. That is, the present invention is as follows. (1) Each of the couplers containing a coupler capable of coloring yellow, magenta, or cyan on the reflective support,
And a silver halide color photographic light-sensitive material having at least three types of photosensitive hydrophilic colloid layers and non-photosensitive hydrophilic colloid layers containing silver halide emulsion grains having different color sensitivities, A reflective support having a composition layer in which a white pigment is mixed and dispersed in a resin whose main component is polyester synthesized by polycondensation from dicarboxylic acid and diol, on the surface of at least the photosensitive hydrophilic colloid coating side of the substrate. And a photosensitive hydrophilic colloid layer having at least one of the following general formula [I]
Containing at least one mercapto compound represented by the formula (1) and silver halide emulsion grains having a silver chloride content of 90 mol% or more, and a carboxyl group-activating type hardener or the following general formula [I
A silver halide color photographic light-sensitive material characterized by being hardened with a compound represented by the formula [I].

[0005]

[Chemical 3]

In the formula [I], Q represents a group of atoms necessary for forming a 5-membered or 6-membered heterocycle or a 5-membered or 6-membered heterocycle condensed with a benzene ring, and M represents a hydrogen atom or Represents a cation.

[0007]

[Chemical 4]

In the formula [II], X ¹ and X ² are -CH = CH.
Is either ₂ or -CH ₂ CH ₂ -Y, X ¹ and X ² may be different even in the same. Y is replaced by a nucleophile (nucleophilic group) or H by a base
It represents a group capable of splitting off in the form of Y. L is a divalent linking group and may be substituted.

(2) The silver halide color photographic light-sensitive material as described in (1) above, wherein the polyester of the reflection support is a polyester containing polyethylene terephthalate as a main component.

(3) The polyester of the reflective support is a polyester synthesized by polycondensation from a dicarboxylic acid and a diol, and the dicarboxylic acid component has a molar ratio of terephthalic acid and isophthalic acid of 9: 1 to 2: 8. (1) A reflective support in which a composition in which a white pigment is mixed and dispersed in polyester, which is a mixture, is coated on at least the surface of the substrate on which the photosensitive hydrophilic colloid layer is coated is described in (1) above. Silver halide color photographic light-sensitive material. (4) The polyester of the reflective support is a polyester obtained by polycondensation of a dicarboxylic acid and a diol, and the dicarboxylic acid component is a mixture of terephthalic acid and naphthalenedicarboxylic acid in a molar ratio of 9: 1 to 2: 8. The halogenated product according to item (1) above, which is a reflective support in which a composition in which a white pigment is mixed and dispersed in polyester is coated on at least the surface of the substrate on which the photosensitive hydrophilic colloid layer is applied. Silver color photographic light-sensitive material.

(5) The silver halide color photographic light-sensitive material as described in any one of (1) to (3) above, wherein the diol is ethylene glycol.

(6) The white pigment of the reflective support is titanium oxide, and the weight ratio (titanium oxide / resin) to the resin containing polyester as a main component is 5/95 to 50/50. Any one of the preceding paragraphs (1) to (5)
A silver halide color photographic light-sensitive material as described in the above item.

(7) Any one of the above items (1) to (6)
A method for forming a color photographic image, which comprises exposing the silver halide color photographic light-sensitive material according to the item 1) by a scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds, and then performing color development processing.

The present invention will be described in detail below. In the present specification, the "main component" means a content rate of 50% by weight or more. The reflective support in the present invention is required to be a reflective support obtained by coating a composition having a polyester as a main component with a white pigment mixed and dispersed on at least the emulsion coating side surface of the substrate. This polyester is a polyester synthesized by polycondensation from a dicarboxylic acid and a diol, and preferable dicarboxylic acids include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and the like. Preferred diols include ethylene glycol, butylene glycol, neopentyl glycol, triethylene glycol, butanediol, hexylene glycol, bisphenol A ethylene oxide adduct (2,2-bis (4- (2-hydroxyethyloxy) phenyl) propane. ), 1,4-dihydroxymethylcyclohexane and the like.

In the present invention, various polyesters obtained by polycondensing these dicarboxylic acids alone or in mixture with the diols alone or in mixture can be used. Among them, at least one kind of dicarboxylic acid is preferably terephthalic acid. As the dicarboxylic acid component, a mixture of terephthalic acid and isophthalic acid (molar ratio 9: 1 to 2: 8) or a mixture of terephthalic acid and naphthalenedicarboxylic acid (molar ratio 9: 1 to 2: 8) is also preferably used. As the diol, it is preferable to use ethylene glycol or a mixed diol containing ethylene glycol. The molecular weight of these polymers is 3
It is preferably from 50,000 to 50,000. The composition of these polyesters is preferably such that polyethylene terephthalate is 50% by weight or more.

It is also preferable to use a mixture of a plurality of these polyesters having different compositions. Furthermore, a mixture of these polyesters and other resins can be preferably used. Other resins to be mixed include polyolefins such as polyethylene and polypropylene, polyethers such as polyethylene glycol, polyoxymethylene and polyoxypropylene, polyester-based polyurethane, polyether polyurethane, polycarbonate,
It can be widely selected as long as it is a resin such as polystyrene that can be extruded at 270 to 350 ° C. These blended resins may be one kind or two or more kinds. For example, 90% by weight of polyethylene terephthalate can be mixed with 6% by weight of polyethylene and 4% by weight of polypropylene. The mixing ratio of polyester and other resins varies depending on the type of resin to be mixed, but in the case of polyolefins, the weight ratio of polyester / other resin = 1
00/0 to 80/20 is suitable. If it exceeds this range, the physical properties of the mixed resin will be rapidly lowered. For resins other than polyolefin, the weight ratio is polyester / other resin = 1
It can be mixed in the range of 00/0 to 50/50.

As the white pigment mixed and dispersed in the polyester of the reflective support of the present invention, titanium oxide, barium sulfate,
Examples include inorganic pigments such as lithopone, aluminum oxide, calcium carbonate, silicon oxide, antimony trioxide, titanium phosphate, zinc oxide, lead white and zirconium oxide, and organic fine powders such as polystyrene and styrene-divinylbenzene copolymer. it can. Among these pigments, the use of titanium dioxide is particularly effective. Titanium dioxide may be of rutile type or anatase type, and may be produced by any of the sulfate method and chloride method. Specific product names include KA-10 and KA-20 manufactured by Titanium Industry, and A-220 manufactured by Ishihara Sangyo.

The average particle size of the white pigment used is 0.1 to 0.
8 μm is preferable. If it is less than 0.1 μm, it is difficult to uniformly mix and disperse in the resin, which is not preferable. If it exceeds 0.8 μm, sufficient whiteness cannot be obtained, and projections are formed on the coated surface, which adversely affects the image quality. The weight ratio of the white pigment to the polyester is 98/2 to 30/70 (polyester / white pigment), preferably 95/5 to 50/5.
0, particularly preferably 90/10 to 60/40. When the amount of the white pigment is less than 2% by weight, the contribution to the whiteness is insufficient. When the amount of the white pigment exceeds 70% by weight, the surface smoothness when used as a support for photographic printing paper is insufficient and the photograph having excellent glossiness is obtained. It is not possible to obtain a support for photographic paper. The polyester and the white pigment are mixed with a kneading machine such as a two-roll, three-roll, kneader or Banbury mixer together with a dispersion aid such as a metal salt of higher fatty acid, higher fatty acid ethyl, higher fatty acid amide or higher fatty acid. It is kneaded into the resin. An antioxidant may be contained in the resin layer, and the content may be 50 to 1000 ppm with respect to the resin.

The thickness of the polyester / white pigment composition coated on the coated surface side of the photosensitive hydrophilic colloid layer of the substrate of the reflective support of the present invention is 5 to 100 μm, and 5 to 80 μm.
μm is preferable, and more preferably 10 to 50 μm. When the thickness is more than 100 μm, the brittleness of the resin is emphasized, and problems such as cracking occur in physical properties. When the thickness is less than 5 μm, the waterproof property, which is the original purpose of the coating, is impaired, the whiteness and the surface smoothness cannot be satisfied at the same time, and the physical properties become too soft, which is not preferable. The resin or resin composition coated on the surface of the substrate which is not the emulsion coated surface is preferably polyester having polyethylene terephthalate as a main component, and the thickness thereof is 5 to 100.
μm is preferable, and more preferable is 10 to 50 μm. When the thickness exceeds this range, the brittleness of the resin is emphasized,
Physical property problems such as the occurrence of cracks will appear. If it is less than this range, the original waterproofing property of the coating is impaired and the physical properties become too soft, which is not preferable. Examples of the method for coating the coating layer on the coated surface side of the photosensitive hydrophilic colloid layer and the back surface layer of the substrate include a melt extrusion lamination method and the like.

The substrate used in the reflective support of the present invention is
It is selected from materials generally used for photographic printing paper. That is, natural pulp selected from softwood, hardwood, etc.,
Synthetic pulp as the main raw material, if necessary, clay, talc,
Calcium carbonate, filler such as urea resin fine particles, rosin, alkyl ketene dimer, higher fatty acid, epoxidized fatty acid amide, paraffin wax, sizing agent such as alkenyl succinic acid, starch, paper strength enhancer such as polyamide polyamine epichlorohydrin, polyacrylamide, etc., The one to which a fixing agent such as a sulfuric acid band or a cationic polymer is added is used. In the present invention, the base material used for the reflective support is preferably the base paper mainly made of the above natural pulp or synthetic pulp. The type and thickness of the substrate are not particularly limited, but the basis weight is 50 g / m ² to 2
50 g / m ² is desirable. For the purpose of imparting smoothness and flatness, the substrate is preferably surface-treated by applying heat and pressure with a machine calender or a super calender.

This "smoothness" is represented by the surface roughness of the support as a scale. The surface roughness of the support of the present invention will be described. The center line average surface roughness is used as the surface roughness. The centerline average surface roughness is defined as: From the roughness curved surface, a portion having an area SM is extracted on the center plane, the orthogonal coordinate axes, the X axis, and the Y axis are placed on the center line of the extracted portion, and the axis orthogonal to the center line is placed on the Z axis. The value given by the formula is defined as the center line average surface roughness (SR _a ), and is expressed in μm.

[0022]

[Equation 1]

The centerline average surface roughness and the height of the protrusions from the centerline are measured, for example, by using a three-dimensional surface roughness measuring instrument (SE-30H) manufactured by Kosaka Laboratory Ltd. Cut-off value of 0.8 mm with needle, horizontal magnification of 20 times, height magnification of 2000 times, 5 mm
It can be obtained by measuring the area of ² . Further, the feeding speed of the measuring needle at this time is preferably about 0.5 mm / sec. A support having a value obtained by this measurement of 0.15 μm or less is preferable, and 0.10 μm or less is more preferable. By using a support having such surface roughness (smoothness), a color print having a surface with excellent smoothness can be obtained.

When the substrate is coated with the above-mentioned mixed composition of polyester and white pigment, it is preferable to pretreat the surface of the substrate such as corona discharge treatment, fire treatment or undercoating.

When a polyester such as polyethylene terephthalate is used, the adhesion to a photographic emulsion is weaker than that of polyethylene. Therefore, after polyester is melt-extruded and laminated on a substrate, the polyester surface is subjected to corona discharge treatment and a hydrophilic colloid layer is applied. Preferably. It is also preferable to apply an undercoat liquid containing a compound represented by the following general formula [U] on the surface of a thermoplastic resin containing polyester as a main component.

[0026]

[Chemical 5]

The coating amount of the compound represented by the general formula [U] is preferably 0.1 mg / m ² or more, more preferably 1 m.
g / m ² or more, most preferably 3 mg / m ² or more,
The larger the amount, the stronger the adhesion can be strengthened, but excessive use is disadvantageous in cost. Further, it is preferable to add alcohols such as methanol in order to improve the suitability for coating the undercoat liquid on the resin surface. In this case, the proportion of alcohols is preferably 20% by weight or more, more preferably 40% by weight or more, and most preferably 6% by weight.
It is 0% by weight or more. Further, in order to further improve the coating suitability, it is preferable to use various surfactants such as anionic, cationic, amphoteric, nonionic, fluorocarbon-based, and organosilicon-based surfactants.

Further, it is preferable to add a water-soluble polymer such as gelatin in order to obtain a good undercoat coated surface. Considering the stability of the compound of the general formula [U], the pH of the solution is pH 4
To pH 11 is preferable, and more preferably pH 5 to pH 1
It is 0. The surface of the thermoplastic resin is preferably surface-treated before applying the undercoat liquid. As the surface treatment, corona discharge treatment, fire treatment, plasma treatment or the like can be used. In applying the undercoat liquid,
Gravure coater, bar coater, dip coating method,
The coating can be carried out by a generally well-known coating method such as an air knife coating method, a curtain coating method, a roller coating method, a doctor coating method or an extrusion coating method. The drying temperature for coating is preferably 30 ° C. to 100 ° C., more preferably 50 ° C. to 100 ° C., and most preferably 70 ° C. to 100 ° C. The upper limit is determined by the heat resistance of the resin, and the lower limit is determined by the productivity efficiency.

The compound represented by the above general formula [I] used in the present invention will be described in detail below. In formula [I], Q represents an atomic group necessary for forming a 5-membered or 6-membered heterocycle or a 5-membered or 6-membered heterocycle condensed with a benzene ring. As the ring, for example, imidazole ring, tetrazole ring, thiazole ring, oxazole ring, selenazole ring, benzimidazole ring, naphthimidazole ring, benzothiazole ring, naphthothiazole ring, benzoselenazole ring,
Examples thereof include naphthoselenazole ring and benzoxazole ring.

Examples of the cation represented by M include an alkali metal (for example, sodium and potassium) and an ammonium group. The mercapto compound represented by the general formula [I] further includes the following [I-1], [I-2],
Mercapto compounds represented by [I-3] and [I-4] are preferable. General formula [I-1]

[0031]

[Chemical 6]

In the formula [I-1], R _A is a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a halogen atom, a carboxyl group or a salt thereof, a sulfo group or a salt thereof,
Alternatively, it represents an amino group, Z represents —NH—, —O—, or —S—, and M has the same meaning as M in formula [I]. General formula [I-2]

[0033]

[Chemical 7]

In the formula [I-2], Ar represents a group represented by the following chemical formula 8 and M has the same meaning as M in the general formula [I].

[0035]

[Chemical 8]

In Chemical Formula 8, R _B is an alkyl group, an alkoxy group, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a hydroxyl group, an amino group, an acylamino group,
It represents a carbamoyl group or a sulfonamide group. n is 0
Represents an integer of 2;

In the general formulas [I-1] and [I-2], examples of the alkyl group represented by R _A and R _B include methyl, ethyl and butyl, and examples of the alkoxy group include methoxy and ethoxy. Examples of the salt of carboxyl group or sulfo group include sodium salt, ammonium salt and the like. The amino group may be an unsubstituted amino group or an amino group substituted with an alkyl group, an aryl group, an acyl group or the like.

In the general formula [I-1], examples of the aryl group represented by R _A include phenyl and naphthyl, and examples of the halogen atom include chlorine atom, bromine atom and the like.

In the general formula [I-2], the acylamino group represented by R _B is, for example, methylcarbonylamino,
Examples thereof include benzoylamino and the like, examples of the carbamoyl group include ethylcarbamoyl and phenylcarbamoyl, and examples of the sulfonamide group include methylsulfoamide, phenylsulfonamide and the like.

The above-mentioned alkyl group, alkoxy group, aryl group, amino group, acylamino group, carbamoyl group, sulfonamide group and the like include those further having a substituent. General formula [I-3]

[0041]

[Chemical 9]

In the formula [I-3], Z represents --NR _A1- , an oxygen atom or a sulfur atom. _RA is a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group,-
_{SR A1, -NR A2 (R A3} ), - NHCOR A4, -NHS
O ₂ R _A5 or a heterocyclic group, R _A1 represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, —COR _A4 , or —SO ₂ R _A5 , and R _A2 and R _A3 represent hydrogen. Represents an atom, an alkyl group, or an aryl group, and R _A4 and R _A5 represent an alkyl group or an aryl group. M has the same meaning as M in formula [I].

R _A , R _A1 , R in the general formula [I-3]
Examples of the alkyl group represented by _A2 , R _A3 , R _A4 and R _A5 include methyl, ethyl, propyl and benzyl, and examples of the aryl group include phenyl and naphthyl.

Examples of the alkenyl group represented by R _A and R _A1 include propenyl and the like, and examples of the cycloalkyl group include cyclohexyl and the like. Examples of the heterocyclic group represented by R _A include furyl and pyridinyl.

Alkyl groups and aryl groups represented by R _A , R _A1 , R _A2 , R _A3 , R _A4 and R _A5 , alkenyl groups and cycloalkyl groups represented by R _A and R _A1 , and R _A The heterocyclic group represented by includes those having a substituent. General formula [I-4]

[0046]

[Chemical 10]

In the formula [I-4], R _A and M each represent the same group as R _A and M in the general formula [I-3]. R _B1 and R _B2 are each represented by the general formula [I-3].
Represents a group having the same meaning as R _A1 and R _{A2 in} .

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

[0049]

[Chemical 11]

[0050]

[Chemical 12]

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

[0054]

[Table 4]

[0055]

[Table 5]

[0056]

[Table 6]

The addition amount of the compound represented by the general formula [I] is 1 × 10 ^{-5 to} 5 × 10 ^-2 per mol of silver halide.
The amount is preferably mol, more preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻² mol. Further, the addition place is not particularly limited, and it may be added in either the photosensitive layer or the non-photosensitive layer. Further, the addition method and addition timing are not particularly limited, and during silver halide grain formation, physical ripening,
It may be either during chemical ripening or during preparation of the coating solution.

The hardener of the present invention represented by the general formula [II] will be described in more detail. In the formula, X ¹ and X ² are either —CH═CH ₂ or —CH ₂ CH ₂ —Y, and X ¹ and X ² may be the same or different. Y is replaced by a nucleophile (nucleophilic group),
It represents a group capable of splitting off in the form of HY by a base. L is 2
It is a valent linking group and may be substituted. Specific examples of preferable examples include the following.

[0059]

[Chemical 13]

Among these, especially

[0061]

[Chemical 14]

Is preferred, and —CH═CH ₂ is most preferred. The divalent linking group L is an alkylene group (including a cycloalkylene group) or an arylene group (2 of a heteroaromatic ring group).
(Including a valent group), or with these groups, -O-, -NR ¹
_{-, - SO 2 -, -} SO 3 -, - S -, - SO -, - SO
NR ^1- , -CO-, -COO-, -CONR ^1- , -N
R ¹ COO-, -NR ¹ CONR ^1- bond 1
Formed by combining two or more
It is a valence group. R ¹ represents a hydrogen atom, or an alkyl group, an aryl group or an aralkyl group having 1 to 15 carbon atoms. In addition, -NR ^1- , -SONR ^1- , -CO
^{NR 1 -, - NR 1 COO} -, - NR 1 CONR 1 - If you combine comprising two or more shown, may be bonded their R ¹ together may form a ring. Further, the above alkylene group and arylene group may have a substituent, and as the substituent, a hydroxy group, an alkoxy group, a carbamoyl group, a sulfamoyl group, a sulfo group or a salt thereof, a carboxyl group or a salt thereof, a halogen atom, Examples thereof include an alkyl group, an aralkyl group and an aryl group. Further, the substituent may be further substituted with one or more groups represented by X ³ —SO ₂ —. X ³ has the same meaning as X ¹ and X ² described above.

The following are typical examples of L. However, a to k in the examples are integers from 1 to 6. Only e may be 0, preferably 2 or 3. 1 or 2 is preferable for a to k excluding e,
1 is particularly preferred. In the formula, R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom, methyl or ethyl.

[0064]

[Chemical 15]

Next, typical examples of the hardener used in the present invention will be given, but the present invention is not limited thereto.

[0066]

[Chemical 16]

The method for synthesizing the hardener used in the present invention is described, for example, in JP-B-47-2429 and 50-3580.
7, JP-A-49-24435 and JP-A-53-41221.
No. 59-18944 and the like. The amount of the hardener used in the present invention is 0.01 to 20% by weight based on the total dry gelatin used in the light-sensitive material.
It is particularly preferably in the range of 0.1 to 10% by weight. In the present invention, the hardener may be added to the coating solution in advance or mixed with the coating solution immediately before coating. The hardener used in the present invention may be used alone or in combination of two or more kinds. Further, it may be used in combination with other known hardeners. A compound that accelerates the hardening reaction of gelatin can be used in combination with the hardening agent of the present invention. For example, it is effective to use a polymer containing a sulfinic acid group described in JP-A-56-4141 as a hardening accelerator together with the hardening agent of the present invention.

Next, preferred examples of the carboxyl group-activating type hardener in the present invention include compounds represented by the following general formulas (2) to (8).

[0069]

[Chemical 17]

In the general formula (2), R ¹¹ and R ¹² have 1 to 1 carbon atoms.
Represents an alkyl group having 10 carbon atoms (eg, methyl, ethyl, 2-ethylhexyl), an aryl group having 6 to 15 carbon atoms (eg, phenyl, naphthyl), or an aralkyl group having 7 to 15 carbon atoms (eg, benzyl, phenethyl), and is the same as each other. Or may be different. It is also preferable that R ¹¹ and R ¹² are bonded to each other to form a heterocycle with a nitrogen atom. Examples of forming a ring include a pyrrolidine ring, a piperazine ring, a morpholine ring and the like. R ¹³ is a hydrogen atom,
Halogen atom, carbamoyl group, sulfo group, sulfooxy group, sulfoamino group, ureido group, alkoxy group having 1 to 10 carbon atoms, alkyl group having 1 to 10 carbon atoms, and 2 carbon atoms
~ 20 represents a substituent such as a dialkyl-substituted amino group. When R ¹³ is an alkoxy group, an alkyl group, a dialkylamino group or an N-alkylcarbamoyl group, those groups may further have a substituent, and examples of the substituent include a halogen atom, a carbamoyl group and a sulfo group. , A sulfooxy group, a sulfoamino group, and a ureido group. X ⁻ represents an anion and serves as a counter ion of the N-carbamoylpyridinium salt. When the substituent of R ¹³ contains a sulfo group, a sulfooxy group or a sulfoamino group,
X ⁻ may be absent by forming an inner salt. Preferred examples of the anion include halide ion, sulfate ion, sulfonate ion, ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ^−.
And so on.

A detailed description of the carbamoyl ammonium salt type hardener represented by the general formula (2) can be found in JP-B-56-12853, JP-A-58-32699 and JP-A-4.
9-51945, 51-59625, 61-9
For more information, please refer to publications such as No. 641.

[0072]

[Chemical 18]

In the general formula (3), the definitions of R ¹¹ , R ¹² , R ¹³ and X ⁻ are exactly the same as those in the general formula (2), and these compounds are described in Belgian Patent No. 825,726.
Detailed in the issue.

[0074]

[Chemical 19]

In the general formula (4), R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each an alkyl group having 1 to 20 carbon atoms (eg methyl, ethyl, butyl, 2-ethylhexyl, dodecyl), and 6 to 6 carbon atoms. 20 aralkyl groups (eg benzyl, phenethyl, 3-pyridylmethyl) or aryl groups having 5 to 20 carbon atoms (eg phenyl, naphthyl, pyridyl), which may be the same or different. R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ may have a substituent, and examples of the substituent include a halogen atom, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. Group, N, N-disubstituted carbamoyl group and the like.

It is also preferable that any two of R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are bonded to form a ring. For example, examples of R ¹⁴ and R ¹⁵ or R ¹⁶ and R ¹⁷ bonded to each other to form a ring together with a nitrogen atom include a case where a pyrrolidine ring, a piperazine ring, a perhydroazepine ring, a morpholine ring and the like are formed. Examples of R ¹⁴ and R ¹⁶ or R ¹⁵ and R ^{17 which} are bonded to each other to form a ring with two nitrogen atoms and a carbon atom sandwiched between them include an imidazoline ring, a tetrahydropyrimidine ring and a tetrahydrodiazepine. The case where a ring etc. are formed is mentioned.

X represents a group capable of leaving when the compound represented by the general formula (4) reacts with a nucleophile, and preferable examples thereof include a halogen atom and a sulfonyloxy group. Y ⁻ represents an anion, a halide ion,
Sulfonate ion, sulfate ion, ClO ₄ ⁻ , BF ₄ ⁻ ,
PF _6- ^{and the} like are preferable. When Y ⁻ represents a sulfonate ion, it may combine with X, R ¹⁴ , R ¹⁵ , R ¹⁶ or R ¹⁷ to form an inner salt.

The amidinium salt hardener represented by the general formula (4) is described in detail in JP-A-60-225148.

General formula (5) R ¹⁸ -N = C = N-R ¹⁹

In the general formula (5), R ¹⁸ is an alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, 2-ethylhexyl), a cycloalkyl group having 5 to 8 carbon atoms (for example, cyclohexyl), and 3 to 3 carbon atoms. It represents an alkoxyalkyl group having 10 carbon atoms (eg methoxyethyl) or an aralkyl group having 7 to 15 carbon atoms (eg benzyl, phenethyl).
In addition to the group defined for R ¹⁸ , R ¹⁹ is preferably a group represented by the following chemical formula 20.

[0081]

[Chemical 20]

In Chemical Formula 20, R ²⁰ represents an alkylene group having 2 to 4 carbon atoms (eg, ethylene, propylene, trimethylene, etc.). R ²¹ and R ²² may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms (for example, methyl or ethyl). It is also preferable that R ²¹ and R ²² are bonded to form a heterocycle (eg, a pyrrolidine ring, a piperazine ring, a morpholine ring) together with a nitrogen atom.
R ²³ represents an alkyl group having 1 to 6 carbon atoms (eg methyl, ethyl, butyl, etc.), but it is also preferably substituted. As examples of the substituent, a substituted or unsubstituted carbamoyl group, a sulfo group and the like are preferable. X ⁻ represents an anion, and halide ion, sulfonate ion, sulfate ion, ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ^{− and the} like are preferable. When R ²³ is substituted with a sulfo group, it may form an inner salt and X ⁻ may not be present.

These carbodiimide type hardeners are described in detail in JP-A-51-126125 and JP-A-52-48311.

[0084]

[Chemical 21]

In the general formula (6), R ²⁴ is an alkyl group having 1 to 10 carbon atoms (eg, methyl, ethyl, butyl), an aryl group having 6 to 15 carbon atoms (eg, phenyl, naphthyl),
Alternatively, it represents an aralkyl group having 7 to 15 carbon atoms (eg, benzyl, phenethyl). These groups may be substituted, and examples of the substituent include a carbamoyl group, a sulfamoyl group and a sulfo group. R ²⁵ and R ²⁶ are hydrogen atom, halogen atom, acylamido group, nitro group, carbamoyl group, ureido group, alkoxy group, alkyl group,
It represents a substituent such as an alkenyl group, an aryl group and an aralkyl group, which may be the same or different. It is also preferable that R ²⁵ and R ²⁶ are bonded to each other to form a condensed ring together with the pyridinium ring skeleton.

X represents a group capable of leaving when the compound represented by the general formula (6) reacts with a nucleophile, and a preferable example thereof is a halogen atom, a sulfonyloxy group or-.
A group represented by OP (= O) (OR ²⁷ ) ₂ (R ²⁷ represents an alkyl group or an aryl group) can be mentioned. X
When R represents a sulfonyloxy group, it is also preferred that X and R ²⁴ are bonded. Y ⁻ represents an anion, which is a halide ion, a sulfonate ion, a sulfate ion,
ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ^{− and the} like are preferable. When R ²⁴ is substituted with a sulfo group, it forms an intramolecular salt to give Y.
^- it may not be present.

Regarding these pyridinium salt type hardeners, JP-B-58-50699 and JP-A-57-4414.
No. 0 and No. 57-46538 have detailed description.

[0088]

[Chemical formula 22]

[0089] In the general formula (7), the definition of R ^11, R ¹² is exactly the same in the general formula (2) and the definition of R ^11, R ^12,
R ²⁸ represents an alkyl group having 1 to 10 carbon atoms (eg, methyl, ethyl, butyl), an aryl group having 6 to 15 carbon atoms (eg, phenyl, naphthyl), or an aralkyl group having 7 to 15 carbon atoms (eg, benzyl, phenethyl). Represents X ⁻ is an anion, and halide ion, sulfonate ion, sulfate ion, ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ^{− and the} like are preferable.

The pyridinium salt hardener represented by the general formula (7) is described in detail in JP-A-52-54427.

[0091]

[Chemical formula 23]

In the general formula (8), R ²⁹ is an alkyl group having 1 to 10 carbon atoms (eg, methyl, ethyl, 2-ethylhexyl), an aryl group having 6 to 15 carbon atoms (eg, phenyl,
Naphthyl etc.) or an aralkyl group having 7 to 15 carbon atoms (eg benzyl, phenethyl etc.) and may be substituted or unsubstituted. Examples of the substituent include a halogen atom, a carbamoyl group, a sulfo group, a sulfoxy group, a ureido group, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, and a dialkyl-substituted amino group having 2 to 20 carbon atoms. There is.

Z represents a group of non-metal atoms necessary for completing the nitrogen-containing heteroaromatic ring, and preferred examples thereof include a pyridine ring, a pyrimidine ring, a pyrazole ring, an imidazole ring, an oxazole ring, and their benzo-fused rings. is there.
R ³⁰ is a hydrogen atom, a halogen atom, a carbamoyl group, a sulfo group, a sulfooxy group, a ureido group, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or 2 carbon atoms.
~ 20 represents a substituent such as a dialkyl-substituted amino group. When R ³⁰ is an alkoxy group, an alkyl group, a dialkylamino group or an N-alkylcarbamoyl group, these groups may be further substituted, and examples of these substituents include a halogen atom, a carbamoyl group and a sulfo group. ,
Examples thereof include sulfooxy group and ureido group. X ⁻ represents an anion. When R ²⁹ , R ³⁰ or a substituent thereof contains a sulfo group or a sulfooxy group, an internal salt is formed and X ⁻ may not be present. Preferred examples of the anion include halide ion, sulfate ion, sulfonate ion, ClO ₄ ⁻ , BF ₄ ⁻ and PF ₆ ⁻ .

As the carboxyl group-activating type hardener used in the present invention, in addition to the compounds represented by the above general formulas (2) to (8), JP-A-50-38540,
JP-A-52-93470, JP-A-56-43353
No. 58-113929, U.S. Pat. No. 3,32
The compounds described in No. 1,313 and the like are also preferable. Particularly preferably, the hardener used in the present invention has the general formula (2)
It is a hardener represented by. Specific examples of the compound (carboxyl group-activating hardener) used in the present invention will be classified below, but the present invention is not limited thereto.

[0095]

[Chemical formula 24]

[0096]

[Chemical 25]

[0097]

[Chemical formula 26]

[0098]

[Chemical 27]

[0099]

[Chemical 28]

[0100]

[Chemical 29]

[0101]

[Chemical 30]

[0102]

[Chemical 31]

[0103]

[Chemical 32]

[0104]

[Chemical 33]

[0105]

[Chemical 34]

The amount of the carboxyl group-activating type hardener used in the present invention can be arbitrarily selected according to the purpose. Normally 0.01 to 20% by weight based on dry gelatin
It can be used in the ratio of the range. Particularly preferably 0.05 to
Used in proportions in the range of 15% by weight. There is no particular limitation on the photographic layer to which the hardener represented by the general formula [II] of the present invention or the carboxyl group-activated hardener is added. It can be used in any gelatin-containing photographic layer such as a layer, a filter layer, an intermediate layer and an overcoat layer.

The hardener of the present invention may be used alone as described above, or two or more hardeners of the present invention may be mixed and used. It may be used in combination with other hardeners known so far. Known hardeners include
For example, aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,3.
5-triazine and others U.S. Pat. No. 3,288,77
5, 2,732,303, British Patent 974,7
No. 23, No. 1,167,207, and the like, compounds having a reactive halogen, 5-acetyl-
1,3-diacryloylhexahydro-1,3,5-triazine, other U.S. Pat. No. 3,635,718,
No. 3,232,763, compounds having reactive olefins described in British Patent No. 994,869, etc., N-hydroxymethylphthalimide, and other U.S. Pat. Nos. 2,732,316, 2, N-methylol compounds described in US Pat. No. 586,168, isocyanates described in US Pat. No. 3,103,437, US Pat. Nos. 3,017,280 and 2,98.
Aziridine compounds described in 3,611, etc.,
US Pat. Nos. 2,725,294 and 2,725,29
5, acid derivatives described in US Pat. No. 3,0
Examples thereof include epoxy compounds described in No. 91,537 and halogen carboxaldehydes such as mucochloric acid.

Alternatively, as the inorganic compound hardener, there are chromium alum, zirconium sulfate and the like. In addition, instead of the above compounds, precursors are used, for example, alkali metal bisulfite aldehyde adducts, methylol derivatives of hydantoin, primary aliphatic nitroalcohols, mesyloxyethylsulfonyl compounds, chloroethylsulfonyl. You may use together with a system compound.
When the hardener of the present invention is used in combination with other hardeners, the use ratio of the hardener of the present invention can be selected arbitrarily according to the purpose and effect, but the hardener of the present invention Agent is 50 mol%
The above is preferable.

Gelatin to which the hardener of the present invention is applied is, in the manufacturing process thereof, so-called alkali-treated (lime-treated) gelatin which is immersed in an alkali bath before extraction of gelatin, acid-treated gelatin which is immersed in an acid bath, and the like. Either double-immersed gelatin that has undergone both treatments or enzyme-treated gelatin may be used. Further, the hardener of the present invention can be applied to low molecular weight gelatin obtained by heating these gelatins in a water bath or causing them to act on a protease to partially hydrolyze them.

In the color light-sensitive material of the present invention, 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 are coated on a support having a reflective layer. It can be installed and configured. In general color photographic paper, color reproduction by the subtractive method can be performed by including a color coupler which forms a dye having a complementary color relationship with the light to which the silver halide emulsion is exposed. In a general color photographic paper, silver halide emulsion grains are spectrally sensitized by the blue-sensitive, green-sensitive and red-sensitive spectral sensitizing dyes in the order of the color-forming layers described above, and on the support in the order described above. It can be constructed by coating. However, the order may be different from this. In other words, from the viewpoint of rapid processing, it is preferable that the photosensitive layer containing the largest silver halide grains having the average grain size comes to the uppermost layer, or from the viewpoint of storage stability under light irradiation, the lowermost layer is the magenta color photosensitive layer. In some cases it may be preferable to do so. Further, the photosensitive layer and the coloring hue may not have the above correspondence, and at least one infrared-sensitive silver halide emulsion layer can be used.

In the present invention, the silver halide grains are 9
It is necessary to use silver chloride, silver chlorobromide, or silver chloroiodobromide grains in which 0 mol% or more is silver chloride. In particular, in the present invention, in order to accelerate the development processing time, a silver chlorobromide or silver chloride containing substantially no silver iodide can be preferably used. The term "substantially free of silver iodide" as used herein means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. On the other hand, 0.01 to 3 mol% is added to the emulsion surface as described in JP-A-3-84545 for the purpose of enhancing high illuminance sensitivity, spectral sensitization sensitivity, or enhancing stability over time of the light-sensitive material. In some cases, high silver chloride grains containing silver iodide are preferably used. The halogen composition of the emulsion may be different or the same between grains, but if an emulsion having the same halogen composition among grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, the so-called uniform structure grains having the same composition in any part of the silver halide grains, or the core inside the silver halide grains and the shell surrounding it. (Shell) [a single layer or a plurality of layers] particles having a so-called laminated structure having a different halogen composition, or a structure having a portion having a different halogen composition inside or on the surface of the particle (edge of the particle when present on the particle surface, It is possible to appropriately select and use particles having a structure in which parts having different compositions are bonded to a corner or a surface. In order to obtain high sensitivity, it is advantageous to use either of the latter two rather than the particles having a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the structure as described above, the boundary between different portions in the halogen composition is an unclear boundary because a mixed crystal is formed due to the composition difference even if the boundary is clear. It may also be one that positively has a continuous structural change.

The high silver chloride emulsion used in the present invention preferably has a structure having a silver bromide localized phase in the inside and / or on the surface of the silver halide grain in the form of layer or non-layer as described above. The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%, more preferably more than 20 mol%. The silver bromide content of the localized silver bromide layer is analyzed by using an X-ray diffraction method (for example, described in "Chemical Society of Japan, New Experimental Chemistry Lecture 6, Structural Analysis" Maruzen). can do. And these localized phases are the inside of the particle, the edge of the particle surface,
It can be on a corner or on a surface, but one preferred example is one that is epitaxially grown on the corner of the grain. It is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the replenishment amount of the developing solution. In such a case, an almost pure silver chloride emulsion having a silver chloride content of 98 mol% to 100 mol% is also preferably used.

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 grain and the number average thereof is taken) is 0. 1 μm to 2 μm is preferable. Further, the particle size distribution thereof is preferably a so-called monodisperse coefficient of variation of 20% or less (standard deviation of particle size distribution divided by average particle size), preferably 15% or less, more preferably 10% or less. . At this time, it is also preferable to use the above monodisperse emulsion by blending it in the same layer for the purpose of obtaining a wide latitude, or to perform multi-layer coating. The shape of silver halide grains contained in a photographic emulsion is one having a regular crystal form such as a cube, a tetradecahedron or an octahedron, an irregular shape such as a sphere or a plate. ) Those having a crystalline form or those having a composite form thereof can be used. It may also be a mixture of materials having various crystal forms. In the present invention, 50% or more, preferably 7% or more of the particles having the above-mentioned regular crystal form are used in the present invention.
It is preferable to contain 0% or more, more preferably 90% or more. In addition to these, an emulsion having tabular grains having an average aspect ratio (diameter in terms of circle / thickness) of 5 or more, preferably 8 or more as a projected area exceeding 50% of all grains can be preferably used.

The silver salt (bromide) bromide emulsion used in the present invention is P.Gl.
Chimie et Phisique Photographique (Paul by afkides
Montel, 1967), by GF Duffin Photographi
c Emulsion Chemistry (Focal Press, 1966
,) By VL Zelikman et al Making and Coating Phot
It can be prepared using the method described in, for example, ographic Emulsion (Focal Press, Inc., 1964). That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be any one of a one-sided mixing method, a simultaneous mixing method, and a combination thereof. You may use. It is also possible to use a method of forming grains in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

The localized phase of the silver halide grain of the present invention or its substrate preferably contains different metal ions or complex ions thereof. The preferred metal is selected from metal ions or metal complexes belonging to Group VIII and Group IIb of the Periodic Table, and lead ions and thallium ions. Ions mainly selected from iridium, rhodium and iron or their complex ions in the localized phase, and metal ions selected mainly from osmium, iridium, rhodium, platinum, ruthenium, palladium, cobalt, nickel and iron as the substrate. Alternatively, the complex ions can be used in combination. Further, the type and concentration of the metal ion can be changed depending on the localized phase and the substrate. Plural kinds of these metals may be used. In particular, iron and iridium compounds are preferably present in the silver bromide localized phase.

These metal ion-providing compounds are used in a gelatin aqueous solution which becomes a dispersion medium when silver halide grains are formed,
Of the silver halide grains of the present invention by means such as adding in an aqueous solution of a halide, in an aqueous solution of a silver salt or other aqueous solution, or in the form of fine silver halide grains containing a metal ion in advance and dissolving the fine grains. It is contained in the localized phase and / or other particle portion (matrix). The metal ion used in the present invention can be incorporated into the emulsion grains either before grain formation, during grain formation, or immediately after grain formation. This can be changed depending on the position of the metal ion contained in the particle.

The silver halide emulsion used in the present invention is
Usually, it is chemically and spectrally sensitized. Regarding the chemical sensitization method, chemical sensitization using a chalcogen sensitizer (specifically, sulfur sensitization represented by the addition of an unstable sulfur compound, selenium sensitization with a selenium compound, and tellurium sensitization with a tellurium compound are performed. Noble metal sensitization typified by gold sensitization, reduction sensitization and the like can be used alone or in combination. As the compound used for the chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used. The effect of the constitution of the light-sensitive material of the present invention is more remarkable than when the gold-sensitized high silver chloride emulsion is used. The emulsion used in the present invention is a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface.

The silver halide emulsion used in the present invention includes various compounds or precursors thereof for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. Can be added. Specific examples of these compounds are described in JP-A-62-2.
Those described on pages 39 to 72 of the specification of Japanese Patent No. 15272 are preferably used. Furthermore, the 5-arylamino-1,2,3,4-thiatriazole compounds described in EP 0447647 (wherein the aryl residue has at least one electron-withdrawing group) are also preferably used.

Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength region to the emulsion of each layer in the light-sensitive material of the present invention. In the light-sensitive material of the present invention, blue, green,
Examples of spectral sensitizing dyes used for spectral sensitization in the red region include, for example, Heterocyclic compounds-Cyanine by FM Harmer.
dyes andrelated compounds (John Wiley & Sons [New
York, London] 1964). As specific examples of compounds and the spectral sensitization method, those described in JP-A-62-215272, page 22, upper right column to page 38 are preferably used. Further, as a red-sensitive spectral sensitizing dye for silver halide emulsion grains having a particularly high silver chloride content, JP-A-3-12 is known.
The spectral sensitizing dye described in No. 3340 is very preferable from the viewpoint of stability, strength of adsorption, temperature dependence of exposure and the like.

In the case of efficiently spectrally sensitizing the infrared region of the light-sensitive material of the present invention, JP-A-3-15049, page 12, upper left column to page 21, lower left column, or JP-A-3-20730, page 4, lower left column to page 15 Lower left column, EP-0,420,011
No. 4, line 21 to page 6, line 54, EP-0, 420, 012
No. 4, page 12, line 10 to page 33, EP-0,443,46
The sensitizing dyes described in US Pat. No. 6, US-4,975,362 are preferably used.

To incorporate these spectral sensitizing dyes in the silver halide emulsion, they may be dispersed directly in the emulsion, or water, methanol, ethanol, propanol, methyl cellosolve, 2,2,2. It may be added to the emulsion by dissolving it in a solvent such as 3,3-tetrafluoropropanol alone or in a mixed solvent. Also, Japanese Patent Publication No.
No. 3389, Japanese Patent Publication No. 44-27555, Japanese Patent Publication No. 57-
As described in 22089 and the like, an acid or a base is allowed to coexist to prepare an aqueous solution, and as described in U.S. Pat. No. 3,822,135 and U.S. Pat. It may be added to the emulsion. Alternatively, the emulsion may be dissolved in a solvent which is substantially immiscible with water, such as phenoxyethanol, and then dispersed in water or a hydrophilic colloid to be added to the emulsion. JP-A-53-102733, JP-A-58-105141
Alternatively, the dispersion may be directly dispersed in a hydrophilic colloid, and the dispersion may be added to the emulsion. The time of addition to the emulsion may be any stage of emulsion preparation known to be useful so far. In other words, before preparing the silver halide emulsion grains, during grain formation, immediately after grain formation, before entering the washing step, before chemical sensitization, during chemical sensitization, immediately after chemical sensitization, until the emulsion is cooled and solidified. You can choose from either. Most commonly, it is carried out after the completion of chemical sensitization and before the application, but is described in US Pat.
No. 5,289,139, and spectral sensitization can be carried out simultaneously with chemical sensitization by adding the chemical sensitizer at the same time as described in JP-A No. 628969 and No. 4225666.
It can be carried out prior to chemical sensitization as described in No. 28, or it can be added before the completion of silver halide grain precipitation to initiate spectral sensitization. It is also possible to add the spectral sensitizing dyes separately, as taught in U.S. Pat. No. 4,225,666, i.e. a portion prior to chemical sensitization and the balance after chemical sensitization. It is possible and can be at any time during silver halide grain formation, including the method taught in US Pat. No. 4,183,756. Of these, it is particularly preferable to add a sensitizing dye before the step of washing the emulsion with water or before the chemical sensitization.

The addition amount of these spectral sensitizing dyes is wide depending on the case and is 0.5 per mol of silver halide.
The range of × 10 ^-6 mol to 1.0 × 10 ^-2 mol is preferable.
More preferably, 1.0 × 10 ^-6 mol to 5.0 × 10 ^-3
It is in the molar range. In the present invention, particularly when a sensitizing dye having a spectral sensitizing sensitivity in the red region to the infrared region is used, the compounds described in JP-A-2-157749, page 13, lower right column to page 22, lower right column, may be used in combination. preferable. By using these compounds, the storability of the light-sensitive material, the processing stability, and the supersensitizing effect can be specifically enhanced. Above all, it is particularly preferable to use the compounds of the general formulas (IV), (V) and (VI) in the same patent in combination. These compounds are used in an amount of 0.5 × 10 ⁻⁵ mol to 5.0 mol per mol of silver halide.
× 10 ^-2 mol, preferably 5.0 × 10 ^-5 mol to 5.0
An amount of × 10 ^-3 mol is used, and is 0.1 to 10,000 times, preferably 0.5 to 500 times per mol of the sensitizing dye.
There is an advantageous amount used in the range of 0 times.

The light-sensitive material of the present invention is used in a printing system using an ordinary negative printer, in addition to a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a solid laser using a semiconductor laser as an excitation light source and a nonlinear laser. It is preferably used for digital scanning exposure using monochromatic high density light such as a second harmonic generation light source (SHG) combined with an optical crystal. In order to make the system compact and inexpensive, it is preferable to use a semiconductor laser, or a second harmonic generation light source (SHG) that is a combination of a semiconductor laser or a solid-state laser and a nonlinear optical crystal. In particular, in order to design an apparatus which is compact, inexpensive, has a long life and high stability, it is preferable to use a semiconductor laser, and it is desirable to use a semiconductor laser as at least one of the exposure light sources.

When using such a scanning exposure light source,
The spectral sensitivity maximum of the light-sensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source used. A solid-state laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser with a nonlinear optical crystal can halve the oscillation wavelength of the laser, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the light-sensitive material can be provided in the normal three regions of blue, green and red. In order to use a semiconductor laser as a light source in order to make the device inexpensive, highly stable and compact, it is preferable that at least two layers have a spectral sensitivity maximum at 670 nm or more. This is because currently available inexpensive and stable III-V semiconductor lasers have emission wavelengths only in the red to infrared regions. However, at the laboratory level, the oscillation of II-VI group semiconductor lasers in the green and blue regions has been confirmed, and if semiconductor laser manufacturing technology is developed, these semiconductor lasers can be used inexpensively and stably. It is fully expected. In such a case, it is less necessary for at least two layers to have a spectral sensitivity maximum at 670 nm or more.

In such scanning exposure, the time for which the silver halide in the photosensitive material is exposed is the time required for exposing a certain minute area. As this minute area, the minimum unit for controlling the light quantity from each digital data is generally used and is called a pixel. Therefore, the exposure time per pixel changes depending on the size of this pixel. The size of this pixel depends on the pixel density and is in a practical range of 50 to 2000 dpi. When the exposure time is defined as the time for exposing 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 light-sensitive material according to the present invention has a hydrophilic colloid layer for the purpose of preventing irradiation and halation and improving safety of safelight. It is preferable to add the dyes which can be decolorized by the treatment (in particular, oxonol dyes and cyanine dyes) described above. Some of these water-soluble dyes may deteriorate color separation and safelight safety when the amount used is increased. As a dye that can be used without deteriorating color separation, Japanese Patent Application No. 03-310
No. 143, Japanese Patent Application No. 03-310189, Japanese Patent Application No. 03-
Water-soluble dyes described in 310139 are preferred.

In the present invention, a colored layer which can be decolorized by treatment is used in place of the water-soluble dye or in combination with the water-soluble dye. The coloring layer that can be decolorized by the treatment used may be in direct contact with the emulsion layer, or may be disposed so as to be in contact with the emulsion layer via an intermediate layer containing a treatment color mixing inhibitor such as gelatin or hydroquinone. This colored layer is preferably provided in the lower layer (support side) of the emulsion layer that develops a primary color of the same kind as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to selectively install only a part of them. It is also possible to install a colored layer that is colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is in the wavelength range used for exposure (from 400 nm to 70 in normal printer exposure).
In the visible light region of 0 nm, the wavelength of the scanning exposure light source used in the case of scanning exposure), the optical density value at the wavelength having the highest optical density is preferably 0.2 or more and 3.0 or less. It is more preferably 0.5 or more and 2.5 or less, and particularly preferably 0.8 or more and 2.0 or less.

A conventionally known method can be applied to form the colored layer. For example, Japanese Patent Laid-Open No. 2-282244-3
The dyes described on page 8 from the upper right column of the page, and JP-A-3-79
No. 31, page 3, upper right column to page 11, lower left column, a method of incorporating a solid fine particle dispersion in a hydrophilic colloid layer, a method of mordanting an anionic dye with a cationic polymer, a halogenation of the dye Examples thereof include a method of adsorbing to fine particles such as silver and fixing in a layer, a method of using colloidal silver as described in JP-A-1-239544, and the like. As a method for dispersing a fine powder of a pigment in a solid state, for example, a method of containing a fine powder dye that is substantially water-insoluble at a pH of 6 or less but is substantially water-soluble at a pH of 8 or more is disclosed. 2-30824
No. 4, pages 4-13. Also, for example,
A method of mordanting an anionic dye on a cationic polymer is described in JP-A-2-84637, pages 18 to 26. For the preparation method of colloidal silver as a light absorber, see US Pat. Nos. 2,688,601 and 3,45.
No. 9,563. Among these methods, the method of incorporating a fine powder dye and the method of using colloidal silver are preferable.

As the binder or protective colloid that can be used in the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. Preferred gelatin has a calcium content of 800 p
It is preferable to use low calcium gelatin of pm or less, more preferably 200 ppm or less. Further, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, it is preferable to add an antifungal agent as described in JP-A-63-271247.

When the light-sensitive material of the present invention is exposed to a printer, it is preferable to use the band stop filter described in US Pat. No. 4,880,726. As a result, light color mixture is removed, and color reproducibility is significantly improved. The exposed light-sensitive material can be subjected to a conventional color development process, but in the case of the color light-sensitive material of the present invention, it is preferable to perform bleach-fixing after color development for the purpose of rapid processing.
Particularly when the above high silver chloride emulsion is used, the pH of the bleach-fixing solution is preferably about 6.5 or less, more preferably about 6 or less for the purpose of promoting desilvering.

Silver halide emulsions and other materials (additives and the like) and photographic constituent layers (layer arrangement and the like) applied to the light-sensitive material according to the present invention, and a processing method applied for processing the light-sensitive material. As the treatment additives, those described in the following patent publications, particularly European Patent EP0,355,660A2 (JP-A-2-139544) are preferably used.

[0132]

[Table 7]

[0133]

[Table 8]

[0134]

[Table 9]

[0135]

[Table 10]

[0136]

[Table 11]

The cyan, magenta, or yellow coupler is impregnated with a loadable latex polymer (eg, US Pat. No. 4,203,716) in the presence (or absence) of the high boiling organic solvents described in the table above. It is preferable that the polymer is dissolved or dissolved with a water-insoluble polymer and an organic solvent-soluble polymer to be emulsified and dispersed in a hydrophilic colloid aqueous solution. Water-insoluble and organic solvent-soluble polymers that can be preferably used are described in US Pat. No. 4,857,449, columns 7 to 15 and International Publication WO88 / 007.
The homopolymers or copolymers described on pages 12 to 30 of the No. 23 specification can be mentioned. It is more preferable to use a methacrylate-based or acrylamide-based polymer, especially an acrylamide-based polymer in terms of color image stability and the like.

In the light-sensitive material according to the present invention, it is preferable to use a color image storability improving compound as described in European Patent EP 0277589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler or a pyrrolotriazole coupler. That is, by chemically bonding with the aromatic amine-based developing agent remaining after color development processing,
A compound chemically bonded to the compound in the above-mentioned patent specification which produces a substantially colorless compound and / or an oxidant of an aromatic amine color developing agent remaining after the color developing treatment It is possible to use the compounds in the above-mentioned patent specification, which form an inactive and substantially colorless compound, simultaneously or alone, for example, the reaction of the coupler with the residual color developing agent in the film or its oxidant and the coupler during storage after processing. It is preferable for preventing the occurrence of stains and other side effects due to the formation of the coloring pigment.

Further, as a cyan coupler, there is disclosed in JP-A-2-
In addition to the diphenylimidazole-based cyan coupler described in Japanese Patent No. 33144, European Patent EP 0333185A2.
3-hydroxypyridine type cyan couplers described in the above specification (in particular, the couplers listed as specific examples (4
(2) 4-equivalent couplers having a chlorine-releasing group to make them 2-equivalent, and couplers (6) and (9) are particularly preferable)
And cyclic active methylene cyan couplers described in JP-A-64-32260 (specifically, coupler examples 3, 8, and 34 listed as specific examples), and pyrrolo described in EP 0456226A1. Pyrazole type cyan coupler, European Patent EP044890
Pyrroylimidazole type cyan couplers described in No. 9, European Patent Nos. EP0488248 and EP04911.
Preference is given to using the pyrrolotriazole type cyan couplers described in 97A1. Of these, use of a pyrrolotriazole type cyan coupler is particularly preferable.

Further, as the yellow coupler, in addition to the compounds described in the above table, European Patent EP0447969 may be used.
Acylacetamide type yellow couplers having a 3- to 5-membered cyclic structure in the acyl group described in A1 specification, Malondianilide type yellow couplers having a cyclic structure described in European Patent EP 0482552A1, US Pat. The acylacetamide type yellow coupler having a dioxane structure described in 118,599 is preferably used. Among them, it is particularly preferable to use an acylacetamide type yellow coupler whose acyl group is a 1-alkylcyclopropane-1-carbonyl group, or a malondianilide type yellow coupler in which one of the anilide constitutes an indoline ring. These couplers can be used alone or in combination.

As the magenta coupler used in the present invention, 5-pyrazolone type magenta couplers and pyrazoloazole type magenta couplers as described in the publicly known documents of the above table are used, and among them, hue, image stability,
A pyrazolotriazole coupler in which a secondary or tertiary alkyl group is directly bonded to the 2, 3 or 6-position of a pyrazolotriazole ring as described in JP-A-61-65245 in terms of color developability, etc. -65246, a pyrazoloazole coupler containing a sulfonamide group in the molecule, a pyrazoloazole coupler having an alkoxyphenyl sulfonamide ballast group as described in JP-A-61-147254, and Europe. Patent No. 226,849
It is preferable to use a pyrazoloazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No. A and No. 294,785A. As the method for processing the color light-sensitive material of the present invention, in addition to the methods described in the above table, 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 to page 18, lower right column, line 20 The treatment method is preferred.

[0142]

EXAMPLES The present invention will be specifically described below with reference to examples, but of course the present invention is not limited thereto. Example 1 (Preparation of base paper) Wood pulp mixture (LBKP / NBS)
(P = 2/1) beat, Canadian freeness 250
cc pulp slurry. Then, after diluting this pulp slurry with water, 1.0% of anionic polyacrylamide per pulp (Arakawa Chemical Co., Ltd.) with stirring.
Made: Polystron 195, molecular weight about 1.1 million), aluminum sulfate 1.0%, and polyamide polyamine epichlorohydrin 0.15% (Kaymen 557: trade name of Dick Hercules Co., Ltd.) were added. Furthermore, 0.4 wt% of epoxidized behenic acid amide and alkyl ketene dimer (compound having an alkyl group of C ₂₀ H ₄₁ ) were added to the weight of the pulp, and sodium hydroxide was added to adjust the pH to 7. And 0.5% cationic polyacrylamide and 0.1% defoamer. The pulp slurry prepared as described above was made into a paper having a weight of 180 g / m ² . The base paper thus prepared was made to have a water content of about 2% in an oven, and then an aqueous solution having the following formulation was size-pressed as a surface sizing solution so that the amount of the adhered solution was 20 g / on the surface of the base paper (on the side coated with photographic emulsion) It was attached so as to be m ² . Polyvinyl alcohol 4.0% Calcium chloride 4.0% Optical brightening agent 0.5% Defoaming agent 0.005% The thickness of the obtained size liquid-adhered paper was adjusted to 180 μm with a machine calender to obtain a base paper.

(Preparation of Support) On the surface of a base paper having a thickness of 180 μm, a polyester synthesized by condensation polymerization from a dicarboxylic acid composition and ethylene glycol shown in Table 12 (intrinsic viscosity = 6.5, average molecular weight: about 40, 000) or polyethylene, and titanium oxide (KA-10 manufactured by Titanium Industry)
The mixed composition of (1) was melt-mixed at 300 ° C. by a biaxial mixing extruder, and melt-extruded from a T-die to form a laminated layer having a thickness of 30 μm. The calcium carbonate-containing resin composition was melt-extruded at 300 ° C. on the other surface to form a laminated layer having a thickness of 30 μm. Corona discharge treatment was applied to the resin surface of this laminated support on which the emulsion was applied, and then a coating solution of the following composition was applied to give 5 cc / m ² and dried at 80 ° C. for 2 minutes. , Photographic supports A to J were obtained. [Undercoat formulation] Compound ExU1 0.2 g Compound ExU2 0.001 g H ₂ O 35 cc Methanol 65 cc Gelatin 2 g pH 9.5

[0144]

[Table 12]

[0145]

[Chemical 35]

(Preparation of Photosensitive Material 101) Various photographic constituent layers were coated on the reflective support (A) to prepare a multilayer color photographic paper (101) having the following layer structure. The coating liquid was prepared as follows.

Preparation of coating solution for first layer Yellow coupler (ExY) 153.0 g, color image stabilizer (Cpd-1) 15.0 g, color image stabilizer (Cpd-2)
7.5 g, color image stabilizer (Cpd-3) 16.0 g, solvent (Solv-1) 25 g, solvent (Solv-2) 25
g and 180 cc of ethyl acetate and dissolved in 10 cc of this solution.
% 10% gelatin aqueous solution 1000c containing 60 cc of sodium dodecylbenzenesulfonate and 10 g of citric acid
c was emulsified and dispersed to prepare an emulsified dispersion A. On the other hand, silver chlorobromide emulsion A-1 (cube, average grain size 0.88μ
m large size emulsion and 0.70 μm small size emulsion 3:
7 mixture (silver molar ratio). The coefficient of variation of the particle size distribution is
0.08 and 0.10, respectively, and 0.3 mol% of silver bromide was locally contained in a part of the grain surface in each size emulsion. 0.1 mg of potassium hexachloroiridium (IV) in total and 1.0 mg of potassium ferrocyanide in total were contained inside the grain and in the silver bromide localized phase. ) Was prepared. In this emulsion, blue-sensitizing dyes A and B shown below were added to large-sized emulsion and small-sized emulsion, respectively, at 2.0 × 10 ⁻⁴ and 2.5 × 10 ⁻⁴ mol per mol of silver, and then sulfur was added. Optimal chemical sensitization was performed by adding a sensitizer and a gold sensitizer in the presence of a decomposed product of nucleic acid. The above emulsified dispersion A and this silver chlorobromide emulsion A-1 were mixed and dissolved to prepare a coating solution for the first layer having the composition shown below.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer. Also, Cpd-14 and C are added to each layer.
The total amount of pd-15 was 25.0 mg / m ² and 5 respectively.
The amount added was 0.0 mg / m ² . The size of the silver chlorobromide emulsion in each light-sensitive emulsion layer was adjusted by the same preparation method as for the silver chlorobromide emulsion A-1, and the following spectral sensitizing dyes were used.

[0149]

[Table 13]

[0150]

[Table 14]

[0151]

[Table 15]

Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole (I-2-6) was added to each of the silver halide 1 layers for the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer. 8.5 × 10 ⁻⁴ per mole, 3.
0 × 10 ⁻³ and 2.5 × 10 ⁻⁴ mol were added. Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer at 1 × 10 ⁻⁴ and 2 × 10 ⁴ per mol of silver halide, respectively. ^-4 mol was added. In order to prevent irradiation, the following dyes were added to each emulsion layer so that each emulsion layer contained the coating amount in parentheses (these dyes are water-soluble and therefore diffuse into all photographic constituent layers). .

[0153]

[Chemical 36]

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver. Support (A) The resin layer on the first layer side contains a bluish dye (ultraviolet).

First layer (blue-sensitive emulsion layer) Said silver chlorobromide emulsion A-1 0.27 Gelatin 1.22 Yellow coupler (ExY) 0.79 Color image stabilizer (Cpd-1) 0.08 Color image Stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.08 Solvent (Solv-1) 0.13 Solvent (Solv-2) 0.13

Second Layer (Color Mixing Prevention Layer) Gelatin 0.90 Color mixing inhibitor (Cpd-4) 0.06 Solvent (Solv-7) 0.03 Solvent (Solv-2) 0.25 Solvent (Solv-3) 0.25

Third layer (green sensitive emulsion layer) Silver chlorobromide emulsion B-1 (cubic, average grain size 0.55)
A 1: 3 mixture of a large size emulsion of μm and a small size emulsion of 0.39 μm (silver molar ratio). The variation coefficients of the grain size distribution were 0.10 and 0.08, respectively, and in each size emulsion, 0.8 mol% of silver bromide was locally contained in a part of the grain surface. Further, 0.1 mg of potassium hexachloroiridium (IV) was added to the inside of the grain and the localized phase of silver bromide, and 1 mg of potassium ferrocyanide was added in total. ) 0.13 Gelatin 1.28 Magenta coupler (ExM) 0.16 Color image stabilizer (Cpd-5) 0.15 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-6) 0 .01 color image stabilizer (Cpd-7) 0.01 color image stabilizer (Cpd-8) 0.08 solvent (Solv-3) 0.50 solvent (Solv-4) 0.15 solvent (Solv-5) 0.15

Fourth Layer (Color Mixing Prevention Layer) Gelatin 0.70 Color mixing prevention layer (Cpd-4) 0.04 Solvent (Solv-7) 0.02 Solvent (Solv-2) 0.18 Solvent (Solv-3) 0.18

Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion C-1 (cubic, average grain size 0.50)
1: 4 mixture of large size emulsion (μm) and small size emulsion (0.41 μm) (silver molar ratio). The variation coefficients of the grain size distribution were 0.09 and 0.11, respectively, and in each size emulsion, 0.8 mol% of silver bromide was locally contained in a part of the grain surface. Further, 0.3 mg of potassium hexachloroiridium (IV) was added to the inside of the grain and the localized phase of silver bromide, and 1.5 mg of potassium ferrocyanide was added in total. 0.18 Gelatin 0.80 Cyan coupler (ExC) 0.33 UV absorber (UV-2) 0.18 Color image stabilizer (Cpd-1) 0.33 Color image stabilizer (Cpd-2) 0. 03 Color image stabilizer (Cpd-6) 0.01 Color image stabilizer (Cpd-8) 0.01 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-10) 0.01 Color Image stabilizer (Cpd-11) 0.01 Solvent (Solv-1) 0.01 Solvent (Solv-6) 0.22

Sixth layer (UV absorbing layer) Gelatin 0.48 UV absorbing agent (UV-1) 0.38 Color image stabilizer (Cpd-5) 0.02 Color image stabilizer (Cpd-12) 0.15

Seventh layer (protective layer) Gelatin 1.10 Polyvinyl alcohol acrylic modified copolymer (modification degree 17%) 0.05 Liquid paraffin 0.02 Color image stabilizer (Cpd-13) 0.01

[0162]

[Chemical 37]

[0163]

[Chemical 38]

[0164]

[Chemical Formula 39]

[0165]

[Chemical 40]

[0166]

[Chemical 41]

[0167]

[Chemical 42]

[0168]

[Chemical 43]

Further, as shown in Table-A, the mercapto compound (general formula [I]) added to the support and the first layer (blue-sensitive emulsion layer) and the hardener used in each layer were changed to prepare a sample. 102-125 were created.

[0170]

[Table 16]

The following experiments were conducted to examine the photographic properties of these samples. First, the coating silver amount of each sample is 3
The exposure was applied so that 0% was developed. The exposed sample was subjected to continuous processing using a paper processor until replenishment with twice the tank capacity of the color developing step in the next processing step. Sensitometry of each sample was performed using the running liquid thus obtained.

To each sample, a sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K) was used to give a gradation exposure for sensitometry through blue, green and red filters. It was The exposure at this time is 1 /
The exposure amount was 250 CMS with the exposure time of 10 seconds.

Treatment process Temperature Time Replenisher ^* Tank capacity Color development 35 ℃ 45 seconds 161 ml 17 liter Bleach fixing 30-35 ℃ 45 seconds 215 ml 17 liter Rinse 30-35 ℃ 20 seconds ―― 10 liter Rinse 30-35 ℃ 20 seconds ―― 10 liters Rinse 30 to 35 ℃ 20 seconds 350 ml 10 liters Dry 70 to 80 ℃ 60 seconds * Replenishment amount per 1 m ² of light-sensitive material (rinse is 3 tank counter current system to →)

The composition of each processing liquid is as follows. Color developer Tank solution Replenisher Water 800 ml 800 ml Ethylenediamine-N, N, N ', N'-tetramethylenesulfonic acid 1.5 g 2.0 g Potassium bromide 0.015 g-Triethanolamine 8.0 g 12.0 g Sodium chloride 1.4 g-potassium carbonate 25 g 25.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-amino aniline sulfate 5.0 g 7.0 g N, N-bis (carboxymethyl) Hydrazine 4.0 g 5.0 g N, N-di (sulfoethyl) hydroxylamine 1Na 4.0 g 5.0 g Optical brightener (WHITEX 4B, Sumitomo Chemical Co., Ltd.) 1.0 g 2.0 g Water added 1000 ml 1000 ml pH (25 ° C) 10.05 10.45

Bleach-fixing solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetic acid disodium 5 g Ammonium bromide 40 g Water was added. 1000 ml pH (25 ° C) 6.0

Rinsing solution (same as tank solution and replenisher) Ion-exchanged water (3 pp each for calcium and magnesium)
m or less)

For the sample treated with the above liquid,
Sensitivity was obtained by measuring the concentration through blue, green and red filters. Sensitivity was defined as the reciprocal of the exposure amount that gives a color density 1.0 higher than the fog density. The fluctuation of the photographic property of the light-sensitive material before exposure under high humidity and high temperature was calculated by measuring the sensitivity by storing each of the obtained samples under the conditions of 50 ° C., 70% RH, and 3 days, and then performing exposure and development. It was expressed as a relative sensitivity with the sensitivity before storage as 100. Further, each of the two pieces of the sample that had been subjected to the above storage conditions was exposed to light, and one of them was immediately developed to calculate the sensitivity. Further, the other sample was stored under the conditions of room temperature for 3 days and then developed, and the sensitivity was calculated. Sensitivity variation was expressed as relative sensitivity with the sensitivity after storage being 100 after the sensitivity before storage. The deviation of the relative sensitivity value from 100 indicates that the photographic property varies greatly. These results are shown in Table-B.
Shown in.

[0178]

[Table 17]

As is clear from Table B above, the use of the hardener of the general formula [II] markedly reduces the fluctuation of photographic properties under severe conditions, but after undergoing severe storage conditions, In the light-sensitive material, the sensitivity increases (changes) due to storage after exposure. However, when the mercapto compound represented by the general formula [I] is contained in the support and the light-sensitive material, which are laminated with a composition in which a white pigment is mixed and dispersed in a resin containing polyester as a main component, this sensitivity increase (fluctuation) occurs. Is significantly improved.

Example 2 The second layer and the third layer of the photosensitive material 101 produced in Example 1,
The fourth layer was changed to the composition shown below, and the other components were the light-sensitive material 1.
A photosensitive material 201 was prepared in the same manner as in 01.

Second layer (color mixing preventing layer) Gelatin 0.99 Color mixing preventing agent (Cpd-A) 0.04 Color mixing preventing agent (Cpd-B) 0.04 Solvent (Solv-10) 0.16 Solvent (Solv- 11) 0.08 Solvent (Solv-12) 0.03

Third Layer (Green Sensitive Emulsion Layer) Silver Chlorobromide Emulsion B-1 0.13 Gelatin 1.24 Magenta Coupler (MA) 0.26 Color Image Stabilizer (Cpd-16) 0.03 Color Image stabilizer (Cpd-17) 0.04 Color image stabilizer (Cpd-18) 0.02 Color image stabilizer (Cpd-19) 0.02 Solvent (Solv-8) 0.30 Solvent (Solv-9) 0.15

Fourth layer (color mixing prevention layer) Gelatin 0.70 Color mixing prevention layer (Cpd-A) 0.03 Color mixing prevention layer (Cpd-B) 0.03 Solvent (Solv-10) 0.11 Solvent (Solv- 11) 0.06 Solvent (Solv-12) 0.02

[0184]

[Chemical 44]

[0185]

[Chemical formula 45]

Further, as in Example 1, as shown in Table-A, a mercapto compound added to the support and the first layer,
Samples 202 to 225 were prepared by changing the hardener used for each layer. The samples 201 to 225 were similarly subjected to the experiment for evaluating the photographic property performed in Example 1. The results obtained are similar to those of Example 1, and in the constitution of the present invention,
The effect was remarkable.

Example 3 Photosensitive materials 101 to 125 prepared in Examples 1 and 2,
Nos. 201 to 225 were processed in the same manner as in Example 1 except that the following exposure was performed, and the same evaluation was performed. The results obtained were similar to those of Examples 1 and 2.

(Exposure) Semiconductor laser GaA as a light source
A YAG solid-state laser (oscillation wavelength, 946 nm) using lAs (oscillation wavelength, 808.5 nm) as an excitation light source is KNb.
473 taken out after wavelength conversion by SHG crystal of O ₃
nm, semiconductor laser GaAlAs (oscillation wavelength, 80
A YVO ₄ solid-state laser (oscillation wavelength: 1064 nm) using 8.7 nm as an excitation light source was wavelength-converted by a KTP SHG crystal and extracted 532 nm, AlGaInP
(Oscillation wavelength, about 670 nm: Toshiba type No.TO
LD9211) was used. The laser light is an apparatus capable of sequentially scanning and exposing on a color photographic paper that moves in a direction perpendicular to the scanning direction by a rotating polyhedron.
Using this apparatus, the amount of light was changed to determine the relationship D-logE between the density (D) of the photosensitive material and the amount of light (E). At this time, the laser light of three wavelengths was modulated in light quantity using an external modulator to control the exposure quantity. This scanning exposure is 400
The average exposure time per pixel at this time is about 5
× 10 ⁻⁸ seconds. The semiconductor laser uses a Peltier device to keep the temperature constant in order to suppress the fluctuation of the light quantity due to the temperature.

[0189]

INDUSTRIAL APPLICABILITY According to the present invention, a silver halide color photographic light-sensitive material which is excellent in rapidity of processing, has little fluctuation in photographic property upon exposure, and has little fluctuation in photographic property even after storage for several days after exposure. Can be obtained. The above effect is
This is particularly remarkable in a color light-sensitive material using a gold-sensitized silver halide emulsion.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G03C 5/08 7/30

Claims (7)

[Claims] 1. At least three types of photosensitive hydrophilic groups each containing a coupler capable of forming yellow, magenta, or cyan color on a reflective support and silver halide emulsion grains having different color sensitivities from each other. In a silver halide color photographic light-sensitive material having a photosensitive colloid layer and a non-photosensitive hydrophilic colloid layer, a white pigment is added to a resin whose main component is a polyester synthesized by polycondensation of dicarboxylic acid and diol. A reflective support having the composition layer mixed and dispersed on at least the surface of the substrate on which the photosensitive hydrophilic colloid layer is coated, and at least one of the photosensitive hydrophilic colloid layers has the following general formula [ I], containing at least one mercapto compound represented by the formula I) and silver halide emulsion grains having a silver chloride content of 90 mol% or more, A silver halide color photographic light-sensitive material characterized by being hardened with a base-active type hardener or a compound represented by the following general formula [II]. [Chemical 1] In the formula [I], Q represents an atomic group necessary for forming a 5- or 6-membered heterocycle or a 5- or 6-membered heterocycle in which a benzene ring is condensed, and M represents a hydrogen atom or a cation. . [Chemical 2] In formula [II], X ¹ and X ² are —CH═CH ₂ or —C.
H ₂ CH ₂ —Y, and X ¹ and X ² may be the same or different. Y represents a group which can be substituted by a nucleophile (nucleophilic group) or can be removed by a base in the form of HY. L is a divalent linking group and may be substituted. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the polyester of the reflective support is a polyester containing polyethylene terephthalate as a main component. 3. The polyester of the reflective support is a polyester synthesized by polycondensation from a dicarboxylic acid and a diol, and the dicarboxylic acid component is a mixture of terephthalic acid and isophthalic acid in a molar ratio of 9: 1 to 2: 8. 2. A reflective support comprising a polyester and a white pigment mixed and dispersed on the surface of at least the photosensitive hydrophilic colloid layer coated side of the substrate.
A silver halide color photographic light-sensitive material described in 1. 4. The polyester of the reflective support is a polyester obtained by polycondensation of a dicarboxylic acid and a diol, and the dicarboxylic acid component is a mixture of terephthalic acid and naphthalenedicarboxylic acid in a molar ratio of 9: 1 to 2: 8. 2. The halogen according to claim 1, which is a reflective support in which a composition in which a white pigment is mixed and dispersed in the polyester is coated on at least the surface of the substrate on which the photosensitive hydrophilic colloid layer is coated. Silver halide color photographic light-sensitive material. 5. The silver halide color photographic light-sensitive material according to claim 1, wherein the diol is ethylene glycol. 6. The white pigment of the reflective support is titanium oxide, and the weight ratio to the resin containing polyester as a main component (titanium oxide / resin) is 5/95 to 50/50. A silver halide color photographic light-sensitive material according to any one of claims 1 to 5. 7. The silver halide color photographic light-sensitive material according to claim 1 is exposed by a scanning exposure method in which an exposure time per pixel is shorter than 10 ⁻⁴ seconds, and then color development processing is performed. A method for forming a color photographic image, which comprises: