JP2000330238A - Silver halide color photographic sensitive material and color image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide color photographic sensitive material small in fluctuation of photographic performance in the case of fluctuation of shorting conditions in the unexposed state of it and to provide the image forming method by using this sensitive material. SOLUTION: The silver halide color photographic sensitive material is provided with at least 3 silver halide emulsion layers different from each other in color sensitivities on a reflective support coated with a moisture resistant resin, and at least one of moisture resistant layers between the support and the silver halide emulsion layers is a biaxially oriented polyeolefin layer having microvoids, and further, the silver halide emulsion in the silver halide emulsion layer comprises silver halide grains containing >=95 silver chloride.

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 having suitability for rapid processing and an image forming method using the same. More specifically, the present invention relates to a silver halide color photographic light-sensitive material having a small fluctuation in photographic performance when the storage state of an unexposed state of the silver halide color photographic light-sensitive material changes.

[0002]

2. Description of the Related Art In recent years, in the field of photographic processing services, there has been a demand for high-quality photographic materials which can be processed simply and quickly as part of improving services to users and as a means of improving productivity. At present, a light-sensitive material containing a high silver chloride emulsion is processed with a color development time of 45 seconds and a total processing time of less than 4 minutes is generally used. In addition, the simplicity and speed of other color systems (for example, an electrostatic transfer system, a thermal transfer system, and an ink jet system) are not yet satisfactory, and further simplification and speed are desired.

[0003] Silver halide color photographic materials are always required to have stable photographic performance after processing. In particular, it has been desired to improve fog and sensitivity fluctuation when the storage state of the photosensitive material in the unexposed state changes. In particular, when the fog changes, the white background is greatly affected and the image quality is greatly deteriorated. Techniques for improving the white background include reducing fog in silver halide emulsions, improving washing out of sensitizing dyes and anti-irradiation dyes, improving by fluorescent whitening, and increasing the white pigment packing density of the support. is there. For example, an attempt to improve the absolute value of whiteness using a support is disclosed in JP-A-10-333.
No. 277, JP-A-11-52513, JP-A-11-6
No. 5024, JP-A-6-250331, JP-A-6-1
67772 and JP-A-6-167775. However, the above technique alone has not led to a drastic improvement, and further improvement has been desired.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic light-sensitive material having rapid processing suitability and an image forming method using the same. More specifically, it is an object of the present invention to provide a silver halide color photographic light-sensitive material having a small fluctuation in photographic performance when the storage state of the silver halide color photographic light-sensitive material in an unexposed state changes, and an image forming method using the same. is there.

[0005]

As a result of intensive studies, the present inventors have found that the following objects can be achieved by the following silver halide color photographic light-sensitive material and color image forming method.

(1) In a silver halide color photographic light-sensitive material having at least three silver halide emulsion layers having different color sensitivity on a reflective support, the reflective support is a water-resistant resin-coated support, In addition, at least one of the water-resistant resin layers between the support and the silver halide emulsion layer is a biaxially stretched polyolefin layer having micropores, and the silver halide emulsion of the silver halide emulsion layer contains silver chloride. A silver halide color photographic light-sensitive material comprising silver halide emulsion grains having a ratio of 95 mol% or more. (2) In a silver halide color photographic light-sensitive material having at least three silver halide emulsion layers having different color sensitivity on a reflective support, the reflective support is a water-resistant resin-coated support, and At least one of the water-resistant resin layers between the polyolefin layer and the silver halide emulsion layer is a biaxially stretched polyolefin layer having micropores, and has no micropores between the polyolefin layer and the silver halide emulsion layer. A silver halide color photographic light-sensitive material, wherein a polyolefin layer is provided, and the silver halide emulsion of the silver halide emulsion layer comprises silver halide emulsion grains having a silver chloride content of 95 mol% or more. (3) A silver halide color photographic material having at least three silver halide emulsion layers having different color sensitivity on a reflective support, wherein the reflective support is a polyester synthesized by polycondensation from a dicarboxylic acid and a diol. At least the emulsion-coated surface is coated with a composition obtained by mixing and dispersing a white pigment in a resin containing at least 50% by weight of
Further, the silver halide emulsion of the silver halide emulsion layer comprises silver halide emulsion grains having a silver chloride content of 95 mol% or more. (4) The silver halide color photographic material as described in (3), wherein the polyester of the reflective support is a polyester containing polyethylene terephthalate as a main component. (5) At least one of the silver halide emulsion layers contains a cyan dye-forming coupler represented by the general formula (PTA-I) or (PTA-II) (1) to (4). The silver halide color photographic light-sensitive material according to any one of the above items.

[0007]

Embedded image

Wherein Za and Zb are each -C
It represents a (R ₃₎ = or -N =. However, either one of Za and Zb is -C (R ₃₎ is = and the other is -N =. R ₁ and R 2 are Hammett's substituent constant σp
Represents an electron-withdrawing group having a value of 0.2 or more, and σ of R ₁ and R ₂
The sum of the p values is 0.65 or more. R ₃ represents a hydrogen atom or a substituent. X represents a hydrogen atom or a group capable of leaving in a coupling reaction with an oxidized form of an aromatic primary amine color developing agent. The group of R ₁ , R ₂ , R _3, or X may be a divalent group and form a homopolymer or a copolymer by bonding to a dimer or higher polymer or a polymer chain. (6) The method according to any one of (1) to (5), wherein at least one of the silver halide emulsion layers contains a magenta dye-forming coupler represented by formula (MI). Silver halide color photographic material.

[0009]

Embedded image

In the formula, Za and Zb are each represented by = C (R ₄ )
— Or ＮN—, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a substituent, and X represents a hydrogen atom or coupling with an oxidized aromatic primary amine color developing agent. Represents a group capable of leaving in the reaction. (7) In an image forming method in which a silver halide color photographic light-sensitive material is scanned and exposed with a light beam modulated based on image information and then developed, the silver halide color photographic light-sensitive material may be any one of (1) to (6). A color image forming method, which is a silver halide color photographic light-sensitive material characterized in any one of the above. (8) A color image forming method, wherein the silver halide color photographic light-sensitive material according to any one of (1) to (6) is processed in a color development processing time of 20 seconds or less.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The silver halide color photographic light-sensitive material of the present invention will be described in detail below. One embodiment of the reflective support that can be used in the silver halide color photographic light-sensitive material according to the present invention includes the following. That is, it is a water-resistant resin-coated reflective support in which at least one of the water-resistant resin layers between the support and the silver halide emulsion layer is a biaxially stretched polyolefin layer having micropores. This will be described in detail below.

[0012] In order to form micropores in the polyolefin, it is preferable to use a pore-inducing substance, and as the pore-inducing substance, a polymer material is preferable. The polymer material is preferably a polymer that can be melt-mixed with the polymer forming the core matrix and that can form dispersed spherical particles when the suspension is cooled, such as polybutylene terephthalate dispersed in polypropylene. The vacancy inducer is 5 to 50% based on the matrix polymer of the core.
It is preferred to use% by weight. The pore-inducing substance particles remaining in the completed sheet core have a diameter of 0.1 to 10 μm,
Preferably it is spherical. The size of the pores depends on the degree of stretching in the vertical and horizontal directions, but is approximately the cross-sectional diameter size of the pore-forming particles.

The polyolefin layer having micropores can form a polyolefin layer containing no micropores adjacent to the layer. The polyolefin layer having micropores is opaque and milky white by itself, but a white pigment such as titanium dioxide, barium sulfate, alumina, or calcium carbonate is added to the micropore-containing layer and / or the adjacent polyolefin layer to obtain a white color. The degree can be improved. In addition, known additives such as pigments, fluorescent whitening agents, and other additives for improving the properties of the polyolefin layer can also be added. In particular, when polypropylene is used, the packing density of titanium oxide or the like can be increased, which is preferable from the viewpoint of improving whiteness. The density of these one or more polyolefin layers is preferably 0.40 to 1.0 g / cc,
0.50 to 0.70 g / cc is more preferable. As a preferred embodiment of the present invention, a unit having a sandwich structure having a polypropylene skin layer containing titanium oxide and not containing micropores on both sides of a core layer of polypropylene having no pores and not containing titanium oxide is exemplified.
In this sandwich structure, the thickness of the core layer is preferably 5 to 150 μm, more preferably 10 to 70 μm,
The thickness of the skin layer is 1 to 50μ, more preferably 3 to 20μ.
It is. Further, in order to improve the adhesion between the hydrophilic photographic constituent layer and the support, microvoids are formed adjacent to the hydrophilic photographic constituent layer between the polyolefin layer containing the microvoids and the hydrophilic photographic constituent layer. It is preferable to provide a polyolefin layer having no polyolefin. The thickness of the polyolefin layer having no micropores is preferably 0.1 to 5 μm. In a particularly preferred embodiment, the polyolefin layer having micropores is preferably mainly composed of polypropylene, and the polyolefin having no micropores is preferably polyethylene. Further, it is more preferable that the polyolefin layer having no microvoids is subjected to corona discharge treatment.

It is also preferable to provide a biaxially oriented polyolefin layer on the side of the support opposite to the emulsion side, from the viewpoint of increasing the rigidity of the reflective support. In this case, the surface of the polyolefin layer on the back surface is preferably made of matte-finished polyethylene or polypropylene containing silica. Also, JP
As described in 1-65024, two or more layers of polypropylene on the back surface may be provided and printing may be performed on the first polyolefin. The thickness of the polyolefin layer on the back surface is preferably 5 to 100 μm, more preferably 10 to 7 μm.
0μ.

The support which can be preferably used in the present invention is a polymer support, a synthetic paper support, a cloth support, a woven polymer fiber support, a cellulose fiber paper support, or a laminate thereof. Particularly preferred is a photographic brand cellulose fiber paper having a base paper pH of 5 to 9 described in JP-A-6-167771. It is also preferable to adjust the thickness and rigidity so as to meet various consumer requirements. For example, for these purposes, a sheet support having a Young's modulus of 2800 MPa to 13000 MPa in the machine direction and a Young's modulus of 1400 MPa to 7000 MPa is provided on both sides of the paper support in the machine direction of 690 MPa to 5520 MPa.
Young's modulus of a and 690MPa-5520MP in the transverse direction
A laminated support having a biaxially stretched sheet having a Young's modulus of a is prepared with a thickness of about 0.18 mm to 0.28 mm
Flexural stiffness of ~ 250 millinewtons can also be achieved. The preferred embodiments of the support of the present invention described above are described in JP-A-10-333277 and JP-A-10-33327.
No. 8, JP-A-11-52513, JP-A-11-650
No. 24, EP-08880065A1, EP-0880
No. 066A1, US-5,888,681, US-
No. 5,888,714 and British Patent No. 2,325,749.

Another embodiment of the reflective support which can be used in the silver halide color photographic light-sensitive material according to the present invention will be described below.

The reflective support of the present invention is a reflective support obtained by coating a composition comprising a resin containing 50% by weight or more of polyester with a white pigment mixed and dispersed on at least the emulsion-coated side of a substrate (preferably base paper). It is. This polyester is a polyester synthesized by polycondensation from a dicarboxylic acid and a diol. Preferred dicarboxylic acids include terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid. 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 polycondensation of these dicarboxylic acids alone or in combination with diols alone or in mixture can be used. Among them, at least one of the dicarboxylic acids is preferably terephthalic acid. In addition, 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 of 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 0000 to 50,000.

It is also preferable to use a mixture of a plurality of polyesters having different compositions. Further, mixtures of these polyesters with other resins can also be preferably used. Other resins to be mixed include polyethylene, polyolefins such as polypropylene, polyethylene glycol, polyoxymethylene, polyethers such as polyoxypropylene, polyester-based polyurethane, polyether polyurethane, polycarbonate,
It can be widely selected as long as it is a resin extrudable at 270 to 350 ° C. such as polystyrene. These resins may be used alone or in combination of two or more. For example, 90% by weight of polyethylene terephthalate may be mixed with 6% by weight of polyethylene and 4% by weight of polypropylene. The mixing ratio of polyester and other resin varies depending on the type of resin to be mixed, but for polyolefins, the weight ratio of polyester / other resin = 1.
00/0 to 80/20 is appropriate. If it exceeds this range, the physical properties of the mixed resin are sharply reduced. In the case of resin other than polyolefin, polyester / other resin = 1 by weight ratio
It can be mixed in the range of 00/0 to 50/50.
If the content of the polyester is less than 50% by weight, the effects of the present invention cannot be sufficiently obtained.

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 any of rutile type and anatase type, and may be manufactured by any of a sulfate method and a 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 0.1.
8 μm is preferred. When it is less than 0.1 μm, it is difficult to uniformly mix and disperse the resin, which is not preferable. When the thickness exceeds 0.8 μm, sufficient whiteness cannot be obtained, and projections are formed on the coated surface, which adversely affects the image quality. The mixing ratio of the white pigment to the polyester is 98/2 to 30/70 (polyester / white pigment) by weight, preferably 95/5 to 50/5.
0, particularly preferably 90/10 to 60/40. When the content of the white pigment is less than 2% by weight, the contribution to the whiteness is insufficient, and when it exceeds 70% by weight, the surface smoothness when used as a photographic paper support is insufficient, and the glossiness is excellent. Photographic paper support cannot be obtained. still,
The polyester and the white pigment are mixed with a dispersing agent such as a metal salt of a higher fatty acid, a higher fatty acid ethyl, a higher fatty acid amide, a higher fatty acid, and the like in a kneader such as a two-roll, three-roll, kneader, or Banbury mixer. It is kneaded in. An antioxidant can be contained in the resin layer, and the content is 50 to 1,000 ppm based on the resin.
Can be added in the range.

The thickness of the polyester / white pigment composition coated on the emulsion-coated side of the substrate of the reflective support of the present invention is 5
To 100 μm, preferably 5 to 80 μm, more preferably 10 to 50 μm. When the thickness is more than 100 μm, the problem of physical properties such as the embrittlement of the resin is emphasized to cause cracks. When the thickness is less than 5 μm, the waterproofness, which is the original purpose of the coating, is impaired, and the whiteness and the surface smoothness cannot be simultaneously satisfied, and the physical properties become too soft, which is not preferable. The thickness of the resin or resin composition to be coated on the side of the substrate other than the side on which the emulsion is coated is 5 to 1
When the thickness exceeds this range, which is preferably 00 μm, and more preferably 10 to 50 μm, there is a problem in physical properties such that the brittleness of the resin is emphasized and cracks occur. If the ratio is less than the above range, the waterproof property which is the original purpose of the coating is impaired and the physical properties are too soft, which is not preferable. Examples of a method for coating the coating layer on the emulsion-coated side and the back surface layer of the substrate include a melt extrusion lamination method.

The substrate used for the reflective support of the present invention comprises:
It is selected from materials generally used for photographic printing paper. That is, natural pulp selected from softwood, hardwood, etc.,
Using synthetic pulp as the main material, clay, talc,
Fillers such as calcium carbonate and urea resin fine particles, rosin, alkyl ketene dimer, sizing agents such as higher fatty acids, epoxidized fatty acid amides, paraffin wax, alkenyl succinic acid, etc., paper strength agents such as starch, polyamide polyamine epichlorohydrin, polyacrylamide, What added a fixing agent such as a sulfuric acid band and a cationic polymer is used. In the present invention, as the substrate used for the reflective support, base paper made of the above-mentioned natural pulp or synthetic pulp as a main raw material is preferable. Although the type and thickness of the substrate are not particularly limited, the basis weight is 50 g / m ^{2 to} 25 g.
0 g / m ² is desirable. For the purpose of imparting smoothness and flatness, the substrate is preferably subjected to surface treatment by applying heat and pressure using a machine calender, a spar calender, or the like.

This “smoothness” is expressed using the surface roughness of the support as a scale. The surface roughness of the support of the present invention will be described. As the surface roughness, the center line average surface roughness is used as this scale. The center line average surface roughness is defined as follows. From the roughness phase, the area S on the center plane
A portion of M is extracted, and orthogonal coordinate axes, an X axis, and a Y axis are placed on a center line of the extracted portion, and an axis orthogonal to the center line is Z.
When the axis is set, the value given by the following equation is defined as the center line average surface roughness (SRa) and is expressed in μm.

[0025]

(Equation 1)

The average surface roughness of the center line and the height of the projection from the center line can be measured by using a three-dimensional surface roughness measuring device (SE-30H) manufactured by Kosaka Laboratory Co., Ltd. It can be obtained by measuring an area of 5 mm ^{2 with} a needle at a cutoff value of 0.8 mm, a magnification of 20 times in the horizontal direction, and a magnification of 2000 times in the height direction. Further, the feeding speed of the measuring needle at this time is preferably about 0.5 mm / sec. The support obtained by this measurement preferably has a value of 0.15 μm or less, more preferably 0.10 μm or less. 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 polyester / white pigment mixture composition, it is preferable that the surface of the substrate is preliminarily subjected to a pretreatment such as a corona discharge treatment, a flame treatment or an undercoat.

When a polyester such as polyethylene terephthalate is used, the adhesion to a photographic emulsion is weaker than that of a polyethylene. Therefore, after the polyester is melt-extruded and laminated on the substrate, the polyester surface is subjected to corona discharge treatment to coat a hydrophilic colloid layer. Is preferred. 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.

[0029]

Embedded image

The coating amount of the compound represented by the general formula [U] is preferably 0.1 mg / m ² or more, more preferably 1 mg / m ^2.
As described above, the content is most preferably 3 mg / m ² or more. As the content is larger, the adhesion can be strengthened, but it is disadvantageous in terms of excessive cost. Further, it is preferable to add alcohols such as methanol in order to improve the suitability of applying the undercoat liquid to 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 60% by weight or more. Further, in order to further improve coating suitability, it is preferable to use various surfactants such as anionic, cationic, amphoteric, nonionic, fluorocarbon, and organic silicon-based.

It is preferable to add a water-soluble polymer such as gelatin to obtain a good undercoating surface. Considering the stability of the compound of the general formula [U], the pH of the solution is
4 to pH 11 are preferable, and pH 5 to p are more preferable.
H10. It is preferable that the surface of the thermoplastic resin is surface-treated before applying the undercoat liquid. As the surface treatment, a corona discharge treatment, a flame treatment, a plasma treatment, or the like can be used. In applying the undercoating liquid, a gravure coater, a bar coater, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a doctor coating method, an extrusion coating method, and the like, by a generally well-known coating method. Can be applied. The drying speed of the coating is preferably 30C to 100C, more preferably 50C to 100C, and most preferably 70C to 100C. The upper limit is determined by the heat resistance of the resin, and the lower limit is determined by the production efficiency.

In the present invention, any cyan coupler which can be preferably used may be any coupler which forms a cyan dye. For example, a phenolic cyan coupler, a naphthol cyan coupler, a heterocyclic coupler and the like can be mentioned. Among them, in the present invention, a pyrroloazole coupler is preferable, and a cyan coupler represented by the following general formula (PTA-I) or (PTA-II).

[0033]

Embedded image

In the formula, Za and Zb each represent -C
It represents a (R ₃₎ = or -N =. However, either one of Za and Zb is -C (R ₃₎ is = and the other is -N =. R ₁ and R ₂ are Hammett's substituent constant σp
Represents an electron-withdrawing group having a value of 0.2 or more, and σ of R ₁ and R ₂
The sum of the p values is 0.65 or more. R ₃ represents a hydrogen atom or a substituent. X represents a hydrogen atom or a group capable of leaving in a coupling reaction with an oxidized form of an aromatic primary amine color developing agent. The group of R ₁ , R ₂ , R _3, or X may be a divalent group and form a homopolymer or a copolymer by bonding to a dimer or higher polymer or a polymer chain. Among them, cyan couplers which can be more preferably used from the viewpoints of rapid processing property, color reproducibility, storage stability of a light-sensitive material in an unexposed state, and the like are cyan couplers represented by the following general formula [I]. .

[0035]

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[0036] In the general formula [I] R ^1, R ² each independently represent an alkyl group or an aryl group, R ^3, R
⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group or an aryl group, Z represents a group of nonmetallic atoms necessary for forming a saturated ring, R ⁶ represents a substituent, and X represents a heterocyclic group. , A substituted amino group or an aryl group, and Y represents a hydrogen atom or a group which leaves during the color development process.

The alkyl group represented by R ^{1 to} R ⁵ in the general formula [I] is a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, preferably a linear alkyl group having 1 to 22 carbon atoms. ,
A branched or cyclic alkyl group, particularly preferably a linear or branched alkyl group having 1 to 8 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, t-butyl, t-amyl, t-octyl , Decyl, dodecyl,
Cetyl, stearyl, cyclohexyl, 2-ethylhexyl are exemplified. The aryl group represented by R ^{1 to} R ⁵ in the general formula [I] is an aryl group having 6 to 20 carbon atoms, preferably an aryl group having 6 to 14 carbon atoms,
Particularly preferred is an aryl group having 6 to 10 carbon atoms, such as phenyl, 1-naphthyl, 2-naphthyl, and 2-phenanthryl.

The group of nonmetallic atoms necessary for forming a saturated ring represented by Z in the general formula [I] is a group of nonmetallic atoms necessary for forming a 5- to 8-membered ring. May be substituted, may be a saturated ring or an unsaturated ring, and the non-metal atom forming the ring may be a carbon atom, an oxygen atom,
Examples thereof include a nitrogen atom and a sulfur atom, preferably a 6-membered saturated carbocyclic ring, and particularly preferably a carbon atom having 1 to 2 carbon atoms at the 4-position.
4 is a cyclohexane ring substituted with an alkyl group.
Examples of the substituent represented by R ⁶ in the general formula [I] include a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom), an aliphatic group (for example, a linear or branched alkyl having 1 to 36 carbon atoms). Group, aralkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, specifically, for example, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, t-amyl, t-octyl, 2-methanesulfonylethyl , 3- (3-pentadecylphenoxy) propyl, 3- {4-} 2- [4
-(4-hydroxyphenylsulfonyl) phenoxy]
Dodecaneamide phenyl propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl, 3-
(2,4-di-t-amylphenoxypropyl), an aryl group (an aryl group having 6 to 36 carbon atoms, such as phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, -Tetradecanamidophenyl, 2-
Methoxyphenyl), a heterocyclic group (a heterocyclic group having 1 to 36 carbon atoms such as 2-furyl, 2-thienyl,
-Pyrimidinyl, 2-benzothiazolyl), a cyano group,
Hydroxyl group, nitro group, carboxy group, amino group,
Alkoxy group (a linear, branched or cyclic alkoxy group having 1 to 36 carbon atoms, such as methoxy, ethoxy,
Butoxy, 2-methoxyethoxy, 2-dodecyloxyethoxy,

2-methanesulfonylethoxy), an aryloxy group (aryloxy group having 6 to 36 carbon atoms, for example, phenoxy, 2-methylphenoxy, 4-t-
Butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), acylamino group (acylamino group having 2 to 36 carbon atoms, for example, acetamido, benzamido,
Tetradecaneamide, 2- (2,4-di-t-amylphenoxy) butanamide, 4- (3-t-butyl-4-
(Hydroxyphenoxy) butanamide, 2- {4- (4
-Hydroxyphenylsulfonyl) phenoxydidecamide, an alkylamino group (an alkylamino group having 1 to 36 carbon atoms such as methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino), an anilino group (having 6 to 6 carbon atoms) 36 anilino groups such as phenylamino, 2-chloroanilino,
Chloro-5-tetradecaneaminoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-5- {2- (3-t-butyl-4-hydroxyphenoxy) dodecaneamide {Anilino), ureido group (ureido group having 2 to 36 carbon atoms, for example, phenylureido, methylureido, N, N-
Dibutylureido), a sulfamoylamino group (sulfamoylamino group having 1 to 36 carbon atoms, for example, N,
N-dipropylsulfamoylamino, N-methyl-N
-Decylsulfamoylamino), an alkylthio group (an alkylthio group having 1 to 36 carbon atoms, such as methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, and 3- (4-
t-butylphenoxy) propylthio), an arylthio group (arylthio group having 6 to 36 carbon atoms, such as phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio), an alkoxycarbonylamino group (2-36 carbon atoms)
For example, methoxycarbonylamino, tetradecyloxycarbonylamino), and sulfonamide group (alkyl and arylsulfonamide groups having 1 to 36 carbon atoms, for example, methanesulfonamide, butanesulfonamide, octanesulfone) Amide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide,

2-methoxy-5-t-butylbenzenesulfonamide), carbamoyl group (carbamoyl group having 1 to 36 carbon atoms, for example, N-ethylcarbamoyl,
N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N- {3- (2,4-di-t-amylphenoxy) propyl} carbamoyl), sulfamoyl Group (sulfamoyl group having 1 to 36 carbon atoms, for example,
N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl,
N, N-diethylsulfamoyl), sulfonyl group (alkyl and arylsulfonyl groups having 1 to 36 carbon atoms, for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group (2 to 36 carbon atoms) For example, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), a heterocyclic oxy group (1 to 36 carbon atoms)
For example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), an azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-
Hydroxy-4-propanoylphenylazo), an acyloxy group (an acyloxy group having 2 to 36 carbon atoms, for example, acetoxy), a carbamoyloxy group (having a carbon number of 1 to 1)
36 carbamoyloxy groups such as N-methylcarbamoyloxy and N-phenylcarbamoyloxy), silyloxy groups (silyloxy groups having 3 to 36 carbon atoms such as trimethylsilyloxy and dibutylmethylsilyloxy), and aryloxycarbonylamino Group (an aryloxycarbonylamino group having 7 to 36 carbon atoms such as phenoxycarbonylamino); an imide group (an imide group having 4 to 36 carbon atoms such as N-succinimide, N-phthalimido and 3-octadece) Nylsuccinimide), a heterocyclic thio group (a heterocyclic thio group having 1 to 36 carbon atoms, for example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio), sulfinyl group (sulfur having 1 to 36 carbon atoms) A Iniru group e.g., dodecane sulfinyl, 3-pentadecylphenyl-sulfinyl, 3-phenoxypropylsulfinyl sulfinyl)

Alkyl / aryl or heterocyclic oxycarbonyl group (for example, methoxycarbonyl, butoxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, phenyloxycarbonyl, 2-pentadecyloxycarbonyl), alkyl / aryl or heterocyclic oxycarbonylamino Groups such as methoxycarbonylamino, tetradecyloxycarbonylamino, phenoxycarbonylamino, 2,4-di-tert
-Butylphenoxycarbonylamino), a sulfonamide group (eg, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy-5-tert-butylbenzenesulfonamide), a carbamoyl group (For example, N-ethylcarbamoyl, N, N
-Dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N- [3- (2,4-di-tert-amylphenoxy) propyl] carbamoyl), a sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl)
Sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), phosphonyl group (for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), sulfamide group (for example, dipropylsulfamoylamino) ), Imide groups (eg, N-succinimide, hydantoinyl, N-phthalimide, 3-octadecenylsuccinimide), azolyl groups (eg, imidazolyl, pyrazolyl, 3-chloro-pyrazol-1-yl, triazolyl), hydroxy groups,
Examples include a cyano group, a carboxy group, a nitro group, a sulfo group, and an unsubstituted amino group.

R ⁶ is preferably an alkyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, an acylamino group, an arylamino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, or an alkoxycarbonylamino group. Group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, Examples thereof include a sulfinyl group, a phosphonyl group, an acyl group, and an azolyl group. More preferred are an alkyl group and an aryl group, and more preferred is an aryl group in which at least the p-position is substituted with an alkyl group.

X represents a heterocyclic ring, a substituted amino group or an aryl group. The heterocyclic ring is a 5- to 8-membered ring having a nitrogen, oxygen or sulfur atom and having 1 carbon atom.
~ 36 are preferred. More preferably, it is a 5- or 6-membered ring linked by a nitrogen atom, of which a 6-membered ring is particularly preferred. Specific examples include imidazole, pyrazole, triazole, lactam compounds, piperidine, pyrrolidine, pyrrole, morpholine, pyrazolidine, thiazolidine, pyrazoline and the like, preferably morpholine and piperidine, and particularly preferably morpholine. Examples of the substituent of the substituted amino group include an aliphatic group, an aryl group and a heterocyclic group. Examples of the aliphatic group include the substituents represented by R ⁶ described above, and further include a cyano group, an alkoxy group (for example, methoxy), an alkoxycarbonyl group (for example, ethoxycarbonyl), a chloro group, a hydroxyl group, and a carboxyl group. May be substituted with a group. As the substituted amino group, disubstitution is preferable to monosubstitution. The aryl group has 6 to 3 carbon atoms.
6 are preferable, and a single ring is more preferable. Specific examples include phenyl, 4-t-butylphenyl, 2-methylphenyl, 2,4,6-trimethylphenyl,
Methoxyphenyl, 4-methoxyphenyl, 2,6-dichlorophenyl, 2-chlorophenyl, 2,4-dichlorophenyl and the like can be mentioned.

Y is a hydrogen atom or a compound which is eliminated in the course of color development. For example, the substituent represented by Y may be eliminated under alkaline conditions as described in JP-A-61-222844. Groups that can be used and JP-A-56-13373
Substituents that couple off by reaction with a developing agent as described in JP-A No. 4 (1994) -104 are mentioned, and preferably, Y is a hydrogen atom. In the coupler represented by the general formula [I], R ⁶ contains a coupler residue represented by the general formula [I] to form a dimer or higher multimer, or R ⁶ is a polymer It may contain a chain and form a homopolymer or a copolymer. The homopolymer or copolymer having a high molecular chain is a typical example of an addition polymer having a coupler residue represented by the general formula [I] homo- or copolymer of an ethylenically unsaturated compound. . In this case, one or more cyan coloring repeating units having a coupler residue represented by the general formula [I] may be contained in the polymer, and an acrylic acid ester, a methacrylic acid ester, or a maleic acid may be used as a copolymer component. It may be a copolymer containing one or more non-color-forming ethylene-type monomers that do not couple with the oxidation product of an aromatic primary amine developer such as esters. Hereinafter, specific examples of the coupler of the present invention are shown, but the present invention is not limited thereto.

[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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The compound represented by the general formula [I] of the present invention can be prepared by a known method, for example, as described in JP-A-5-255333,
Nos. 5-202004, 7-48376, 8-1
The compound can be synthesized by the method described in No. 10623.

The magenta coupler used in the present invention is preferably represented by formula (MI). One of the objects of the present invention is to provide a light-sensitive material suitable for rapid processing. As described above, for this purpose, it is necessary to use a coupler having high activity and / or a high molecular extinction coefficient. preferable.

The general formula (MI) will be described in detail. R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom or a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, a sulfo group, an amino group, an alkoxy group, an aryloxy group, an acylamino group, and an alkylamino group. , Anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group,
Sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxy It represents a carbonyl group, an acyl group or an azolyl group, and among these groups, a group which can have a substituent may be substituted with the above substituent.

More specifically, a halogen atom (for example, a chlorine atom or a bromine atom) or an aliphatic group (for example, having 1 to 3 carbon atoms)
2 straight-chain or branched-chain alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, for example, methyl, ethyl, propyl, isopropyl, tert-butyl, tridecyl,
2-methanesulfonylethyl, 3- (3-pentadecylphenoxy) propyl, 3- {4-} 2- [4- (4-
Hydroxyphenylsulfonyl) phenoxy] dodecanamido {phenyl} propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,
4-di-tert-amylphenoxy) propyl), an aryl group (eg, phenyl, 4-tert-butylphenyl, 2,4-di-tert-amylphenyl, 2,
4,6-trimethylphenyl, 3-tridecanamide-
2,4,6-trimethylphenyl, 4-tetradecanamidophenyl, tetrafluorophenyl), heterocyclic group (for example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxy group, nitro Group, carboxy group, sulfo group, amino group, alkoxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy, 2-methanesulfonylethoxy), aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, 3-tert-butoxycarbamoylphenoxy, 3-methoxycarbamoylphenoxy), acylamino group (for example, acetamido, benzamide, tetradecaneamide, 2- (2,4
-Di-tert-amylphenoxy) butanamide, 4
-(3-tert-butyl-4-hydroxyphenoxy) butanamide, 2- [4- (4-hydroxyphenylsulfonyl) phenoxy] decaneamide), an alkylamino group (for example, methylamino, butylamino, dodecylamino, diethylamino, methyl Butylamino),
Anilino group (for example, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino,
2-chloro-5-dodecyloxycarbonylanilino,
N-acetylanilino, 2-chloro-5- [2- (3-
tert-butyl-4-hydroxyphenoxy) dodecanamido] anilino), carbamoylamino group (for example, N-phenylcarbamoylamino, N-methylcarbamoylamino, N, N-dibutylcarbamoylamino), sulfamoylamino group (for example, N, N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino), alkylthio group (for example, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3-
(4-tert-butylphenoxy) propylthio),
Arylthio groups (for example, phenylthio, 2-butoxy-5-tert-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-
Tetradecanamidophenylthio), an alkoxycarbonylamino group (eg, methoxycarbonylamino, tetradecyloxycarbonylamino), a sulfonamide group (eg, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfone) Amide, 2-methoxy-5-tert-butylbenzenesulfonamide), carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methyl-N- Dodecylcarbamoyl, N- [3- (2,4-di-tert
-Amylphenoxy) propyl] carbamoyl), a sulfamoyl group (e.g., N-ethylsulfamoyl,
N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), sulfonyl group (for example, methanesulfonyl, octane) Sulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group (for example, methoxycarbonyl, butoxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), heterocyclic oxy group (for example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyrani) Oxy), an azo group (eg, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), an acyloxy group (eg,
Acetoxy), a carbamoyloxy group (eg, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), a silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy), an aryloxycarbonylamino group (eg, phenoxycarbonylamino), imide Groups (eg, N-succinimide, N-
Phthalimide, 3-octadecenylsuccinimide),
Heterocyclic thio group (for example, 2-benzothiazolylthio,
2,4-di-phenoxy-1,3,5-triazole-
6-thio, 2-pyridylthio), a sulfinyl group (eg, dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), a phosphonyl group (eg, phenoxyphosphonyl,
Octylphosphonyl, phenylphosphonyl), aryloxycarbonyl group (eg, phenoxycarbonyl), acyl group (eg, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), azolyl group (eg, imidazolyl, pyrazolyl) , 3-chloro-pyrazol-1-yl, triazolyl).

Among these substituents, preferred substituents are an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, a carbamoylamino group, an aryloxycarbonylamino group, an alkoxycarbonylamino group, Examples thereof include an alkylacylamino group and an arylacylamino group.

X represents a group capable of leaving in the reaction with a hydrogen atom or an oxidized form of an aromatic primary amine color developing agent. When the group capable of leaving is specifically described, a halogen atom, an alkoxy group, an aryloxy group, Acyloxy, alkyl or arylsulfonyloxy, acylamino, alkyl or arylsulfonamido, alkoxycarbonyloxy, aryloxycarbonyloxy, alkyl, aryl or heterocyclic thio, carbamoylamino, 5- or 6-membered There are a nitrogen-containing heterocyclic group, an imide group, an arylazo group, and the like, and these groups may be further substituted with a group allowed as a substituent of R _{1 to} R ₄ .

More specifically, halogen atoms (eg, fluorine, chlorine, bromine), alkoxy groups (eg, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, ethoxycarbonylmethoxy), aryl An oxy group (for example, 4-methylphenoxy, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarboxyphenoxy,
4-methoxycarbonylphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy), acyloxy group (for example, acetoxy, tetradecanoyloxy, benzoyloxy), alkyl or arylsulfonyloxy group (for example, methanesulfonyloxy,
Toluenesulfonyloxy), acylamino groups (eg, dichloroacetylamide, heptafluorobutyrylamino), alkyl or arylsulfonamide groups (eg, methanesulfonamino, trifluoromethanesulfonamino, p-toluenesulfonylamino), alkoxycarbonyloxy Groups (eg, ethoxycarbonyloxy, benzyloxycarbonyloxy), aryloxycarbonyloxy groups (eg, phenoxycarbonyloxy), alkyl, aryl or heterocyclic thio groups (eg, dodecylthio, 1-carboxydodecylthio, phenylthio, 2- Butoxy-5-tert
-Octylphenylthio, 2-benzyloxycarbonylaminophenylthio, tetrazolylthio), carbamoylamino group (for example, N-methylcarbamoylamino, N-phenylcarbamoylamino), 5- or 6-membered nitrogen-containing heterocyclic group (for example, 1-imidazolyl,
1-pyrazolyl, 1,2,4-triazol-1-yl, tetrazolyl, 3,5-dimethyl-1-pyrazolyl, 4-cyano-1-pyrazolyl, 4-methoxycarbonyl-1-pyrazolyl, 4-acetylamino- 1-pyrazolyl, 1,2-dihydro-2-oxo-1-pyridyl), imide group (eg, succinimide, hydantoinyl), arylazo group (eg, phenylazo, 4-
Methoxyphenylazo) and the like. Preferred X is a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, or a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active site with a nitrogen atom. It is an aryloxy group, a substituted arylthio group or a substituted 1-pyrazolyl group.

In the formula (MI), preferred magenta couplers are those represented by the following formula (M-II) or (M-III)
It is represented by Particularly preferred is represented by the formula (M-II).

[0061]

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(Wherein, R ₁ , R ₂ , R ₃ and R ₄ have the same meanings as described above)

[0063]

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(In the formula, R ₁ , R ₂ , R ₃ and R ₄ have the same meanings as described above.) Preferred groups in formulas (M-II) to (M-III) are as follows: is there. Preferred groups for X include a halogen atom, an alkoxy group and an aryloxy group, and among them, a chlorine atom is preferred. Preferred substituents for R _{1 to} R ₄ include an alkyl group, an aryl group,
Examples thereof include an anilino group and an alkoxy group. Among them, an alkyl group or an aryl group is preferable, and R ₁ , R ₂ , and R ₃ are particularly preferable.
Is preferably a methyl group, and R ₄ is preferably an alkyl group or an aryl group (preferably substituted). Most preferred R ₄ is an aryl group in the general formula (M-II),
In formula (M-III), it is an alkyl group. The magenta coupler according to the present invention comprises a photosensitive silver halide 1 in the same layer.
0.001-1 mol, preferably 0.001, per mol
It is used in a range of 3 to 0.3 mol. The molecular weight of the coupler is preferably 600 or less. Specific examples of the magenta coupler represented by the general formula (MI) are shown below, but the present invention is not limited thereto.

[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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Silver halide emulsions, furthermore, foreign metal ion species doped in silver halide grains, storage stabilizers or antifoggants for silver halide emulsions, chemical sensitization (sensitizers), spectral sensitization Methods (spectral sensitizers), cyan couplers, magenta or yellow couplers which can be used in combination, and emulsifying and dispersing methods thereof, color image preservability improvers (anti-stain agents and anti-fading agents), dyes (colored layers), gelatin species, Regarding the layer constitution of the material and the coating pH of the photosensitive material, those described in the patents in Tables 1 and 2 can be preferably applied to the present invention.

[0077]

[Table 1]

[0078]

[Table 2]

The cyan, magenta and yellow couplers which can be used or used in combination in the present invention include those described in Table 1 above, page 4, upper right column, line 91 to page 121 upper left column of JP-A-62-215272. The sixth line, line 14 in the upper right column of page 3 to the last line in the upper left column of page 18 and line 11 in the upper right column of page 30 to the lower right column of page 35 of JP-A-2-33144, EP 0355,660A2. Page 4, lines 15 to 2
Line 7, page 30, line 30 to page 28, line 45, page 29 to line 31, page 47, line 23 to page 63, line 50, JP-A-8-122984, JP-A-9-222704 The couplers described in (1) and (2) are also useful.

In the present invention, known color mixing inhibitors can be used, and among them, those described in the following patents are preferable. For example, a redox compound having a high molecular weight described in JP-A-5-333501, Japanese Patent Application No. 9-14 / 1990.
No. 0719, U.S. Pat. No. 4,923,787 and the like, and phenidone and hydrazine compounds described in JP-A-5-249.
637, JP-A-10-282615, and German Patent No. 19629142A1 can be used. In particular, when increasing the pH of a developer to speed up development, German Patent No. 19618 is used.
No. 786A1, EP 839623 A1, EP 842975 A1, DE 198 06 846
It is also preferable to use the redox compounds described in A1 and French Patent No. 276046A1. In the present invention, it is preferable to use a compound having a tridian bone nucleus having a high molar extinction coefficient as an ultraviolet absorber. For example, the compounds described in the following patents can be used. JP-A-46-3335 and JP-A-55-152776;
No. 1970074, No. 5-232630, No. 5-30
No. 7232, No. 6-211813, No. 8-53427
Nos. 8-234364, 8-239368, 9-31067, 10-115988, and 10-
147577, 10-182621, German Patent No. 19739797A, European Patent No. 711804A and Japanese Patent Publication No. 8-501291.

As the antibacterial and antifungal agents that can be used in the present invention, those described in JP-A-63-271247 are useful.
Gelatin is preferred as the hydrophilic colloid used in the photographic layer constituting the light-sensitive material. Particularly, heavy metals contained as impurities such as iron, copper, zinc and manganese are preferably at most 5 ppm, more preferably at most 3 ppm. . Also,
The amount of calcium contained in the light-sensitive material is preferably 20
mg / m ² or less, more preferably 10 mg / m ² or less, and most preferably 5 mg / m ² or less. The protective layer used in the present invention may be any protective layer as long as the lower layer is protected. U.S. Pat.
It is also preferable to use those described in JP-A-53,926.

The light-sensitive material of the present invention is suitable for a scanning exposure method using a cathode ray (CRT), in addition to being used for a printing system using a normal negative printer. A cathode ray tube exposure apparatus is simpler, more compact, and lower in cost than an apparatus using a laser. Further, adjustment of the optical axis and color is also easy. Various light emitters that emit light in a spectral region are used as necessary for a cathode ray tube used for image exposure. For example, any one of a red light emitter, a green light emitter, and a blue light emitter, or a mixture of two or more thereof is used. The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in a yellow, orange, purple, or infrared region is also used. In particular, a cathode ray tube which emits white light by mixing these light emitters is often used.

When the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions and the cathode ray tube also has a phosphor which emits light in a plurality of spectral regions, a plurality of colors are exposed at a time, ie, the cathode ray tube is exposed. The image signal of a plurality of colors may be input to the display unit to emit light from the display screen. A method of sequentially inputting image signals for each color, sequentially emitting light of each color, and exposing through a film that cuts a color other than that color (plane sequential exposure)
In general, plane-sequential exposure is preferable for high image quality because a cathode ray tube with high resolution can be used.

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

When such a scanning exposure light source is used,
The spectral sensitivity maximum wavelength of the light-sensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source used.
In a solid-state laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal, the laser oscillation wavelength can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be provided in the usual three wavelength ranges of blue, green and red. If the exposure time in such scanning exposure is defined as the exposure time for the pixel size when the pixel density is 400 dpi, the preferred exposure time is 10 ^-4 seconds or less, more preferably 10 ^-6 seconds or less. In the present invention, for the purpose of preventing unauthorized copying of the processed photosensitive material, a latent image of a pattern of microdots can be given to the photosensitive material. This method is described in JP-A-9-226227.

Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the above table. Further, for processing the light-sensitive material of the present invention, the lower right column of page 26, lower right column of page 26 to the upper right column of page 34 of JP-A-2-207250, and the upper left column of page 5 of JP-A-4-97355 can be used. The processing materials and processing methods described in line 17 to page 20, lower right column, line 20 can be preferably applied. As the preservative used in this developer, the compounds described in the patents listed in the above table are preferably used.

The high silver chloride emulsion used in the present invention generally has poor intrinsic sensitivity of the emulsion grains to blue light of 400 to 500 nm. For this reason, the lack of saturation due to the insensitivity of the emulsion grains to blue light, particularly the lack of tone reproducibility of shadows in high-density red areas, is desirably improved by a conventionally known technique. For example, EP 304,29
No. 7A2, a method of adding a green-sensitive spectral sensitizing dye to a cyan-coupler-containing red-sensitive emulsion layer;
No. 29628, No. 4-134336, No. 8-8708
For example, a method of adding a blue-sensitive and / or green-sensitive spectral sensitizing dye to a cyan coupler-containing red-sensitive high silver chloride emulsion layer described in No. 9 or the like is preferably used. Here, each color photosensitive sensitizing dye of the present invention has a peak wavelength of spectral sensitivity when adsorbed on a silver chloride emulsion, and the red photosensitive sensitizing dye has a peak wavelength of about 590 to 720 nm. The dye preferably has a wavelength between about 510 and 590 nm, and the blue-sensitive sensitizing dye preferably has a wavelength between about 390 and 510 nm. As a means for improving the whiteness of the support, a fluorescent whitening agent can be contained in the water-resistant resin layer of the support of the present invention. Preferred fluorescent whitening agents are described in JP-A-9-203984 and JP-A-9-204001.
Nos. 6-123949, 2-188573, 3-91740, 3-65948, 2-254
440, 2-71256, 2-168249
No. 1-262538, JP-A-50-66234
No. 4,794,071, U.S. Pat.
No. 298 can be used.

The silver halide grains in the silver halide emulsion used in the present invention are preferably cubic or tetradecahedral crystal grains having substantially {100} faces (these grains have rounded apex and higher Or octahedral crystal grains, or 50 of total projected area
% Or more are tabular grains having an aspect ratio of 2 or more composed of {100} planes or {111} planes. The aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of a particle. In the present invention, a cubic or tabular grain having a {100} plane as a principal plane or a tabular grain having a {111} plane as a principal plane is preferably applied. In addition, $ 10
In the case of 0 ° tabular grains, tabular grains having an adjacent side ratio of 10 or less are preferred. The adjacent side ratio is a value obtained by dividing a larger one of two adjacent sides by a smaller one. The adjacent side ratio is
The closer to 1, the closer the main plane is to a square.

The silver halide emulsion used in the present invention is silver chloride, silver chlorobromide, silver chloroiodide or silver chloroiodobromide having a silver chloride content of 95 mol% or more. Silver chloride content is 95-9
9.9 mol% is preferable, and 98-99.% Is more preferable.
9 mol%. The silver iodide content is preferably 0.01
To 1 mol%, more preferably 0.1 to 0.5 mol%. The silver bromide content is preferably 0.05
To 5 mol%, more preferably 0.1 to 2 mol%.

Tabular high silver chloride emulsion grains having a {100} plane or a {111} major plane are described in
No. 138,619, U.S. Pat. Nos. 4,399,215 and 5,061,617 and U.S. Pat. No. 5,320,938.
No. 5,264,337, 5,292,632
Nos. 5,314,798 and 5,413,904
, WO94 / 22051 and the like.

The average grain size of the silver halide grains is preferably from 0.2 μm to 2 μm. The distribution state is preferably as monodispersed. A monodispersed emulsion has a coefficient of variation (S / average r) relating to the grain size of silver halide grains of 0.1.
An emulsion having a particle size distribution of 25 or less, preferably 0.15 or less. Here, the average r is the average particle size, and S is the standard deviation related to the particle size. That is, when the particle size of each emulsion particle is ri and its number ni, the average particle size r is:

[0092]

(Equation 2)

And its standard deviation S is

[0094]

(Equation 3)

Is defined as In the present invention, the term "individual grain size" means that a silver halide emulsion is defined as T.V. H. James et al., “T
he Theory of the Photogra
Phys Process, 3rd Edition, pp. 36-43, published by Macmillan, Inc. (1966). Is the equivalent projected area diameter. Here, the projected area equivalent diameter of the silver halide grains is defined by the diameter of a circle equal to the projected area of the silver halide grains as described in the above-mentioned book.

In the present invention, silver halide grains include
It is preferable to provide a silver bromide rich phase. The silver bromide rich phase can be formed near the apex of the grain through the following process. First, bromine ions or silver bromide fine particles are supplied to the host silver halide grains to precipitate a new silver halide phase rich in silver bromide on the surface of the host silver halide grains. This process by bromine ions proceeds in a process called “halogen conversion” by an exchange reaction with a halogen ion on the surface of the host silver halide grain. The process using the other silver bromide fine particles proceeds by a reaction called "recrystallization" between the host silver halide particles and the silver bromide fine particles, which attempts to form crystals having a more stable composition, and the conversion reaction takes place. Is a content that can be considered separately. In such a recrystallization reaction, the driving force of the reaction is an increase in entropy, which is completely different from Ostwald ripening. This is described, for example, in H. C. Yut
zy "Journalof American Ch"
Chemical Society, "p. 59916 (193)
7). Totally different two like these
Although species reactions, both reactions are surprising, but well-known phenomena, to select near the apex of the host grain as the site for the formation of a new phase richer in silver bromide.

In the silver halide emulsion used in the present invention, various polyvalent metal ion impurities can be introduced during the process of emulsion grain formation or physical ripening. Examples of compounds used include iron, iridium, ruthenium, osmium, rhenium, rhodium, cadmium, zinc, lead,
Salts or complex salts of metals of Group VIII of the periodic table such as copper and thallium can be used in combination. In the present invention, metal compounds having at least four cyano ligands, such as iron, ruthenium, osmium, and rhenium, are particularly preferred in that they further increase the high illuminance sensitivity and also suppress the latent image sensitization. The addition amount of these compounds varies widely depending on the purpose, but is preferably from 10 ^-9 to 10 ^-2 mol per mol of silver halide. These metal ions will be described in more detail, but are not limited thereto.

The iridium ion-containing compound is a trivalent or tetravalent salt or complex salt, preferably a complex salt. For example, iridium (III) chloride, iridium bromide (II)
I), iridium (II) chloride, sodium hexachloroiridate (III), hexachloroiridium (I
V) Potassium acid, hexaammine iridium (IV) salt,
Halogens such as trioxalatoiridium (III) salt and trioxalatoiridium (IV) salt, amines, and oxalato complex salts are preferred. The platinum ion-containing compound is a divalent or tetravalent salt or complex salt, preferably a complex salt. For example, platinum (IV) chloride, potassium hexachloroplatinum (IV), tetrachloroplatinum (II), tetrabromoplatinum (II), tetrakis (thiocyanato)
Sodium platinum (IV), hexaammine platinum (IV) chloride and the like are used.

The palladium ion-containing compound is usually a divalent or tetravalent salt or complex salt, and a complex salt is particularly preferred. For example, sodium tetrachloropalladium (II), sodium tetrachloropalladium (IV), potassium hexachloropalladium (IV), tetraamminepalladium (II) chloride, tetracyanopalladium (II)
Potassium acid or the like is used. As the nickel ion-containing compound, for example, nickel chloride, nickel bromide, potassium tetrachloronickelate (II), hexaamminenickel (II) chloride, sodium tetracyanonickelate (II) and the like are used.

The rhodium ion-containing compound is usually preferably a trivalent salt or complex salt. For example, potassium hexachlororhodate, sodium hexabromorhodate, ammonium hexachlororhodate and the like are used. The iron ion-containing compound is a divalent or trivalent iron ion-containing compound, preferably an iron salt or an iron complex salt having water solubility in the concentration range used. Particularly preferred is an iron complex salt which can be easily contained in silver halide grains. For example, ferrous chloride,
Ferric chloride, ferrous hydroxide, ferric hydroxide, ferrous thiocyanate, ferric thiocyanate, iron hexacyano (II)
Complex salts, hexacyanoiron (III) complex salts, ferrous thiocyanate complex salts, and ferric thiocyanate complex salts. Further, a six-coordinate metal complex having at least four cyan ligands as described in EP 336,426A is also preferably used.

The above-mentioned metal ion-providing compound is prepared by dispersing a metal ion in an aqueous gelatin solution, an aqueous halide solution, an aqueous silver salt solution, or another aqueous solution when silver halide grains are formed, or in an aqueous solution. The silver halide grains of the present invention can be contained in the silver halide grains of the present invention by adding silver halide grains and dissolving the grains. The metal ions used in the present invention can be contained in the particles either before, during or immediately after the formation of the particles. This can be changed depending on where the metal ions are contained in the particles.

As is generally well known, the steps of preparing a silver halide emulsion in the present invention include a step of forming silver halide grains by a reaction between a water-soluble silver salt and a water-soluble halide, a step of desalting, and a step of chemical ripening. Process.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization. Regarding the chemical sensitization method, sulfur sensitization represented by addition of an unstable sulfur compound, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compounds used for chemical sensitization, those described in JP-A-62-215272, from page 18, lower right column to page 22, upper right column, are preferably used.

The silver halide emulsion used in the present invention is:
It is preferably subjected to gold sensitization known in the art. This is because, by performing gold sensitization, fluctuations in photographic performance when scanning exposure is performed with a laser beam or the like can be further reduced. For gold sensitization, compounds such as chloroauric acid or a salt thereof, gold thiocyanates or gold thiosulfates can be used. The addition amount of these compounds may vary widely depending on the case, but is from 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably from 1 × 10 ⁻⁶ to 1 × 10 ⁻⁴ mol per mol of silver halide. is there.

In the present invention, gold sensitization is carried out by other sensitization methods,
For example, it may be combined with sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, or noble metal sensitization using a compound other than a gold compound.

The silver halide emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the emulsion or the photographic material, during storage or during photographic processing, or for stabilizing photographic performance. It can be contained. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles mercaptobenzimidazoles, mercaptothiaidiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (particularly 1-phenyl-5-mercaptotetrazole and the like), mercaptopyrimidines,
Mercaptotriazines and the like; thioketo compounds such as oxadrinethione; azaindenes such as triazaindenes and tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindene) pentaazaindene Many compounds known as antifoggants or stabilizers, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonamide, etc., can be added. Particularly preferred are mercaptotetrazoles. This is preferable because it has a function of further increasing the high illuminance sensitivity in addition to preventing and stabilizing fog.

The developing solution and the developing replenisher contain a color developing agent, and preferred examples thereof include known aromatic primary amine color developing agents, particularly p-phenylenediamine derivatives. Representative examples are shown below. It is not limited to these. In recent years, some black-and-white photosensitive materials have been added so that a coupler is added so as to form a black color, and a black-and-white image is formed using a general-purpose general color developing solution. Is also applicable to this type of photosensitive material processing.

1) N, N-diethyl-p-phenylenediamine 2) 4-amino-N, N-diethyl-3-methylaniline 3) 4-amino-N- (β-hydroxyethyl) -N-
Methylaniline 4) 4-amino-N-ethyl-N- (β-hydroxyethyl) aniline 5) 4-amino-N-ethyl-N- (β-hydroxyethyl) -3-methylaniline 6) 4-amino- N-ethyl-N- (3-hydroxypropyl) -3-methylaniline 7) 4-amino-N-ethyl-N- (4-hydroxybutyl) -3-methylaniline 8) 4-amino-N-ethyl- N- (β-methanesulfonamidoethyl) -3-methylaniline 9) 4-amino-N, N-diethyl-3- (β-hydroxyethyl) aniline 10) 4-amino-N-ethyl-N- (β -Methoxyethyl) -3-methylaniline 11) 4-Amino-N- (β-ethoxyethyl) -N-
Ethyl-3-methylaniline 12) 4-amino-N- (3-carbamoylpropyl-
Nn-propyl-3-methylaniline 13) 4-amino-N- (4-carbamoylbutyl-N
-N-propyl-3-methylaniline 15) N- (4-amino-3-methylphenyl) -3-
Hydroxypyrrolidine 16) N- (4-amino-3-methylphenyl) -3-
(Hydroxymethyl) pyrrolidine 17) N- (4-amino-3-methylphenyl) -3-
Pyrrolidine carboxamide

Among the p-phenylenediamine derivatives, particularly preferred are the exemplified compounds 5), 6), 7), 8) and 12), among which the compounds 5) and 8) are preferred. Also, these p-phenylenediamine derivatives are
In the state of solid material, usually sulfate, hydrochloride, sulfite,
It is in the form of a salt such as naphthalenedisulfonic acid and p-toluenesulfonic acid. The concentration of the aromatic primary amine developing agent in the developer or replenisher is preferably 2 to 200 mmol, more preferably 12 to 200 mmol, and still more preferably 12 to 150 mmol per liter of the developer. Yes, the replenisher is designed to have a higher concentration than the developer by the amount consumed by development, so the amount of replenishment supplied to the developer tank and the amount consumed by the reaction, and the amount lost due to carry-out and overflow to the next tank are balanced. Thus, the concentration of the replenisher is determined so that the concentration in the developing tank is kept constant. Therefore, in the case of the low replenishment process, which is a preferred embodiment of the present invention, the developing agent concentration is set high in order to secure a necessary supply amount with a small replenisher amount. In the practice of the present invention, it is preferable to use a developer that does not substantially contain benzyl alcohol. Here, "substantially free" means that the benzyl alcohol concentration is preferably 2 ml / liter or less, more preferably 0.5 ml / liter or less, and most preferably no benzyl alcohol is contained.

It is more preferable that the developer used in the present invention does not substantially contain sulfite ions. Sulfite ions have a function of dissolving silver halide and reacting with an oxidized form of the developing agent, and at the same time, function as a preservative of the developing agent to lower the dye formation efficiency. Such an action,
It is presumed to be one of the causes of the increase in the fluctuation of the photographic characteristics due to the continuous processing. Here, “substantially free” means that the concentration of sulfite ions is preferably 3.0 × 10 ⁻³ mol / liter or less, and most preferably no sulfite ions are contained. However, in the present invention, a very small amount of sulfite ion used for preventing oxidation of a processing agent kit in which a developing agent is concentrated before preparing a working solution is excluded.
The developer used in the present invention preferably does not substantially contain sulfite ions, and more preferably does not substantially contain hydroxylamine. This is because hydroxylamine itself has silver developing activity at the same time as functioning as a preservative of the developer, and fluctuations in the concentration of hydroxylamine are considered to greatly affect photographic characteristics. The term "substantially free of hydroxylamine" as used herein means that the hydroxylamine concentration is preferably 5.0 × 10 ⁻³ mol / liter or less, and most preferably contains no hydroxylamine at all.

The developer used in the present invention more preferably contains an organic preservative in place of the above-mentioned hydroxylamine and sulfite ions. Here, the organic preservative refers to all organic compounds that reduce the deterioration rate of an aromatic primary amine color developing agent by being added to a processing solution of a photosensitive material. That is, organic compounds having a function of preventing oxidation of a color developing agent by air or the like, among which hydroxylamine derivatives (excluding hydroxylamine; the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, alicyclic amines, and the like are particularly preferred. It is an effective organic preservative. These are disclosed in JP-A-63-4235 and JP-A-63-30845.
No. 63-21647, No. 63-44655, No. 63-53551, No. 63-43140, No. 63-
No. 56654, No. 63-58346, No. 63-431
No. 38, No. 63-146041, No. 63-44657
No. 63-44656, U.S. Pat. No. 3,615,5
No. 03, 2,494, 903, JP-A-52-143.
No. 020, JP-B-48-30496, and the like.

Other preservatives are described in JP-A-57-441.
Nos. 48 and 57-53749, various metals, salicylic acids described in JP-A-59-180588, alkanolamines described in JP-A-54-3532, and JP-A-56-379. If necessary, polyethyleneimines described in U.S. Pat. No. 94349, aromatic polyhydroxy compounds described in U.S. Pat. No. 3,746,544 and the like may be contained. In particular, addition of alkanolamines such as triethanolamine, dialkylhydroxylamine such as diethylhydroxylamine, hydrazine derivatives or aromatic polyhydroxy compounds is preferred. Among the above organic preservatives, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides) are particularly preferable. For details, refer to JP-A-1-97953, JP-A-1-186939, and 1-1.
86940 and 1-187557. It is more preferable to use the hydroxylamine derivative or the hydrazine derivative in combination with an amine in terms of improving the stability of the color developing solution, and further improving the stability during continuous processing. Examples of the amines include cyclic amines described in JP-A-63-239647, amines described in JP-A-63-128340, and other amines described in JP-A-1-1869.
Amines such as those described in JP-A Nos. 39 and 1-187557 are exemplified.

A chlorine ion may be added to the developing solution as needed. A color developer (especially a developer for a color print material) usually contains chloride ions of 3.5 × 10 ^-2 or ^less .
Although it often contains 1.5 × 10 ^-1 mol / liter,
Chlorine ions are usually released into a developer as a by-product of development, and thus often need not be added to a replenisher. The amount of chloride ions in the replenisher is set so that the chloride ion concentration in the developing tank when the running equilibrium composition is reached is at the above-mentioned concentration level. If the chloride ion concentration is more than 1.5 × 10 ⁻¹ mol / liter, it has the disadvantage of delaying the development, and is unfavorable because the speed and color density are impaired. On the other hand, if it is less than 3.5 × 10 ^-2 mol / l, it is not preferable in many cases to prevent fog.

Regarding the content of bromine ions, the situation is the same as in the case of chlorine ions. The amount of bromine ions in the color developer is preferably about 1 to 5 × 10 ⁻³ mol / liter in the processing of a photographic material, and 1.0 × 10 ⁻³ mol / liter or less in the processing of a printing material. If necessary, bromine ions may be added to the developing replenisher so that the bromine ion concentration falls within this range. When these are included in the developing solution or the replenisher as necessary, as a chloride ion supplying substance, sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride,
Manganese chloride and calcium chloride can be mentioned, and preferred are sodium chloride and potassium chloride. Examples of the bromine ion supply material include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cerium bromide, and thallium bromide. Among them, preferred are potassium bromide and sodium bromide.

When the photosensitive material to be developed is color photographic paper, it is important that the white background of the screen is white, so that it is important to apparently make it white with a fluorescent whitening agent. The fluorescent whitening agent is contained in the light-sensitive material depending on its properties, but it may be penetrated from the processing solution into the light-sensitive material during the development processing. In that case, an appropriate processing solution to be added is selected according to the properties of the fluorescent whitening agent so as to obtain a high whitening effect. Therefore, it may be added to a color developing solution having a high pH, or may be added to a bleach-fixing solution or a stabilizing bath so as to be contained in a large amount in a developed print without being washed out during processing. Generally, stilbene-based fluorescent brighteners are frequently used, and among them, di (triazylamino) stilbene-based stilbene represented by the following formula,
4,4'-Diamino-2,2'-disulfostilbene-based fluorescent whitening agents are preferred.

[0116]

Embedded image

In the above formula, R ⁷ and R ⁹ each represent a hydrogen atom, an alkyl group having 1 or 2 carbon atoms,
Represents an alkoxy group or a hydroxyalkyl group having 1 or 2 carbon atoms. R ⁸ and R ¹⁰ each represent a substituted or unsubstituted amino group or an alkoxy group having 2 or less carbon atoms. When the amino group is substituted, the substituent is an alkyl group having 2 or less carbon atoms, The following hydroxyalkyl group, sulfoalkyl group having 2 or less carbon atoms, or phenyl group. M ³ represents a hydrogen atom, a sodium atom or a potassium atom.

All of these compounds are known and can be easily obtained or can be easily synthesized by a known method. This stilbene-based fluorescent whitening agent can be added to any of a processing agent composition for a color developing solution or a desilvering solution or a photosensitive material. When it is contained in the processing solution, its preferable concentration is 1 × 10 ^{−4 to} 5 × 10 ⁻² mol / l, more preferably 2 × 10 ⁻⁴ to 1 ×.
10 ^-2 mol / l. The processing agent composition of the present invention is added in such an amount that the development in use contains the optical brightener at this concentration level.

The pH of the color developer or replenisher is 9.5.
To 13.0, more preferably 9.8 to 12.5. In order to maintain this pH, it is preferable to use various buffers. As the buffer, in addition to the above-mentioned potassium carbonate and sodium carbonate, other carbonates, phosphates, borates, tetraborates, hydroxybenzoates, glycyl salts, N, N-dimethylglycine salts, Leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane Salts, lysine salts and the like can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates have excellent buffering ability in a high pH range of pH 9.0 or higher, and adversely affect photographic performance (fog) even when added to a color developer. ) And the advantage of being inexpensive, and it is particularly preferable to use these buffers.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate,
Potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, o-hydroxybenzoate Sodium (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like Can be mentioned. However, the invention is not limited to these compounds. The amount of the above buffer is such that the concentration in the color developer replenisher is 0.04 to 2.0 mol / liter in total of the buffer,
In particular, it is 0.1 mol / L to 0.4 mol / L.

The color developing solution of the present invention may contain other color developing solution components, for example, various chelating agents which are precipitation inhibitors for calcium and magnesium, or are also agents for improving the stability of the color developing solution. . For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenesulfonic acid, ethylenediamine-N, N-disamber Acid, N, N-di (carboxylate) -L-aspartic acid, β-alanine disuccinic acid, ethylenediamine
N, N, N ', N'-tetramethylenesulfonic acid, transsilohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2 , 4-Tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'-
Bis (2-hydroxybenzyl) ethylenediamine-
N, N'-diacetic acid, 1,2-dihydroxybenzene-
4,6-disulfonic acid and the like. These chelating agents may be used in combination of two or more as necessary. The amount of these chelating agents may be an amount sufficient to block metal ions in the color developer. Usually, the concentration of the developer or replenisher is 0.1 g to 10 g per liter.

An optional development accelerator can be added to the developer and the replenisher as needed. Examples of the development accelerator include JP-B-37-16088, JP-B-37-5987, and JP-B-38-7.
No. 826, No. 44-12380, No. 45-9019 and U.S. Pat. No. 3,813,247.
P-phenylenediamine compounds disclosed in JP-A-49829 and JP-A-50-15554;
No. 7726, JP-B-44-30074, JP-A-56-
Quaternary ammonium salts described in 156826 and 52-43429; U.S. Pat.
903, 3,128,182, 4,230,7
No. 96, No. 3, 253, 919, Japanese Patent Publication No. 41-114
No. 31, U.S. Pat. Nos. 2,482,546 and 2,591
Nos. 6,926 and 3,582,346, and the like, and amine compounds described in the specification or JP-B-37-160.
No. 88, No. 42-25201, U.S. Pat.
8,183, JP-B-41-11431, 42-2
No. 3,883, U.S. Pat. No. 3,532,501, etc., or polyalkylene oxides described in the specification, other 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as necessary. .

Further, an optional antifoggant can be added as required. As the antifoggant, the above-mentioned alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used.
Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Representative examples include nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine. In addition to the surfactant in the present invention, various surfactants such as alkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added as necessary.
The color developing replenisher or developer used in the present invention has been described above.

The processing temperature of color development in the present invention is 3 when the photosensitive material to be developed is a color print material.
It is 0-55 degreeC, Preferably it is 35-55 degreeC, More preferably, it is 38-45 degreeC. Development processing time is 5
This is from 90 to 90 seconds, preferably from 8 to 60 seconds, and in particular, the present invention is suitable for extremely rapid development of 10 to 30 seconds as described above. The replenishment amount is preferably smaller, but ^{20 to} 600 ml per m2 of the light-sensitive material is applied, preferably 30 to 120 ml, and particularly preferably 15 to 60 ml. On the other hand, in the case of color development of a color negative or color reversal film, the development temperature is 20 to 55 ° C., preferably 30 to 55 ° C.
55 ° C., more preferably 38 to 45 ° C. The development processing time is 10 seconds to 6 minutes. It is preferable that the replenishing amount is small, but ^{20 to} 500 ml per 1 m ^{2 of} the photosensitive material.
Is suitable, preferably 30 to 200 ml,
Particularly preferred is 50 to 160 ml.

In practicing the present invention, a desilvering step is carried out after the development step using a color developing solution, and the processing is performed using a bleaching solution and a bleach-fixing solution. In the case of a photosensitive material intended for color printing, this processing solution may contain an appropriate compound of the above-mentioned fluorescent whitening agent, preferably a stilbene-based fluorescent whitening agent. As the bleaching agent used in the bleaching solution or the bleach-fixing solution, a known bleaching agent can be used.
Organic acids such as malic acid, persulfates, hydrogen peroxide and the like are preferred.

Of these, organic complex salts of iron (III) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Iron (II
Aminopolycarboxylic acids or salts thereof useful for forming the organic complex salt of I) are listed as biodegradable ethylenediaminedisuccinic acid (SS form), N- (2-carboxylateethyl) -L -Aspartic acid, beta-alanine diacetate, methyliminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,
In addition to 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, glycol etherdiaminetetraacetic acid and the like, the general formula (I) of European Patent 0789275
Or the compound represented by (II) can be mentioned.
These compounds may be any of the sodium, potassium, lithium or ammonium salts. Among these compounds, ethylenediamine disuccinic acid (SS form), N- (2-
(Carboxylate ethyl) -L-aspartic acid, beta-alanine diacetate, ethylenediaminetetraacetic acid, 1,3
-Diaminopropanetetraacetic acid and methyliminodiacetic acid are preferred because their iron (III) complex salts have good photographic properties. These ferric ion complex salts may be used in the form of a complex salt,
Ferric salts such as ferric sulfate, ferric chloride, ferric nitrate
A ferric ion complex salt may be formed in a solution using iron, ferric ammonium sulfate, ferric phosphate or the like and a chelating agent such as aminopolycarboxylic acid. In addition, the chelating agent may be used in excess of forming a ferric ion complex salt. Of the iron complexes, aminopolycarboxylate iron complexes are preferable, and the amount of addition is 0.01 to 1.0 mol / l, preferably 0.05 to 0.50 mol / l, and more preferably 0.10 to 0 mol / l. .50 mol / l, more preferably 0.15 to 0.40 mol / l.
The bleaching time is usually 5 seconds to 6 minutes and 30 seconds, preferably 10 seconds to 2 minutes.

The fixing agent used in the bleach-fixing solution or the fixing solution includes known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate;
Ethylenebisthioglycolic acid, 3,6-dithia-1,
Thioether compounds such as 8-octanediol and water-soluble silver halide dissolving agents such as thioureas;
These can be used alone or in combination of two or more. Also, a special bleach-fixing solution comprising a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of the fixing agent per liter is preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.0 mol.

The pH range of the bleach-fixing solution or fixing solution used in the present invention is preferably from 3 to 8, and more preferably from 4 to 7. When the pH is lower than this, the desilvering property is improved,
The deterioration of the liquid and the leuco conversion of the cyan dye are promoted. Conversely, if the pH is higher than this, desilvering is slow and stain is likely to occur. The pH range of the bleaching solution used in the present invention is 8
It is the following, 2-7 are preferred, and 2-6 are especially preferred. If the pH is lower than this, the deterioration of the solution and the leuco-formation of the cyan dye are accelerated. On the other hand, if the pH is higher than this, desilvering is delayed and stain is easily generated. To adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate and the like can be added as necessary. Further, the bleach-fixing solution may contain other various types of fluorescent whitening agents, defoamers or surfactants, and organic solvents such as polyvinylpyrrolidone and methanol. Bleaching-fixing solutions and fixing solutions include sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives, Metabisulfites (eg, potassium metabisulfite, sodium metabisulfite,
It is preferable to contain a sulfite ion releasing compound such as ammonium metabisulfite and the like, and an arylsulfinic acid such as p-toluenesulfinic acid and m-carboxybenzenesulfinic acid. These compounds are used in an amount of about 0.02 to 1 in terms of sulfite ion or sulfinate ion.
It is preferable to contain 0 mol / liter.

As a preservative, in addition to the above, ascorbic acid, carbonyl bisulfite adduct, or carbonyl compound may be added. Further, a buffer, an optical brightener, a chelating agent, an antifoaming agent, a fungicide, and the like may be added as necessary. The bleach-fix processing according to the present invention requires a processing time of 5
２４０240 seconds, preferably 10-60 seconds. The processing temperature is from 25C to 60C, preferably from 30C to 50C.
The replenishing rate is ²⁰ ml to 250 per m ² of the photosensitive material.
ml, preferably 30 ml to 100 ml, particularly preferably 15 ml to 60 ml.

After desilvering such as fixing or bleach-fixing, washing and / or stabilization are generally performed. The amount of rinsing water in the rinsing step can be set in a wide range depending on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (the number of stages), and various other conditions.
Among them, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in Journal of the Society of Motion Picture and Television Engineers (Journal of the Society).
ty of Motion Picture and
Television Engineers) Vol. 64,
p. 248-253 (May, 1955). Usually, the number of stages in the multistage countercurrent system is preferably 3 to 15, and particularly preferably 3 to 10.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, and bacteria increase due to an increase in the residence time of water in the tank, and the generated suspended matter adheres to the photosensitive material. Occurs. As a solution to such a problem, the method for reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542,
Chlorinated fungicides such as chlorinated sodium isocyanurate described in JP-A-120145;
No. benzotriazole, copper ion, and others, written by Hiroshi Horiguchi, Chemistry of Bactericidal and Antifungal (1986), Sankyo Publishing,
Sanitary Technology Association, “Microbial Sterilization, Sterilization, and Antifungal Technology” (1
982) The disinfectant described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986), edited by the Japan Society of Industrial Technology, Japan Society of Antimicrobial and Antifungal Agents can also be used.

Further, aldehydes such as formaldehyde, acetaldehyde and pyruvaldehyde which inactivate the remaining magenta coupler to prevent discoloration of the dye and generation of stain, methylol compounds described in US Pat. No. 4,786,583, Hexamethylenetetramine, hexahydrotriazines described in JP-A-2-153348, formaldehyde bisulfite adduct described in U.S. Pat. No. 4,921,779, European Patent Publication 504
No. 609, No. 519190 and the like are added.

Further, in the washing water, a surfactant can be used as a draining agent, and a chelating agent represented by EDTA can be used as a hardening agent. Continue with the above washing process or
Alternatively, it can be treated directly with a stabilizing solution without going through a washing step. A compound having an image stabilizing function is added to the stabilizing solution, and examples thereof include an aldehyde compound typified by formalin, a buffering agent for adjusting a membrane pH suitable for dye stabilization, and an ammonium compound. Further, in order to prevent the growth of bacteria in the liquid and impart fungicidal properties to the processed photosensitive material, the above-mentioned various bactericides and fungicides can be used.

Further, a surfactant, an optical brightener and a hardener may be added. In the processing of the light-sensitive material of the present invention, when stabilization is directly performed without going through a washing step, JP-A-57-8543, JP-A-58-14834,
All known methods described in JP-A-60-220345 can be used. In addition, it is also a preferable embodiment to use a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid or ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound.

A so-called rinsing liquid is also used as a washing liquid or a stabilizing liquid used after the desilvering treatment. The preferred pH of the washing step or the stabilizing step is 4 to 10, and more preferably 5 to 8. The temperature can be set variously depending on the use and characteristics of the photosensitive material, but is generally from 2.0 ° C. to 50 ° C.
Preferably it is 25 to 45 degreeC. The time can be set arbitrarily, but a shorter time is desirable from the viewpoint of reducing the processing time. Preferably 10 seconds to 60 seconds, more preferably 15 seconds to 45 seconds
Seconds. It is preferable that the replenishing amount is small in view of running cost, reduction of discharge amount, handleability, and the like. A specific preferable replenishing amount is 0.5 to 50 times, preferably 3 to 40 times the carry-in amount from the previous bath per unit area of the photosensitive material. Alternatively, the amount is 500 ml or less, preferably 300 ml or less per m ^{2 of the} photosensitive material. Replenishment may be performed continuously or intermittently. The liquid used in the water washing and / or stabilizing step can be further used in the previous step. As an example of this, the overflow of the washing water reduced by the multi-stage countercurrent method is caused to flow into a bleach-fixing bath as a preceding bath, and the bleach-fixing bath is replenished with a concentrated solution to reduce the amount of waste liquid.

For the stirring of each processing tank of the present invention, a well-known method such as a method of spraying a liquid, a method using mechanical stirring or an ultrasonic wave can be used. In particular, a method that directly affects the surface of the photosensitive material is preferable, and examples thereof include a method of jet agitation and a method of using pressure during passage between roller pairs as described in JP-A-3-83058 and JP-A-4-145434. Can be used.

A drying step usable in the present invention will be described. The drying time is preferably from 5 seconds to 120 seconds, especially 8 seconds.
Seconds to 20 seconds are more preferred. As a means for shortening the drying time, a means on the photosensitive material side can be improved by reducing the amount of water carried into the film by reducing the amount of a hydrophilic binder such as gelatin. Further, from the viewpoint of reducing the carry-in amount, it is also possible to speed up drying by absorbing water with a squeeze roller or cloth immediately after leaving the washing bath. As a means of improvement from the dryer side, as a matter of course, as described in JP-A-8-304980, increasing the temperature and changing the shape of the spray nozzle to increase the drying wind It is possible to hasten the drying by doing. Further, as described in Japanese Patent Application Laid-Open No. 3-157650, drying can be accelerated by adjusting the blowing angle of the drying air to the photosensitive material and removing the exhaust air.

The processing method of the present invention is performed using an automatic developing machine. The automatic developing machine preferably used in the present invention is described below. In the present invention, it is preferable that the linear velocity of conveyance of the automatic developing machine is 5000 mm / min or less. More preferably, 200 mm / min to 4500 mm /
Min, particularly preferably 500 to 3000 mm / min.
In the treatment tank and the replenisher tank of the treatment liquid according to the present invention, the area (opening area) where the liquid comes into contact with air is preferably as small as possible. For example, assuming that a value obtained by dividing an opening area (cm ² ) by a liquid tank (cm ³ ) in the tank is an opening ratio, the opening ratio is preferably 0.01 (cm ⁻¹ ) or less, more preferably 0.005 or less. And most preferably 0.001 or less.

In order to reduce the area of contact with air, it is preferable to provide a solid or liquid air non-contact means floating on the liquid surface in the processing tank and the replenishing tank. Specifically, it is preferable to float a float made of plastic or the like on the liquid surface, or to cover with a liquid that does not mix with the processing liquid and does not cause a chemical reaction. Preferred examples of the liquid include liquid paraffin and liquid saturated hydrocarbon.

In the present invention, in order to perform processing quickly, the air time, ie, the crossover time, when the photosensitive material moves between processing solutions is preferably as short as possible, preferably 10 seconds or less, more preferably 7 seconds or less. The time is not more than seconds, more preferably not more than 5 seconds. In order to achieve the above-mentioned short-time crossover, the present invention preferably employs a cine-type automatic developing machine, and particularly preferably employs a leader transport system. Such a system is developed by Fuji Photo Film Co., Ltd. automatic developing machine FP-56.
0B. Japanese Patent Application Laid-Open Nos. 60-191257 and 60-19 describe examples of a reader and a means for transporting photosensitive material.
No. 1258 and No. 60-191259 are preferred. Particularly, as a transport mechanism, Japanese Patent Application No. Hei.
-265794, 1-266915, 1-26
It is preferable to adopt each system described in No. 6916.
Further, in order to shorten the crossover time and prevent the treatment liquid from being mixed, the crossover rack preferably has a mixing prevention plate described in Japanese Patent Application No. 1-265975.

It is preferable to perform so-called evaporation correction, in which water corresponding to the amount of evaporation of the processing liquid is supplied to each processing liquid in the present invention. Particularly, it is preferable in a color developing solution, a bleaching solution or a bleach-fixing solution. A specific method for replenishing such water is not particularly limited. Among them, a monitor water tank different from the bleaching tank described in JP-A Nos. 1-254959 and 1-254960 is installed. The amount of water in the inside of the bleaching tank is calculated, the amount of water in the bleaching tank is calculated from the amount of evaporation of the water, and the water is replenished to the bleaching tank in proportion to the amount of evaporation. 2-4
No. 7777, No. 2-47778, No. 2-47779
And an evaporation correction method using a liquid level sensor and an overflow sensor described in JP-A-2-117972. The most preferable evaporation correction method is to predict and add water corresponding to the amount of evaporation.
As described in JP-A-4-49925, page 1, right column, line 26 to page 3, left column, line 28, and Japanese Patent Application No. 2-103894, the operation time, stop time and temperature control time of the automatic developing machine are described. The amount of water calculated by a coefficient determined in advance based on the information is added.

It is also necessary to take measures to reduce the amount of evaporation, and it is necessary to reduce the opening area and adjust the air volume of the exhaust fan. For example, the preferable aperture ratio of the color developing solution is as described above, but it is preferable to similarly reduce the opening area in other processing solutions. As means for reducing the amount of evaporation, it is particularly preferable to "maintain the humidity of the upper space of the processing tank at 80% RH or more" described in JP-A-6-110171, and the evaporation prevention rack shown in FIGS. It is particularly preferable to have a roller automatic cleaning mechanism. Exhaust fan is mounted in order to prevent dew condensation at the temperature control, preferred emissions, per minute 0.1 m ³ to 1 m ^3, a particularly preferred displacement volume, 0.2 m ³ ~0 0.4 m ³ . The drying conditions of the photosensitive material also affect the evaporation of the processing liquid. A replenishing pump is used for replenishing the processing solution, and a bellows type replenishing pump is preferable. Further, as a method of improving the replenishment accuracy, it is effective to reduce the diameter of the liquid feeding tube to the replenishment nozzle in order to prevent backflow when the pump is stopped.
A preferable inner diameter is 1 to 8 mm, and a particularly preferable inner diameter is 2 to 5 mm.

Various component materials are used in the automatic developing machine. Preferred materials are described below. The tank material such as the treatment tank and the temperature control tank is preferably a modified PPO (modified polyphenylene oxide) or a modified PPE (modified polyphenylene ether) resin. The modified PPO includes "Noryl" manufactured by Nippon GE Plastics Co., Ltd., and the modified PPE includes "Zylon" manufactured by Asahi Kasei Kogyo, "Iupiece" manufactured by Mitsubishi Gas Chemical, and the like. In addition, these materials are suitable for parts that may come into contact with the processing liquid, such as processing racks and crossovers.

As the roller material of the processing section, resins such as PVC (polyvinyl chloride), PP (polypropylene), PE (polyethylene), and TPX (polymethylpentene) are suitable. These materials can also be used for other treatment liquid contact parts. In addition, PE resin is also preferable for the material of the replenishment tank formed by blowing. Materials for processing parts, gears, sprockets, bearings, etc. include PA (polyamide), PBT (polybutylene terephthalate), UH
Resins such as MPE (ultra high molecular weight polyethylene), PPS (polyphenylene sulfide), and LCP (fully aromatic polyester resin, liquid crystal polymer) are suitable. The PA resin is a polyamide resin such as 66 nylon, 12 nylon, 6 nylon, and the like, and a resin containing glass fiber, carbon fiber, or the like is strong against swelling due to the treatment liquid and can be used.

A high molecular weight product such as MC nylon or a compression-formed product can be used without fiber reinforcement. Unreinforced products are suitable for UHMPE resin. Mitsui Petrochemical Co., Ltd. "Lybuma", "HIZEX Million" Sakushin Kogyo Co., Ltd. "New Light", Asahi Kasei Kogyo Co., Ltd. "Sun Fine" etc. Are suitable. The molecular weight is preferably 1,000,000 or more, more preferably 100
10,000 to 5 million. The PPS resin is preferably glass fiber or carbon fiber reinforced. The LCP resin includes “Victrex” by ICI Japan Co., Ltd., “Econol” by Sumitomo Chemical Co., Ltd., “Zyder” by Nippon Oil Co., Ltd., and “Vectra” by Polyplastics Co., Ltd. Particularly, as the material of the transport belt, an ultra-high-strength polyethylene fiber or polyvinylidene fluoride resin described in Japanese Patent Application No. 2-276886 is preferable. As a soft material such as a squeeze roller,
A foamed vinyl chloride resin, a foamed silicone resin, and a foamed urethane resin are suitable. Examples of the urethane foam resin include “Rubicel” manufactured by Toyo Polymer Co., Ltd. As a rubber material such as a pipe joint, an agitation jet pipe joint, or a sealing material, EPDM rubber, silicon rubber, viton rubber, or the like is preferable.

The treating agent applicable to the present invention may be supplied as a concentrated solution having a single or plural part composition, or may be supplied in the form of a powder, tablet, granule, paste or the like.
Also, it may be supplied in the state of use liquid, concentrated solution, powder, tablet,
Any combination of granules, pastes, and use solutions may be used.

In the case of a single concentrated solution, it is diluted and used as a replenisher. In this case, it is preferable to automatically dilute with water in the replenisher tank by setting the concentrate in the developing machine. As this water, it is preferable to use water from a washing water replenishing tank. Alternatively, the processing solution may be directly replenished with the concentrated liquid, and water suitable for the dilution ratio may be directly refilled into the processing solution. It is particularly preferable for a compact developing machine having no replenishing tank.

The same applies to the concentrated solution having a plurality of parts. It is preferable that the concentrated solution is set in the developing machine and automatically diluted with water in the replenisher tank. As this water, it is preferable to use water from a washing water replenishing tank. Further, the processing tank may be directly replenished for each part, and water corresponding to the dilution rate may be directly replenished to the processing tank.

Similarly, in the case of a powder, tablet, granule, or paste-like treatment agent, it is also preferable to add the drug directly to the treatment tank and to add water suitable for the dilution ratio to the treatment tank. It is also preferable that the solution is automatically dissolved and diluted in a replenishing tank and used as a replenishing solution.

As the material of the replenishment cartridge used in the present invention, any material such as paper, plastic, and metal can be used. In particular, a plastic material having an oxygen permeability coefficient of 50 ml / m ² · atm · day or less is preferable. . In addition, the oxygen permeability coefficient is "O ₂ permeation.
Of Plastic Container, Modern Packing "(O ₂ permeation of pls
tic container, Modern Pack
ing; J. (Galyan, 1968), December, pages 143 to 145. Preferable examples of the plastic material include vinylidene chloride (PVDC) and nylon (N
Y), polyethylene (PE), polypropylene (P
P), polyester (PES), ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl alcohol copolymer (EVAL), polyacrylonitrile (PAN),
Examples thereof include polyvinyl alcohol (PVA) and polyethylene terephthalate (PET). In the present invention, in order to reduce oxygen permeability, PVDC, NY, P
The use of E, EVA, EVAL and PET is preferred.

These materials may be used singly and may be used after shaping, or a method in which a film is formed and a plurality of kinds are bonded and used (so-called composite film) may be used. Further, as the shape of the container, various shapes such as a bottle type, a cubic type, and a pillow type can be used, but the present invention provides a cubic type which is flexible, easy to handle, and can be reduced in volume after use. Structures similar to are particularly preferred.

When used as a composite film, the following structures are particularly preferred, but the invention is not limited thereto. PE / EVAL / PE, PE / aluminum foil / PE, NY / PE / NY, NY / PE / EVA
L, PE / NY / PE / WVAL / PE, PE / NY /
PE / PE / PE / NY / PE, PE / SiO ₂ film / P
E, PE / PVDC / PE, PE / NY / aluminum foil / PE, PE / PP / aluminum foil / PE, NY /
PE / PVDC / NY, NY / EVAL / PE / EVA
L / NY, NY / PE / EVAL / NY, NY / PE /
PVDC / NY / EVAL / PE, PP / EVAL / P
E, PP / EVAL / PP, NY / EVAL / PE, N
Y / aluminum foil / PE, paper / aluminum foil / P
E, paper / PE / aluminum foil / PE, PE / PVDC
/ NY / PE, NY / PE / aluminum foil / PE, P
ET / EVAL / PE, PET / aluminum foil / P
E, PET / aluminum foil / PET / PE,

The thickness of the composite film is about 5 to 1500 microns, preferably about 10 to 1000 microns. The content of the completed container is 100 ml to 20 liter, preferably 500 ml to
It is about 10 liters. The above container (cartridge)
May have a cardboard or plastic outer box,
It may be formed integrally with the outer box. The cartridge of the present invention can be filled with various processing liquids. For example, a color developer, a black-and-white developer, a bleaching solution, an adjusting solution, a reversing solution, a fixing solution, a bleach-fixing solution, a stabilizer and the like can be mentioned. It is preferred to use a developer, a fixer and a bleach-fixer.

Conventional processing solution containers include high-density polyethylene (HDPE) and polyvinyl chloride resin (PV
C), a rigid container using a one-layer material such as polyethylene terephthalate (PET) or a multilayer material such as nylon / polyethylene (NY / PE) can be used. Also, after the contents are discharged and emptied, the volume of the container can be reduced, that is, a flexible liquid container that can easily reduce the required space can be used. In the present invention, it is preferable to use a container having the above flexibility.
As a specific example of the flexible container, there is provided a liquid container in which a hard mouth projecting upward from a flexible container body is opened and closed by a lid member engaged with the flexible body, and the container body and the mouth Is integrally formed and has a bellows portion in at least a part of the height of the container body (Japanese Patent Application Laid-Open No.
1 and 2) described in Japanese Patent No. 5670 can be mentioned.

As the method of developing the photosensitive material of the present invention after exposure, there are a conventional method of developing with a developing solution containing an alkali agent and a developing agent, and an alkaline solution containing a developing agent incorporated in the photosensitive material and containing no developing agent. In addition to a wet method such as a method of developing with an activator solution, a thermal developing method without using a processing solution can be used. In particular, since the activator method does not contain a developing agent in the processing liquid, it is easy to manage and handle the processing liquid, and is a preferable method from the viewpoint of environmental protection because it has a small load when processing the waste liquid. In the activator method, examples of the developing agent or its precursor incorporated in the photosensitive material include, for example, JP-A-8-2343.
No. 88, No. 9-152686, No. 9-152693
, Japanese Patent Application No. 7-334197, Japanese Patent Application Laid-Open No. 9-16019.
The hydrazine-type compound described in No. 3 is preferred.

Further, a developing method in which the amount of silver applied to the light-sensitive material is reduced and image amplification processing (intensification processing) using hydrogen peroxide is preferably used. In particular, it is preferable to use this method for the activator method. Specifically, Japanese Patent Application Hei 7
An image forming method using an activator solution containing hydrogen peroxide described in JP-A-63587 and JP-A-9-152699 is preferably used. In the activator method, after processing with an activator solution, usually a desilvering process is performed, but in an image amplification processing method using a low silver content photosensitive material,
The desilvering process can be omitted, and a simple method such as washing with water or stabilizing process can be performed. Further, in a method in which image information is read from a photosensitive material by a scanner or the like, a processing mode that does not require desilvering processing can be adopted even when a photosensitive material having a high silver content such as a photosensitive material for photography is used.

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

[0158]

The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 Preparation of Cellulose Paper Support A pulp furnish consisting of bleached hardwood kraft 50%, bleached hardwood sulphite 25%, and bleached softwood sulphite was subjected to double disc refiner and then to Jordan Photographic paper support was prepared by purification in a conical refiner to a Canadian Standard Freeness of 200 cc. To the obtained pulp furnish, on a dry basis, 0.2% of alkyl ketene dimer, 1.0% of cationic corn starch, 0.5% of polyamide epichlorohydrin, 0.26% of anionic polyacrylamide, and 5.0% TiO ₂ was added. The paper base obtained by pressing to a Sheffield porosity of 160 Sheffield units and an apparent density of 0.70 g / cc is then 10
The surface was glued with a corn starch solution that had been hydrolyzed to give a starch loading of 3.3% by weight. The surface-glued support has an apparent density of 1.04 g / cc.
The cellulose paper support was obtained by calendering. A polymer layer having the following composition was formed on this paper support, subjected to corona discharge treatment on the emulsion side, and then subbed to prepare a reflective support. In the polymer layer on the emulsion side,
4′-bis (5-methylbenzoxazolyl) stilbene contained 10 mg / m ² and ultramarine.

Reflective support A (comparative support) Emulsion surface side polymer composition: polyethylene layer containing titanium oxide at 20% by weight (35μ)

Back side polymer composition: polyethylene layer (30μ)

Reflective support B (support of the present invention) Emulsion surface side polymer composition: polyethylene terephthalate layer containing titanium oxide at 20% by weight (35μ) Back surface polymer composition: polyethylene layer (30μ)

Reflective support C (support of the present invention) Emulsion surface side polymer composition: polyethylene layer without micropores (1μ) from emulsion side Polypropylene skin containing titanium oxide and not containing micropores Layer (4μ) Polypropylene core layer containing micropores (22μ) Polypropylene skin layer containing titanium oxide and not containing micropores (4μ) Polyethylene layer containing titanium oxide and containing no micropores (4μ) Back surface Polymer composition: polyethylene layer (30μ)

Reflective support D (support of the present invention) Emulsion surface polymer composition: from the emulsion side, a polyethylene layer containing no micropores (3μ) A polypropylene layer containing titanium oxide and containing micropores (7μ) ) Polypropylene layer containing no micropores (9μ) Polypropylene layer containing titanium oxide and containing micropores (7μ) Polyethylene layer containing titanium oxide and containing no micropores (4μ) Backside polymer composition: polyethylene Layer (30μ)

Reflective support B2 (support of the present invention) Emulsion surface polymer composition: same as reflective support B Back surface polymer composition: polyethylene layer (28μ) from support side Polyethylene layer containing silica (2μ)

Reflective support C2 (support of the present invention) Emulsion surface polymer composition: Same as reflective support C Back surface polymer composition: Polyethylene layer (9μ) Polypropylene layer (24μ) Silica-containing polyolefin layer from the support side (3μ)

Reflective support D2 (support of the present invention) Emulsion surface polymer composition: same as reflective support D Back surface polymer composition: polyethylene layer (6μ) polypropylene layer (27μ) silica-containing polyolefin layer (3μ) The first to seventh photographic constituent layers are sequentially coated on the support A prepared as described above to prepare a sample (001A) of a silver halide color photographic light-sensitive material having the following layer structure. did. The coating solution for each photographic constituent layer was prepared as follows.

Preparation of Coating Solution for Fifth Layer 50 g of cyan coupler (ExC-1), 220 g of cyan coupler (ExC-2), color image stabilizer (Cpd-1) 2
20 g, 10 g of color image stabilizer (Cpd-9), 10 g of color image stabilizer (Cpd-10), color image stabilizer (Cpd-12)
20 g, UV absorber (UV-1) 140 g, UV absorber (UV-3) 30 g and UV absorber (UV-
4) Dissolve 60 g in 200 g of solvent (Solv-6) and 350 ml of ethyl acetate, and dissolve this solution in 10% sodium dodecylbenzenesulfonate containing 200 ml of 10%.
Emulsified dispersion C was prepared by emulsifying and dispersing in 6,500 g of an aqueous gelatin solution. On the other hand, silver chlorobromide emulsion C (cubic, large-sized emulsion C having an average grain size of 0.50 μm and 0.41 μm
1: 4 mixture (silver molar ratio) with the small size emulsion C. The coefficient of variation of the particle size distribution was 0.09 and 0.1, respectively.
One. In each size emulsion, 0.5 mol% of silver bromide was locally contained on a part of the surface of the silver chloride-based grain). This emulsion contains red-sensitive sensitizing dyes G and H shown below.
However, 6.0 × 10 ^-5 mol of the large-size emulsion C and 9.0 × 10 ^-5 mol of the small-size emulsion C were added per mol of silver. The chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion C and the silver chlorobromide emulsion C were mixed and dissolved to prepare a fifth layer coating solution having the composition described below. The emulsion coating amount indicates a coating amount in terms of silver amount.

The coating solutions for the first to fourth layers and the sixth to seventh layers were prepared in the same manner as the coating solution for the fifth layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Also, Ab-1, Ab-2 , Ab-3 and Ab-4 the total amount respectively 15.0 mg / m ² in each layer, 60.0mg / m ^2,
It was added to a 5.0 mg / m ² and 10.0 mg / m ^2.

[0170]

Embedded image

The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer. Blue-sensitive emulsion layer

[0172]

Embedded image

(Sensitizing dyes A, B and C were added in an amount of 1.4 ×
^10-4 moles, ^1.7x each for small size emulsions
10 ^-4 mol was added. Green sensitive emulsion layer

[0174]

Embedded image

(Sensitizing dye D was added per mole of silver halide,
3.0 × 10 for large emulsions ^-FourMol, small size
3.6 × 10 for emulsion^-FourMol and sensitizing dye E
Per mole of silver halide and for large emulsions
4.0 × 10^-Five7.0 × for mole, small size emulsions
10^-FiveMole of sensitizing dye F per mole of silver halide.
2.0 × 10 for large emulsions^-FourMole, small
2.8 × 10 for size emulsion^-FourMole was added. ) Red-sensitive emulsion layer

[0176]

Embedded image

(Sensitizing dyes G and H were converted to silver halide 1
6.0 × 1 per mole for large size emulsions
0 ^-5 mol, respectively 9.0 × 1 to the small size emulsion
0 ^-5 mol was added. Further, the following compound I was added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide. )

[0178]

Embedded image

Further, a blue-sensitive emulsion layer, a green-sensitive emulsion layer and
1- (3-methylureidophenyl) was added to the red-sensitive emulsion layer.
) -5-mercaptotetrazole
3.3 × 10 per mole of silver halide^-FourMol, 1.0 × 10^-3
Mol and 5.9 × 10^-FourMole was added. Furthermore, the second
Layer, the fourth layer, the sixth layer and the seventh layer, respectively.
mg / m ^Two0.2 mg / m^Two, 0.6 mg / m^Two, 0.
1mg / m^TwoWas added so that Blue-sensitive emulsion
Layer and the green-sensitive emulsion layer.
Chill-1,3,3a, 7-tetrazaindene,
Per mole of silver halide^-FourMole, 2 × 1
0^-FourMole was added. Also, methacrylic acid is added to the red-sensitive emulsion layer.
And butyl acrylate copolymer (weight ratio 1: 1, average
(200,000 to 400,000)) at 0.05 g / m^Two
Was added. In addition, the second, fourth, and sixth layers
Disodium col-3,5-disulfonate was added to each
6mg / m^Two, 6mg / m^Two, 18mg / m^TwoSo that
Was added. Also, to prevent irradiation,
Add the following dye to the agent layer
Was.

[0180]

Embedded image

(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion is
It represents the silver equivalent coating amount. First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, 3: 7 mixture of large size emulsion A having an average grain size of 0.72 μm and small size emulsion A having a size of 0.60 μm (silver molar ratio). The coefficient of variation of the size distribution was 0.08 and 0.10, respectively. In each size emulsion, 0.3 mol% of silver bromide was locally contained on a part of the surface of the silver chloride-based grain.) 25 Gelatin 1.35 Yellow coupler (ExY-1) 0.41 Yellow coupler (ExY-2) 0.21 Color image stabilizer (Cpd-1) 0.08 Color image stabilizer (Cpd-2) 0.04 colors Image stabilizer (Cpd-3) 0.08 Color image stabilizer (Cpd-8) 0.04 Solvent (Solv-1) 0.23

Second layer (color mixture prevention layer) Gelatin 1.00 Color mixture inhibitor (Cpd-4) 0.05 Color mixture inhibitor (Cpd-5) 0.07 Color image stabilizer (Cpd-6) 0.007 colors Image stabilizer (Cpd-7) 0.14 Color image stabilizer (Cpd-13) 0.006 Solvent (Solv-1) 0.06 Solvent (Solv-2) 0.22

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion B (cubic, 1: 3 mixture of large-size emulsion B with an average grain size of 0.45 μm and small-size emulsion B of 0.35 μm (silver mole The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively. In each size emulsion, 0.4 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride.) 0.12 Gelatin 1.20 Magenta coupler (ExM-1) 0.10 Magenta coupler (ExM-2) 0.05 Ultraviolet absorber (UV-1) 0.05 Ultraviolet absorber (UV-2) 0.02 Ultraviolet Absorbent (UV-3) 0.02 Ultraviolet absorber (UV-4) 0.03 Color image stabilizer (Cpd-2) 0.01 Color image stabilizer (Cpd-4) 0.002 Color image stabilizer ( Cpd-7) 0.08 Color image stabilizer (Cpd-8) 0.01 Color image stabilizer (Cpd-9) 0.03 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-11) 0.0001 Color image stabilizer (Cpd-13) 0.0. 004 Solvent (Solv-3) 0.10 Solvent (Solv-4) 0.19 Solvent (Solv-5) 0.17

Fourth layer (color mixture prevention layer) Gelatin 0.71 Color mixture prevention agent (Cpd-4) 0.04 Color mixture prevention agent (Cpd-5) 0.05 Color image stabilizer (Cpd-6) 0.005 colors Image stabilizer (Cpd-7) 0.10 Color image stabilizer (Cpd-13) 0.004 Solvent (Solv-1) 0.04 Solvent (Solv-2) 0.16

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion C (cubic, 1: 4 mixture of large emulsion C having an average grain size of 0.50 μm and small emulsion E of 0.41 μm (silver mole The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively. In each size emulsion, 0.5 mol% of silver bromide was contained locally on a part of the grain surface based on silver chloride.) 0.17 Gelatin 0.98 Cyan coupler (ExC-1) 0.05 Cyan coupler (ExC-2) 0.22 UV absorber (UV-1) 0.14 UV absorber (UV-3) 0.03 UV Absorbent (UV-4) 0.06 Color image stabilizer (Cpd-1) 0.22 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-12) 0.02 Solvent (Solv-6) 0

Sixth layer (ultraviolet absorbing layer) Gelatin 0.46 Ultraviolet absorbing agent (UV-1) 0.14 Ultraviolet absorbing agent (UV-2) 0.05 Ultraviolet absorbing agent (UV-3) 0.05 Ultraviolet absorbing Agent (UV-4) 0.04 Ultraviolet absorber (UV-5) 0.03 Ultraviolet absorber (UV-6) 0.04 Solvent (Solv-7) 0.18 Seventh layer (protective layer) Gelatin 1. 00 Acrylic-modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-14) 0.01 Surfactant (Cpd-15) 0.01

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[0195]

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Further, a sample 101A was prepared in which the composition of the fifth layer was changed as follows from the silver halide color photographic light-sensitive material 001A prepared as described above.

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion C (cubic, 1: 4 mixture of large emulsion C having an average grain size of 0.50 μm and small emulsion C of 0.41 μm (silver mole The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively. In each size emulsion, 0.8 mol% of silver bromide was contained locally on a part of the grain surface based on silver chloride.) 0.11 Gelatin 1.13 Cyan coupler (ExC-2) 0.05 Cyan coupler (ExC-3) 0.10 Cyan coupler (ExC-4) 0.01 Color image stabilizer (Cpd-7) 0.06 colors Image stabilizer (Cpd-9) 0.04 Color image stabilizer (Cpd-13) 0.01 Color image stabilizer (Cpd-16) 0.01 Color image stabilizer (Cpd-17) 0.12 Color image stabilizer Agent (Cpd-18) 0.04 Color image stabilizer (Cpd -19) 0.07 Color image stabilizer (Cpd-20) 0.07 Solvent (Solv-5) 0.14

Further, a sample 201A was prepared in which the composition of the fifth layer was changed as follows from the silver halide color photographic light-sensitive material 001A prepared as described above.

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion C (cubic, 1: 4 mixture of large emulsion C having an average grain size of 0.50 μm and small emulsion C of 0.41 μm (silver mole) The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively. In each size emulsion, 0.8 mol% of silver bromide was contained locally on a part of the grain surface based on silver chloride.) 0.16 Gelatin 1.00 Cyan coupler (ExC-1) 0.05 Cyan coupler (ExC-2) 0.18 Cyan coupler (ExC-3) 0.024 Ultraviolet absorber (UV-1) 0.04 Ultraviolet absorption Agent (UV-3) 0.01 Ultraviolet absorber (UV-4) 0.01 Color image stabilizer (Cpd-1) 0.23 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd) -12) 0.01 color image stabilizer (Cpd-1) 3) 0.01 Solvent (Solv-6) 0.23

Samples 001A and 101 produced as described above
A and 201A, Samples 1001 to 1021 were prepared in which the type of cyan coupler of the fifth layer and the support were changed.
(The fifth layer of Samples 1001 to 1004 is the same as Sample 201A, and the fifth layer of Samples 1005 to 1010 is Sample 20A.
The comparative coupler was substituted so as to be equimolar to the total amount of the cyan coupler of 1A. The fifth layer of Samples 1011 to 1014 is the same as Sample 001A. Samples 1015 to 1018
Is the same as that of the sample 101A,
The fifth layer 1021 is obtained by changing the cyan coupler in (1) of Sample 101A to (2) in an equimolar amount. )
The numbers of the basic compositions of the emulsion layers in Table 3 were the same as those of Samples 001A, 101A and 201A except for the cyan coupler of the fifth layer, which were designated as 001, 101 and 201, respectively. These samples were evaluated for the following a and b.

Evaluation test a (D _min increase after high temperature storage):
Each sample was prepared at 25 ° C.-55% RH for 10 days and at 40 ° C.
After storage under two conditions of 55% RH for 10 days, a treatment was performed in a treatment step A described later. The D _min of the unexposed area after treatment were measured, fog increases from D _min after storage 40 ℃ -55% RH 10 days by subtracting the D _min value after storage 25 ℃ -55% RH 10 days ([Delta] D _min ) Was calculated.

Evaluation test b (sensitivity change after high-temperature storage): Each sample was stored under the same conditions as in test a, and then passed through a three-color separation wedge for 0.1 second using a sensitometer at 200 CMS.
, And processing was performed in processing step A described below. The logarithmic value (log) of the exposure required to give a color density of 0.5
E) was measured and calculated. The change in sensitivity (Δlog E) was calculated by subtracting the log E value after storage at 25 ° C. and 55% RH for 10 days from the log E value after storage at 40 ° C. and 55% RH for 10 days.

The processing steps will be described below. Processing A The above photosensitive material 201A was processed into a 127 mm wide roll, and was imagewise exposed using a minilab printer processor PP1258AR manufactured by Fuji Photo Film Co., Ltd.
Continuous processing (running test) was performed. This treatment using the running liquid was designated as treatment A. Processing process Temperature Time Replenishment amount ^* Color development 38.5 ° C 45 seconds 45 ml Bleaching and fixing 38.0 ° C 45 seconds 35 ml Rinse (1) 38.0 ° C 20 seconds-Rinse (2) 38.0 ° C 20 seconds -Rinse (3) ** 38.0 ° C for 20 seconds-Rinse (4) ** 38.0 ° C for 30 seconds 121 ml * Replenishment amount per 1 m ^{2 of} photographic material ** Rinse phosphorus screening system RC50D manufactured by Fuji Photo Film Co., Ltd. Install in (3), take out the rinse liquid from rinse (3) and send it to reverse osmosis membrane module (RC50D) by pump. The permeated water obtained in the tank is supplied to the rinse (4), and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and the temperature was circulated for 10 hours a day. (Rinsing was carried out in a tank countercurrent system from (1) to (4).)

The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 ml 800 ml Dimethylpolysiloxane-based surfactant 0.1 g 0.1 g (Silicone KF351A / Shin-Etsu Chemical Co., Ltd.) Tri (isopropanol) amine 8.8 g 8 8.8 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Polyethylene glycol (molecular weight 300) 10.0 g 10.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.5 g 0.5 g Potassium chloride 10.0 g-odor Potassium iodide 0.040 g 0.010 g Triazinylaminostilbene-based fluorescence 2.5 g 5.0 g Brightener (Hakor FWA-SF / Showa Chemical Co., Ltd.) Sodium sulfite 0.1 g 0.1 g Disodium-N, N- Bis (sulfonatoethyl) hydroxylamine 8.5 g 11.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-amino-4-aminoaniline / 3/2 sulfuric acid monohydrate 5.0 g 15.7 g potassium carbonate 3g 26.3g Add water 1000ml 1000ml pH (25 ° C / adjusted with potassium hydroxide and sulfuric acid) 10.15 12.50

[Bleach-fixing solution] [Tank solution] [Replenisher] Water 700 ml 600 ml iron (III) ammonium ethylenediaminetetraacetate 47.0 g 94.0 g 1.4 g 2.8 g m-carboxybenzeneflufine ethylenediaminetetraacetic acid Acid 8.3 g 16.5 g Nitric acid (67%) 16.5 g 33.0 g Imidazole 14.6 g 29.2 g Ammonium thiosulfate (750 g / l) 107.0 ml 214.0 ml ammonium sulfite 16.0 g 32.0 g Ammonium sulfate 23.1 g 46.2 g Add water 1000 ml 1000 ml pH (adjusted at 25 ° C / acetic acid and ammonia) 6.0 6.0

[Rinse liquid] [Tank liquid] [Refill liquid] 0.02 g 0.02 g of chlorinated sodium isocyanurate Deionized water (conductivity of 5 μs / cm or less) 1000 ml 1000 ml pH 6.5 6.5

Process B The photosensitive material 201A was processed into a roll having a width of 127 mm, and after the imagewise exposure, a continuous process (running test) was carried out until the color developing tank capacity was replenished twice in the following process. The processing using the running liquid was referred to as processing B. For processing, a minilab printer processor PP1258AR manufactured by Fuji Photo Film Co., Ltd., which was modified to increase the transport speed in order to shorten the processing time, was used. Processing process Temperature Time Replenishment amount ^* Color development 45.0 ° C 15 seconds 45 ml Bleaching and fixing 40.0 ° C 15 seconds 35 ml Rinse (1) 40.0 ° C 7 seconds-Rinse (2) 40.0 ° C 7 seconds-Rinse (3) ** 40.0 ° C. 7 sec - rinse (4) ** 40.0 ° C. 7 sec 121 ml * photosensitive material 1 m ² per replenishment amount ** Fuji Photo Film Co., Ltd. rinse cleaning system RC50D rinsing (3 ), Take out the rinse liquid from the rinse (3), and send it to the reverse osmosis membrane module (RC50D) by a pump. The permeated water obtained in the tank is supplied to the rinse (4), and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and the temperature was circulated for 10 hours a day. (Rinsing was carried out in a tank countercurrent system from (1) to (4).)

The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 ml 800 ml Dimethylpolysiloxane-based surfactant 0.1 g 0.1 g (Silicone KF351A / Shin-Etsu Chemical Co., Ltd.) Tri (isopropanol) amine 8.8 g 8 8.8 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Polyethylene glycol (molecular weight 300) 10.0 g 10.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.5 g 0.5 g Potassium chloride 10.0 g-odor Potassium iodide 0.040 g 0.010 g Triazinylaminostilbene-based fluorescence 2.5 g 5.0 g Brightener (Hakor FWA-SF / Showa Chemical Co., Ltd.) Sodium sulfite 0.1 g 0.1 g Disodium-N, N- Bis (sulfonatoethyl) hydroxylamine 8.5 g 11.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-amino-4-aminoaniline / 3/2 sulfuric acid monohydrate 10.0 g 22.0 g potassium carbonate 26. 3g 26.3g Water was added to add 1000ml 1000ml pH (25 ° C / adjusted with potassium hydroxide and sulfuric acid) 10.15 12.50

[Bleach-fixing solution] [Tank solution] [Replenishing solution] Water 700 ml 600 ml iron (III) ammonium ethylenediaminetetraacetate 75.0 g 150.0 g 1.4 g 2.8 g m-carboxybenzeneflufine ethylenediaminetetraacetic acid Acid 8.3 g 16.5 g Nitric acid (67%) 16.5 g 33.0 g Imidazole 14.6 g 29.2 g Ammonium thiosulfate (750 g / l) 107.0 ml 214.0 ml ammonium sulfite 16.0 g 32.0 g Ammonium sulfate 23.1 g 46.2 g Add water 1000 ml 1000 ml pH (adjusted at 25 ° C / acetic acid and ammonia) 5.5 5.5

[Rinse solution] [Tank solution] [Refill solution] 0.02 g 0.02 g of chlorinated sodium isocyanurate Deionized water (conductivity of 5 μs / cm or less) 1000 ml 1000 ml pH 5.5 5.5

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[Table 3]

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According to Table 3, the light-sensitive material of the present invention in which a silver halide emulsion having a silver chloride content of 95 mol% or more was coated on the support of the present invention had a small rise in fog during high-temperature storage. I understand. Further, when the cyan coupler of the present invention was used, the rise in fog could be further suppressed.

Example 2 The sample of Example 1 was processed in processing step B with a color development time of 20 seconds or less, and the fog increase was evaluated in the same manner as in Example 1. As a result, the same result as in Example 1 was obtained.

Example 3 Samples 2001 to 2016 were prepared by changing the magenta coupler of the third layer and the support in the sample 201A.
When changing the type of magenta coupler, it was changed to be equimolar. Evaluation b was performed using these samples. Table 4 shows the results.

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[Table 4]

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According to Table 4, the light-sensitive material of the present invention in which a silver halide emulsion having a silver chloride content of 95 mol% or more was coated on the support of the present invention showed that the sensitivity fluctuation during high-temperature storage was small. I understand. Further, when the magenta coupler of the present invention was used, the sensitivity fluctuation could be further suppressed.

Example 4 Each sample of Example 3 was subjected to processing according to the evaluation "b" by changing the exposure time to 10 ^-4 seconds. As a result, substantially the same effects as in Example 3 were obtained.

Example 5 In Examples 1 and 3, a sample was prepared in which the support B was changed to B2, the support C was changed to C2, and the support D was changed to D2. According to this, it was found that fog and change in sensitivity when the storage state of the photosensitive material was changed could be reduced.

Example 6 In Example 1, the following compound was added to the fifth layer in an amount of 1.0 × 10 ⁻⁵ mol per mol of silver halide, and the same evaluation as in Example 1 was carried out. The effect was obtained.

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Example 7 A running process was carried out using the photosensitive material 201A in the same manner as in the process A, except that the composition of the bleach-fixing solution was changed to the following composition in the process A.

[Bleach-fixing solution] [Tank solution] [Replenisher] Water 800 ml 800 ml ammonium thiosulfate (750 g / l) 107.0 ml 214.0 ml m-carboxymethylbenzene sulfinic acid 8.3 g 16.5 g ethylenediamine Succinic acid (SS form) 42 g 84 g Ferric nitrate 9-hydrate 48.5 g 97 g 90% acetic acid 6.7 g 13.4 g Nitric acid 0.18 mol 0.36 mol Imidazole 14.6 g 29.2 g Ammonium sulfite 16.0 g 32.0 g Potassium metabisulfite 23.1 g 46.2 g Add water 1000 ml 1000 ml pH (adjusted at 25 ° C / acetic acid and ammonium) 6.5 6.5 (Note) *: Chelating agent-1 and chelating agent Agent-2 is Aminocarboxylic acid component of the bleach -1 and bleaching agent-2, the addition amount thereof is 10 mol% amount of bleach -1 and bleach agent-2, respectively. **: The total amount of bleach-1 and bleach-2 is 120 mmol in the tank solution and 240 mmol in the replenisher.

In Examples 1 and 3, the bleach-fixing solution of Process A was changed to the above solution, and fog and sensitivity fluctuation were evaluated. The same results were obtained.

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According to the present invention, a silver halide color photographic light-sensitive material having rapid processing suitability and an image forming method using the same can be provided. Further, it is possible to provide a silver halide color photographic light-sensitive material having a small change in photographic performance when the storage state of an unexposed state of the silver halide color photographic light-sensitive material changes, and an image forming method using the same. .

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 7/407 G03C 7/407

Claims (8)

[Claims] 1. A silver halide color photographic material having at least three silver halide emulsion layers having different color sensitivity on a reflective support, wherein the reflective support is a water-resistant resin-coated support, and At least one of the water-resistant resin layers between the support and the silver halide emulsion layer has micropores.
A silver halide color photographic light-sensitive material, which is an axially stretched polyolefin layer, wherein the silver halide emulsion of the silver halide emulsion layer comprises silver halide emulsion grains having a silver chloride content of 95 mol% or more. 2. A silver halide color photographic material having at least three silver halide emulsion layers having different color sensitivity on a reflective support, wherein the reflective support is a water-resistant resin-coated support, and At least one of the water-resistant resin layers between the support and the silver halide emulsion layer has micropores.
An axially stretched polyolefin layer, wherein a polyolefin layer having no micropores is provided between the polyolefin layer and the silver halide emulsion layer, and the silver halide emulsion of the silver halide emulsion layer has a silver chloride content A silver halide color photographic material comprising 95 mol% or more of silver halide emulsion grains. 3. A silver halide color photographic material having at least three silver halide emulsion layers having different color sensitivity on a reflective support, wherein the reflective support is synthesized from a dicarboxylic acid and a diol by polycondensation. At least on the emulsion-coated surface side of the composition containing a mixture of a white pigment and a resin containing at least 50% by weight of the obtained polyester. The silver halide emulsion of the silver halide emulsion layer has a silver chloride content of A silver halide color photographic material comprising 95 mol% or more of silver halide emulsion grains. 4. The silver halide color photographic light-sensitive material according to claim 3, wherein the polyester of the reflection support is a polyester containing polyethylene terephthalate as a main component. 5. The silver halide emulsion layer according to claim 1, wherein at least one of the silver halide emulsion layers contains a cyan dye-forming coupler represented by formula (PTA-I) or (PTA-II). The silver halide color photographic light-sensitive material according to any one of the above items. Embedded image In the formula, Za and Zb are each -C (R ₃ ) = or -N
= Represents However, one of Za and Zb is -C
(R ₃₎ is = and the other is -N =. R ₁ and R ₂
Represents an electron withdrawing group having a Hammett's substituent constant σp value of 0.2 or more, and the sum of σp values of R ₁ and R ₂ is 0.6
5 or more. R ₃ represents a hydrogen atom or a substituent. X represents a hydrogen atom or a group capable of leaving in a coupling reaction with an oxidized form of an aromatic primary amine color developing agent.
The group of R ₁ , R ₂ , R _3, or X may be a divalent group and form a homopolymer or a copolymer by bonding to a dimer or higher polymer or a polymer chain. 6. The method according to claim 1, wherein at least one of the silver halide emulsion layers contains a magenta dye-forming coupler represented by formula (MI).
6. The silver halide color photographic light-sensitive material according to item 1. Embedded image In the formula, Za and Zb are each ＝ C (R ₄ )-or ＮN-
Wherein R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a substituent, and X can be eliminated in a coupling reaction with a hydrogen atom or an oxidized form of an aromatic primary amine color developing agent. Represents a group. 7. An image forming method in which a silver halide color photographic light-sensitive material is scanned and exposed with a light beam modulated based on image information and then developed, wherein the silver halide color photographic light-sensitive material is characterized by the following: A color image forming method, which is a silver halide color photographic light-sensitive material characterized in any one of the above. 8. The color development processing time of the silver halide color photographic light-sensitive material according to claim 1 is 20.
A color image forming method, wherein the processing is performed in seconds or less.