JP2000352790A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a processed sample less liable to take scratches and excellent in curl resistance and to suppress a change of photographic performance due to a change of storage conditions in the unexposed state by using a biaxially drawn polyolefin layer having micropores as at least one of the water resistant resin layers of a reflective substrate and incorporating a matting agent into the outermost one of nonphotosensitive layers. SOLUTION: The silver halide color photographic sensitive material has a biaxially drawn polyolefin layer having micropores as at least one of the water resistant resin layers of the reflective substrate and contains a matting agent in the outermost one of the nonphotosensitive layers. The micropores are formed around a nucleus forming material by adding the material whose affinity for the pplyolefin is not great to the polyolefin and carrying out drawing. The matting agent is discontinuous solid particles of an inorganic material such as silicon dioxide or titanium or an organic material such as cellulose esters or polymethyl methacrylate dispersible in a hydrophilic organic colloidal binder.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material, which has a small fluctuation in photographic performance when the storage state changes in an unexposed state, has excellent curl resistance, and is suitable for processed print samples. The present invention relates to a silver halide color photographic light-sensitive material which is hardly damaged.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material is prepared by including three types of photographic couplers of yellow, magenta and cyan on a support in three types of light-sensitive emulsion layers having different color sensitivities. A method for subjecting the photosensitive material described above to color development processing with a color developing agent is widely known. As a support, a white opaque support is used. In particular, as a support for a color paper, a so-called RC base paper obtained by laminating a polyolefin on paper is used.

In the case of color papers, glossy printed photographs have recently been favored by general users. In particular, if the gloss due to the light reflection is strong, the printed screen may be difficult to observe. Conversely, when a user who does not like gloss prints, or when a print with a solid feeling is required, printing is performed on color paper using a so-called typed RC base paper such as a matte surface or a silk surface that has been processed in advance. However, prints of color paper using these molded RC base papers have strong light reflection depending on the position of the observation light source, and a solid pattern has not yet been sufficiently obtained.

A method for improving the surface gloss by containing fine particles on the surface or inside of a photosensitive material to obtain a matting effect is disclosed in JP-A-61-147248 and JP-A-1-14626.
No. 30, JP-A-6-75331, JP-A-7-2613
No. 42, etc., the prints obtained by these methods can provide a somewhat profound picture, but are disadvantageous in that the processed prints are easily damaged when transported or transported. And when the print is left under low humidity, the curl is apt to be formed.

[0005] Japanese Patent Application Laid-Open No. 10-104794 discloses a method in which a fixed amount or more of porous fine particles and latex are used together in a light-sensitive material so that prints are hardly damaged and curl under low humidity is suppressed. , But
Curling when a print is left under high humidity is not sufficient.

On the other hand, silver halide color photographic light-sensitive materials are required to always 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. Techniques for improving the white background include reducing fog on silver halide emulsions,
Improved washing out of sensitizing dyes and anti-irradiation dyes,
There are techniques such as improvement by fluorescent whitening and improvement of white pigment filling density of a support. For example, attempts to improve the absolute value of whiteness using a support are disclosed in JP-A-10-333277 and JP-A-11-133277.
No. 52513, JP-A-11-65024, and
-250331, JP-A-6-167772, and JP-A-6-167775. However, the above technique alone has not led to a drastic improvement, and further improvement has been desired.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a processed sample which is hard to be scratched, has excellent curl resistance, and has a small change in photographic performance when the storage state in an unexposed state changes. An object of the present invention is to provide a silver color photographic light-sensitive material.

[0008]

Means for Solving the Problems 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 materials. (1) A photographic structure comprising a yellow coupler-containing silver halide emulsion layer, a magenta coupler-containing silver halide emulsion layer, a cyan coupler-containing silver halide emulsion layer, and a non-light-sensitive layer having different color sensitivity on a reflective support. In a silver halide color photographic light-sensitive material having at least one layer, at least one of the water-resistant resin layers of the reflective support is a biaxially oriented polyolefin layer having micropores, and the outermost layer of the non-photosensitive layers A silver halide color photographic material comprising a matting agent. (2) A photographic structure comprising a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler, a silver halide emulsion layer containing a cyan coupler, and a non-light-sensitive layer having different color sensitivities on a reflective support. In a silver halide color photographic light-sensitive material having at least one layer, at least one of the water-resistant resin layers of the reflective support is a biaxially stretched polyolefin layer having micropores, and a layer between the polyolefin layer and the silver halide emulsion layer is provided. A silver halide color photographic light-sensitive material, characterized in that a polyolefin layer having no micropores is provided thereon, and a matting agent is contained in the outermost layer of the non-photosensitive layers. (3) A photographic structure comprising a yellow coupler-containing silver halide emulsion layer, a magenta coupler-containing silver halide emulsion layer, a cyan coupler-containing silver halide emulsion layer and a non-light-sensitive layer having different color sensitivity on a reflective support. In a silver halide color photographic light-sensitive material having a layer, a composition obtained by mixing and dispersing a white pigment in a resin containing at least 50% by weight of a polyester synthesized by polycondensation from a dicarboxylic acid and a diol, and A silver halide color photographic light-sensitive material which is coated on the emulsion-coated side surface and which comprises a matting agent in the outermost layer among the non-light-sensitive layers. (4) The silver halide color photographic material as described in (3) above, wherein the polyester of the reflective support is a polyester containing polyethylene terephthalate as a main component. (5) The silver halide color photographic light-sensitive material as described in any one of (1) to (4) above, which contains a matting agent in an amount of 10 mg / m ² or more. (6) Latex is 1 m ^{2 in the} outermost layer of the non-photosensitive layer.
The silver halide color photographic light-sensitive material as described in any one of (1) to (5) above, wherein the content is 40 mg or more. (7) hydrophobic polymer particles having an average particle size of 0.01 to 1 μm and a melting point of 55 ° C. to 200 ° C.
At least one coated material comprising 95% by weight and 5 to 70% by weight of gelatin is coated on the silver halide photosensitive emulsion layer, and has a protective layer formed by fusing polymer particles (1). (6) The silver halide color photographic light-sensitive material as described in any one of items (6) to (6). (8) At least one aqueous coating composition comprising 5 to 50% by weight of polymer particles having an average particle size of 0.01 to 50 μm and 1 to 3% by weight of a polymer latex binder is coated on the silver halide photosensitive emulsion layer, The silver halide color photographic material according to any one of (1) to (6), further comprising a protective layer formed by fusing polymer particles. (9) The silver halide color photographic light-sensitive material according to any one of (1) to (8), wherein the gelatin hardener is a compound represented by the following general formula (HI). material.

[0009]

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In the general formula (HI), R ¹ is a hydroxyl group, —O
An M group (M represents a monovalent metal atom), an alkyl group, -N
(R ² ) (R ³ ) group (R ² and R ³ each independently represent an alkyl group or an aryl group), —NHCOR ⁴ group (R ⁴ is a hydrogen atom, an alkyl group, an aryl group, an alkylthio group or an arylthio group Or an alkoxy group.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The silver halide color photographic light-sensitive material of the present invention will be described below in more detail.

The matting agent of the present invention will be described. Matting agents are defined as discontinuous solid particles of an inorganic or organic material that can be dispersed in a hydrophilic organic colloid binder.

The matting agent used in the present invention may be any solid particles which do not adversely affect the photographic properties. Examples of inorganic matting agents include silicon dioxide, oxides of titanium and aluminum, carbonates of zinc and calcium, sulfates of barium and calcium, and silicates of calcium and aluminum. Examples include matting agents for organic polymers such as esters, polymethyl methacrylate, polystyrene or polydivinylbenzene and copolymers thereof.

In the present invention, the porous matting agent described in JP-A-3-109542, page 2, lower left column, line 8 to page 3, upper right column, line 4, JP-A-4-127142, page 3 upper right column A matting agent surface-modified with an alkali described in line 7 to page 5, lower right column, line 4, an organic polymer described in JP-A-6-118542, page 2, line 25 to page 8, page 39, right It is more preferable to use the matting agent.

Further, two or more of these matting agents may be used in combination. For example, a combination of an inorganic matting agent and an organic matting agent, a combination of a porous matting agent and a non-porous matting agent, a combination of an amorphous matting agent and a spherical matting agent, mats having different average particle sizes. (For example, JP-A-6-1185)
No. 42, a matting agent having an average particle size of 1.5 μm or more and a matting agent having an average particle size of 1 μm or less).

In the present invention, the amount of the matting agent applied is preferably 5 to 1000 mg / m ² , particularly 10 to 200 mg. The average particle diameter of the preferred matting agent is 20 μm or less, and particularly in the range of 0.4 to 10 μm.

The latex may be any generally known polymer latex. Examples of the polymer include a homopolymer of an alkyl ester of acrylic acid or a copolymer with acrylic acid or styrene, a styrene-butadiene copolymer, an active methylene group, a water-soluble polymer. A polymer or copolymer comprising a monomer having a functional group or a crosslinkable group with gelatin can be preferably used. In particular,
In order to increase affinity with gelatin which is a binder,
Most preferably, a copolymer with a monomer having a water-soluble group or a crosslinkable group with gelatin mainly containing a hydrophobic monomer such as an alkyl ester of acrylic acid or styrene is used.

Preferred examples of the monomer having a water-soluble group include acrylic acid, methacrylic acid, maleic acid, 2-
Desirable examples of monomers having a crosslinkable group with gelatin, such as acrylamide-2-methylpropanesulfonic acid and styrenesulfonic acid, include glycidyl acrylate, glycidyl methacrylate, and N-methylolacrylamide.

The polymer latex and the method for synthesizing it are described in detail in JP-A-2-41 and US Pat.
No. 2,386, No. 2,853,457, No. 3,4
No. 11,911, No. 3,411,912, No. 4
197, 127, JP-B-45-5331, JP-A-Showa 6
No. 0-18540, for example, an emulsion polymerization method, a method of redispersing a polymer obtained by solution polymerization, and the like. As an example, in the emulsion polymerization method, water is used as a dispersion medium, and 10 to 50% by weight of the monomer and 0.1% of the monomer are used.
About 30 to 100 ° C., preferably 60 to 90%, using 0.5 to 5% by weight of a polymerization initiator and 0.1 to 20% by weight of a dispersant.
It is obtained by polymerizing under stirring at a temperature of 3 to 8 hours.

Examples of the polymerization initiator include water-soluble peroxides and water-soluble azo compounds. Examples of the dispersant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant in addition to the water-soluble polymer. These may be used alone or in combination.

Hereinafter, specific examples of the polymer latex according to the present invention will be shown, but the present invention is not limited thereto.

[0022]

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The Tg (glass transition temperature) of the polymer forming the polymer latex used in the present invention is preferably 40 ° C. or less. Tg of polymer is "Polymer Handbook (1966, Wiley &Sons)"
The Tg (、 K) of the copolymer is represented by the following equation.

Tg (copolymer) = v ₁ Tg ₁ + v ₂ Tg ₂
+ · · · + V in _W Tg _{W type, v 1, v 2 ··· v} W represents the weight fraction of the monomer in the _{copolymer, Tg 1, Tg 2 ··· Tg} W each in the copolymer It represents the Tg (゜ K) of a monomer homopolymer. Tg calculated according to the above equation has an accuracy of ± 5 ° C.

Any average particle diameter of the polymer latex used in the present invention may be preferably used if it has a mean particle size of 0.5 to 300 nm. The average particle size of the polymer latex is described in "Chemistry of Polymer Latex (1973,
Electron microscopy described in “Polymer Press Association”),
It can be measured by a soap titration method, a light scattering method, or a centrifugal sedimentation method, but the light scattering method is preferably used.

The molecular weight of the polymer is not specifically defined, but is preferably 1,000 to 1,000,000 in terms of the total molecular weight.
00.

In the present invention, the amount of the applied latex is preferably from 40 mg / m ^{2 to} 10 mg / m ² , more preferably from 50 mg / m ^{2 to} 5 mg / m ² .

One of the embodiments of the reflective support which can be used in the silver halide color photographic light-sensitive material according to the present invention is as follows. 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.

In the present invention, as a method of forming micropores in the polyolefin, a substance which becomes a nucleus having a low affinity for the polymer is added to the polyolefin, and then stretched to form pores around the nucleation substance. Is preferred. The substance that becomes the core of the vacancy is called a vacancy inducer,
Although an inorganic pigment or a polymer material can be used, it is preferable to use a polymer material. The polymer material can be melt-mixed with a polymer forming a core matrix,
A polymer that can form dispersed spherical particles when the suspension is cooled is preferred, such as polybutylene terephthalate dispersed in polypropylene. The pore-inducing substance is 5 to 50% by weight based on the matrix polymer of the core.
It is preferred to use. The pore-inducing material particles remaining in the completed sheet core have a diameter of 0.1 to 10 μm and are preferably 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.

In a preferred embodiment of the present invention, a unit having a sandwich structure having a polypropylene skin layer containing titanium oxide and containing no fine pores is provided on both sides of a core layer of polypropylene containing no titanium oxide and containing fine pores. No. In this sandwich structure, the thickness of the core layer is preferably 5 to 150 μm, more preferably 10 to 70 μm, and the thickness of the skin layer is 1 to 50 μm, more preferably 3 to 20 μm. 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 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 opposite side of the emulsion surface of the support 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 Pat. No. 5,888,681, US Pat. No. 5,888,714 and British Patent No. 23257.
No. 49, for example.

Another preferred 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 reflection support in the present invention is a reflection support obtained by coating a composition containing a polyester containing 50% by weight or more 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 case of the present invention, various polyesters obtained by polycondensation of these dicarboxylic acids alone or in combination with diols alone or in mixtures 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 0.5.
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 above-mentioned polyester and white pigment are mixed together with a dispersing agent such as a metal salt of higher fatty acid, higher fatty acid ethyl, higher fatty acid amide, higher fatty acid and the like by using 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 polyester / white pigment composition coated on the emulsion-coated side of the substrate of the reflective support of the present invention has a thickness of 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, the base paper used for the reflective support is preferably a base paper mainly made of the natural pulp or the synthetic pulp described above. 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, a portion of the area SM is extracted on the center plane, the orthogonal coordinate axes, the X axis, and the Y axis are set on the center line of the extracted portion, and the axis orthogonal to the center line is set as the Z axis. Is defined as the center line average surface roughness (SRa) and is expressed in μm.

[0043]

(Equation 1)

The values of the center line average surface roughness and the height of the protrusion from the center line were measured using, for example, a three-dimensional surface roughness measuring instrument (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 polyethylene. Therefore, after the polyester is melt-extruded and laminated on a substrate, the surface of the polyester 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.

[0047]

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The 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, a protective layer can be formed by incorporating a hydrophobic polymer having a melting point of 55 ° C. to 200 ° C. into the layer containing the matting agent or further over the layer, and fusing the polymer particles after image formation. As the hydrophobic polymer, compounds described in EP 0 893 733 A1, page 3, lines 24 to 30 are preferred. The average particle size of the preferred hydrophobic polymer is 0.01 to 1 μm, particularly 0.01 to 0.5 μm.
It is in the range of μm. The content in the hydrophobic polymer coating layer is preferably from 30 to 95% by weight, and more preferably from 5 to 70% by weight. Further, it may contain 5 to 45% by weight of a water-soluble polymer. Preferred examples of the water-soluble polymer are compounds described in EP 0 893 733 A1, page 4, lines 6 to 10. The step of fusing the polymer particles after image formation is not particularly limited,
A press with heating and pressurizing is preferred.

In the present invention, an aqueous coating comprising a polymer of 0.1 to 50 μm and 1 to 3% by weight of a polymer latex binder is applied on the layer containing the matting agent, and the polymer particles are formed after image formation. Can be fused to form a protective layer, and the polymer is EP 0 893 735 A
The compounds described in page 1, line 3, lines 14 to 29 are preferred. As the polymer latex, compounds described in EP 0 893 735 A1, page 3, lines 48 to 50 are preferable. The average particle diameter of a preferable polymer is 0.01 to 50 μm.
m, especially in the range of 0.01 to 15 μm. The content of the polymer is preferably 5 to 50% by weight. The step of fusing the polymer particles after image formation is not particularly limited, but a press involving heating and pressurization is preferable.

The method of forming a protective layer by fusing a polymer to the matting agent-containing layer or a further layer thereof in the present invention is described in EP0915372A1, EP0915373A1,
The method described in EP0915377A1 may be used.

The light-sensitive material of the present invention requires a gelatin hardener. In particular, hardening is important in rapid processing, and preferred examples of the hardening agent include a compound represented by the following formula (HI).

[0054]

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In the formula, R ¹ is a hydroxyl group, an —OM group (M is a monovalent metal atom), an alkyl group,

[0056]

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The group (R^Two, R^ThreeRepresents an alkyl group and an ant, respectively.
Represents a group. ), -NHCOR ^Four(R^FourIs hydrogen field
, Alkyl group, aryl group, alkylthio group, aryl
Represents a luthio group. ) Or an alkoxy group
I forgot. ) R of the general formula (HI)¹An alkyl group represented by
Preferred are a methyl group, an ethyl group, a butyl group, etc.
The methoxy group is preferably a methoxy group, an ethoxy group, a butoxy group, etc.
No. Also

[0058]

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A specific example of a group is -NH_Two, -NHCH_Three, -N
HC_TwoH_FiveAnd -NHCOR ^FourAs a specific example of the group
-NHCOCH_Three, -NHCOC₆H_FiveEtc. Sa
Rani R¹Represents -M in the OM group is, for example, sodium
And a potassium atom and the like are particularly preferred. Also, the general formula
The cyanuric chloride-based hardener represented by (HI)
No. 47-6151, 47-33380,
No. 54-25411, JP-A-56-130740
There is a detailed description. Compounds of the general formula (HI)
JP-B-53-2726 and JP-A-50-50, which have similar structures
-61219, 56-135, 56-60
Nos. 430 and 57-40244
Articles are also useful in the present invention.

Specific examples of the compounds used in the present invention will be described below, but the present invention is not limited thereto. a. Compound according to general formula (HI)

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The couplers usable in the present invention are described, for example, in JP-A-62-215272 and JP-A-2-215272.
No. 33144, EP355660A.
Examples of the cyan coupler include a diphenylimidazole cyan coupler described in JP-A-2-33144, and a 3-hydroxypyridine cyan coupler described in European Patent No. EP 0333185A2 (among them, specific examples thereof). 4-equivalent coupler (42) having a chlorine leaving group to give a 2-equivalent coupler, couplers (6) and (9) are particularly preferred), and JP-A 64-64.
No. 32260, cyclic active methylene cyan couplers (coupler examples 3, 8, and 34 listed as specific examples are particularly preferred), and EP 045.
Pyrolopyrazole-type cyan coupler described in 6226A1, specification of European Patent EP 0484909, pyrroloimidazole-type cyan coupler described in EP 0484909, and EP 04
Preference is given to using the pyrrolotriazole type cyan couplers described in the specifications of 88248 and EP 0 411 197 A1. Among them, use of a pyrrolotriazole type cyan coupler is particularly preferred.

As the yellow coupler, in addition to the compounds described in the above-mentioned known documents, European Patent EP04
No. 47969A1, an acylacetamide type yellow coupler having a 3- to 5-membered cyclic structure in the acyl group, a malondianilide type yellow coupler having a cyclic structure described in EP 0 482 552 A1, described in U.S. Pat. An acylacetamide type yellow coupler having a dioxane structure described in JP-A-118,599 is preferably used. Among them, it is particularly preferable to use an acylacetamide type yellow coupler in which the acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide type yellow coupler in which one of the anilides forms an indoline ring. These couplers can be used alone or in combination.

As the magenta coupler used in the present invention, a 5-pyrazolone-based magenta coupler or a pyrazoloazole-based magenta coupler described in the above-mentioned known documents are used. Pyrazolotriazole couplers in which a secondary or tertiary alkyl group is directly bonded to the 2, 3 or 6 position of the pyrazolotriazole ring as described in JP-A-61-65245; Pyrazoloazole couplers containing a sulfonamide group in the molecule as described in JP-A-61-147254, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254, and European Patent No. No. 6,286,849A and No. 294,785A. Use of pyrazoloazole couplers having a proxy group. Specific examples of the coupler are shown below, but the present invention is not limited by these.

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In the present invention, the compound represented by the following general formula (A), (B) or (C) which is chemically bonded to an aromatic primary amine color developing agent at a pH of 8 or less to produce a substantially colorless product. At least one selected from lipophilic compounds represented by the formula (1) and / or a chemical bond with an oxidized form of an aromatic primary amine color developing agent under the condition of pH 8 or less to produce a substantially colorless product: It is preferable to contain at least one selected from lipophilic compounds represented by D).

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The compound represented by formula (A), (B), (C) or (D) will be described in detail. R _a1 and R _a2 will be described. Aliphatic groups are, for example, methyl, i
-Propyl, t-butyl, benzyl, 2-hydroxybenzyl, cyclohexyl, t-octyl, vinyl, allyl, n-pentadecyl, and preferably has 1 carbon atom.
To 30 optionally substituted alkyl groups. The aromatic group includes, for example, phenyl and naphthyl, and is preferably a phenyl group having 6 to 36 carbon atoms which may be substituted. Heterocyclic groups include, for example, phenyl, furyl, chromanyl, morpholinyl, piperazyl, indolyl. The acyl group for R _a2 includes, for example, acetyl, tetradecanoyl and benzoyl, and preferably has 2 carbon atoms.
To 37 optionally substituted acyl groups. The sulfonyl group includes, for example, methanesulfonyl and benzenesulfonyl, and is preferably a sulfonyl group having 1 to 36 carbon atoms which may be substituted. Examples of the carbamoyl group include methylcarbamoyl, diethylcarbamoyl, octylcarbamoyl, phenylcarbamoyl, and N-methyl-N-phenylcarbamoyl, and preferably have 2 to 37 carbon atoms.
Is a carbamoyl group which may be substituted. The sulfamoyl group includes, for example, methylsulfamoyl, diethylsulfamoyl, octylsulfamoyl, phenylsulfamoyl, N-methyl-N-phenylsulfamoyl, preferably having 2 to 37 carbon atoms. Is a good sulfamoyl group.

[0091] Z is a heterocyclic group bonded to the nitrogen atom mentioned _a2 e.g. 1-pyrrolyl, 1-imidazolyl, 1-pyrazolyl, 2-indolyl, 1-indole, 7-purinyl, and the like, to form an aromatic ring Heterocycles are preferred.
Aromatic group in R _a3, R _a4 and R _a5, aliphatic group in the heterocyclic group, and R _a5 represents the same meaning as the aromatic ring, heterocyclic group and aliphatic group in R _a1 and R _a2.

The aliphatic group for R _b1 includes R _a1 and R _a2
Has the same meaning as the aliphatic group in Examples of the halogen atom for Z _b1 include chloro, bromo and iodine.

Next, Z _c1 will be described. An acyl group, a carbamoyl group, a sulfamoyl group and a sulfonyl group have the same meanings as those in R _a2 . Examples of the aliphatic oxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, i-propoxycarbonyl, benzyloxycarbonyl, cyclohexyloxycarbonyl, n-hexadecyloxycarbonyl, allyloxycarbonyl, and pentadecenyloxycarbonyl. A substituted or unsubstituted alkyloxycarbonyl group represented by Formulas 2 to 31. The aromatic oxycarbonyl group includes, for example, phenyloxycarbonyl and naphthyloxycarbonyl, and is preferably a phenyloxycarbonyl group having 7 to 37 carbon atoms which may be substituted. R _c1 , R
The aliphatic, aromatic and heterocyclic groups of _c2 and _Rc3 are
aromatic ring in _a1 and R _a2, represents the same meaning as the heterocyclic group and aliphatic group.

R_d1~ R_d10And R_d12Aliphatic groups in
An aromatic group, and R_d2~ R_d9And R _d12Heterocyclic group
Is R_a1And R_a2Aromatic, heterocyclic and aliphatic
It has the same meaning as an aliphatic group. Inorganic or organic in Y
Examples of atoms or atomic groups forming a salt of Li, N
a, K, Ca, Mg, triethylamine, methylamino
And ammonia. R_d4, R_d5, R_d7and
R_d8Is an acyl group or a sulfonyl group represented by R_a2In
Represents the same meaning as an aliphatic oxycarbonyl group
Is Z_c1Has the same meaning as in R_d4,
R_d5, R_d7And R_d8The ureido group in
Luureido, methylureide, N, N-dibutylurei
, N-phenyl-N-methyl-N'-methylureide
And preferably a ureido group having 2 to 37 carbon atoms.
There are urethane groups such as methyl urethane and phenyl urethane.
Urethane, preferably urethane having 2 to 37 carbon atoms
Group.

The acyl group for R _d6 has the same meaning as that for R _a2 , and the aliphatic oxycarbonyl group and aromatic oxycarbonyl group have the same meaning as those for Z _c1 . Examples of the aliphatic amino group for R _d6 include methylamino, diethylamino, octylamino, benzylamino, cyclohexylamino, dodecylamino, allylamino, and hexadecylamino, preferably an alkylamino group having 1 to 30 carbon atoms which may be substituted. It is.
Examples of the aromatic amino group include anilino, 2,4-dichloroanilino, 4-t-octylanilino, N-methyl-anilino, 2-methylanilino, and N-hexadecylanilino, and preferably have 6 to 37 carbon atoms. It is an anilino group which may be substituted. Examples of the aliphatic oxy group include methoxy, ethoxy, t-butyloxy, benzyloxy, and cyclohexyloxy, and are preferably an optionally substituted alkoxy group having 1 to 30 carbon atoms. The aromatic oxy group is, for example, phenoxy, 2,4-di-
t-butylphenoxy, 2-chlorophenoxy and 4-methoxyphenoxy, preferably having 6 to 3 carbon atoms.
7 is a phenoxy group which may be substituted. R _d10
Examples of the halogen atom include chloro, bromo and iodine, and the acyloxy group includes, for example, acetyloxy and benzoyloxy, and is preferably an acyloxy group having 2 to 37 carbon atoms which may be substituted. The sulfonyl group for R _{d10 has} the same meaning as that for R _a2 . R _d11
Examples of the hydrolyzable group include an acyl group, a sulfonyl group, an oxalyl group, and a silyl group.

The compounds represented by formulas (A) to (C) are described in JP-A-63-158545 (EP 0,258,66).
2) The secondary reaction rate constant k ₂ (80 ° C.) with p-anisidine measured by the method described in the above is 1.0 liter / mol · sec.
Compounds in the range of 1 × 10 ⁻⁵ liter / mol · sec are preferred.

Of the compounds represented by the general formula (D),
Preferably, R _d1 is an aromatic group. When Z _d1 is —SO ₂ Y and Y is a hydrogen atom, an atom or an atomic group forming an inorganic or organic salt, R _d1 is a phenyl group and the substituent on the phenyl group is based on —SO ₂ Y Compounds having a total Hammett σ value of 0.5 or more are preferred. The sum of σ values is σ _o , σ _m , σ _p , which is the σ value of the ortho, meta and para positions.
In this case, the σ _o value is substituted with the σ _p value. Among the compounds represented by formulas (A) to (D), preferred are compounds represented by formulas (A) and (D).

Among the compounds represented by the general formula (A),
Those represented by the following general formulas (AI) to (AV) are preferred.

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In the general formulas (AI) to (AV),
R _e1 has the same meaning as R _{a1 in} formula (A). L _e1 represents a single bond or -O-, L _e2 represents -O- or -S
Represents-. A _r represents an aromatic group. R _{e2 to} R _e4 may be the same or different and each represent a hydrogen atom, an aliphatic group,
Aromatic group, heterocyclic group, aliphatic oxy group, aromatic oxy group, heterocyclic oxy group, aliphatic thio group, aromatic thio group, heterocyclic thio group, amino group, aliphatic amino group, aromatic amino group A heterocyclic amino group, an acyl group, an amide group, a sulfonamide group, a sulfonyl group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, a sulfo group, a carboxyl group,
Represents a formyl group, hydroxy group, acyloxy group, ureido group, urethane group, carbamoyl group or sulfamoyl group. At least two of R _{e2 to} R _e4 may combine with each other to form a 5- to 7-membered ring. _Ze1 and _Ze2 are 5
Represents a group of nonmetallic atoms necessary to form a 7-membered ring,
_Ze3 represents a group of nonmetallic atoms necessary to form a 5- to 7-membered aromatic ring. The ring formed by Z _{e1 to} Z _e3 may have a substituent, may form a spiro ring or a bicyclo ring, and may be further condensed with a benzene ring, an alicyclic ring or a heterocyclic ring .

Among the compounds represented by the general formulas (AI) to (AV), those represented by (AI) and (A-III) are particularly preferred. The representative examples of these compounds are shown below, but the compounds used in the present invention are not limited thereto.

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These compounds are disclosed in JP-A-62-14304.
No. 8, No. 63-115855, No. 63-115866
No. 63-158545, EP-A-2557.
The compound can be synthesized by the method described in No. 22 and a method analogous thereto. Preferred compounds of the present invention are described in the above-mentioned patents and JP-A-62-17665 and JP-A-62-283338.
No. 62-229145, No. 64-86139,
Also included are compounds specifically exemplified in JP-A-1-271748, Hatsumei Kyokai Disclosure Technical Report No. 90-9416.

The amount (single or total) of each compound represented by formulas (A) to (D) of the present invention is preferably 0.5 × 10 ⁻⁶ to 2 × 10 ⁻³ mol / m ^2. , More preferably 1 × 10 ^{-6 to} 5 × 10 ^-4 mol / m ² , and most preferably ² × 10 ^-6 mol / m ² .
It is 10 ^{-6 to} 3 × 10 ^-4 mol / m ² . When these compounds are used in the same layer as the coupler, the amount used (single or total) is 0.5 to 1 mol of the coupler.
In the range of ~ 300 mol%, preferably 1-200 mol%, most preferably 5-150 mol%. The compounds represented by formulas (A) to (D) of the present invention may be used in a non-photosensitive layer, but are preferably used after being co-emulsified with a coupler. In particular, a combination of a pyrazolotriazole coupler, a pyrrolotriazole coupler, or an acylacetamide-type yellow coupler whose acyl group is a 1-alkylcyclopropane-1-carbonyl group with these compounds is particularly preferable.

The compounds represented by formulas (A) to (D) of the present invention may be used in combination with a known anti-fading agent.
In that case, the fading prevention effect is further enhanced. Similarly, two or more compounds represented by formulas (A) to (D) may be used in combination.

Known anti-fading agents include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarins, spirochromans, p-alkoxyphenols, hindered phenols such as bisphenols, gallic acid derivatives, and the like. Methylenedioxybenzenes,
Representative examples include aminophenols, hindered amines, ultraviolet absorbers, and ether or ester derivatives in which the phenolic hydroxyl group of each of these compounds is silylated or alkylated. Further, a metal complex represented by a (bissalicylaldoximato) nickel complex and a (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

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

In the present invention, as the silver halide grains, 9
It is necessary to use silver chloride, silver chlorobromide, or silver chloroiodobromide grains in which 5 mol% or more is silver chloride. In particular, in the present invention, silver bromochloride or silver chloride substantially free of silver iodide can be preferably used in order to speed up the development processing time. Here, "contains substantially no silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. On the other hand, 0.01 to 3 mol% of the emulsion surface described in JP-A-3-84545 is used for the purpose of increasing the high illuminance sensitivity, increasing the spectral sensitization sensitivity, or increasing the stability over time of the photosensitive material. In some cases, high silver chloride grains containing silver iodide are preferably used. The halogen composition of the emulsion may be different or the same between grains. However, when an emulsion having the same halogen composition between grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, grains having a so-called uniform structure having the same composition in any part of the silver halide grains, a core inside the silver halide grains and a shell surrounding the core are used. (Shell) [Layer or plural layers] and a so-called laminated type particle having a different halogen composition, or a structure having a non-layered portion having a different halogen composition inside or on the surface of the particle (when the particle is on the particle surface, the edge of the particle, Particles having a structure in which portions having different compositions are joined on corners or surfaces) can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use one of the latter two particles rather than particles having a uniform structure, and this is also preferable from the viewpoint of pressure resistance. In the case where the silver halide grains have the above-described structure, even if the boundary between different portions in the halogen composition is a clear boundary, it is an unclear boundary by forming a mixed crystal due to a composition difference. It is also possible to employ a structure in which a continuous structural change is positively provided.

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

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is calculated) is 0.1. 1 μm to 2 μm is preferred. The particle size distribution is preferably a so-called monodisperse coefficient of variation (a standard deviation of the particle size distribution divided by the average particle size) of 20% or less, preferably 15% or less, more preferably 10% or less. . At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating. Silver halide grains contained in photographic emulsions have a regular shape such as cubic, tetrahedral or octahedral.
Those having a (regular) crystal form, those having an irregular crystal form such as a sphere, a plate, or the like, or those having a complex form thereof can be used. Further, it may be composed of a mixture of those having various crystal forms. In the present invention, among these, 50% or more, preferably 7%, of the particles having the above-mentioned regular crystal form are contained.
The content is preferably 0% or more, more preferably 90% or more. In addition to these, emulsions in which tabular grains having an average aspect ratio (diameter / circle diameter in circle) of 5 or more, preferably 8 or more, as projected areas exceed 50% of all grains can be preferably used.

The silver chloro (bromo) chloride emulsion used in the present invention is P.Gl
afkides, Chimie etPhisique Photographique (Paul Mo
ntel, 1967), Photographic E by GFDuffin
mulsion Chemistry (Focal Press, 1966
Year), Making and Coating Photo by VLZelikman et al
It can be prepared using the method described in graphic Emulsion (Focal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halide may be any method such as a one-sided mixing method, a simultaneous mixing method, and a combination thereof. May be used. A method of forming particles in an atmosphere containing excess silver ions (so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

It is preferable that the localized phase of the silver halide grains of the present invention or the substrate thereof contains a foreign metal ion or a complex ion thereof. Preferred metals are selected from metal ions or metal complexes belonging to Groups VIII and IIb of the periodic table, lead ions and thallium ions. Ion selected from iridium, rhodium, iron, etc. or its complex ion for the localized phase, and metal ion selected from osmium, iridium, rhodium, platinum, ruthenium, palladium, cobalt, nickel, iron, etc. for the substrate Alternatively, the complex ions can be used in combination. Further, the type and concentration of the metal ion can be changed depending on the localized phase and the substrate. A plurality of these metals may be used. In particular, the iron and iridium compounds are preferably present in the silver bromide localized phase.

These metal ion-providing compounds are added to an aqueous gelatin solution serving as a dispersion medium when silver halide grains are formed.
The silver halide grains of the present invention may be dissolved in an aqueous halide solution, an aqueous silver salt solution or other aqueous solution, or in the form of silver halide fine particles containing metal ions in advance and dissolving the fine particles. Include in the localized phase and / or other particle parts (substrates). The metal ions used in the present invention can be contained in the emulsion grains either before, during or immediately after grain formation. This can be changed depending on where the metal ions are contained in the particles.

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

The silver halide emulsion used in the present invention contains various compounds or their precursors for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. Can be added. Specific examples of these compounds are disclosed in the above-mentioned JP-A-62-2.
Those described on page 39 to page 72 of JP-A-15272 are preferably used. Further, a 5-arylamino-1,2,3,4-thiatriazole compound (the aryl residue has at least one electron-withdrawing group) described in EP0447647 is also preferably used.

Spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength region to the emulsion of each layer in the light-sensitive material of the present invention. In the light-sensitive material of the present invention, blue, green,
Examples of spectral sensitizing dyes used for spectral sensitization in the red region include, for example, FM Harmer's Heterocyclic compounds-Cyanine
dyes and related compounds (John Wiley & Sons New
York, London, 1964). As specific examples of compounds and spectral sensitization methods, those described in the above-mentioned JP-A-62-215272, from page 22, upper right column to page 38, are preferably used. Particularly, as a red-sensitive spectral sensitizing dye of silver halide emulsion grains having a high silver chloride content, JP-A No. 3-12 / 1991
The spectral sensitizing dye described in No. 3340 is very preferable from the viewpoints of stability, strength of adsorption, temperature dependency of exposure and the like.

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

To incorporate these spectral sensitizing dyes into a silver halide emulsion, they may be directly dispersed in the emulsion, or may be dispersed in water, methanol, ethanol, propanol, methylcellosolve, 2,2, It may be dissolved in a solvent such as 3,3-tetrafluoropropanol alone or in a mixed solvent and added to the emulsion. In addition, Tokiko Sho 44-2
No. 3389, JP-B-44-27555, JP-B-57-
22089 or the like to form an aqueous solution by coexisting with an acid or a base, or to an aqueous solution or colloidal dispersion by coexisting a surfactant as described in U.S. Pat. No. 3,822,135, US Pat. May be added to the emulsion. After dissolving in a substantially water-immiscible solvent such as phenoxyethanol, a dispersion in water or a hydrophilic colloid may be added to the emulsion. JP-A-53-102733, JP-A-58-105
As described in No. 141, the dispersion may be directly dispersed in a hydrophilic colloid, and the dispersion may be added to the emulsion. The timing of addition to the emulsion may be at any stage in the preparation of the emulsion which has hitherto been known to be useful. In other words, before the silver halide emulsion is formed, during the grain formation, immediately after the grain formation, before entering the washing step, before the chemical sensitization, during the chemical sensitization, and immediately after the chemical sensitization until the emulsion is cooled and solidified, during the preparation of the coating solution. , You can choose from. Most commonly, it is carried out after completion of chemical sensitization and before coating, but as described in U.S. Pat. Nos. 3,628,969 and 4,225,666, it is added simultaneously with a chemical sensitizer and spectrally added. It is also possible to perform sensitization simultaneously with chemical sensitization as described in JP-A-58-1.
It can be carried out prior to chemical sensitization as described in No. 13928, or it can be added before completion of precipitation of silver halide grains to start spectral sensitization. It is also possible to add the spectral sensitizing dye separately, as taught in U.S. Pat. No. 4,225,666, i.e. to add part prior to chemical sensitization and to add the remainder after chemical sensitization. It is possible at any time during silver halide grain formation, including the method taught in U.S. Pat. No. 4,183,756. Among them, it is particularly preferable to add a sensitizing dye before the step of washing the emulsion or before the chemical sensitization.

The addition amount of these spectral sensitizing dyes may vary over a wide range depending on the case, and may be 0.5 to 0.5 mol per mol of silver halide.
The range is preferably from × 10 ^-6 mol to 1.0 × 10 ^-2 mol.
More preferably, 1.0 × 10 ⁻⁶ mol to 5.0 × 10 ^−3.
Range of moles. In the present invention, particularly when a sensitizing dye having spectral sensitization sensitivity from the red region to the infrared region is used, the compounds described in JP-A-2-157747, page 13, lower right column to page 22, lower right column may be used in combination. preferable. By using these compounds, the preservability of the photographic material, the stability of the processing, and the supersensitizing effect can be specifically enhanced. Among them, it is particularly preferable to use the compounds of the general formulas (IV), (V) and (VI) in the same patent in combination. These compounds are used in an amount of from 0.5 × 10 ^-5 mol to 5.0 per mol of silver halide.
× 10 ⁻² mol, preferably 5.0 × 10 ⁻⁵ mol to 5.0.
× 10 ^-3 mol is used, and 0.1 to 10,000 times, preferably 0.5 to 500 times per mol of the sensitizing dye.
There is an advantageous usage in the 0-fold range.

The light-sensitive material of the present invention can be used not only in a printing system using a normal negative printer but also in a gas laser, a light-emitting diode, a semiconductor laser, a solid-state laser using a semiconductor laser as an excitation light source, and a nonlinear laser. It is preferably used for digital scanning exposure using monochromatic high-density light such as a second harmonic generation light source (SHG) combined with an optical crystal. The system is compact,
It is preferable to use a second harmonic generation light source (SHG) in which a semiconductor laser, a semiconductor laser or a solid-state laser and a nonlinear optical crystal are combined in order to reduce the cost. Particularly, in order to design a device which 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.

In the case of using such a scanning exposure light source,
The maximum spectral sensitivity of the light-sensitive material of the present invention can be arbitrarily set depending on the wavelength of the scanning exposure light source used. Solid-state laser using a semiconductor laser as an excitation light source or SHG obtained by combining a semiconductor laser with a nonlinear optical crystal
In the light source, 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 regions of blue, green and red. In order to use a semiconductor laser as a light source in order to make the device inexpensive, highly stable and compact, it is preferable that at least two layers have a spectral sensitivity maximum at 670 nm or more. This is because the currently available, inexpensive and stable III-V semiconductor laser has an emission wavelength range only in the red to infrared region. However, at the laboratory level, oscillation of II-VI group semiconductor lasers in the green and blue regions has been confirmed, and if semiconductor laser manufacturing technology is launched, these semiconductor lasers can be used stably at low cost. It is fully anticipated. In such a case, the necessity for at least two layers to have a spectral sensitivity maximum at 670 nm or more is reduced.

In such scanning exposure, the time during which the silver halide in the photosensitive material is exposed is the time required to expose a small area. As the minute area, a minimum unit for controlling the amount of light from each digital data is generally used and is called a pixel. Therefore, the exposure time per pixel changes depending on the size of the pixel. The size of this pixel depends on the pixel density and is a practical range of 50 to 2000 dpi. Exposure time is preferably defined as ^10-4 seconds or less, more preferably ^10-6 seconds or less, when the exposure time is defined as the exposure time of the pixel size when the pixel density is 400 dpi.

The light-sensitive material according to the present invention may have a hydrophilic colloid layer for the purpose of preventing irradiation or halation or improving safelight safety, etc., as described in EP-A-0 337 490 A2, pp. 27-76. It is preferable to add the dyes that can be decolorized by the treatment described above (among them, oxonol dyes and cyanine dyes). Some of these water-soluble dyes deteriorate color separation and safelight safety when used in an increased amount. Dyes that can be used without deteriorating color separation are described in Japanese Patent Application No. 03-310.
No. 143, JP-A-05-127325, JP-A-05-
Water-soluble dyes described in EP 127324 are preferred.

In the present invention, a colored layer that can be decolorized by treatment in place of the water-soluble dye or in combination with the water-soluble dye is used. The colored layer that can be decolorized by the processing used may be in direct contact with the emulsion layer, or may be arranged so as to be in contact with an intermediate layer containing a processing color mixture inhibitor such as gelatin or hydroquinone. This colored layer is preferably provided below the emulsion layer (on the side of the support) that develops the same primary color as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to arbitrarily select and install only a part of them. It is also possible to provide a colored layer which is colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is in the wavelength range used for exposure (400 nm to 700 nm in normal printer exposure).
It is preferable that the optical density value at the wavelength having the highest optical density in the visible light region of nm and the wavelength of the scanning exposure light source used in the case of scanning exposure) is 0.2 or more and 3.0 or less. More preferably, it is 0.5 or more and 2.5 or less, in particular, 0.
It is preferably from 8 to 2.0.

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

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

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

The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the light-sensitive material according to the present invention, and the processing method applied for processing this light-sensitive material As the additives for the treatment, those described in the following patent publications, in particular, those described in European Patent EP 0,355,660 A2 (JP-A-2-139544) are preferably used.

[0143]

[Table 1]

[0144]

[Table 2]

[0145]

[Table 3]

[0146]

[Table 4]

[0147]

[Table 5]

The processing method of the color light-sensitive material of the present invention includes:
Other than the methods described in the above table, JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-4-97355, page 5, upper left column, lines 17 to 18 The processing material and processing method described in the lower right column, line 20 are preferred.

[0149]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

Example 1 Preparation of Cellulose Paper Support A pulp furnish comprising 50% bleached hardwood kraft, 25% bleached hardwood sulphite, and bleached softwood sulphite was subjected to a 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.
This was calendered to obtain a 145 μm thick cellulose paper support. A polymer layer having the following composition was formed on the paper support, subjected to corona discharge treatment on the emulsion side, and then subbed to prepare a reflective support. The polymer layer on the emulsion side contained 4,4'-bis (5-methylbenzoxazolyl) stilbene at 10 mg / m ² and ultramarine.

Preparation of Reflective Support A (Comparative Support) Emulsion surface side polymer composition: polyethylene layer containing titanium oxide at 20% by weight (35μ) Back surface side polymer composition: polyethylene layer (30μ)

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

Preparation of reflective support C (support of the present invention) Emulsion surface side polymer composition: polyethylene layer not containing micropores from emulsion side (1μ) containing titanium oxide and not containing micropores Polypropylene skin 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)

Preparation of Reflective Support D (Support of the Present Invention) Emulsion surface polymer composition: polyethylene layer not containing micropores (3μ) from the emulsion side (polypropylene layer containing titanium oxide and containing micropores) (7μ) Polypropylene layer not containing micropores (9μ) Polypropylene layer containing titanium oxide and containing micropores (7μ) Polyethylene layer containing titanium oxide and not containing micropores (4μ) Back surface polymer composition ： Polyethylene layer (30μ)

The thus-obtained photographic supports A to
On D, a multilayer color photographic paper having the following layer constitution was prepared. (Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. 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 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 preventing layer) Gelatin 0.71 Color mixture inhibitor (Cpd-4) 0.04 Color mixture inhibitor (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-sized emulsion C having an average grain size of 0.50 μm and small-sized emulsion C of 0.41 μm (silver 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 Color image stabilizer (Cpd-21) 0.01 Solvent (Solv-6) 0.23

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

[0161]

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[0162]

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[0163]

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[0164]

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[0165]

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[0166]

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[0167]

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As the gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Further, the total amount of Ab-1, Ab-2, Ab-3 and Ab-4 was 15.0 mg / m ² , 6 in each layer.
0.0 mg / m ² , 5.0 mg / m ² and 10.0 mg
/ M ² .

[0169]

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

[0171]

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(The sensitizing dyes A, B and C were used 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

[0173]

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(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

[0175]

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(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. )

[0177]

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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

Also, 4-hydroxy-6-methyl-1,3,3a, 7 was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
Tetrazindene was added in an amount of 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol per mol of silver halide. In the red-sensitive emulsion layer, a copolymer of methacrylic acid and butyl acrylate (weight ratio 1: 1, average molecular weight 200000-4)
00000) was added at 0.05 g / m ² .

[0180] Also, the second layer was added the fourth layer and the sixth layer in disodium catechol-3,5-disulfonate as respectively a ^{6mg / m 2, 6mg / m} 2, 18mg / m 2. To prevent irradiation, the following dyes were added to the emulsion layer (the amount in parentheses indicates the coating amount).

[0181]

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The sample thus obtained on the support A was designated as Sample 101. Next, as shown in Table 6, the composition of the seventh layer and the support were changed to prepare Samples 102 to 114.

These samples were evaluated for the following a, b, c, and d.

Evaluation test a (Dmin increase after high-temperature storage): Each sample was tested at 25 ° C. and 55% RH for 10 days and 4 days.
After storing 20 sheets at 0 ° C. and 55% RH under two conditions for 10 days, the 10th sample was processed in processing step A described later. The Dmin of the unexposed portion after the treatment was measured (using an HPD-18 densitometer manufactured by Fuji Photo Film Co., Ltd.), and the Dmin after storage at 40 ° C. and 55% RH for 10 days.
The fog rise (ΔDmin) was calculated by subtracting the Dmin value after storage at 25 ° C. and 55% RH for 10 days from the value.

Evaluation test b (change in sensitivity after storage at high temperature): Each sample was stored under the same conditions as in the above-mentioned evaluation test a.
Use a sensitometer (manufactured by Fuji Photo Film Co., Ltd., FWH type, light source color temperature 3200 ° K) through a color separation wedge to obtain a value of 0.
Exposure of 200 CMS was given for 1 second, and processing was performed in processing step A described below. The logarithmic value (logE) of the exposure amount required to give a color density of 0.5 was measured and calculated (using an HPD-18 densitometer manufactured by Fuji Photo Film Co., Ltd.). 40
25 ° C from the log E value after storage at 55 ° C and 55% RH for 10 days
The sensitivity change (ΔlogE) was calculated by subtracting the logE value after storage at 55% RH for 10 days.

Evaluation test c (high-humidity curl): The treated sample was cut into 10 cm × 10 cm, left at a constant temperature of 30 ° C. and 80% RH and a constant humidity of 24 hours, and then left at 30 ° C. and 80% R
The curl degree was determined by the reciprocal of the radius of curvature under a constant temperature and constant humidity of H. The larger the + number, the stronger and worse the + curl (curving upward with the image side up).

Curl = 1 / radius of curvature (m)

Evaluation Test d (Scratch Resistance Test of Treated Sample): A black background sample that had been exposed to white light and was treated was cut into wedge sizes and measured by the following method. A sample was set on a continuous load-type scratch strength tester (Haydon) type 18 (manufactured by Shinto Kagaku Co., Ltd.) according to the prescribed method, and when a continuous load of 0 to 100 g was applied, scratches began to be generated on the sample surface. The weight (g) applied at the time of the test was measured by a prescribed method, and the raw sample was evaluated for a scratch resistance test. The larger the value, the better the scratch resistance. The needle used was a 0.1 mm diamond needle.

Processing Step A Using a paper processing machine, continuous processing was carried out using a liquid having the following processing step and processing liquid composition, and a development processing state in a running equilibrium state was prepared.

Processing Step Temperature Time Replenisher * Tank capacity Color development 35 ° C. 45 seconds 100 ml 5 liter Bleaching and fixing 30-35 ° C. 45 seconds 215 ml 5 liter Rinse 30 ° C. 90 seconds 350 ml 5 liter Drying 70-80 ° C. 60 seconds * replenishment rate is per photosensitive material 1 m ²

The composition of each processing solution is as follows. Color developer Tank solution Replenisher Water 800 ml 800 ml Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 1.5 g 2.0 g Potassium bromide 0.015 g-Triethanolamine 8.0 g 12.0 g Sodium chloride 1.4 g-Potassium carbonate 25 g 25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g 7.0 g N, N-bis (carboxymethyl) hydrazine 4.0 g 5.0 g N, N-di (Sulfoethyl) hydroxylamine / 1Na 4.0 g 5.0 g Fluorescent whitening agent (WHITEX 4B, manufactured by Sumitomo Chemical) 1.0 g 2.0 g Add water 1000 ml 1000 ml pH (25 ° C.) 10.05 10.45

Bleach-fix solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 17 g Iron (III) ammonium ethylenediaminetetraacetate 55 g Disodium ethylenediaminetetraacetate 5 g Ammonium bromide 40 g Add water 1000ml pH (25 ℃) 6.0 Rinse solution (Tank solution and replenisher are the same) Ion exchange water (Calcium and magnesium are less than 3ppm each)

The results obtained are summarized in Table 6.

[0194]

[Table 6]

From the results shown in Table 6, it can be seen that the present invention is superior to Comparative Examples by combining the support of the present invention with a matting agent.

Example 2 Samples 201 to 206 were prepared by changing the composition of the seventh layer of Sample 101 as shown in Table 7 below. These samples were evaluated by the method of c in Example 1 and the method of e shown below.

Evaluation test e (low humidity curl) Evaluation was carried out in the same manner as in evaluation test c except that the temperature and humidity were changed to 20 ° C. and 20% RH at 30 ° C. and 80% RH.

[0198]

[Table 7]

From the results shown in Table 7 above, the support of the present invention,
It can be seen that the present invention is superior to the comparative example by combining the matting agent and the latex.

Example 3 Before the sample 101, 106-109, 112-114 was subjected to the treatment step A, a bar coat was manually applied so as to have the following composition and composition at 40 ° C./80° C.
% RH at a constant temperature and humidity for 24 hours, and then subjected to the treatment of treatment step A, and then subjected to surface heating and pressure treatment (110 ° C. 65
psi) Samples 301 to 305 were prepared. These samples were evaluated by the method d in Example 1.

Composition High-density polyethylene (manufactured by ChemCor) having an average particle diameter of 0.05 μm and a melting point of 131 ° C. ^* 1.2 g / m ² gelatin 0.4 g / m ² * Value measured by differential scanning calorimetry (DSC)

Composition Average particle diameter 12 μm Polyester 6 g / m ² Gelatin 4 g / m ² Latex binder (butyl acrylate) 0.6 g / m ² Sodium dodecylbenzenesulfonate 0.1 g / m ²

[0203]

[Table 8]

From the results shown in Table 8 above, the support of the present invention
It can be seen that the coating of the matting agent and the surface protective layer provided further scratch resistance.

Example 4 In Example 1, when the exposure seconds were similarly evaluated at 10 ^-4 , almost the same results were obtained.

[0206]

According to the present invention, a silver halide color photographic light-sensitive material is provided in which a processed sample is hardly scratched, has excellent curl resistance, and has little fluctuation in photographic performance when the storage state in an unexposed state fluctuates. Is obtained.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (for reference) G03C 7/00 520 G03C 7/00 520

Claims (9)

[Claims] 1. The method according to claim 1, wherein the color sensitivity is different on the reflective support.
In a silver halide color photographic light-sensitive material having a photographic constitution layer comprising a yellow coupler-containing silver halide emulsion layer, a magenta coupler-containing silver halide emulsion layer and a cyan coupler-containing silver halide emulsion layer and a non-light-sensitive layer, A silver halide color photograph wherein at least one of the water-resistant resin layers of the body is a biaxially oriented polyolefin layer having micropores, and a matting agent is contained in the outermost layer of the non-photosensitive layers. Photosensitive material. 2. The method according to claim 1, wherein the color sensitivity is different on the reflective support.
In a silver halide color photographic light-sensitive material having a photographic constitution layer comprising a yellow coupler-containing silver halide emulsion layer, a magenta coupler-containing silver halide emulsion layer and a cyan coupler-containing silver halide emulsion layer and a non-light-sensitive layer, At least one of the water-resistant resin layers of the body is a biaxially stretched polyolefin layer having micropores, and a polyolefin layer having no micropores is provided between the polyolefin layer and the silver halide emulsion layer; and A silver halide color photographic light-sensitive material characterized in that a matting agent is contained in the outermost layer among the non-light-sensitive layers. 3. The method according to claim 1, wherein the color sensitivity is different on the reflective support.
In a silver halide color photographic light-sensitive material having a photographic constitution layer comprising a yellow coupler-containing silver halide emulsion layer, a magenta coupler-containing silver halide emulsion layer and a cyan coupler-containing silver halide emulsion layer and a non-light-sensitive layer, A composition obtained by mixing and dispersing a white pigment in a resin containing 50% by weight or more of a polyester synthesized by polycondensation from a dicarboxylic acid and a diol, and coating the composition on at least the emulsion-coated side of the substrate. A silver halide color photographic material comprising a matting agent in the outermost layer of the photosensitive layer. 4. The silver halide color photographic 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 color photographic light-sensitive material according to claim 1, which contains a matting agent in an amount of 10 mg or more per 1 m ² . 6. The silver halide color photographic material according to claim 1, wherein the outermost layer of the non-photosensitive layer contains at least 40 mg of latex per m ² . 7. A coated material comprising 30 to 95% by weight of hydrophobic polymer particles having an average particle size of 0.01 to 1 μm and a melting point of 55 ° C. to 200 ° C. and 5 to 70% by weight of gelatin, At least one on the photosensitive emulsion layer
7. A protective layer formed by coating a layer and fusing polymer particles.
6. The silver halide color photographic light-sensitive material according to item 1. 8. An aqueous coating composition comprising 5 to 50% by weight of polymer particles having an average particle size of 0.01 to 50 μm and 1 to 3% by weight of a polymer latex binder is coated on the silver halide photosensitive emulsion layer in at least one layer. The silver halide color photographic material according to any one of claims 1 to 6, further comprising a protective layer formed by fusing polymer particles. 9. The gelatin hardener according to the following general formula (HI)
The silver halide color photographic light-sensitive material according to any one of claims 1 to 8, which is a compound represented by the following formula: Embedded image In the general formula (HI), R ¹ is a hydroxyl group and a —OM group (M is 1
Valent metal atom), an alkyl group, -N (R ² )
A (R ³ ) group (R ² and R ³ each independently represent an alkyl group or an aryl group), a —NHCOR ⁴ group (R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, an alkylthio group or an arylthio group), Or represents an alkoxy group.