JPH10161290A - Silver halide photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material and its image forming method capable of forming a black-and-white image using a dye image adapted to a seal print even in the case of processing the sensitive material with a color developing solution containing no benzyl alcohol. SOLUTION: This silver halide photographic sensitive material is provided with an adhesive layer and a strippable layer on the reverse side of a plastic film and at least one silver halide emulsion layer on the surface, and silver halide grains in this emulsion layer has a silver chloride content of >=95mol% and contains all each one kind of yellow, magenta, and cyan couplers. This photographic sensitive material is processed with a color developing solution containing no benzyl alcohol.

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 suitable for so-called seal printing and an image forming method, and more particularly to a benzyl silver halide photographic light-sensitive material having an adhesive layer and a release sheet on the back surface. The present invention relates to a silver halide photographic material which can be processed with a color developer containing substantially no alcohol, and an image forming method using a dye image.

[0002]

2. Description of the Related Art A photographic light-sensitive material having a pressure-sensitive adhesive layer or an adhesive layer and a release layer provided on the back surface, that is, a so-called seal print is known. For example, JP-A-53-139524 discloses a paper support, an image layer provided on one surface of the paper support, a pressure-sensitive adhesive layer provided on the other surface of the paper support, and A photographic element consisting of a peelable ethylene polymer layer provided adjacent to a pressure-sensitive adhesive layer is described. JP-A-64-78251 describes a dye image-forming element having an adhesive layer, a thin-layer support and a dye image-forming layer on a temporary support. JP 5
JP-A-249615 discloses that a re-peelable adhesive layer and a release film for protecting the adhesive layer are provided on one surface of a film-like plastic substrate, and a black-and-white silver halide photosensitive layer is provided on the opposite surface of the film-like plastic substrate. The provided stripping film is described. The image forming layers described in these prior arts merely describe layers for forming a so-called color photographic image or layers for forming a black and white image by a silver image.

[0003] Generally, silver halide color photographic light-sensitive materials contain several silver halide emulsion layers containing a coupler which reacts with an oxidation product of a color developing agent to form a dye, namely, blue light, green light and A silver halide emulsion layer showing sensitivity to red light and containing a yellow coupler, a magenta coupler and a cyan coupler, respectively, is provided on a support, and each of these halogen emulsions is subjected to color development processing after exposure. The layers form dye images of cyan, magenta and cyan respectively. Also, cyan,
A photographic system for forming a black-and-white image using a combination of magenta and yellow dyes is also known (for example, JP-A-6-505580). In this system, the dye is formed from a mixture of cyan, magenta and yellow dye-forming couplers during the color development step, and the coupler forms a neutral image when reacted with the oxidized color developing agent. Occurs. However, the support described in this publication merely describes a standard color photographic paper support, a polyester support, and a display support.

Further, when a black-and-white image is formed from a conventional silver image, development processing is performed using a black-and-white developing agent such as hydroquinone. However, there are few laboratories and photo shops capable of performing this development processing. On the other hand, in the current processing of color paper, it is common to carry out development processing with a color developer substantially not containing benzyl alcohol. Processors suitable for this processing are widely used in laboratories, photo shops, and the like, and black-and-white image forming materials applicable to this processing are preferable.

[0005]

SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is to provide a silver halide photographic light-sensitive material capable of obtaining a black-and-white image with a dye image suitable for seal printing. A second object of the present invention is to provide an image forming method suitable for seal printing in which a black-and-white image based on a dye image is obtained by developing with a color developer substantially containing no benzyl alcohol.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a plastic film having an adhesive layer and a release sheet on the back surface, and having at least one silver halide emulsion layer on the surface. The silver halide content of the silver halide grains is 95 mol% or more, and the silver halide emulsion layer contains at least one yellow coupler, at least one magenta coupler, and at least one cyan coupler. This was achieved by an image forming method in which a light-sensitive material and this silver halide photographic light-sensitive material were developed with a color developer substantially free of benzyl alcohol.

The basic constitution of the silver halide photographic light-sensitive material of the present invention comprises a plastic film, an adhesive layer provided on the back surface thereof, a release sheet provided on the adhesive layer,
And at least one silver halide emulsion layer provided on the surface of the plastic film. The plastic film used for the photographic light-sensitive material of the present invention includes:
Cellulose triacetate, cellulose diacetate,
Examples thereof include films made of synthetic polymers such as polyvinyl acetal, polystyrene, polyethylene terephthalate, polycarbonate, polypropylene, polyvinyl chloride, nylon, and polyethylene. Polyethylene terephthalate, polystyrene and triacetate films are particularly preferred. The plastic film may be colored using a dye or a pigment. When using such a plastic film as a reflective material, it is preferable to add a white pigment to the film. Examples of the white pigment include titanium dioxide, barium sulfate, zinc oxide, zinc sulfide, calcium carbonate, antimony trioxide, silica white, alumina white, and titanium phosphate.
In particular, titanium dioxide, barium sulfate, and zinc oxide are useful. The surface of these plastic films is generally subbed to improve adhesion with the photographic emulsion.
The surface of the support may be subjected to a treatment such as corona discharge or ultraviolet irradiation before or after the undercoating treatment. Further, a mixture of a water-soluble resin and an oil-soluble resin may be applied in advance. When these plastic films are used for a reflective material, a hydrophilic colloid layer containing a high density of white pigment is further provided between the plastic film and the emulsion layer to improve whiteness and sharpness of a photographic image. Can be.

In the photographic light-sensitive material of the present invention, when a plastic film into which a white pigment is kneaded is used, a photographic image which is excellent not only in smoothness, glossiness and sharpness but also in saturation, depiction of dark areas, etc. can be obtained. can get. In this case, polyethylene terephthalate and cellulose acetate are particularly useful as the plastic film, and barium sulfate and titanium oxide are particularly useful as the white pigment. The thickness of the plastic film is 20 to 150 μm, preferably 30 to 100 μm.
m. If the thickness is less than 20 μm, it is difficult to handle when attaching to another. If it is thicker than 150 μm,
When formed into a roll (for example, when the emulsion is applied and wound up), the plastic film and the release sheet tend to be displaced, which is not preferable.

The pressure-sensitive adhesive layer used in the photographic light-sensitive material of the present invention is composed of a synthetic polymer having elasticity, a tackifier for giving tackiness to an elastomer, a softener, and the like. For example, synthetic polymers and elastomers include polyacrylate, acrylic copolymer, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyvinyl isobutyl ether, polyvinyl alcohol, natural rubber, butyl rubber, polyisoprene rubber, recycled rubber, chloroprene, polyisobutylene, and silicone rubber. , Chlorinated rubber, chlorinated butyl and the like. Examples of the tackifier include, for example, rosin, ester gum, polyolefin-based petroleum resin, polyterpene-based polymer, coumarone, indene-based polymer, styrene-based polymer, phenolic resin, xylene-based polymer, gum arabic, dextrin, glue and the like. it can.

Examples of the softener include plasticizers of the above polymers, polybutene, polyisobutylene low polymer, polyvinyl isobutyl ether low polymer, rosin oil, rubber depolymer, lanolin, wax, vegetable oil and the like. . In addition, an antioxidant, a stabilizer, an anti-binder, and the like can be added. The substance forming the above-mentioned adhesive layer,
Dissolve or disperse and mix in a suitable organic solvent to form a solution,
Preferably, it is dispersed in water and emulsified and provided on the plastic film. Preferred emulsion latexes include, for example, TR-881 and TS-88
2 (all manufactured by Nippon Carbide Co., Ltd.).

As a method for providing an adhesive layer, a method usually used for an adhesive tape, an adhesive sheet, a label paper, a free album, a seal print, or the like can be selected and used. For example, Japanese Unexamined Patent Application Publication No.
Nos. 60771, 61-83276 and 61-
Nos. 103975, 61-148279, 61-148282, 61-174283, and 61-179559 can be used. The coating amount of the pressure-sensitive adhesive layer is in the range of 0.1 to 30 g, preferably 0.5 to ²⁰ g per 1 m ² , and is 0.0 when the thickness of the plastic film is 1.
A thickness in the range of 1 to 0.5 is preferable for production and use.

The release sheet of the present invention must have a function of protecting the pressure-sensitive adhesive layer until the time of lamination, and having a function of quickly peeling off the laminate during use. The material of the release sheet, in addition to the plastic film similar to the plastic film, polypropylene, polystyrene, synthetic paper made of a material such as polyvinyl chloride, metal foil, paper, etc., from the viewpoint of stable production It is preferably of the same quality as the plastic film.

The surface of the release sheet that is in contact with the adhesive layer is preferably treated with a release agent. Preferred release agents include, for example, silicone oils such as methylhydrogenpolysiloxane, hydroxyl-terminated dimethylsiloxane, dimethylpolysiloxane, etc., silicone oil emulsions, silicone water-producing agents such as sodium methylsiliconate, and silicone water-producing agents. Butyl titanate, or an organic acid salt of aluminum, tin, lead, zinc or the like added as an auxiliary agent, paraffin wax, wax emulsion, zirconium salt, quaternary ammonium salts such as stearoylmethylamide and methylenepyridinium salt, N- such as N-methylol stearamide
Fluorocarboxylic acids such as methylol fatty acid amides, perfluoromonocarboxylic acid chloro complex salts and fluorinated alkyl acrylates, N, N-diethanololeamide,
Amides such as N, N-diethanolerucamide and N, N-diethanolstearylerquamide can be mentioned. Further, polyvinyl carbamates, acrylate copolymers, polyvinyl acetate copolymers and the like can also be preferably used. The amount of the release agent used varies depending on various conditions, but is 0.1 to 1 m ^2.
A range of 1.0 g is preferred.

Although the thickness of the release sheet is not particularly limited,
It is preferable that the entire thickness of the photographic material is 50 to 150 μm in the manufacturing process and the developing process. On the other hand, the plastic film and the adhesive layer are preferably thinner. The overall thickness of the material can be controlled to the above thickness. By these operations, it is possible to keep the respective thicknesses to be optimal at the time of bonding in the manufacturing process, the developing process, and the like.

The halogen composition of the silver halide emulsion used in the present invention is such that 95 mol% or more of the silver halide grains are silver chloride, and are composed of silver chlorobromide containing substantially no silver iodide. preferable. Average grain size of silver halide grains (in the case of spherical or spherical particles, the grain diameter,
In the case of a cubic particle, the length of the ridge is defined as the particle size, and is represented by an average based on the projected area. The particle size distribution may be narrow or wide. The silver halide grains may have a regular crystal form such as a cube or an octahedron, or may have an irregular crystal form such as a sphere or a plate, or a composite of these crystal forms. May be. It may consist of a mixture of particles of various crystal forms. Further, an emulsion may be used in which tabular silver halide grains having a diameter of 5 times or more of the thickness thereof occupy 50% or more of the total projected area. The particles may be such that the latent image is mainly formed on the surface, or may be the particles that are mainly formed inside the particle. The silver halide grains may have a layered structure having layers with different halogen compositions on the inside and the outside, or may be joined to silver halide grains having different halogen compositions by epitaxial joining.

In the present invention, the silver halide grains of the silver halide emulsion are those in which a localized layer having a silver bromide content of 30 to 60 mol% is locally epitaxially grown on the surface of the halogen grains, particularly on the corners of the grains. preferable. This localized phase accounts for 0.5 to 5% of the total silver constituting the silver halide grains.
Of silver. The method for producing the epitaxial silver halide grains is described in EP-A-273,430. The silver halide emulsion used in the present invention is a P.I. Glafide
s, Chimie et Physique Pho
tographique (published by PaulMontel,
1967); F. Photograph by Duffin
raphic Emulsion Chemistry
(Published by The Focal Press, 1966
Year), V. L. By Zelikman et al, Ma
King and Coating Photogra
phy Emolsion (The Focal P
Ress Co., 1964) and the like. That is, acid method, neutral method,
Any method such as an ammonia method may be used, and a method of reacting a soluble silver salt with a soluble halogen salt may be any of a forward flow method, a reverse flow method, a double jet method, and a combination thereof.

One of the simultaneous mixing methods is to keep the pAg in the solution in which silver halide is formed constant.
The so-called control double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained. Two or more types of silver halide emulsions formed separately may be used as a mixture. At the time of silver halide grain formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt, or a complex salt thereof, rhodium salt or a complex salt thereof,
An iron salt or a complex salt thereof may coexist. Silver halide emulsions are usually chemically sensitized. For example, compounds containing sulfur that can react with active gelatin or silver (eg, thiosulfates, thioureas, mercapto compounds, rhodanines, etc.)
Sulfur sensitization method using a reducing substance (for example, stannous salt, amines, hydrazine derivative, formamidine sulfinic acid, silane compound), a noble metal compound (for example, gold, platinum, iridium, A noble metal sensitization method using a complex salt of a metal such as palladium or the like can be used alone or in combination.

The silver halide emulsion of the present invention comprises at least one sensitizing dye represented by the general formula (I), at least one sensitizing dye represented by the general formula (II), and
It is preferable that at least one of the sensitizing dyes represented by the general formula (III) or (IV) is spectrally sensitized.

[0019]

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[0020]

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In the general formula (I), R ₁ and R _{2 each} have 1 carbon atom.
To 6 alkyl groups (e.g., methyl group, ethyl group, n-
Propyl group, isopropyl group, n-butyl group, isobutyl group, n-hexyl group, isohexyl group, etc.), carbon number 1
To 4 substituted alkyl groups [for example, hydroxylalkyl group (for example, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, etc.), sulfoalkyl group (for example, 2-sulfoethyl group, 3-sulfopropyl group) Group, 3-sulfobutyl group, 4-sulfobutyl group, etc.), carboxyalkyl group (eg, 2-carboxyethyl group, 3-carboxypropyl group, 3-carboxybutyl group, 4-carboxybutyl group, etc.)], aralkyl group ( For example, a benzyl group or a 2-phenylethyl group). It is preferable that _one of R ₁ and R ₂ is a substituted alkyl group. Z ₁ and Z ₂ represent a substituent (for example, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a cyano group, an alkoxycarbonyl group, a trifluoromethyl group, an alkylsulfonyl group, an alkylsulfamoyl group, an acylamino group, an alkylcarbamoyl Group, acetoxy group, etc.) represents a group of non-metallic atoms necessary for forming a benzene nucleus or a naphthalene nucleus which may have a nucleus. X ₁ represents a commonly used anion group (for example, chloride ion, bromine ion, iodine ion, perchlorate ion, p-toluenesulfonic acid ion, ethyl sulfate ion, etc.). P ₁ represents 1 or 2, and when P ₁ is 1, an internal salt is formed.

In the general formula (II), R ₃ and R ₄ represent an alkyl group having 1 to 6 carbon atoms which may have a sulfo group as a substituent (for example, a methyl group, an ethyl group, an n-propyl group) ,
A ₁ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (such as an isopropyl group, an n-butyl group, an isobutyl group, an n-hexyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, and a 3-sulfobutyl group). For example, a methyl group, an ethyl group,
Y ₁ and Y ₂ are a sulfur atom, an oxygen atom, a selenium atom, N—R ₅ , and R ₅ is a carbon atom having 1 to 3 carbon atoms. (For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, etc.). Z ₃ and Z ₄ represent a substituent (for example, a halogen atom, an alkyl group, an alkoxy group,
Aryl group, carbonyl group, alkoxycarbonyl group,
A non-metallic atom group necessary for forming a benzene ring or a naphthalene ring which may have a cyano group or the like. X ₂ represents an anion group (for example, chloride ion, bromine ion, iodine ion, perchlorate ion, p-toluenesulfonic acid ion, ethyl sulfate ion, etc.). P ₂ represents 1 or 2, and when P ₂ is 1, an internal salt is formed.

In the general formulas (III) and (IV),
R ₆ , R ₇ , R ₈ and R ₉ represent an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-hexyl group) , Isohexyl group, etc.), a substituted alkyl group having 1 to 4 carbon atoms [for example, a hydroxylalkyl group (for example, 2-
Hydroxyethyl group, 3-hydroxypropyl group, 2-
Hydroxypropyl group, etc.), sulfoalkyl group (for example, 2-sulfoethyl group, 3-sulfopropyl group, 3-
Sulfobutyl group, 4-sulfobutyl group, etc.), carboxyalkyl group (eg, 2-carboxyethyl group, 3-carboxypropyl group, 3-carboxybutyl group, 4-carboxybutyl group, etc.)], aralkyl group (eg, benzyl group) , 2-phenylethyl group, etc.). R ₆ and R ₇
Is preferred when any one of them is a substituted alkyl group. Similarly, it is preferable that one of R ₈ and R ₉ is a substituted alkyl group. A ₂ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (eg, a methyl group, an ethyl group, n
-Propyl group, isopropyl group, etc.) and aryl group (for example, phenyl group etc.). Z ₅ , Z ₆ , Z ₇ and Z ₈ represent a substituent (for example, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a cyano group, an alkoxycarbonyl group,
Trifluoromethyl group, alkylsulfonyl group, alkylsulfamoyl group, acylamino group, alkylcarbamoyl group, acetoxy group, etc.), which represents a group of non-metallic atoms necessary for forming a benzene nucleus or a naphthalene nucleus. . Z ₉ represents a nonmetallic atom group necessary for forming a 6-membered ring nucleus which may have a substituent (for example, an alkyl group). X ₃ and X _{4 each} represent a commonly used anion group (for example, chloride ion, bromine ion, iodine ion, perchlorate ion, p-toluenesulfonic acid ion, ethyl sulfate ion, etc.). P ₃ and P ₄ represent 1 or 2, and when P ₃ and P ₄ are 1, an internal salt is formed.

Specific examples of these sensitizing dyes are described in Japanese Patent Application No. Hei.
192965. These sensitizing dyes are used per mole of silver halide in the silver halide emulsion.
It is used at a concentration of 10 ^-6 to 10 ^-3 molar. When such a sensitizing dye is added to a silver halide emulsion, a method of directly dispersing the sensitizing dye in the silver halide emulsion may be used, or a suitable solvent such as methyl alcohol, ethyl alcohol, After dissolving in acetone, N, N-dimethylformamide, ethyl acetate or a mixed solvent thereof, or in a solvent containing a surfactant therein,
A method of adding to a silver halide emulsion can be applied. These sensitizing dyes can be added to a silver halide emulsion during silver halide grain formation or after completion of physical ripening. Preferably, after physical ripening, before chemical ripening,
It is added to the silver halide emulsion during or after chemical ripening. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye,
The emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. For example, aminostyryl compounds substituted with nitrogen-containing heterocyclic groups (for example, compounds described in U.S. Pat. Nos. 2,933,390 and 3,635,721), and aromatic organic acid formaldehyde It may contain condensates (for example, compounds described in U.S. Pat. No. 3,743,510), cadmium salts, azaindene compounds and the like.

Examples of the yellow coupler that can be used in the present invention include oil-protected acylacetamide couplers. Specific examples are:
U.S. Pat. Nos. 2,407,210 and 2,875,0
No. 57 and No. 3,265,506. In the present invention, the use of 2-equivalent yellow couplers is described in U.S. Pat. No. 3,408,19.
No. 4, No. 3,447,928, No. 3,933,5
No. 01 and 4,401,752, etc., and an oxygen atom-elimination type yellow coupler described in Japanese Patent Publication No.
No. 8-10739, U.S. Pat. No. 4,022,620
No. 4,326,024, Research Disclosure 18,053 (April 1987), British Patent No. 1,425,020, West German Published Patent No. 2,219,917, No. 2 , 261,361, 2,329,587, and 2,433,812, and the like. α-pivaloylacetanilide-based couplers are characterized by the fastness of coloring dyes, while α-benzoylacetanilide-based couplers are characterized by good coloration.

As the magenta coupler which can be used in the present invention, mention may be made of oil-protected indazolone-based or cyanoacetyl-based couplers, preferably pyrazoloazole-based couplers such as 5-pyrazolone- and pyrazolotriazole-based couplers. Can be. As the 5-pyrazolone-based coupler, those in which the 3-position is substituted with an arylamino group or an acylamino group are preferable from the viewpoint of the hue and color developing speed of the coloring dye, and specific examples thereof are described in US Pat.
No. 1,082, No. 2,343,703, No. 2,6
No. 00,788, No. 2,908,573, No. 3,
No. 3,152,896 and 3,936,015, and the couplers described in the respective specifications. 2-equivalent 5-pyrazolone couplers are particularly preferred, and the leaving group is US Pat.
A nitrogen atom leaving group described in JP-A-310,619;
An arylthio group described in U.S. Pat. No. 4,351,897 can be mentioned. Further, a 5-pyrazolone-based coupler having a ballast group described in European Patent No. 73,636 is a preferred coupler having high color-forming reactivity. Examples of pyrazoloazole-based couplers include pyrazolo [1,5-b] [1,2,4] triazoles described in European Patent No. 119,860 and US Pat. No. 3,369,897. , The pyrazolotetrazole described in Research Disclosure 24, 220 (June 1984), and the pyrazolopyrazoles described in Research Disclosure 24, 230 (June 1984). Can be mentioned. JP 59
The imidazopyrazoles and pyrazolo [1,5-b] [1,2,4] triazoles described in JP-A-162548 are preferable because they have low yellow side absorption of the coloring dye and high light fastness.

Examples of the cyan coupler usable in the present invention include oil-protected naphthol couplers and phenol couplers. The naphthol couplers described in US Pat. No. 2,474,293 can be used. Couplers, preferably U.S. Pat. No. 4,052,21
No. 2, No. 4,143,396, No. 4,228,2
No. 33, No. 4,296,200, and high-activity two-equivalent naphthol couplers of the oxygen atom-elimination type described in the respective specifications. Examples of phenol couplers include U.S. Pat. Nos. 2,369,929 and 2,42.
No. 3,730, No. 2,772,162, No. 2,8
And couplers described in each specification such as No. 01,171 and No. 2,895,826.
Cyan couplers which are robust to temperature and humidity are preferred, and phenolic cyan couplers described in U.S. Pat. No. 3,772,022, U.S. Pat. Nos. 2,772,162, 3, 2,5-diacylamino-substituted phenols described in JP-A Nos. 758,308, 4,126,396, and 4,327,137, and JP-A-59-166956. Couplers, U.S. Pat. Nos. 3,446,622 and 4,3
No. 33,999, No. 4,451,559 and No. 4,427,767.
A phenolic coupler having a phenylureido group at the -position and an acylamino group at the 5-position. next,
Specific examples of the coupler used in the present invention will be described.

[0028]

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[0035]

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[0036]

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[0038]

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[0040]

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[0041]

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[0042]

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[0043]

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[0046]

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The coupler used in the present invention can be introduced into a silver halide emulsion by various dispersion methods. For example, a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, more preferably an oil-in-water dispersion method can be used. In the oil-in-water dispersion method, a high-boiling organic solvent having a boiling point of 175 ° C. or higher and a low-boiling auxiliary solvent are dissolved in a single solution or a mixture thereof, and then water or gelatin is dissolved in the presence of a surfactant. Finely dispersed in an aqueous medium such as an aqueous solution. The high boiling point organic solvent is described in U.S. Pat. No. 2,322,027. The dispersion may be accompanied by a phase inversion, and if necessary, the auxiliary solvent can be used for coating after being removed or reduced by distillation, noodle washing, ultrafiltration or the like.
In the silver halide photographic light-sensitive material of the present invention, the yellow coupler (Y), the magenta coupler (M) and the cyan coupler (C) are preferably used in a molar ratio of Y: M: C =
2.5-4.5: 1: 2.0-4.5.

Examples of the high boiling organic solvent include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, didodecyl phthalate, etc.), and esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate) ,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, trididecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphate, benzoic acid ester (2-ethylhexyl benzoate, dodecyl benzoate, 2-ethyloxyl-p-hydroxybenzoate, etc.), amide (diethyldodecaneamide, N-tetradecylpyrrolidone, etc.), alcohol or phenol (isostearyl alcohol, 2,4-di-
t-amylphenol, etc.), aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2-butoxy-5-t-) Octylaniline, etc.), and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). As the auxiliary solvent, those having a boiling point of about 30 ° C. to about 60 ° C. can be used. Specific examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, and 2-ethoxyethyl acetate. And dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,36.
No. 3, West German Published Patent Nos. 2,541,274 and 2,541,230. Other exemplified compounds can be synthesized in the same manner as described above. As the binder or protective colloid that can be used in the emulsion layer or other hydrophilic colloid layers of the photographic light-sensitive material of the present invention, mainly gelatin is used.
For example, gelatin derivatives, albumin, proteins such as casein, ethyl cellulose, cellulose derivatives such as carboxymethyl cellulose, sugar derivatives such as starch derivatives, polyvinyl alcohol, polyacrylic acid, polyacrylamide, mono- or copolymers such as polymethacrylic acid Such hydrophilic polymers can be used.

The emulsion layer and other hydrophilic colloid layers of the photographic light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging during the production process, storage or development processing, or stabilizing photographic performance. Can be added. Examples of the compound include azoles such as nitroindazoles, nitrobenzimidazoles, mercaptothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, mercaptotetrazole (particularly,
-Phenyl-5-mercaptotetrazole), mercaptotriazines, thioketone compounds, azaindenes, for example, triazaindenes and tetraazaindenes (particularly, 4-hydroxy-1,3,3a, 7-tetrazaindene) ), Pentaazaindenes, benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, and many other compounds conventionally known as antifoggants or stabilizers. Of these, particularly preferred are benzotriazoles and nitroindazoles. These compounds may be contained in a processing solution used for the development processing. In the emulsion layer and other hydrophilic colloid layers of the photographic light-sensitive material of the present invention,
Hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives, and the like can be contained as color fog inhibitors.

The emulsion layer and other hydrophilic colloid layers of the photographic light-sensitive material of the present invention may contain an inorganic or organic hardener. Examples of the hardener include a chromium salt (such as chrome alum), an N-methylol compound, a dioxane derivative, and an active vinyl compound (for example, 1,2,5-triacryloyl-hexahydro-s-triazine,
3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (eg, 2,4-dichloro-6-hydroxy-s-triazine, etc.), and mucohalic acids (eg, mucochloric acid, mucophenoxycyclolic acid, etc.). These hardeners can be used alone or in combination. Emulsion layer and other hydrophilic colloid layers of the photographic light-sensitive material of the present invention, coating aid, antistatic,
Surfactants can be contained for various purposes such as improving slipperiness, emulsifying and dispersing, preventing adhesion, and improving photographic properties (for example, acceleration of development, high contrast, sensitization, etc.). Examples of the surfactant include saponins, alkylene oxide derivatives (polyethylene glycol, polyethylene glycol alkyl ethers, etc.), glycidol derivatives (alkenyl succinic acid polyglycerides, alkylphenol polyglycerides, etc.), fatty acid esters of polyhydric alcohols, and sugars. Nonionic surfactants such as alkyl esters, anions having an acidic group such as carboxy group, sulfo group, sulfate group, phosphate group such as alkyl carboxylate, alkyl sulfate, alkyl phosphate, etc. Amphoteric surfactants, amino acids, aminoalkylsulfonic acids, amphoteric surfactants such as aminoalkylsulfuric acid or phosphate esters, aliphatic or aromatic quaternary ammonium salts, or heterocyclic quaternary ammonium salts Etc. It can be exemplified emissions surfactant.

The emulsion layer and other hydrophilic colloid layers of the photographic light-sensitive material of the present invention may contain a dispersion of a water-soluble or poorly-soluble synthetic polymer for the purpose of improving dimensional stability and the like. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, (meth) acrylamide, vinyl ester, glycidin (meth) acrylate, acrylonitrile, styrene, etc., alone or in combination, or acrylic acid, methacrylic acid, It can be used in combination with a polymer having a combination of α, β-unsaturated dicarboxylic acid, styrenesulfonic acid and the like as a monomer component. Other hydrophilic colloid layers other than the silver halide emulsion layer in the present invention include a surface protective layer, a filter layer, an antihalation layer, and an antistatic layer. A hydrophilic colloid layer such as a surface protective layer may contain a matting agent for the purpose of preventing adhesion and improving the surface condition. As matting agents, US Pat. Nos. 2,701,245 and 2,992,101
No. 4,142,894, No. 4,396,70
Fine particles such as polymethyl methacrylate homopolymers, copolymers of methyl methacrylate and methacrylic acid, starch, silica, and magnesium oxide described in the specifications of No. 6 can be used. The surface protective layer includes a silicone compound described in each of U.S. Pat. Nos. 3,489,576 and 4,047,958.
No. 23139, colloidal silica, paraffin wax, higher fatty acid esters and the like can be added.

The photographic light-sensitive material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, U.S. Patent Nos. 3,533,794 and 4,236,013
Benzotriazoles substituted with an aryl group described in U.S. Pat. No. 4,195,999 described in Japanese Patent Publication No. 51-6540 and European Patent No. 57,160. Butadiene described, U.S. Pat. Nos. 3,705,805 and 3,70
7,375, cinnamic acid esters described in the specifications of US Pat. No. 3,215,230 and British Patent No. 1,321,355, benzophenones described in the specifications of US Pat. Polymer compounds having an ultraviolet absorbing group described in the specifications of 3,761,272 and 4,431,726 can be used. U.S. Pat. Nos. 3,499,762 and 3,700,455
UV-absorbing optical brighteners described in the above-mentioned specifications may be used. The photographic material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes,
Hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes are included. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

In the photographic light-sensitive material of the present invention, an anti-fading agent can be used in the emulsion layer and other hydrophilic colloid layers, and the anti-fading agent can be used alone or in combination of two or more. Examples of the discoloration inhibitor include, for example, JP-A-59-12
Phenols or phenyl ether compounds described in JP-A-5732, metal complexes described in JP-A-60-97353, hindered amines or hindered phenol compounds described in JP-A-62-115157, Examples thereof include metal complexes described in Japanese Unexamined Patent Publication No. 61-140941. In the emulsion layer and other hydrophilic colloid layers of the photographic light-sensitive material of the present invention, polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol and glycerin can be used as plasticizers. Further, a fluorescent whitening agent, a development accelerator, a pH adjuster, a thickener, an antistatic agent and the like can be added to the emulsion layer and other hydrophilic colloid layers.

The silver halide photographic light-sensitive material of the present invention can form a black-and-white image by exposing from a black-and-white negative film or from a color negative film. The color developer that can be used in the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine developing agent. As a developing agent, 4-
Amino-N, N-diethylaniline, 3-methyl-4-
Amino-N, N-diethylaniline, 4-amino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N
-Β-methanesulfonamidoethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline and the like. Color developers include carbonates, pH buffers such as borates and phosphates, bromides,
Antifoggants such as iodides and organic antifoggants can be included. If necessary, a water softener, a sulfite of an alkali metal, a development accelerator such as diethylene glycol, polyethylene glycol, a quaternary ammonium salt, an amine, a competing coupler, a fogging agent such as sodium boron hydride, 1-phenyl Auxiliary developing agents such as -3-pyrazolidone, viscosity-imparting agents, US Pat. No. 4,082,7
It may contain a polycarboxylic acid-based chelating agent described in JP-A No. 23, an antioxidant described in West German Patent Application No. 2,622,950, and the like. The fact that benzyl alcohol is not substantially contained in the developer means that even if benzyl alcohol is contained in the developer, it is not more than 5 ml / l. More preferably, it does not contain benzyl alcohol.

The silver halide photographic light-sensitive material of the present invention is usually subjected to bleaching after color development. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI), and copper (II), peracids, quinones, and nitroso compounds are used. For example, ferricyanide, dichromate, an organic acid salt of iron (III) or cobalt (III), for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3
-Aminopolycarboxylic acids such as -diamino-2-propanoltetraacetic acid or complex salts of organic acids such as citric acid, tartaric acid and malic acid, persulfates, manganates, nitrosophenols and the like can be used. Of these, sodium ethylene (III) ethylenediaminetetraacetate and ammonium (III) ethylenediaminetetraacetate are particularly useful. The iron (III) complex salt of ethylenediaminetetraacetate is useful both in an independent bleaching solution and in a single-bath bleach-fixing solution. After the color development or the bleach-fixing process, a water washing process may be performed. Color development can be performed at any temperature between 18 ° C and 55 ° C. Preferably, it is performed at 30 ° C. or higher, particularly preferably at 35 ° C. or higher. The time required for development is in the range of about 1 minute 30 seconds to about 20 seconds, and a shorter one is preferred. For continuous development processing, liquid replenishment is preferable, and 100 ml or more, preferably 160 ml to 330 ml of liquid is replenished per square meter of processing area. Bleaching and fixing can be carried out at any temperature between 18 ° C. and 50 ° C., preferably 30 ° C. or higher. When the temperature is set to 35 ° C. or more, the processing time can be reduced to one minute or less, and the replenishing amount of the liquid can be reduced. The time required for rinsing after color development or bleach-fixing is usually within 1 minute, and processing can be performed within 1 minute using a stabilizing bath.

The colored dye deteriorates and fades due to mold during storage, in addition to being deteriorated by light, heat or humidity. The cyan dye is particularly susceptible to deterioration by mold, and it is preferable to use a fungicide. A specific example of a fungicide is disclosed in
Examples thereof include 2-thiazolylbenzimidazoles described in JP-A-7-157244. The fungicide may be incorporated in the silver halide photographic material,
It may be added from the outside in the development processing step, and can be added in any step as long as it coexists with the processed photosensitive material.

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DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments. Example 1 Preparation of Reflective Composite Support A roll of polyethylene terephthalate film (thickness: 36 μm) was subjected to a hydrophilic treatment on both surfaces of the base.
An opaque layer of titanium dioxide was provided using the technique of No. 7-53937 (film thickness on one side after drying was 15 μm), and the backside of this film was coated with a solid content of 50 using a Mayer bar No. 25 using a solvent drying type coating machine. % Acrylic acid ester-based water-based pressure-sensitive adhesive TS-882 (manufactured by Nippon Carbide Co., Ltd.) diluted to 40% and applied with a wet weight of 27 g / m ² (film thickness after drying: 12 μm) Were pasted together. The release sheet was prepared by diluting a release agent for release paper KS-774 (manufactured by Shin-Etsu Chemical Co., Ltd.) to 1% with toluene on a 50 μm-thick polyethylene terephthalate film with a solvent drying type coater. 5 g / m ^{2 was} wet-coated (0.035 μm in thickness after drying) and then dried. Similarly, a support was prepared in which the thicknesses of the plastic film and the release sheet were changed.

Preparation of silver halide emulsion Solution I Deionized water 1,000 ml Sodium chloride 4.0 g Inert gelatin 30 g Citric acid 2.4 g Solution II 1,3-dimethyl-2-imidazolidinthione (1% aqueous solution) 2 ml Solution III Ionized water 200 ml Sodium chloride 13.6 g Potassium bromide 0.28 g IV solution Deionized water 200 ml Silver nitrate 40 g V solution Deionized water 400 ml Sodium chloride 27.25 g Potassium bromide 0.56 g VI solution Deionized water 400 ml Silver nitrate 80 g

After dissolving solution I at 55 ° C.,
The solution was added, and after 1 minute, Solution III and Solution IV were added simultaneously over 20 minutes. After aging for 10 minutes, Solution V and Solution VI were simultaneously added over 30 minutes.
Aged for minutes. After completion of the physical ripening of each emulsion, excess salts were removed by the method described in Example 1 of U.S. Pat. No. 2,613,928. To each emulsion thus obtained, water and gelatin were added to redissolve, and the pH was adjusted to 6.
0. Next, the temperature was raised to 55 ° C., sodium thiosulfate was added, and after optimal chemical sensitization,
The mixture was cooled to 0 ° C., and sensitizing dye A was added thereto per mole of silver.
× 10 ^-4 mol, sensitizing dye B of 1.3 × 10 ^-4 mol, and sensitizing dye C of 4 × 10 ^-5 mol were added. After standing for 20 minutes, 4-hydroxy-6-methyl-1,
50 mg of 3,3a, 7-tetrazaindene was added per mole of silver halide.

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A coupler dispersion was prepared as follows. After dissolving the coupler in dibutyl phthalate and ethyl acetate, in the presence of a surfactant, added to an aqueous gelatin solution,
Fine dispersion was performed using an ultrasonic homogenizer.

Preparation of photographic light-sensitive material The above-mentioned silver halide emulsion and a coupler dispersion were mixed, and the mixture was made to have the following layer structure.
Three layers were simultaneously coated (5.5 μm in thickness after drying) on the composite reflective support. Top protective layer Gelatin 1.0 g / m ² 2-imidazolidinone 0.5 g / m ² 1,3-vinylsulfonyl-2-propanol 0.04 g / m ² UV absorbing layer UV absorber A 0.15 g / m ² UV absorber B 0.20 g / m ² High boiling solvent 0.2 g / m ² Gelatin 0.6 g / m ² Silver halide emulsion layer Silver halide emulsion Silver 0.7 g / m ² Coupler (C-6) 37 g / m ² coupler (M-10) 0.17g / m 2 coupler (Y-8) 0.68g / m 2 high-boiling solvent 1 g / m ² gelatin 1.5 g / m ² anti-irradiation dye A 0.03 g / M ² anti-irradiation dye B 0.03 g / m ² 1,3-vinylsulfonyl-2-propanol 0.02 g / m ²

The couplers and other additives used are as follows. High boiling point solvent n-dibutyl phthalate

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Thus, Sample 1 of the present invention was produced. As comparative samples, Samples 2 to 5 were prepared in the same manner as Sample 1 except that the plastic film and the release sheet were changed as shown in Table 1.
Was prepared.

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[Table 1]

When the sample 5 was wound into a roll, the winding was slightly shifted. Using a printer for this sample,
After exposure through a negative film, the following color development,
Processed by bleach-fixing and washing with water and dried. Processing process Processing temperature Processing time Color development 35 ° C 45 seconds Bleaching and fixing 35 ° C 45 seconds Rinse 35 ° C 90 seconds

Color developer 4-amino-3-methyl-N-ethyl-N- (β-methylsulfonamidoethyl) aniline sesquisulfate monohydrate 6.1 g triethanolamine 8.2 g nitrilotriacetic acid 1.5 g 1-hydroxyethylidene-1,1'-diphosphonic acid (60% aqueous solution) 1.6 g potassium hydroxide 4.2 g tivanol SFP 0.8 g potassium carbonate 0.9 g N, N-diethylhydroxylamine 4.0 g water And adjusted to pH 10.10 by adding 10% sulfuric acid or 20% potassium hydroxide aqueous solution. In addition,
CIVANOL SFP is a fluorescent whitening agent manufactured by Ciba-Geigy Actien Gesellschaft.

Bleaching / fixing solution Sodium ferric ethylenediaminetetraacetate monohydrate 48.0 g Disodium ethylenediaminetetraacetate dihydrate 24.0 g Ammonium thiosulfate (70% aqueous solution) 148 ml Sodium bisulfite (anhydrous) 15.0 g Water And adjusted to pH 6.10 with 25% aqueous ammonia or 90% acetic acid.

Washing solution methanol 4.0 ml p-hydroxybenzoic acid-n-butyl ester 0.01 g thiabendazole 0.10 g ethylene glycol 6.0 ml Add water to make 1 liter. pH was 7.45.

In Sample 5, an image distortion occurred at the portion where the winding deviation occurred. Sample 4 had no problem with the image, but was slightly unwieldy when pasted after being peeled off because the plastic film was thin. Samples 1 to 3 had no problem in the images, and could be easily and neatly stuck when they were stuck to another after peeling.

Example 2 Preparation of Transmission Type Composite Support A roll-shaped polystyrene film (50 μm thick) was subjected to a corona discharge treatment, and then an alkali-insoluble polymethyl methacrylate polymer latex was applied (after drying). A transparent support having a thickness of 0.1 μm) and further subjected to a corona discharge treatment and subjected to a hydrophilic treatment was obtained. Using a Meyer bar No. 25 on the back of this plastic film, using a Meyer bar No. 25, dilute the aqueous PSA TS-882 (manufactured by Nippon Carbide Co., Ltd.) to 50% with a solid content of 50%. Then, 27 g / m ^{2 was} applied by a wet method (film thickness after drying: 12 μm), and at the same time as drying was completed, a release sheet was bonded. The release sheet was coated on a polystyrene film having a thickness of 50 μm with a solvent drying type coater using a KNS-
500 2A. B (manufactured by Shin-Etsu Chemical Co., Ltd.) was diluted to 2% with hexane, applied and dried at 3.5 g / m ² (wet) (dry thickness: 0.035 μm), and cured by UV light. Similarly, a support was prepared in which the thicknesses of the plastic film and the release sheet were changed. Preparation of Photographic Material A sample was prepared in the same manner as in Example 1 except that the reflective composite support of Example 1 was changed to a transparent composite support.

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[Table 2]

When the sample 10 was wound into a roll, the winding slightly shifted, and the image was distorted at the portion where the winding was shifted. Sample 9 had no problem with the image,
After the plastic film was peeled off because it was thin, it was a little unwieldy when pasting it on another. Samples 6 to 8 had no problem in the image, and could be easily and neatly stuck when they were stuck to another after peeling.

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The silver halide photographic light-sensitive material of the present invention comprises:
Even when processed with a color developer substantially free of benzyl alcohol, a black-and-white image using a dye image suitable for seal printing can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 7/407 G03C 7/407

Claims (3)

[Claims] 1. A plastic film having a pressure-sensitive adhesive layer and a release sheet on the back surface, and having at least one silver halide emulsion layer on the surface, wherein the silver halide content of the silver halide grains in the silver halide emulsion layer is A silver halide photographic light-sensitive material, wherein the silver halide emulsion layer contains at least one kind of a yellow coupler, at least one kind of a magenta coupler and at least one kind of a cyan coupler. 2. The silver halide photographic material according to claim 1, wherein the total thickness of the silver halide photographic material is 50 to 150 μm. 3. A plastic film having a pressure-sensitive adhesive layer and a release sheet on the back surface, and at least one silver halide emulsion layer on the surface, wherein the silver halide content of the silver halide grains in the silver halide emulsion layer is 95 mol% or more, and the silver halide emulsion layer contains a silver halide photographic light-sensitive material containing at least one of a yellow coupler, at least one of a magenta coupler and at least one of a cyan coupler. An image forming method characterized by treating with a developing solution containing no lacquer.