JPH09281675A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to obtain color images having always good graininess with simple thermal development processing by superposing an imagewise exposed photosensitive member and a processing member on each other and subjecting the members to thermal development under specific conditions, then reading the image information on the photosensitive member and forming color images on another recording material. SOLUTION: The photosensitive member N having at least three kinds of photosensitive layers varying in absorption wavelength regions of dyestuff and the processing member contg. bases and/or base precursors are used. After the photosensitive member N is subjected to imagewise exposure, water of the volume of 0.1 to 1 times the volume required for swelling all the coating films exclusive of the back layers of both of the photosensitive member N and the processing member is applied on the photosensitive member N or the processing member and both are superposed on each other in the form that the photosensitive layers and the processing layers face each other. The members are then heated for 5 to 60 seconds at 60 to 100 deg.C to form the images based on the nondiffusive dyestuff on the photosensitive member. The photosensitive member N is peeled from the processing member and the image information is read in the wavelength region where various kinds of the dyestuff may be absorbed by a CCD 5 at a film plane temp. of <=60 deg.C within 30 seconds after the end of the development. The color images are thus formed on another recording material (image signal recording medium) 4.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel method for obtaining a color image using a novel photographic material.

[0002]

BACKGROUND OF THE INVENTION In a process known as conventional color photography, so-called color negatives are usually
It includes a layer that records yellow light to form a yellow dye image, a layer that records green light to form a magenta dye image, and a layer that records red light to form a cyan dye image. The developer is oxidized in the process of reducing silver halide grains containing an image to silver, and a dye image is formed by a reaction (coupling) between the oxidized product and a coupler. Undeveloped silver halide and developed silver are removed in a subsequent bleach-fixing process, color paper is exposed through the resulting negative dye image, and a similar print, bleaching and fixing process is followed to obtain a color print. Also, a method is known in which after image information included in the color negative is photoelectrically read, image processing is performed to obtain image information for recording, and a color image is obtained on another print material by using the image information. . In particular, the development of a digital photo printer in which the above image information is converted into a digital signal, and a photosensitive material such as color paper is scanned and exposed by a recording light modulated in accordance with the digital signal to obtain a finished print is being developed.
15593. Digital photo printers are free to edit print images such as combining multiple images or dividing images, editing characters and images, and various image processing such as color / density adjustment, scaling, and edge enhancement. It is possible to output the finished print which is freely edited and image-processed according to the purpose. Also, in conventional printing using surface exposure, it is not possible to reproduce all the image density information recorded on the film in terms of density resolution, spatial resolution, color / density reproducibility, etc. A print in which almost 100% of the recorded image density information is reproduced can be output. The above methods are based on ordinary wet development, bleaching and fixing, and the process is complicated.

On the other hand, as a method for processing a photosensitive material using silver halide, a simple and quick method using heat development has been developed. Examples are 3M dry silver,
Products such as a pictrograph and a pictrostat of Fuji Photo Film Co., Ltd. are known. However, these are black-and-white or color print materials, and no known photosensitive material for photography by thermal development has been hitherto known. As a form of heat development, a method of performing heat development in the presence of a small amount of water and a base and / or a base precursor is known,
For example, Japanese Patent Publication No. 2-51494 discloses such an example. However, the image forming method described therein uses a dye-providing substance that is reducible to photosensitive silver halide and reacts with the photosensitive silver halide by heating to release a hydrophilic dye. The dye released during heat development is transferred to an image receiving material, and the transfer side is used as a color print. On the other hand, Japanese Patent Application No. 7-33
No. 1512 describes a system in which a non-diffusible dye is produced by a coupling reaction between an oxidized product of a developing agent and a coupler during heat development to form a color image on a light-sensitive material. These are excellent methods in which a color image can be quickly obtained by a simple heat development process, but in some cases, the minimum density is increased during reading and only an image with a poor S / N ratio can be obtained, and the graininess is deteriorated. found.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an image forming method using a photosensitive material for photographing by a simple heat development process and always obtaining a color image with good graininess on another material. is there.

[0005]

The above object is to provide at least a photosensitive silver halide, a color-developing agent, on a transparent support,
A photosensitive member comprising a dye-donating coupler and a binder, and having at least three types of photosensitive layers having different light-sensitive wavelength regions and different absorption wavelength regions of the dye formed from the color developing agent and the dye-donating coupler, and a support. Amount required for maximum swelling of the entire coating film excluding the back layer of both the photosensitive member and the processing member after imagewise exposing the photosensitive member using a processing member having a processing layer containing at least a base and / or a base precursor thereon. 0.1 to 1 times the amount of water is applied to the photosensitive member or the processing member, and then the photosensitive member and the processing member are superposed so that the photosensitive layer and the processing layer face each other. After heating for 5 to 60 seconds, an image based on at least three colors of non-diffusible dyes is formed on the photosensitive member, and the photosensitive member is peeled off from the processing member. In order to convert the image information into electrical information, the image information is read within 30 seconds after the development at a film surface temperature of 60 ° C. or less in a wavelength range in which the dye contained in each photosensitive layer of the photosensitive member can absorb. Achieved by an imaging method that obtains a color image on another recording material based on information. Further, the color developing agent is preferably at least one compound selected from the compounds represented by the following general formulas (1) to (5).

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[Chemical 6]

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In the formula, R _{1 to} R ₄ are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkyl carbonamide group, an aryl carbonamide group, an alkyl sulfonamide group, an aryl sulfonamide group, an alkoxy group,
Aryloxy group, alkylthio group, arylthio group,
Alkylcarbamoyl group, arylcarbamoyl group, carbamoyl group, alkylsulfamoyl group, arylsulfamoyl group, sulfamoyl group, cyano group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylcarbonyl group, R ₅ represents a substituted or unsubstituted alkyl group, aryl group or heterocyclic group; Z represents an atomic group forming an aromatic ring (including a heteroaromatic ring), and when Z is a benzene ring, the total value of the Hammett constants (σ) of the substituents is 1 or more. R ₆ represents a substituted or unsubstituted alkyl group. X represents an oxygen atom, a sulfur atom, a selenium atom, or an alkyl group-substituted or aryl-substituted tertiary nitrogen atom. R _7, R ₈ represents a hydrogen atom or a substituent, R _7,
R ₈ may combine with each other to form a double bond or a ring.

[0012]

DETAILED DESCRIPTION OF THE INVENTION According to the research conducted by the present inventor, in a photothermographic material, the development reaction in the photosensitive member is progressing even after the development is completed and the processing member is peeled from the photosensitive member. I found out. If the photosensitive member is left to stand for a long time after development, a coupling reaction occurs in the photosensitive member and the dye concentration increases. Further, when reading the image information on the photosensitive member, if the film surface temperature of the photosensitive member rises, the development reaction remarkably progresses, and the increase of the dye concentration was remarkable. When the image processing is performed on the light-sensitive material in which the dye density of the unexposed area is increased,
It was found that the graininess was remarkably deteriorated. According to the study by the present inventor, it was found that if the image information is read at a film surface temperature of 60 ° C. or less within 30 seconds after the completion of development, the increase in the minimum density is suppressed and the graininess is not deteriorated. The lower limit of the film surface temperature at the time of reading is not particularly limited, but around room temperature is preferable in normal operation.

The silver halide which can be used in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide. The silver halide emulsion used in the present invention may be a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or light fogging. Further, a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases may be used, and silver halides having different compositions may be joined by epitaxial joining. The silver halide emulsion may be monodispersed or polydispersed.
No. 167,743 and No. 4-223,463, the method of mixing the monodisperse emulsion and adjusting the gradation is preferably used. The particle size is 0.1 to 2 μm, in particular 0.
2 to 1.5 μm is preferable. The crystal habits of silver halide grains include those having regular crystals such as cubic, octahedral, and tetrahedral, those having irregular crystal systems such as spheroids and high aspect ratio tabular, and those having twin planes. It may be one having such a crystal defect, or a composite system thereof, or any other. Specifically, US Pat. No. 4,500,626 No. 5
Column 0, No. 4,628,021, Research Disclosure (hereinafter abbreviated as RD) No. 17,029
(1978), No. 17, 643 (December 1978)
Mon., pages 22-23, ibid. No. 18,716 (1979, 1)
(Jan.) 648, pp. 307, 105 (January 1989)
January) pages 863 to 865, JP-A-62-253,159.
No. 64-13,546, JP-A-2-236,54
No. 6, No. 3-110,555 and "The Physics and Chemistry of Photography" by Graphide, published by Paul Monte (P.Glafkides, C
hemie etPhotographique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (G.
F. Duffin, Photographic Emulsion Chemistry, Focal Pre
ss, 1966), "Production and Coating of Photographic Emulsions" by Zelikmann et al., published by Focal Press (VLZelikman et al., Ma.
king and Coating Photographic Emalusion, Focal Pre
Any of the silver halide emulsions prepared by the method described in ss, 1964) can be used.

In the process of preparing the photosensitive silver halide emulsion of the present invention, it is preferable to carry out so-called desalting for removing excess salt. As a means for this, a Nudel washing method performed by gelling gelatin may be used, and inorganic salts composed of polyvalent anions (eg, sodium sulfate), anionic surfactants, anionic polymers (eg, polystyrenesulfonic acid) Sodium) or a precipitation method using a gelatin derivative (for example, aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.). The sedimentation method is preferably used.

The photosensitive silver halide emulsion used in the present invention may contain heavy metals such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron and osmium for various purposes. These compounds may be used alone or in combination of two or more. The addition amount depends on the purpose of use, but is generally about 10 ^-9 to 10 ^-3 mol per mol of silver halide. When it is contained, it may be uniformly added to the particles, or may be localized inside or on the surface of the particles. Specifically, the emulsions described in JP-A-2-236542, JP-A-1-116637, and JP-A-4-126629 are preferably used.

In the step of forming grains of the light-sensitive silver halide emulsion of the present invention, rhodan salt, ammonia, 4-substituted thiourea compound or JP-B-47-11 is used as a silver halide solvent.
No. 386, or an organic thioether derivative described in
For example, a sulfur-containing compound described in 3-144,319 can be used.

For other conditions, see the above-mentioned "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte (P. Glaf).
kides, Chemie et Phisique Photographique, Paul Mon
tel, 1967), Duffin's "Photoemulsion Chemistry", published by Focal Press (GFDuffin, Photographic Emulsion Ch.
emistry, Focal Press, 1966), "Production and Coating of Photographic Emulsion" by Zerikuman et al., Published by Focal Press (VLZe)
likman et al., Making and Coating Photographic Emalu
sion, Focal Press, 1964). That is, any of an acidic method, a neutral method, and an ammonia method may be used, and a method of reacting a soluble silver salt and a soluble halide may be any of a one-sided mixing method, a double-sided mixing method, and a combination thereof. In order to obtain a monodisperse emulsion, a simultaneous mixing method is preferably used. A back mixing method in which the grains are formed in the presence of excess silver ions can also be used. As one type of the double jet method, a so-called controlled double jet method in which pAg in a liquid phase in which silver halide is formed is kept constant can be used.

Further, in order to accelerate the grain growth, the addition concentration, the addition amount and the addition speed of the silver salt and the halogen salt to be added may be increased (JP-A-55-142329 and JP-A-55-158, JP-A-55-142329). No. 124, U.S. Pat. No. 3,650,75
No. 7). Further, the method of stirring the reaction solution may be any known stirring method. The temperature and pH of the reaction solution during the formation of silver halide grains may be set as desired depending on the purpose. The preferred pH range is 2.2 to 8.5, more preferably 2.5 to 6.0.

The photosensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion. For the chemical sensitization of the photosensitive silver halide emulsion of the present invention, a chalcogen sensitizing method such as a sulfur sensitizing method, a selenium sensitizing method, a tellurium sensitizing method, or the like, which is known in emulsions for conventional light-sensitive materials, gold, platinum, A noble metal sensitization method using palladium or the like and a reduction sensitization method can be used alone or in combination (for example, JP-A-3-110,55).
No. 5, Japanese Patent Application No. 4-75,798, etc.). These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Application Laid-Open No. 62-253,159). Further, an antifoggant described later can be added after the completion of the chemical sensitization. Specifically, JP-A-5-45,833 and JP-A-62-4
0,446 can be used. The pH at the time of chemical sensitization is preferably 5.3 to 10.5, more preferably 5.5 to 8.5, and the pAg is preferably 6.0.
１10.5, more preferably 6.8 to 9.0. The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

In order to impart green, red and infrared sensitivity to the photosensitive silver halide used in the present invention, the photosensitive silver halide emulsion is spectrally sensitized with a methine dye or the like. . If necessary, the blue-sensitive emulsion may be subjected to spectral sensitization in the blue region. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Specifically, U.S. Pat.
617,257, JP-A-59-180,550, JP-A-64-13,546, JP-A-5-45,828 and JP-A-5-45,834. These sensitizing dyes may be used alone, or a combination thereof may be used. The combination of sensitizing dyes is often used particularly for the purpose of supersensitization or wavelength adjustment of spectral sensitivity. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a compound that does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. 615, 641 and those described in JP-A-63-23, 145). These sensitizing dyes may be added to the emulsion at or before or after chemical ripening, or according to U.S. Pat. Nos. 4,183,756 and 4,225,666 before and after nucleation of silver halide grains. Good. These sensitizing dyes and supersensitizers may be added as a solution of an organic solvent such as methanol, a dispersion of gelatin or the like, or a solution of a surfactant. The addition amount is generally from 10 ^-8 to 10 per mol of silver halide.
^-2 moles.

The additives used in such a process and the known photographic additives that can be used in the present invention are described in the above-mentioned RD.
No. 17, 643, No. 18, 716 and No. 3
07, 105, and the corresponding portions are summarized in the following table. Type of additive RD17643 RD18716 RD307105 Chemical sensitizer page 23 page 648 right column page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column 866 to 868, supersensitizer, page 649, right column 4. Whitening agent, page 24, page 648, right column, page 868 5. Antifoggant page 24-26 page 649 right column 868-870 page stabilizer 6. Light absorber page 25-26 page 649 right column page 873 filter dye-page 650 left column ultraviolet absorber 7. dye image stabilizer page 25 650 page left column page 872 8. 8. Hardener page 26 page 651 left column pages 874 to 875 Binder page 26 page 651 left column 873-874 10. Plasticizer, lubricant page 27 page 650 right column page 876 11. Coating aid page 26-27 page 650 right column 875-876 surfactant 12. static 27 Page 650 Right column Page 876-877 Inhibitor 13. Matting agent Page 878-879

In the present invention, an organic metal salt can be used in combination with the photosensitive silver halide as an oxidizing agent. Among such organic metal salts, organic silver salts are particularly preferably used. Organic compounds that can be used to form the above-described organic silver salt oxidizing agents include US Pat.
There are benzotriazoles, fatty acids and other compounds described in No. 0,626, columns 52 to 53 and the like. The acetylene silver described in U.S. Pat. No. 4,775,613 is also useful. Two or more organic silver salts may be used in combination. The above organic silver salt is used in an amount of 0.01 to 1 mol per mole of the photosensitive silver halide.
10 mol, preferably 0.01 to 1 mol, can be used in combination. The total coating amount of the photosensitive silver halide and the organic silver salt is 0.05 to 10 g / m ^{2 in} terms of silver, preferably 0.1 to 10 g / m ² .
4 g / m ² is suitable.

A hydrophilic material is preferably used for the photosensitive material and the binder of the constituent layers. Examples thereof include Research Disclosure and JP-A-64-13, Sho.
No. 546, pages (71) to (75). Specifically, a transparent or translucent hydrophilic binder is preferable, and examples thereof include proteins such as gelatin and gelatin derivatives or cellulose derivatives, starch, gum arabic,
Examples include natural compounds such as polysaccharides such as dextran and pullulan, and synthetic high molecular compounds of polyvinyl alcohol, polyvinylpyrrolidone, and acrylamide polymer sugar.
Also, U.S. Pat. No. 4,960,681, JP-A-62-162
Superabsorbent polymers according to 245,260 No. etc., i.e. -COOM or -SO ₃ M (M is a hydrogen atom or an alkali metal) copolymerizing the homopolymer or the vinyl monomer together or with other vinyl monomers of the vinyl monomer having a (For example, sodium methacrylate, ammonium methacrylate, Sumikagel L- manufactured by Sumitomo Chemical Co., Ltd.)
5H) is also used. These binders can be used in combination of two or more kinds. Particularly, a combination of gelatin and the above binder is preferable. Gelatin is lime-treated gelatin, acid-treated gelatin,
What is necessary is just to select from what is called demineralized gelatin which reduced the content of calcium etc., and it is also preferable to use in combination. In the present invention, the coating amount of the binder is preferably 30 g or less per 1 m ² , and particularly preferably 15 g or less.

The color developing agent may be p-phenylenediamines or p-aminophenols, but the compounds represented by the above general formulas (1) to (5) are preferably used.

The compounds represented by the general formula (1) are compounds collectively called sulfonamide phenol. Where R
_{1 to} R ₄ are each a hydrogen atom, a halogen atom (for example, a chloro group or a bromo group), an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, an n-butyl group, a t-butyl group),
Aryl groups (eg, phenyl, tolyl, xylyl), alkylcarbonamide groups (eg, acetylamino, propionylamino, butyroylamino),
Arylcarbonamide group (eg, benzoylamino group), alkylsulfonamide group (eg, methanesulfonylamino group, ethanesulfonylamino group), arylsulfonamide group (eg, benzenesulfonylamino group, toluenesulfonylamino group), alkoxy group (eg, methoxy Group, ethoxy group, butoxy group), aryloxy group (eg, phenoxy group), alkylthio group (eg, methylthio group, ethylthio group, butylthio group), arylthio group (eg, phenylthio group, tolylthio group), alkylcarbamoyl group (eg, methylcarbamoyl) Group, dimethylcarbamoyl group, ethylcarbamoyl group, diethylcarbamoyl group, dibutylcarbamoyl group, piperidylcarbamoyl group, morpholylcarbamoyl group), arylcarbamoy Groups (eg, phenylcarbamoyl, methylphenylcarbamoyl, ethylphenylcarbamoyl, benzylphenylcarbamoyl), carbamoyl, alkylsulfamoyl (eg, methylsulfamoyl, dimethylsulfamoyl, ethylsulfamoyl) , Diethylsulfamoyl group, dibutylsulfamoyl group, piperidylsulfamoyl group, morpholylsulfamoyl group), arylsulfamoyl group (for example, phenylsulfamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group) Famoyl group, benzylphenylsulfamoyl group), sulfamoyl group, cyano group, alkylsulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group), arylsulfonyl group (eg, phenylsulfonyl group) 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group), alkylcarbonyl group (for example, acetyl group, Represents a propionyl group, a butyroyl group), an arylcarbonyl group (eg, a benzoyl group, an alkylbenzoyl group), or an acyloxy group (eg, an acetyloxy group, a propionyloxy group, a butyroyloxy group). Among R _{1 to} R ₄ , R ₂ and R ₄ are preferably a hydrogen atom. It is preferable that the sum of the Hammett constants σ _p values of R _{1 to} R ₄ is 0 or more.

R ₅ is an alkyl group (eg, methyl group, ethyl group, butyl group, octyl group, lauryl group, cetyl group,
A stearyl group), an aryl group (for example, phenyl, tolyl, xylyl, 4-methoxyphenyl, dodecylphenyl, chlorophenyl, trichlorophenyl, nitrochlorophenyl, triisopropylphenyl, 4-dodecyloxyphenyl, 3,5-di-
(Methoxycarbonyl) group) or a heterocyclic group (eg, a pyridyl group).

The compounds represented by the general formula (2) are compounds collectively called sulfonylhydrazine. The compound represented by the general formula (4) is a compound generally called carbamoylhydrazine.

In the formula, Z represents an atomic group forming an aromatic ring. The aromatic ring formed by Z needs to be sufficiently electron-attracting in order to impart silver developing activity to the present compound. For this reason, an aromatic ring which forms a nitrogen-containing aromatic ring or has an electron-withdrawing group introduced into a benzene ring is preferably used. As such an aromatic ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a quinoline ring, a quinoxaline ring and the like are preferable.

In the case of a benzene ring, its substituent is
Alkylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group), halogen atom (for example, chloro group,
Bromyl group), alkylcarbamoyl group (eg, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, diethylcarbamoyl group, dibutylcarbamoyl group, piperidylcarbamoyl group, morpholylcarbamoyl group), arylcarbamoyl group (eg, phenylcarbamoyl group, methylphenyl) Carbamoyl group, ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), carbamoyl group, alkylsulfamoyl group (for example, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, dibutylsulfamoyl group) A famoyl group, a piperidylsulfamoyl group, a morpholylsulfamoyl group), an arylsulfamoyl group (for example, a phenylsulfamoyl group,
Methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group),
Sulfamoyl group, cyano group, alkylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group),
Arylsulfonyl group (for example, phenylsulfonyl group,
4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group), alkylcarbonyl group (for example, acetyl group, Examples thereof include a propionyl group, a butyroyl group) and an arylcarbonyl group (for example, a benzoyl group and an alkylbenzoyl group). The sum of the Hammett constant σ values of the above substituents is 1 or more.

The compounds represented by the general formula (3) are collectively called sulfonylhydrazones. The compound represented by the general formula (5) is a compound generally called carbamoylhydrazone.

In the formula, R ₆ represents a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group). X represents an oxygen atom, a sulfur atom, a selenium atom or an alkyl- or aryl-substituted tertiary nitrogen atom, preferably an alkyl-substituted tertiary nitrogen atom. R ₇ and R ₈ represent a hydrogen atom or a substituent, and R ₇ and R ₈ may combine with each other to form a double bond or a ring.

Specific examples of the compounds represented by the general formulas (1) to (5) are shown below, but the compounds of the present invention are not limited thereto.

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Next, the coupler will be described. The coupler in the present invention is a compound that forms a dye by a coupling reaction with the oxidant of the color developing agent. The couplers preferably used in the present invention include compounds having a structure represented by the following general formulas (6) to (17). These are compounds generally called active methylene, pyrazolone, pyrazoloazole, phenol and naphthol, respectively.

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The general formulas (6) to (9) represent couplers called active methylene couplers, in which R ²⁴ represents an acyl group which may have a substituent, a cyano group, a nitro group or an aryl group. , A heterocyclic group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, and an arylsulfonyl group.

In the general formulas (6) to (9), R ²⁵ is an optionally substituted alkyl group, aryl group or heterocyclic group. In the general formula (9), R ²⁶ is an aryl group or a heterocyclic group which may have a substituent. R
Examples of the substituent that ²⁴ , R ²⁵ and R ²⁶ may have include, for example, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a cyano group and a halogen. Examples include various substituents such as an atom, an acylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylamino group, an arylamino group, a hydroxyl group, and a sulfo group.
Preferred examples of R ²⁴ include an acyl group, a cyano group, a carbamoyl group, and an alkoxycarbonyl group.

In the general formulas (6) to (9), Y is a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized product of a developing agent. As an example of Y, groups acting as an anionic leaving group of the 2-equivalent coupler include a halogen atom (eg, chloro group, bromo group), an alkoxy group (eg, methoxy group, ethoxy group), an aryloxy group (eg, phenoxy group, 4-cyanophenoxy group, 4-alkoxycarbonylphenyl group), alkylthio group (for example, methylthio group, ethylthio group, butylthio group), arylthio group (for example, phenylthio group, tolylthio group),
Alkylcarbamoyl group (for example, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group,
Diethylcarbamoyl group, dibutylcarbamoyl group, piperidylcarbamoyl group, morpholylcarbamoyl group), arylcarbamoyl group (eg phenylcarbamoyl group, methylphenylcarbamoyl group, ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), carbamoyl group, alkylsulfamoyl group Group (eg, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, dibutylsulfamoyl group, piperidylsulfamoyl group, morpholylsulfamoyl group), arylsulfa Moyl group (eg, phenylsulfamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group), sulfamoyl group, cyano group Alkylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group), arylsulfonyl group (for example, phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkylcarbonyloxy group (for example, acetyloxy group, propionyloxy group, Butyroyloxy group), arylcarbonyloxy group (for example, benzoyloxy group, toluyloxy group, anisyloxy group), nitrogen-containing heterocyclic group (for example, imidazolyl group, benzotriazolyl group) and the like.

The group acting as the cationic leaving group of the 4-equivalent coupler is a hydrogen atom, a formyl group, a carbamoyl group, or a methylene group having a substituent (the substituent is an aryl group, a sulfamoyl group, a carbamoyl group, Alkoxy group, amino group, hydroxyl group, etc., acyl group,
And a sulfonyl group.

In the general formulas (6) to (9), R ²⁴ and R
²⁵ , R ²⁴ and R ²⁶ may combine with each other to form a ring.

The general formula (10) represents a coupler called a 5-pyrazolone type magenta coupler, in which R ²⁷ represents an alkyl group, an aryl group, an acyl group or a carbamoyl group. R ²⁸ represents a phenyl group or a phenyl group substituted by one or more halogen atoms, an alkyl group, a cyano group, an alkoxy group, an alkoxycarbonyl group, or an acylamino group. Y is the same as in general formulas (6) to (9).

Among the 5-pyrazolone-based magenta couplers represented by the general formula (10), R ²⁷ is preferably an aryl group or an acyl group, and R ²⁸ is a phenyl group substituted with one or more halogen atoms.

Describing these preferable groups in detail, R ²⁷ is phenyl, 2-chlorophenyl, 2-methoxyphenyl, 2-chloro-5-tetradecanamidophenyl, 2-chloro-5- (3-octadecenyl-1-succinimide). Phenyl, 2-chloro-5-octadecylsulfonamidophenyl or 2-chloro-5- [2
-(4-hydroxy-3-t-butylphenoxy) tetradecanamido] aryl group such as phenyl, acetyl, pivaloyl, tetradecanoyl, 2- (2,4-
Di-t-pentylphenoxy) acetyl, 2- (2,4
An acyl group such as -di-t-pentylphenoxy) butanoyl, benzoyl, 3- (2,4-di-t-amylphenoxyacetamido) benzoyl, and these groups may further have a substituent. Is an organic substituent or a halogen atom linked by a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom.

R ²⁸ is 2,4,6-trichlorophenyl,
Substituted phenyl groups such as 2,5-dichlorophenyl and 2-chlorophenyl groups are preferred.

The general formula (11) represents a coupler called a pyrazoloazole coupler, and in the formula, R ²⁹ represents a hydrogen atom or a substituent. Z represents a nonmetallic atom group necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms,
The azole ring may have a substituent (including a condensed ring). Y is the same as in general formulas (6) to (9).

Among the pyrazoloazole type couplers represented by the general formula (11), the imidazo [1,2] described in US Pat.
-B] pyrazoles, pyrazolo [1,5-b] [1,2,4] triazoles described in U.S. Pat. No. 4,540,654, and pyrazolo [[3,25,067] described in U.S. Pat. No. 3,725,067. 5,1-c] [1,2,4] triazoles are preferable, and from the viewpoint of light fastness, pyrazolo [1,5-b] [1,2,4] triazoles are preferable.

The details of the substituents of the azole ring represented by the substituents R ²⁹ , Y and Z are described in, for example, US Pat.
No. 540,654, column 2, line 41 to column 8, line 27. Preferably, JP-A-61
-65245, a pyrazoloazole coupler having a branched alkyl group directly bonded to the 2, 3 or 6-position of a pyrazolotriazole group, JP-A-61-65245.
Pyrazoloazole couplers containing a sulfonamide group in the molecule described in JP-A-61-147254
Pyrazoloazole couplers having an alkoxyphenyl sulfonamide ballast group described in JP-A-62-
209457 or 63-307453, pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position, and JP-A-2-2
No. 01443, a pyrazolotriazole coupler having a carbonamide group in the molecule.

The general formulas (12) and (13) are couplers called phenol couplers and naphthol couplers, respectively, wherein R ³⁰ is a hydrogen atom or --NHCO.
R ³² , -SO ₂ NR ³² R ³³ , -NHSO ₂ R ³² , -NH
COR ³² , -NHCONR ³² R ³³ , -NHSO ₂ NR ³²
It represents a group selected from R ^33. R ³² and R ³³ represent a hydrogen atom or a substituent. In the general formulas (12) and (13), R ³¹
Represents a substituent, 1 is an integer selected from 0 to 2, and m is 0
Represents an integer selected from Y is the same as in general formulas (6) to (9). As R ^{31 to} R ³³ , those mentioned as the substituents of R ^{24 to} R ²⁶ can be mentioned.

Preferred examples of the phenolic coupler represented by the general formula (12) include US Pat. No. 2,369,9.
No. 29, No. 2,801,171, No. 2,772
No. 162, No. 2,895,826, No. 3,77
2,002 and the like, 2-alkylamino-5-alkylphenols, U.S. Pat. No. 2,772,162,
No. 3,758,308, No. 4,126,396
No. 4,334,011, No. 4,327,17
No. 3, West German Patent Publication No. 3,329,729,
9,166,956 and the like, U.S. Patent Nos. 3,446,622, 4,333,999, 4,451,559, and 4,427. , 767, etc., and the like.

Preferred examples of the naphthol coupler represented by the general formula (13) include US Pat. No. 2,474,29.
No. 3, 4,052, 212 and 4,146, 3
No. 96, No. 4,228,233, No. 4,296,
2-carbamoyl-1-naphthol described in US Pat. No. 200 and the like, and 2-carbamoyl-1-naphthol described in US Pat.
Carbamoyl-5-amide-1-naphthol and the like can be mentioned.

The general formulas (14) to (17) are couplers called pyrrolotriazole, and R ⁴² , R ⁴³ and R ⁴⁴ represent a hydrogen atom or a substituent. For Y, general formula (6)-
It is similar to (9). As the substituents for R ⁴² , R ⁴³ and R ⁴⁴ , those described above as the substituents for R ^{24 to} R ²⁶ can be mentioned. Preferred examples of the pyrrolotriazole-based couplers represented by the general formulas (14) to (17) include European Patent No. 48.
No. 8,248A1, No. 491,197A1, No. 5
No. 45,300, a coupler in which at least one of R ⁴² and R ⁴³ is an electron withdrawing group.

In addition, condensed ring phenol, imidazole,
Pyrrole, 3-hydroxypyridine, active methine, 5,
Couplers having a structure such as a 5-fused heterocycle and a 5,6-fused heterocycle can be used.

As the condensed ring phenol couplers, US Pat. Nos. 4,327,173 and 4,564,586 are known.
And the couplers described in JP-A Nos. 4,904,575 and the like can be used.

As the imidazole-based coupler, the couplers described in US Pat. Nos. 4,818,672 and 5,051,347 can be used.

Japanese Patent Application Laid-Open No. 4-1 as a pyrrole coupler
The couplers described in Nos. 88137 and 4-190347 can be used.

As the 3-hydroxypyridine type coupler, couplers described in JP-A-1-315736 can be used.

As the active methine couplers, the couplers described in US Pat. Nos. 5,104,783 and 5,162,196 can be used.

As the 5,5-fused heterocyclic coupler,
Pyrrolopyrazole couplers described in U.S. Pat. No. 5,164,289 and pyrroloimidazole couplers described in JP-A-4-17429 can be used.

As the 5,6-condensed heterocyclic coupler,
Pyrazolopyrimidine couplers described in U.S. Pat. No. 4,950,585, pyrrolotriazine couplers described in JP-A-4-204730, EP 556,70.
The couplers described in No. 0 can be used.

In the present invention, in addition to the above-mentioned coupler, West German Patent Nos. 3,819,051A and 3,823,049 are also included.
No. 4,840,883, US Pat.
No. 4,930, No. 5,051,347, No. 4,4
No. 81,268, European Patent Nos. 304,856A2, 329,036, 354,549A2, 374,781A2, 379,110A2, 386,930A1, 63-141055
Nos. 64-32260 and 32261, JP-A No. 2
No. -297475, No. 2-44340, No. 2-110
555, 3-7938, 3-160440,
Nos. 3-172839, 4-172247, 4-
No. 179949, No. 4-182645, No. 4-184
Nos. 437, 4-188138, 4-188139
And couplers described in JP-A Nos. 4-194847, 4-204532, 4-204731, and 4-204732.

Specific examples of the coupler that can be used in the present invention are shown below, but the present invention is of course not limited thereto.

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Further, the following functional couplers may be contained. As a coupler for correcting unnecessary absorption of a color forming dye, a yellow colored cyan coupler described in EP456,257A1, a yellow colored magenta coupler described in the EP, a magenta colored cyan coupler described in US Pat. No. 4,833,069, US 4,8
No. 37,136, (2), a colorless masking coupler represented by the formula (A) in claim 1 of WO92 / 11575 (especially the exemplified compounds on pages 36 to 45). Compounds (including couplers) that react with oxidized developing agents to release photographically useful compound residues include the following. Development inhibitor releasing compounds: compounds represented by formulas (I) to (IV) described on page 11 of EP 378,236A1, formula (I) described on page 7 of EP 436,938 A2
The compound represented by the formula of Japanese Patent Application No. 4-134523.
A compound represented by the formula (I), a compound represented by the formula (I) (II) or (III) described on pages 5 and 6 of EP 440,195 A2; a compound represented by the formula (I) of claim 1 of Japanese Patent Application No. 4-325564; Compounds represented by the formula: ligand releasing compounds, US Pat.
A compound represented by LIG-X according to claim 1 of 5,478.

Hydrophobic additives such as couplers and color developing agents can be incorporated into the layer of the photographic material by known methods such as the method described in US Pat. No. 2,322,027. In this case, U.S. Pat. No. 4,555,470,
No. 4,536,466, No. 4,536,467, No. 4,587,206, No. 4,555,476, No. 4,599,296, No. 3-62,256, etc. A high boiling organic solvent such as
It can be used in combination with an organic solvent having a low boiling point of 0 ° C to 160 ° C. Two or more kinds of these dye donating couplers and high boiling point organic solvents can be used in combination. The amount of the high boiling organic solvent is 10 per 1 g of the hydrophobic additive used.
g or less, preferably 5 g or less, more preferably 1 g or more.
0.1 g. Further, 1 cc or less, more preferably 0.5 cc or less, particularly 0.3 cc or less is suitable for 1 g of the binder. JP-B-51-39,853, JP-A-51-59,
A dispersion method using a polymer described in U.S. Pat. No. 943 or a method of adding a fine particle dispersion described in JP-A-62-30242 can also be used. In the case of a compound which is substantially insoluble in water, it can be dispersed and contained as fine particles in a binder in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, JP-A-59-15763
No. 6, pages 37 to 38, and the surfactants described in the above-mentioned Research Disclosure can be used. Also, Japanese Patent Application Nos. 5-204325 and 6-19.
The phosphate ester type surfactants described in No. 247 and West German Laid-Open Patent No. 1,932,299A can also be used.

The photosensitive member used in the present invention contains at least three types of photosensitive layers having different spectral sensitivities and different hues of the coloring dyes. Each photosensitive layer may be divided into a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. The above-mentioned three types of photosensitive layers are preferably layers that are sensitive to any of blue light, green light, and red light. In general, the order of arrangement is from the support side to the red photosensitive layer, the green photosensitive layer, and the blue photosensitive layer.
However, other arrangements may be used depending on the purpose. For example, an arrangement as described in column 162 of JP-A-7-152129 may be used. In the present invention, the silver halide, the dye-donating coupler and the color developing agent may be contained in the same layer, but if they are in a reactive state, they may be added separately in separate layers. For example, when the layer containing the color developing agent and the layer containing silver halide are formed as separate layers, the raw storability of the light-sensitive material can be improved. The relationship between the spectral sensitivity of each layer and the hue of the coupler is arbitrary, but when a cyan coupler is used for the red photosensitive layer, a magenta coupler is used for the green photosensitive layer, and a yellow coupler is used for the blue photosensitive layer, it is possible to directly add to conventional color paper and the like. Projection exposure is possible. In the photosensitive member, various non-photosensitive layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, and an antihalation layer are provided between and above the silver halide emulsion layer and the lowermost layer. Various auxiliary layers such as a back layer can be provided on the opposite side of the support. Specifically, the layer structure described in the above patent, the undercoat layer described in US Pat. No. 5,051,335, JP-A-1-167,838, JP-A-6
1-20,943, an intermediate layer having a solid pigment as described in JP-A-1-120,553 and JP-A-5-34,884.
And DIR as described in No. 2-64,634
Intermediate layer with compound, US Pat. No. 5,017,454
No. 5,139,919 and JP-A-2-23504.
4, an intermediate layer having an electron transfer agent as described in
It is possible to provide a protective layer having a reducing agent as described in JP-A-249,245 or a layer in which these are combined.

The dye that can be used in the yellow filter layer and the antihalation layer is preferably a dye that is decolored or removed during development and does not contribute to the density after processing. The fact that the dye in the yellow filter layer and the antihalation layer is erased or removed at the time of development means that the amount of the dye remaining after the processing is 1/3 or less, preferably 1 /
The dye component may be 10 or less, and the components of the dye may be transferred from the photosensitive member to the processing member at the time of development, or may be converted to a colorless compound by reacting at the time of development.

Specifically, European patent application EP 549,4
No. 89A and the dye described in JP-A-7-152129.
xF2 to 6 dyes. Japanese Patent Application No. 6-25980
No. 5, a solid-dispersed dye can also be used. In addition, a mordant and a binder can be dyed with a dye. In this case, as the mordant and dye, those known in the field of photography can be used.
No. 0,626, columns 58 to 59 and JP-A-61-8825.
No. 6, pages 32 to 41, JP-A-62-244043, JP-A-62-244036, and the like. It is also possible to use a compound that reacts with a reducing agent to release a diffusible dye and a reducing agent, to release the active dye with an alkali at the time of development, and transfer and remove the active dye. Specifically, U.S. Pat. Nos. 4,559,290 and 4,783,396, and EP 220,746 A2
And Japanese Patent Application Publication No. 87-6119, paragraphs 0080 to 0081 of Japanese Patent Application No. 6-259805.
It is described in.

It is also possible to use a leuco dye capable of decoloring. Specifically, a silver halide containing a leuco dye which has been previously developed with a developer of an organic acid metal salt in JP-A-1-150,132. A light sensitive material is disclosed. The leuco dye and the developer complex are decolorized by reacting with heat or an alkali agent. Known leuco dyes can be used, and Moriga and Yoshida “Dyes and Chemicals” 9, page 84 (Chemical Industry Association), “New Edition Dye Handbook”, page 242 (Maruzen, 1970),
R. Garner "Reports on the Progress of Appl. Chem"
56, p. 199 (1971), "Dyes and chemicals" 19, 2
30 (Chemical Products Association, 1974), "Coloring Materials" 62,
288 (1989), "Dyeing Industry", 32, 208 and the like. As the developer, a metal salt of an organic acid is preferably used in addition to the acid clay-based developer and phenol formaldehyde resin. As metal salts of organic acids, metal salts of salicylic acids, metal salts of phenol-salicylic acid-formaldehyde resin, rhodan salts, metal salts of xanthogenates, and the like are useful, and zinc is particularly preferable as the metal. Among the above developers, oil-soluble zinc salicylate is disclosed in U.S. Pat.
Nos. 46,941 and Japanese Patent Publication No. 52-1327 can be used.

The coating layer of the photosensitive member of the present invention is preferably hardened with a hardener. Examples of hardeners include U.S. Pat. Nos. 4,678,739, column 41, and 4,791,0.
No. 42, JP-A-59-116,655 and JP-A-62-24
5,261, 61-18,942, JP-A-4-24-2
Examples include hardeners described in No. 18,044. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.), N-methylol hardeners (dimethylolurea, etc.), boric acid, metaboric acid or polymer hardeners (JP-A-62-234157).
And the compounds described in No. 1). These hardeners are used in an amount of 0.001 to 1 g, preferably 0.005 to 0.5 g, per 1 g of the hydrophilic binder.

Various antifoggants or photographic stabilizers and their precursors can be used in the light-sensitive member. Specific examples thereof include the aforementioned Research Disclosure, U.S. Pat. Nos. 5,089,378, 4,500,627 and 4,614,702, and JP-A-64-13564 (7). Pages (9), (57)-(71) and (81)-(97), U.S. Patent No. 4,775,610,
Nos. 4,626,500 and 4,983,494, JP-A-62-174,747 and JP-A-62-239,148.
No., JP-A-1-150,135 and 2-110,55
No. 7, 178, 650, RD 17, 643 (1978), pages (24) to (25) and the like. These compounds are used in an amount of 5 × 10 ^-6 to 1 / mol silver.
× 10 ^-1 mol is preferable, and 1 × 10 ^-5 to 1 × 10
^-2 mol is preferably used.

Various surfactants can be used in the photosensitive member for the purposes of coating aid, improvement of peeling property, improvement of sliding property, antistatic property, acceleration of development and the like. Specific examples of the surfactant are known in the art No. 5 (March 22, 1991, published by Aztec Co., Ltd.), pp. 136-138, JP-A-62-17.
3,463 and 62-183,457. The photosensitive member may contain an organic fluoro compound for the purpose of preventing slippage, preventing static charge, and improving releasability. Representative examples of organic fluoro compounds include Japanese Patent Publication No. 57
No. 9053, columns 8 to 17, JP-A-61-20944
No. 62-135826 and hydrophobic fluorine compounds such as oily fluorine compounds such as fluorine oil or solid fluorine compound resins such as ethylene tetrafluoride resin. Can be

It is preferable that the photosensitive member has slipperiness.
The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. A preferable slip property is 0.2 in dynamic friction coefficient.
5 or less and 0.01 or more. The measurement at this time represents the value when the stainless steel ball having a diameter of 5 mm was conveyed at 60 cm / min (25 ° C., 60% RH). In this evaluation, even when the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level.
Usable slip agents include polyorganosiloxane,
Higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and the like, and polydimethylsiloxane, polydiethylsiloxane, polystyrylmethylsiloxane, polymethylphenylsiloxane, and the like can be used as the polyorganosiloxane. The additional layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane or an ester having a long-chain alkyl group is preferable.

In the present invention, an antistatic agent is preferably used. Examples of these antistatic agents include carboxylic acids and carboxylates, polymers containing sulfonates, cationic polymers, and ionic surfactant compounds. The most preferred antistatic agent is Zn
O ₂ , TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO,
Particle size 0.001 to 1.0 μm crystal in which at least one selected from MoO ₃ and V ₂ O ₅ has a volume resistivity of 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less. Metal oxides or their complex oxides (Sb, P, B, In, S,
Fine particles of Si, C, etc., and fine particles of a sol-shaped metal oxide or a composite oxide thereof. Preferably 5 to 500 mg / m ² as the content of the sensitive material, particularly preferably from 10 to 350 mg / m ^2. The ratio of the amount of the conductive crystalline oxide or the composite oxide to the binder is from 1/300 to
100/1 is preferable, and 1/100 to 1 is more preferable.
00/5.

The composition of the photosensitive member or the processing member described later (including the back layer) is for the purpose of improving physical properties of the film such as dimensional stability, curl prevention, adhesion prevention, film cracking prevention, pressure increase / decrease prevention, etc. Various polymer latices can be included. Specifically, JP-A-62-245258
And the polymer latexes described in JP-A Nos. 62-136648 and 62-110066 can be used.
In particular, when a polymer latex having a low glass transition point (40 ° C. or lower) is used for the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used for the back layer, the curl prevention effect is reduced. can get.

The photosensitive member of the present invention preferably contains a matting agent. The matting agent may be on either the emulsion side or the back side, but is particularly preferably added to the outermost layer on the emulsion side. The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethyl methacrylate, poly (methyl methacrylate /
Methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles, and the like are preferable. 0.8 to 10 as particle size
μm is preferable, and the particle size distribution is preferably narrow. It is preferable that 90% or more of the total number of particles is contained between 0.9 and 1.1 times the average particle size. It is also preferable to simultaneously add fine particles having a size of 0.8 μm or less in order to enhance the matting property.
m), poly (methyl methacrylate / methacrylic acid = 9)
/ 1 (molar ratio), 0.3 µm)), polystyrene particles (0.25 µm), colloidal silica (0.03 µm)
Is mentioned. Specifically, it is described in JP-A-61-88256 (page 29). Other examples include benzoguanamine resin beads, polycarbonate resin beads, AS resin beads, and the like, as disclosed in JP-A-63-274944 and JP-A-63-274.
No. 4952. Other research
The compounds described in the disclosure can be used.

In the present invention, the support for the photosensitive member is transparent and can withstand the processing temperature. In general, the Photographic Society of Japan, "Basics of Photographic Engineering-Silver halide photography-", Corona Co., Ltd. (1979) (2)
Photographic supports such as paper and synthetic polymers (films) described on pages 23 to 240. Specific examples include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, and celluloses (for example, triacetyl cellulose). In addition to this, JP-A-62-1
No. 253, 159, pages (29) to (31), JP-A-1-161,
No. 36, pages 14 to 17; JP-A-63-316,848;
The supports described in JP-A-2-22,651, JP-A-3-56,955, and US Pat. No. 5,001,033 can be used.

Particularly when heat resistance and curl characteristics are severely demanded, a support for a photosensitive member is disclosed in JP-A-6-41281,
6-43581, 6-51426, 6-51
No. 437, No. 6-51442, and Japanese Patent Application No. 4-25184.
No. 5, 4-231825, 4-253545,
4-258828, 4-240122, 4-
No. 221538, No. 5-21625, No. 5-1592
6, No. 4-331919, No. 5-199704,
Supports described in JP-A-6-13455 and JP-A-6-14666 can be preferably used. Further, a support which is mainly a styrene polymer having a syndiotactic structure can also be preferably used.

[0127] In order to bond the support and the light-sensitive material constituting layer, it is preferable to perform a surface treatment. Surface activation treatments such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, and the like. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable.
Next, the undercoating method will be described. It may be a single layer or two or more layers. As the binder for the undercoat layer, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, including copolymers starting from monomers selected from maleic anhydride, as a starting material, Examples include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin. Compounds that swell the support include resorcin and p-chlorophenol. In the undercoat layer, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates,
Active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine etc.), epichlorohydrin resin,
Examples thereof include active vinyl sulfone compounds.
SiO ₂ , TiO ₂ , inorganic fine particles or polymethylmethacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

As a support, for example, JP-A-4-14-1
24645, 5-40321, 6-35092
It is preferable to record photographic information and the like using a support having a magnetic recording layer described in Japanese Patent Application Nos. 5-58221 and 5-106979.

The magnetic recording layer is obtained by coating an aqueous or organic solvent-based coating solution in which magnetic particles are dispersed in a binder on a support. Magnetic particles include ferromagnetic iron oxide such as γFe ₂ O _3, Co deposited γFe ₂ O _3, Co-coated magnetite,
Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite can be used. Co
Co-coated ferromagnetic iron oxide, such as γ-Fe ₂ O _3, is preferred. The shape may be needle-like, rice grain-like, spherical, cubic, plate-like or the like. Preferably at least 20 m ² / g in S _BET is the specific surface area, and particularly preferably equal to or greater than 30 m ² / g. The saturation magnetization (σs) of the ferromagnetic material is preferably from 3.0 × 10 ^{4 to} 3.0.
× 10 ⁵ A / m, particularly preferably 4.0 × 10 ⁴ to
2.5 × 100 ⁵ A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, magnetic particles are disclosed in JP-A-6-1610.
As described in No. 32, the surface thereof may be treated with a silane coupling agent or a titanium coupling agent. Also, magnetic particles having a surface coated with an inorganic or organic substance described in JP-A-4-259911 and JP-A-5-81652 can be used.

The binder used for the magnetic particles may be a thermoplastic resin, a thermosetting resin, a radiation-curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer, a natural product described in JP-A-4-219569. Polymers (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. Tg of the above resin is −40 ° C. to 300 ° C.,
The weight average molecular weight is 20,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose derivatives such as cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins and polyvinyl acetal resins, and gelatin is also preferable. Particularly, cellulose di (tri) acetate is preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of the isocyanate-based crosslinking agent include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate,
Isocyanates such as xylylene diisocyanate, reaction products of these isocyanates with polyalcohols (for example, reaction product of 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane), and condensation products of these isocyanates. Examples of the polyisocyanate include, for example, JP-A-6-5935.
No. 7.

As a method for dispersing the above-mentioned magnetic substance in the above-mentioned binder, a kneader, a pin type mill, an annular type mill and the like are preferably used, as in the method described in JP-A-6-35092. JP-A-5-08828
The dispersant described in No. 3 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm, more preferably 0.3 μm to
3 μm. The weight ratio of the magnetic particles to the binder is preferably 0.5: 100 to 60: 100, more preferably 1: 100 to 30: 100. The coating amount of magnetic particles is 0.005 to 3 g / m ² , preferably 0.01.
~ ² g / m ² , more preferably 0.02-0.5 g / m ²
It is. The transmission yellow density of the magnetic recording layer is 0.01 to
0.50 is preferable, 0.03 to 0.20 is more preferable, and 0.04 to 0.15 is particularly preferable. The magnetic recording layer can be provided on the entire back surface of the photographic support by coating or printing, or in a stripe shape. As a method for applying the magnetic recording layer, air doctor, blade, air knife, squeeze, impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray, dip, bar, extrusion, etc. can be used. The coating solution described in 341436 is preferred.

In the magnetic recording layer, lubricity improvement, curl control,
It may have functions such as antistatic, anti-adhesion and head polishing, or may be provided with another functional layer to impart these functions, and at least one kind of particles has a Mohs hardness of 5 or more. The above-mentioned non-spherical inorganic particle abrasives are preferable. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. Photosensitive materials having a magnetic recording layer are described in US Pat. Nos. 5,336,589, 5,250,404, 5,229,259, 5,215,874 and EP466,130. .

The polyester support preferably used in the above-mentioned photosensitive material having the magnetic recording layer will be further described. For details including the photosensitive material, processing, cartridge and examples, refer to Kokai Giho, JP-A-94-6023. (Invention Society; 1994. 3.15). Polyester is formed by using diol and aromatic dicarboxylic acid as essential components, and the aromatic dicarboxylic acid is 2,6-, 1,5.
-, 1,4-, and 2,7-naphthalenedicarboxylic acid,
Terephthalic acid, isophthalic acid, phthalic acid, and diols include diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol. Examples of the polymerized polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is 2,6-naphthalenedicarboxylic acid in an amount of 50 mol% to 10 mol%.
It is a polyester containing 0 mol%. Among them, polyethylene 2,6-naphthalate is particularly preferable. The average molecular weight ranges from about 5,000 to 200,000. The Tg of the polyester is 50 ° C. or higher, and 9
0 ° C. or higher is preferred.

Next, the polyester support is heat-treated at a heat treatment temperature of 40 ° C. or more and less than Tg, more preferably Tg−20 ° C. or more and less than Tg, in order to make it difficult to form a curl. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. This heat treatment time is 0.1 hours or more and 1500 hours or less, and more preferably 0.5 hours or more and 200 hours or less. The heat treatment of the support may be performed in the form of a roll, or may be performed while being transported in the form of a web. The surface is provided with irregularities (for example,
Conductive inorganic fine particles such as SnO ₂ and Sb ₂ O ₅ ) may be applied) to improve the surface condition. It is also desirable to take measures such as applying knurls to the ends and making the ends slightly higher so as to prevent the cut end of the core from appearing. These heat treatments may be performed at any stage after the formation of the support, after the surface treatment, after the application of the back layer (antistatic agent, slip agent, etc.), and after the application of the undercoat. Preferably after application of the antistatic agent. An ultraviolet absorber may be incorporated into this polyester. In order to prevent light piping, the purpose can be achieved by kneading dyes or pigments commercially available for polyesters such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku.

Next, a film cartridge in which a photosensitive member can be loaded will be described. The main material of the patrone used in the present invention may be metal or synthetic plastic. Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, patrone may contain various antistatic agents, such as carbon black, metal oxide particles, nonions,
Anions, cations and betaine-based surfactants or polymers can be preferably used. These antistatic patrones are disclosed in JP-A 1-312537 and 1
No. 3,12,538. Especially 25 ° C, 25
The resistance at% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded in order to impart light shielding properties. The size of the patrone may be the same as the current 135 size.
It is also effective to set the diameter of a cartridge having a size of 25 mm to 22 mm or less. The volume of the patrone case is 30
cm ³ or less, preferably 25 cm ³ or less. The weight of the plastic used for the patrone and the patrone case is preferably 5 g to 15 g.

Further, a patrone for feeding a film by rotating a spool may be used. Further, a structure may be employed in which the leading end of the film is housed in the patrone main body, and the leading end of the film is sent out from the port portion of the patrone by rotating the spool shaft in the film sending direction. These are U
S4, 834, 306 and 5, 226, 613. The above photosensitive member is a Japanese Patent Publication No. 2-32615.
And a film unit with a lens described in JP-B-3-39784.

The treating layer of the treating member used in the present invention contains at least a base and / or a base precursor. An inorganic or organic base can be used as the base. Examples of the inorganic base include hydroxides of alkali metals or alkaline earth metals (for example, potassium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, etc.) described in JP-A-62-209448,
Phosphates (for example, secondary or tertiary phosphates such as dipotassium hydrogen phosphate, disodium hydrogen phosphate, ammonium sodium phosphate, calcium hydrogen phosphate, etc.),
Carbonates (eg, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, magnesium carbonate, etc.), borates (eg, potassium borate, sodium borate, sodium metaborate, etc.), and organic acid salts (eg, potassium acetate, sodium acetate, oxalate) Potassium citrate, sodium oxalate, potassium tartrate, sodium tartrate, sodium malate,
Sodium palmitate, sodium stearate, etc.) and acetylides of alkali metals or alkaline earth metals described in JP-A-63-25208.

Examples of the organic base include ammonia, aliphatic or aromatic amines (for example, primary amines (eg, methylamine, ethylamine, butylamine, n-hexylamine, cyclohexylamine, 2-ethylhexylamine, allylamine, ethylenediamine, 1,4
-Diaminobutane, hexamethylenediamine, aniline, anisidine, p-toluidine, α-naphthylamine, m-phenylenediamine, 1,8-diaminonaphthalene, benzylamine, phenethylamine, ethanolamine, thallium, etc., secondary amine (for example, dimethyl) Amine, diethylamine, dibutylamine, diallylamine, N-methylaniline, N-methylbenzylamine,
N-methylethanolamine, diethanolamine, etc., tertiary amines (for example, N-methylmorpholine, N-hydroxyethylmorpholine, N-methylpiperidine, N-hydroxyethylpiperidine, N, N described in JP-A-62-170954) '-Dimethylpiperazine, N,
N'-dihydroxyethylpiperazine, diazabicyclo [2,2,2] octane, N, N-dimethylethanolamine, N, N-dimethylpropanolamine, N-methyldiethanolamine, N-methyldipropanolamine, triethanolamine, N , N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetrahydroxyethylethylenediamine, N, N,
N ', N'-tetramethyltrimethylene diamine, N-
Methylpyrrolidine, etc.), polyamines (diethylenetriamine, triethylenetetramine, polyethyleneimine,
Polyallylamine, polyvinylbenzylamine, poly-
(N, N-diethylaminoethylmethacrylate), poly- (N, N-dimethylvinylbenzylamine etc.), hydroxylamines (eg hydroxylamine, N-
Hydroxy-N-methylaniline etc.), heterocyclic amines (eg pyridine, lutidine, imidazole, aminopyridine, N, N-dimethylaminopyridine, indole, quinoline, isoquinoline, poly-4-vinylpyridine, poly-2-vinyl) Pyridine), amidines (eg monoamidine, (eg acetamidine, imidazotane, 2-methylimidazole, 1,4,5,6-tetrahydropyrimidine, 2-methyl-1,4,5,6-tetrahydropyrimidine, 2- Phenyl-1,4,5,6-
Tetrahydropyrimidine, iminopiperidine, diazabicyclononene, diazabicycloundecene (DBU)
Etc.), bis or tris or tetraamidine, guanidines (eg, water-soluble monoguanidine (eg, guanidine, dimethylguanidine, tetramethylguanidine, 2-aminoimidazoline, 2-amino-1,4,5)
-Tetrahydropyrimidine, etc.), JP-A-63-70,8
No. 45 water-insoluble mono- or bisguanidine,
Bis, tris, tetraguanidine, quaternary ammonium hydroxides (eg, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, trioctylmethylammonium hydroxide, methylpyridinium hydroxide, etc. )
And the like.

As the base precursor, decarboxylation type, decomposition type, reaction type and complex salt forming type can be used. In the present invention, European Patent Publication 210,660
As described in U.S. Pat. No. 4,740,445, a basic metal compound which is hardly soluble in water as a base precursor and a complex formation reaction with a metal ion constituting the basic metal compound and water as a medium. It is effective to employ a method of generating a base with a combination of compounds that can be used (referred to as complex forming compounds). In this case, it is desirable to add the basic metal compound that is poorly soluble in water to the photosensitive member and the complex-forming compound to the processing member, but the reverse is also possible.

The amount of base or base precursor used is
It is 0.1 to 20 g / m ² , preferably 1 to 10 g / m ² . As the binder of the processing layer, a hydrophilic polymer similar to the photosensitive member can be used. The processing member is preferably hardened with a hardener similarly to the photosensitive member. The same hardening agent as that for the photosensitive member can be used.

As described above, the processing member may contain a mordant for the purpose of transferring and removing the dye used in the yellow filter layer and antihalation layer of the photosensitive member. As the mordant, a polymer mordant is preferable. Examples thereof include polymers having a secondary and tertiary amino group, polymers having a nitrogen-containing heterocyclic moiety, and polymers having a quaternary cation group and having a molecular weight of 5,000 to 20.
000, especially 10,000 to 50,000. For example, U.S. Pat. Nos. 2,548,564 and 2,484,430;
U.S. Pat. No. 3,625,694; vinylpyridine polymer and vinylpyridinium cationic polymer disclosed in JP-A-3148061 and JP-A-6756814;
Polymer mordants crosslinkable with gelatin and the like disclosed in JP-A Nos. 3859096 and 4128538 and British Patent No. 1277453;
Aqueous sol-type mordants disclosed in JP-A Nos. 3,988,088 and 5,271,852, 2,798,063, JP-A-54-115228, JP-A-54-145529, and JP-A-54-126027. Disclosed water-insoluble mordants; reactive mordants capable of forming a covalent bond with the dyes disclosed in U.S. Pat. No. 4,168,976 (Japanese Patent Application Laid-Open No. 54-137333); Id 364
No. 2482, No. 3488706, No. 3557066
Nos. 3,271,147, 3,271,148, JP-A-50-71332, JP-A-53-133028, and JP-A-52-302.
155528, 53-125, and 53-1024.
And mordants disclosed in the specification.
Other examples include mordants described in U.S. Pat. Nos. 2,675,316 and 2,882,156.

In the present invention, the processing member may contain a development stopper, and the development stopper may act simultaneously with the development. The term "development terminator" as used herein means that after appropriate development, the base is quickly neutralized or reacts with the base to reduce the base concentration in the film, and interact with a compound that stops development or silver and silver salts to suppress development. Compound. Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. Further details are described in JP-A-62-253,159, pages (31) to (32). Further, a combination in which a zinc salt of mercaptocarboxylic acid described in Japanese Patent Application No. 6-190529 is contained in a photosensitive member and the complex forming compound described above is contained in a processing member is advantageous. Similarly, a silver halide print-out preventing agent may be included in the processing member so that its function is exhibited simultaneously with development. As an example of the printout prevention agent, Japanese Examined Patent Publication No.
No. 64, monohalogen compounds described in JP-A-53-460.
A trihalogen compound described in No. 20, JP-A-48-452;
Compounds described in No. 28, in which a halogen is bonded to an aliphatic carbon atom, and polyhalogen compounds represented by tetrabromoxylene described in JP-B-57-8454. Further, a development inhibitor such as 1-phenyl-5-mercaptotetrazole described in British Patent 1,005,144 is also effective. In addition, Japanese Patent Application No. 6-337531.
The viologen compounds described in the above publication are also effective.
The use amount of the printout inhibitor is preferably 10 ^-4 to 1.
Mol / Ag 1 mol, particularly preferably 10 ⁻³ to 10 ⁻¹ mol / Ag ¹ mol.

Further, the processing member may contain physical development nuclei and a silver halide solvent so that the silver halide of the photosensitive member is solubilized and fixed to the processing layer at the same time of development. The physical development nucleus is for reducing soluble silver salt diffused from the light-sensitive material to convert it into physical developed silver, and to fix it to the processing layer. Physical development nuclei, heavy metals such as zinc, mercury, lead, cadmium, iron, chromium, nickel, tin, cobalt, copper, ruthenium, or noble metals such as palladium, platinum, silver, gold, or sulfur, selenium, All known physical development nuclei such as colloidal particles of chalcogen compounds such as tellurium can be used. These physical development nuclei substances are prepared by reducing the corresponding metal ions with a reducing agent such as ascorbic acid, sodium borohydride, hydroquinone to form a metal colloid dispersion, or soluble sulfides, selenides or tellurides. Mix the solution,
Obtained by making a colloidal dispersion of water-insoluble metal sulfide, metal selenide or metal telluride. These dispersions are preferably formed in a hydrophilic binder such as gelatin. A method for preparing colloidal silver particles is described in U.S. Pat. No. 2,688,601. If necessary, a desalting method for removing an excessive salt known in the method for preparing a silver halide emulsion may be performed. The size of these physical development nuclei is preferably 2 to 200 nm. These physical development nuclei are usually contained in the processing layer in an amount of 10 ^{−3 to} 100 mg / m ² , preferably 10 ^{−2 to} 10 mg / m ² . Physical development nuclei can be separately prepared and added to a coating solution, but in a coating solution containing a hydrophilic binder, for example, silver nitrate and sodium sulfide, or gold chloride and a reducing agent are reacted. It may be produced. Silver, silver sulfide, palladium sulfide and the like are preferably used as physical development nuclei. When physical developed silver transferred to the complexing agent sheet is used as an image, palladium sulfide, silver sulfide, and the like are preferably used because Dmin is cut off and Dmax is high.

Known silver halide solvents can be used. For example, sodium thiosulfate, thiosulfates such as ammonium thiosulfate, sulfites such as sodium sulfite and sodium bisulfite, potassium thiocyanate,
Thiocyanates such as ammonium thiocyanate, 1,8-di-3,6-dithiaoctane, 2,2'-thiodiethanol, 6,9- described in JP-B-47-11386.
Dioxa-3,12-dithiatetradecane-1,14-
Thioether compound such as diol, Japanese Patent Application No. 6-32
Compounds having a 5- or 6-membered imide ring such as uracil and hydantoin described in JP-A-5350;
The compound of the following general formula (I) described in No. 4319 can be used. Analytica Chemica Acta
Chemica Acta) 248, pp. 604-614 (1991), trimethyltriazolium thiolate is also preferred. The compounds capable of fixing and stabilizing silver halide described in Japanese Patent Application No. 6-206331 can also be used as a silver halide solvent.

General Formula (I) N (R ¹ ) (R ² ) —C (═S) —X—R ^{3 In the} formula, X represents a sulfur atom or an oxygen atom. R ¹ and R ² may be the same or different and each represents an aliphatic group, an aryl group, a heterocyclic residue or an amino group.
R ³ represents an aliphatic or aryl group. R ¹ and R ² or R ² and R ³ may combine with each other to form a 5- or 6-membered heterocycle. You may use together the said silver halide solvent. Among the above compounds, compounds having a 5- or 6-membered imide ring such as sulfite, uracil and hydantoin are particularly preferable. In particular, uracil and hydantoin are preferably added as a potassium salt in terms of improving the deterioration of gloss of the treated member during storage.

The content of the total silver halide solvent in the processing layer is 0.01 to 50 mmol / m ² , and preferably,
0.1 to 30 mmol / m ² . More preferably, 1
２０20 mmol / m ² . The molar ratio is 1/20 to 20 times, preferably 1/10, relative to the amount of silver applied to the light-sensitive material.
It is 10 times, more preferably 1/3 to 3 times. The silver halide solvent may be added to a solvent such as water, methanol, ethanol, acetone, dimethylformamide, methylpropyl glycol or the like, or an alkaline or acidic aqueous solution, or may be dispersed in solid fine particles and added to the coating solution.

Further, the concentration of a silver image in a light-sensitive material is increased by incorporating a polymer having a repeating unit of vinylimidazole and / or vinylpyrrolidone described in Japanese Patent Application No. 6-325350 as a constituent component into the processing layer. Is possible. Like the photosensitive member, the processing member may have various auxiliary layers such as a protective layer, an undercoat layer, a back layer and the like. The processing member is preferably provided with a processing layer on a continuous web. The continuous web of the processing member here, the length of the processing member is sufficiently longer than the long side of the corresponding photosensitive material at the time of processing, when used for processing without cutting a part thereof, A form having a length capable of processing a plurality of light-sensitive materials. Generally, it means that the length of the processing member is 5 times or more and 1000 times or less of the width. The width of the processing member is arbitrary, but it is preferable that it is equal to or larger than the width of the corresponding photosensitive material.

It is also preferable that a plurality of sensitive materials are processed in parallel, that is, a plurality of sensitive materials are arranged and processed. In this case, the width of the processing member is preferably equal to or larger than the width of the photosensitive material × the number of simultaneous processings. Such a continuous web processing member is particularly effective when the length of the photosensitive material is 50 cm or more and when a plurality of photosensitive materials are continuously processed. Further, when such a continuous web processing member is used, it becomes easy to separate the photosensitive material and the processing member after development. It is preferable that the processing member for the continuous web is supplied from a feeding roll, wound on a winding roll, and discarded. Particularly, in the case of a photosensitive material having a large size, disposal is easy. As described above, the handling member of the continuous web is remarkably improved in handleability as compared with the conventional sheet-shaped member.

The thickness of the support used in the treatment member of the present invention is arbitrary, but is preferably thin, and particularly preferably 4 μm or more and 40 μm or less. In this case, since the amount of the processing member per unit volume increases, the processing member roll can be made compact. The material of the support is not particularly limited, and a material that can withstand the processing temperature is used. In general, the Photographic Society of Japan, "Basics of Photographic Engineering-Silver Halide Photography-", published by Corona Co., Ltd. (Showa 5)
4 years) Papers described on pages (223) to (240), photographic supports such as synthetic polymers (films). Specifically, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those containing pigments such as titanium oxide in these films, Synthetic paper made from polypropylene or the like, mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (particularly cast coated paper) and the like are used.

These can be used alone or
It can also be used as a support laminated on one or both sides with a synthetic polymer such as polyethylene. In addition, JP-A-62-253159 (29)-(31)
Page, JP-A-1-161,236 (14)-(17)
Page, JP-A-63-316,848, JP-A-2-22,
No. 651, No. 3-56,955, U.S. Pat.
The support described in No. 1,033 or the like can be used.
Further, a support which is mainly a styrene polymer having a syndiotactic structure can also be preferably used.

On the surface of these supports, a hydrophilic binder and a semiconductive metal oxide such as alumina sol or tin oxide,
Carbon black or another antistatic agent may be applied. A support on which aluminum is deposited can also be preferably used.

In the present invention, as a method for developing a photosensitive member photographed by a camera or the like, the amount required to swell the entire coating film excluding the back layer of both the photosensitive member and the processing member is increased from 0.1 to 1 times. After applying the corresponding water to the photosensitive member or the processing member, the photosensitive member and the processing member are superposed with the photosensitive layer and the processing layer facing each other, and heated at a temperature of 60 ° C. to 100 ° C. for 5 seconds to 60 seconds. Any water may be used as long as it is generally used. Specifically, distilled water, tap water, well water, mineral water and the like can be used. In the present invention, the photosensitive member and / or the processing member are pasted together in a state of being swollen with water and heated.
The state of the film at the time of swelling is unstable, and it is important to limit the amount of water to the above range in order to prevent local uneven coloring. The amount of water required for maximum swelling is determined by immersing the photosensitive member or processing member with the coating film to be measured in the water used, measuring the film thickness when it swells sufficiently, and calculating the maximum swelling amount before applying. It can be determined by reducing the weight of the membrane. An example of a method for measuring the degree of swelling is also described in Photographic Science Engineering, Volume 16, page 449 (1972). As a method for applying water, there is a method in which a photosensitive member or a processing member is immersed in water and excess water is removed with a squeeze roller. However,
It is preferable to apply a certain amount of water to the photosensitive member or the processing member by coating. Further, a plurality of nozzle holes for injecting water are linearly arranged at a constant interval along a direction intersecting the conveying direction of the photosensitive member or the processing member, and a nozzle in the previous period is a photosensitive member or a processing member on the conveying path. A method of spraying water with a water application device having an actuator for displacing the water toward the direction is particularly preferable. The temperature of the applied water is preferably 30C to 60C. As an example of a method of superposing a photosensitive member and a processing member, JP-A-62-253,1.
59 and JP-A 61-147,244.

As the heating method in the developing step, a heated block or plate is brought into contact, or a hot plate, a hot presser, a heat roller, a heat drum, a halogen lamp heater, an infrared or far infrared lamp heater or the like is brought into contact. Alternatively, there is a method of passing through a high temperature atmosphere.
Any of various heat developing apparatuses can be used in the processing of the present invention. For example, Japanese Unexamined Patent Publication Nos.
177, 547, 59-181, 353, 60
-18,951, Japanese Utility Model Application Laid-Open No. 62-25,944, Japanese Patent Application Nos. 4-277,517, 4-243,072, 4-244,693, and 6-164,421. 6
An apparatus described in JP-A-164,422 or the like is preferably used. As a commercially available device, there can be used Pictrostat 100, Pictrostat 200, Pictrostat 300, Pictrostat 330, Pictrostat 50, Pictrograph 3000, Pictograph 2000, etc., manufactured by Fuji Photo Film Co., Ltd. .

The photosensitive member and / or the processing member used in the present invention may have a form having a conductive heating element layer as a heating means for heat development. As the heat generating element of the present invention, those described in JP-A-61-145544 can be used.

When reading the image information of the photosensitive member,
A method of irradiating the entire surface with light in a wavelength region that can be absorbed by at least three dyes or performing slit scanning to measure the amount of reflected light or transmitted light is preferable. Particularly, it is preferable to measure the amount of transmitted light that can take a wide concentration range. In this case, it is preferable to use diffused light because it is possible to remove information such as the matting agent and scratches on the film, rather than using parallel light. Further, it is preferable to use a semiconductor image sensor (for example, an area type CCD or a CCD line sensor) for the light receiving unit.

In the present invention, the image signal thus read is output to form a color image on another recording material. As a method of outputting, normal projection exposure may be used, or image information may be read photoelectrically by measuring the density of transmitted light, and output using the signal. The material to be output need not be a photosensitive material, and may be, for example, a sublimation type thermosensitive recording material, an ink jet material, a full color direct thermosensitive recording material, or the like. An example of a preferred embodiment of the present invention is that after forming a color image by thermal development, the image information is transmitted by using a diffused light and a CCD image sensor without performing an additional process of removing the remaining silver halide and developed silver. After reading photoelectrically by density measurement and converting it to digital signal,
The image is processed and output by a heat development color printer, for example, Pictrography 3000 of Fuji Photo Film Co., Ltd. In this case, a good print can be obtained quickly without using the processing solution used in conventional color photography. Also, in this case,
Since the digital signal can be processed and edited arbitrarily, the photographed image can be freely modified, transformed, processed and output.

[0157]

EXAMPLES Hereinafter, the effects of the present invention will be described in detail with reference to examples.

Example 1 <Preparation Method of Light-Sensitive Silver Halide Emulsion> Well-stirred aqueous gelatin solution (inert gelatin 3 in 1000 ml of water).
0 g, potassium bromide 2 g) and ammonia
Add ammonium nitrate and keep the temperature at 75 ° C. 1000 ml of an aqueous solution containing 1 mol of silver nitrate and 1000 ml of an aqueous solution containing 1 mol of potassium bromide and 0.03 mol of potassium iodide
Was added simultaneously over 78 minutes. After washing with water and desalting, the mixture was redispersed by adding inert gelatin to prepare a silver iodobromide emulsion having an equivalent sphere diameter of 0.76 μm and an iodine content of 3 mol%. The equivalent sphere diameter was measured with a model TA-II manufactured by Coulter Counter. To the above emulsion, potassium thiocyanate at 56 ° C,
Chloroauric acid and sodium thiosulfate were added for optimum chemical sensitization. A sensitizing dye corresponding to each spectral sensitivity was added to this emulsion.
It was added at the time of coating preparation to give color sensitivity.

<Preparation Method of Zinc Hydroxide Dispersion> 31 g of zinc hydroxide powder having a primary particle size of 0.2 μm,
1.6 g of carboxymethyl cellulose, 0.4 g of sodium polyacrylate, 8.5 g of lime-treated ossein gelatin, and 158.5 ml of water were mixed as a dispersant, and the mixture was dispersed in a mill using glass beads for 1 hour. After dispersion
The glass beads were separated by filtration to obtain 188 g of a dispersion of zinc hydroxide.

<Preparation Method of Emulsion Dispersion of Color Developing Agent and Coupler> The oil phase component and the water phase component having the compositions shown in Table 1 are dissolved to form a uniform solution at 60 ° C. Combine the oil phase component and the water phase component in a 1 liter stainless steel container,
The mixture was dispersed at 10,000 rpm for 20 minutes by a dissolver equipped with a disperser having a diameter of 5 cm. To this, warm water in an amount shown in Table 1 was added as post-water and mixed at 2000 rpm for 10 minutes. Thus, an emulsified dispersion of couplers of three colors of cyan, magenta and yellow was prepared.

[0161]

[Table 1]

[0162]

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[0163]

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<Preparation of Dye Composition for Yellow Filter and Antihalation Layer> The dye composition was prepared and added as an emulsified dispersion as follows. The leuco dye, the developer and, if necessary, the high-boiling organic solvent are weighed, and ethyl acetate is added, and the mixture is heated and dissolved at about 60 ° C. to form a uniform solution. For 100 cc of this solution, one surfactant (7) is added. 1.0 g, 6.6% aqueous solution of lime-processed gelatin heated to about 60 ° C. 1
Add 90cc and 10,000 rp for 10 minutes with homogenizer
m. Two types of dye dispersions shown in Table 2 were prepared.

[0165]

[Table 2]

[0166]

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Using the materials thus obtained, a photosensitive member 101 having a multilayer structure shown in Tables 3 and 4 was prepared.

[0168]

[Table 3]

[0169]

[Table 4]

[0170]

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[0171]

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[0172]

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Further, the processing members R- having the contents shown in Tables 5 and 6
1 was created.

[0174]

[Table 5]

[0175]

[Table 6]

[0176]

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[0177]

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<Structure of Image Information Reading Unit> The structure of the reading unit will be described with reference to FIG. FIG. 1 is a view of the reading unit viewed from a direction perpendicular to the conveyance direction of the photosensitive member N indicated by the arrow B.
The photosensitive member N developed by the developing unit is conveyed to the reading unit by a conveyance rotor (not shown) and reaches a predetermined reading position E sandwiched by the conveyance rollers 7 and 8. A light source 11 that emits light toward the reading position E is installed in the reading unit,
A mirror box 9 and a diffusion plate 10 for preventing unevenness in the amount of light are sequentially arranged on the downstream side in the light emission direction (direction of arrow L). Further, a lens 6 is arranged on the downstream side beyond the conveying path of the photosensitive member N, and on the downstream side, C for reading a transmission image by light transmitted through the photosensitive member N is provided.
The CD sensor 5 is arranged. The lens 6 has a function of focusing the light transmitted through the photosensitive member N on the CCD sensor 5. The CCD sensor 5 is a CCD image sensor having an RGB sensor as shown in FIG. 2, and digitally reads an image by light transmitted through the photosensitive member N passing through the reading position E line by line for each color component. In order to suppress the increase in the film surface temperature during reading, a powerful cooling fan 12 is installed to suppress the increase in the film surface temperature.

The formed photosensitive member 101 was cut into a normal 135 negative film size, punched, and loaded into a camera to photograph a person and a Macbeth chart. Water of 40 ° C. was applied to this photographed photosensitive member at 15 cc / m ² (corresponding to 45% of the maximum swelling amount), and then it was overlapped with the processing member R-1 and was heated with a heat drum at 83 ° C. for 20 seconds from the back surface of the photosensitive member. Heated. When the processing member R-1 was peeled off from the photosensitive member 101, a negative image was obtained on the photosensitive member. The elapsed time after the development and the film surface temperature of the photosensitive material were changed as shown in Table 7, and the image information was read by the image information reading device. After image processing on a personal computer, a thermal development printer (PICTROG
RAPHY3000, manufactured by Fuji Photo Film Co., Ltd.), and the graininess of the obtained image was visually determined. Table 7 shows the results. In the table, x indicates that the B, G, and R transmission densities of the unexposed portion when the image information was read by the scanner was 1.5 or more, and the printer output result after the image processing had extremely poor graininess. Means From the results in Table 7, it can be seen that the image is deteriorated when the photosensitive material is left for a long time after the development and the film surface temperature is increased.

[0180]

[Table 7]

Example 2 In the same manner as in Example 1, except that the combination of the color developing agent and the coupler used in the photosensitive member 101 was changed as shown in the following item 8, the photosensitive members 102 to 105 were carried out in the same manner.
It was created. The amount of each material used is equimolar to that of the photosensitive member 101.

[0182]

[Table 8]

When the obtained photosensitive members 102 to 105 were photographed and developed in the same manner as in Example 1, a negative image was obtained on each of the photosensitive members, which was read in the same manner as in Example 1 and after image processing. , Thermal development printer (PICTROGRAPHY3000)
When a film surface temperature of 60 ° C. or lower was read within 30 seconds after development, a good image was obtained. When read at high temperature or after being left for a long time, the graininess was poor.

[0184]

According to the present invention, a color image excellent in graininess and sharpness can be rapidly obtained by a simple heat development treatment.

[Brief description of drawings]

FIG. 1 is a schematic diagram illustrating a configuration of an image information reading unit used in an example.

FIG. 2 is a schematic diagram showing a configuration of a CCD sensor in FIG.

[Explanation of symbols]

 1: Image reading control unit 2: Look-up table 3: Image signal recording unit 4: Image signal recording medium 5: CCD sensor 6: Lens 7, 8: Conveying roller 9: Mirror box 10: Diffuser 11: Light source 12: Cooling fan

Claims (2)

[Claims] 1. A transparent support containing at least a photosensitive silver halide, a color-developing agent, a dye-donating coupler, and a binder, which is formed from the light-sensitive wavelength region and the color-developing agent and the dye-donating coupler. Using a photosensitive member having at least three types of photosensitive layers having different absorption wavelength regions of dyes, and a processing member having a processing layer containing at least a base and / or a base precursor on a support,
After the imagewise exposure of the photosensitive member, 0.1 to 1 times the amount of water required for maximum swelling of the entire coating film excluding the back layer of both the photosensitive member and the processing member is given to the photosensitive member or the processing member. After that, the photosensitive member and the processing member are overlapped with each other so that the photosensitive layer and the processing layer face each other.
At a temperature of 5 to 60 seconds to form an image based on at least three colors of non-diffusible dyes on the photosensitive member, and after peeling the photosensitive member from the processing member, the image information on the photosensitive member is electrically changed. In order to convert it into information, the image information is read within 30 seconds after the development at a film surface temperature of 60 ° C. or less in a wavelength range in which the dye contained in each photosensitive layer of the photosensitive member can absorb, and the image information is separated based on the information. Image forming method for obtaining a color image on the recording material. 2. A color developing agent is represented by the following general formula (1) to
The image forming method according to claim 1, wherein the image forming method is at least one of the compounds represented by (5). Embedded image Embedded image Embedded image Embedded image Embedded image In the formula, R _{1 to} R ₄ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group, an aryloxy group, an alkylthio group. Group, arylthio, alkylcarbamoyl, arylcarbamoyl, carbamoyl, alkylsulfamoyl, arylsulfamoyl, sulfamoyl, cyano, alkylsulfonyl, arylsulfonyl, alkoxycarbonyl, aryloxycarbonyl , An alkylcarbonyl group, an arylcarbonyl group, or an acyloxy group, and R ₅ represents a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic group. Z represents an atomic group forming an aromatic ring (including a heteroaromatic ring), and when Z is a benzene ring, the total value of the Hammett constants (σ) of the substituents is 1 or more. R ₆ represents a substituted or unsubstituted alkyl group.
X represents an oxygen atom, a sulfur atom, a selenium atom, or an alkyl group-substituted or aryl-substituted tertiary nitrogen atom.
R ₇ and R ₈ represent a hydrogen atom or a substituent, and R ₇ and R ₈
May combine with each other to form a double bond or a ring.