JPH1165057A - Photosensitive member for heat development and processing member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to obtain a black-and-white picture excellent in a picture keeping quality in a short time and provide low fog, high D-max, high gradation, and to prevent generation of photographic density irregularity. SOLUTION: A photosensitive member, which is used in a heat development picture forming method, contains at least one kind of compound selected from a group of compounds expressed by expressions I to IV. In the expression I, R1 and R2 are the same or different and denote aliphatic hydro-carbon radicals the number of whose carbon atoms is 1 to 20. In the expression II, R1 denotes a bivalent aliphatic hydro-carbon radical the number of whose carbon atoms is 1 to 8. R2 and R3 are the same or different and denote aliphatic hydro-carbon radicals the number of whose carbon atoms is 1 to 20. In the expression III, R1 to R4 are the same or different and denote aliphatic hydro-carbon radicals the number of whose carbon atoms is 1 to 20. In the expression IV, R1 to R4 are the same or different and denote aliphatic hydro-carbon radicals the number of whose carbon atoms is 1 to 20 or aromatic hydro-carbon radicals the number of whose carbon atoms is 6 to 15.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive member and a processing member used in a heat development image forming method, and more particularly to a photosensitive member and a processing member excellent in image storability.

[0002]

[Prior art]

A photographic method using silver halide has been used most widely since it has superior photographic characteristics such as sensitivity, gradation control and resolution compared to other photographic methods, for example, electrophotography and diazo photography. It has been. At present, as image information, black-and-white images have largely changed from black-and-white images to color images due to the large amount of information and ease of expression, but black-and-white images are preferred and used in certain fields, for example, medical relations. I have. Further, in the printing field, plate making materials for color images are also used as black and white images for each printing ink, and there is still a great demand mainly for industrial applications.

[0004] In recent years, the image formation processing method of a photosensitive material using silver halide has been simplified from the conventional wet processing to an instant system incorporating a developing solution, and a dry thermal development processing by heating or the like. A system that can obtain images has been developed from the viewpoint of environmental protection. Such photothermographic materials are described in “Basics of Photographic Engineering (Non-Silver Photography), Corona”, pages 242 to 25.
5, JP-B-43-4921, JP-B-43-49
No. 24, and the like. For example, as a product, in the case of black-and-white systems, 3M company's dry silver sensitive material has been released.

[0005] Like dry silver, silver halide,
In a mono-sheet photosensitive material comprising an organic silver salt and a reducing agent, unused silver halide and organic silver salt remain in the heat-developed image. Therefore, when exposed to intense light or stored for a long period of time, the remaining silver halide or organic silver salt is printed out and the white background is colored, and the contrast is lost. Further, since the reducing agent and the silver halide coexist in the same light-sensitive material, there is a disadvantage that the preservability of the light-sensitive material before processing is poor. A method of obtaining a black color image by dry processing is described in Research Disclosure Magazine (hereinafter abbreviated as RD), September, 1978, pp. 49-51 (RD17326). Since it is an unfixed type containing a silver salt in an image, it has the same drawbacks as described above.

In order to improve these drawbacks, a movable (diffusible) dye is formed or released in the form of an image by heating, and the movable dye is converted into a dye-receiving substance by using various transfer solvents. For example, a method for forming a black-and-white image having improved image storability by transferring to a dye-fixing material containing a mordant, a heat-resistant organic polymer, or the like is disclosed in Japanese Patent Publication No. 3-7861.
No. 7, No. 3-45820.
However, since these methods are methods of transferring after thermal development, the number of steps is large and the processing time is long.

Further, Japanese Patent Application Laid-Open No. 3-260645 discloses a heat development transfer type black-and-white image forming method utilizing a coupling reaction, a method of transferring after development and a method of simultaneously performing development and transfer. However,
This method also requires a high temperature and a long time for processing because it does not have an effective development transfer accelerator.

Japanese Patent Application Laid-Open No. Sho 62-129848 discloses that a black-and-white image can be formed with a transferred dye image by performing thermal development using a small amount of water. However, in order to obtain an image at a transmission density of 2 or more, preferably 3 or more, required for many black-and-white images in a short time by a dye transfer method, the thickness of the photosensitive material, particularly the binder amount, should be reduced as much as possible.
It is necessary to use a large amount of the dye-providing compound. For this reason, there arises a problem that the film quality is reduced and the manufacturing cost is increased. In addition, there is a problem that applications are limited due to a decrease in sharpness due to transfer. Further, it is difficult to synthesize a black dye-donating compound, and it is also difficult to obtain a neutral gray color image by mixing yellow, magenta, and cyan dye-donating compounds.

Further, a method of forming a silver image by thermal development silver salt diffusion transfer using a silver halide photosensitive material is described in JP-A Nos. 62-283332 and 63-198.
No. 050, No. 60-194448, etc., these methods also use a transferred silver image, and can be used to reduce images having a transmission density of 2 or more, preferably 3 or more, and high sharpness. It was difficult to obtain in time and needed improvement.

JP-A-8-179458 and JP-A-8-3
JP-A-39065 and the like disclose an image forming method utilizing silver remaining in a photosensitive material by a heat-developed silver salt diffusion transfer method, and an image having high density and high sharpness can be obtained by this method. However, since many developing agents are incorporated, there have been various problems of image storability.

[0011]

SUMMARY OF THE INVENTION It is an object of the present invention to
In the image forming method, black-and-white images with excellent image storability
Provided are a photosensitive member and a processing member that can be provided.
It is in. Another object of the present invention is to provide the heat-developable image forming method.
Low fog, high Dmax, high gradation, density
Photosensitivity that can give a black-and-white image without unevenness in a short time
It is to provide a member and a processing member.

[0012]

According to the present invention, a photothermographic member containing silver halide and a developing agent and a processing member are superimposed and heated in the presence of water to heat the photothermographic member. Alternatively, a heat-developable photosensitive member used in a heat-developable image forming method for forming an image on a processing member, wherein the photosensitive member is represented by the following general formulas (1), (2), and (3)
And (4) a photothermographic member comprising at least one compound selected from the group of compounds represented by (4), further comprising a silver halide and a developing agent. And a processing member are superposed in the presence of water and heated to form an image on a photosensitive member or a processing member. A processing member characterized by containing at least one compound selected from the group of compounds represented by formulas (1), (2) and (3) is provided, and the above object of the present invention is achieved. You.

[0013]

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(In the formula, R ₁ and R ₂ are the same or different and each represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms.)

[0015]

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(Wherein R₁Is a divalent fat having 1 to 8 carbon atoms
Represents an aliphatic hydrocarbon group. R_TwoAnd R _ThreeAre the same or
Differently, an aliphatic hydrocarbon group having 1 to 20 carbon atoms is represented.
You. )

[0017]

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Wherein R ₁ , R ₂ , R ₃ and R ₄ are
The same or different, and represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms. )

[0019]

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(In the formula, R ₁ , R ₂ and R ₃ are the same or different and each represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 15 carbon atoms.) The present invention will be described in detail, and other objects, advantages and effects of the present invention will become apparent.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION First, the compounds represented by formulas (1) to (4) used in the present invention will be described.
In the general formula (1), R ₁ and R ₂ are the same or different,
Represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms. The aliphatic hydrocarbon group may be substituted with a group containing an oxygen atom. Further, the aliphatic hydrocarbon group may be linear or branched. Preferred examples of R ₁ and R ₂ include methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, Examples include a heptadecyl group and an octadecyl group. Examples of the group containing an oxygen atom include a hydroxyl group, an alkoxy group, a glycidyl group, and an alkylglycidyl group. Note that R ₁ and R ₂
Is the number of carbon atoms including the carbon atom of the substituent. In the general formula (2), R ₁ represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms. The aliphatic hydrocarbon group may be linear or branched. Preferred examples include a methylene group, an ethylene group, a propylene group,
Examples include a tetramethylene group, a hexamethylene group, and a cyclohexylene group. R ₂ and R ₃ are the same or different and represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms. The aliphatic hydrocarbon group may be linear or branched. Preferred examples of R ₂ and R ₃ are the same as the preferred examples of R ₁ and R ₂ in formula (1). In the general formula (3), R ₁ , R ₂ , R ₃ and R ₄ are the same or different and represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms. The aliphatic hydrocarbon group may be linear or branched. Each preferred example is the same as the preferred examples of R ₁ and R _{2 in} the general formula (1). In the general formula (4), R ₁ , R ₂ and R ₃ are the same or different and each have an aliphatic hydrocarbon group having 1 to 20 carbon atoms or 6 to 6 carbon atoms.
And 15 aromatic hydrocarbon groups. The aliphatic hydrocarbon group may be linear or branched. As a preferable example of R _{1 to} R ₃ , R ₁ of the general formula (1)
Aliphatic hydrocarbon group and listed in the preferred embodiment ₁ and R _2, phenyl group, substituted phenyl group (e.g., tolyl group,
(Xylyl group, isobutylphenyl group), naphthyl group and the like.

Specific examples of the compound corresponding to the general formula (1) include the following.

[0023]

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Specific examples of the compound corresponding to the general formula (2) include the following.

[0025]

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Specific examples of the compound corresponding to the general formula (3) include the following.

[0027]

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Specific examples of the compound corresponding to the general formula (4) include the following.

[0029]

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The compounds represented by the general formulas (1) to (4) are not limited to the above specific examples.

When the compounds represented by the general formulas (1) to (4) are used in a photosensitive member according to an embodiment of the present invention, they may be used in a processing member or both members. The above compound may be used in any part of each member. Examples of layers to be added include a protective layer, an emulsion layer, an intermediate layer, a developing agent layer, an alkali (precursor) layer, and an intermediate layer. Further, it may be added to one layer, or may be added to a plurality of layers separately. The compounds represented by the general formulas (1) to (4) may be used alone or in combination of two or more. When a plurality of compounds are used, they may be added to the same layer or may be added separately to a plurality of layers. Further, it may be added separately to the photosensitive member and the processing member.

The compounds represented by the general formulas (1) to (4) may be added in the form of a solution, emulsified and dispersed, or impregnated in a polymer or latex. Preferred is a method of adding the compound in a solution of water or a water-soluble organic solvent or a method of adding the compound in the form of an emulsified dispersion. The addition amount may be arbitrary, but is preferably 1
mg / m ^{2 to} 10 g / m ² . More preferably, when added to the photosensitive member, it is 5 mg / m ^{2 to} 500 mg / m ² , and when added to the processing member, it is 50 mg / m ^{2 to 5} g / m ² .
m ² .

In the present invention, as the base and the base precursor, known compounds used in the development processing of the photothermographic material can be used. Examples of the base precursor include a salt of an organic acid and a base that are decarboxylated by heat, a compound that releases an amine by an intramolecular nucleophilic substitution reaction, Lossen rearrangement or Beckmann rearrangement, and the like. Specific examples thereof are described in U.S. Pat.
657,848 and the known art No. 5 (1991)
(Aztec Co., Ltd., March 22, 2008), pp. 55-86. In addition, European Patent No. 2
No. 10,660, U.S. Pat. No. 4,740,445.
Use of a combination of a basic metal compound hardly soluble in water and a compound capable of forming a complex with a metal ion constituting the basic metal compound (referred to as a complex-forming compound) as described in the specification In this case, the basic metal compound which is hardly soluble in water is preferably added to the photosensitive material, and the complex forming compound is preferably added to the processing layer of the processed image receiving member. The amount of the base or base precursor used is 0.1 to 20 g / m
² , preferably 1 to 10 g / m ² .

In the present invention, it is preferable that, after dampening water is applied to the photothermographic member, the photothermographic member is superposed on a processed image receiving member provided with a processing layer, and is heated and developed. In particular, it is effective when a combination of the above-mentioned basic metal compound which is hardly soluble in water and a complex-forming compound is used as the base precursor. As the binder for the treatment layer, a hydrophilic binder is preferably used. Examples thereof include those described in the aforementioned Research Disclosure and JP-A-64-13546, pages (71) to (75). Specifically, transparent or translucent hydrophilic binders are preferred, for example, gelatin, proteins or cellulose derivatives such as gelatin derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan and polyvinyl alcohol, Synthetic polymer compounds such as polyvinylpyrrolidone and acrylamide polymer are exemplified. Also,
U.S. Pat. No. 4,960,681;
No. 245,260, etc., ie, a homopolymer of a vinyl monomer having —COOM or —SO ₃ M (M is a hydrogen atom or an alkali metal) or a mixture of the vinyl monomers or other vinyl monomers. (For example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd.) are also used. These binders can be used in combination of two or more kinds. In particular, a combination of gelatin and the above binder is preferable.The gelatin may be selected from lime-processed gelatin, acid-processed gelatin, and so-called demineralized gelatin in which the content of calcium and the like is reduced according to various purposes. Is also preferred. The amount of binder is 20 per m ²
g or less, and particularly suitably 10 g or less. It is useful to provide a protective layer on the processed image receiving member.

The photothermographic member containing silver halide preferably used in the present invention is described in JP-A-8-22.
No. 0686, a black-and-white silver image can be obtained, a color image can be obtained by coupling as described in the above-mentioned publicly known examples, and a device which emits a diffusible dye in the form of an image can be used. is there. When a black-and-white silver image is obtained, it is preferable that the silver halide has a silver chloride content of 80 mol% or more, and the processing layer contains a physical development nucleus and a silver halide solvent. 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 include zinc, mercury, lead, cadmium, iron, chromium, nickel,
Heavy metals such as tin, cobalt, copper, ruthenium, or noble metals such as palladium, platinum, silver, and gold, or those known as physical development nuclei such as colloidal particles of chalcogen compounds such as sulfur, selenium, and tellurium are used. it can. These physical development nuclei substances reduce the corresponding metal ion with a reducing agent such as ascorbic acid, sodium borohydride, or hydroquinone to form a metal colloid dispersion, or form a soluble sulfide, selenide or telluride. It is obtained by mixing the solutions to form 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. The preparation of colloidal silver particles is described in US Pat.
8,601 and the like. If necessary, a desalting method for removing an excessive salt known in the method for preparing a silver halide emulsion may be performed. The physical development nuclei preferably have a particle size of 2 to 200 nm. These physical development nuclei are usually added to the processing layer.
10 ^{-3 to} 100 mg / m ² , preferably 10 ^{-2 to} 10 mg / m ²
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. May be created. 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 described in JP-B-47-11386.
-Dithiaoctane, 2,2'-thiodiethanol, 6,
9-dioxa-3,12-dithiatetradecane-1,1
Thioether compounds such as 4-diol;
5 such as uracil and hydantoin described in 179458;
Or a compound having a 6-membered imide ring,
The compound of the following general formula (5) described in JP-A-144319 can be used. Analytica Chemica Ak
Also preferred are trimethyltriazolium thiolate and meso-ion thiolate compounds described in lytica Chemica Acta, 248, pp. 604-614 (1991). The compounds described in JP-A-8-69097 which can fix and stabilize silver halide can also be used as a silver halide solvent.

Formula (5) N (R ₁ ) (R ₂ ) —C (（S) —X—R ₃ (wherein X represents a sulfur atom or an oxygen atom. R ₁ and R ₂ are the same 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. The above-mentioned silver halide solvents may be used in combination. Among the above compounds, compounds having a 5- or 6-membered imide ring such as sulfite, uracil and hydantoin are particularly preferred. In particular, uracil or hydantoin is preferably added as a potassium salt since the reduction in gloss during storage of the processed image receiving member can be improved.

The total silver halide solvent content in the processing layer is from 0.01 to 50 mmol / m ² , 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 photosensitive member.
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, methylpropylglycol, or an alkali or acidic aqueous solution, or may be added to a coating solution after dispersing solid fine particles.

Further, by incorporating a polymer having a repeating unit of vinylimidazole and / or vinylpyrrolidone as a constituent component described in JP-A-8-179458 in the processing layer, the density of the silver image in the photosensitive member can be increased. Is possible.

Hereinafter, a photothermographic member mainly used for forming a color image, particularly for photographing will be described.

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.
As described in JP-A-167743 and JP-A-4-223463, a method of mixing monodispersed emulsions and adjusting the gradation is preferably used. The particle size is preferably from 0.1 to 2 μm, particularly preferably from 0.2 to 1.5 μm. 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, column 50, US Pat. No. 4,628,021, Research Disclosure Magazine (hereinafter abbreviated as RD) N
o. 17,029 (1978), No. 17,643
(December 1978) p. 22-23, ibid., No. 18, 71
6 (November 1979), p. 648, ibid.
05 (November 1989), pages 863 to 865, JP-A-6
JP-A-2-253159, JP-A-64-13546,
JP-A-2-236546 and JP-A-3-110555, and "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte (P.Glafkides, ChemieetPhisiquePhotogra
phique, PaulMontel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photograp)
hic Emulsion Chemistry, FocalPress, 1966), "Manufacture and Coating of Photographic Emulsions" by Zerikuman et al., Focal Press (VLZelikman et al., Making and Coating Photo).
Any of silver halide emulsions prepared by the method described in Graphic Emalusion, Focal Press 1964) can be used.

In the process of preparing a photosensitive silver halide emulsion, it is preferable to carry out so-called desalting for removing excess salts. 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 amount of addition 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 contained in the particles, or may be localized inside or on the surface of the particles. Specifically, emulsions described in JP-A-2-236542, JP-A-1-116637, and JP-A-5-181246 are preferably used.

In the step of forming the grains of the photosensitive silver halide emulsion, as a silver halide solvent, a rhodan salt, ammonia, a 4-substituted thiourea compound, an organic thioether derivative described in JP-B-47-11386, or JP-A-53-1986 is used.
For example, a sulfur-containing compound described in JP-A-144319 can be used.

Other conditions are described in the above-mentioned "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte (P. Glaf).
kides, Chemie et Phisique Photographique, Paul Mon
tel., 1697), "Photographic Emulsion Chemistry" by Duffin, Focal Press (GFDuffin, Photographic Emulsion Che)
mistry, Focal Press, 1966), "Production and Coating of Photographic Emulsions", by Zerikman et al., Focal Press (VLZe)
likman et al., Makingand Coating Photographic Emul
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. An inverse mixing method in which 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 concentration, amount and rate of silver salt and halogen salt to be added may be increased (JP-A-55-142329,
No. 55-158124, U.S. Pat.
No. 7, etc.). Further, the stirring method of 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 in any manner depending on the purpose. The preferred pH range is 2.2-7.0, more preferably 2.5-6.0.

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 sulfur sensitization method, a selenium sensitization method, a chalcogen sensitization method such as a tellurium sensitization method, and gold, platinum, and the like, which are known for an emulsion for a normal photosensitive member, are used. A noble metal sensitization method and a reduction sensitization method using palladium or the like can be used alone or in combination (for example, see JP-A-3-110555).
And JP-A-5-241267. These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Application Laid-Open No. 62-253159). Further, an antifoggant described later can be added after the completion of the chemical sensitization. Specifically, the methods described in JP-A-5-45833 and JP-A-62-40446 can be used. The pH at the time of chemical sensitization is preferably 5.3 to 10.5,
It is more preferably 5.5 to 8.5, and the pAg is preferably 6.0 to 10.5, more preferably 6.8 to 9.0.
It is. The coating amount of the photosensitive silver halide emulsion 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-59-180550, JP-A-64-13546, and JP-A-5-4582.
Sensitizing dyes described in JP-A Nos. 8 and 5-45834. These sensitizing dyes may be used alone, or a combination thereof may be used. The combination of sensitizing dyes is often used for the purpose of adjusting the wavelength of supersensitization or spectral sensitization. . Along with the sensitizing dye, a dye which does not itself have a spectral sensitizing effect or a compound which 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-63-23145). These sensitizing dyes may be added to the emulsion at the time of chemical ripening or before or after chemical ripening.
It may be before or after nucleation of silver halide grains in accordance with the specifications of US Pat. These sensitizing dyes and supersensitizers may be added as a solution of an organic solvent such as methanol, a dispersion such as gelatin, or one solution of a surfactant. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

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 1. Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, page 23-24, page 648, right column, pages 866-868 Color sensitizer ~ page 649, right column 4. Brightener 24, page 648, right column, page 868 5. Fogging prevention 24 ~ 25, page 649, right column, 868 ~ 870 page Agents, stabilizers 6. Light absorbers, 25 ~ Page 26 Page 649 Right column Page 873 Filters-Page 650 Left column Dye, UV absorber 7. Dye image Page 25 650 Page Left column 872 Stabilizer 8. Hardening agent Page 26 651 Left column 874-875 9 Binder page 26 page 651 left column 873-874 10. Plasticizer, page 27 650 page right column 876 lubricant 11. Coating aid, page 26-27 page 650 right column 875-876 surfactant 12. Static 27 pages 650 right column 876-877 Inhibitor 13. Matting agent 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, an organic silver salt is 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 JP-A No. 0,626, columns 52 to 53 and the like. Acetylenes described in U.S. Pat. No. 4,775,613 are also useful. Two or more organic silver salts may be used in combination. The above organic silver salts can be used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per 1 mol of the photosensitive silver halide. Total coating amount of the photosensitive silver halide and organic silver salts 0.05 to 10 g / m ² in terms of silver, and preferably from 0.1-4 g / m ^2. The kind and amount of the binder of the photosensitive member of the present invention are the same as those of the processed image receiving member.

In the present invention, when a color image is obtained by coupling, the photosensitive member contains a coupler.

The coupler usable in the present invention may be a 4-equivalent coupler or a 2-equivalent coupler. Further, the diffusion-resistant group may form a polymer chain. Specific examples of couplers
THJames "The Theory of the Photographic Proces
s ", 4th edition, pages 291 to 334, and 354 to 361
Page, JP-A-58-123533, and JP-A-58-149.
No. 046, No. 58-149047, No. 59-
No. 111148, No. 59-124399, No. 59-174835, No. 59-231439, No. 59-231540, No. 60-2950, No. 60-2951, No. 60-14242. JP, JP-A-60-23474, JP-A-60-66249
JP-A-8-110608 and JP-A-8-14655
No. 2, No. 8-146578, and the like.

It is preferable to use the following couplers. Yellow coupler: a coupler represented by the formula (I) or (II) in European Patent No. 502,424A;
Couplers represented by formulas (1) and (2) in the specification of 513,496A,
A coupler represented by the general formula (I) of claim 1 of JP-A-5-307248; a coupler represented by a general formula D of column 1, lines 45 and 55 of U.S. Pat. No. 5,066,576; Paragraph [000]
8] couplers of the general formula D; EP 498,
The coupler described in claim 1 on page 40 of 38A1, the coupler of the formula (Y) on page 4 of EP 447,969 A1, the column 7-3 of US Pat. No. 4,476,219.
6. Couplers represented by formulas (I) to (IV) on lines 6, 58. Magenta coupler: JP-A-3-39737, 6
-43611, 5-204106, and 4
Couplers described in JP-A-3626. Cyan coupler: JP-A-4-208443, JP-A-4-43345, JP-A-6-67385. Polymer coupler: JP-A-2-44345.

Examples of couplers in which a coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237 and British Patent 2,1.
25,570, European Patent 96,570, West German Patent 3,23
Those described in the specification of 4,533 are preferred.

The photosensitive member may contain the following functional coupler. Couplers for correcting unnecessary absorption of color-forming dyes include yellow colored cyan couplers described in European Patent No. 456,257A1, yellow colored magenta couplers described in the European Patent, and magenta described in U.S. Patent No. 4,833,069. Colored cyan coupler, U.S. Pat.No. 4,837,136 (2), WO92 / 1157
5. A colorless masking coupler represented by the formula (A) of claim 1 of claim 5 (especially the exemplified compound on pages 36 to 45). Examples of the compound (including a coupler) which releases a photographically useful compound residue by reacting with an oxidized developing agent include the following. Development inhibitor releasing compound: a compound represented by formulas (I) to (IV) described on page 11 of EP 378,236A1, a compound represented by formula (I) described on page 7 of EP 436,938 A2. The compound represented by the formula (1) described in JP-A-5-307248
A compound represented by the formulas (I), (II) and (III) described on pages 5 and 6 of EP 440,195 A2, and a compound represented by the formula (1) of JP-A-6-59411. (I)
Compound-ligand releasing compound represented by the formula:
A compound represented by LIG-X described in claim 1 of 4,555,478.

In the photosensitive member used in the present invention, an oxidant formed by silver development is coupled with the above-mentioned coupler to form a dye for the purpose of shortening a developing time, improving sensitivity, and improving image density. A preferred embodiment is one in which a color developing agent capable of developing is incorporated. In this case, U.S. Pat. No. 3,531,
No. 256, phenol or an active methylene coupler as a p-phenylenediamine developing agent;
No. 761,270, a combination of a p-aminophenol developing agent and an active methylene coupler can be used. A combination of a sulfonamide phenol and a 4-equivalent coupler described in U.S. Pat. No. 4,021,240 and JP-A-60-128438 is excellent in raw storage when incorporated in a photosensitive member. This is a preferred combination. When incorporating a color developing agent,
A precursor of a color developing agent may be used. For example, indoaniline compounds described in US Pat. No. 3,342,597, US Pat. No. 3,342,599, Research Disclosure No. 14,850.
And Schiff base-type compounds described in Nos. 15,159,
Examples thereof include aldol compounds described in JP-A-13,924, metal salt complexes described in U.S. Pat. No. 3,719,492, and urethane-based compounds described in JP-A-53-135628.

Further, the sulfonamide phenol-based active compound described in Japanese Patent Application No. Hei.
The combination of a hydrazine-based drug and a coupler described in JP-A-9287 and JP-A-8-234388 is also preferable for use in the photosensitive member of the present invention.

When a diffusion-resistant developing agent is used,
If necessary, an electron transfer agent and / or an electron transfer agent precursor can be used in combination to promote electron transfer between the diffusion-resistant developing agent and the developable silver halide. Particularly preferably, said US Pat.
9, 919 and EP 418,743 are used. Japanese Patent Application Laid-Open No. Hei 2-230
As described in JP-A Nos. 143 and 2-235044, a method of stably introducing a compound into a layer is preferably used. The electron transfer agent or its precursor can be selected from the above-mentioned developing agents or its precursors. It is desirable that the electron transfer agent or its precursor has a higher mobility than the diffusion-resistant developing agent (electron donor).
Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols. In addition, Japanese Patent Laid-Open No. 3-1
An electron donor precursor as described in JP-A-60443 is also preferably used. Further, various reducing agents can be used in the intermediate layer and the protective layer for various purposes such as preventing color mixing and improving color reproduction. Specifically, European Patent Publication No. 524,6
No. 49, 357, 040, JP-A-4-
The reducing agents described in JP-A-249245, JP-A-2-46450 and JP-A-63-186240 are preferably used. Also, Japanese Patent Publication No. 3-63333, Japanese Patent Application Laid-Open
Nos. 150135, 2-46450, 2-
Development inhibitor releasing reducing compounds as described in JP-A-64634, JP-A-3-43735, and EP-A-451,833 can also be used.

In addition, the following reducing agents may be incorporated in the light-sensitive material. Examples of the reducing agent used in the present invention include U.S. Pat. No. 4,500,626, 49-50.
Column, JP-A-4,839,272, JP-A-4,330,6
No. 17, No. 4,590,152, No. 5,
Nos. 177,454 and 5,139,919, and JP-A-60-140335, Nos. (17) to (18).
Pp. 57-40245 and 56-138736.
JP-A-59-178458 and JP-A-59-538.
No. 31, JP-A-59-182449, JP-A-59-1
Nos. 82450, 60-119555 and 6
Nos. 0-128436, 60-128439, 60-198540, 60-18174.
No. 2, No. 61-259253, No. 62-24
Nos. 4044 and 62-131253 and 62
Nos. 131256 and 64-13546.
There are reducing agents and reducing agent precursors described on pages (40) to (57), JP-A-1-120553 and EP-A-220,746A2, pages 78-96. Also, combinations of various reducing agents such as those disclosed in U.S. Pat. No. 3,039,869 can be used.

The developing agent or reducing agent may be incorporated in the processed image receiving member, but is preferably incorporated in the photosensitive member.

In the present invention, the total amount of the developing agent and the reducing agent is from 0.01 to 20 mol, particularly preferably from 0.1 to 10 mol, per mol of silver.

Next, the case where the diffusible dye is released in the form of an image will be described. In the present invention, a non-diffusible coloring material which emits a diffusible dye in correspondence with silver development or reversely is used. This type of compound can be represented by the following general formula [L1]. ((Dye) m-Y) n-Z [L1] Dye represents a diffusible dye group, Y represents a simple linking group, and Z corresponds to or inversely corresponds to a photosensitive silver salt having an image-like latent image. To release diffusible (Dye) m -Y, and L
1 itself represents a non-diffusible group,
m represents an integer of 1 to 5, n represents 1 or 2, m,
When both n are not 1, a plurality of Dyes may be the same or different. Specific examples of the coloring material represented by the general formula [L1] include the following compounds (A) to (D). Incidentally, the following (a) to (c) release diffusible dyes in reverse correspondence to the development of silver halide.
(D) releases a diffusible dye in response to the development of silver halide. (A) U.S. Pat. No. 3,134,764,
362,819, 3,597,200, 3,544,545, 3,482,9
No. 72, JP-B-3-68387, etc., a dye developing agent in which a hydroquinone-based developing agent and a dye component are linked. This dye developer is diffusible in an alkaline environment, but becomes non-diffusible when reacted with silver halide. (B) As described in U.S. Pat. No. 4,503,137, a non-diffusible compound which releases a diffusible dye in an alkaline environment but loses its ability when reacted with silver halide is also used. Can be used. Examples thereof include compounds which release a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat. No. 3,980,479 and the like, and compounds described in US Pat. No. 4,199,354 and the like. And a compound that releases a diffusible dye by an intramolecular rewinding reaction of the isoxazolone ring.

(C) US Pat. No. 4,559,290, EP 220,746 A2, US Pat. No. 4,783,396, and Technical Publication 87-6.
199, JP-A-64-13546, and the like, a non-diffusible compound which reacts with a reducing agent remaining without being oxidized by development to release a diffusible dye can also be used. Examples include U.S. Pat. No. 4,139,389.
No. 4,139,379, JP-A-59
Compounds which release a diffusible dye by a nucleophilic substitution reaction in a molecule after reduction described in U.S. Pat. No. 4,232,107 described in JP-A-185,333 and JP-A-57-84,453. No., JP-A-59-101,6
No. 49, 61-88, 257, RD24,
025 (1984) and the like, compounds which release a diffusible dye by an intramolecular electron transfer reaction after reduction, and are described in West German Patent No. 3,008,588A, JP-A-56-142,530. Gazette, U.S. Pat.
Nos. 8,931,884 and 4,619,884, which release a diffusible dye by cleavage of a single bond after reduction, and US Pat. No. 4,450,223. Examples thereof include a nitro compound which releases a diffusible dye after electron acceptance as described, and a compound which emits a diffusible dye after electron acceptance described in US Pat. No. 4,609,610.

Further, as more preferable, European Patent No. 220,746A2, published technical report 87-6,1
99, U.S. Pat. No. 4,783,396, JP-A-63-201,653, JP-A-63-201,654.
Compounds having an NX bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule described in JP-A Nos. 64-13,546;
No. 6,842, the SO ₂ -X is contained in one molecule.
(X is as defined above) and a compound having an electron-withdrawing group, and a PO-X bond (X is as defined above) and an electron-withdrawing group in a molecule described in JP-A-63-271,344. Compounds having a C-X 'bond (X' has the same meaning as X or-) in one molecule described in JP-A-63-271,341.
SO2-) and a compound having an electron-withdrawing group. Also, Japanese Patent Application Laid-Open Nos.
A compound disclosed in Japanese Patent No. 161342, in which a single bond is cleaved after reduction by a π bond conjugated to an electron accepting group to release a diffusible dye, can also be used. Among them, a compound having an NX bond and an electron-withdrawing group in one molecule is particularly preferable. Specific examples thereof include compounds (1) to (3), (7) to (10) described in European Patent No. 220,746A2 or US Patent No. 4,783,396.
(12), (13), (15), (23) to (26),
(31), (32), (35), (36), (40),
(41), (44), (53)-(59), (64),
(70), compounds (11) to (23) described in Published Technical Report 87-6199, and compounds (1) to (84) described in JP-A-64-13546.

(D) A compound (DRR compound) that is reducible to silver halide or an organic silver salt and releases a diffusible dye when the partner is reduced. Since this compound does not need to use another reducing agent, it is preferable because there is no problem of image contamination due to oxidized decomposition products of the reducing agent. Typical examples thereof are described in U.S. Pat. Nos. 3,928,312 and 4,053.
Nos. 312, 4,055,428, 4,336,322 and JP-A-59-65839.
JP-A-59-69839, JP-A-53-3819
JP, JP-A-51-104343, RD 17, 46
No. 5, U.S. Pat. Nos. 3,725,062, 3,728,113, 3,443,939, JP-A-58-11637, and 57-1.
No. 79840, U.S. Pat. No. 4,500,626 and the like. Specific examples of the DRR compound are described in US Pat. No. 4,500,626, US Pat.
The compounds described in Columns 2 to 44 can be mentioned, and among them, the compounds (1) to
(3), (10) to (13), (16) to (19),
(28)-(30), (33)-(35), (38)-
(40), (42) to (64) are preferred. The compounds described in U.S. Pat. No. 4,639,408, columns 37 to 39 are also useful.

In a system in which a diffusible dye is released in the form of an image and is diffused and transferred to a processed image receiving member, it is preferable to include a mordant in the processed layer. As the mordant, those known in the field of photography can be used, and specific examples thereof are described in U.S. Pat. No. 4,500,626, columns 58 to 59, and
Mordants described on pages 32-41 of JP-A-1-88256, JP-A-62-244043, JP-A-62-244.
No. 036 can be mentioned. Further, a dye-receiving polymer compound as described in U.S. Pat. No. 4,463,079 may be used.

Hydrophobic additives such as coloring materials, couplers, color developing agents, and diffusion-resistant reducing agents are described in US Pat. No. 2,322,0.
It can be introduced into the layer of the photosensitive member by a known method such as the method described in JP-A No. 27. In this case, US Pat. Nos. 4,555,470 and 4,536,4
No. 66, No. 4,536,467, No. 4,
587,206, 4,555,476, 4,599,296, and JP-B3-622.
A high-boiling organic solvent as described in JP-A-56-56 can be used in combination with a low-boiling organic solvent having a boiling point of 50 ° C to 160 ° C, if necessary. Two or more of these dye-donating compounds, nondiffusible reducing agents, high-boiling organic solvents, and the like can be used in combination. The amount of the high boiling organic solvent is 10 g or less, preferably 5 g or less, more preferably 1 g to 0.1 g, per 1 g of the dye-donating compound used. In addition, 1 cc or less per gram of the binder, further 0.5 cc
Below, especially 0.3cc or less is suitable. Tokiko Sho 51-
JP-A-39853, JP-A-51-59943 and JP-A-62-302.
No. 42, for example, can be used as a method of adding a fine particle dispersion. 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, those described as the surfactants described in Research Disclosure, pages 37 to 38 of JP-A-59-157636, can be used. Also, JP-A-7-56267, JP-A-7-56267
-228579, West German Patent No. 1,932,2
The phosphate ester type surfactant described in 99A can also be used. In the present invention, a compound capable of activating development and stabilizing an image at the same time can be used in the photosensitive member. Specific compounds preferably used are described in U.S. Pat. No. 4,500,626, columns 51 to 52.

The photographic photosensitive member includes at least three types of photosensitive layers having different spectral sensitivities and different hues of color materials. Each photosensitive layer may be divided into a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. The three types of photosensitive layers are preferably layers sensitive to any one of blue light, green light, and red light. In this arrangement order, generally, a red-sensitive layer,
The order is a green photosensitive layer and a 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 and the coloring material may be contained in the same layer, but they may be added separately in separate layers as long as they can react. For example, when a layer containing a coloring material which is originally colored is disposed below a layer containing silver halide, a decrease in sensitivity can be prevented. The relationship between the spectral sensitivity of each layer and the hue of the colorant is arbitrary, but if a cyan colorant is used for the red photosensitive layer, a magenta colorant is used for the green photosensitive layer, and a yellow colorant is used for the blue photosensitive layer, the conventional color Projection exposure can be performed directly on paper or the like.

In the light-sensitive member, various non-light-sensitive 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 layers and a lowermost layer. May be provided, and various auxiliary layers such as a back layer may be provided on the side opposite to the support. Specifically, a layer constitution as described in the above patent, an undercoat layer as described in U.S. Pat. No. 5,051,335, JP-A-1-1677838, JP-A-61-20943.
JP-A-1 (Kokai) No. 1 (Japanese Unexamined Patent Publication (Kokai) No. 1) discloses an intermediate layer having a solid pigment as described in
JP-A-120553, JP-A-5-34884 and JP-A-5-34884
Intermediate layers having a reducing agent or a DIR compound as described in JP-A-64634, U.S. Pat. Nos. 5,017,454 and 5,139,919, and JP-A-2-2350.
No. 44, an intermediate layer having an electron transfer agent, a protective layer having a reducing agent as described in JP-A-4-249245, or a combination thereof can be provided.

A thermal solvent may be added to the photosensitive member for the purpose of promoting thermal development. Examples include U.S. Pat. Nos. 3,347,675 and 3,667,9.
Organic compounds having polarity as described in JP-A-59-59 are mentioned. Specifically, amide derivatives (benzamide and the like), urea derivatives (methyl urea, ethylene urea and the like), sulfonamide derivatives (compounds described in Japanese Patent Publication No. 1-40974 and Japanese Patent Publication No. 4-13701, etc.), Polyol compounds (such as sorbitol),
And polyethylene glycols. When the thermal solvent is insoluble in water, it is preferably used as a solid dispersion. The layer to be added may be either a photosensitive layer or a non-photosensitive layer depending on the purpose. The amount of the hot solvent added is from 10% by weight to 500% by weight, preferably 20% by weight, of the binder of the layer to be added.
% By weight to 300% by weight.

The photosensitive member and the processed image receiving member used in the present invention are preferably hardened with a hardener. Examples of hardeners include U.S. Pat. No. 4,678,739, No. 4,
Column 1, JP-A-4,791,042, JP-A-59-1
Nos. 16655, 62-245261, 6
Hardening agents described in, for example, JP-A-1-18942 and JP-A-4-218044 can be used. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.), N-methylol-based hardeners (such as dimethylol urea), boric acid, metaboric acid, and polymer hardeners (compounds described in JP-A-62-234157). These hardeners are used in an amount of 0.001 to 1 g, preferably 0.1 to 1 g per 1 g of the hydrophilic binder.
005 to 0.5 g are used.

In the photosensitive member, various antifoggants or photographic stabilizers and precursors thereof can be used. Specific examples thereof include the aforementioned Research Disclosure, US Pat. Nos. 5,089,378, 4,500,627 and 4,614,7.
No. 02, JP-A-64-13564 (7)-
Pages (9), (57) to (71) and (81) to (9)
7), U.S. Pat. Nos. 4,775,610, 4,626,500, 4,983,494, JP-A-62-174747, and 62-2.
JP-A-39148, JP-A-1-150135, JP-A-2-110557, JP-A-2-178650,
RD 17, 643 (1978) (24) to (25). These compounds are silver 1
It is preferably from 5 × 10 ^-6 to 1 × 10 ^-1 mol, more preferably from 1 × 10 ^-5 to 1 × 10 ^-2 mol per mol.

For the photosensitive member and the processed image receiving member, various surfactants can be used for the purpose of improving coating properties, improving releasability, improving slipperiness, preventing static charge, and accelerating development. Specific examples of the surfactant are known in the art, No. 5 (March 2, 1991)
(Aztec Co., Ltd., 2nd), pp. 136-138, JP-A-62-173463, 62-183.
457, etc. The photosensitive member and the processed image receiving member may contain an organic fluoro compound for the purpose of improving slipperiness, preventing static charge, and improving releasability. Representative examples of the organic fluoro compound include JP-B-57-9053.
No. 8-17, JP-A-61-20944,
And hydrophobic fluorine compounds such as oily fluorine compounds such as fluorine oil or solid fluorine compound resins such as tetrafluoroethylene resin described in JP-A-62-135826 and the like. .

A matting agent can be used for the photosensitive member. As the matting agent, those similar to those used for the processed image receiving member are used. In the present invention, the support for the photosensitive member and the processed image receiving member is not particularly limited as long as it can withstand the processing temperature. Generally, The Photographic Society of Japan, "Basics of Photonic Engineering-Silver Halide Photography", Corona Co., Ltd. (1979) (223)-
Photographic supports such as paper described on page (240) and 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, and further, 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 (especially cast-coated paper) and the like are used. Further, a film obtained by depositing aluminum on a synthetic polymer film is also preferably used. Further, a support which is mainly a styrene polymer having a syndiotactic structure can also be preferably used. Even if a hydrophilic binder and a semiconductive metal oxide such as alumina sol or tin oxide, carbon black or another antistatic agent are applied to the surface of the support opposite to the side where the photosensitive element and the processing element are applied. Good. When using an aluminum vapor-deposited film, it is preferable to add a boron compound to the lowermost layer of the photosensitive member and the processed image receiving member. Preferred boron compounds include
Borate esters.

In particular, JP-A-6-41281 and JP-A-6-43 are difficult to curl as a support for a photosensitive member.
Nos. 581, 6-51426, 6-514
Nos. 37, 6-51442, 6-8296
No. 1, JP-A-6-82960, JP-A-6-82959
JP-A-6-67346, JP-A-6-67346 and JP-A-6-202277
JP-A-6-175282, JP-A-6-175282
No. 1, No. 7-219129, No. 7-2191
The support described in JP-A-44-44 can be preferably used. Also, JP-A-4-124645 and JP-A-5-4.
0321, 6-35092, 6-31
It is preferable to record photographing information and the like using a support having a magnetic layer described in JP 7875 or the like.

The photographing photosensitive member used in the present invention can be processed directly in the same manner as a normal color negative, and can be directly photographed by being loaded into a camera. Japanese Patent Publication No. 2-32615, Jitsuhei 3-
It can also be preferably used for the film unit with a lens described in 39784.

The photosensitive member and / or the processed image receiving member include
A form having a conductive heating element layer as a heating means for heat development may be used. As the heat generating element in this case, those described in JP-A-61-145544 can be used.

The heating temperature in the heat development step is about 50 ° C. to 2
It is 50 ° C, but especially about 60 ° C to 180 ° C is useful. In a system using the release of a diffusible dye, the diffusion transfer step of the dye may be performed simultaneously with the thermal development, or may be performed after the completion of the thermal development step. In the latter case, the heating temperature in the transfer step can be transferred in the range from the temperature in the heat development step to room temperature, but it is particularly preferably at least 50 ° C. and about 10 ° C. lower than the temperature in the heat development step. In a system that uses the release of diffusible dyes, the movement of the dyes is caused only by heat,
The above-mentioned thermal solvent and other solvents may be used to promote dye transfer.

In the present invention, a method of performing development by heating in the presence of a small amount of fountain solution is useful. In this method, the heating temperature is preferably 50 ° C. or higher and the boiling point of water or lower. Examples of the fountain solution used for accelerating development and / or diffusing and transferring the dye include water, a basic aqueous solution containing an inorganic alkali metal salt and an organic base (these bases include The low-boiling solvent or a mixed solution of the low-boiling solvent and water or the basic aqueous solution can be used. Further, a surfactant, an antifoggant, a compound forming a complex with a hardly soluble metal salt, a fungicide, and a bactericide may be contained in the solvent. Any fountain solution may be used as the fountain solution for use in the thermal development and / or diffusion transfer processes. Specifically, distilled water, tap water, well water, mineral water and the like can be used. Further, in the heat developing apparatus using the photosensitive member and the image receiving element of the present invention, the water may be used up or may be circulated and used repeatedly. In the latter case, water containing components eluted from the member will be used. JP-A-63-144354 and JP-A-63-14435.
No. 5, JP-A-62-38460, JP-A-3-21.
The apparatus and water described in Japanese Patent No. 0555 and the like may be used.

In the present invention, the amount of fountain solution applied to the photosensitive member may be not more than the weight of water corresponding to the maximum swelling volume of the entire coating film of the photosensitive member and the processed image receiving member. As a method for applying water, for example, the methods described in JP-A-62-253159, page (5), JP-A-63-85544, and the like are preferably used. Further, the solvent can be used by being encapsulated in a microcapsule or incorporated in the photosensitive member or the dye fixing element or both in advance in the form of a hydrate. The temperature of the water to be applied is as described in JP-A-63-855.
The temperature may be 30 to 60 ° C. as described in Japanese Patent No. 44-44.

The heating method in the development and / or transfer step includes contacting with a heated block or plate, heating plate, hot presser, heating roller, heating drum, halogen lamp heater, infrared and far infrared lamp heater. For example, or by passing through a high-temperature atmosphere. As a method of superposing the photosensitive member and the processed image receiving member, the methods described in JP-A-62-253159 and JP-A-61-147244, page 27 can be applied.

In the heat development process of the present invention, any of various heat development devices can be used. For example, see JP-A-59-752.
Nos. 47, 59-177547 and 59-1
Nos. 81353, 60-18951, 62-25944, Japanese Patent Application No. 6-164421,
An apparatus described in JP-A-6-164422 or the like is preferably used. Examples of commercially available devices include the Pictrostat 100, the Pictrostat 200, the Pictrostats 300 and 330, the Pictrostat 50, and the Pictrostat Digital 40 manufactured by Fuji Photo Film Co., Ltd.
0, the same picture 2000, the same picture 3000, the same picture 4000 and the like can be used.

In the present invention, no additional development stop processing is required after the development processing. However, a development stopping agent may be included in the processing image receiving member, and the development stopping agent 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. More preferably, JP-A-62-25
No. 3,159, pages (31) to (32). Also, a combination described in JP-A-8-54705, in which a zinc salt of mercaptocarboxylic acid is contained in a photosensitive element and a complex-forming compound is contained in a processed image-receiving member, is advantageous. Similarly, a printout inhibitor of silver halide may be included in the processing sheet, and the function may be developed simultaneously with the development. Examples of the printout inhibitor include monohalogen compounds described in JP-B-54-164, trihalogen compounds described in JP-A-53-46020, and halogens described in JP-A-48-45228 as aliphatic carbon compounds. Compound bonding to an atom, Japanese Patent Publication No. 57-8
No. 454, polyhalogen compounds represented by tetrabromoxylene. Further, a development inhibitor such as 1-phenyl-5-mercaptotetrazole described in British Patent No. 1,005,144 is also effective. Further, a viologen compound described in JP-A-8-184936 is also effective. The use amount of the printout inhibitor is preferably 10 ^-4 to 1 mol / Ag, and particularly preferably 10 ^-3 to 10 ^-1 mol / A.
g1 mol.

[0084]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Example 1 First, the production of the black-and-white photosensitive member (K01) will be described.

First, the method for preparing the photosensitive silver halide emulsion (1) will be described. Solution (I) and solution (II) shown in Table 2 were simultaneously added over 9 minutes to a well stirred aqueous solution of gelatin having a composition shown in Table 1 and pH 4.4, and after 3 minutes, (III) ) Solution and (IV) solution were added simultaneously over 10 minutes.

[0086]

[Table 1]

[0087]

Embedded image

[0088]

[Table 2]

After washing with water and desalting (using a precipitant (1) represented by the following formula and adjusting the pH to 3.1 with sulfuric acid) according to a conventional method, 25 g of lime-processed gelatin was added, and the pH was adjusted to 6.0.
3. After adjusting the pAg to 7.6, a preservative (1) represented by the following formula was added, and the mixture was chemically sensitized at 60 ° C. The compounds used for chemical sensitization were added sequentially as shown in Table 3. The particle size was 0.22 μm on average side length and 0.022 standard deviation.
The resulting emulsion was a silver chlorobromide cubic emulsion having a silver bromide content of 2.2 μm in terms of μm. The yield of this emulsion is 704 g.

[0090]

[Table 3]

[0091]

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A method for preparing the silver bromide fine grain emulsion (2) shown in Table 3 will be described. The gelatin aqueous solution having the composition shown in Table 4 that was well stirred was cooled to 30 ° C., and Solution (I) and Solution (II) shown in Table 5 were added simultaneously over 3 minutes and 40 seconds. Thereafter, the solution (III) and the solution (IV) were simultaneously added over 2 minutes while controlling the flow rate of the solution (IV) so that the silver potential became 50 mV.

[0093]

[Table 4]

[0094]

[Table 5]

After washing with water and desalting (adjusted to pH 4.1 with phosphoric acid using a precipitant (2) represented by the following formula) according to a conventional method, 22 g of lime-processed gelatin was added to adjust the pH to 6.0.
1. Adjusted pAg 7.8 (by KBr). As a preservative, a preservative (2) represented by the following formula was used. It was a silver bromide cubic emulsion having a grain size of 0.05 μm. The yield is 630 g.

[0096]

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This photosensitive silver halide emulsion (1) 100
g of a methanol solution containing 9 mg of a sensitizing dye (3) represented by the following formula, and 4,4′-bis [4,6
-Di (naphthyl-2-oxy) pyrimidin-2-ylamino] stilbene-2,2'-disulfonate disodium salt (1.2 cc) in 1% methanol was added, and the mercapto compound (1) represented by the following formula was added. % Aqueous solution 0.65cc
And a water-soluble polymer (1) 1.7 represented by the following formula:
g, and 1.9 g of butyl acrylate latex as a dispersion was further added to prepare a coating solution for an emulsion layer.

[0098]

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Next, a method for preparing a dispersion of the reducing agent 1,5-diphenyl-3-pyrazolidone will be described. 10 g of 1,5-diphenyl-3-pyrazolidone and 0.2 g of Demol made by Kao were added to 90 cc of 5.7% lime-processed gelatin, and dispersed in a mill using glass beads having an average particle diameter of 0.75 mm for 30 minutes. The glass beads were separated to obtain a gelatin dispersion of a reducing agent.

Next, a method for preparing a dispersion of zinc hydroxide will be described. 12.5 g of zinc hydroxide having an average particle size of 0.2 μm, 1 g of carboxymethylcellulose as a dispersant, and 0.1 g of sodium polyacrylate were added to 100 cc of a 4% aqueous gelatin solution, and glass beads having an average particle size of 0.75 mm were used. And dispersed in a mill for 30 minutes. The glass beads were separated to obtain a gelatin dispersion of zinc hydroxide.

A dispersion of a leuco dye and a developer was prepared as shown in Table 6. The oil phase component heated and dissolved at about 60 ° C.
After adding to the aqueous phase component heated to 60 ° C and stirring and mixing,
After dispersion with a homogenizer for 10 minutes at 10,000 rpm, water was added to obtain a uniform dispersion.

[0102]

[Table 6]

[0103]

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The above materials were applied to a support in accordance with the constitution and the amount of addition as shown in Table 7 to prepare a photosensitive material K01.

[0105]

[Table 7]

[0106]

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Next, as shown in Table A, photosensitive materials K02 to K20 obtained by adding the compounds represented by the general formulas (1) to (4) or the comparative compounds to K01 were used.
It was produced in the same manner as described above. At that time, K02-07, K11-2
For 0, the compound was added to a dispersion of the reducing agent (1,5-diphenyl-3-pyrazolidone) and added in the form of a mixed dispersion. In K08, 09, and 10, the above compounds were added as a single emulsified dispersion. When preparing this emulsified dispersion, the surfactant (4) is used.

[0108]

[Table 8]

[0109]

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The preparation of a processing member used for forming an image on a light-sensitive material by processing in combination with a photosensitive member will be described.

First, a method for preparing an emulsified dispersion of the high-boiling organic solvent (A) represented by the following formula will be described.

[0112]

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Preparation of Solution 1 1000 g of gelatin powder was mixed with 6465 ml of ion-exchanged water and a 7% aqueous solution 1 of a preservative (A) represented by the following formula.
Add to 2.5 ml and heat dissolve at 65-70 ° C. Preparation of Solution 2 High-boiling organic solvent (A) 2000 g, high-boiling organic solvent (B) 200 g, surfactant (B) 2 represented by the following formula
5 g are mixed, heated and stirred at 65 to 70 ° C., and made uniform. Preparation of Solution 3 53 g of a surfactant (C) represented by the following formula was added to MEK40.
and heat to 65-70 ° C for dissolution. Emulsification Add Solution 2 and Solution 3 to Solution 1 and stir and emulsify with a mixer. Thereafter, the pressure emulsification treatment is performed twice. After emulsification, 300 ml of ion-exchanged water is added and stirred. Filter and store with nylon mesh 100. As a result, an emulsified dispersion having an average particle size of 0.2 to 0.3 μm was obtained.

[0114]

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The above-mentioned emulsified dispersion and the raw materials shown in Table R1 were applied to a support in accordance with the constitution and the amount of addition shown in Table R1 to prepare a treated member R01.

[0116]

[Table 9]

[0117]

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[0118]

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[0119]

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The compounds represented by the general formulas (1) to (3) or the comparative compounds were added as in Table B except that
R02 to R17 were prepared in the same manner as in R01. At that time, the compound was used in place of the high boiling organic solvent (A) added to the second layer of Table R1.

[0121]

[Table 10]

The photosensitive member (K01) is 610 m wide.
m, a length of 470 mm, and using a semiconductor laser having an output peak wavelength at 670 nm, one pixel (100 μm).
Exposure was performed while changing the amount of light in 1 / 1,000,000 ^second per m ² ). Separately, the processed image receiving member (R01) processed into a roll having a width of 635 mm and a length of 76 m was wound around a roll-shaped core (feeding side) having a diameter of 3 inches so that the application surface faces outward. Thereafter, the leading end of the processed image receiving member was partially wound around another winding core (winding side).

The processing image receiving member was set such that the film surface of the processing image receiving member was in contact with the outer surface of the curved heater during the feeding and winding. Next, the exposed photosensitive member is bonded to water kept at 50 ° C. for 3.2 seconds so that the film surface of the photosensitive member and the film surface of the processed image receiving member are evenly overlapped, and then the processed image receiving member and the photosensitive member are curved. While moving over the heater, the processing was performed by adjusting the speed and the heater temperature so that the photosensitive member was heated at 85 ° C. for 23 seconds until the photosensitive member was separated from the processed image receiving member. Next, the photosensitive member was separated from the processed image receiving member. Thereafter, the photosensitive member was immersed in water for 2.5 seconds in a water washing step on-line, and then squeezed with a roller so that the amount of water on the photosensitive member was about 15 ml / m ² or less. Then 5
It was dried with hot air at 0 ° C. to obtain a processed photosensitive member. Similarly, an image was obtained using K02 to K20 instead of the photosensitive member K01.

After measuring the glossiness of the highest density portion of the dried image at 20 ° with a gloss meter, the gloss was measured at 30 ° C.
Stored in a 75% environment for one week. Thereafter, the gloss was measured in the same manner. The change in gloss before and after storage is summarized in Table A. The smaller the value, the smaller the decrease in glossiness and the better the storability. As can be seen from Table A, K04-20 using the compound of the present invention has a very small change in gloss as compared to the case where no compound is used (K01) and the case where the comparative compound is used (K02, 03). Excellent in image storability. However, as the amount of addition increases, the concentration decreases like K07.

In the same manner, an image was obtained by using K01 and using R02 to R17 in Table B instead of R01. After measuring the glossiness of the highest density portion of the dried image at 20 degrees with a gloss meter, the image was stored for 2 weeks in a 30 ° C.-60% environment. Thereafter, the gloss was measured in the same manner. The change in gloss before and after storage is summarized in Table A. The smaller the value, the smaller the decrease in glossiness and the better the storability. As can be seen from Table B, when the compounds of the present invention were used, R04 to R17 were not used (R02) or the comparative compounds were used (R02).
03), the change in glossiness is very small and the image storability is excellent.

As described above, the photosensitive member, the processing member, and the image forming method of the present invention are excellent in image storability.

[0127]

According to the heat development image forming method using the photosensitive member and the processing member provided by the present invention, a black-and-white image excellent in image storability can be obtained in a short time. This black and white image has low fog, high Dmax, and high gradation, and has no density unevenness.

Claims (2)

[Claims] Claims: 1. A silver halide and a developing agent are contained.
Laminate photothermographic member and processing member in the presence of water
Heating the photothermographic member or processing member
Used in a heat development image forming method for forming an image on a surface
An image photosensitive member, wherein the photosensitive member has the following general formula:
Compounds represented by (1), (2), (3) and (4)
Contains at least one compound selected from
A photothermographic member, characterized in that: Embedded image(Where R₁And R_TwoAre the same or different
Represents an aliphatic hydrocarbon group of Formulas 1 to 20. )(Where R₁Is a divalent aliphatic hydrocarbon having 1 to 8 carbon atoms
Represents a group. R_TwoAnd R _ThreeAre the same or different, charcoal
Represents an aliphatic hydrocarbon group having a prime number of 1 to 20; )(Where R₁, R_Two, R_ThreeAnd R_FourAre the same or different
Represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms. )(Where R₁, R_TwoAnd R_ThreeAre the same or different
And an aliphatic hydrocarbon group having 1 to 20 carbon atoms or 6 carbon atoms.
To 15 aromatic hydrocarbon groups. ) 2. A photothermographic image in which an image is formed on a photosensitive member or a processing member by superposing and heating a photothermographic member containing silver halide and a developing agent and a processing member in the presence of water. A processing member used in a forming method, wherein the processing member contains at least one compound selected from the compound group represented by the general formulas (1), (2) and (3) according to claim 1. A processing member characterized in that: