JPH11174620A - Thermally processed photosensitive member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermally processed photosensitive member improved in film quality, especially in flaw resistance. SOLUTION: In a thermally processed photosensitive member for forming a silver image having at least one layer of photosensitive silver halide emulsion and at least one layer of hydrophilic colloid containing a reducing agent on the same side on a support, a main photosensitive layer containing photosensitive silver halide of the thermally processed photosensitive member is positioned on the support side from a main layer containing a reducing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic member used for forming a silver image by thermal development, a processing member used for forming a silver image together with the photothermographic member, the photothermographic member, The present invention relates to a photographic member comprising a processing member, and a method for forming a silver image using both of these members, and particularly to a system for obtaining a black-and-white image having high scratch resistance even when used for short-time rapid processing and having good storage stability after processing. It is about.

[0002]

2. Description of the Related Art A photographic method using silver halide is superior to other photographic methods such as electrophotography and diazo photography in photographic characteristics such as sensitivity, gradation control and resolution, and thus has been the most widely used. Has been used for At present, image information has largely changed from black-and-white images to color images due to the large amount of information and ease of expression.
Black and white images are favorably used in medical fields.
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 a great demand mainly for industrial applications.

In recent years, image forming methods for photosensitive materials using silver halide have been changed from conventional wet processing to an instant system incorporating a developing solution, and further to a dry thermal development processing such as heating. A system has been developed that can easily and quickly obtain an image without using a liquid. For such photothermographic materials,
"Basics of Photo Engineering (Non-Silver Photography), published by Corona" 242
Pp.-255, JP-B-43-4921, JP-B-43-
No. 4924, etc. For example, as a product, in the case of black-and-white systems, 3M company's dry silver sensitive material has been released.

[0004] Like dry silver, silver halide,
Monosheet photographic materials comprising an organic silver salt and a reducing agent have a fundamental drawback that the preservability of the photographic material before processing is poor because the reducing agent and silver halide coexist in the same photographic material. doing. In addition, unused silver halide and organic silver salts remain in the heat-developed image. For this reason, when exposed to intense light or stored for a long period of time, there is a disadvantage that the residual silver halide is printed out and a white background is colored. A method of obtaining a black color image by dry processing is described in Research Disclosure Magazine (hereinafter referred to as R).
D) September 1978, pages 49-51 (RD1
No. 7326), this method is also an unfixed type in which a silver salt remains in an image, and has the same drawbacks as described above.

In order to improve these drawbacks, a movable (diffusible) dye is formed or released imagewise by heating, and then the movable dye is transferred to a dye-fixing material to thereby improve image preservation. Are described in Japanese Patent Publication Nos. 3-78617 and 3-45820. However, these methods are transfer methods after thermal development, and therefore have a large number of steps, so that the processing time is long and not suitable for rapid processing.

Further, JP-A-3-260645 discloses that
Regarding a thermal development transfer type black-and-white image forming method using a coupling reaction, a method of transferring after development and a method of simultaneously performing development and transfer are disclosed. However, in this method, an effective development transfer accelerator has not been developed, and long-time processing at a high temperature is required.

Japanese Patent Application Laid-Open No. 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, it is necessary to use a large amount of a dye-donating compound. A problem arises that the thickness is increased, the sharpness is reduced, and the manufacturing cost is increased. 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-62-283332 and JP-A-63-19805.
No. 0, No. 60-194448 and the like,
These methods also use a transferred silver image, and it is difficult to obtain an image with a transmission density of 2 or more, preferably 3 or more, and high sharpness in a short time, and improvement has been required.

JP-A-8-179458 and JP-A-8-339
No. 065 and the like disclose an image forming method using silver remaining on a heat-developable photosensitive member by a heat-developable silver salt diffusion transfer method. In this method, a heat-developable photosensitive member having at least one photosensitive silver halide emulsion layer on a support and containing a reducing agent (developing agent) in the emulsion layer or another hydrophilic colloid layer; Preparing a processing member having at least one physical development nucleus-containing layer on the body and containing a silver halide solvent (fixing agent) in this layer or another hydrophilic colloid layer; After or simultaneously with imagewise exposure of the photosensitive member, the photothermographic material and the processing member are overlapped and thermally developed in the presence of water, whereby the photothermographic member and / or Alternatively, a silver image is formed on the processing member. According to this method, it is possible to obtain an image having a higher density and a higher sharpness than before, but there is a problem that the film quality (scratch resistance) of the photothermographic member is poor.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and has as its object to provide a photothermographic member having improved film quality, especially scratch resistance, and a photothermographic member having the same. It is an object of the present invention to provide a processing member particularly suitable for use in combination with a member, a photographic member comprising the photothermographic member and the processing member, and a method for obtaining a high-density silver image in a short time by using the photographic member. Further, by providing a photographic member comprising a heat-developable photothermographic member and a processing member capable of obtaining a high-density high-density lower low-density image and a good black-and-white image with good sharpness in a short time. is there.

[0011]

The above objects have been achieved by the present invention described below. (1) Thermal development for forming a silver image having at least one photosensitive silver halide emulsion layer and at least one hydrophilic colloid layer containing a reducing agent on the same side on a support A photothermographic member, wherein the main photosensitive layer containing photosensitive silver halide of the photothermographic member is located closer to the support than the main layer containing a reducing agent. (2) In the photothermographic member according to (1), the peak wavelength of the spectral absorption in the gelatin film of at least one layer on the photothermographic member is ± 50 nm of the maximum spectral sensitivity wavelength of the main photosensitive layer. A heat-developable photosensitive member containing at least one water-soluble dye. (3) A processing member used for image formation processing of the photothermographic member according to the above (1) or (2), comprising at least one layer containing a physical development nucleus on a support, wherein Alternatively, a processing member characterized in that another hydrophilic colloid layer contains a silver halide solvent (fixing agent) and at least one thioether compound. (4) The photothermographic member according to (1) or (2), and at least one layer containing a physical development nucleus on a support, and a silver halide solvent is added to the layer or another hydrophilic colloid layer. A photographic member comprising a processing member containing (fixing agent). (5) The photographic member according to claim 4, wherein the processing member contains at least one thioether compound in the layer containing physical development nuclei or another hydrophilic colloid layer. (6) The photothermographic material according to the above (1) or (2) is subjected to imagewise exposure or simultaneously with the imagewise exposure, and at the same time, the photothermographic material is overlapped with the processing member according to the above (3). A method of forming a silver image on the photothermographic member and / or the processing member by heat development in the presence of water.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the photothermographic member will be referred to as a silver halide photographic material or a silver halide photographic sheet. On the other hand, the above-mentioned processing member may be called a processing material or a processing sheet. The layer constitution of the photothermographic member used in the present invention is as follows.

The photothermographic member according to the present invention has at least one photosensitive silver halide emulsion layer and at least one hydrophilic colloid layer containing a reducing agent on the same side of the support. In the present invention, in addition, preferably, at least one alkali supply layer and at least one protective layer are provided. An intermediate layer may be provided between the layers as needed. In addition, the support may be provided with a lowering. The layer structure conventionally known in a heat-developable photographic member for forming a black-and-white image by superposing and developing in the presence of a small amount of water after imagewise exposure consisting of a heat-developable photosensitive member and a processing member is usually From the support side, an alkali supply layer, a reducing agent-containing layer,
The order is a photosensitive silver halide emulsion layer and a protective layer.

In the present invention, any layer structure may be used as long as the main layer containing the photosensitive silver halide of the photothermographic member is located closer to the support than the main layer containing the reducing agent. Here, the main layer containing photosensitive silver halide means a layer having the largest amount of silver halide emulsion coated in the above-mentioned photosensitive silver halide emulsion layers, and has only one emulsion layer. The case means that layer. Further, the main layer containing the reducing agent means a layer having the largest amount of the reducing agent applied in the hydrophilic colloid layer containing the above reducing agent,
When there is only one reducing agent-containing layer, this means that layer. Particularly preferred layer constitution in the present invention (in order from the support side)
Is described below, but is not limited thereto.

Example 1 support / alkali supply layer / photosensitive silver halide emulsion layer / reducing agent-containing layer / protective layer Example 2 support / antihalation layer / alkali supply layer / photosensitive silver halide emulsion layer / reducing agent Containing layer / protective layer Example 3 support / alkali supply layer / primary photosensitive silver halide emulsion layer / reducing agent-containing layer / secondary photosensitive silver halide emulsion layer / protective layer Example 4 support / subbing layer / alkali Supply layer / photosensitive silver halide emulsion layer / reducing agent-containing layer / protective layer Example 5 Support / alkali supply layer / photosensitive silver halide emulsion layer / reducing agent-containing layer / protective layer 1 / protective layer 2 (matting agent) Example 6 support / alkali supply layer / intermediate layer / photosensitive silver halide emulsion layer / reducing agent containing layer / protective layer Example 7 support / alkali supply layer / antihalation layer / photosensitive silver halide emulsion layer / Reducing agent-containing layer / protective layer Example 8 support / alkali supply layer / photosensitive silver halide emulsion layer / intermediate layer / reducing agent-containing layer / protective layer

The thickness of each layer is not particularly limited as long as the function that the layer should have can be sufficiently exhibited.
It is preferable that the thickness is not less than 4 microns and not more than 4 microns.
It is preferably from 2 microns to 2 microns. The layer name referred to in the layer configuration described as a preferred example indicates a main function of the layer and is not limited to this function. For example, the alkali supply layer is mainly composed of a basic metal compound that is hardly soluble in water (as described later, an alkali-generating precursor is formed together with a complex-forming compound that causes a complex-forming reaction with a metal ion of the compound to generate an alkali). Is a compound that
And may also have an antihalation function. The photosensitive silver halide emulsion layer is
The layer containing silver halide sensitized to the spectral sensitivity matched to the light source of the exposure apparatus may contain an auxiliary reducing agent or a stabilizer. The reducing agent-containing layer is a layer mainly containing a reducing agent, and may contain an antioxidant and the like. The protective layer is a layer mainly composed of a binder that physically protects the image forming layer,
Usually contains matting agents, slip agents, charge control agents and the like. The undercoat layer is a layer for enhancing the adhesion between the upper layer and the support, and the intermediate layer is a layer having an isolation function used when it is not preferable that the layers having the respective functions are adjacent to each other in terms of performance.

In the present invention, at least one layer on the heat-developable photosensitive member contains at least one water-soluble dye having a peak wavelength of spectral absorption in the gelatin film within ± 50 nm of the maximum spectral sensitivity wavelength of the main photosensitive layer. It is preferable to contain one kind. As a water-soluble dye, for example, USP2
Pyrazolone oxonol dyes described in 274772, etc., diallylazo dyes described in US Pat. No. 2,956,879, styryl dyes described in US Pat. No. 3,423,207, butadienyl dyes described in US Pat. No. 3,384,487, merocyanine dyes described in US Pat. No. 3,384,487, US Pat. Same 3652284
No. 3,718,472 and the like, merocyanine and oxonol dyes described in US Pat. No. 3,976,661 and the like can be preferably used.

The water-soluble dyes used in the present invention may be used in combination of two or more. The water-soluble dye used in the present invention may be used in any layer such as a subbing layer, an antihalation layer, an alkali supply layer, a photosensitive silver halide emulsion layer, a reducing agent-containing layer, a protective layer, and an intermediate layer. It may be added.

In order to add the water-soluble dye used in the present invention to these layers, the compound may be added as it is to the coating solution for forming the layers or a solvent which does not adversely affect the photographic member, for example, water. Or an alcohol such as methanol or ethanol at a suitable concentration. The preferable addition amount of the water-soluble dye of the present invention is such that the optical density is 0.1 at the peak value of the dye absorption in the coating film.
The amount which becomes 05 or more and 2.0 or less is preferable. Further, the optical density is preferably from 0.1 to 0.8, more preferably from 0.2 to 0.5.
The following are particularly preferred.

In order to form an image using the above photothermographic material, the photothermographic material and the processing member may be combined with the photothermographic material after or after the imagewise exposure. Superimpose and heat develop in the presence of water. This processing member has at least one layer containing a physical development nucleus on a support, and the layer or another hydrophilic colloid layer contains a silver halide solvent (fixing agent). With the combination of the physical development nucleus and the silver halide solvent, the silver halide remaining in the photothermographic member after development is dissolved and precipitated on the physical development nucleus on the processing member, thereby exhibiting a fixing action.

In the present invention, at least one thioether compound is preferably contained in at least one layer of the processing member. The thioether compound preferably used can be represented by the following general formula (1). The general formula (1) R1-O- (CH 2) 2 -S-R2 Formula (1) R1 and R2 represent a monovalent substituent, respectively. R1 and R2 may be linked together to form a ring. Particularly preferred compounds are those represented by the following general formula (1)
a) or (1b). Formula _{(1a) R3- (CH 2)} m-CH 2 -S- (CH 2) 2 -X- (R
_{4) n- (CH 2) 2} - (R5) p-S-CH 2 - (CH
₂₎ q-R6 general formula _{(1b) R3- (CH 2)} m-CH 2 -S- (CH 2) n-S-CH
_{2 - (CH 2) q-} R6 in formula (1a) or (1b), R4, R5 represents an ethylene oxide group, X is a divalent oxygen atom, a sulfur atom, carbamyl, carbonyl group, or an oxycarbonyl M and q are integers of 0 to 4, n and p are 0 to 3
R3 and R6 represent a hydroxy group, a carboxy group, or an alkoxy group having 1 to 5 carbon atoms. Also, R3,
R6 represents an example of a compound contained in the general formula (1) which may be bonded to form a ring, but is not particularly limited thereto.

(Compound 101) OH—CH ₂ CH ₂ —S—CH ₂ CH ₂ OH (Compound 102) OH— (CH ₂ CH ₂ —S) ₂ —CH ₂ CH ₂ OH (Compound 103) OH— (CH _{2 CH 2 -S) 3 -CH 2} CH 2 OH ( compound _{104) (OH-C 2 H} 4 -S-C 2 H 4 -O-C 2 H 4) 2 O ( compound 105) (OH- (C _{2 H 4 -S-C 2 H} 4 -O) 2 -C
₂ H _{4) 2} O (Compound _{106) S (-CH 2 CH 2} -O-CH 2 CH 2 -) 2 S ( Compound _{107) S (- (CH 2} CH 2 -O) 2 -CH 2 CH 2 - ) ₂ S (Compound 108) (OH—CH ₂ CH (OH) CH ₂ —S—CH ₂ —) ₂ These compounds can be synthesized, for example, by the method described in JP-B-47-11386. Two or more thioether compounds may be used in combination.

The thioether compound of the present invention may be used in the form of a layer containing a physical development nucleus, a layer containing a silver halide solvent or a layer containing both additives, a protective layer, an intermediate layer, an alkali supply layer, an unnecessary processing agent after processing. It may be added to any of the constituent layers provided in the processing member such as the component absorption layer, but an undercoat layer and a layer containing a silver halide solvent are particularly preferred. The names of these layers are merely representative of the names of one additive contained in the layer, and the present invention is not limited to the case where these additives are always added to another layer.
For example, the silver halide solvent and the physical development nuclei may be contained in the same layer or may be added to separate layers. The alkali supply agent may be added to any layer such as a layer containing physical development nuclei, a layer containing a silver halide solvent, an undercoat layer and a protective layer.

To add the thioether compound used in the present invention to these layers, a solvent which does not adversely affect the photographic member, such as water, may be used in the coating solution for forming the layers. It can be added by dissolving it in an appropriate concentration in alcohols such as methanol and ethanol. The thioether compound of the present invention may be added at any time during the production process, but is generally preferably immediately before coating. The preferable addition amount of the thioether compound of the present invention is 10 ^-7 to 1 mol per m ² ,
More preferably, 10 ^-5 to 10 ^-2 mol, particularly preferably 1 to 10 mol
0 ^-4 to 10 ^-3 mol.

The physical development nucleus is for reducing soluble silver salt diffused from the photothermographic member to convert it into physically developed silver, which is fixed 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 diameter of 2 to 200 nm. These physical development nuclei usually contain 10
^{-3 to} 100 mg / m ² , preferably 10 ^-2 to 10 mg / m ² .

The physical development nucleus can be separately prepared and added to a coating solution. However, in a coating solution containing a hydrophilic binder, for example, silver nitrate and sodium sulfide, or
It may be prepared by reacting gold chloride with a reducing agent or the like. Silver, silver sulfide, palladium sulfide and the like are preferably used as physical development nuclei. When using physically developed silver transferred to the complexing agent sheet as an image, palladium sulfide, silver sulfide, etc.
It is preferably used because min is short and Dmax is high. The physical development nucleus may be added to any layer on the processing member, but is preferably as high as possible. Particularly, the uppermost layer is preferable.

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, compounds having a 5- or 6-membered imide ring such as uracil and hydantoin described in JP-A-8-179458, and compounds represented by formula (I) described in JP-A-53-144319. Compounds can be used. The compounds described in JP-A-8-69097 which can fix and stabilize silver halide can also be used as a silver halide solvent.

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 preferred. Further, it is particularly preferable that hydantoin is added as a potassium salt since the reduction in gloss during storage of the treated 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 the amount of silver applied to the photothermographic member, preferably 1 to 20 times.
It is / 10 to 10 times, and 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 described in JP-A-8-179458 into the processing layer, the density of the silver image in the photothermographic member can be increased. It is possible.

As the binder for the constituent layer of the processing member,
A hydrophilic material is preferably used. Examples include the above-mentioned Research Disclosure and
No. 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. U.S. Pat. No. 4,960,681;
No. 45260, etc., the superabsorbent polymer,
Homopolymer of a vinyl monomer having COOM or —SO ₃ M (M is a hydrogen atom or an alkali metal) or a copolymer of the vinyl monomers or other vinyl monomers (for example, sodium methacrylate, ammonium methacrylate, Sumitomo Chemical Sumikagel L-5 manufactured by Co., Ltd.
H) is 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 the binder is preferably 20 g or less per 1 m ² , and particularly preferably 10 g or less. Also,
It is useful to provide a protective layer on the processing member.

In the present invention, the image forming step is preferably performed in the presence of a base (alkali). As the base or base precursor that can be used in the present invention, known compounds used in the development processing of a 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. A specific example is US4.
Nos. 514,493 and 4,657,848 and No. 5 of the prior art (issued by Aztec Co., Ltd. on March 22, 1991)
Pages 55-86. Particularly preferred are EP 210,660, US Pat.
A combination of a basic metal compound which is 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 US Pat. Is to use. In this case, it is preferable that the basic metal compound which is hardly soluble in water is added to the constituent layer of the photothermographic member and the complex forming compound is added to the constituent layer of the processing 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 .
g / m ² .

The photothermographic member and the processing member of the present invention are preferably bonded together in the presence of water and developed at a temperature as low as possible for as long as possible. The heating temperature in the thermal development step is usually about 5
The temperature is from 0 ° C to 250 ° C, particularly preferably from 70 ° C to 90 ° C, more preferably from 70 ° C to 80 ° C. The development time in the heat development step is from 1 second to 120 seconds, and particularly preferably from 10 seconds to 60 seconds. Particularly preferred combinations of development temperature and time are described below, but are not limited thereto. Example 1 70 ° C-50 seconds Example 2 75 ° C-40 seconds Example 3 75 ° C-30 seconds Example 4 80 ° C-25 seconds Example 5 80 ° C-20 seconds Example 6 80 ° C-15 seconds

In the present invention, it is preferable that after the dampening water is applied to the photothermographic member, the photothermographic member is superposed on the processing member and heat-developed. This method is particularly effective when a combination of a basic metal compound and a complex-forming compound that is hardly soluble in water is used as the base precursor.

Silver halide which can be used in the photothermographic member includes silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide,
Any of silver chloroiodobromide may be used. For the purpose of the present invention, silver halide having a silver chloride content of 80 mol% or more is preferably used.

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-743-743 and JP-A-4-223463, a method of mixing monodispersed emulsions and adjusting gradation is preferably used. Particle size is 0.1-2 μm, especially 0.2-1.5
μm is preferred. The crystal habit of silver halide grains is cubic, 8
Those having regular crystals such as tetrahedron, tetrahedron, those having irregular crystal system such as spherical, high aspect ratio plate-like, those having crystal defects such as twin plane, or those thereof Any of a composite system and other types may be used.

Specifically, US Pat. No. 4,500,62
No. 6, Column 50, No. 4,628,021, Research Disclosure Magazine (hereinafter abbreviated as RD) No. 17,
029 (1978), No. 17, 643 (1978)
No. 18,716 (197)
Nov. 1997), p. 648, ibid. No. 307, 105 (19
Nov. 89, pp. 863-865, JP-A-62-253.
No. 159, 64-13546, JP-A-2-2365
No. 46, No. 3-110555 and "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte (P. Glafkid)
es, Chemie et Phisique Photographique, Paul Monte
l, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsio).
n Chemistry, Focal Press, 1966), "Production and Coating of Photographic Emulsions", by Zerikman et al., Focal Press (V.
L. Zelikman et al., Making and Coating Photographi
c Emulsion, Focal Press 1964), etc., any of which 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, JP-A-2-236542, JP-A-1-116637, and JP-A-5-116637.
Emulsions described in 181246 and the like 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-53-14.
Sulfur-containing compounds described in No. 4319 can be used.

Other conditions are described in the above-mentioned "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte (P. Gla
fkides, Chemie et Phisique Photographique, Paul Mo
ntel, 1967), Photographic Emulsion Chemistry by Duffin, Focal Press (GF Duffin, Photographic Emulsion Che)
mistry, Focal Press, 1966), "Production and coating of photographic emulsions" by Zerikuman et al., Focal Press (VL Zelikm)
an et al., Making and Coating Photographic Emulsio
n, 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 addition concentration, the addition amount and the addition rate of the silver salt and the halogen salt to be added may be increased (JP-A-55-142329, JP-A-5-142329).
No. 5-158124, U.S. Pat. No. 3,650,757). 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 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 tellurium sensitization method, and a gold, Noble metal sensitization method and reduction sensitization method using platinum, palladium or the like can be used alone or in combination (for example, JP-A-3-110).
No. 555 and No. 5-241267). These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253159). Further, an antifoggant described later can be added after the completion of the chemical sensitization. Specifically, JP-A-5-45833, JP-A-62-404
The method described in No. 46 can be used.

The pH at the time of chemical sensitization is preferably 5.3 to 1
0.5, more preferably 5.5 to 8.5, and pAg
Is preferably 6.0 to 10.5, more preferably 6.8.
９9.0. The coating amount of the photosensitive silver halide emulsion used in the present invention is 1 mg to 10 g / m ² in terms of silver.
Range.

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, 6
4-135546, JP-A-5-45828, 5-4
Sensitizing dyes described in US Pat.

These sensitizing dyes may be used alone, or a combination thereof may be used. The combination of sensitizing dyes is particularly used for the purpose of adjusting the wavelength of supersensitization or spectral sensitization. Often used. 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 or before or after chemical ripening, or according to US Pat. Nos. 4,183,756 and 4,225,666. It may be before or after formation. These sensitizing dyes and supersensitizers may be used as a solution of an organic solvent such as methanol, a dispersion such as gelatin, or a surfactant.
What is necessary is just to add in a liquid. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

The additives used in such a step 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, page 866-868 Color sensitizer ~ page 649, right column 4. Brightener page 24, page 648, right column, page 868 5. Fogging prevention page 24-25, page 649, right column, pages 868-870 Agents, stabilizers

6. Light absorber, pages 25 to 26, page 649, right column, page 873, filter to page 650, left column, dye, ultraviolet absorber 7. Dye image, page 25, page 650, left column, page 872 Stabilizer 8. Hardener Page 26, page 651, left column 874-875 9. Binder page 26, page 651, left column 873-874

10. Plasticizer, page 27, page 650, right column, page 876 Lubricant 11. Coating aid, pages 26-27, page 650, right column 875-876, surfactant 12. Static page 27, page 650, right column, 876- Page 877 Inhibitor 13. Matting agent 878 to 879

In the present invention, an organic metal salt can be used as an oxidizing agent together with the photosensitive silver halide. 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 No. 0,626, columns 52 to 53 and the like. The 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-mentioned organic silver salt is used in an amount of 0.01 per mole of photosensitive silver halide.
10 to 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 0.1 g / m ² .
To 4 g / m ² are suitable. The binder type and amount of the photothermographic member of the present invention are the same as those of the processing member.

The photothermographic member of the present invention has at least one
And a layer containing a reducing agent. Specifically, European Patent Publication Nos. 524,649 and 357,040, JP-A-4-249245, JP-A-2-46450, and JP-A-6-45045
The reducing agent described in 3-186240 is preferably used. JP-B-3-63733, JP-A-1-1501
No. 35, No. 2-46450, No. 2-64634, No. 3-43735 and EP-A-451,833, and development inhibitor releasing and reducing agent compounds are also used.

In addition, US Pat. Nos. 4,500,626, columns 49-50, 4,839,272 and 4,3.
No. 30,617, No. 4,590,152, No. 5,01
7,454,5,139,919;
140,335, pp. (17)-(18), pp. 57-4024
No. 5, 56-138736, 59-178458
No. 59-53831, No. 59-182449,
No. 59-182450, No. 60-119555, No. 60-128436, No. 60-128439, No. 6
Nos. 0-198540, 60-181742, 61
-259253, 62-4244, 62-
No. 131253, No. 62-131256, No. 64-1
No. 3546, pp. (40) to (57), JP-A-1-120553
And reducing agent precursors described in EP-A-220,746 A2, pp. 78-96, etc., and those disclosed in U.S. Pat. No. 3,039,869. Combinations of various reducing agents can also be used.

Particularly preferred compounds as the reducing agent used in the present invention are phenidones and catechols. In the present invention, the total amount of the reducing agent is 0.01 to 20 mol, particularly preferably 0.1 to 10 mol, per 1 mol of silver.

A hydrophobic additive such as a reducing agent or a diffusion-resistant reducing agent can be introduced into a layer of a photothermographic member by a known method such as the method described in US Pat. No. 2,322,027. In this case, US Pat. No. 4,555,47
Nos. 0, 4,536,466 and 4,536,467
Nos. 4,587,206 and 4,555,476
No. 4,599,296, JP-B-3-62256, etc., using a high-boiling organic solvent in combination with a low-boiling organic solvent having a boiling point of 50 ° C. to 160 ° C. as necessary. Can be. Two or more of these diffusion-resistant reducing agents and high-boiling organic solvents 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 hydrophobic compound used. In addition, 1 cc or less, more preferably 0.5 cc or less, especially 0.1 cc, per 1 g of the binder.
3cc or less is appropriate. Japanese Patent Publication No. 51-39,853,
A dispersion method using a polymer described in JP-A-51-59,943 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-59-157636, pages (37) to (38),
The surfactants described in the above Research Disclosure can be used. Also, Japanese Patent Application Laid-Open
Phosphate ester type surfactants described in US Pat. Nos. 5,56,267 and 7,228,589 and West German Patent Application No. 1,932,299A 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 photothermographic member. Specific compounds preferably used are described in U.S. Pat. No. 4,500,626, Nos. 51-5.
It is described in column 2.

The photothermographic member may be further provided with various non-photosensitive layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer and an antihalation layer, and a back layer on the side opposite to the support. And various other auxiliary layers. Specifically, a layer structure as described in the above patent, an undercoat layer as described in U.S. Pat. No. 5,051,335, a solid pigment as described in JP-A-1-1677838 and JP-A-61-20943. Intermediate layer having
Nos. 53, 5-34884 and 2-64634, an intermediate layer having a reducing agent and a DIR compound, U.S. Pat. Nos. 5,017,454 and 5,139,919;
An intermediate layer having an electron transfer agent as described in JP-A-2-235444, a protective layer having a reducing agent as described in JP-A-4-249245, or a layer obtained by combining these can be provided.

A heat solvent may be added to the photothermographic member for the purpose of promoting heat development. Examples include U.S. Patent Nos. 3,347,675 and 3,667,95.
Organic compounds having a polarity as described in No. 9 are exemplified. Specifically, amide derivatives (benzamide and the like), urea derivatives (methyl urea, ethylene urea and the like), sulfonamide derivatives (compounds described in JP-B-1-40974 and JP-B-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 10% of the binder of the layer to be added.
% To 500% by weight, preferably 20% to 300% by weight.
% By weight.

The photothermographic member and the processing member used in the present invention are preferably hardened with a hardener. Examples of hardeners include U.S. Pat. No. 4,678,739, No. 41.
No. 4,791,042, JP-A-59-11665.
No. 5, 62-245261, 61-18942
And hardening agents described in JP-A-4-218044. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-
Bis (vinylsulfonylacetamide) ethane, etc., N
A methylol hardener (such as dimethylol urea), boric acid, metaboric acid or a polymer hardener (JP-A-62-2);
No. 34157). These hardeners are used in an amount of 0.001 per gram of hydrophilic binder.
To 1 g, preferably 0.005 to 0.5 g.

In the photothermographic member, various antifoggants or photographic stabilizers and precursors thereof can be used. Specific examples include the research
Disclosure, U.S. Pat. No. 5,089,378
Nos. 4,500,627 and 4,614,702
No., JP-A-64-13564, pages (7) to (9), (57) to (7)
Pages 1) and (81)-(97), U.S. Pat.
0, 4,626,500, 4,983,494
And JP-A-62-174747 and JP-A-62-23914.
No. 8, JP-A-1-150135 and 2-110557
No. 2-178650, RD17,643 (1978
Years) (24)-(25). These compounds are preferably used in an amount of 5 × 10 ^-6 to 1 × 10 ^-1 mol, more preferably 1 × 10 ^-5 to 1 × 10 ^-2 mol, per mol of silver.

For the photothermographic member and the processing member, various surfactants can be used for the purpose of coating aid, improvement of releasability, improvement of slipperiness, antistatic, 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 Nos. 62-173463 and 62-18345.
No. 7, etc.

The photothermographic member and the processing member may contain an organic fluoro compound for the purpose of improving the slipperiness, preventing static charge, and improving the releasability. Representative examples of the organic fluoro compound include fluorine surfactants described in JP-B-57-9053, columns 8 to 17, JP-A-61-20944, JP-A-62-135826, and fluorine oils. And a hydrophobic fluorine compound such as a solid fluorine compound resin such as an tetrafluoroethylene resin.

A matting agent can be used for the photothermographic member. The same matting agent as that used for the processing member is used. In the present invention, the support for the photothermographic member and the processing member is not particularly limited as long as it can withstand the processing temperature.
Generally, The Photographic Society of Japan, "Basics of Photographic Engineering-Silver Halide Photography-", Corona Co., Ltd. (1979) (223)-(24)
0) Photographic supports such as paper described on page, synthetic polymers (films) and the like. Specifically, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene,
Polyimide, cellulose (for example, triacetylcellulose) or a film containing a pigment such as titanium oxide in these films, a synthetic paper made of polypropylene or the like, a synthetic resin pulp such as polyethylene, and a mixture made of natural pulp. Papermaking, Yankee paper, baryta paper,
Coated paper (especially cast-coated paper) or the like is 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.

A hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black or another antistatic agent is coated on the surface of the support opposite to the side where the photosensitive element and the processing element are coated. May be. When using an aluminum vapor deposition film, it is preferable to add a boron compound to the lowermost layer of the photothermographic member and the processing member. Preferred boron compounds include borate esters.

In particular, JP-A-6-41281 and JP-A-6-4128 which are hard to be rolled up as a support for a photothermographic member.
No. 3581, No. 6-51426, No. 6-51437
Nos. 6-51442, 6-82961, 6-
No. 82960, No. 6-123937, No. 6-8295
Nos. 9, 6-67346, 6-118561, 5-21625, JP-A-6-202277, and 6-67
Nos. 175282, 6-118561, 7-219
The supports described in JP-A-129-129 and JP-A-7-219144 can be preferably used. Also, Japanese Patent Application Laid-Open No.
No. 4645, No. 5-40321, No. 6-35092
It is preferable to record exposure information and the like using a support having a magnetic layer described in JP-A-6-317875.

In the image forming method of the present invention, a method of performing development by heating in the presence of water is useful. In this method, the heating temperature is preferably 50 ° C. or higher and the boiling point of water or lower.
A small amount of fountain solution is sufficient for the amount of water. Examples of the fountain solution used for accelerating development and / or diffusing and transferring the fixed silver include water, a basic aqueous solution containing an inorganic alkali metal salt or an organic base (these bases include an image forming accelerator The low-boiling solvent or a mixed solution of the low-boiling solvent and water or the above-mentioned 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.

As the dampening water used in the steps of the thermal development and / or the diffusion transfer (fixing), any water can be used as long as it is generally used. Specifically, distilled water, tap water, well water, mineral water and the like can be used. Further, in the heat developing apparatus using the photothermographic member and the image receiving element of the present invention, the water may be used up or may be used repeatedly. In the latter case, water containing components eluted from the member will be used. JP-A-63-144354 and JP-A-63-144.
355, 62-38460, JP-A-3-2105
The device described in No. 55 or the like or water may be used.

In the present invention, the amount of fountain solution present at the time of thermal development may be not more than the weight of water corresponding to the maximum swelling volume of the entire coating film of the photothermographic member and the processing member. As a method of applying the water, for example, JP-A-62-25315
No. 9, 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 advance in the photothermographic member and / or the processing member in the form of a hydrate. Preferably, the dampening solution is applied to the photothermographic member after imagewise exposure, and then the processing member and the photothermographic member are superposed face-to-face and heated. As described in JP-A-63-85544, etc., the temperature of the water to be applied is 3.
The temperature may be 0 ° C to 60 ° C.

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. The method of superposing the photothermographic member and the processing member is described in JP-A-62-253159 and JP-A-6-253159.
The method described in 1-1147244, 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.
No. 47, 59-1777547, 59-18135
No. 3, No. 60-18951, Shokai 62-25944
JP-A-6-130509, JP-A-6-95338,
Nos. 6-95267, 8-29955, 8-29
No. 954 and the like are preferably used. Examples of commercially available devices include Pictrostat 100 and Pictrostat 200 manufactured by Fuji Photo Film Co., Ltd.
Pictrostats 300 and 330, Pictrostat 50, Pictrostat Digital 400, Pictography 2000, Pictography 300
0, the same pictography 4000, the same chemical free system, and the like.

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 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-62-253159
Nos. (31) to (32). Further, Japanese Patent Application Laid-Open No.
It is advantageous to combine a zinc salt of mercaptocarboxylic acid described in JP-A-4705 and the like in a photosensitive element and a complex forming compound in a processing member.

Similarly, a printout inhibitor of silver halide may be included in the processing sheet so that its function can be exhibited simultaneously with the development. Examples of the printout inhibitor include a monohalogen compound described in JP-B-54-164, a trihalogen compound described in JP-A-53-46020, and a halogen described in JP-A-48-45228 bonded to an aliphatic carbon atom. And polyhalogen compounds represented by tetrabromoxylene described in JP-B-57-8454. Also, UK Patent No. 1,005,1
Development inhibitors such as 1-phenyl-5-mercaptotetrazole described in No. 44 are also effective. Also,
The viologen compounds described in JP-A-8-184936 are also effective. The use amount of the printout inhibitor is preferably 10 ^-4 to 1 mol / Ag1 mol, particularly preferably 10 ^-3 to 10 ^-1 mol / Ag1 mol.

[0074]

EXAMPLES Hereinafter, the effects of the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

Example 1 First, the production of the photothermographic member (K101) will be described. 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.

[0076]

[Table 1]

[0077]

Embedded image

[0078]

[Table 2]

After washing with water and desalting (adjusted to pH 3.1 with sulfuric acid using the sedimentation agent (1)), 25 g of lime-processed gelatin was added to adjust pH 6.03 and pAg 7.6 by a conventional method. Thereafter, preservative (1) was added, and the mixture was chemically sensitized at 60 ° C. The compounds used for chemical sensitization were added sequentially as shown in Table 1. The particle size is 0.22 μm on average side length,
This was a silver chlorobromide cubic emulsion having a standard deviation of 0.022 μm and a silver bromide content of 2.2 mol%. The yield of this emulsion was 704.
g.

[0080]

[Table 3]

[0081]

Embedded image

The preparation method of 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.

[0083]

[Table 4]

[0084]

[Table 5]

After washing with water and desalting (adjusted to pH 4.1 with phosphoric acid using a precipitant (2)) according to a conventional method, 22 g of lime-treated gelatin was added, and the pH was 6.1 and the pAg was 7.8.
Adjusted (by KBr). Preservative (2) was used as a preservative. It was a silver bromide cubic emulsion having a grain size of 0.05 μm. The yield is 630 g.

[0086]

Embedded image

100 g of this emulsion (1) was added with sensitizing dye (3) 9
4.5 cc of a methanol solution containing 4,4'-
1.2 ml of a 1% methanol solution of bis [4,6-di (naphthyl-2-oxy) pyrimidin-2-ylamino] stilbene-2,2'-disulfonic acid disodium salt was added, and the mercapto compound (1) 2 % Aqueous solution (0.65 cc), water-soluble polymer (1) (1.7 g) was added, and butyl acrylate latex (1.9 g) was further added as a dispersion to prepare a coating solution for an emulsion layer.

[0088]

Embedded image

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.
Milling using glass beads with an average particle size of 0.75 mm
Dispersed for 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. Zinc hydroxide 1 with an average particle size of 0.2 μm
2.5 g, 1 g of carboxymethylcellulose as a dispersant, and 0.1 g of sodium polyacrylate were added to 100 cc of a 4% aqueous solution of gelatin, and dispersed in a mill for 30 minutes using glass beads having an average particle size of 0.75 mm. 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 8. 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.

[0092]

[Table 6]

[0093]

Embedded image

The above materials were applied to a support in accordance with the composition and the amount of addition shown in Table 7 to prepare a light-sensitive material K101.

[0095]

[Table 7]

[0096]

Embedded image

Next, as shown in Table 8, photosensitive materials K102 to 111 were prepared in the same manner as K101, except that the layer constitution of the present invention was changed and water-soluble dyes A-1 and -2 were added.

[0098]

[Table 8]

[0099]

Embedded image

Example 2 A processing member (R20) used for forming an image on a photographic material by processing in combination with a photothermographic member was used.
The fabrication of 1) will be described. First, a method for producing an emulsified dispersion of the high-boiling organic solvent (A) will be described.

[0101]

Embedded image

[Preparation of Solution 1] 1000 g of gelatin powder
To 6465 ml of ion-exchanged water and 7% of preservative (A)
The solution is added to 12.5 ml of an aqueous solution and dissolved by heating at 65 to 70 ° C. [Preparation of Solution 2] 2000 g of high-boiling organic solvent (A), 200 g of high-boiling organic solvent (B), 25 g of surfactant (B)
And heated and stirred at 65-70 ° C. to make it uniform. [Preparation of Solution 3] 53 g of surfactant (C) was added to MEK40.
and heat to 65-70 ° C to dissolve.

[Emulsification] Solutions 2 and 3 are added to solution 1, and the mixture is stirred and emulsified by 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.

[0104]

Embedded image

Using the above emulsified dispersion and the raw materials shown in Table 9, coating was performed on a support in accordance with the constitution and the amount of addition shown in Table 9, thereby producing a treated member R201.

[0106]

[Table 9]

[0107]

Embedded image

[0108]

Embedded image

[0109]

Embedded image

R202 to 204 were prepared in the same manner as R201 except that the compound of the present invention was added as shown in Table 12.

[0111]

[Table 10]

Example 3 The photothermographic member (K101) described in Example 1 was used with a width 59
It is cut into 0 mm and 470 mm in length. Using a semiconductor laser having an output peak wavelength at 670 nm, one pixel (100 μm) is cut.
Exposure was performed by changing the amount of light in 1/10000 ^second per m ² ). Separately, the processing member (R201) described in Example 2 processed into a roll having a width of 635 mm and a length of 76 m was wound around a 3-inch diameter roll-shaped core (feeding side) such that the application surface faces outward. . Thereafter, the leading end of the processing member was partially wound around another winding core (winding side).

The processing member was set so that the film surface of the processing member was in contact with the outer surface of the curved heater during feeding and winding. Next, the exposed photothermographic member is bonded to water maintained at 50 ° C. for 3.2 seconds so that the film surface of the photothermographic member and the film surface of the processing member uniformly overlap. While moving the photosensitive member on the curved surface heater, the speed and the heater temperature were adjusted so that the photothermographic member was heated at 85 ° C. for 23 seconds until the photothermographic member was separated from the processing member, and the processing was performed. Next, the photothermographic member was peeled from the processing member.

Thereafter, the photothermographic material is immersed in water for 2.5 seconds in an on-line washing step, and then squeezed with a roller so that the amount of water on the photothermographic material becomes approximately 15 ml / m ² or less. I made it. Thereafter, the sample was dried with hot air at 50 ° C. to obtain a processed photothermographic member sample No. 301. The resulting heat-developable photothermographic member was evaluated for scratch resistance from the ease of rubbing at the bottom of a plastic stick container made of plastic.

In the same manner, processed photothermographic member samples No. 302 to 305 were obtained using K102 to 104 instead of the photothermographic member K101, and evaluated. Table 11 shows the results.
Shown in

[0116]

[Table 11]

As can be seen from Table 11, Sample Nos. 302 to 305, which are the layer constitutions of the present invention, are Comparative Examples 301 and 30.
On the other hand, it can be seen that scratches are hardly formed and the scratch resistance is excellent.

Example 4 A similar process was performed using K101 and K103 described in Example 1 and adding R202 to R202 to R201 described in Example 2.
04 was used to obtain an image. Table 12 shows the evaluation results.
After processing, the samples were stored under 4000 lux illumination for 2 hours.
Leave for 4 hours and increase the density increase of the white background (Dmin) to 400 nm.
Of light.

[0119]

[Table 12]

As can be seen from Table 12, Sample Nos. 402 to 405 having the constitution of the present invention had better scratch resistance than Comparative Example 401, and Sample No. 403 in a more preferable embodiment.
~ 405 indicates that the storage stability after the treatment is excellent.

Example 5 The same processing was carried out by using the photothermographic member described in Example 1
Images were obtained by using the combinations shown in Table 13 for the treatment members described in Example 2. Evaluation of character breakage is described in Example 3.
Using a light exposure machine used for the above, several 50-micron striped straight lines were exposed, and after development, the edges of the stripes were visually observed and evaluated with a 100-fold loupe. Table 13 shows the results.
Shown in

[0122]

[Table 13]

As can be seen from Table 13, Sample No. 5 in which the heat-developable photosensitive member contained the water-soluble dye desired in the present invention was used.
Nos. 02 to 508 show that in addition to scratch resistance and preservability after treatment, the breakage of characters is also excellent.

Example 6 A similar process was carried out with the photothermographic member described in Example 1,
An image was obtained using the combination of the photothermographic member and the processing member described in Table 14 for the processing member described in Example 2, and further using the developing conditions (processing temperature and processing time). The evaluation of the processing unevenness was performed by processing the unexposed photothermographic member sample using the processing method used in Example 3 and measuring 590 mm in width and 47 mm in length.
Obtain a 0 mm sample and develop unevenness (density unevenness) in the white background
Was visually determined. Table 14 shows the results.

[0125]

[Table 14]

As can be seen from Table 14, when the sample of the present invention was combined with the treatment at a temperature lower than 85 ° C., the storage stability after the treatment was good, and the treatment was extremely excellent without any unevenness in the treatment.

[0127]

As described above, in a photographic member comprising a photothermographic member and a processing member, the main layer containing the photosensitive silver halide of the photothermographic member is located closer to the support than the main layer containing the reducing agent. As a result, a photographic member having a short development time and good film quality can be obtained. Further, by containing a thioether compound in the processing member, it is possible to provide a photographic member having a short development time and excellent storage stability after processing.

Claims (6)

[Claims] 1. A method for forming a silver image comprising at least one light-sensitive silver halide emulsion layer and at least one hydrophilic colloid layer containing a reducing agent on the same side of a support. In the photothermographic member, the main photosensitive layer containing the photosensitive silver halide of the photothermographic member is located closer to the support than the main layer containing the reducing agent. 2. The photothermographic member according to claim 1, wherein at least one layer on the photothermographic member has a peak wavelength of spectral absorption in a gelatin film of plus or minus the maximum spectral sensitivity wavelength of the main photosensitive layer. A photothermographic member comprising at least one water-soluble dye having a size within 50 nm. 3. A processing member used for image formation processing of the photothermographic member according to claim 1 or 2, comprising at least one layer containing a physical development nucleus on a support. A processing member characterized in that another hydrophilic colloid layer contains a silver halide solvent (fixing agent) and at least one thioether compound. 4. A photothermographic member according to claim 1 or 2, and at least one layer containing a physical development nucleus on a support, wherein said layer or another hydrophilic colloid layer contains a silver halide solvent. A photographic member comprising a processing member containing a fixing agent. 5. The photographic member according to claim 4, wherein the processing member contains at least one thioether compound in a layer containing a physical development nucleus or another hydrophilic colloid layer. 6. The photothermographic material according to claim 1, wherein the photothermographic material is superimposed on the photothermographic material after imagewise exposure or simultaneously with imagewise exposure. Forming a silver image on the photothermographic member and / or the processing member by heat developing in the presence of water.