JPH09222690A - Processing member and method for forming image by heat development by using the processing member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To facilitate operation of the processing member in a system for using a heat-developable photosensitive material and the processing member and utilizing an image formed on this photosensitive material. SOLUTION: This processing member is used for forming an image on this heat-developable photosensitive material by laying this member on this photosensitive material and heating them, and this member is obtained by forming a processing layer on the aluminum surface of an aluminum vapor-deposited base having a thickness of 4-40μm, and an image is formed on this photo-sensitive material by adding dampening water to this material and then, laying this material on this processing member provided with the processing layer, and heating them on a continuous web.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing member and a heat development image forming method using the same. Furthermore, the present invention relates to a processing member having an improved handleability.

[0002]

2. Description of the Related Art Photothermographic materials containing silver halide are known, and the photothermographic materials and their processes are described, for example, in "Basics of Photographic Engineering", Non-silver Photographic Edition (198).
242 to 255, published by Corona Publishing Co., Ltd., U.S. Pat. No. 4,500,626 and the like.

In addition, for example, a method of forming a dye image by a coupling reaction between an oxidized product of a developing agent and a coupler is disclosed in US Pat. Nos. 3,761,270 and 4,021,2.
No. 40, etc. Also, a method of forming a positive color image by a photosensitive silver dye bleaching method is disclosed in US Pat. No. 4,23.
5,957, etc.

Recently, there has been proposed a method of releasing or forming a diffusible dye imagewise by heat development and transferring the diffusible dye to a dye fixing element. In this method, a negative dye image or a positive dye image can be obtained by changing the kind of dye-donor compound used or the kind of silver halide used. More specifically, U.S. Pat. Nos. 4,500,626 and 4,483,914.
No. 4,503,137, 4,559,290
JP-A-58-149046, JP-A-60-133.
No. 449, No. 59-218443, No. 61-2380.
56, European Patent Publication 220746A, Technical Report 87
-6199, European Patent Publication 210660A2, and the like.

Many methods have been proposed for obtaining a positive color image by thermal development. For example, in U.S. Pat. No. 4,559,290, a so-called DRR compound, which is an oxidized type compound having no color image releasing ability, is allowed to coexist with a reducing agent or a precursor thereof, and the amount of silver halide is changed by heat development. A method has been proposed in which the reducing agent is oxidized by the above method, and the diffusible dye is released by reducing the remaining reducing agent without being oxidized. In European Patent Publication No. 220746A and Kokai Giho No. 87-6199 (Vol. 12, No. 22), NX bond (X is oxygen atom, nitrogen atom or sulfur) is used as a compound that releases a diffusible dye by a similar mechanism. Photothermographic materials are described which use compounds which release diffusible dyes by the reductive cleavage of (representing atoms).

In the above example, when the light-sensitive material is heat-developed, the image-receiving sheets are superposed and heated to transfer the diffusible dye to obtain a dye image on the image-receiving sheet. In this case, an image is formed facing both the photosensitive material and the image receiving sheet. When the image on the side of the photosensitive material is used, the image receiving sheet can be considered as a processing member. It is desired that the processing member has excellent handleability.

[0007]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to improve the handling property of a processing member in a system using a photothermographic material and a processing member and utilizing an image formed on the photosensitive material. Especially.

[0008]

The above object is to provide a processing member used for forming an image on a photothermographic material by superposing and heating the photothermographic material, the processing member being aluminum vapor-deposited. A processing member characterized in that a processing layer is provided on the aluminum vapor deposition surface of the base, and after dampening water is applied to the photothermographic material, it is superposed on the processing member having the processing layer provided on the continuous web. This is achieved by a heat development image forming method in which an image is formed on the light-sensitive material by heating.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The aluminum-deposited base of the processing member according to the present invention is a base made of plastic or the like having a thin layer of aluminum on one or both sides, and various commercially available supports are used. be able to. A thin layer of aluminum can be generally prepared by dissolving and evaporating metallic aluminum in a reduced pressure environment and then cooling and solidifying on the base.

The thickness of the support used in the treatment member of the present invention is arbitrary, but it is preferably thin, particularly preferably 4 μm or more and 40 μm or less. In this case, since the amount of the processing member per unit volume increases, the processing member roll can be made compact. In particular, when the treating member is used for treatment, when it is used in a continuous web form, it is preferable to use a particularly thin support.

The material for the support is not particularly limited as long as it can withstand the processing temperature.
In general, “The Basics of Photographic Engineering-Silver Salt Photography” edited by The Photographic Society of Japan, published by Corona Publishing Co., Ltd. (1979) (223).
To (240) pages, photographic supports such as synthetic polymers (films). Specifically, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those containing pigments such as titanium oxide in these films, Synthetic paper made from polypropylene etc., mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (particularly cast coated paper)
Are used.

A synthetic polymer film is suitable for aluminum vapor deposition and is preferably used. Further, a support which is mainly a styrene polymer having a syndiotactic structure can also be preferably used. A hydrophilic binder and a semiconductive metal oxide such as alumina sol or tin oxide on the surface opposite to the aluminum vapor deposition surface of these supports,
Carbon black or another antistatic agent may be applied.

In the treated member of the present invention, a boron compound is preferably used in the lowermost layer. Preferred as the boron compound is borate. Borate exists naturally in a form that can be written by a number of chemical formulas. For example KB ₅ O ₈ / 4H
₂ O, Na ₂ B ₄ O ₇ · 10H ₂ O, CaB ₂ O ₄ , Mg ₃ B ₇ O ₁₃ Cl and the like. This diversity is due to the nature of boron,
When expressed by a general formula, it becomes Xp (BO ₃ ) _m (BO ₄ ) _n Yq. X
Is a cation, Y is an anion, p, m, n, and q are natural numbers, and the combination thereof generally takes a neutral charge.

It is preferable to further provide an aluminum vapor-deposited layer on the side on which the treatment layer is provided and on the opposite side of the support because the transportability of the treatment member is improved.

In addition to the purpose of transferring the diffusible dye mentioned in the above example, the processing member of the present invention blocks air during heat development, prevents the material from volatilizing from the photosensitive material, and is used for processing. It is used for supplying a material to a light-sensitive material and for removing a material in a light-sensitive material that becomes unnecessary after development or an unnecessary component generated during development. In the present invention, it is preferable to use a base or a base precursor for promoting image formation, but it is preferable to include them in the treatment layer of the treatment member from the viewpoint of storability. When a base is generated by the reaction of two or more substances, the present invention also includes a mode in which only one of them is contained in the treatment layer. 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. A specific example is US 4,514,493.
No. 4,657,848 and known technology No. 5 (19
Issued on March 22, 1991, by Aztec Co., Ltd.), pages 55 to 86, etc. Also, EP21
No. 0,660, US Pat. No. 4,740,445, and a compound capable of forming a complex with a water-insoluble basic metal compound and a metal ion constituting the basic metal compound (referred to as a complex-forming compound). When the combination of 2) is used as a base precursor, it is preferred that the poorly water-soluble basic metal compound is added to the light-sensitive material and the complex-forming compound is added to the processing 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 .
a m ^2. In the present invention, it is preferable that after dampening water is applied to the photothermographic material, it is heat-developed by superposing it on a processing member having a processing layer provided on the continuous web. In particular, it is effective when a combination of the above-mentioned water-insoluble basic metal compound and complex-forming compound is used as the base precursor.

A hydrophilic binder is preferably used as the binder of the treatment layer. Examples thereof include Research Disclosure mentioned above and JP-A-64-13,54.
Examples thereof include those described in No. 6, 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. 45,260, etc., that is, a 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 with each other or with another vinyl monomer Copolymers (for example, sodium methacrylate, ammonium methacrylate, Sumikagel L- manufactured by Sumitomo Chemical Co., Ltd.)
5H) is also used. These binders can be used in combination of two or more kinds. Particularly, a combination of gelatin and the above binder is preferable. Gelatin is lime-treated gelatin, acid-treated gelatin,
It may be selected from so-called demineralized gelatin having a reduced content of calcium and the like, and it is preferable to use it in combination. The amount of binder is preferably 20 g or less per 1 m ² , and particularly preferably 10 g or less. Further, it is useful to provide a protective layer on the processing member.

As the photothermographic material containing silver halide preferably used in the present invention, Japanese Patent Application No. 7-45 is available.
No. 018, which obtains a black and white silver image, one which obtains a color image by the coupling described in the above-mentioned known examples, and one which releases a diffusible dye in an image form. .

When a black and white silver image is to be obtained, it is preferable that the silver halide has a silver chloride content of 80 mol% or more, and the processing layer contains physical development nuclei 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 heavy metals such as zinc, mercury, lead, cadmium, iron, chromium, nickel, tin, cobalt, copper and ruthenium, or precious metals such as palladium, platinum, silver and gold, or sulfur thereof.
All known physical development nuclei such as colloidal particles of chalcogen compounds such as selenium and tellurium can be used. These physical development nuclei substances reduce the corresponding metal ions with a reducing agent such as ascorbic acid, sodium borohydride, hydroquinone, etc. to form a metal colloid dispersion,
Alternatively, it is obtained by mixing soluble sulfide, selenide or telluride solutions to form a water insoluble colloidal dispersion of metal sulfide, metal selenide or metal telluride. These dispersions are preferably formed in a hydrophilic binder such as gelatin. A method for preparing colloidal silver particles is described in U.S. Pat. No. 2,688,601. If necessary, a desalting method for removing an excessive salt known in the method for preparing a silver halide emulsion may be performed. The size of these physical development nuclei is 2 to
Those having a particle size of 200 nm are preferably used. These physical development nuclei are usually contained in the processing layer in the range of 10 ^{−3 to} 100 mg /
m ^2, preferably, 10 ^-2 ~10mg / m ² is contained. 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. As a physical development nucleus,
Silver, silver sulfide, palladium sulfide and the like are preferably used.
When the physically developed silver transferred to the complexing agent sheet is used as an image, palladium sulfide, silver sulfide, etc. have a Dmin cutoff and D
It is preferably used because of its high max.

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

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

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

Further, the concentration of a silver image in a light-sensitive material is increased by incorporating a polymer having a repeating unit of vinylimidazole and / or vinylpyrrolidone as a constituent component described in Japanese Patent Application No. 6-325350 into a processing layer. Is possible.

The photothermographic material mainly used for color image formation, especially for photographing, will be described below.

The silver halide usable in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide. The silver halide emulsion used in the present invention may be a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or light fogging. Further, a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases may be used, and silver halides having different compositions may be joined by epitaxial joining. The silver halide emulsion may be monodispersed or polydispersed.
No. 167,743 and No. 4-223,463, the method of mixing the monodisperse emulsion and adjusting the gradation is preferably used. The particle size is 0.1 to 2 μm, in particular 0.
2 to 1.5 μm is preferable. The crystal habits of silver halide grains include those having regular crystals such as cubic, octahedral, and tetrahedral, those having irregular crystal systems such as spheroids and high aspect ratio tabular, and those having twin planes. It may be one having such a crystal defect, or a composite system thereof, or any other. Specifically, US Pat. No. 4,500,626 No. 5
Column 0, No. 4,628,021, Research Disclosure (hereinafter abbreviated as RD) No. 17,029
(1978), No. 17, 643 (December 1978)
Mon., pages 22-23, ibid. No. 18,716 (1979, 1)
No. 307, 105 (November 1989), pages 863 to 865, JP-A-62-253,15.
No. 9, No. 64-13,546, JP-A-2-236,5
No. 46, No. 3-110, 555, "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte (P. Glafkide)
s, Chemieet Phisique Photographique, Paul Montel, 196
7), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographic Emulsion Chemistry, Fo
cal Press, 1966), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., Focal Press (VLZelikman et al., Maki
ng and Coating Photographic Emulsion ， Focal Press
Any of the silver halide emulsions prepared by the method described in 1964) can be used.

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

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

In the step of forming grains of a light-sensitive silver halide emulsion, rhodan salt, ammonia, 4-substituted thiourea compound, or JP-B-47-11,386 is used as a silver halide solvent.
Or an organic thioether derivative described in JP-A-53-1
The sulfur-containing compounds described in No. 44,319 and the like can be used.

For other conditions, see the above-mentioned "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte (P. Glaf).
kides, Chemie et Phisique Photographique, Paul Monte
L., 1697), "Photographic Emulsion Chemistry" by Duffin, GF Duffin, Photographic Emulsion Chemis
try, Focal Press, 1966), "Production and coating of photographic emulsions" by Zelikmann et al., Focal Press (VLZelikman e
t al., Making and Coating Photographic Emulsion, Foc
Al Press, 1964) etc. may be referred to. That is, any of the acidic method, the neutral method, and the ammonia method may be used,
As a method of reacting the soluble silver salt and the soluble halogen salt, any of a one-side mixing method, a simultaneous mixing method, and a combination thereof may be used. In order to obtain a monodisperse emulsion, a reverse mixing method in which grains, which are preferably used in the simultaneous mixing method, 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 and JP-A-55-158, JP-A-55-142329). 124, U.S. Pat. No. 3,650,575). 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 to 7.0, more preferably 2.5 to 6.0.

The light-sensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion. For the chemical sensitization of the photosensitive silver halide emulsion of the present invention, a chalcogen sensitizing method such as a sulfur sensitizing method, a selenium sensitizing method, a tellurium sensitizing method, or the like, which is known in emulsions for conventional light-sensitive materials, gold, platinum, A noble metal sensitization method using palladium or the like and a reduction sensitization method can be used alone or in combination (for example, JP-A-3-110,55).
No. 5, Japanese Patent Application No. 4-75,798, etc.). These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Application Laid-Open No. 62-253,159). Further, an antifoggant described later can be added after the completion of the chemical sensitization. Specifically, JP-A-5-45,833 and JP-A-62-4
0,446 can be used. The pH at the time of chemical sensitization is preferably 5.3 to 10.5, more preferably 5.5 to 8.5, and the pAg is preferably 6.0.
１10.5, more preferably 6.8 to 9.0. The coating amount of the photosensitive silver halide 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-59-180,550, JP-A-64-13,546, JP-A-5-45,828 and JP-A-5-45,834. These sensitizing dyes may be used alone, or a combination thereof may be used, and a combination of sensitizing dyes is often used particularly for the purpose of adjusting the wavelength of supersensitization or spectral sensitization. . Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a compound that does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. 615, 641 and those described in JP-A-63-23, 145). These sensitizing dyes may be added to the emulsion at or before or after chemical ripening, or according to U.S. Pat. Nos. 4,183,756 and 4,225,666 before and after nucleation of silver halide grains. Good. These sensitizing dyes and supersensitizers may be added as a solution of an organic solvent such as methanol, a dispersion such as gelatin, or one solution of a surfactant. The addition amount is generally from 10 ^-8 to 10 per mol of silver halide.
^-2 moles.

Additives used in such steps and known photographic additives usable in the present invention are 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. Types of additives 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 to 24, page 648, right column 866 to 868, strong Color sensitizer: page 649, right column 4. Brightening agent: page 24, page 648, right column 868, page 5, fogging prevention page 24, page 25, page 649, right column 868-870 page, agent, light stabilizer, 25- Page 26 Page 649 Right column Page 873 Filter-Page 650 Left column Dye, UV absorber 7. Dye image Page 25 650 Page Left column 872 Stabilizer 8. Hardener 26 Page 651 Left column 874-875 9 Binder page 26 page 651 left column 873 to 874 10. plasticizer, page 27 650 right column 876 lubricant 11. coating aid, page 26 to 27 650 right column 875 to 876 surface active agent 12. Static page 27 page 650 right column page 876-877 inhibitor 13. matting agent page 878-879

In the present invention, an organic metal salt may be used as an oxidizing agent together with the photosensitive silver halide. Among such organic metal salts, organic silver salts are particularly preferably used. Organic compounds that can be used to form the above-described organic silver salt oxidizing agents include US Pat.
There are benzotriazoles, fatty acids and other compounds described in No. 0,626, columns 52 to 53 and the like. The acetylenes described in US Pat. No. 4,775,613 are also useful. Two or more organic silver salts may be used in combination. The above organic silver salt is 0.01 mol per mol 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 light-sensitive material of the present invention are the same as those of the processing member.

In the present invention, when a color image is obtained by coupling, the light-sensitive material contains a coupler.

The couplers usable in the present invention may be 4-equivalent couplers or 2-equivalent couplers. 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
Pp. 58-123533 and 58-149046,
Nos. 58-149047, 59-111148, 59-124399, 59-174835, and 5
Nos. 9-231439, 59-231540, 60
-2950, 60-2951, 60-1424
No. 2, No. 60-23474, No. 60-66249,
The details are described in Japanese Patent Application Nos. 6-270700, 6-3007049, and 6-321380.

Further, it is preferable to use the following couplers. Yellow couplers: couplers represented by formulas (I) and (II) of EP502,424A; couplers represented by formulas (1) and (2) of EP513,496A, the general formula of claim 1 of Japanese Patent Application No. 4-134523. Coupler represented by (I); column 1 of US 5,066,576
Couplers represented by general formula D on lines 45 and 55 of
-274425 coupler represented by general formula D in paragraph 0008; coupler described in claim 1 on page 40 of EP498,38A1, coupler represented by formula (Y) on page 4 of EP447,969A1, column 7 of US 4,476,219. Formula (I) on lines 36 and 58
To (IV), magenta couplers; JP-A-3-39737, and Japanese Patent Application No. 4-
234120, Japanese Patent Application No. 4-36917, Japanese Patent Application No. 4-36
A coupler according to item 26. Cyan coupler: JP-A-4-204843, JP-A-4-20443
43345, Japanese Patent Application No. 4-23333, Polymer Coupler: JP-A-2-44345.

Examples of couplers in which the coloring dye has an appropriate diffusibility include US4,366,237, GB2,125,570, EP96,570, DE3,
Those described in 234,533 are preferable.

Further, the light-sensitive material may contain the following functional couplers. The coupler for correcting the unnecessary absorption of the color forming dye is a yellow colored cyan coupler described in EP456,257A1, a yellow colored magenta coupler described in the EP, a magenta colored cyan coupler described in US4,833,069, and US4,837,136. (2), WO92 / 11
A colorless masking coupler of the formula (A) in claim 1 of 575 (in particular, the exemplified compounds on pages 36-45). 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: Compound represented by formula (I) to IV) described on page 11 of EP378,236A1 EP436,938A
2, a compound represented by the formula (I) on page 7, a compound represented by the formula (1) of Japanese Patent Application No. 4-134523, EP44
Formulas (I), (II) and (III) described on pages 5 and 6 of 0,195A2.
A compound represented by formula (I) in claim 1 of Japanese Patent Application No. 4-325564-a ligand releasing compound, and a compound represented by LIG-X described in claim 1 of US4,555,478.

In the light-sensitive material used in the present invention, the oxidant produced by silver development is coupled with the above-mentioned coupler to produce a dye for the purpose of shortening development time, improving sensitivity, improving image density and the like. A preferred embodiment is one in which a color developing agent that can be used is incorporated. In this case, U.S. Pat. No. 3,531,
256, phenol or active methylene couplers as p-phenylenediamine developing agents;
1,270, a combination of a p-aminophenol-based developing agent and an active methylene coupler can be used.
U.S. Pat. No. 4,021,240, JP-A-60-128
A combination of a sulfonamide phenol and a 4-equivalent coupler as described in JP No. 438, etc. is excellent in raw storage when incorporated in a light-sensitive material and is a preferable combination.
When the color developing agent is incorporated, a precursor of the color developing agent may be used. For example, US 3,342,5
No. 97, Indoaniline compounds, US Pat.
2,599, Research Disclosure No. 14,
850 and Schiff base-type compounds described in Nos. 15 and 159, aldol compounds described in No. 13,924, US
No. 3,719,492;
There can be mentioned urethane compounds described in JP-A-135628.

Further, a sulfonamidephenol-based main agent described in Japanese Patent Application No. 7-180,568, Japanese Patent Application No. 7-492
The combinations of hydrazine-based main agents and couplers described in JP-A No. 87 and JP-A No. 7-63572 are also preferable for use in the light-sensitive material 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.
Those described in JP-A No. 9,919 and European Patent Publication No. 418,743 are used. In addition, JP-A-2-230,143,
As described in JP-A-2-235,044, a method of stably introducing into the 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 mobility higher than that of a diffusion-resistant developing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols. Also, an electron donor precursor described in JP-A-3-160,443 is 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 Nos. 524,649 and 357,
040, JP-A-4-249,245, JP-A-2-46,
No. 450 and JP-A-63-186,240 are preferably used. In addition, Japanese Patent Publication 3-63,733
No., JP-A-1-150,135, JP-A-2-46,450
Nos. 2,64,634, 3-43,735 and EP-A-451,833 are also used.

In addition, the following reducing agents may be incorporated in the photosensitive material. Examples of the reducing agent used in the present invention include U.S. Pat. No. 4,500,626, columns 49 to 50, 4,839,272, 4,330,617, and 4,590,152. Nos. 5,017,454, 5,139,919, JP-A-60-140,335, pages (17) to (18), 57-40,245, 5;
6-138,736, 59-178,458, 59-53,831, 59-182,449, 59-182,450, 60-119,555,
No. 60-128,436, No. 60-128,439
No. 60-198,540, 60-181,74
No. 2, No. 61-259,253, No. 62-244,0
No. 44, No. 62-131, 253, No. 62-131,
Nos. 256 and 64-13,546 (40) to (57)
Page, JP-A-1-120,553, EP 220,
746A2, pages 78 to 96, and the like. No. 3,039, U.S. Pat.
Combinations of various reducing agents, such as those disclosed in US Pat. No. 869, may also be used.

The developing agent or reducing agent may be incorporated in the processing member, but is preferably incorporated in the photosensitive material.

In the present invention, the total amount of the developing agent and the reducing agent added is 0.01 to 20 mol, and particularly preferably 0.1 to 10 mol, based on 1 mol of silver.

Next, the case of releasing the diffusible dye imagewise will be described. In the present invention, a non-diffusible coloring material that releases a diffusible dye corresponding to or opposite to silver development 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 mere linking group, and Z corresponds to or corresponds to a photosensitive silver salt having a latent image in an image form. Release diffusible (Dye) m -Y, and L
1 itself represents a group having the property of being non-diffusible,
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. The following compounds 1 to 4 can be mentioned as specific examples of the coloring material represented by the general formula [L1].
The following 1 to 3 are for releasing the diffusible dye corresponding to the development of silver halide, and 4 are for releasing the diffusible dye in response to the development of silver halide. 1 U.S. Pat. Nos. 3,134,764 and 3,362
819, 3,597,200, 3,544,5
No. 45, No. 3,482,972, Japanese Patent Publication No. 3-68,3
No. 87, etc., a dye developer in which a hydroquinone-based developer and a dye component are linked. This dye developer is diffusible in an alkaline environment, but becomes non-diffusible when reacted with silver halide. 2 As described in US 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 can be used. Examples include U.S. Pat.
Compounds releasing a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat. No. 4,199,
Compounds that release a diffusible dye by the intramolecular rewinding reaction of the isoxazolone ring described in JP-A No. 354 and the like.

3 US Pat. No. 4,559,290, European Patent 220,746A2, US Pat. No. 4,78
No. 3,396, Published Technical Report 87-6,199, JP-A-64
As described in JP-A-13-13546, 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. For example,
U.S. Pat. Nos. 4,139,389 and 4,139,37
9, JP-A-59-185333, and JP-A-57-84,
No. 453, and the like, compounds which release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction, U.S. Pat. No. 4,232,107, and JP-A-59-1011.6.
No. 49, No. 61-88, 257, RD24, 025
(1984) and the like, compounds which release a diffusible dye by an electron transfer reaction in the molecule after being reduced, West German Patent No. 3,008,588A, JP-A-56-14.
No. 2,530, U.S. Pat. Nos. 4,343,893 and 4,619,884, which release a diffusible dye by cleavage of a single bond after reduction; U.S. Pat. For example, nitro compounds which release a diffusible dye after electron acceptance described in 450,223 and the like, compounds which release a diffusible dye after electron acceptance described in US Pat. No. 4,609,610 and the like can be mentioned. Can be

As more preferable ones, European Patent No. 220,746A2, Open Technical Report 87-6,199,
U.S. Pat. No. 4,783,396, JP-A-63-20
No. 1,653, No. 63-201, No. 654, No. 64-1
No. 3,546, etc., an NX bond (X
Oxygen, a sulfur or nitrogen atom) with a compound having an electron withdrawing group, SO ₂ -X (X in one molecule described in JP-A No. 1-26,842 is as defined above) and electron attracting A compound having a PO-X bond (X is as defined above) and an electron-withdrawing group in one molecule described in JP-A-63-271,344;
No. 41, a C—X ′ bond (X ′ is X
Synonymous or or -SO ₂ - compound having an electron withdrawing group and are expressed) can be mentioned. In addition, JP-A-1-161,23
Nos. 7 and 1-161,342, compounds capable of releasing a diffusible dye by cleavage of a single bond after reduction by a π bond conjugated to an electron accepting group 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 are described in European Patent No. 220,74.
Compounds (1) to (3), (7) to (10), (12), (13), (1 described in 6A2 or U.S. Pat. No. 4,783,396.
5), (23)-(26), (31), (32), (35), (36), (40), (4
1), (44), (53) to (59), (64), (70), Published Technical Report 87-
Compounds (11) to (23) described in U.S. Pat.
Compounds (1) to (84) described in No. 13,546.

4 A compound (DRR compound) that is reducing to a 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 US Pat. Nos. 3,928,312 and 4,053,312.
No. 4,055,428, No. 4,336,322
Nos. 59-65,839 and 59-69,83.
No. 9, No. 53-3, 819, No. 51-104, 343
No. RD17,465, US Pat. No. 3,725,06
No. 2, No. 3,728,113, No. 3,443,939
No. 58-116,537, 57-179,
840, U.S. Pat. No. 4,500,626 and the like. Specific examples of the DRR compound include the compounds described in the above-mentioned U.S. Pat. No. 4,500,626, columns 22 to 44. Among them, the compounds (1) to (3), (10) to (13), (16) to (1
9), (28)-(30), (33)-(35), (38)-(40), (42)-(64)
Is preferred. Also, U.S. Pat. No. 4,639,408 No. 3
The compounds described in columns 7 to 39 are also useful.

In a system in which a diffusible dye is imagewise released and diffusion-transferred to a processing member, it is preferable that the processing layer contains a mordant. As the mordant, those known in the photographic field can be used, and specific examples thereof include US 4,500,
626, columns 58-59 and JP-A-61-88256.
Mordants described on pages 2-41, JP-A-64-2440.
No. 43, No. 62-244036, etc. can be mentioned. Further, a dye-receptive polymer compound as described in US Pat. No. 4,463,079 may be used.

Hydrophobic additives such as colorants, couplers, color developing agents and diffusion resistant reducing agents are described in US Pat. No. 2,322,0.
It can be incorporated into the layer of the light-sensitive material by a known method such as the method described in No. 27. In this case, U.S. Pat. Nos. 4,555,470, 4,536,466, 4,536,467, 4,587,206, 4,555,476, 4, The high boiling point organic solvent as described in 599, 296 and Japanese Patent Publication No. 3-62,256 can be used in combination with a low boiling point organic solvent having a boiling point of 50 ° C. to 160 ° C., if necessary. In addition, two or more kinds of these dye donating compounds, diffusion resistant reducing agents, high boiling point organic solvents and the like can be used in combination. The amount of the high boiling point organic solvent is 10 g or less per 1 g of the dye-donor compound used,
It is preferably 5 g or less, more preferably 1 g to 0.1 g. Further, 1 cc or less, more preferably 0.5 cc or less, particularly 0.3 cc or less is suitable for 1 g of the binder. A dispersion method using a polymer described in JP-B-51-39,853 and JP-A-51-59,943 or JP-A-62-3
No. 0,242 or the like and a method of adding it in the form of a fine particle dispersion 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, the surfactants described in the above-mentioned Research Disclosure, JP-A-59-157636, pages (37) to (38) can be used. Also, Japanese Patent Application Nos. 5-204325 and 6-19.
The phosphate ester type surfactants described in No. 247 and West German Laid-Open Patent No. 1,932,299A can also be used. In the present invention, a compound capable of activating development and simultaneously stabilizing an image can be used in the light-sensitive material. Specific compounds preferably used are described in US Pat. No. 4,500,62.
No. 6, columns 51 to 52.

The photographic light-sensitive material contains at least three types of light-sensitive 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 above-mentioned three types of photosensitive layers are preferably layers that are sensitive to any of blue light, green light, and red light. In this arrangement order, generally, a red-sensitive layer,
The order is the green photosensitive layer and the blue photosensitive layer. However, other arrangements may be used depending on the purpose. For example, an arrangement as described in column 162 of JP-A-7-152129 may be used. In the present invention, the silver halide 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.

The light-sensitive material includes various non-light-sensitive layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer and an antihalation layer between the silver halide emulsion layers and the uppermost layer and the lowermost layer. May be provided, and various auxiliary layers such as a back layer can be provided on the opposite side of the support. Specifically, the layer structure described in the above patent, the undercoat layer described in US Pat. No. 5,051,335,
No. 167,838, an intermediate layer having a solid pigment as described in JP-A No. 61-20,943, JP-A No. 1-120,
553, 5-34,884, 2-64,634.
An intermediate layer having a reducing agent or a DIR compound,
US Pat. Nos. 5,017,454 and 5,139,91
9, an intermediate layer having an electron transfer agent as described in JP-A-2-235,044, a protective layer having a reducing agent as described in JP-A-4-249,245, or a layer in which these are combined. be able to.

A heat solvent may be added to the light-sensitive material for the purpose of promoting heat development. Examples thereof include polar organic compounds as described in US Pat. Nos. 3,347,675 and 3,667,959. Specifically, amide derivatives (benzamide, etc.),
Urea derivatives (methylurea, ethyleneurea, etc.), sulfonamide derivatives (Japanese Patent Publication No. 1-40974 and Japanese Patent Publication No. 4)
No. -13701), polyol compounds (sorbitol, etc.), 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 addition amount of the thermal solvent is from 10% by weight of the binder of the layer to be added.
It is 500% by weight, preferably 20% to 300% by weight.

The light-sensitive material 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, column 41, U.S. Pat. No. 4,791,042, JP-A-59-116,655.
Nos. 62-245,261 and 61-18,942
And hardening agents described in JP-A-4-218,044. More specifically, aldehyde hardeners (formaldehyde etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.),
N-methylol type hardener (such as dimethylolurea), boric acid, metaboric acid or polymer hardener (JP-A-62-
234,157 and the like).
These hardeners are used in an amount of 0.0
01 to 1 g, preferably 0.005 to 0.5 g is used.

Various antifoggants or photographic stabilizers and their precursors can be used in the light-sensitive material. Specific examples thereof include the aforementioned Research Disclosure, U.S. Pat. Nos. 5,089,378, 4,500,627, 4,614,702 and JP-A-64-13,564 (7). (9) page, (57) ~
Pages (71) and (81) to (97), U.S. Pat. Nos. 4,775,610, 4,626,500, 4,983,494, and JP-A-62-174,747.
No. 62-239,148, JP-A-1-150,1.
No. 35, No. 2-110, 557, No. 2-178, 65
No. 0, RD 17, 643 (1978) (24)-(2
5) Compounds described on page and the like. These compounds are preferably used in an amount of 5 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol, and more preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol, per mol of silver.

For the photosensitive material and the processing member, a coating aid,
Various surfactants can be used for the purposes of improving peelability, improving slipperiness, preventing electrification, and promoting development. Specific examples of the surfactant are known in the art No. 5 (March 22, 1991).
136-138, published by Aztec Co., Ltd., JP 62-173,463, 62-183.
457, etc. The photosensitive material and the processing member may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification, improving peelability and the like. Typical examples of organic fluoro compounds include Japanese Examined Patent Publication No. 57-9053 No. 8 to
Column 17, JP-A-61-2944, JP-A-62-1358
No. 26, etc., or a hydrophobic fluorine compound such as an oily fluorine compound such as fluorine oil or a solid fluorine compound resin such as tetrafluoroethylene resin.

A matting agent can be used in the light-sensitive material. Examples of the matting agent include silicon dioxide, polyolefin and polymethacrylate.
No. 29, benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads.
No. 952. In addition, the compounds described in the above Research Disclosure can be used. In the present invention, the same support as that used for the above-mentioned processing member is preferably used as the support of the photosensitive material.

In particular, as a support for a light-sensitive material, it is difficult to curl up and rolls over.
No. 1, No. 6-51426, No. 6-51437, No. 6
-51442, Japanese Patent Application No. 4-251845, 4-2
No. 31825, No. 4-253545, No. 4-2588
No. 28, No. 4-240122, No. 4-221538.
Nos. 5-21625, 5-15926, 4-
Nos. 331928, 5-199704, and 6-134
The supports described in JP-A-55 and JP-A-6-14666 can be preferably used. Further, a support which is mainly a styrene polymer having a syndiotactic structure can also be preferably used. Also, JP-A-4-124
No. 645, No. 5-40321, No. 6-35092,
It is preferable to record photographing information and the like using a support having a magnetic layer described in Japanese Patent Application Nos. 5-58221 and 5-106979.

The photographic light-sensitive material used in the present invention is subjected to the same processing as an ordinary color negative, and can be loaded into a camera to directly photograph. Japanese Examined Patent Publication No. 2-352615, Jikken 3-39
The film unit with a lens described in Japanese Patent No. 784 can also be preferably used.

The photosensitive material and / or the processing member may have a form having a conductive heating element layer as a heating means for heat development. In this case, the heat generating element described in JP-A-61-145544 can be used.

The heating temperature in the heat development step is about 50 ° C. to 2 ° C.
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 hot solvent or other solvent may be used for promoting dye transfer.

In the present invention, a method of heating and developing 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 not higher than the boiling point of water. 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 forter, or the like can be used. Further, in the thermal developing apparatus using the photosensitive material and the image receiving element of the present invention, water may be used up or may be used repeatedly. In the latter case, water containing components eluted from the material will be used. Further, JP-A-63-144,354 and JP-A-63-144,35.
5, 62-38,460, JP-A-3-210,5.
The device described in No. 55 or the like or water may be used.

In the present invention, the amount of dampening water applied to the light-sensitive material may be not more than the weight of water corresponding to the maximum swelling volume of the entire coating film of the light-sensitive material and the processing member. As the method of applying water, for example, the methods described in JP-A-62-253,159, page (5) and JP-A-63-85,544 are preferably used. Further, the solvent can be used by being encapsulated in a microcapsule or incorporated in the photosensitive material or the dye-fixing element or both in advance in the form of a hydrate. The temperature of the water to be applied is determined by the method described in JP-A-63-85,54.
As described in No. 4 etc., it may be 30 ° to 60 °.

As a heating method in the developing and / or transferring step, a heated block or plate is brought into contact with a heating plate, a hot presser, a heating roller, a heating drum, a halogen lamp heater, an infrared and far infrared lamp heater. There is a method of contacting with, etc. or passing through in a high temperature atmosphere. A method of superimposing a light-sensitive material and a processing member is disclosed in JP-A-62-253,159 and JP-A-61-161.
The method described in page 147, 244 (27) can be applied.

Any of various heat developing apparatuses can be used in the heat developing treatment of the present invention. For example, JP-A-59-75,
247, 59-177, 547, 59-18.
No. 1,353, No. 60-18,951, No. 62-
No. 25,944; Japanese Patent Application No. 4-277,517;
243,072, 4-244,693, 6-1
The devices described in JP-A-64421 and JP-A-6-164422 are preferably used. As a commercially available device, there is a Pictrostat 100 manufactured by Fuji Photo Film Co., Ltd.
Pictrostat 200, Pictrostat 30
0, Pictography 3000, Pictography 2000, etc. can be used.

In the present invention, no additional development stop processing is required after the development processing. However, a development stopper may be included in the processing member so that the development stopper works at the same time as 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 specifically, JP-A-62-253,159
Nos. (31) to (32). Further, a combination in which a zinc salt of mercaptocarboxylic acid described in Japanese Patent Application No. 6-190529 is contained in a photosensitive element and a complex forming compound is contained in a processing 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. As an example of the printout prevention agent, Japanese Examined Patent Publication No.
No. 64, monohalogen compounds described in JP-A-53-460.
A trihalogen compound described in No. 20, JP-A-48-452;
Compounds described in No. 28, in which a halogen is bonded to an aliphatic carbon atom, and polyhalogen compounds represented by tetrabromoxylene described in JP-B-57-8454. Further, a development inhibitor such as 1-phenyl-5-mercaptotetrazole described in British Patent 1,005,144 is also effective. In addition, Japanese Patent Application No. 6-337531.
The viologen compounds described in the above publication are also effective.
The use amount of the printout inhibitor is preferably 10 ^-4 to 1.
Mol / Ag 1 mol, particularly preferably 10 ⁻³ to 10 ⁻¹ mol / Ag ¹ mol.

[0067]

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 a color negative film photosensitive material (K01) will be described. A method for preparing a zinc hydroxide dispersion will be described.

12.5 g of zinc hydroxide having an average particle size of 0.2 μm, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate were added to 100 ml of a 4% gelatin aqueous solution, and the average particle size was 0.75 mm with a mill. It was ground for 30 minutes using glass beads. The glass beads were separated to obtain a dispersion of zinc hydroxide.

Next, a method for preparing a dispersion of the electron transfer agent will be described.

10 g of the following electron transfer agent and 0.5 of polyethylene glycol nonyl phenyl ether as a dispersant
g, 0.5 g of the following surfactant (1) was added to a 5% gelatin aqueous solution, and the mixture was pulverized with a mill for 60 minutes using glass beads having an average particle size of 0.75 mm. The glass beads were separated to obtain a dispersion of the electron transfer agent having an average particle size of 0.35 μm.

[0071]

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[0072]

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Next, a method for preparing a gelatin dispersion of a hydrophobic additive will be described.

Cyan, magenta, and yellow dye-donor compounds and electron-donor gelatin dispersions are shown in Table K1, respectively.
I adjusted the prescription. That is, each oil phase component was heated and dissolved at about 60 ° C. to form a uniform solution. This solution and the aqueous phase component heated at about 60 ° C. were added, mixed with stirring, and dispersed with a homogenizer for 13 minutes at 12,000 rpm. Water was added thereto and stirred to obtain a uniform dispersion.

[0075]

[Table 1]

[0076]

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[0077]

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[0078]

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[0079]

[Chemical 6]

[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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[0087]

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[0088]

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[0089]

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Next, a method for preparing a photosensitive silver halide emulsion will be described.

Photosensitive Silver Halide Emulsion (1) [For red-sensitive emulsion layer] Well-stirred aqueous gelatin solution (in 700 ml of water, 20 g of gelatin, 0.5 g of potassium bromide, 2.5 g of sodium chloride and the following chemicals) (A) Add 15mg and 42 ℃
The solution (I) and the solution (II) shown in Table K2 were simultaneously added to the sample (which was kept warm) at a constant flow rate for 8 minutes. Then, 8 minutes after the addition of the solutions (I) and (II) was completed, an aqueous solution of a gelatin dispersion of a dye (1.9 g of gelatin in 160 ml of water, the following dye (a) 12) was added.
7 mg, the following dye (b) 253 mg, the following dye (c) 8
which contained mg and was kept at 35 ° C.) was added. After 2 minutes, the solutions (III) and (IV) in Table 2 were further added simultaneously at the same flow rate for 32 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin and 50 mg of the following chemical (B) were added to adjust pH to 6.2 and pAg to 7.8, and then 4-hydroxy-6-. Methyl-1,3,3a, 7-tetrazaindene was added, and then sodium thiosulfate and chloroauric acid were added to optimally perform chemical sensitization at 68 ° C. Then, an antifoggant (1) described below, After adding 80 mg of the chemical (C) and 3 g of the chemical (D), the mixture was cooled. Thus, the average particle size of 0.
635 g of 21 μm monodisperse cubic silver chlorobromide emulsion were obtained.

[0093]

[Table 2]

[0094]

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[0095]

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[0096]

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Photosensitive silver halide emulsion (2) [for red-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide and 9 g of sodium chloride in 700 ml of water).
g and the above-mentioned chemical (A) (15 mg) and kept at 53 ° C.), the liquids (I) and (II) in Table K3 were added at the same time to 10 parts.
Add at an equal flow rate for minutes. Then, 6 minutes after the addition of the solutions (I) and (II) is completed, an aqueous solution of a gelatin dispersion of the dye (water 115
1.2 g of gelatin, 77 mg of the above dye (a), 153 mg of the above dye (b), and 5 mg of the above dye (c), which had been kept at 45 ° C., were added to each ml. After 4 minutes, the solutions (III) and (IV) in Table K2 were further added simultaneously at the same flow rate for 30 minutes.

After washing with water and desalting by a conventional method, 33 g of lime-treated ossein gelatin and 50 mg of the above-mentioned chemical (B) were added to adjust pH to 6.2 and pAg to 7.8, and then 4-hydroxy-6-. Methyl-1,3,3a, 7-tetrazaindene was added, and then sodium thiosulfate and chloroauric acid were added to optimally perform chemical sensitization at 68 ° C., and then an antifoggant (1) described later, After adding 80 mg of the chemical (C) and 3 g of the chemical (D), the mixture was cooled. Thus, the average particle size of 0.
635 g of a 45 μm monodisperse cubic silver chlorobromide emulsion was obtained.

[0099]

[Table 3]

Photosensitive Silver Halide Emulsion (3) [For Green Sensitive Emulsion Layer] Well stirred gelatin aqueous solution (20 g gelatin in 690 ml water, 0.5 g potassium bromide, 5 sodium chloride)
g and the above-mentioned chemical (A) (15 mg) and kept at 41 ° C.) simultaneously with liquid (I) and liquid (II) in Table K4.
Add at an equal flow rate for minutes. 10 minutes later (III) of Table K4
The solution and the solution (IV) were simultaneously added at an equal flow rate for 32 minutes. Also
One minute after the addition of the solutions (III) and (IV) was completed, 280 mg of the following dye (d) was added to a methanol solution of the dye (47 ml of methanol).
Which was kept at 30 ° C.) was added all at once.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin, 50 mg of the above-mentioned chemical (B) and 3 g of chemical (D) were added to adjust pH to 6.0 and pAg to 7.1. 4-hydroxy-6-methyl-1,3,3a, 7
-Tetrazaindene was added, then sodium thiosulfate was added for optimum chemical sensitization at 60 ° C, and then the antifoggant (1) described later was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.23 μm was obtained.

[0102]

[Table 4]

[0103]

Embedded image

Photosensitive Silver Halide Emulsion (4) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide and 9 g of sodium chloride in 710 ml of water).
g and the above-mentioned chemical (A) 7.5 mg were added and kept at 63 ° C.) at the same time with the solutions (I) and (II) in Table K5.
It was added at an equal flow rate for 0 minutes. After 10 minutes, (II in Table K5
Solution (I) and solution (IV) were added simultaneously at the same flow rate for 20 minutes.
One minute after the addition of the solutions (III) and (IV), a dye solution in methanol (the following dye (d-1) was added to 35 ml of methanol).
210 mg and (d-2) 42.7 mg, which were kept at 46 ° C.) were added all at once.

After washing with water and desalting by a conventional method, 33 g of lime-treated ossein gelatin, 50 mg of the above-mentioned chemical (B) and 3 g of chemical (D) were added to adjust pH to 6.0 and pAg to 7.2. 4-hydroxy-6-methyl-1,3,3a, 7
-Tetrazaindene was added, sodium thiosulfate and chloroauric acid were added, and the mixture was optimally chemically sensitized at 60 ° C. Then, the following antifoggant (1) was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.45 μm was obtained.

[0106]

[Table 5]

[0107]

[Chemical 21]

Photosensitive Silver Halide Emulsion (5) [For blue-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin in 690 ml of water, 0.5 g of potassium bromide, 5 parts of sodium chloride)
g and the above-mentioned chemical (A) (15 mg) and kept at 46 ° C.) simultaneously with liquid (I) and liquid (II) in Table K6.
Add at an equal flow rate for minutes. After 10 minutes, (III) in Table K6
Solution and (IV) solution were added simultaneously at the same flow rate for 18 minutes. Also
One minute after the addition of the solutions (III) and (IV) was completed, the following dye (e) 225 was added to an aqueous solution of the dye (in 95 ml of water and 5 ml of methanol:
mg and 225 mg of the following dye (f) and kept at 30 ° C.) were added all at once.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin, 50 mg of the above-mentioned chemical (B) and 3 g of chemical (D) were added to adjust pH to 6.0 and pAg to 7.7. 4-hydroxy-6-methyl-1,3,3a, 7
-Tetrazaindene was added, then sodium thiosulfate was added for optimum chemical sensitization at 65 ° C, and then the antifoggant (1) described later was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.27 μm was obtained.

[0110]

[Table 6]

[0111]

Embedded image

Photosensitive Silver Halide Emulsion (6) [For Blue Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide, 9 g of sodium chloride in 710 ml of water).
g and the above-mentioned chemical (A) (15 mg) and kept at 59 ° C.), the solution (I) and the solution (II) in Table K7 are added at the same time.
Add at an equal flow rate for minutes. 10 minutes later (III) of Table K7
Solution and (IV) solution were added simultaneously at the same flow rate for 18 minutes. Also
One minute after the addition of the solutions (III) and (IV) was completed, the dye (e) 113 was added to an aqueous solution of the dye (82 ml of water and 6 ml of methanol).
mg and the above dye (f) (113 mg, kept at 40 ° C.) were added all at once.

After washing with water and desalting by a conventional method, 33 g of lime-treated ossein gelatin, 50 mg of the above-mentioned chemical (B) and 3 g of chemical (D) were added to adjust pH to 6.0 and pAg to 7.7. 4-hydroxy-6-methyl-1,3,3a, 7
-Tetrazaindene was added, sodium thiosulfate and chloroauric acid were added, and the mixture was optimally chemically sensitized at 65 ° C. Then, the following antifoggant (1) was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.47 μm was obtained.

[0114]

[Table 7]

Photosensitive material K01 shown in Table K8 was prepared using the above materials.

[0116]

[Table 8]

[0117]

[Table 9]

[0118]

[Table 10]

[0119]

Embedded image

Next, production of a processing member used for forming an image on a light-sensitive material by processing in combination with the light-sensitive material will be described.

A method for preparing a dispersion of the additive (2) will be described.

[0122]

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1 g of the additive (2) and 1.2 g of the anionic surfactant (3) were added to 100 g of the high boiling point solvent (1) at 50 ° C.
Dissolve by heating. Separately, 30 g of lime-treated gelatin 60 g
After swelling in 0 cc of deionized water, dissolve at 70 ° C,
Add preservative. Both are mixed at 40 ° C. and then emulsified and dispersed by an ultrasonic dispersion device. By this operation, an emulsified dispersion having an average particle diameter of the additive (2) of 0.1 μ to 1 μ is obtained.

[0124]

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Using the above dispersion and the raw materials listed in Table R1, the treatment member R101A coated on the support A1 listed in Table A1 according to the construction listed in Table R1 and the support having the construction listed in Table A2. Processing member R101B applied to
Was prepared.

[0126]

[Table 11]

[0127]

[Table 12]

[0128]

[Table 13]

[0129]

Embedded image

[0130]

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[0131]

Embedded image

[0132]

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Similarly, processing members 101A and 101B
Processing members 102A and 10A were manufactured in exactly the same manner except that the structure of the first layer was replaced with that shown in Table B1.
2B was created. Further, treated members 103A to 105A and 103B to 105B were prepared in the same manner except that the boron compound in the first layer was replaced with one shown in Table V1. At that time, the pH of the coating liquid for the layer was adjusted using sodium hydroxide or sulfuric acid.

[0134]

[Table 14]

[0135]

[Table 15]

[0136]

[Table 16]

The above-mentioned photosensitive element (K01) was replaced with a conventional 35 mm
36 pieces of color negative film were cut, punched, loaded into a camera, and a standard image was taken in close-up. Separately, the above-mentioned processing member (R101) cut into a sheet having a width of 40 mm and a length of 2 m was wound around a roll-shaped core (delivery side) having a diameter of 1 inch so that the coated surface was outward. Then, the tip 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 drum heater during feeding and winding. Next, the dampening water kept at 40 ° C. was spread on the exposed photosensitive material surface at a rate of 13 ml / m ² . The processing member is attached to the drum heater so that the surface of the photosensitive material and the film surface of the processing member are evenly overlapped, and the photosensitive material is moved while the processing member and the photosensitive material are moved at the same speed as the rotation speed of the drum heater. The treatment was performed by adjusting the speed and the heater temperature so that the treatment member was heated at 80 ° C. for 20 seconds before being separated from the treatment member. Next, the processing member was peeled from the photosensitive material at a position separated from the heater drum. At this time, the treatment member adhered to the photosensitive material side, and even if a part of the film was peeled off from the treatment member support, the adhesiveness was evaluated as ×, and the other one was evaluated as ○, and Table V
1 The combination of the aluminum vapor-deposited support of the present invention and the addition of the boron compound at the lowermost layer of the treatment member had good adhesiveness and handleability.

It was recognized that the handling superiority due to the good adhesion was slight even when the layer containing the boron compound was not the lowermost layer but the upper layer. In addition, the support is P
Similar results were obtained with PEN as well as with ET. Further, instead of the drum heater as described above, a conveying member is provided on a flat or curved heater, and when the photosensitive material and the processing member are processed so that the photosensitive material and the processing member are moved on the conveying member, the adhesion is also the same. The handleability was good.

Example 2 The production of the color positive photosensitive material (K02) is described below.

Next, a method for preparing a gelatin dispersion of the compound (d) will be described. Compound (d) 0.4 g, high boiling point organic solvent (1) 1.2 g, compound (f) 0.12 g,
0.25 g of compound (g) and 0.05 of compound (h)
g, 0.2 g of surfactant (1), 9.5 cc of ethyl acetate was added, and the mixture was heated and dissolved at about 60 ° C. to form a uniform solution. This solution and an 18% solution of lime-processed gelatin 29.1
g, and then mixed with a homogenizer for 100 minutes for 10 minutes.
Dispersed at 00 rpm. After dispersion, add 18.5 cc of water for dilution.
added. This dispersion is referred to as a dispersion of the compound (d).

[0142]

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Next, a method for preparing a gelatin dispersion of the dye-donor compound will be described. Cyan dye-donating compound (A
1) 7.3 g, cyan dye-donating compound (A2) 11.0 g, surfactant (1) 0.8 g, compound (h) 1 g, compound (i) 2.2 g, high boiling point 7 g of the organic solvent (1) and 3 g of the high boiling organic solvent (2) are weighed,
Ethyl acetate (26 ml) and water (1.2 ml) were added and dissolved by heating at about 60 ° C. to form a uniform solution. This solution, 65 g of a 16% solution of lime-processed gelatin, and 87 cc of water were stirred and mixed, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. After dispersion, 216 cc of water for dilution was added. This dispersion is referred to as a dispersion of a cyan dye-donating compound.

[0144]

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[0145]

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3. The magenta dye-donating compound (B) was added to 4.
50 g, 0.05 g of the compound (m), 0.05 g of the compound (h), 0.094 g of the surfactant (1), and 2.25 g of the high boiling organic solvent (2) were weighed, and 10 ml of ethyl acetate was weighed.
And heated and dissolved at about 60 ° C. to form a uniform solution. This solution, 15.2 g of a 16% solution of lime-processed gelatin, and 23.5 cc of water were stirred and mixed, and then dispersed with a homogenizer for 10 minutes at 10,000 rpm. Then, add 42 water for dilution.
cc added. This dispersion is referred to as a dispersion of a magenta dye-donating compound.

[0147]

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The yellow dye-donor compound (C) was added to 15
g, 2.3 g of compound (d) and 0.9 g of compound (h)
g, 0.88 g of surfactant (1), 3.9 g of compound (J), 1.9 g of compound (K), and 16.9 g of high boiling organic solvent (1), and 49 ml of ethyl acetate was added. ,
It was heated and dissolved at about 60 ° C. to obtain a uniform solution. This solution, 63.5 g of a 16% solution of lime-processed gelatin, and 103 cc of water were mixed with stirring, and then the mixture was mixed with a homogenizer for 10 minutes to obtain 1000
Dispersed at 0 rpm. Thereafter, 94 cc of water for dilution was added. This dispersion is referred to as a yellow dye-donating compound dispersion.

[0149]

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By these, a photothermographic material K02 as shown in Table L1 was constructed.

[0151]

[Table 17]

[0152]

[Table 18]

Processing members R101A to 1 used in Example 1
When 05B was used to perform the same preparation, treatment, and evaluation of the members as in Example 1, it was possible to confirm very good adhesion. However, the temperature during processing is 8
The treatment was carried out at 3 ° C. for 35 seconds. When the processing members were processed to have a width of 160 mm and a length of 2 m, and four photosensitive elements K02 processed to have a width of 35 mm were arranged in parallel at the same time, substantially the same results were obtained.

Example 3 First, the photosensitive element (K03) will be described.

The dye composition was prepared and added as an emulsified dispersion as follows. The leuco dye, the color developer and, if necessary, the high boiling point organic solvent are weighed, and ethyl acetate is added to
100 cc of this solution
On the other hand, 1.0 g of the surfactant (1) and 190 cc of a 6.6% aqueous solution of lime-processed gelatin heated to about 60 ° C. were added and dispersed at 10,000 ppm for 10 minutes with a homogenizer. Two types of dye dispersions shown in Table M1 were prepared.

[0156]

[Table 19]

[0157]

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A method for preparing a photosensitive silver halide emulsion will be described.

Photosensitive Silver Halide Emulsion (1) [For red-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 2.5 g of sodium chloride and the following chemicals in 700 ml of water) (A) Add 15mg and 42 ℃
The solution (I) and the solution (II) shown in Table M2 were simultaneously added to the sample (which was kept warm) at an equal flow rate for 8 minutes. Then, 8 minutes after the addition of the solutions (I) and (II) was completed, an aqueous solution of a gelatin dispersion of a dye (1.9 g of gelatin in 160 ml of water, the following dye (a) 12) was added.
7 mg, the following dye (b) 253 mg, the following dye (c) 8
which contained mg and was kept at 35 ° C.) was added. After 2 minutes, the solutions (III) and (IV) in Table 2 were further added simultaneously at the same flow rate for 32 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin and 50 mg of the following chemical (B) were added to adjust pH to 6.2 and pAg to 7.8, and then 4-hydroxy-6- Methyl-1,3,3a, 7-tetrazaindene was added, and then sodium thiosulfate and chloroauric acid were added for optimum chemical sensitization at 68 ° C., and then the following antifoggant (1), chemical (C ) 80 mg and 3 g of the chemical (D) were added and then cooled. Thus, the average particle size is 0.21 μm
635 g of a monodispersed cubic silver chlorobromide emulsion was obtained.

[0161]

[Table 20]

[0162]

Embedded image

[0163]

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[0164]

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Photosensitive silver halide emulsion (2) [for red-sensitive emulsion layer] An aqueous solution of well-stirred gelatin (in 700 ml of water, 20 g of gelatin, 0.3 g of potassium bromide, 9 g of sodium chloride)
g and the above-mentioned chemical (A) (15 mg) and kept at 53 ° C.), the solution (I) and the solution (II) shown in Table M3 were added at the same time.
Add at an equal flow rate for minutes. Then, 6 minutes after the addition of the solutions (I) and (II) is completed, an aqueous solution of a gelatin dispersion of the dye (water 115
1.2 g of gelatin, 77 mg of the above dye (a), 153 mg of the above dye (b), and 5 mg of the above dye (c), which had been kept at 45 ° C., were added to each ml. After 4 minutes, solution (III) and solution (IV) in Table 2 were further added simultaneously at the same flow rate for 30 minutes.

After washing with water and desalting in the usual way, 33 g of lime-treated ossein gelatin and 50 mg of the above-mentioned chemical (B) were added to adjust pH to 6.2 and pAg to 7.8, 4-hydroxy-6-. Methyl-1,3,3a, 7-tetrazaindene was added, and then sodium thiosulfate and chloroauric acid were added to optimally perform chemical sensitization at 68 ° C., and then the antifoggant (1), chemical (C ) 80 mg and 3 g of the chemical (D) were added and then cooled. Thus, the average particle size is 0.45 μm
635 g of a monodispersed cubic silver chlorobromide emulsion was obtained.

[0167]

[Table 21]

Photosensitive Silver Halide Emulsion (3) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 5 g of sodium chloride in 690 ml of water).
g and the above-mentioned chemical (A) (15 mg) and kept at 41 ° C.), the liquid (I) and the liquid (II) in Table M4 are added at the same time.
Add at an equal flow rate for minutes. After 10 minutes, solutions (III) and (IV) shown in Table 4 were simultaneously added at the same flow rate for 32 minutes. Also (I
II), 1 minute after the addition of the solution (IV), a dye solution in methanol (47 ml of methanol was added with the following dye (d-1) 2810)
mg and (d-2) 57.3 mg which were kept at 30 ° C.) were added all at once.

After washing with water and desalting by a conventional method, lime-treated ossein gelatin 50 mg of the above-mentioned drug (B), 3 g of the drug (D)
Was added to adjust pH to 6.2 and pAg to 7.8.
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, followed by sodium thiosulfate to give 60
Optimum chemical sensitization at ℃, then the following antifoggant (1)
And then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.23 μm was obtained.

[0170]

[Table 22]

[0171]

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Photosensitive Silver Halide Emulsion (4) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide, 9 g of sodium chloride in 710 ml of water).
g) and 7.5 mg of the above-mentioned chemical (A) were added, and the mixture was kept at 63 ° C.).
It was added at an equal flow rate for 0 minutes. After 10 minutes, (III) in Table 5
The solution and the solution (IV) were simultaneously added at an equal flow rate for 20 minutes. Also
One minute after the completion of the addition of the solution (III) or (IV), a methanol solution of the dye (the dye (d-1) 21 in 35 ml of methanol) was added.
0 mg and (d-2) containing 42.7 mg and kept at 46 ° C.) were added all at once.

After washing with water and desalting by a conventional method, 33 g of lime-treated ossein gelatin, 50 mg of the above chemical (B) and 3 g of chemical (D) were added to adjust pH to 6.0 and pAg to 7.2. , 4-hydroxy-6-methyl-1,3,3a,
7-Tetrazaindene was added, then sodium thiosulfate and chloroauric acid were added for optimum chemical sensitization at 60 ° C, and then the following antifoggant (1) was added and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.45 μm was obtained.

[0174]

[Table 23]

Photosensitive Silver Halide Emulsion (5) [For Blue Sensitive Emulsion Layer] Well stirred gelatin aqueous solution (20 g gelatin in 690 ml water, 0.5 g potassium bromide, 5 sodium chloride)
g and the above-mentioned chemical (A) (15 mg) and kept at 46 ° C.), the solution (I) and the solution (II) in Table M6 are added at the same time.
Add at an equal flow rate for minutes. After 10 minutes, solutions (III) and (IV) shown in Table 6 were simultaneously added at the same flow rate for 18 minutes. Also (I
II), 1 minute after the addition of solution (IV) is completed, an aqueous solution of the dye (water 9
225 mg of the following dye (e) in 5 ml and 5 ml of methanol
And the following dye (f) containing 225 mg and kept at 30 ° C.) were added all at once.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin, 50 mg of the above-mentioned chemical (B) and 3 g of chemical (D) were added to adjust pH to 6.0 and pAg to 7.7. 4-hydroxy-6-methyl-1,3,3a, 7
-Addition of tetrazaindene, then sodium thiosulfate, optimal chemical sensitization at 65 ° C, then addition of the following antifoggant (1) followed by cooling. Thus, a monodisperse cubic silver chlorobromide emulsion 63 having an average grain size of 0.27 μm was prepared.
5 g were obtained.

[0177]

[Table 24]

Photosensitive Silver Halide Emulsion (6) [For Blue Sensitive Emulsion Layer] Well stirred gelatin aqueous solution (20 g of gelatin, 0.3 g of potassium bromide, 9 g of sodium chloride in 710 ml of water).
g and the above-mentioned chemical (A) (15 mg) and kept at 59 ° C.), the solution (I) and the solution (II) in Table M7 are added at the same time.
Add at an equal flow rate for minutes. After 10 minutes, solutions (III) and (IV) in Table 7 were simultaneously added at the same flow rate for 18 minutes. Also (I
II), 1 minute after the addition of the solution (IV), an aqueous solution of the dye (water 8
113 mg of the following dye (e) in 2 ml and 6 ml of methanol
And the above-mentioned dye (f) containing 113 mg and kept at 40 ° C.) were added all at once.

After washing with water and desalting in the usual way, 33 g of lime-treated ossein gelatin, 50 mg of the above-mentioned chemical (B) and 3 g of chemical (D) were added to adjust pH to 6.0 and pAg to 7.7. 4-hydroxy-6-methyl-1,3,3a, 7
-Tetrazaindene was added, sodium thiosulfate and chloroauric acid were added, and the mixture was optimally chemically sensitized at 65 ° C. Then, the following antifoggant (1) was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.47 μm was obtained.

[0180]

[Table 25]

<Preparation Method of Zinc Hydroxide Dispersion>

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

Next, a method for preparing a dispersion of the electron transfer agent will be described.

10 g of the following electron transfer agent (a), 0.5 g of polyethylene glycol nonyl phenyl ether as a dispersant, 0.5 g of the following anionic surfactant (a)
Is added to a 5% gelatin aqueous solution and the average particle size is 0.75 with a mill.
Milled for 60 minutes with mm glass beads. The glass beads were separated to obtain a dispersion of the electron transfer agent having an average particle size of 0.35 Am.

[0185]

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<Preparation Method of Emulsion Dispersion of Coupler>

The oil phase component and the water phase component having the compositions shown in Table M8 were dissolved to obtain a uniform solution at 60 ° C. Combine the oil phase component and the water phase component in a 1 liter stainless steel container,
A disperser having a diameter of 5 cm was used and dispersed by a dissolver at 10,000 rpm for 20 minutes. To this was added hot water in an amount shown in Table 4 as post-water and mixed at 2000 rpm for 10 minutes. Thus, an emulsified dispersion of couplers of three colors of cyan, magenta and yellow was prepared.

[0188]

[Table 26]

[0189]

Embedded image

Using the thus obtained material, a multilayer heat-developable color photosensitive material K03 shown in Table N1 was produced.

[0191]

[Table 27]

[0192]

[Table 28]

[0193]

Embedded image

Next, preparation of the processing member will be described. Table R
According to the constitution described in 2, a treatment material R201A applied on the support having the constitution of Table A1 was produced. Similarly, table A2
A processing member R201B applied on the support having the above constitution was produced.

[0195]

[Table 29]

Similarly, the boron compounds shown in Table V1 were prepared as shown in Table B.
1 and treating members R202A to R205A and R201B in exactly the same manner as described in Table V1.
~ R205B was created. When the same members as in Example 1 were prepared, treated, and evaluated, the treated members (R203B, R204B, R205) of the combination of the present invention were obtained.
B) showed good adhesion as well. However, the development temperature was 83 ° C. and the development time was 30 seconds. Also,
The processing member was processed to have a width of 40 mm and a length of 6 m, and three photosensitive elements K03 processed to have a width of 35 m and a length of 1.5 m were connected in series in the longitudinal direction and processed by one continuous development. , An image was obtained in the same manner, showing good handleability.

Example 4 A method for producing a photosensitive silver halide emulsion will be described. To a well-stirred aqueous gelatin solution having the composition shown in Table B1,
Solution (I) and solution (II) shown in Table B2 were added simultaneously for 10 minutes, and 2 minutes after that, solution (III) and solution (IV) were added simultaneously for 18 minutes.

[0198]

[Table 30]

[0199]

[Table 31]

[0200]

Embedded image

Using the compound (a) according to a conventional method, pH of 3.
After demineralization by sedimentation at 0, decalcified gelatin 50 g
Was added to adjust the pH to 5.7 and pAg to 7.5, 0.1 g of the antifoggant (a) was added, and then chemical sensitization was performed at 60 ° C. Hypo as a sulfur sensitizer is 0.0 for chemical sensitization.
03 g and 0.015 g of chloroauric acid as a gold sensitizer were added, respectively, and after 60 minutes, 0.1 g of a preservative (a) and 0.02 g of a stabilizer (a) were added to obtain a silver chlorobromide emulsion. The average grain size of the obtained silver halide was 0.20 μm.

To 100 g of this emulsion was added 1 part of the sensitizing dye (a).
8.0 g was added, and 1.25 ml of 1% methanol solution of compound (a), 7.5% 0.8% methanol solution of compound (c) and 160 mg of surfactant (a), water-soluble polymer (a) Was added to each to obtain an emulsion layer solution, and coating was performed so that the silver amount was 1.4 g / m ² .

[0203]

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[0204]

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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.
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.

Then, a solid-state dispersion of the antihalation dye (a) was also prepared according to the above method to obtain a gelatin dispersion of the antihalation dye.

[0207]

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Next, a method for preparing a zinc hydroxide dispersion will be described. Zinc hydroxide with an average particle size of 0.2 μm 1
2.5 g, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate were added to 100 cc of a 4% gelatin aqueous solution, and dispersed with 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 photosensitive material K04 shown in Table B3 was prepared using the following materials.

[0210]

[Table 32]

[0211]

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The photosensitive element (K04) was set to a width of 550 mm,
It was processed to a length of 760 mm. The light-sensitive element, a semiconductor laser having an output peak wavelength of 670 nm, was exposed by changing the amount of light one pixel (100 [mu] m ²⁾ 1000 per million per second. Separately, the processing element (R201), which was cut into a sheet having a width of 580 mm and a length of 21 m, was wound around a roll-shaped winding core (feeding side) having a diameter of 2 inches so that the coated surface was inward. Then, the tip of the treatment element was partially wound around another winding core (winding side).

The processing member was set such that the film surface of the processing element during the delivery and the winding contacted the outer surface of the curved heater. Next, the exposed photosensitive element was dipped in water kept at 40 ° C. for 2.5 seconds and then squeezed with a roller to adjust the amount of water on the photosensitive element to about 14 ml / m ² . After pasting so that the photosensitive element film surface and the processing element film surface may be evenly overlapped, while moving the processing member and the photosensitive element at the same speed as the rotation speed of the curved surface heater, until the photosensitive element is separated from the processing element. The speed and heater temperature were adjusted so that the sample was heated at 80 ° C. for 25 seconds, and the treatment was performed. Next, the processing member and the photosensitive element were simultaneously separated from the curved heater, and then the processing member was peeled from the photosensitive element. By this operation, the processing members (R203B, R204B, R2) of the combination of the present invention are
In 05B), there was no problem in bonding and peeling, an image was formed on the photosensitive element with silver, and the adhesion and handleability were good.

Claims (5)

[Claims] 1. A processing member used for forming an image on a photothermographic material, which comprises superimposing a heat-developable photosensitive material containing silver halide, on the photosensitive material, wherein the processing member is an aluminum-deposited base. A processing member having a processing layer provided on an aluminum vapor deposition surface. 2. The base thickness according to claim 1, wherein the base thickness is 4 μm.
A processing member having a thickness of at least 40 μm. 3. The treatment member according to claim 2, wherein the lowest layer of the treatment layers provided on the base contains a boron compound. 4. The processing member according to claim 2, wherein a support on which aluminum is vapor-deposited is used on the side opposite to the support on which the processing layer is provided. 5. A heat-developable photosensitive material containing silver halide is dampened with water, and then superposed with a treatment member having a treatment layer provided on the aluminum vapor-deposited surface of an aluminum vapor-deposited base, and heated. A heat-development image forming method, which comprises forming an image on the light-sensitive material.