JPS62245258A - Image forming method - Google Patents

Abstract

PURPOSE:To prevent transferring irregularity and deterioration of image quality due to cracks of the image by incorporating a mordant and a polymer latex having <=40 deg.C of glass transition point to a fixing element of a coloring matter. CONSTITUTION:The fixing element of the coloring matter contains the mordant and the polymer latex having <=40 deg.C of glass transition point, when a dye image is formed on the fixing element of the coloring matter by heating the combination of a photosensitive element and the prescribed fixing element which fixes a movable coloring matter formed on the photosensitive element, in the presence of water and a base and/or its base precursor. The polymer latex may be a homopolymer or a copolymer having <=40 deg.C glass transition and is preferably, the polymer of an acrylic ester, or the copolymer of an acrylic ester and a methacrylic ester. The used amount of the polymer latex is preferably 5-20vol% per the total vol. of the polymer contd. in the latex. When the used amount is <=5vol%, the effect of preventing the cracks of the image is low, while, when the used amount is >=200vol%, the strength of the formed film is weakened.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for forming a dye image by heating, and particularly to an image forming method for forming an excellent dye image on a dye fixing element.

(Prior art and its problems) Heat-developable photosensitive materials are well known in this technical field, and for information about heat-developable photosensitive materials and their processes, see, for example, "Fundamentals of Photographic Engineering" Non-Silver Salt Photography Edition (published by Corona Publishing, 1982). 2
Pages 42 to 255, Published in April 1978 Video information page 40, N5blets Handbook
of Pholography andReprog
raphF) 7th Edition (7th Ed,) Van Nostr Line Hold Kanno Knee (VanNostr
and Re1nhold Company) 32~
33 pages, U.S. Patent No. 3,152,904, U.S. Patent No. 3,3
No. 01,678, No. 3,392,020, No. 3.
457,075, British Patent No. 1,131,108;
No. 1,167,777 and Research Disclosure Magazine, June 1978 issue, pages 9-15 (RD-170
29).

For information on how to obtain color images through heat development,
Many methods have been proposed. Regarding a method of forming a color image by combining an oxidized developer with a cazoler, U.S. Pat. No. 761,270 describes p-amine phenolic reducing agents as described in Belly Patent No. 802,519 and Research Disclosure, September 3, 1975.
On page 1.32, a sulfonamidophenolic reducing agent is proposed, and in US Pat. No. 4,021,240, a combination of a sulfonamidophenolic reducing agent and a 4-equivalent Kaglar is proposed.

However, in this method, a reduced silver image and a color image are simultaneously generated in the exposed area after thermal development, resulting in a problem that the color image becomes cloudy.

To solve this problem, there are methods to remove the silver image by liquid processing or to transfer only the dye to another layer, such as a sheet with an image-receiving layer. It has the disadvantage that it is not easy to transfer.

Furthermore, the above-mentioned methods generally require a relatively long time for development, and the resulting images have the disadvantage of only high capri and low density.

In order to improve these drawbacks, a method is proposed in which a mobile dye is released imagewise by heating and the mobile dye is transferred to a dye fixing material having a mordant using a solvent such as water, or a high boiling point organic solvent. A method of transferring to a dye-fixing material,
A method has been proposed in which the dye is transferred to a dye-fixing material using a hydrophilic heat solvent incorporated in the dye-fixing material, and a method in which a mobile dye is heat-diffusible or sublimable and is transferred to a dye-receiving material such as a support. There is. (U.S. Patent No. 4,463,079, U.S. Patent No. 4.474,867, U.S. Patent No. 4,478,927,
No. 4,507,380, No. 4,500,626, No. 4,483,914; JP-A-58-14904
No. 6, No. 58-149047, No. 59-152440
No. 59-154445, No. 59-165054, No. 59-180548, No. 59-168439,
(No. 59-174832, No. 59-174833, No. 59-174834, No. 59-174835, etc.) In the above methods, the developing temperature is still high, and the processing time required to obtain a dye image is insufficient. I can't say it's short.

Therefore, development is accelerated by heat development in the presence of a small amount of water, a base and/or a base precursor, and further transfer of the released dye.

A method that lowers the developing temperature, simplifies processing, and shortens processing time is disclosed in Japanese Patent Application Laid-Open No. 59-218,443 and Japanese Patent Application No. 6.
No. 0-79,709.

In the above image forming method, a dye fixing element containing a mordant is used to fix the mobile dye.

These mordants are usually used by coating a hydrophilic colloid such as gelatin on a support or other coating film. However, coatings with polymeric mordants and hydrophilic colloids of this type exhibit significantly different mechanical properties compared to coatings formed with hydrophilic colloids alone. That is, it has been found that a mixed film of an I remer mordant and, for example, gelatin has significantly lower tensile strength and elongation at break, and becomes a brittle film, compared to a film containing only gelatin. Such deterioration of the brittleness of the coating film causes cracking due to thermal and mechanical strain that occurs during the film coating and drying processes, and significantly restricts manufacturing conditions such as spraying and drying.

It has also been found that when thermal or mechanical strain is applied during handling of the dye-fixing element, the mordant layer in the dye-fixing element breaks (cracks).

When performing the above image forming method using a dye fixing element with such cracks, uneven development and/or dye transfer may occur9, or the image may appear to have cuts. , the image quality will deteriorate significantly.

(Object of the Invention) An object of the present invention is to provide an image forming method in which a dye image is formed by heat development in the presence of a small amount of water, which does not cause uneven transfer due to cracks or deterioration of image quality. .

(Structure of the Invention) The object of the present invention is to provide a photosensitive element containing at least a photosensitive silver halide, a binder, and a dye-providing substance on a support, and a dye that fixes a mobile dye formed on the photosensitive element. A method of forming a dye image on a dye fixing element by heating a combination of fixing elements in the presence of water and a base and/or a base precursor, wherein the dye fixing element comprises a mordant and a latex of a polymer having a glass transition point of 40°C or less. This was achieved by an image forming method characterized by containing.

Examples of monomers constituting the polymer latex used in the present invention include acrylic esters, methacrylic esters, crotonic esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, and acrylamides. , methacrylamides, vinyl ethers, styrenes, etc.

More specific examples of these monomers include acrylic esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isozolobyl acrylate, n-butyl acrylate, isobutyl acrylate, t@rt-butyl acrylate, and hexyl acrylate. Acrylate, 2-ethylhexyl acrylate, acetoxyethyl acrylate, phenyl acrylate, 2-methyl acrylate, 2-ethoxy acrylate, 2-(
Examples include 2-methoxyethoxy)ethyl acrylate. Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, and 2-ethoxyethyl methacrylate. Examples of crotonate esters include butyl crotonate, hexyl crotonate, and the like. Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxy acetate, vinyl benzoate, and the like. Examples of maleic acid diesters include diethyl maleate, dimethyl maleate, diptyl maleate, and the like. Examples of fumaric acid diesters include diethyl fumarate, dimethyl fumarate, and diptyl hexamalate. Examples of itaconic acid diesters include diethyl itaconate, dimethyl itaconate, diptyl itaconate, and the like.

Acrylamides include acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, n-butylacrylamide, tart-butylacrylamide, cyclohexylacrylamide, 2-
Examples include methoxyethyl acrylamide, dimethyl acrylamide, diethyl acrylamide, and phenyl acrylamide.

Examples of methacrylamide include methylmethacrylamide,
Examples include ethylmethacrylamide, n-butylmethacrylamide, tert-butylmethacrylamide, 2-methoxymethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, and the like. Vinyl ethers include methyl vinyl ether, butyl vinyl ether,
Examples include hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, and the like. Styrenes include styrene, methylstyrene,
Dimethylstyrene, trimethylstyrene, ethylstyrene, inzolovylstyrene, butylstyrene, chloromethylstyrene, methoxystyrene, butoxystyrene,
Acetoxystyrene, chlorstyrene, dichlorostyrene, bromustyrene, vinylbenzoic acid methyl ester,
Examples include 2-methylstyrene.

The polymer composed of these monomers may be a homopolymer or a copolymer as long as it has a glass transition point of 40° C. or lower. Preferred are acrylic esters, copolymers of acrylic esters and methacrylic esters, and copolymers of acrylic esters and acrylic acid or methacrylic acid.

Free radical polymerization of ethylenically unsaturated solid monomers can be carried out by thermal decomposition of chemical initiators or by the action of reducing agents on oxidizing compounds (redox initiators) or by physical action such as ultraviolet light or other high-energy radiation, radiofrequency, etc. It is initiated by the addition of free radicals to monomer molecules that are formed.

II as the main chemical initiator? - sulfates (ammonium and potassium persulfate), hydrogen peroxide, 4,4'-azobis (4-cyanoparelian rR)
etc. (which are water-soluble), azoisobutyronitrile, penzoylno-9-oxide, chloropenzoyl-9-oxide, and other compounds (which are insoluble in water).

Common redox initiators include hydrogen peroxide-iron (ID salt,
Potassium persulfate-potassium bisulfate, cerium salt alcohol, etc.

Examples of initiators and their effects are given by F. Bov@y r E
Mulsion Polym@rization J
Interscreen＊Publish@s 1ne
, Ntw York, 1955, pp. 59-93.

As the emulsifier, a surface-active compound is used, and preferred examples include soaps, sulfonates and sulfates, cationic compounds, amphoteric compounds, and polymeric protective colloids. Examples of these groups and their effects are B*1
g1sch@Ch@mlacheIndustrle, Vol. 28, pp. 16-20 (1963).

In the present invention, a polymer latex having a glass transition point of 20° C. or lower is particularly preferred.

Specific examples of the polymer latex used in the present invention are described below, but the present invention is not limited thereto.

C00CH20H.

coocu2cm2cH3 COOCH2CC20CH2CMs P-6-(0M2-CM← Tg=-53℃
COOCH2CC00CH2C.

P-7 US CH2-CH-)-Tg=-45℃COOCH
C00CH2C.

P-8be0M2-CM +-Tg=-36℃coo+c
H2cm2o momme CB.

coo÷CM2CM2O hinoki CH5 CH.

Forty , :oocu, Oiqumaheden.

(Copolymerization ratio represents molti) The amount of polymer latex added is defined as the ratio of the total volume of the polymer in the latex added to the layer to the total volume of the hydrophilic binder in the layer, preferably 5 to 5. 20
0 maoL%, more preferably 10 to 100 maoL
%. If it is less than 5 MaoL%, the crack prevention effect will be small, and if it is more than 200 MaoLTo, the film strength will be weak and the maximum concentration will tend to decrease. Expressed in terms of coating amount, the weight of 4 rimers in the latex is preferably 11-51/-, more preferably 10-211/-.

The effect of the polymer latex used in the present invention is particularly remarkable when a 4-limer mordant having a high glass transition point is used.

The polymer latex used in the present invention is preferably contained in a layer adjacent to a mordant layer containing a polymer mordant, but may be contained in the mordant layer.

There are no particular limitations on the /IJ mom-dye used in the present invention, but it contains one vinyl monomer unit having a tertiary amino group or a quaternary ammonio group represented by the following general formula (1). j? IJ Mama - Preferred.

General formula (1) [In the formula, R1 represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms. L represents a divalent linking group having 1 to 20 carbon atoms. E represents a heterocycle containing as a constituent a nitrogen atom having a double bond with a carbon atom. n is ot or 1. ] General formula (10% formula%) [In the formula, 81, LN n represents the same as general formula (10). R4 and R5 are the same or different alkyl groups having 1 to 12 carbon atoms, or 7 It represents an aralkyl group having ~20 carbon atoms, and R4,8, may be interconnected to form a cyclic structure together with a nitrogen atom.] In the general formulas (1) to (translation), R1 is a hydrogen atom. Or a lower alkyl group having 1 to 6 carbon atoms, such as methyl group, ethyl group, n-propyl group, n-butyl group, n-amyl group, n-
It represents a hexyl group, etc., and a hydrogen atom or a methyl group is particularly preferred.

L is a divalent linking group having from 1 to about 20 carbon atoms, such as an alkylene group (e.g., methylene, ethylene, trimethylene, hexamethylene, etc.), a phenylene group (e.g., O-phenylene, p-7 enylene group, m-phenylene group (Nato), represents an alkylene group of about 12.

), -CO□-1-〇〇□-R, - (wherein R5 represents an alkylene group, phenylene group, or arylene alkylene group), -CONH-R, - (however, R5 represents the same as above).

-CON-R, - (however, R1 and R3 represent the same as above), -co□-CH2CH2CH2-1-CONHCH2-
1-CONHCH2CH2-1-CONHCH2CI(
2CH2- and the like are particularly preferred.

General formula (2) % formula % [In the formula, R1 and LN n represent the same as in general formula (1). Go represents a heterocyclic ring which is quaternized and contains as a constituent a nitrogen atom having a double bond with a carbon atom. xe represents a monovalent anion. ] General formula axis [In the formula, R,, X, and %n represent the same as in general formula (1). R4 and R represent the same thing as in general formula (6). R
6 is selected from the same ones that represent R4, R,. xe represents the same thing as the general formula (to). R4, R6
, R6 may be interconnected to form a cyclic structure together with the nitrogen atom. ] In the general formula (1), E represents a heterocycle containing as a constituent a nitrogen atom having a double bond with a carbon atom, for example, an imidazole ring and a pyricine ring are particularly preferred.

Preferred specific examples of the polymer containing one vinyl monomer unit having a tertiary amino group represented by the general formula (1) include U.S. Pat. No. 4,282,305, U.S. Pat.
The following may be mentioned, including the mordants described in No. 124 and No. 3,148,061.

(Number 2 moles qb) In the general formula (2), R4 and R5 are alkyl groups having 1 to 12 carbon atoms, such as unsubstituted alkyl groups (methyl group, ethyl group, n-deropyl group, n-butyl group, n-amyl group, hexyl group, n-nonyl group, n-decyl group, n-dodecyl group, etc.), substituted alkyl groups (methoxyethyl group,
3-cyanopropyl group, ethoxyl is nylethyl group,
Acetoxyethyl group, hydroxyethyl group, 2-butenyl group, etc. ), or an aralkyl group having 7 to 20 carbon atoms, such as an unsubstituted aralkyl group (benzyl group, phenethyl group, diphenylmethyl group, naphthylmethyl group, etc.), substituted aralkyl group (4-methpenzyl group, 4 -isopropylbenzyl group, 4-methoxybenzyl group, 4-(4-methoxyphenyl)benzyl group, 3-chlorobenzyl group, etc.).

Further, as an example in which R4 and R5 are interconnected to form a cyclic structure together with a nitrogen atom, for example, a preferable specific example of a primer containing one vinyl unit having a tertiary amino group represented by the general formula (6) is as follows. , include the following:

In the general formula (to), G represents a quaternized heterocycle containing a nitrogen atom having a double bond with carbon as a constituent, examples of which include imidazolium salts, among which Imidazolium salts and pyridinium salts are particularly preferred.

Therefore, R4 represents the same as the general formula (0), and a methyl group, an ethyl group, and a benzyl group are particularly preferable.

In the general formulas (to) and (Iv), Xθ represents an anion, such as a halodane ion (e.g. chloride ion, bromide ion,
iodine ion), alkyl sulfate ion (e.g. methyl sulfate ion, ethyl sulfate ion), alkyl or aryl sulfonate ion (e.g. methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, P-)luenesulfonic acid) l-[ion, Examples include sulfate ion, and chloride ion (NP-)toluenesulfonate ion is particularly preferred.

stomach.

Preferred specific examples of polymers containing one vinyl monomer unit having a quaternary ammonio group represented by the general formula (to) include British Patent Nos. 2,056,101, 2.093,
No. 041, No. 1,594,961, U.S. Patent No. 4,1
No. 24,386, No. 4,115,124, No. 4.27
No. 3,853, No. 4,450,224, Japanese Unexamined Patent Publication No. 1973-
The following may be mentioned, including the mordants described in No. 28225 and the like.

On the general formula axis, an example in which R4 and R5 are interconnected to form a cyclic structure together with a nitrogen atom is an example in which t R4, R5, and R6 form a cyclic structure. Preferred specific examples of polymers containing one vinyl monomer unit having a class ammonio group include U.S. Pat. No. 3,709,690, U.S. Pat.
The following may be mentioned, including the mordants described in No. 088 and No. 3,958,995.

H3 C2β (number 2 mordants) Examples of polymer mordants that can be used include U.S. Pat. No. 2,548,564, U.S. Pat. , 814, etc., and vinylpyridinium cation I remer; U.S. Patent No. 3,
No. 625,694, No. 3,859,096, No. 4
, No. 128,538, British Patent No. 1.277,453, etc., which can be crosslinked with gelatin etc.
Mordant; U.S. Patent No. 3,958,995, No. 2
, No. 721,852, No. 2,798,063, Japanese Patent Application Laid-open No. 115228/1980, No. 145529/1987, No. 126027 of 1987, etc.: Aqueous sol type mordants disclosed in U.S. Pat. Water-insoluble mordants disclosed in U.S. Pat. No. 3,898,088; U.S. Pat. No. 4,168
, 976 (Japanese Unexamined Patent Publication No. 54-137333), etc., a reactive mordant capable of forming a covalent bond with a dye; furthermore, U.S. Pat.
No. 8,855, No. 3,642,482, No. 3.4
No. 88,706, No. 3,557,066, No. 3.
271,147, 3,271,148, JP 50-71332, 53-30328, 52-
No. 155528, No. 53-125, No. 53-1024
Mordants disclosed in US Pat. No. 2,675
, No. 316 and No. 2,882,156.

The molecular weight of the /IJ mama dye used in the present invention is preferably 1,000 to 1,000,000. Especially 10,00
0 to 200,000.

Such polymeric mordants are used in combination with hydrophilic colloids as binders in mordant layers in dye-fixing elements. Representative examples of hydrophilic colloids include proteins such as gelatin and gelatin derivatives, cellulose derivatives,
Natural substances such as starch, gum arabic, etc.
Includes synthetic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, and polyacrylamide.

Among these, gelatin and I-rivinyl alcohol are particularly preferred.

The mixing ratio of the polymer mordant and hydrophilic colloid and the coating amount of the polymer mordant can be easily determined by those skilled in the art depending on the amount of dye to be mordant, the type and composition of the polymer mordant, and the image forming method to be applied. However, it is appropriate that the mordant/hydrophilic colloid ratio is 20/80 to 80/20 (weight ratio), and the amount of mordant applied is about 0.2 to about 15 f7m, especially 0.5 to 8. ?/m" is preferable.

Polymeric mordants can be used in combination with metal ions in dye fixing elements to increase dye transfer density. This metal ion can be added to the mordant layer containing the mordant, or to a layer adjacent thereto (either near or far from the support supporting the mordant layer). The metal ion used here is desirably colorless and stable against heat and elements. That is, Cu2+, z n2
+, Nt 2 +, pt2+, p d2 +, Co3+
Polyvalent ions of reduction metals such as ions are preferred, and zn2+ is particularly preferred. This metal ion is usually in the form of water-soluble compounds, such as Z n SO4, zn(cH3c
o, ) 7. The amount added is approximately 0. O1 to about 5
5'/m" is appropriate, preferably 0.1 to 1.5
f/m”.

A hydrophilic polymer can be used as a binder in the layer to which these metal ions are added. As the hydrophilic binder, hydrophilic colloids such as those specifically listed above regarding the mordant layer are useful.

The mordant layer containing a polymer mordant can contain various surfactants to improve coating properties.

A gelatin hardener can also be used in the mordant layer.

Gelatin hardeners that can be used in the present invention include:
For example, aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds (1,3,5- ) acryloyl-hexahydro-1-)'J azine, bis(vinylsulfonyl) methyl ether, N,N'-ethyl, renupis(vinylsulfonylacetamide), Ne
N'-) y methylene-bis(vinylsulfonylacetamide), etc.],] active vinyl compound 2,4-dichloro-
6-hydroxy-5-)! j ajinnato), mukoha o
Specific examples include c TiRWi (mucochloric acid, mucophenoxychloric acid, etc.), epoxy compounds (for example, oxazoles, dialdehyde starch, 1-chloro-6-hydroxytriazinylated gelatin, etc.). , U.S. Patent No. 1,870.354, U.S. Patent No. 2,0
No. 80,019, No. 2.726,162, No. 2,87
No. 0,013, No. 2.983,611, No. 2,992
．． No. 109, No. 3.047, No. 394, No. 3.057.
No. 723, No. 3, No. 103.437, No. 3,321,3
No. 13, No. 3,325,287, No. 3,362,82
No. 7, No. 3,490,911, No. 3,539,644
No. 3.543,292, British Patent No. 676.628
German Patent No. 825,544, German Patent No. 1,270,578, German Patent No. 872,153, German Patent No. 1.990.427,
It is described in Japanese Patent Publication No. 2.749.260, Japanese Patent Publication No. 34-7133, Japanese Patent Publication No. 46-1872, etc.

Among these gelatin hardeners, aldehydes, active vinyl compounds, and active rogone compounds are particularly preferred.

These hardeners may be added directly to the mordant layer coating solution, but they may also be added to other coating solutions and diffused into the mordant layer during the process of multilayer coating.

The amount of gelatin hardener used in the present invention can be arbitrarily selected depending on the purpose. Usually, from about 0.1 to about 20 wt(i) of the binder such as gelatin used is suitable, preferably from 1 to 8 wt(i).

In the present invention, a dye fixing element and a photosensitive element are combined and heated in the presence of water and a base and/or a base precursor,
The mobile dye is transferred to the dye-fixing element simultaneously with heating to form an imagewise distribution of the mobile dye. for that,
The photographic material of the present invention has a photosensitive layer on a support containing at least silver t2rnide, optionally an organic silver salt oxidizing agent, optionally a reducing agent, a dye-donating substance, and a binder.
), a dye fixing layer (II) capable of receiving a hydrophilic and diffusible dye formed in
).

The above-mentioned photosensitive layer (1) and dye fixing layer (II) may be formed on the same support, or may be formed on separate supports. Photosensitive layer (1)
For example, after imagewise exposure and uniform heat development, the dye-fixing layer or photosensitive layer can be peeled off. Furthermore, when the photosensitive element having the photosensitive layer (1) coated on the support and the dye fixing element having the dye fixing layer ω) coated on the support are formed side by side, the photosensitive element is subjected to imagewise exposure. When the fixing elements are layered and heated uniformly in the presence of water, the K and diffusible dyes can be transferred to the fixing layer ω), and then both are peeled off to observe the dye image.

In the present invention, water may be supplied by any method. For example, it may be ejected as a jet from pores, or it may be wetted with a web roller.
Alternatively, a pot filled with water may be crushed, and the method is not limited to these or other methods. Further, some of the water may be incorporated into the element as crystal water or microcapsules.

The water used in the present invention is so-called 1K pure water.
water in the widely customary sense of the term. Alternatively, a mixed solvent of pure water and a low boiling point solvent such as methanol, DMF, acetone, or diisobutyl ketone may be used. Furthermore, a liquid containing an image formation accelerator, a hydrophilic heat solvent, etc., which will be described later, may also be used.

When water is supplied externally, it is necessary to supply a certain amount of water to the photosensitive element and/or dye fixing element in order to obtain a uniform image, but a small amount of water is supplied below the maximum swelling amount of the membrane. In some cases, image unevenness is likely to occur due to repellency on the element surface, uneven penetration of water into the film, etc. Therefore, it is possible to improve the spread of water on the material surface by impregnating the water with a surfactant. .

As the above-mentioned surfactant, surfactants known in the photographic industry and generally as wetting agents can be used. These surfactants are described in many well-known documents, such as Surfactant Handbook, Surfactant Science Series (edited by Martin Soei-Schick, Mar*), K.F” Y Kerr Publishing, 196
7 years) [5urfactant Seienc@5er
les (Edited by Martin*LS
ehick, Marc@l Dakker Inc.
a 1967)] and others. Surfactants are classified into cationic, anionic, amphoteric, and nonionic surfactants, but any surfactant can be used as long as it satisfies the requirements described below. Two or more surfactants may be used in combination.

The amount of surfactant used in the present invention varies depending on the type of surfactant, but the surface tension of the aqueous solution is 40 dyn//
It is desirable that the amount added be less than cm.

The amount of water used in the present invention is at least 0.1 times the weight of the total coating of the photosensitive element and dye fixing element, preferably 0.1 times the weight of the total coating to the maximum swelling volume of the total coating. Within the range of the corresponding weight of water, more preferably 0.1 times the weight of the entire coating film to the weight of water corresponding to the maximum swelling volume of the entire coating film minus the weight of the entire coating film. Within range.

The state of the film during swelling is unstable, and depending on the conditions, local K bleeding may occur.To avoid this, the volume of the entire coated film of the photosensitive element and dye fixing element at maximum swelling should be adjusted. It is preferable to place it under a water plate. Specifically, the total area of the photosensitive element and dye fixing element is 1 square meter.
? ~50y-1 especially 2? ~35? , even 3? ~25?
A range of is preferred.

However, the effect of the present invention is the same even when the amount of water is greater than the above-mentioned amount, only the above-mentioned disadvantages occur, and the effect is exhibited in the same way as when the amount of water is within the desired range.

The degree of swelling of the gelatin film varies significantly depending on the degree of hardening, but the degree of hardening is usually adjusted so that the film thickness at the time of large swelling is 2 to 6 times the dry film thickness.

In the present invention, heating is performed, but since the present invention contains a relatively large amount of a solvent called water, the maximum temperature of the photosensitive element is the boiling point of the aqueous solution (various additives dissolved in the added water) in the photosensitive element. It's decided. The minimum temperature is preferably 50°C or higher. The boiling point of water is 100°C under normal pressure, and when heated above 100°C water may evaporate and lose its moisture. It is preferable to supply water vapor of .

In this case, since the boiling point of the aqueous solution also rises, the temperature of the photosensitive material also rises, which is advantageous.

The heating means may be a simple heating plate, an iron, a heating roller, a heating plate using carton, titanium white, or the like. It is also possible to provide the photosensitive element and/or the dye fixing element with an electrically conductive heating layer, and to heat the element by applying electricity to this layer.

The base and/or base precursor used in the present invention may be contained in the water described above, or may be contained in the photosensitive element and/or the dye fixing element.

The bases used in the present invention include hydroxides, carbonates, bicarbonates, borates, secondary and tertiary phosphates, quinoline, etc. of alkali metals, alkaline earth metals, ammonium, quaternary alkylammonium, etc. Inorganic bases such as acid salts and metaborate; aliphatic amines (triple kylamines, hydroxylamines, aliphatic/IJ amines), aromatic amines (N-alkyl substituted aromatic amines, N-hydro Medium silalkyl-substituted aromatic amines and bis(p-(
dialkylamino) phenylcomethanes), heterocyclic amines, amidines, cyclic amidines, guanidines,
Organic bases such as cyclic guanidines and their carbonates,
Bicarbonates, borates, secondary and tertiary phosphates, etc. are mentioned, and US Pat. No. 506.444 describes organic compounds containing amino acids such as urea and 6-7 minocaproic acid, which are useful in the present invention.
Those having a Ka value of 8 or more are particularly useful.

The base precursor used in the present invention is thermal decomposition, 1
A dissolving agent releases or generates a base through a complex formation reaction or the like.

Examples of base precursors include salts of organic acids and bases that are decarboxylated and decomposed by heating, compounds that decompose by Rossen rearrangement, Beckmuff rearrangement, etc. to release amines, and other compounds that cause some kind of reaction when heated to form bases. Examples include those that emit

Examples of the base used in the organic base salt include the above-mentioned inorganic bases and organic bases.

Examples of organic acids include trichloroacetic acid, trifluoroacetic acid, zolopiolic acid, cyanoacetic acid, sulfonylacetic acid, acetoacetic acid, and 2-calgexical poxamide described in U.S. Pat. No. 4,088,496. Can be mentioned.

In addition to salts of organic acids and bases, for example, hydroxamic carbamates described in JP-A-59-168440 using Rossen rearrangement, and JP-A-59-1576 which produce nitriles.
Aldoxime carbamates described in No. 37 are effective, and also Research Disclosure Magazine 1977
Amine imides described in May 15776, aldone amides described in JP-A-50-22625, etc. are preferably used because they decompose at high temperatures to produce bases.

Examples of base precursors that generate bases by electrolysis include the following.

For example, electrolysis of various fatty acid salts can be cited as a typical method using electrolytic oxidation. By this reaction IC, carbonates of alkali metals and organic bases such as guanidines and amidines can be obtained extremely efficiently.

In addition, methods using electrolytic reduction include the production of amines by reduction of nitro and nitroso compounds; the production of amines by reduction of nitriles; dinitro compounds, a! Compound,
Examples include the production of p-7 minophenols, p-2 enylene diamines, and hydrazines by reduction of azoxy compounds and the like. In addition to being used as bases, p-aminophenols, p-phenylenediamines, and hydrazines can also be used directly as color image-forming substances.

Of course, it is also possible to generate a dialkali component by electrolysis of water in the coexistence of various inorganic salts.

Next, as a base precursor for generating a base using a complex-forming reaction, for example, a complex-forming reaction with a sparingly soluble metal compound and a metal ion constituting this sparingly soluble metal compound described in Japanese Patent Application No. 169585/1985 is used. Compound (
(referred to as a complex-forming compound). For example, poorly soluble metal compounds include carbonates, hydroxides, and oxides of zinc, aluminum, calcium, barium, and the like. In addition, for complex-forming compounds, H1 example, t
tf! - E. Marchill, R. M. Smith (A
s E++ Mart@ll, Re M@Sm1
th) co-author, [Critical Stability Funstanz (Cr1t1cal 5tabi11ty Co.
n5tants) J Volumes 4-5, Plenum Press (P1@numPress). Specifically, aminocarunic acids, iminodiacetic acids, biridylcargenic acids, aminophosphoric acids, carboxylic acids (mono-, di-, tri-, di-carboxylic acids and further), sulfur nano, hydroxy, oxo, ester, amide, alkoxy , mercapto, °alkylthio, funasphino, etc.), salts with alkali metals such as hydroxamic acids, polyacrylates, tetraphosphoric acids, guanidines, amidines, or quaternary ammonium salts.

It is advantageous to add the poorly soluble metal compound and the complex-forming compound to the light-sensitive element and the dye-fixing element separately.

The base and/or base precursor can be used alone or in combination of two or more.

The amount of base and/or base precursor used in the present invention can be used within a wide range. When used in a conventional photosensitive layer and/or dye fixing layer, it is appropriate to use the coating film in an amount of 50% by weight or less, more preferably 0.01% to 40% by weight.
Weight ranges of - are useful. In addition, when used in the present invention by dissolving in water, 0.005 mole/J
A concentration of 2 mol/l to 2 mol/l is preferred, especially 0.05
A concentration of mole/J to 1 mol·/l is preferred.

In the present invention, development by heating is used, so the developer is spread in the film unit and development is caused at around room temperature.
Development can be carried out at much lower temperatures. If - is increased, the amount of turnip increases significantly, which is rather inconvenient. Therefore, during development and heating for dye transfer, the -
is preferably 12 or less, more preferably 11 or less.

- If the male voice is too low, the development by heating will not proceed, so it is desirable that the pH is high (pH 7 or higher).
8 or more is particularly preferred.

Within the voice range described above, an image with low pitch and high density can be obtained in a short time.

The - value of the film is determined by heating the photosensitive material in exactly the same manner as developing, except that the photosensitive material is not exposed to light, and when it returns to room temperature, the photosensitive material has a 20μ value! It can be determined by dropping a drop of water, immediately bringing the PH electrode into close contact with it, and measuring the value of the equilibrium state.

Silver halides that can be used in the present invention include silver chloride, silver bromide,
Alternatively, silver chlorobromide, silver chloroiodide, or silver chloroiodobromide may be used.

Specifically, pages 35 to 36 of Japanese Patent Application No. 59-228551.
Page, U.S. Patent No. 4,500,626 No. 50 Kiri, Research Disclosure Magazine, June 1978 issue, pages 9-10 (RD17029), Patent Application No. 3, No. 60-225176
Any of the silver halide emulsions described in pages 2 to 47 and Examples, and pages 24 to 39 and Examples of Japanese Patent Application No. 60-228267 can be used.

Although silver halide emulsions may be used unripe, they are usually used after being chemically sensitized.0 Emulsions for conventional light-sensitive materials include well-known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-58-126526, JP-A-58-215644).
.

The silver halide emulsion used in the present invention may be a surface latent image type in which a latent image is mainly formed on the grain surface or an internal latent image type in which a latent image is formed inside the grain. Direct inversion emulsions combining emulsions and nucleating agents can also be used.

The coating strength of the photosensitive silver halide used in the present invention is in the range of 1 Da to 10 t/m'' in terms of silver.

In the present invention, an organic metal salt can also be used as an oxidizing agent together with photosensitive silver halide.

In this case, the photosensitive silver halide and the organic metal salt need to be in contact or at a close distance.

Among such organic metal salts, organic silver salts are particularly preferably used.

Examples of organic compounds that can be used to form the above-mentioned organic silver salt oxidizing agent include Japanese Patent Application No. 59-228551, page 37-
Page 39, U.S. Pat. No. 4,500,626, columns 52-5.
There are compounds listed in column 3, etc. Also, the patent application 1986-221
Also useful are silver salts of calgenic acids having alkynyl groups, such as phenylzolopiol, described in No. 535.

The above organic silver salts contain 1 mol of photosensitive silver halide,
, 0.01 to 10 mol, preferably 0.01 to 1 mol. Application of photosensitive silver nologonide and organic silver salt! The accounting is 50 drops or 10 in terms of silver.
77m” is appropriate.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and others. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes,
Included are hemicyanine dyes, styryl dyes and hemioxonol dyes.

Specifically, Japanese Patent Publication Nos. 59-180550 and 60-1
No. 40335, Research Disclosure Magazine 197
Sensitizing dyes described in June 1988 issue, pages 12-13 (RD17029), JP-A-60-111239, Special Edition 1983
Examples include heat-decolorizable sensitizing dyes described in Japanese Patent No. 172,967 and the like.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of one-strong color sensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may be included in the emulsion (for example, U.S. Pat. No. 2,933,390, U.S. Pat. No. 3,635,721, U.S. Pat.
, No. 615,641, No. 3.617,295, No. 3,
No. 635,721).

These sensitizing dyes may be added to the emulsion at or before chemical ripening, or as described in US Pat. No. 4.183.
It may be carried out before or after the nucleation of silver halide grains according to No. 756 and No. 4,225,666.

The amount added is generally per mole of silver rodanide, iD 10
``It's about 8 to 10 moles.

In the present invention, when silver ions are reduced to silver, a compound that generates or releases a mobile dye in response to or inversely to this reaction, that is, a dye-donating substance is contained.

Next, the dye-donating substance will be explained.

Examples of dye-donating substances that can be used in the present invention include couplers that can react with a developer. This system using a coupler, in which an oxidized product of the developer produced by an oxidation-reduction reaction between a silver salt and a developer reacts with the coupler to form a dye, is described in numerous documents. The coupler may be a 4-equivalent Kazoler or a 2-Equivalent Kazoller. Also preferred is a 2-equivalent Kaglar which has a diffusion-resistant group as a leaving group and produces a diffusible dye by reaction with an oxidized form of a developer. Specific examples of developers and couplers can be found in ``The Theory of the Spiky Process'' by James James, 4th edition (To He J.
ames @Th@Th@ory of thePho
tographia Proc@ss') 291~
334 pages and 354-361 pages, JP-A-58-12
No. 3533, No. 58-149046, No. 58-149
No. 047 No. 59-111148, No. 59-12439
No. 9, No. 59-174835, No. 59-231539
No. 59-231540, No. 60-2950, No. 60-2951, No. 60-14242, No. 60-2
It is described in detail in No. 3474, No. 60-66249, etc.

Further, a dye silver compound in which an organic silver salt and a dye are combined can also be cited as an example of the dye-donating substance. Specific examples of dye silver compounds are described in Research Database Magazine, May 1978 issue, pages 54-58 (RD-16966).

Furthermore, azo dyes used in heat-developable silver dye bleaching methods can also be cited as examples of dye-donating substances.

Specific examples of azo dyes and bleaching methods are disclosed in US Pat. No. 423
No. 5957, Research Disclosure Magazine, 197
It is described in the April 2006 issue, pages 30-32 (RD-14433). Further, leuco dyes described in US Pat. No. 3,985,565, US Pat. No. 4,022,617, etc. can also be cited as examples of dye-donating substances.

Another example of the dye-donating substance is a compound that has the function of releasing or diffusing a diffusible dye in an imagewise manner. This type of compound can be represented by the following general formula (Ll).

(Dy・-X)n-Y [LI] Here,
Dy represents a dye group, a temporarily shortened dye group or a dye precursor group; Correspondingly, a difference is created in the diffusivity of the compound represented by (Dy・-x)ny, or Dy・ is released and the released Dye and (Dy・−x)ny are combined. It represents a group having a property that causes a difference in diffusivity between them, n represents 1 or 2, and when n is 2, the two Dy+e-X may be the same or different.

As a specific example of the dye-donating substance represented by the general formula (LI), for example, a dye developer in which a hydroquinone developer and a dye component are linked is disclosed in US Pat. No. 3,134,764.
No. 3,362,819, No. 3,597,20
No. 0, No. 3,544,545, No. 3,482,9
It is described in No. 72, etc. In addition, a substance that releases a diffusible dye through an intramolecular nucleophilic substitution reaction was disclosed in JP-A-51-6
3618, etc., substances that release diffusible dyes through an intramolecular rewinding reaction of the isoxacilone ring are disclosed in JP-A No. 49
-111628 etc. In all of these methods, the diffusible dye is released or diffused in areas where no development has occurred, and the dye is neither released nor diffused in areas where development has occurred.

Furthermore, there is a group of compounds described in Japanese Patent Application No. 60-244873 that release all of the diffusible dye by a similar mechanism. Those compounds are fiN due to the remaining reducing agent.
-0 bond is cleaved to give a diffusible dye.

Another method is to make the dye-releasing compound into an oxidized form without dye-releasing ability, coexist with a reducing agent or its precursor, and after development, reduce it with the reducing agent that remains unoxidized to release the diffusible dye. A method has also been devised to release
A specific example of the dye-donating substance used therein is
No. 3-110827, No. 54-130927, No. 56
-164342 and No. 53-35533.

On the other hand, as a substance that releases a diffusible dye in the area where development has occurred, a substance that releases a diffusible dye through the reaction between a coupler having a diffusible dye as a decooking group and an oxidized form of a developer is disclosed in British Patent No. 1330524. No., Special Publication Showa 48-3916
No. 5, British Patent No. 3443940, etc.

In addition, in systems using these color developers, li! due to oxidative decomposition products of the developer is generated. VIII! In order to improve this problem, no developer is required since contamination is a serious problem. Dye-releasing compounds that themselves have reducing properties have also been devised. Representative examples include U.S. Patent No.
No. 928,312, No. 4.053,312, No. 4
, No. 055,428, No. 4.336,322, JP-A-59-65839, No. 59-69839, No. 53
-3819, No. 51-104343, Research Disclosure No. 17465, U.S. Patent No. 3.72
No. 5,062, No. 3,728,113, No. 3, 4
No. 43,939, JP-A-58-116537, JP-A No. 57
-179840, US Pat. No. 4,500,626, and the like.

Specific examples of dye-providing substances that can be used in the present invention include those described in columns 22 to 44 of the aforementioned U.S. Pat. No. 4,500,626.
Among them, compounds (1) to (3), (10) to
(13), (1s) to (19), (28) to (30)
, (33) to (35)% (38) to (40), (4
2) to (64) are preferred. Also, patent application No. 59-2464
Compounds described in No. 68, 80-87 are also useful. The amount added is 0.01 to 10 mmol/m”, preferably 0
．． 05-5 mmol/m! is appropriate.

Hydrophobic additives such as the dye-providing compounds described above and the imaging promoters described below are described in U.S. Pat. No. 2,322.02.
They can be incorporated into the layers of the photosensitive element by known methods such as the method described in No. 7. In this case, JP-A-59-
No. 83154, 59-17R1; 1-1i! [! '
+9-178452 committee, H59-178453, same 5
No. 9-178454, No. 59-178455, No. 59
A high boiling point organic solvent such as that described in Japanese Patent No. 178457 can be used in combination with a low boiling point organic solvent having a boiling point of 50° C. to 160° C., if necessary.

High boiling point organic solvent fleas are used as dye-donating substances 1y-
Against IO? It is preferably 51 or less.

Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-5994
The dispersion method using a polymer described in No. 3 can also be used.

In the case of a compound that is substantially insoluble in water, in addition to the above-mentioned method, it can be made into fine particles and dispersed in the binder.

When dispersing a hydrophobic substance into a hydrophilic colloid, various surfactants can be used.
38) The surfactants listed in I can be used.

In the present invention, it is desirable to contain a reducing substance in the photosensitive element. Reducing substances include those generally known as reducing agents, as well as the aforementioned dye-donating substances having reducing properties. Also included are reducing agent precursors that do not themselves have reducibility but exhibit reducibility through the action of nucleophiles and heat during the development process.

Examples of reducing agents used in the present invention include U.S. Pat.
No. 500,626, $49-50 column, 4.483,9
No. 14, columns 30-31, JP-A-60-140335, pages (17)-(18), JP-A-60-128438
No. 60-128436, No. 60-128439, No. 60-128437, etc. can be used. Also, JP-A-56-138736, JP-A No. 57-40
Reducing agent precursors described in US Pat. No. 245, US Pat. No. 4,330,617, and the like can also be used.

Combinations of various developers can also be used, such as those disclosed in US Pat. No. 3,039,869.

In the present invention, the amount of reducing agent added is 0 per mole of silver.
．． 01 to 20 mol, particularly preferably 0.1 to 10 mol.

In the present invention, an image formation accelerator may be used in the photosensitive element. The image formation accelerator may be used to promote the redox reaction between a silver salt oxidizing agent and a reducing agent, to generate a dye from a dye-providing substance, or to generate a dye. It has functions such as promoting reactions such as decomposition or release of diffusible dyes, and promoting the movement of dyes from the photosensitive element ta to the dye fixing layer.Physicochemical functions include bases or base precursors, and nucleophilic properties. It is classified into chemical compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, and compounds that interact with silver or silver ions.

However, these groups of substances generally have multiple functions and usually have some of the above-mentioned promoting effects.

Details of these are described on pages 67 to 71 of Japanese Patent Application No. 59-213978.

In the present invention, various development stoppers can be used in order to always obtain a constant image despite fluctuations in processing temperature and processing time during development.

The development stopper referred to here is a compound that neutralizes the base immediately after proper development or reacts with the base to lower the base concentration in the film and stop development, or a compound that inhibits development by interacting with silver and silver salts. It is a compound that

Specifically, an acid precursor that releases acid upon heating;
Examples include electrophilic compounds, nitrogen-containing heterocyclic compounds, mercapto compounds, and their precursors that undergo a substitution reaction with a coexisting base upon heating (for example, Japanese Patent Application No. 1983-21).
No. 6928, No. 59-48305, No. 59-8583
Compounds described in No. 4 or No. 59-85836, etc.)
.

Compounds that release mercapto compounds upon heating are also useful, for example, Japanese Patent Application No. 190173/1982;
-268926, 59-246468, 60-
No. 26038, No. 60-22602, No. 60-260
No. 39, No. 6G-24665, No. 60-29892,
There is a compound described in No. 59-176350.

In addition, in the present invention, it is possible to activate the development in the photosensitive element, and to provide exclusive control of the image to the L-dark by using a material. Specific compounds preferably used are described in columns 51-52 of US Pat. No. 4,500,626.

Various antifogging agents can be used in the present invention. Examples of anti-fogging agents include azoles and nitrogen-containing carbonaceous agents described in JP-A-59-168442. phosphoric acids and phosphoric acids, or the mercapto compounds and metal salts thereof described in JP-A No. 59-111636, as described in patent application (B) dated 10/14/1985 ('FF patent applicant: Fuji Film Co., Ltd.) Acetylene compounds and the like are used.

In the present invention, the photosensitive element may contain an image toning agent if necessary. Specific examples of effective toning agents include the compounds described in Japanese Patent Application No. 59-268926, pages 92-93.

The light-sensitive element and dye-fixing element of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other binder layer.

Specific examples of hardening agents are given in pages 94 and 95 of the specification of % Application No. 59-268926 and JP-A-52-157636 (
Examples include those described on page 38), and these can be used alone or in combination.

The support used in the photosensitive element and dye-fixing element in the present invention is one that can withstand processing temperatures. Common supports include glass, paper, cast-coated paper, synthetic paper, polymer films, metals and their analogues; Those listed as supports can be used.

When the photosensitive element used in the present invention contains a colored dye-donating substance, the photosensitive element may further contain an anti-irradiation substance, an anti-staining substance, aluminum, or various dyes. Although it is not so necessary, see Japanese Patent Application No. 59-268926, pages 97-98, and U.S. Patent No. 4,500.
Filter dyes, absorbent substances, etc. described in the literature exemplified in column 55 (lines 41 to 52) of No. 0,626 can be contained.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta and cyan, the light-sensitive element used in the present invention comprises at least three layers of silver halide, each sensitive to a different spectral region. It is necessary to have an emulsion layer.

A typical combination of at least three light-sensitive silver halide emulsion layers sensitive to different spectral regions is described in JP-A-59-180550.

The photosensitive element used in the present invention may have two or more emulsion layers sensitive to the same spectral region, depending on the sensitivity of the emulsion, if necessary.

The photosensitive element used in the present invention may optionally contain various additives known as heat-developable photosensitive materials, layers other than the photosensitive layer, such as an antistatic layer, a conductive layer, a protective layer, an intermediate layer, A
It can contain an H layer, a release layer, a matte layer, etc. For various additives, see Research Disclosure Magazine 1.
June 978 issue, pages 9 to 15 (RD17029)
, additives described in Japanese Patent Application No. 59-209'563, etc., such as plasticizers, sharpness improving dyes, AH dyes,
There are additives such as sensitizing dyes, matting agents, surfactants, fluorescent whitening agents, ultraviolet absorbers, anti-slip agents, antioxidants, and anti-fading agents.In particular, the first protective layer contains additives to prevent adhesion. Usually, organic or inorganic matting agents are added to the matting agent. Further, this protective layer may contain a mordant and a UV absorber. Each of the protective layer and the intermediate layer may be composed of two or more layers.

In addition, the intermediate layer contains a reducing agent to prevent color fading and color mixing.
UV absorber % A white pigment such as TiO2 may be included. The white pigment may be added not only to the intermediate layer for the purpose of increasing sensitivity but also to the emulsion layer.

The dye fixing element used in the present invention has at least one layer containing a mordant, and when the dye fixing layer is located on the surface, a protective layer can be further provided as required.

The layer structure of the dye fixing element, the binder, additives, the installation position of the mordant addition layer, etc. are described in Japanese Patent Application No. 1982-268926, page 62, line 9 to page 63, line 18, and the patent specifications cited therein. Those described in can also be applied to this application.

In addition to the above-mentioned layers, the dye fixing element used can be provided with auxiliary layers such as a release layer, a matte layer, and an anti-curl layer, if necessary.

One or more of the above layers may include a base and/or base precursor to promote dye transfer, a hydrophilic heat solvent, an anti-fade agent to prevent dye fading, a UV absorber, a slip agent, a matte It may also contain an agent, an anti-rgt' agent, a dispersion vinyl compound for increasing dimensional stability, a fluorescent whitening agent, and the like.

Specific examples of these additives are described on pages 101 to 120 of Japanese Patent Application No. 59-209563.

The binder in the above layer is preferably hydrophilic, and transparent or translucent hydrophilic colloids are typical. The above-mentioned binder is used in a specific example.

In the present invention, the coating method for the heat-developable photosensitive layer, film-retaining layer, intermediate layer, undercoat layer, pack layer, and other layers is described in U.S. Patent No. 4,500.
, No. 626, Nos. 55 to 569 can be applied.

As a light source for image exposure for writing an image on a heat-developable photosensitive element, radiation including visible light can be used,
For example, the light source described in Japanese Patent Application No. 59-268926, page 100 and US Pat. No. 4,500,626, No. 56tI/4 can be used.

Further, in order to promote dye transfer, a hydrophilic thermal solvent which is solid at room temperature and dissolves at high temperature may be incorporated into the photosensitive element or dye fixing element. The hydrophilic thermal solvent may be incorporated into either the light-sensitive element or the dye-fixing element, or may be incorporated into both.The layer in which it is incorporated may also be an emulsion layer, an intermediate layer, a protection layer, or a dye-fixing layer. , dye fixing layer and/or
Alternatively, it is preferable to incorporate it into a layer adjacent thereto.

Examples of hydrophilic heat solvents include ureas, f-lysines, amides WA1 sulfonamides, imides, alcohols,
There are oximes and other heterocycles.

(Examples) Hereinafter, specific examples of the present invention will be shown and the present invention will be explained in further detail.

Example 1 This article describes how to make a benzotriazole silver emulsion.

Gelatin 28? and benzotriazole 13.2P to water 3
Dissolved in 00-. This solution was kept at 40°C and stirred.

To this solution, add 20% of a solution of 17P of silver nitrate dissolved in 100% of water.
Added in minutes.

This benzotriazole silver emulsion was prepared and precipitated to remove excess salt. Thereafter, - was adjusted to 6.30 to obtain a benzotriazole silver emulsion with a yield of +007.

Next, we will discuss how to prepare an acetylene silver emulsion.

Zelatene 28F and potassium 4-acetylaminophenylpropiolate (26.7) were dissolved in 500 g of water. This solution was kept at 40°C and stirred. Add 17 silver nitrate to this solution.
? Add a solution of 100% of water dissolved in 100% of water over 2 minutes, and then add
Stirred for 0 minutes.

The - of this emulsion was adjusted to 6.30 K and centrifuged to obtain an acetylene silver emulsion with a high yield of 4009 -.

This article describes how to prepare silver halide emulsions for the fifth and first layers.

A well-stirred aqueous gelatin solution (containing 20 ml of gelatin and 3 ml of sodium chloride in 1000 ml of water, kept at 75°C), 600 ml of an aqueous solution containing sodium chloride and potassium bromide, and an aqueous silver nitrate solution ( 0.59 mol of silver nitrate dissolved in 600 ml of water) was simultaneously added at an equal flow rate over a period of 40 minutes. In this way, the average particle size Q, 40#! A monodispersed cubic silver chlorobromide emulsion (50 mol of bromine) was prepared.

After washing with water and desalting, 5 kg of sodium thiosulfate and 20 wIg of 4-hydroxy-6-methyl-1,3,3m,7-thitradeindene were added to carry out chemical sensitization at 60°C.

The yield of emulsion is 600? Met.

Next, we will explain how to prepare a silver halide emulsion for the third WI.

A well-stirred gelatin aqueous solution (containing 20 P of gelatin and 3 P of sodium chloride in water, kept at 75°C), K an aqueous solution containing sodium chloride and potassium bromide (600 °C), and a silver nitrate aqueous solution (600 °C of water). 0.59 mol of silver nitrate was dissolved in - and nine pieces of silver nitrate were simultaneously added at an equal flow rate over 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (80 mol % bromine) with an average grain size of 0.35 μm was prepared.

After washing with water and desalting, sodium thiosulfate 5W9 and 20 μl of 4-hydroxy-6-methyl-113t3ap futetrazaindene were added to carry out chemical sensitization at 60°C. The yield of emulsion was 600P.

Next, how to make a gelatin dispersion of a dye-donating substance will be described.

51 yellow dye-donating substance (6), surfactant, sodium succinate (2-ethyl-hexyl ester sulfonate o, sP, triisononyl phosphate) 1
0p was weighed out, 30 - of ethyl acetate was added thereto, and the mixture was heated and dissolved at about 60°C to form a homogeneous solution. This solution and 100 y of a 10% solution of lime-treated gelatin were stirred and mixed, and then dispersed using a homogenizer at 110,000 rpm for 10 minutes. This dispersion is called a yellow dye-providing substance dispersion.

A dispersion of a magenta dye-providing substance was prepared in the same manner as described above, except that the magenta dye-providing substance (B) was used and tricresillphate sulfate was used as a high boiling point solvent.

In the same manner as the yellow dye dispersion, a cyan dye dispersion was prepared using a cyan dye-providing substance ().

Using these materials, color photosensitive materials with a multilayer structure as shown in the following table were made.

Dye-donating substance OC16Hs 5(n) H sensitizing dye (D-1) (D-2) (D-3) reducing agent (to) Next, we will discuss how to prepare the dye fixing material.

A dye fixing material (A) was prepared by coating the composition shown in the following table on a paper support laminated with 4-lyethylene.

G and R, in which a tungsten light bulb is used as the color photosensitive material with the above multilayer structure for SO2, and the Ka degree is continuously changed.

! R three-color separation filter G is 500 to 600n-1
1 is a 600-700 nm pantone filter,
The sample was exposed to 500 lux for 1 second through an IR filter (constructed using a filter that transmits at least 700 nm).

7 d1 m'' of water was supplied to the emulsion surface of this exposed light-sensitive material using a wire parer, and then the dye-fixing material [A] was superimposed so that the film surface was in contact with the material.

After heating for 20 seconds using a heat roller whose temperature was adjusted so that the temperature of the water-absorbed film was 90 to 95°C, the dye-fixing material was peeled off from the light-sensitive material and examined for brittleness and photographic performance. I got good results.

Next, dye fixing material CB was prepared in the same manner as dye fixing material (A) except that 0.15 t/m" of polymer latex (ps) was further added to the first layer of dye fixing material (A). )
made.

A dye fixing material (C) was prepared in the same manner as the dye fixing material (A) except that 0.8)/- of polymer latex (ps) was further added to the second layer of the dye fixing material [A]. made.

Using these dye-fixing materials (BE, (C1), the same operations as in the case of dye-fixing material [A] were performed, and the brittleness and photographic performance were investigated, and the results are shown in Table @1.

Table 1 *Evaluation method for brittleness is that the dye-fixing material was heated at 25°C and 25SR.
After placing it in a constant temperature bath of H for 2 hours to adjust the humidity, the dye fixing material was bent into a circular shape with the coated side facing outward, and the radius of curvature (III) at which cracks began to appear was shown.

Table 1 shows that the dye-fixing material of the present invention has much improved brittleness compared to the comparative dye-fixing material. Furthermore, the dye-fixing material of the present invention did not crack under normal handling, and images of good quality were obtained.

(Effects of the Invention) The present invention has the effect of improving the brittleness of the dye-fixing material. It also had the effect of producing images of good quality without uneven transfer or deterioration of image quality due to cracks in the dye-fixing material. \, / Procedural amendment 1985 Patent Application No. 89508M 2, Name of invention Image forming method 3, Person making the amendment Relationship to the case: Patent applicant name: (52G) Fuji Shasuke Film Co., Ltd. 4, Agent 5. Date of amendment order: (voluntary) 6. Number of inventions increased by amendment 207. Target of amendment: Typewritten engraving of Mingmat Zenbun I1 store (however, no change in content). As per attached sheet.

Procedural amendment June 1986/? Day

Claims (1)

[Claims] A combination of a photosensitive element containing at least a photosensitive silver halide, a binder and a dye-providing substance, and a dye fixing element for fixing a mobile dye formed on the photosensitive element is prepared on a support by water, a base and/or A method for forming a dye image on a dye-fixing element by heating in the presence of a base precursor, wherein the dye-fixing element contains a mordant and a latex of a polymer having a glass transition point of 40° C. or less. .