JPS62234157A - Image forming method - Google Patents

Abstract

PURPOSE:To shorten the swelling time or/and transfer time of a photosensitive element or/and dye fixing element by application of water and to improve the strippability of the photosensitive element and dye fixing element after development and dye transfer by incorporating a high molecular hardening agent into at least one layer of the photosensitive element and the dye fixing element. CONSTITUTION:The high molecular film hardening agent is added into at least one layer of an emulsion layer, intermediate layer, protective layer, etc., which are the photosensitive element and a dye fixing layer, intermediate layer, protective layer, etc., which are the dye fixing element. The amt. of the high molecular film hardening agent to be used is evaluated by the melting time and is so set that the melting time of the uppermost layer is slightly longer than the melting time of the layers lower than said layer, more preferably larger by <=1.5 times. The photographic sensitive element and dye fixing element to be used contain inorg. or org. diffusive film hardening agents of low mol.wt. to be ordinarily used in this field.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an image forming method using thermal development, and in particular, to a method for forming an image using thermal development, and in particular, it reduces the processing time to obtain a final image, and the process of forming a photosensitive element after development and dye transfer. and a dye-fixing element.

(Prior art) Photography using silver halide has been the most widely used method since it has superior photographic properties such as sensitivity and gradation control compared to other photographic methods such as electrophotography and diazo photography. has been used.

In recent years, a technology has been developed that can easily and quickly obtain images by changing the image forming method for photosensitive materials using silver halide from the conventional wet processing using a developer, etc. to a dry processing using heating, etc. has been developed.

Photographic materials used in such image forming processing methods include:
For example, JP-A-58-58543, JP-A-58-79247
A heat-developable color photosensitive material comprising a photosensitive silver halide and a dye-donating substance that generates or releases a hydrophilic diffusible dye in response to or inversely to a heat development reaction, as described in and combinations with dye-fixing materials for transfer and fixation in the presence of large amounts of water. Also, JP-A No. 58-42092, No. 58-48750, No. 5
No. 8-48751, No. 58-48752, No. 58-4
Examples include a combination of a heat-developable color photosensitive material and a dye-fixing material containing a hydrophilic thermal solvent, as described in No. 8753 and the like.

Recently, when obtaining a transferred image using such a photographic material, the peelability between the photographic material and the dye fixing material after development and dye transfer has become a problem.

(Problems to be solved by the invention) In other words, in the heat development color image forming method,
Transfer aids such as water and/or hydrophilic thermal solvents can increase the rate of transfer of the diffusible dye to the dye-fixing material. At this time, the lower the degree of hardness of the coating film of the photosensitive material and/or the dye fixing material, the faster the transfer speed of the diffusible dye can be.

Similarly, when applying a certain amount of water, the photosensitive material or/
The lower the degree of hardening of the dye fixing material, the faster the water absorption rate can be. However, when the degree of hardness is lowered (softened), when the photosensitive material is peeled off from the dye fixing material after dye transfer, part or all of the coating film of the photosensitive material becomes integrated with the coating film of the dye fixing material. If the coating film is peeled off forcibly, the coating film may peel off, causing damage or stains on the peeling surface, and a satisfactory clear image cannot be obtained. .

In this way, shortening the processing time (ie, swelling time and/or transfer time) and improving releasability are contradictory issues. That is, if the amount of hardener added is reduced to soften the film, the processing time will be shortened, but the releasability will deteriorate. Conversely, if the amount of hardener added is increased, the peelability will be improved, but the processing time will become longer. It has been desired to develop an image forming method that simultaneously solves these contradictory problems of shortening processing time and improving releasability.

(Object of the Invention) Therefore, an object of the present invention is to shorten the swelling time and/or transfer time of a photosensitive element and/or dye fixing element by adding water, and to shorten the swelling time and/or transfer time of the photosensitive element and/or dye fixing element after development and dye transfer. An object of the present invention is to provide an image forming method with improved #I releasability.

Another object of the present invention is to reduce the transfer time when transferring a diffusible hydrophilic dye in the presence of a hydrophilic thermal solvent, and to improve the peelability between the photosensitive element and the dye fixing element after development and transfer. An object of the present invention is to provide a method for forming an image.

(Means to solve the problem) These objects are achieved by the invention described below.

That is, the present invention provides a photosensitive material containing at least a small amount of photosensitive silver halide, a binder, and a dye-providing substance that generates or releases a diffusible dye in response to or inversely thermal development under high temperature conditions. An imaging method in which an element is heated after or simultaneously with imagewise exposure and the diffusible dye formed or released is transferred to a dye-fixing layer in the presence of a transfer aid simultaneously and/or after said thermal development. An image forming method characterized in that one layer of the photosensitive element and the dye fixing element (both of which contain a polymer hardening agent) is provided.

Hereinafter, a specific configuration of the present invention will be explained in detail.

In the image forming method of the present invention, the light-sensitive material is usually heated after or simultaneously with the imagewise exposure, and the generated or released diffusible dye is usually heated during the heating for development in the presence of a transfer aid. The generated or released diffusible dye is transferred to the dye fixing layer, preferably in the presence of a transfer aid to simplify the process, and simultaneously heated for thermal development to generate or release the diffusible dye. Heating is performed to diffuse the dye into the dye fixing layer.

Here, the transfer aid may be any compound that is liquid at least when heated and can dissolve the diffusible dye. If the diffusible dye is hydrophilic, a hydrophilic thermal solvent such as water or urea (described later) or a mixed solvent such as water and methanol, ethanol, acetone or methyl cellosolve may be used, but transfer efficiency and stability may be From this point of view, water is most preferred.

In addition, hydrophilic thermal solvents are preferable because they can be incorporated into dye fixing materials and the processing steps can be simplified. When the diffusible dye is lipophilic, transfer aids include low-boiling organic solvents such as methanol, ethanol, acetone, benzene, toluene, methyl cellosolve, ethyl acetate, and dimethyl formamide, and phthalate esters (dibutyl phthalate). etc.), phosphate esters (trioctyl phosphate, etc.), benzoate esters (benzoic acid dodecyl ester, etc.), citric acid esters, maleic esters, fumaric esters, itaconic esters, lactic esters, fatty acid esters, amide oils, etc. A high boiling point solvent (liquid oil) can be used, and a solid oil described in Japanese Patent Application No. 57-193080, etc., which is solid at room temperature but becomes liquid when heated, can be used.

The dye fixing layer used in the present invention may be provided in a photosensitive material having a photosensitive layer, or may be provided in a material provided separately from the photosensitive material. That is, the light-sensitive element and the dye-fixing element used in the present invention may be coated on the same support, or the light-sensitive element and the dye-fixing element may be coated on separate supports.

The polymeric hardener used in the present invention can be used in the emulsion layer of a light-sensitive element,
It is added to at least one of the intermediate layer, protective layer, etc., and the dye fixing layer, intermediate layer, protective layer, etc. of the dye fixing element. For example, when a polymeric hardener is added to the emulsion layer of a light-sensitive element, it has the advantage of accelerating development. Furthermore, when a polymer hardener is added only to the intermediate layer, there is almost no possibility that the polymer hardener will diffuse into other layers, such as the emulsion layer or the mordant layer (dye-fixed N). It has the advantage of eliminating the negative effects of delaying development or reacting with mordants.

In the present invention, the polymeric hardener is preferably added to the top layer of the light-sensitive element or/and dye-fixing element. That is, the layer containing the polymeric hardener used in the present invention is preferably at least one of the layers that transfer the dye and form the surface layer (and upper layer) of the light-sensitive element or dye-fixing element after peeling. .

The layer forming the surface layer (top layer) includes a surface protective layer of a photosensitive element or/and dye fixing element, a photosensitive layer of a photosensitive element,
Examples include a dye fixing layer of a dye fixing element.

Accordingly, a preferred embodiment of the present invention provides a photosensitive element containing on a support at least a photosensitive silver halide, a binder, and a dye-donor material that forms or releases a diffusible dye under elevated temperature conditions. In an image forming method, the above-mentioned photosensitive element or An image forming method characterized by containing a polymer hardener in the uppermost layer of the dye fixing element.

A more preferred embodiment of the present invention is an image forming method characterized in that, in the above embodiment, heat development is carried out in the presence of a base and/or a base precursor.

The amount of polymer hardener used is determined by the melting time (melting time).
ime; the time it takes for the film to start melting when immersed in a 0.2N NaOH solution kept at 75°C), and preferably the melting time of the top layer is longer than the melting time of the lower layer. is set to be 1.5 times or more, particularly preferably 2 times or more larger. More specifically, the amount is 1% by weight or more, preferably 5% by weight or more, based on the amount of the binder that can react with and crosslink with the hardening agent in the polymer hardening agent added layer.

By doing so, when a certain amount of water is supplied to the photosensitive element and/or dye fixing element, which will be described in detail later, the swelling time of the photosensitive element and/or dye fixing element due to water absorption and the transfer time of the hydrophilic dye are determined. It has been shortened and the peelability between the photosensitive element and the dye-fixing element has been improved. Similarly, when a hydrophilic dye is transferred to a dye-fixing element in the presence of a hydrophilic hot solvent, the transfer time can be shortened and the peelability between the photosensitive element and the dye-fixing element has been improved.

That is, the photographic light-sensitive element and dye-fixing element used in the present invention contain an inorganic or organic low molecular weight diffusible hardener commonly used in this field in the photographic emulsion layer or other binder layer.

Due to its diffusive properties, the diffusible hardener also diffuses into the uppermost layer of the light-sensitive element and/or dye-fixing element, thereby hardening the uppermost layer. Therefore, since the uppermost layer of the photosensitive element and/or dye-fixing element is hardened with both the polymeric hardener and the diffusive hardener, the releasability is improved. Also a photosensitive element or/
Since the coated layers other than the top layer of the dye-fixing element are hardened only with a diffusible hardener, a long swelling time is not required, that is, the swelling time is shortened. Furthermore, since the degree of hardness of the coating film other than the top layer can be lowered, the diffusion of the diffusible dye within the film can be made faster. That is, the transfer time is shortened.

The polymer hardener used in the present invention is disclosed in JP-A-56-668.
No. 41, British Patent No. 1.322,971, U.S. Patent No. 3.671.256, etc., and M. Burr.
ness, J. Pouradier”The The
ory of the Photographic
Process″4th ed.

(T.H. James ed.), Macmi 1f.
an New York, 1977, ppst.

G, A, Camp be l 1. L, R, H
amilton, 1. S., Ponticello.

”Polymeric Am1ne and Ammm
on i umSalts” (E,
J.

Pergamon Press, New York
1979, pp321-332. It is a polymer with a functional group that reacts with gelatin, which is well known as a base material such as gelatin. Particularly preferred are polymeric hardeners with a molecular weight of 10,000 or more.

This polymer hardener has the following general formula (1), (f
f) and (III) are preferred, especially those of the general formula (I
) is preferred.

R.

In the formula, A represents an ethylenically unsaturated monomer copolymerizable with the monomer unit shown to the right.

In the formula, R1 represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms. Q is -CO2-1-Co
Contains at least one of the following bonds: -N- (wherein R1 represents the same as mentioned above) or an arylene group having 6 to 10 carbon atoms; L represents -CR1 3 to 1
It is either a divalent group having 5 carbon atoms, or a divalent group having 1 to 12 carbon atoms containing at least one of R1) bonds.

R2 represents a vinyl group or a functional group serving as a precursor thereof, and is either CH=CHz or CHz CHz X. X represents a group that can be substituted by a nucleophilic group or a group that can be eliminated in the form of HX by a base.

In the formula, x and y represent molar percentage, and X is O to 99,
y takes a value from 1 to 100.

Examples of the ethylenically unsaturated monomer represented by A in formula (r) are ethylene, propylene, l-butene, isobutyne, styrene, chloromethylstyrene, hydroxymethylstyrene, sodium vinylbenzenesulfonate, sodium vinylbenzylsulfonate, N, N, N-)dimethyl-N
-vinylbenzylammonium chloride, N,N-dimethyl-N-benzyl-N-vinylbenzylammonium chloride, α-methylstyrene, vinyltoluene,
4-vinylpyridine, 2-vinylpyridine, benzylvinylpyridinium chloride, N-vinylacetamide, N-vinylpyrrolidone, 1-vinyl-2-methylimidazole, monoethylenically unsaturated esters of aliphatic acids (
(e.g. vinyl acetate, allyl acetate), ethylenically unsaturated mono- or dicarboxylic acids and their salts (e.g. acrylic acid, methacrylic acid, itaconic acid, maleic acid, sodium acrylate, potassium acrylate, sodium methacrylate), anhydrous Maleic acid, esters of ethylenically unsaturated monocarboxylic or dicarboxylic acids (e.g. n-butyl acrylate, n-hexyl acrylate,
Hydroxyethyl acrylate, cyanoethyl acrylate, N, N-diethylaminoethyl acrylate, methyl methacrylate, n-butyl methacrylate,
Benzyl methacrylate, hydroxyethyl methacrylate, chloroethyl methacrylate, methoxyethyl methacrylate, N,N-diethylaminoethyl methacrylate, N,N,N-triethyl-N-methacryloyloxyethylammonium p-toluenesulfonate,
N,N-diethyl-N-methyl-N-methacryloyloxyethylammonium p-)luenesulfonate, dimethyl itaconate, maleic acid monobenzyl ester)
, amides of ethylenically unsaturated monocarboxylic or dicarboxylic acids (e.g. acrylamide, N.

N-dimethylacrylamide, N-methylolacrylamide, N-(N,N-dimethylaminopropyl)acrylamide, N,N,N-trimethyl-N-(N-acryloylpropyl)ammonium p-)luenesulfonate, 2-acrylamide -2-Methylpropanesulfonic acid salt, acryloylmorpholine, methacrylamide, N.

N-dimethyl-N'-acryloylpropanediamine propionate betaine, N,N-dimethyl-N'-methacryloylpropanediamine acetate betaine).

In addition, when the polymer of the present invention is used as a crosslinked latex, in addition to the above-mentioned ethylenically unsaturated monomers, at least two copolymerizable ethylenically unsaturated groups are used as A.
Monomers having more than 100% monomer (for example, divinylbenzene, methylene bisacrylamide, ethylene glycol diacrylate, trimethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, etc.) are used.

Examples of R1 in formula (I) include a methyl group, an ethyl group, a butyl group, and an n-hexyl group.

Q includes the following groups.

L includes the following groups.

-CH, Co, CH2-.

CHz COz CHt Ct (□ -1CHz CH
Z COz CHt CHz.

+CHt -)-s COz G Hz G Hz
.

+CHZ +-r. G OZ G Hz CHz -9
-CH2NHCOCH,-.

CHz N HCOCHZ CHz -1+CHz
+-:+NHCOCHHz.

+CHz←sN HCOCHz CHz.

+CHz++oNHCOCHtCHz.

-CH! OCH! +.

CHzCHzOCHzCHzCHz -2COCHz
CHz −1 −CH, COCHzCR2−.

5OCHtGHz -1 CHzSOCHzCHz.

-SO□CH,CHI-.

S Oz CHz CHz S Oz CHz CH2
.

5OzCHHzCHHzSOtCHzCHCHz.

island S　O3CHz　CHz　CHt.

-3 OffCH! GoICH, CH2-.

-3O3CH2CHzCO2CH2CH,-.

5OzNHCH2CO□CH,CH,-.

-3O,NHCH2CHICoICHICH! -.

-NHCONHCH,CH2-.

CHzNHCONHCHzCHz.

-NHCO□CHICH, +.

CHz N HCOz CHz CHz- etc.

R2 in formula (I) includes the following groups.

CH=CHz, CHzCHzCl, CHzC
HzBr.

CHz CH20H, CHz CHz Oz CCHs
.

CHz　CHz　Oz　CCF　x.

CHz　CHZ　Oz　CCHCII　z etc.

Other preferred examples of polymeric hardeners are disclosed in U.S. Pat. No. 4,161.
No. 407, and has a repeating unit represented by the following formula (II).

+1 In the formula, A is an ethylenically unsaturated monomer unit or a mixture of monomers that can be copolymerized with the monomer unit shown to the right.

In the formula, x and y represent mole percentages, where X takes a value of 10 to 95% and y takes a value of 5 to 90%. R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R/ is -CH=CH2, or -CH
, CH, X. X represents a group that can be substituted by a nucleophilic group or a group that can be eliminated in the form of HX by a base.

L' is alkylene, more preferably alkylene having 6 carbon atoms, such as methylene, ethylene,
a linking group selected from isobutylene, etc.), an arylene having 6 to 12 carbon atoms (for example, a linking group selected from phenylene, tolylene, naphthalene, etc.), or
-COZ-1 or -COZR3-1 [where R3 is alkylene having 1 to 6 carbon atoms, or 6
arylene having 12 carbon atoms, Z is an oxygen atom or NH].

Examples of A in formula (II) include the same as A in formula (I). An example of R in formula [■] is R1 in formula (1)
Contains the same example. Examples of R' in formula (II) include the same examples as R2 in formula (r).

Still other preferred polymeric hardeners are disclosed in British Patent No. 1°534.
As described in No. 455, it has a repeating unit represented by the following formula (I[I).

In the formula, A represents one unit of an ethylenically unsaturated monomer copolymerizable with one unit of the monomer shown to the right; R is a hydrogen atom or an alkyl having 1 to 6 carbon atoms; MAL is an alkyl having 1 to 20 carbon atoms; A divalent linking group having a carbon atom (more preferably a divalent group having 1 to 12 carbon atoms containing at least one of -CONH- or -C〇- bond); X is an active ester group + Xs y is a mole percentage , X takes a value from O to 95, y takes a value from 5 to 100, and m takes a value from 0 or 1.
It is.

Examples of A in formula (III) include the same examples as A in II (I).

R in formula (III) includes the same examples as R in formula (I) and is described above.

The formula (III) includes the following groups.

-CONHCH□-, -CONHCH2CH2-.

-CONHCH2CH□CH,-.

CON HCHz CHz CHz CHt CHz
.

COCHt CHt OCOCHz CHZ
.

-CONHCH□CON HCHZ.

CON HCHz CON HCHz CON HCH
z −5 COCHz.

-CONHCH,NHCOCHICH! SCH,CH2
−.

-CONHCH20COCH2CH! -, etc.

X in formula (I[I) includes the following groups.

C0zCHzCN, C0zCHzC
O2CzHs.

-C0zCHzCNH, -COZCH2COCH3.

-COzN=CHCH3, -GOZN=C(CH+)z
.

C0zCHzCHzB r, C0zCHzCH
zCN.

Next, specific examples of polymeric hardeners that can be used in the present invention will be shown, but the invention is not limited thereto.

JONtlC(CH3) zcHzsc)+NaJOO
(CHz) 3503N a H Chang OM 6 Hz N HCOCHX CHz S Oz C1
1=CHt However, M is a hydrogen atom, a sodium atom, or a potassium atom, and x and y are the mole percentages of each unit, and are not limited to the above, but x is 0 to 99, and y is 1 to 100. It can take the value of

The polymer hardening agent used in the present invention is, for example,
It can be synthesized according to the method described in No. 9-31944.

The polymeric hardener used in the present invention is added to the top layer of the light-sensitive element and/or dye-fixing element, and an example of such a top layer is preferably a protective layer. The protective layer may consist of two or more layers, in which case the layer to which the polymeric hardener is added is the top layer.

A surface protective layer is particularly preferred.

The protective layer usually contains an organic or inorganic matting agent to prevent adhesion. In addition, the protective layer contains a mordant, UV
An absorbent, a slipping agent, etc. may be included.

The photographic light-sensitive element and dye fixing element used in the present invention contain an inorganic or organic low molecular weight diffusible hardener in the photographic emulsion layer or other binder layer.

A specific example of this diffusible hardening agent is disclosed in Japanese Patent Application No. 59-268926.
No. 94-95 specification and JP-A-59-15763
Examples include those described in No. 6, page (38), and these can be used alone or in combination.

For example, chromium salts (chromium alum, chromium acetate, etc.),
Aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds (1,3,5-trihydroxydioxane, etc.) acryloyl-hexahydro-S-)riazine, , mucophenoxychloroic acid, etc.) can be used alone or in combination.

The above hardeners and other hardeners that can be used in the present invention are described in US Patent No. 1. 870°354, 2,080,019, 2,726.162, 2
, No. 870.013, No. 2゜983.611, No. 2,
No. 992.109, No. 3.047,394, No. 3.0
No. 57,723, No. 3,103,437, No. 3,32
No. 1,313, No. 3,325,287, No. 3. 36
2. No. 827, No. 3,543,292, British Patent 6
No. 76.628, No. 825,544, No. 1,270.
578, German Patent No. 872,153, German Patent No. 1.090
, No. 427, Special Publication No. 34-7133, No. 46-187
No. 2 (and Re5earch Disclosure
It is described in Vol. 176, p. 26 (December 1978).

In the light-sensitive element and dye-fixing element used in the present invention, the above-mentioned diffusible hardener is contained in an amount of 10% by weight or less, preferably O81-4, based on the total amount of binder that can react with the hardener and crosslink.
It is contained in an amount of 0.5 to 2% by weight, particularly preferably 0.5 to 2% by weight.

The binder is preferably hydrophilic, and transparent or translucent hydrophilic colloids are typical.

For example, proteins such as gelatin and gelatin derivatives, polyvinyl alcohol, cellulose misforms, and multi-IJs such as starch.
! natural substances such as gum arabic, dextrins,
Synthetic polymeric substances such as pullulan, polyvinyl alcohol, polyvinylpyrrolidone, and water-soluble polyvinyl compounds such as acrylamide polymers are used. Among these, gelatin and polyvinyl alcohol are particularly effective.

In the present invention, the binder has a coating weight of 20 g or less per 1 d, preferably 10 g or less, more preferably 7 g or less.
g or less is appropriate.

The ratio of the high boiling point organic solvent dispersed in the binder together with a hydrophobic compound such as a dye-donating substance and the binder is 1 cc or less of solvent per 1 g of binder, preferably 0.
．． A suitable amount is 5 cc or less, more preferably 0.3 cc or less.

In the present invention, water may be supplied to the dye fixing element or to the photosensitive element. Alternatively, it may be supplied to both the dye fixing element and the photosensitive element. It is preferable that the hydrophilic heat solvent is contained in the dye fixing element during production.

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 methods or other methods. It may also be incorporated into the element as crystal water or microcapsules.

The water used in the present invention is not limited to so-called "pure water", but includes water in the widely customary sense. Also, water that can be used in a complex-forming reaction with a base and/or a base precursor, or a metal ion, as described below. It may be an aqueous solution containing a compound that absorbs water, or a mixed solvent with a low boiling point solvent such as methanol, DMF, acetone, or diisobutyl ketone.Furthermore,
An aqueous solution containing a dye release aid, an accelerator, and a hydrophilic heat solvent, which will be described later, may also be used.

The amount of water in the present invention corresponds to at least 0.1 times the weight of the total coating film of the photosensitive element and dye fixing element, preferably 0.1 times the weight of the total coating film to the maximum swelling volume of the total coating film. It is within the range of the weight of water, more preferably 0.0% of the weight of the total coating film. The amount ranges from 1 to the amount obtained by subtracting the weight of the entire coating from the weight of water corresponding to the maximum swelling volume of the entire coating.

The state of the film during swelling is unstable, and depending on the conditions, local bleeding may occur.To avoid this, add water equivalent to the maximum swelling volume of the entire coated film of the photosensitive element and dye fixing element. Mass sales are preferable.

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, Patent Application No. 59-228551, 35-36
Any of the silver halide emulsions described in U.S. Pat.

Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. For emulsions for conventional light-sensitive materials, 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 complex compound (JP-A-58-126526, JP-A-58-215644).
.

The silver halide emulsion used in the present invention may be of the surface latent image type in which latent images are mainly formed on the grain surfaces, or may be of the internal latent image type in which the latent images are formed inside the grains. Direct reversal emulsions combining internal latent image type emulsions and nucleating agents can also be used.

The coating amount of the photosensitive silver halide used in the present invention is in the range of fmg to 10 g/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, US Patent 4. 500. No. 626, column 52 ~
There are compounds described in column 53, etc. Also, special application 1986-2
Silver salts of carboxylic acids having alkynyl groups, such as silver phenylpropiolate described in No. 21535, are also useful.

The above-mentioned organic silver salts contain, per mol of photosensitive silver halide,
0.01 to 10 mol, preferably 00O1 to 1
Moles can be used together. The total coating amount of photosensitive silver halide and silver salt is 50 to 10 g/silver equivalent.
rd is appropriate.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments, composite cyanine pigments, composite merocyanine pigments, holopolar cyanine pigments,
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 12-13 Shin (RDI7029), Japanese Patent Application Laid-open No. 111239/1980, Japanese Patent Application No. 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 supersensitization.

Along with aggravating pigments, pigments that do not themselves have spectral sensitizing effects or substances that do 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. 3,615.641, No. 3,617.295, No. 3.635.721).

These enhancing dyes may be added to the emulsion during or before or after chemical ripening.
No. 756, same No. 4. 225. It may be carried out before or after nucleation of silver halide grains according to No. 666.

The amount added is generally on the order of 10-a to 10-'' mole per mole of silver halide.

The image-forming substance used in the present invention reacts with or inversely to the reaction when a photosensitive silver halide or/and a silver salt such as an organic silver salt oxidizing agent is reduced to silver under high temperature conditions. compounds that produce or release mobile pigments;
That is, it is a dye-donating substance.

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 method 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 coupler or a 2-equivalent coupler. Also preferred are two-equivalent couplers that have a diffusion-resistant group as a leaving group and produce a diffusible dye upon reaction with an oxidized developer. Specific examples of developers and couplers can be found in “The Theory of the Photographic Process” by James James, 4th edition (T.H.
es″The The.

ry of the Photographic
Process”) pages 291-334, and 354-
361 pages, JP-A-58-123533, JP-A No. 5B-14
No. 9046, No. 58-149047, No. 59-111
No. 148, No. 59-124399, No. 59-1748
No. 35, No. 59-231539, No. 59-23154
No. 0, No. 60-2950, No. 60-2951, No. 6
No. 0-14242, No. 60-23474, No. 60-6
It is described in detail in No. 6249, 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 Disclosure 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 U.S. Patent No. 4.2.
No. 35,957, Research Disclosure Magazine, 1
It is described in the April 1976 issue, pages 30-32 (RD-14433). Also, U.S. Patent No. 3.985,56
Leuco dyes described in No. 5, No. 4,022゜617, etc. can also be mentioned 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).

(Dye-X)n-Y (Ll) Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, X represents a simple bond or a connecting group, and Y represents a latent image Correspondingly or inversely to the photosensitive root salt having y e-X) represents a group having a property that causes a difference in diffusivity between n-Y, n represents 1 or 2, and when n is 2, two D
ye-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. No. 819, No. 3,597,
No. 200, No. 3,544.545, No. 3,482
．． It is described in No. 972, etc. In addition, a substance that releases a diffusible dye through an intramolecular nucleophilic substitution reaction was published in JP-A-51
JP-A-49-111,628 discloses a substance that releases a diffusible dye through an intramolecular rewinding reaction of an isoxacilone ring. In all of these methods, the diffusible dye is released or diffused in areas where development has not occurred, and the dye is neither released nor diffused in areas where development has occurred.

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 coexistence substance used therein is given in JP-A No. 5
No. 3-110°827, No. 54-130.927, No. 56-164.342, and No. 53-35,533.

On the other hand, as a substance that releases a diffusible dye in the area where development occurs, a substance that releases a diffusible dye through the reaction between a coupler having a diffusible dye as a leaving group and an oxidized form of a developer is disclosed in British Patent No. 1. ．． No. 330゜524, Special Publication No. 48-3
No. 9.165, British Patent No. 3,443.940, etc.

In addition, in systems using these color developers, image contamination due to oxidative decomposition products of the developer is a serious problem. Dye-releasing compounds have also been devised. A representative example is, for example, U.S. Patent No. 3,928.31.
No. 2, No. 4゜053.312, No. 4,055,4
No. 28, No. 4,336.322, JP-A-59-65
No. 839, No. 59-69839, No. 53-3819, No. 51-104.343, Research Disclosure No. 17465, U.S. Patent No. 3゜725.062
No. 3,728,113, No. 3.443,93
No. 9, JP-A-58-116゜537, JP-A No. 57-179
840, US Pat. No. 4,500,626, and the like.

Specific examples of the dye-providing substance that can be used in the present invention include the compounds described in columns 2a to 44 of the aforementioned U.S. Pat. No. 4,500.626; Compounds of (1) to (3), (10) to
(13), (16) to (19), (28) to (30),
(33)-(35), (38)-(40), (42
) to (64) are preferred. Also, patent application No. 59-24646
Compounds described on pages 80-87 of No. 8 are also useful.

Hydrophobic additives such as the dye-providing compounds described above and the image-forming accelerators described below are disclosed in U.S. Pat.
It can be introduced into the photosensitive material by a known method such as the method described in No. 7.

In this case, Japanese Patent Application Laid-open Nos. 59-83154 and 59-1
No. 78451, No. 59-178452, No. 59-17
No. 8453, No. 59-178454, No. 59-178
455, No. 59-178457, etc., with a boiling point of 50°C to 160°C, as necessary.
It can be used in combination with a low boiling point organic solvent.

The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g or less, per 1 g of the dye-providing substance used.

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, it can be dispersed and contained in the form of fine particles in the binder in addition to the method described above.

When dispersing a hydrophobic substance into a hydrophilic colloid, various surfactants can be used.
The surfactants listed on page 8) 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 reducing properties but develop reducing properties 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, columns 49-50, 4.483.9
No. 14, No. 30-31jIrA1 JP-A 1986-1403
No. 35, pages (17) to (18), JP-A-60-128
No. 438, No. 60-128436, No. 60-1284
Reducing agents described in No. 38, No. 60-128437, etc. can be used. Also, JP-A No. 56-138.736, No. 5
Reducing agent precursors such as those described in US Pat. No. 7-40,245 and U.S. Pat.

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

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

In the present invention, an image formation accelerator can be used in the photosensitive element. Image formation accelerators include accelerating redox reactions between silver salt oxidizing agents and reducing agents, accelerating reactions such as generation of dyes from dye-donating substances, decomposition of dyes, and release of diffusible dyes, and It has functions such as promoting the movement of the dye to the dye fixing layer, and from a physicochemical function, it has the following functions: base or base precursor, nucleophilic compound, high boiling point a solvent (oil), thermal solvent, surfactant, silver. It is also classified as a compound that interacts with silver ions. However, these substance groups 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 addition to the above-mentioned image formation accelerators, there are various methods of generating bases, and all of the compounds used in these methods are useful as base precursors. For example, patent application 1986-1
No. 69585, a method of generating a base by mixing a poorly soluble metal compound and a compound (referred to as a complex-forming compound) that can undergo a complex formation reaction with the metal ions constituting this poorly soluble metal compound, and Japanese Patent Application No. 1983- There is a method of generating a base by electrolysis as described in No. 74702.

The former method is particularly effective. Examples of poorly soluble metal compounds include carbonates, hydroxides, and oxides of zinc, aluminum, calcium, barium, and the like. Regarding complex-forming compounds, for example, N.E. Martell, R.M. Smith (A.E., Martell, R.M.
, Smith), [Critical Stability Constances]
tyConstants) J, Volumes 4 and 5, Plenum Press. Specifically, aminocarboxylic acids, iminodiacetic acids, pyridylcarboxylic acids, aminophosphoric acids, carboxylic acid M (mono, di, tri, and tetracarboxylic acids, and also phosphono, hydroxy, oxo, ester, amide, alkoxy, mercapto, alkylthio, compounds with substituents such as phosphino), hydroxamic acids,
Examples include salts with alkali metals such as polyacrylates and polyphosphoric 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.

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 or reacts with the base to reduce the base concentration in the film and stop development, or a compound that interacts with silver and silver salts to inhibit development. It is a compound that

Specifically, an acid precursor that releases acid upon heating;
Examples include electrophilic compounds that undergo a substitution reaction with a coexisting base when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and their precursors (for example, Japanese Patent Application No. 1983-2
No. 16928, No. 59-48305, No. 59-858
34 or 59-85836).

Compounds that release mercapto compounds upon heating are also useful;
-268926, 59-246468, 60-
No. 26038, No. 60-22602, No. 60-260
There are compounds described in No. 39, No. 60-24665, No. 60-29892, and No. 59-176350.

Further, in the present invention, a compound that activates development and simultaneously stabilizes the image can be used in the photosensitive element. For specific compounds preferably used, see US Patent No. 4.
No. 500.626, columns 51-52.

Various antifoggants can be used in the present invention. Antifoggants include azoles, nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442, mercapto compounds and their metal salts as described in JP-A-59-111636, and mercapto compounds and their metal salts as described in JP-A-59-111636;
Acetylene compounds described in No. 228267 are used.

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

The supports used in the light-sensitive elements and dye-fixing elements of the present invention are those that can withstand processing temperatures. Common supports include glass, paper, polymeric films, metals and their analogs, as well as
Those listed as supports on pages 95 to 96 of Japanese Patent Application No. 59-268926 can be used.

When the light-sensitive element used in the present invention contains a colored dye-donating substance, it is not so necessary to further contain an irradiation-preventing substance, an anti-halation substance, or various dyes. Although there is no
Filter dyes, absorbent substances, etc. described in the literature exemplified in No. 0.626, No. 5541jl (lines 41 to 52) may 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 must have at least three layers, each with a silver 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 contain various additives known as heat-developable photosensitive elements and layers other than the photosensitive layer, such as an antistatic layer, a conductive layer, a protective layer, an intermediate layer, an 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. 59-209563, such as plasticizers, sharpness improving dyes, AH dyes, enhancing dyes, matting agents, surfactants, fluorescent whitening agents, ultraviolet absorbers, Additives include anti-slip agents, antioxidants, and anti-fading agents.

A device may also be provided in which each intermediate layer is composed of two or more layers.

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

The photographic element used in the present invention essentially includes a photosensitive element that forms or releases a dye by heat development and a dye fixing element that fixes the dye. In a typical form, the photosensitive element and the dye fixing element are arranged on two supports. Usually, they are coated separately on the same support, but they can also be coated on the same support.

The relationship between the photosensitive element and the dye fixing element, the relationship with the support,
Regarding the relationship with the white reflective layer, the relationship described in Japanese Patent Application No. 59-268926, pages 58-59, and U.S. Pat. No. 4,500,626, column 57 can be applied to the present application.

Typical embodiments in which a photosensitive element and a dye fixing element are coated on the same support include, for example, JP-A-56-67840;
Canadian Patent No. 674.082, U.S. Patent No. 3.730
, No. 718, there is a form in which part or all of the photosensitive element is peeled off from the dye fixing element, and a peeling layer is coated at an appropriate position.

In this case, the release layer and its adjacent layer correspond to the uppermost layer of the aforementioned light-sensitive element and dye-fixing element.

The photosensitive element or dye-fixing element may have a conductive heating layer as a heating means for thermal development or diffusion transfer of the dye.

The transparent or opaque heating element in this case can be made using conventionally known techniques for producing resistive heating elements.

As a resistance heating element, there are two methods: a method using a thin film of an inorganic material exhibiting semiconductivity, and a method using a thin film of an organic material in which conductive fine particles are dispersed in a binder.

Materials that can be used in these methods are disclosed in Japanese Patent Application No. 59-151.
Those described in the specification of No. 815 etc. can be used.

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 necessary.

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 in the present invention can be provided with auxiliary layers such as a release layer, a matting agent 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 Agents, antioxidants, dispersed vinyl compounds to increase dimensional stability, fluorescent brighteners, etc. may also be included.

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. Specific examples include the binders listed above for the photosensitive element.

The image receiving layer in the present invention includes a dye fixing layer used in a heat-developable color photosensitive element, and can be arbitrarily selected from commonly used mordants, but polymer mordants are particularly preferred. Here, the polymer mordant includes a polymer containing a tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer containing these quaternary cation groups, and the like.

Regarding this specific example, please refer to Japanese Patent Application No. 59-268926.
~100 pages and US patents 4. 500. No. 5 of 626
It is described in columns 7 to 60.

In the present invention, the coating method for the heat-developable window light layer, protective layer, intermediate layer, undercoat layer, bank layer, and other layers is disclosed in U.S. Pat. No. 4,500.
, No. 626, Nos. 55-56! The method described in rA can be applied.

As a light source for image exposure for recording 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 U.S. Pat. No. 4,500,626, column 56 can be used.

The heating temperature in the heat development step is about 50°C to about 250°C, but a temperature of about 0°C to about 180°C is particularly useful. Transfer is possible at a temperature ranging from room temperature to room temperature, but it is particularly preferable to transfer at a temperature of 50° C. or higher, which is about lθ° C. lower than the temperature in the heat development step.

As a heating means in the development and/or transfer process, a hot plate, an iron, a hot roller, a heating element using carbon, titanium white, etc. can be used.

Also, Japanese Patent Application Publication No. 59-218443, Japanese Patent Application No. 60-79
As detailed in No. 709, etc., a method in which development and transfer are performed simultaneously or continuously by heating in the presence of a small amount of a solvent such as water is also useful. In this method, the above-mentioned image formation accelerator may be included in advance in either or both of the dye fixing element and the photosensitive element, or may be supplied from the outside.

In the method in which the above-mentioned development and transfer are carried out simultaneously or continuously, the heating temperature is preferably 50° C. or higher and below the boiling point of the solvent. For example, when the solvent is water, it is preferably 50° C. or higher and 100° C. or lower.

Further, a solvent may be used to transfer the mobile dye to the dye fixed layer.

Examples of solvents used to accelerate development and/or transfer mobile dyes to the dye fixed layer include water or basic aqueous solutions containing inorganic alkali metal salts or organic bases (these bases may be Those described in the section on formation promoters can be used. Furthermore, a low boiling point solvent or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can also be used. Further, a surfactant, an anti-capri agent, a poorly soluble metal salt and a complex-forming compound, etc. may be included in the medium.

However, the solvent used to promote heat development and/or transfer during heat development and/or transfer is preferably water from the viewpoint of ease of handling and safety during processing, and furthermore, photographically useful substances such as bases and antifoggants are preferably used. It is preferable to include it in the photosensitive element and/or dye fixing element in advance.

Furthermore, the base is preferably a precursor type.

Further, in order to promote dye transfer, a method may be adopted in which a hydrophilic thermal solvent that is solid at room temperature and dissolves at high temperature is incorporated into the photosensitive element or dye fixing element. The hydrophilic thermal solvent may be incorporated into either the photosensitive element or the dye fixing element, or may be incorporated into both. Further, the layer to be incorporated may be any of an emulsion layer, an intermediate layer, a protective layer, and a dye fixing layer, but it is preferably incorporated in the dye fixing layer and/or a layer adjacent thereto.

Examples of hydrophilic heat solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocycles.

The heating means in the transfer process is disclosed in Japanese Patent Application No. 59-26892.
There is a means described in No. 6, page 102, line 14 to page 103, line 11. Alternatively, the dye fixing element may be coated with a layer of a conductive material such as graphite, carbon black, metal, etc., and the conductive layer may be heated directly by passing an electric current through it.

The pressure conditions and method of applying pressure when overlapping the heat-developable photosensitive element and the dye-fixing element and bringing them into close contact are described in Japanese Patent Application No. 59-2.
The method described on pages 103 to 104 of No. 68926 can be applied.

Hereinafter, the present invention will be explained in more detail by showing specific examples of the present invention.

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

28g of gelatin and 13.2g of benzotriazole to 33g of water
0 Qmj! dissolved in. This solution was kept at 40°C and stirred. A solution prepared by dissolving 17 g of silver nitrate in 100 ml of water was added to this solution over a period of 2 minutes.

The pH of the benzotriazole silver emulsion was adjusted and allowed to settle to remove excess salt. Thereafter, the pH was adjusted to 6.30, and a benzotriazole silver emulsion with a yield of 1400 g was obtained.

This article describes how to make silver halide emulsions for the 5th and 1st layers.

Add 600 mJ of an aqueous solution containing 17 g of sodium chloride and 35 g of potassium bromide to a well-stirred aqueous gelatin solution (20 g of gelatin and 3 g of sodium chloride in 1000 ml of water, kept at 75°C) and an aqueous solution of silver nitrate (600 mJ of water). ! in which 0.59 mol of silver nitrate was dissolved) was simultaneously added at an equal flow rate over 40 minutes.

In this way, a monodisperse cubic silver chlorobromide emulsion (bromine 50 mol %) having an average grain size of 0.40 μm was prepared.

After washing with water and desalting, 5 mg of sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3a,? - Chemical sensitization was carried out at 60''C by adding 29 mg of tetrazaindene.

The yield of emulsion was 600 g.

Next, I will explain how to make a silver halide emulsion for tertiary N.

Add 7 g of sodium chloride and 5 g of potassium bromide to a well-stirred gelatin aqueous solution (containing 20 g of gelatin and 3 g of sodium chloride in 10,100 O of water, kept at 75°C).
600m# of aqueous solution containing 6g and silver nitrate aqueous solution (
0.59 mol of silver nitrate dissolved in 600 ml of water was simultaneously added at an equal flow rate over 40 minutes. In this way, a monodisperse cubic temperature silver bromide emulsion (bromine 80 mol %) having an average grain size of 0.35 μm was prepared.

After washing with water and desalting, 5 mg of sodium thiosulfate and 20 ml of 4-hydroxy-6-methyl-1,3,3a,7-chitrazaindene were added to perform chemical sensitization at 60°C.

The yield of emulsion was 600 g.

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

Weighed 5 g of the following yellow dye-donating substance (Y), 0.5 g of sodium succinate-2-ethyl-hexyl ester sulfonate as a surfactant, and 2.5 g of triisononyl phosphate as a high-boiling solvent, and added acetic acid. Ethyl 30m
1 was added and dissolved by heating at about 60°C to form a homogeneous solution. 100g of a 10% solution of this solution and lime-treated gelatin
After stirring and mixing, use a homogenizer for 10 minutes.
It was dispersed at ooorpm. This dispersion is called a yellow dye-providing substance dispersion.

Dispersions of magenta and cyan dye-providing substances were prepared in exactly the same manner as in the preparation of dispersions of yellow dye-providing substances, except that the following magenta dye-providing substances (M) and cyan dye-providing substances (C) were respectively used. made.

As a result, we changed the type and amount of the polymer hardener added to the protective layer. Color photosensitive materials 101 to 108 having multilayer structures as shown in Table 1 below were prepared.

Dye-donating substance (Y) Sushi + allziLnJ (C) OH Ushi + hNx3 (n) Table 1 * l: (i 30C9H190), P = 0 * 1
112-bis(vinylsulfonylacetamido)ethane*4: The compound shown in Table 2 was used in the amount shown in Table 2.

*5: Size 3 to 5 μm *6: Polyethylene terephthalate support (D-1) 1 polymer hardener used in Table 1 is as shown in Table 2 below.

Table 2 $11.2-bis(vinylsulfonylacetamide)
Ethane Next, we will discuss how to make the dye fixing material.

A dye-fixing material was prepared by coating on a paper support laminated with polyethylene according to the composition shown in Table 3 below.

Table 3 *l) 1.2-bis(vinylsulfonylacetamido)ethane *2) A tungsten light bulb is used as the multi-layered color glow material, and the three colors of G, R1 and R whose concentration changes continuously Resolving filter (G is 500-600 nm.

R is a 600-700 nm bandpass filter, IR
was constructed using a filter that transmits at least 700 nm), and was exposed to light at 500 lux for 1 second.

This exposed light-sensitive material was immersed in water for 2 seconds, the water adhering to the surface was squeezed out with a roller, and then the dye-fixing material and the film surface were overlapped so that they were in contact with each other. The temperature of the membrane that absorbed water was 90
Using a heat roller whose temperature is adjusted to ℃,
After heating for 0 seconds, the dye-fixing material was peeled off from the light-sensitive material and examined for peelability and photographic performance, and the results shown in Table 4 were obtained.

*l) Water absorption Wk: Determined by measuring the weight of the photosensitive material before and after water supply.

*2) There is almost no peeling of the film, but? The force required for JI AI is greater than that of photosensitive materials 103-108.

As is clear from Table 4, the photosensitive materials of the present invention 103-
Regarding No. 108, the dye-fixing material could be easily peeled off, and a clear image was obtained without any scratches or stains on the peeled surface.

However, the photosensitive material 101 could not be peeled off due to adhesion with the fixing material, and if it was forcibly peeled off, the coating film of the photosensitive material would peel off, making it impossible to obtain a satisfactory image.

Further, although the photosensitive material 102 has good releasability, water is not sufficiently absorbed by immersing it in water for about 2 seconds, and the transferability of the dye decreases, resulting in a low transfer density.

Example 2 In the photosensitive material 101 of Example 1, Nos. 2.4 and 6
A photosensitive material 201 was prepared in the same manner as in Example 1, except that 0.6 g and 1 g of 4-methylsulfonylphenylsulfonylacetate guanidine was used in place of the basic zinc carbonate used in the layers.

Next, dye fixing materials 211 to 21 are prepared as shown in Table 5.
3 was created.

Table 5 *1) 1.2-bis(vinylsulfoniacetamido)ethane *2) Polymer hardener P-2 *3) Mordant: Same as the mordant of the dye-fixing material in Example 1. Color photosensitive material 201 uses a tungsten light bulb, and G, R, and JR whose density changes continuously.
Three-color separation filter (G: 500-600 nm, 1R: 6
Bandpass filter from 00 to 700 nm, IR is 70
The sample was exposed to light at 500 lux for 1 second through a filter (constructed using a filter that transmits at least 0 nm).

Thereafter, it was heated uniformly for 30 seconds on a heat block heated to 140°C.

Next, the dye-fixing materials 211 to 213 are immersed in water for about 2 seconds, and the water adhering to the surface is immediately squeezed out through a roller, so that the respective film surfaces are in contact with the photosensitive material 201 that has been subjected to the heat treatment. Superimposed.

After heating this for 10 seconds on a heat block at 80° C., the dye fixing material was peeled off from the light-sensitive material and examined for peelability and photographic properties. The results are shown in Table 6.

As is clear from Table 6, the dye fixing material 21 of the present invention
Sample No. 3 could be easily peeled off from the photosensitive material, and a clear image was obtained with no emulsion attached to the peeled surface.

However, the dye-fixing material 211 adheres to the photosensitive material and has insufficient releasability, and if it is forcibly removed, the film of the photosensitive material peels off and adheres to the surface of the dye-fixing material, making it impossible to obtain a satisfactory image. There wasn't.

Furthermore, although the dye fixing material 212 could be easily peeled off, due to its low water absorption, dye transfer was delayed and only an image with a low transfer rate of 4 degrees was obtained.

(Effect of the invention) By containing a polymer hardening agent in the uppermost layer of the photosensitive element or/and dye fixing element and making the degree of hardness of the layers other than the uppermost layer lower than that of the uppermost layer, The swelling time of the dye-fixing element was shortened, and the peelability between the photosensitive element and the dye-fixing element after dye transfer was improved.

Claims (1)

[Claims] A photosensitive element containing on a support at least a photosensitive silver halide, a binder, and a dye-providing substance that forms or releases a diffusible dye under high temperature conditions is thermally developed after or simultaneously with imagewise exposure to produce a photosensitive element. Alternatively, in an image forming method in which the released diffusible dye is transferred to a dye fixing layer in the presence of a transfer aid simultaneously/or after the heat development, at least one layer of the light-sensitive element and the dye element is coated with a polymer hardening layer. An image forming method characterized by containing an agent.