JPS63100452A - Image forming method - Google Patents

Abstract

PURPOSE:To obtain good strippability in a heat development transfer system by incorporating a matte agent of the amt. equiv. to 0.5-10vol% of the content of the binder is the uppermost layer of a photosensitive element into said uppermost layer. CONSTITUTION:The matte agent of the amt. equiv. to 0.5-10vol% of the content of the binder is the uppermost layer of the photosensitive element is incorporated into said uppermost layer. The matte agent to be added to a protective layer is discontinuous solid particles of an inorg. or org. material which can be dispersed into a hydrophilic org. colloidal binder. The matte agent suitable for use in this case is preferably the agent which is less deformed by the effect of heat. The use of the inorg. matte agent is particular gives a desirable result. The example of the inorg. matte agent includes oxide, alkaline earth metal salt, silver halide particles which do not form images, and glass, etc. The org. matte agent which obviates generation of softening by heat at <=60 deg.C is more preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method of forming a dye image by thermal development.

(Prior art and its problems) Regarding the method of obtaining a color image by heat development,
Many methods have already been proposed.

Methods for forming color images by combining oxidized developer and couplers are described in U.S. Pat. No. 3,531,286, U.S. Pat. No. 3,761,270, and Belgian Patent No.
No. 02,519, Research Disclosure 197
September 5th issue, pages 31-32, U.S. Patent No. 4.021.2
It has been proposed in No. 40, etc.

Further, regarding the method of forming a positive color image by the photosensitive silver dye bleaching method, for example, Research Disclosure, April 1976 issue, pages 30 to 32 (RD-14433
), December 1976 issue, pages 14-15 (RD-15
227) and US Pat. No. 4,235,957.

However, the above method has a problem in that a clear dye image cannot be obtained because the formed dye image and silver image coexist.

Various methods have been proposed to improve this drawback.

For example, a method in which a movable dye is imagewise released from a heat-developable photosensitive element by heating, and the movable dye is transferred to a dye fixing material having a mordant using a solvent such as water; A method of transferring to a dye-fixing material using a hydrophilic heat solvent built into the dye-fixing material, a method of transferring a mobile dye to a dye-receiving material such as a support by using a heat-diffusible or sublimable dye, etc. (U.S. Patent No. 4,463,079, U.S. Patent No. 4.
No. 474.867, No. 4.478°927, No. 4
, 507,380, 4゜500.626, 4,483.914; JP-A-58-149046;
No. 58-149047, No. 59-152440, No. 59-154445, No. 59-165054, No. 5
No. 9-180548, No. 59-168439, No. 59
-174832, 59-174833, 59-
No. 174834, No. 59-174835, No. 59-2
18443, Japanese Patent Application No. 60-79709, etc.).

Incidentally, the photothermographic elements used in the above-mentioned image forming method are usually cut into sheets or sheets and stacked in a plurality for storage or installation in a thermal development apparatus. At this time, the front surface (the surface coated with the photosensitive layer) and the back surface of the heat-developable photosensitive element come into contact with each other, but depending on the conditions (especially under high humidity conditions), the surface coating film and the back coating film may come into contact with each other. They may adhere and cannot be peeled off, or a portion of one coating may stick to the other and remain. In order to prevent this failure, the technology usually involves adding a matting agent to the top layer of the photosensitive layer side of the heat-developable photosensitive element to reduce the contact area between the back coating film and the front coating film, thereby making it difficult for adhesion to occur. is used.

However, in a heat development transfer method in which a heat development photosensitive element and a dye fixing element are pressed together using a nip roller or the like and heated in the presence of a trace amount of water, a base, and/or a base precursor, a large amount of the matting agent in the top layer is used. If it is too long, there is a problem in that it may become impossible to separate the dye-fixing element from the heat-developable photosensitive element after the heat-developable transfer process.

Therefore, an object of the present invention is to provide an image forming method with good releasability in the thermal development transfer system. Another object of the present invention is to provide a photosensitive element that can prevent adhesion between the coated surface and the back surface of the photosensitive element even during storage.

(Structure of the Invention) Therefore, the present inventors have devised a method in which the function of the matting agent during storage of the photosensitive element is not lost in this heat development transfer method, and the function is fully exhibited during the heat development transfer process. It has been found that the above problems can be solved by setting the amount of matting agent used within a certain range.

That is, in the present invention, a photosensitive element containing at least a photosensitive silver halide, a binder, and a dye-providing substance that produces or releases a diffusible dye upon thermal development is superimposed on a dye-fixing element on a support, and water and In an image forming method that involves heating in the presence of a base and/or a base precursor and then peeling off the photosensitive element and the dye fixing element, the uppermost layer of the photosensitive element has a binder content of 0.5 to 0.5 of the binder amount of the uppermost layer.
This image forming method is characterized in that it contains a matting agent in an amount of 1%.

Matting agents added to the top layer, preferably the protective layer, of the photosensitive element used in the present invention are well known in the photographic art and include inorganic or organic materials dispersible in a hydrophilic organic colloidal binder. It can be defined as a continuous solid particle. Among these, matting agents suitable for use in the present invention are preferably those that are less deformed by heat. The use of inorganic matting agents gives particularly favorable results.

Examples of inorganic matting agents include oxides (e.g. silicon dioxide, titanium oxide, zinc oxide, magnesium oxide, aluminum oxide, etc.), alkaline earth metal salts (e.g. sulfates and carbonates), and (barium sulfate, calcium carbonate, magnesium sulfate, etc.), silver halide particles that do not form images (silver chloride, silver bromide, etc., and may also contain a small amount of iodine as a halogen component), glass, etc. .

Further, it is desirable that the organic matting agent be one that does not soften due to heat at 60° C. or lower.

Examples of such organic matting agents include cellulose esters (eg, cellulose acetate propionate, etc.), cellulose ethers (eg, ethyl cellulose, etc.), and synthetic resins. Examples of synthetic resins include alkyl methacrylate, alkoxyalkyl methacrylate, glycidyl methacrylate, acrylamide, methacrylamide, styrene, etc. alone or in combination, or combinations thereof with acrylic acid, methacrylic acid, α, β-
Polymers having a combination of unsaturated dicarboxylic acids, hydroxyalkyl-acrylates or -methacrylates, sulfoalkyl-acrylates or -methacrylates, styrene sulfonic acid, etc. as monomer components can be used. Among them, polymethyl methacrylate is preferred.

The amount of matting agent used is 0.5 to 0.5 of the amount of binder in the top layer.
It is added in an amount of 1 Ovol%, preferably 1 to 5vol%.

Here, the amount of binder refers to the dry volume of the binder constituting the layer of gelatin, such as lime-treated gelatin, acid-treated gelatin, acylated gelatin, etc., or a water-soluble polymer compound such as polyvinyl alcohol or polyvinylpyrrolidone. means.

Although there are no particular limitations on the particle shape and particle size of the cloak agent, particles having an average particle size of usually 0.5 to 10 μm, particularly 1 to 5 μm are preferred.

Further, an inorganic matting agent and an organic matting agent may be used alone or in combination.

In addition, the poorly soluble metal compounds described in the section on base precursors described below can also function as an inorganic matting agent, and therefore can be applied within the range described above.

In addition, in the contact layer (i.e., the dye fixing layer or its upper part N) of the dye fixing element that is weighted with the photosensitive element,
There is no particular need to add a matting agent, and the effects of the present invention do not change even if it is not added. When added, it is preferably in the range of 0.5vol% to 10vo1% of the binder amount in the contact layer.

Furthermore, the photosensitive element used in the present invention can be used without the need for a bank layer containing a capping agent on the back surface of the support.
This is advantageous because adhesion between the photosensitive element and the bank layer can be prevented during storage.

The photosensitive element and the dye fixing element may be formed on the same support as long as they can be peeled off after image formation.
The present invention is effective in methods using each element formed on separate supports.

In the present invention, the uppermost layer of the photosensitive element means the layer furthest from the support having the photosensitive element when both elements are peeled off.

(Hereinafter, blank space) In the present invention, a preferable image forming method is to use mff1 water and a base and/or after or simultaneously with image exposure.
Alternatively, by heating in the presence of a base precursor, the diffusible dye generated in the area corresponding to or inversely corresponding to the silver image is transferred to the dye fixing layer simultaneously with development. According to this method, the production or release reaction of the diffusible dye proceeds extremely quickly, and the movement of the diffusible dye to the dye fixing layer also proceeds rapidly, so that a high-density color image can be obtained in a short time.

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 sea urchin 7 roller. It may also be used in the form of squeezing a pot filled with water.
The invention is not limited to these and 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 not limited to so-called "pure water", but includes water in the widely conventional sense. 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 tends to occur due to repellency on the surface of the element, uneven penetration of water into the film, etc. Therefore, the water may contain a surfactant to improve the spread of the water on the surface of the material.

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 G.I. Schick, Marcel Detzker, 1967).
(Surfactant 5science 5eri
es (Edited by Martin, J, 5c
hick, Marcel Dekker Inc.
1967) etc.

There are three types of surfactants: cationic, anionic, amphoteric, and nonionic, but as long as they meet the requirements listed below,
All can be used. 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 dyne/c.
It is desirable that the amount added be less than m.

The amount of water used in the present invention is at least 0.001 times the weight of the total coating of the light-sensitive element and the dye-fixing element, preferably 0.1 times the weight of the total coating to correspond to the maximum swelling volume of the total coating. Within the range of the weight of water, more preferably within the range of 0.1 times the weight of the entire coating film to the amount of water corresponding to the large swelling volume minus the weight of the entire coating film. It is.

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. It is preferable that the amount is less than that amount. In particular, in the present invention, 1 to 50 g/rd, preferably 2 to 35 g/nl,
Furthermore, amounts of water from 3 to 25 g/% are used.

The degree of swelling of a gelatin film varies significantly depending on the degree of hardening, but the degree of hardening is usually adjusted so that the film thickness at maximum 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 depends on 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 content. It is preferable to supply

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 hot plate, an iron, a hot roller, a heat generating plate using carbon, titanium white, etc., or the like. It is also possible to provide a tetraelectric heating layer on the photosensitive element and/or the dye fixing element and 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 metaborates; aliphatic amines (trialkylamines, hydroxylamines, aliphatic polyamines), aromatic amines (N-alkyl-substituted aromatic amines, N-hydroxylalkyl-substituted organic bases such as aromatic amines and bisCp-(dialkylamine) phenylcomethane (often), heterocyclic amines, amidines, cyclic amidines, guanidines, cyclic guanidines, and carbonates and bicarbonates thereof; Examples include borates, secondary and tertiary phosphates, and US Pat. No. 2,410,644 discloses betaine tetramethylammonium iodide, diaminobutane dihydrochloride, US Pat. 506. No. 444 describes organic compounds containing amino acids such as urea and 6-aminocaproic acid, which are useful. In the present invention, those having a pKa value of 8 or more are particularly useful.

The base precursor used in the present invention is one that releases or generates a base through thermal decomposition, electrolysis, complex formation reaction, or the like.

Base precursors include salts of organic acids and bases that are decarboxylated and decomposed by heating, compounds that decompose by Loacene rearrangement, Beckmann rearrangement, etc. and release amines, and those that cause some kind of reaction when heated to release bases. can be mentioned.

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

Examples of organic acids include trichloroacetic acid, trifluoroacetic acid, propiolic acid, cyanoacetic acid, sulfonylacetic acid, acetoacetic acid, and 2-carboxycarboxamides described in US Pat. No. 4,088,496.

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;
Amine imides described in May 15776, aldoneamides 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. Through this reaction, carbonates of alkali metals and organic bases such as guanidines and amidines can be efficiently obtained.

In addition, methods using electrolytic reduction include the production of amines by reduction of nitro and nitroso compounds; production of amines by reduction of nitriles; nitro compounds, azo compounds,
Examples include the production of p-aminophenols, p-phenylenediaminos, and hydrazines by reduction of azoxy compounds and the like. In addition to being used as bases, p-aminophenols, p-phenylene diaminos, and hydrazines can also be used directly as color image-forming substances.

Of course, it is also possible to generate an alkaline component by electrolyzing 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. Regarding complex-forming compounds, for example, N. E. Martill, R. M. Smith (A, E.
, Martell, R.M., Sm1th), [Critical Stability Constances (Crt t
icalStability Con5tants)
J Volumes 4-5, Plenum Press
Press). Specifically, aminocarboxylic acids, iminodiacetic acids, pyridylcarboxylic acids,
Aminophosphoric acids, carboxylic acids (mono, di, tri, and tetracarboxylic acids and compounds with further substituents such as phosphono, hydroxy, oxo, ester, amide, alkoxy, mercapto, alkylthio, and phosphino), hydroxamic acids, polyacrylates, Examples include salts with alkali metals such as 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.

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. % ranges are useful. Further, when used in the present invention by dissolving in water, 0. 005
mole/1 or 2 mole/l? The agricultural degree is preferable, especially 0. 05 mole/1 to 1 mole
/ j! A concentration of is preferred.

Since the present invention utilizes development by heating, development is performed at a pH much lower than the pH in the film during development in the so-called color diffusion transfer method, in which a developer is spread in a film unit and development occurs at around room temperature. be able to.

Increasing the pH significantly increases fogging, which is rather inconvenient. Therefore, the pH of the film during heating for development and dye transfer is preferably 12 or less, more preferably 11 or less.

On the other hand, if the pH is too low, development by heating will not proceed, so it is desirable that the pH is high to some extent (pH 7 or higher), and pH 8 or higher is particularly preferred.

Within the above pH range, images with low fog and high density can be obtained in a short time.

To determine the pH value of the film, heat the photosensitive material in exactly the same manner as for development, except that it is not exposed to light, and when it returns to room temperature, drop 20μβ water onto the photosensitive material and immediately bring the pHf4 pole into close contact with it. It can be determined by measuring the equilibrium pH (!!).

In the present invention, as a base precursor, a basic metal compound that is sparingly soluble in water and a compound that can undergo a complex formation reaction with metal ions constituting the sparingly soluble metal compound using water as a medium are contained, and these two compounds are combined during heating. It is particularly effective in an image forming method in which the pH of the system is increased by the reaction.

The poorly soluble metal compound and the complex forming compound need to be added at least in separate layers in order to prevent them from reacting before the development process. For example, in a so-called monosheet material in which a photosensitive element and a dye-fixing element are provided on the same support, it is preferable that the above-mentioned two additive layers be separate layers, with one or more layers interposed between them. A more preferred embodiment is one in which the poorly soluble metal compound and the complex-forming compound are contained in layers provided on separate supports. For example, it is preferable to contain the poorly soluble metal compound in the photosensitive element and the complex-forming compound in a dye fixing element having a support separate from the photosensitive element. The complex-forming compound may be supplied after being dissolved in water to be coexisting. Slightly soluble metal compounds are disclosed in JP-A-56-1748.
It is desirable to contain it as a fine particle dispersion prepared by the method described in No. 30, No. 53-102733, etc.
The average particle size is preferably 50 microns or less, especially 5 microns or less. The poorly soluble metal compound may be added to any layer of the photosensitive element, such as the photosensitive layer, intermediate layer, or protective layer.
It may be added by dividing into more than one layer.

The amount of a poorly soluble metal compound or complex-forming compound to be added to the layer on the support depends on the type of compound, the particle size of the poorly soluble metal compound, the rate of complex formation reaction, etc. It is appropriate to use it in an amount of 50 weight percent or less, and more preferably a range of 0.01 weight percent to 40 weight percent. In addition, when supplying a complex-forming compound dissolved in water,
0.005mof, especially O035m per liter
A concentration of 0.1 to 2 m01 is preferred. Further, in the present invention, the content of the complex-forming compound in the reaction system is preferably from 1/100 to 100 times, particularly from 1/10 to 20 times, in molar ratio to the content of the poorly soluble compound.

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, U.S. Pat. No. 4,500.626, column 50;
Research Disclosure+-LH June 978 issue, pages 9-10 (RD17029), JP-A-61-10724
No. 0, Japanese Patent Application No. 60-225176, No. 60-2282
Any of the silver halide emulsions described in No. 67 and the like can be used.

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. It may also be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases. Further, in the present invention, a direct reversal emulsion in which an internal latent image type emulsion and a nucleating agent are combined can also be used.

Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. For emulsions for conventional light-sensitive materials, well-known sulfur sensitization methods, reduction enhancement methods, noble metal sensitization methods, and the like 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 coating amount of photosensitive silver halide used in the present invention is 1 mg to 10 g/n in terms of silver. is within the range of

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.

Organic compounds that can be used to form the above organic silver salt oxidizing agent include (10) of JP-A-61-107240.
pp.-(11), U.S. Pat. No. 4,500.626, No. 52
There are compounds described in columns to column 53, etc. Also, special request in 1986
Silver salts of carboxylic acids containing phenylpropiol described in Japanese Patent Application No. 113235 and acetylene silver described in Japanese Patent Application No. 60-90089 are also useful. Two or more types of organic silver salts may be used in combination.

The above-mentioned organic silver salts contain, per mol of photosensitive silver halide,
0.01 to 10 mol, preferably 0.

01 to 1 mole can be used in combination. The total coating amount of photosensitive silver halide and organic silver salt is suitably 50 mg to 10 g/m in terms of silver.

The silver halide used in the present invention may be spectrally enhanced by methine dyes or the like. 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, pages 12-13 (RDI7029), etc., and heat-decolorizable sensitizing dyes described in JP-A-60-111239, Japanese Patent Application No. 60-172967, etc. can be mentioned.

These sensitizing dyes may be used alone or in combination, and combinations of enhancing dyes are often used particularly for the purpose of supersensitization.

Along with aggravating pigments, pigments that do not themselves have spectral aggravating 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. Nos. 2,933,390, 3,635.721, 3,743,510, 3,615,61
No. 3, No. 3,615,641, No. 3,617,29
No. 5, as described in No. 3,635,721).

These enhancing dyes may be added to the emulsion at or before chemical ripening, and US Pat. No. 4,183.
It may be carried out before or after nucleation of silver halide grains according to No. 756 and No. 4.225.666.

The amount added is generally about 10-8 to 10-2 mol per mol of silver halide.

In the present invention, the image-forming substance is a compound that, when silver ions are reduced to silver under high temperature conditions, generates or releases a mobile dye in response to or inversely to this reaction, i.e. Contains a dye-donating substance.

Examples of dye-donating substances that can be used in the present invention include:
Compounds that form pigments by oxidative coupling reactions (
couplers).

Even though this coupler is a 4-equivalent coupler, it is a 2-equivalent cuff.

It may be ra. Also preferred are two-equivalent couplers that have a diffusion-resistant group as a leaving group and form a diffusible dye through an oxidative coupling reaction. Specific examples of developers and couplers are given in "The Theory of the Photographic Process" by James, 4th edition (T, H.

J ames “The Theory of the
Photographic Process”) 291
〜334 pages, and 354-361 pages, Japanese Patent Application Laid-open No. 58-1
No. 23533, No. 58-149046, No. 5B-14
No. 9047, No. 59-111148, No. 59-124
No. 399, No. 59-174835, No. 59-2315
No. 39, No. 59-231540, No. 60-2950, No. 60-2951, No. 60-14242, No. 60
It is described in detail in No. 23474, No. 60-66249, etc.

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 (A).

(Dye -B), -D (A) Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, B represents a simple bond or a connecting group, and D represents a latent image in the image form. Corresponding or inversely to the photosensitive silver salt having (Dye-B)+.

-Creating a difference in the diffusivity of the compound represented by D,
Alternatively, Dye is released and the released Dye and (Dye
-B) and -D represent a group having properties that cause a difference in diffusivity, p represents 1 or 2, and when p is 2, the two Dye-Bs may be the same or different. You can.

Specific examples of the dye-donating substance represented by the general formula (A) include dye developers in which a hydroquinone developer and a dye component are linked, U.S. Pat. , No. 819, No. 3,597,200
No. 3.544,545, No. 3.482,97
It is stated in No. 2, etc. In addition, a substance that releases a diffusible dye through an intramolecular nucleophilic substitution reaction is disclosed in U.S. Patent No. 3,980.
．． 479, etc., a substance that releases a diffusible dye through an intramolecular rewinding reaction of the isoxacilone ring is disclosed in JP-A-49-
111.628 etc.

Another example is to make a 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 produce a diffusible dye. A method of releasing dye has also been devised, and a specific example of the dye-donating substance used therein is disclosed in Japanese Patent Application Laid-Open No. 53
-110.827, 54-130,927, 5
No. 6-164.342 and No. 53-35.533. Japanese Patent Application No. 60-244873 describes a compound that releases a diffusible dye when the N-0 bond is cleaved by a remaining reducing agent as a dye-donating substance that releases a diffusible dye by a similar mechanism. There is.

Furthermore, as described in JP-A-59-185333, a donor-acceptor reaction occurs in the presence of a base and releases a diffusible dye, but when it reacts with an oxidized form of a reducing agent, dye release does not substantially occur. Non-diffusible compounds (LDA compounds) can also be used.

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.

On the other hand, as a substance that releases a diffusible dye in the area where development occurs, it is a coupler that has a diffusible dye as a leaving group and that releases a diffusible dye by reaction with an oxidized form of a reducing agent (DDR coupler). However, British Patent No. 1.330.52
No. 4, Special Publication No. 48-39゜165, British Patent No. 3.4
No. 43,940, etc., and is preferably used in the present invention.

In addition, in methods using these reducing agents, image contamination due to oxidative decomposition products of the reducing agent becomes a serious problem. Release compounds (DRR compounds) have also been devised and are particularly advantageously used in the present invention. Typical examples are U.S. Patent Nos. 3,928,312 and 4,05.
No. 3,312, No. 4,055,428, No. 4,3
No. 36,322, JP-A-59-65839, JP-A No. 59-
No. 69839, No. 53-3819, No. 51-104゜343, Research Disclosure Magazine 17465
No. 3.725.062, U.S. Patent No. 3.728
．． No. 113, No. 3,443,939, Japanese Unexamined Patent Publication No. 1983-
It is a dye-donating substance described in No. 116.537, No. 57-179840, and US Pat. No. 4,500,626. Specific examples of this type of dye-donating substance include the compounds described in columns 22 to 44 of the aforementioned U.S. Pat. No. 4,500,626, among which Compounds (1) to (3), (
10) - (13), (16) - (19), (28) -
(30), (33)~(35), (38)~(
40), (42) to (64) are preferred. Also, JP-A-6
Compounds described on pages (21) to (27) of No. 1-124941 are also useful.

In addition, as a dye-donating substance other than those mentioned above, a dye silver compound in which an organic silver salt and a dye are combined (Research Disclosure magazine, May 1978 issue, pages 54-58, etc.)
, azo dyes used in heat-developable silver dye bleaching methods (U.S. Patent No. 4.235.957, Research Disclosure magazine, April 1976 issue, pp. 30-32, etc.), leuco dyes (U.S. Pat. No. 3,985) , No. 565, 4,022.
617 etc.) can also be used.

Hydrophobic additives such as the dye-providing compounds described above and the image-forming accelerators described below are disclosed in U.S. Pat.
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, No. 59-178451, No. 59-17
No. 8452, No. 59-178453, No. 59-178
No. 454, No. 59-178455, No. 59-1784
A high boiling point organic solvent such as that described in No. 57 may be used in combination with a low boiling point organic solvent having a boiling point of 50° C. to 160° C., if necessary.

The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g or less, based on the dye donor fig 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.

Various surfactants can be used when dispersing hydrophobic substances into hydrophilic colloids. For example, JP-A-59-
The surfactants listed on pages (37) to (38) of No. 157636 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. 30-31 (fund), JP-A-60-14033
No. 5, pages (17) to (18), JP-A-1284-1984
No. 38, No. 60-128436, No. 60-12843
Reducing agents described in No. 9, No. 60-128437, etc. can be used. Also, JP-A-56-138.736, JP-A No. 57
Reducing agent precursors described in US Pat. No. 4,330,617 and the like can also be used.

Combinations of various reducing agents 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, a compound that activates development and simultaneously stabilizes images can be used in the photosensitive element. For specific compounds preferably used, see U.S. Patent No. 4,50.
No. 0,626, columns 51-52.

Various antifoggants or photographic stabilizers can be used in the present invention. For example, research
Disclosure magazine December 1978 issue No. 24-25
Azoles and azaindens described on page, JP-A-59-
Nitrogen-containing carboxylic acids and phosphoric acids described in No. 168442, or mercapto compounds and metal salts thereof described in JP-A-59-111636, Japanese Patent Application No. 60-228
Acetylene compounds described in No. 267 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.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta, and cyan, it is necessary to use a light-sensitive element having at least three silver halide emulsion layers each sensitive to a different spectral region. good. For example, the blue-sensing layer,
A combination of three layers: a green-sensitive layer, a red-sensitive layer, a green-sensitive layer, a red-sensitive layer,
There are combinations of infrared-sensitive layers, etc. Each of these photosensitive layers may be divided into two or more layers, if necessary.

The photosensitive element used in the present invention may optionally contain various additives known for use in heat-developable photosensitive elements and layers other than the photosensitive layer, such as a protective layer, an intermediate layer, an antistatic layer, an antihalation layer, etc. can have. Examples of various additives include plasticizers, sharpness-improving dyes, antihalation dyes, and surfactants, which are described in Research Disclosure Magazine, June 1978 issue, pages 9 to 15, and Japanese Patent Application Laid-Open No. 61-88256. There are additives such as whitening agents, optical brighteners, anti-slip agents, antioxidants, and anti-fading agents.

The protective layer may contain an ultraviolet absorber.

Each of the protective layer and the intermediate layer may be composed of two or more layers.

Further, the intermediate layer may contain a reducing agent to prevent color fading and color mixing, an ultraviolet absorber, and a white pigment such as titanium dioxide. A white pigment may be added not only to the intermediate layer but also to the emulsion layer for the purpose of improving sensitivity.

The photographic element of the present invention essentially includes a light-sensitive element and a dye-fixing element, and typically the light-sensitive element and the dye-fixing element are coated on two supports on the same support. It is broadly divided into forms in which it is coated on top. The relationship between the photosensitive element and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer are as described in Japanese Patent Application No. 59-268926, 58-59.
The relationships set forth in page 1 and column 57 of U.S. Pat. No. 4,500,626 are also applicable to the present application.

On the other hand, the dye fixing element preferably used in the present invention has at least one layer that fixes the dye produced or released by heat development. The dye fixing layer may be a layer containing a mordant, and may be a layer containing a mordant, as described in JP-A-57-179840 and JP-A-57-179840.
A layer composed of a dye-receiving polymer described in Japanese Patent No. 7-198458 and the like may also be used.

The dye fixing element preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include those described in JP-A-61-88256. A protective layer is added to the dye fixing element as necessary.
Auxiliary layers such as a release layer and an anti-curl layer can be provided. In particular, it is useful to provide a protective layer. One or more of the above layers may include hydrophilic heat solvents, plasticizers, anti-fade agents, UV absorbers, slip agents, matting agents, antioxidants, and dispersed vinyl to increase dimensional stability. Compounds, surfactants, optical brighteners, etc. may also be included.

Specific examples of these additives are described on pages (26) to (31) of JP-A-61-88256.

In the present invention, an image formation accelerator can be used in the photosensitive element and/or the dye fixing 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 photosensitive material layers. It has functions such as promoting the movement of dye from the dye to the dye fixed layer, and from a physicochemical function, it has the above-mentioned base or base precursor, nucleophilic compound, high boiling point organic solvent (oil), thermal solvent, and surfactant. It is classified as a compound that interacts with silver or 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 in (18) to (19) of JP-A-61-93451.

Various development stoppers can be used in the photosensitive element and/or dye fixing element of the present invention.

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 when heated (for example, JP-A No. 60-10
No. 8837, No. 60-192939, No. 60-230
133 or 60-230134).

Compounds that release mercapto compounds are also useful;
For example, JP-A-61-67851, JP-A No. 61-14724
No. 4, No. 61-124941, No. 61-185743
No. 61-182039, No. 61-185744, No. 61-184539, No. 61-188540,
There is a compound described in No. 61-53632.

A hydrophilic binder can be used for the photosensitive element and/or dye fixing element of the present invention.

Typical hydrophilic binders are transparent or translucent hydrophilic binders, such as gelatin, proteins such as gelatin derivatives, cellulose derivatives, and natural substances such as starch, polysaccharides such as gum arabic, polyvinylpyrrolidone, Includes synthetic polymeric materials such as water-soluble polyvinyl compounds such as acrylamide polymers. Dispersed vinyl compounds, which are used in latex form and increase the dimensional stability of the photographic material, can also be used. These binders can be used alone or in combination.

The total amount of each binder in each element is 20 g or less per 1 d, preferably 10 g or less, more preferably 7
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.

The constituent layers (photographic emulsion layer, dye fixing layer, etc.) of the light-sensitive element and/or dye fixing element of the present invention may contain an inorganic or organic hardening agent.

Specific examples of hardening agents are given in JP-A-61-147244, pages 24 to 25) and JP-A-59-15763.
Examples include those described in No. 6, page 38, and these can be used alone or in combination.

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.

Further, in order to promote dye transfer, a high boiling point organic solvent may be contained in the photosensitive element and/or the dye fixing element.

The support used in the photosensitive element and/or dye-fixing element of the present invention is one that can withstand processing temperatures.

Commonly used supports include glass, paper, cast-coated paper, synthetic paper, polymer films, metals, and their analogues. Those described as supports can be used.

The heating layer that can be provided on the photosensitive element and/or the dye fixing element can be formed by using a thin film of an inorganic material exhibiting semiconductivity or by 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 include those described in JP-A-61-29835 and the like.

In the present invention, the method described in U.S. Pat. No. 4,500,626 No. 55 to 5,641jl can be applied to the heat-developable photosensitive layer, protective layer, intermediate layer, undercoat layer, bank layer, dye fixing layer, and other layers. .

Radiation, including visible light, can be used as a light source for imagewise exposure to record an image on the photosensitive element. In general, light sources used for normal color printing, such as tungsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser light sources, CRT light sources, light emitting diodes (LEDs), etc.
The light source described on page (26) of No. 44 and column 56 of US Pat. No. 4,500,626 can be used.

The pressure conditions and method of applying pressure when overlapping the photosensitive element and the dye fixing element and bringing them into close contact are described in Japanese Patent Application Laid-Open No. 1472-1986.
The method described on page (27) of No. 44 can be used.

Any of a variety of thermal development equipment can be used to process the photographic elements of this invention. For example, JP-A No. 59-75247,
Apparatuses described in Japanese Patent No. 59-177547, No. 59-181353, No. 60-18951, Japanese Utility Model Application No. 116734-1980, etc. are preferably used.

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

This article describes how to make benzotriazole silver emulsion.

28g of gelatin and 13.2g of benzotriazole to 33g of water
00mJ! 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 yield of 400 g of benzotriazole silver emulsion was obtained.

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

28 g of gelatin and 26.7 g of potassium 4-acetylaminophenylpropiolate were dissolved in 500 mg of water. This solution was kept at 40°C and stirred.

A solution prepared by dissolving 17 g of silver nitrate in 100 mg of water was added to this solution over 2 minutes, and the mixture was further stirred for 10 minutes.

The pH of this emulsion was adjusted to 6.30, and centrifugation yielded 31,400 g of acetylene silver emulsion.

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

A well-stirred gelatin aqueous solution (water ioo.

Contains 20g of gelatin and 3g of sodium chloride per ml,
8,600 ml of an aqueous solution containing sodium chloride and potassium bromide and an aqueous silver nitrate solution (110.59 mol of nitric acid dissolved in 60 QmJ of water) were simultaneously added at equal flow rates over a period of 40 minutes. . In this way, a monodisperse cubic silver chlorobromide emulsion (50 mol % of bromine) with 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 20 mg of tetrazaindene.

The yield of emulsion was 600 g.

Next, we will explain how to make a silver halide emulsion for the third layer.

600 mj of an aqueous solution containing sodium chloride and potassium bromide in 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)! and silver nitrate aqueous solution (water 600
0.59 mol of silver nitrate dissolved in mj+) was 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, 5 mg of sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3a, ? - Chemical sensitization was carried out at 60° C. by adding 20 mg of tetrazaindene. The yield of emulsion was 600 g.

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

5 g of yellow dye-donating substance (A), 0.5 g of sodium succinate 2-ethyl-hexyl ester sulfonate, and triisononyl phosphate as surfactants.
0g was weighed, 30 ml 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 g of a 3% 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 7.5 g of tricresyl phosphate was used as a high boiling point solvent.

A yellow dye dispersion was prepared using a cyan dye-providing substance (C) in the same manner as the yellow dye dispersion.

Next, a method for preparing a dispersion of zinc hydroxide will be described. 12.5 g of zinc hydroxide, 1 g of carboxymethyl cellulose as a dispersant, and 100 mj of a 4% gelatin aqueous solution! In addition, it was ground for 30 minutes in a mill using glass beads with an average particle size of 0.75+ nm. The glass beads were separated to obtain a dispersion of zinc hydroxide.

With these, a color photosensitive element 101 having a multilayer structure as shown in the following table was made.

Table 2 = Jin Oz N q　′″ O- B　　　　　　　　− １　　　　　　　　 ■7 0ri Engineering ○ 11 ~ :e Z i.

Two Xi − , :! :　　　　　　　　”.

:I:U :I: , 11H O-00 1ν Tech 2 U, Tech = = Tech ○ = A method for forming a dye fixing element having an image-receiving layer will be described.

First, 15 g of a polymer with the following structure was dissolved in 200 ml of water, 100 g of 10% lime-treated gelatin, and the following compound (
b) Log was mixed uniformly. This mixed solution was uniformly applied onto a paper support laminated with polyethylene in which titanium oxide was dispersed to form a wet film of 85 μm, and then dried.

Next, gelatin hardener H-10.75g, H-20.2
5 g and 160 ml of water and 100 g of 10% lime treated gelatin were mixed uniformly.

This mixed solution was uniformly applied onto the above-mentioned coating material to a wet film thickness of 60 μm and dried to obtain a dye fixing element.

Polymer SO, compound (a) Gelatin hardener H-1 C1lt= Cll5O□CHzCONH (C1lz)
J)ICON)ItsO! cll = C1l□gelatin hardener H-2 C)1. =Cl1SO□CHzCONII(CHz)
JHCOC) Its (hcH=cHt Tungsten bulbs are used for each of the color photosensitive elements 101 to 105 of the above multilayer structure, and G, R, and IR three-color separation filters with continuously changing concentrations (G is 500 to 600 nm, R is 6
00-70Qnm bandpass filter, IR is 70
(constructed using a filter that transmits 0 nm or more), and was exposed to light at 500 lux for 1 second.

1'l m each on the emulsion side of this exposed light-sensitive element.
j! /rd of water was supplied using a wire bar, and then the dye-fixing element and the membrane surface were overlapped so that they were in contact with each other.

After heating for 25 seconds using a heat roller whose temperature was adjusted so that the temperature of the water-absorbed film was 93°C, the dye fixing element was peeled off from the photosensitive element, and G, R, I
Corresponding to the R three-color separation filter, clear images of yellow, magenta, and cyan were obtained. Maximum density of each color (Dm
ax) and the minimum density (Dmin) were measured using a Macbeth reflection densitometer (RD-519).

Next, the photosensitive elements 101 to 105 are heated at 30° 80% RH.
After adjusting the humidity in a high humidity environment, the membrane surface was overlapped with a polyethylene terephthalate film, left for 3 days, then peeled off, the presence or absence of adhesion marks was observed, and a compulsory test regarding storage in a roll state at high humidity was conducted.

As is clear from the above results, if the amount of mantle agent is too small, it will cause adhesion failure when stored in a roll or sheet form, and if it is too large, the photosensitive element and dye will not bond together after heat development using a nip roller. When the fixing element is peeled off, a film peeling failure of the emulsion layer occurs, but if used in the amount ratio within the range specified in the present invention, there will be no adhesion failure, and no film peeling failure will occur during peeling. I understand.

Claims (1)

[Claims] A photosensitive element containing on a support at least a photosensitive silver halide, a binder, and a dye-donating substance that produces or releases a diffusible dye upon thermal development is superimposed with a dye-fixing element to form water and a base and/or a base precursor. In the image forming method, the uppermost layer of the photosensitive element contains a matting agent in an amount of 0.5 to 10 vol% based on the amount of binder in the uppermost layer. An image forming method characterized by: