JPS61205935A - Image forming method - Google Patents

Abstract

PURPOSE:To prevent curling by forming a hydrophilic colloidal layer on the back side of a support supporting a dye fixing layer on which a dye image is formed by moving a dye released by heating. CONSTITUTION:A mobile dye distributed imagewise in a photosensitive material is moved to a dye fixing material having a dye fixing layer, and the photosensitive materials is stripped from the dye fixing material. In this image forming method, at least one hydrophilic colloidal layer (back layer) is formed on the back side of the support supporting the dye fixing layer by applying and drying hydrophilic colloid. Natural or synthetic hydrophilic polymer is used as a hydrophilic colloid forming substance, and various additives such as a matting agent and colloidal silica as well as a binder are added to the polymer so as to increase the adhesion resistance and to prevent curling.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a new method for forming dye images by heating in a substantially water-free state.

The present invention further relates to a new image forming method using a new photosensitive material having a dye-donating substance that reacts with photosensitive silver halide to release a hydrophilic dye upon heating in a substantially water-free state. .

The present invention relates to a new method for obtaining a dye image by transferring the released dye (particularly by heating) to a dye fixing layer.

(Prior art) Photography using silver halide has been the most widely used method since it has excellent photographic properties such as sensitivity and gradation control compared to other photographic methods such as electrophotography and diazo photography. I've been exposed to it. In recent years, a technology has been developed that allows images to be easily and quickly obtained by changing the image forming method for photosensitive materials using silver halide from the conventional wet processing using a developing solution to a dry processing using heating, etc. It has been.

Many methods have been proposed for obtaining color images. U.S. Pat.
, 531,286, a p-phinidine diamine reducing agent and a phenolic or activated methylene coupler; in U.S. Pat. No. 3,761,270, a p-amine phenolic reducing agent; No. 519 and Research Disclosure Magazine September 1975 No. 31, 3
2-? In US Pat. No. 4,021,240, a combination of a sulfonamidophenol reducing agent and a 4-equivalent coupler is proposed.

A method of introducing a nitrogen-containing heterocyclic group into a dye, forming a silver salt, and releasing the dye by heat development is described in Research Disclosure Magazine, May 1978 issue, pp. 54-58, RD.
-16966.

Further, regarding the method of forming positive color images using the photosensitive silver dye bleaching method, for example, see Research Disclosure Magazine, April 1976 issue, pp. 30-32 (RD-144
33), December 1976 issue of the same magazine, 14-15-! '-di (RD-15227), U.S. Patent No. 4,235,957
Useful dyes and bleaching methods are described in the issue.

Further, regarding methods of forming color images using leuco dyes, for example, US Pat. No. 3,985,565 and US Pat.
, No. 022,617.

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

In order to improve these drawbacks, an image forming method using silver halide has been proposed in which a movable dye is formed in the form of an image and the dye is moved to a dye fixing layer. (JP 58-58543, JP 58-79247, JP 58-14
9046, 58-149047).

As one specific method of these image forming methods, a dye-fixing material having a dye-fixing layer on a support is brought into contact with a light-sensitive material, and a mobile color or element formed in the form of an image is transferred to the dye-fixing layer. There is a method in which the photosensitive material and the dye-fixing material are then peeled off. Dye-fixing materials tend to cause curling when the humidity is low or high, especially when a heating process is involved. The curled dye fixing material is
This may cause poor contact with the photosensitive material, resulting in insufficient transfer of the mobile dye to the dye fixing layer, and mechanical troubles are likely to occur when contacting with the photosensitive material. This results in a decrease in image quality. Furthermore, even after peeling, problems such as poor transportation and stacking are likely to occur, which poses a serious constraint on device design. Further, even in dye images after image formation, curling poses a serious problem in storing the images, and also has the disadvantage of significantly detracting from the aesthetic appearance of the images.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to provide an image forming method in which a mobile dye is transferred to a dye fixing layer and fixed using a dye fixing material with improved curling. It is in.

(Means for solving the problem) The above problem involves moving the mobile dye distributed in the photosensitive material in an imagewise manner to the dye fixing material having a dye fixing layer, and then peeling off the photosensitive material and the dye fixing material. The above object is achieved by an image forming method characterized by having at least one hydrophilic colloid layer on a support surface on the back side of the support surface having a dye fixing layer. be able to.

In particular, in the present invention, at least (1)
A photosensitive material comprising a photosensitive silver halide, (2) a binder, and (3) a compound that generates or releases a mobile dye when the photosensitive silver halide is reduced to silver under high temperature conditions. It is advantageous to implement an image forming method according to the present invention in which heating is performed after or simultaneously with image exposure and in the presence of a transfer aid, since curling of the dye fixing material due to heating can be effectively prevented. .

In the present invention, with respect to a support of a dye fixing material having a dye fixing layer, at least one hydrophilic colloid layer provided on the surface of the support opposite to the dye fixing layer is hereinafter referred to as a back layer. This back layer is usually formed by applying a colloidal hydrophilic colloid to a support and drying it.

The hydrophilic colloid-forming substance contained in the back layer is preferably a hydrophilic organic polymer compound, and may be a commonly used hydrophilic natural or synthetic polymer, but preferably,
Examples include proteins such as gelatin, gelatin derivatives, and cellulose derivatives, natural substances such as starch and polysaccharides such as gum arabic, and water-soluble polyvinyl compounds such as polyvinylpyrrolidone and acrylamide polymers, which may be used alone or in combination. good.

Furthermore, even in a laminated heat developable material in which a photosensitive layer and a dye fixing layer are provided on the same support, curling can be prevented by providing a back layer on the opposite side of the support having the photosensitive layer and dye fixing layer. Improved.

The thickness of the back layer to improve curling is 1 to 15
μm1 is preferably 3 to 10 μm, and the thickness of the dye fixing layer/thickness of the back layer is 10.5 to 1/2, preferably 10.7 to 110.5.

The back layer may be formed of hydrophilic colloid alone, but
It is preferable to use a hydrophilic cotetraid as a binder together with a wide range of additives. Preferred additives include matting agents, colloidal silica, oil droplets, polymer latex, etc. for improving the adhesion resistance of the back layer.

The back layer containing these additives will be specifically explained.

Matting agents are well known in the photographic art and can be defined as discrete solid particles of inorganic or organic material dispersible in a hydrophilic organic binder. Examples of inorganic matting agents include oxides (e.g. silicon dioxide, titanium oxide, magnesium oxide, aluminum oxide, etc.), alkaline earth metal salts (e.g. sulfates and carbonates, specifically barium sulfate, carbonate, etc.). (calcium, magnesium sulfate, calcium carbonate, etc.), silver halide particles that do not form an image (silver chloride, silver bromide, etc., and may further include a small amount of iodine atoms as a halogen component), glass, and the like.

Examples of organic matting agents include starch, cellulose esters (e.g., cellulose acetate propionate, etc.),
These include cellulose ether (for example, ethyl cellulose, etc.), synthetic resins, and the like. Examples of synthetic resins include water-insoluble or sparingly soluble synthetic polymers, such as alkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, and vinyl esters (such as acetic acid 9-vinyl). ), acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid, methacrylic acid, α,
A polymer containing a combination of β-unsaturated dicarboxylic acid, human 10-xyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used. Among them, polymethyl methacrylate is preferred.

The average particle size of these matting agents is approximately 0.1-10μ
The thickness is suitable, preferably 0.5-8μ, more preferably 1-6μ.

The thickness of the back layer containing the matting agent is preferably about 1/1 to about 1/2 of the average particle size (average diameter) of the matting agent from the viewpoint of improving releasability.

The back layer may be multi-layered, in which case the matting agent is contained in the outermost layer, and in the case of a two-layered structure, for example, oil droplets are preferably dispersed in at least one of these layers. .

The appropriate size of the oil droplets is approximately 0.01μ to 20μ,
．． 05μ to 10μ is preferred.

As the substance that forms these oil droplets, it is useful to use high-boiling organic compounds that are usually used for dispersing photographic couplers.As the high-boiling organic compounds, those having a boiling point of 1000 or more at normal pressure are preferable, such as those in the United States. Patent No. 2,322,027
Phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl 7
oxphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters/I/ (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (eg, dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (eg, tributyl trimesate), and the like.

The polymer latex used as the additive is an aqueous dispersion of a water-insoluble polymer with an average particle size of 20 mμ to 200 mμ, and the preferable amount used is 0.01 to 1 in dry weight ratio to the hydrophilic colloid binder. ．． O is particularly preferably 0.1 to 0.8.

Preferred examples of this polymer latex include alkyl esters of acrylic acid, 90-oxyalkyl esters, glycidyl esters, etc., alkyl esters of methacrylic acid, hydroxyalkyl esters,
or has glycidyl ester etc. as one monomer unit, and has an average molecular weight of 100,000 or more, particularly preferably 300,000 to 5
A specific example is shown by the following formula.

Polymer 1 MoCH2-CH+Y COOC4H9 Polymer 2 (-CH2-CH + Yuchi COOC3H7 Polymer 3 +0M2-CH+Y COOC2H5 Polymer 4 CH (-CH2-C- C00C,H.

Polymer 5 OH Polymer 6
CH Furthermore, regarding polymer latex, the above-mentioned Japanese Patent Publication No. 45-5331, U.S. Pat. No. 2,852,386, U.S. Pat.
The descriptions in the specifications of No. 911 and No. 3411912 can be referred to.

The colloidal silica has an average particle diameter of 7 mμ to 120 mμ, and the main component is silicon dioxide and reed, and may contain alumina, sodium aluminate, etc. as a minor component.

These colloidal silicas may also contain, as stabilizers, inorganic bases such as hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, and organic salts such as tetramethylammonium ion. In particular, colloidal silica consisting of potassium hydroxide or ammonium hydroxide is preferred as a stabilizer for colloidal silica.

For these colloidal silicas, e.g. Egon M
Edited by atij evic, 5urface and Co.
11oidScience, Volume 6, pp. 3-100 (1
973 1, Tohn Wiley & 5ons)
is described in detail.

A specific example of colloidal silica is E.

du Pont de Nemours & Co.
(USA) to Ludox AM, Ludox AS
, Ludox LS, Ludox TM, L
Under product names such as udox H8, manufactured by Yasan Kagaku Co., Ltd. (Japan,
From Tokyo) Snowtex 201 Snowtex C,
With product names such as Snowtex N1 and Snowtex O, M
on5anto Co, (USA) 5
yton C-30.

With product names such as 5yton 200, and Na1co C
hem, Co.

(USA) Nalcoag 1030, Nalc
oag 1060° Commercially available from Nalcoag under trade names such as -21-64.

The preferred amount of colloidal silica used is 0.05 to 1.0, particularly preferably 0.2 to 0.7 in terms of dry weight ratio to gelatin used as a binder for the back layer.
It is.

Furthermore, a back layer Hesbery agent can be applied. Preferred slipping agents include higher alkyl sodium sulfate, higher alkyl sodium sulfate, higher fatty acid higher alcohol ester,
Examples include carbowax, higher alkyl phosphate esters, and silicone compounds. Specifically, U.S. Patent No. 2.88
No. 2,157, No. 3,121,060, No. 3,8
The compounds described in No. 50,640 and JP-A-51-141623 are particularly effective when used alone or in combination of two or more.

The amount of slip agent applied to the back layer is approximately 51n9~200cm
/m is appropriate.

In the present invention, the dye fixing material having a back layer is preferably a dye fixing layer containing a mordant. Adjacent layers include a water-absorbing layer (usually composed of gelatin and a hardening agent) coated between the dye-fixing layer and its supporting layer, and a protective layer for the dye-fixing material (which also serves as a peel-promoting layer). (usually mainly composed of gelatin), etc.

In the above case, the mordant can be arbitrarily selected from commonly used mordants, and among them, 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.

Preferred specific examples of homopolymers and copolymers containing one vinyl monomer unit having a tertiary amino group include the following. The number per monomer unit represents A/% (the same applies hereinafter).

H3 4CH2-CH+□o.

Specific examples of homopolymers and copolymers containing one vinyl monomer unit having a tertiary imidazole group include U.S. Pat. No. 58-226497,
The following may be mentioned, including the mordant described in No. 58-232071.

÷CH2−CH,. .

Preferred specific examples of homopolymers and copolymers containing one vinyl monomer unit having a quaternary imidazolium salt include British Patent Nos. 2,056,101 and 2,093,0.
No. 41, No. 1,594,961, U.S. Patent No. 4,12
No. 4,386, No. 4,115,124, No. 4,273
, No. 853, No. 4,450,224, Japanese Unexamined Patent Publication No. 48-2
The following may be mentioned, including the mordants described in No. 8,225 and the like.

+CH2-CH-)-1o.

l (-CH2-CH-)-1o.

CH20H2-OH ie CH3 turbidity Other preferred specific examples of homopolymers and copolymers containing one vinyl monomer unit having a quaternary ammonium salt include U.S. Pat. Nos. 3,709,690 and 3,89
No. 8,088, No. 3,958,995, Patent Application No. 1982-
No. 166135, No. 58-169012, No. 58-2
No. 32070, No. 58-232072, No. 59-91
The following may be mentioned, including the mordant described in No. 620.

CH et al., U.S. Patent Nos. 2,548,564 and 2,4
No. 84,430, No. 3,148,061, No. 3.
Vinylpyridine polymers and vinylpyridinium cationic polymers disclosed in U.S. Pat. No. 756,814 and others; U.S. Pat.
, No. 096, No. 4,128,538, British Patent No. 1
, 277.453, etc.; a polymer mordant capable of crosslinking with gelatin, etc.; US Pat. No. 3,958
, No. 995, No. 2,721,852, No. 2,79
No. 8,063, JP-A-54-115228, JP-A No. 54-
Aqueous sol type mordant disclosed in No. 145529, No. 54-26027, etc.; U.S. Pat.
Water-insoluble mordant disclosed in US Pat. No. 4,168,976 (% 1973-13733
No. 3) A reactive mordant capable of forming a covalent bond with the dye disclosed in the specification, etc.; furthermore, U.S. Pat. No. 3,709,690
No. 3,788,855, No. 3.642,48
No. 2, No. 3,488,706, No. 3.557,0
No. 66, No. 3,271,147, No. 3.271,
No. 148, JP-A-50-71332, JP-A No. 53-303
No. 28, No. 52-155528, No. 53-125,
The mordant disclosed in Japanese Patent No. 53-1024 can be mentioned.

Others: U.S. Patent No. 2,675,316, U.S. Patent No. 2.8
Mention may also be made of the mordants described in US Pat. No. 82,156.

Usually, the dye fixing layer is composed of the above-mentioned mordant and a hydrophilic colloid (binder).

Gelatin is the most typical hydrophilic colloid.
Other materials such as polyvinyl alcohol can also be used in the present invention. The mixing ratio of the polymer mordant and gelatin and the coating amount of the polymer mordant can be easily determined by those skilled in the art depending on the amount of dye to be mordanted, the type and composition of the polymer mordant, the image forming process to be used, etc. However, it is appropriate that the mordant/gelatin ratio is 20/80 to 80/20 (weight ratio) and the amount of mordant applied is 0.2 to 15117 m2, preferably o, sy to 811 m2. is preferable. The molecular weight of the polymer mordant of the present invention is i,
o o.

~1,000,000 is suitable, especially 10,000~
200.000 is preferred.

In the present invention, in order to imagewise distribute the mobile dye in the dye-fixing material, the photosensitive silver halide, the binder and the photosensitive silver halide are reduced to silver under high temperature conditions. It is preferable to use a method in which a heat-developable photosensitive material having a dye-providing substance on a support that forms or releases a diffusible dye in a reverse manner is exposed and then heated.

Furthermore, the effects of the present invention are particularly remarkable when a method of heating is used to transfer the dye.

Dye transfer from the photosensitive layer to the dye fixing layer is carried out in the presence of a dye transfer aid. As the dye transfer aid, a liquid or a hot solvent that can dissolve the dye to be transferred at least in a heated state can be used. That is, if the pigment to be transferred is a hydrophilic pigment, a hydrophilic liquid or a hydrophilic hot solvent is used, and in the case of a lipophilic pigment, an organic solvent, an oil-lipophilic hot solvent, etc. that can dissolve the pigment is used. Can be used. Further, depending on the degree of hydrophilicity or lipophilicity of the dye, suitable amounts of a hydrophilic liquid, a hydrophilic heat solvent, a lipophilic solvent, and a lipophilic heat solvent may be mixed and used. The dye transfer aid may be used by moistening the dye fixing layer and/or the photosensitive layer of the photosensitive material, preferably the dye fixing layer, with a solvent, or it may be directly incorporated in the layer in advance, or it may be adsorbed onto a polymer or crystal. Alternatively, it may be incorporated as crystal water or as microcapsules.

Specific examples of the hydrophilic or lipophilic solvent used as the dye transfer aid include those described on page 121 of Japanese Patent Application No. 59-209563.

When a hydrophilic thermal solvent is incorporated into a photosensitive material and/or a dye fixing material as a dye transfer aid, the hydrophilic dye is transferred to the dye fixing material by heating in the presence of the dye transfer aid. Can be fixed.

In an image forming method in which the dye is transferred to the fixed dye layer by heating in the presence of a dye transfer aid, the transfer of the mobile dye may begin at the same time as the dye is released, but may occur after the dye release is completed. It may be. Therefore, heating for transfer may be performed after heat development or at the same time as heat development.

The above-mentioned hydrophilic thermal solvent has the physical properties described on page 123 of Japanese Patent Application No. 59-209563.

Further, as for the method of adding the hydrophilic heat solvent, the addition position, and specific examples, those described on pages 124 to 125 of Japanese Patent Application No. 59-209563 can be applied.

In the present invention, the dye-fixing material is used in combination with a photosensitive material as described above, and after image exposure or heat development on the photosensitive material, the coated surface of the photosensitive material and the coated surface of the dye-fixing material are overlapped and heated. After the transfer image is formed, the photosensitive material is immediately peeled off from the dye fixing material. Depending on whether the final image is of a reflection type or a transmission type, the support for the dye-fixing material can be an opaque support or a transparent support. Further, a white reflective layer may be coated if necessary.

In the present invention, in order to form an image having a wide range of colors in the chromaticity diagram on a dye-fixing material using the three primary colors yellow, magenta, and cyan, the light-sensitive material used in the present invention has at least three layers. It is necessary to have silver halide emulsion layers each sensitive to different spectral regions.

Typical combinations of at least three light-sensitive silver halide emulsion layers sensitive to different wavelength regions include a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, and a green-sensitive emulsion layer. , a combination of a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and an infrared-sensitive emulsion layer, a blue-sensitive emulsion layer, a red-sensitive emulsion layer and an infrared-sensitive emulsion layer There are combinations of emulsion layers.

Note that the infrared light-sensitive emulsion layer herein refers to an emulsion layer that is sensitive to light of 700 nm or more, particularly 740 nm or more.

The light-sensitive material 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.

Each of the above emulsion layers and/or the non-photosensitive layer adjacent to each emulsion layer includes a dye-providing substance that releases or forms a yellow dye, a dye-donor substance that releases or forms a magenta dye, and a cyan dye. It is necessary to each contain one kind of dye-donating substance that releases or forms . In other words, each emulsion layer and/or the non-photosensitive layer adjacent to each emulsion layer must contain a dye-providing substance that releases or forms dyes of different hues. If desired, two or more dye-providing substances having the same hue may be used in combination. Particularly when the dye-providing substance is colored from the beginning, it is advantageous to contain the dye-providing substance in a layer separate from the emulsion layer.

In addition to the above-mentioned layers, the photosensitive material may be provided with auxiliary layers such as a protective layer, an intermediate layer, an antistatic layer, an anti-curl layer, a release layer, and a matte layer, if necessary.

In particular, the protective layer (PC) preferably contains an organic or inorganic matting agent to prevent adhesion. Further, this protective layer may contain a mordant, an ultraviolet absorber, and the like. 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 (eg, hydroquinone, etc.) for preventing color mixture, an ultraviolet absorber, and a white pigment such as TtO□. A white pigment may be added not only to the intermediate layer but also to the emulsion layer for the purpose of increasing sensitivity.

In order to impart the above-mentioned color sensitivities to the silver halide emulsions, each silver halide emulsion may be dye-sensitized using a known sensitizing dye to obtain the desired spectral sensitivity.

The silver halide that can be used in the present invention is disclosed in Japanese Patent Application No. 59-20
The contents described on pages 17 to 22 of the specification of No. 9563 are also included. Further, organic silver salts described on pages 24 to 28 of the same specification can also be used in combination.

The silver halogenide used in the present invention may be spectrally sensitized with methine dyes or the like. The pigments used include pages 78 to 83 of Japanese Patent Application No. 59-209563.
There are sensitizing dyes listed on the page.

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

In the present invention, when photosensitive silver halide is reduced to silver under high temperature conditions, a compound that generates or releases a mobile dye in response to or inversely to this reaction, i.e., a dye-donating compound, is used. Contains sexual substances.

The compound of Tonono is disclosed in Japanese Patent Application No. 59-209563, page 30~
It can be expressed by the general formula (L) described on page 53.

In the present invention, the dye-donating substance is U.S. Pat.
They can be incorporated into the layers of the photosensitive material by known methods such as the method described in No. 2,027. In that case, the special application
The methods and methods described on pages 88 and 89 of Specification No. 9-209563 can be used.

In the present invention, the binder contained in the photosensitive material is
They can be used alone or in combination.

A hydrophilic binder can be used for this binder. Typical examples of hydrophilic binders include transparent or translucent hydrophilic binders, such as gelatin, gelatin derivatives, cellulose derivatives, and natural substances such as starch and polysaccharides such as gum arabic. and synthetic polymeric materials such as water-soluble polyvinyl compounds such as polyvinylpyrrolidone and acrylamide polymers. Other synthetic polymeric materials include dispersed vinyl compounds in the form of latexes, which increase the dimensional stability of photosensitive materials, among other things.

In the present invention, the back layer of the dye fixing material may contain an inorganic or organic hardening agent. For example, chromium salt (
Chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, !rutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), active Vinyl compound (1,3,5-triacryloyl-hexahydro-
8-) Ryazine, 1,3-vinylsulfonyl-2-pronozonol, 1,2-his(vinylsulfonylacetamido)ethane, etc.), active halogen compounds (2゜4-dichloro-6-hydroxy-8-triazine, etc.) ), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. can be used alone or in combination.

The supports used in the light-sensitive materials and dye-fixing materials in the present invention are those that can withstand processing temperatures. Common supports include glass, paper, metal and their analogs, but also cellulose acetate film, cellulose ester film, polyvinyl acetal film, polystyrene film, polycarbonate film, Includes polyethylene terephthalate films and their related films or resin materials. Paper supports laminated with polymers such as polyethylene can also be used. Polyesters described in US Pat. No. 3,634,089 and US Pat. No. 3,725,070 are preferably used.

The dye fixing material used in the present invention preferably has at least one dye fixing layer containing a mordant on the support opposite to the back layer, and the dye fixing layer is located on the surface. If necessary, a protective layer can be further provided.

Furthermore, a water absorption layer or a layer containing a dye transfer aid can be provided in order to sufficiently contain a dye transfer aid or to control the dye transfer aid if necessary. These layers may be adjacent to the dye fixing layer or may be applied via an intermediate layer.

The dye fixing layer used in the present invention may be composed of two or more layers using mordants having different mordant powers, if necessary.

In the dye fixing material used in the present invention, in addition to the above-mentioned layers, auxiliary layers such as a release layer, a matting agent layer, and an anti-curl layer may be provided on the support opposite to the back layer, if necessary.

One or more of the layers excluding the back layer include:
Bases and/or base precursors to promote dye transfer, hydrophilic thermal solvents, antifade agents to prevent color mixing of dyes, UV absorbers, additional dispersed vinyl compounds to increase dimensional stability, fluorescence. A brightener or the like may be included.

The binder for these additives is preferably hydrophilic;
Transparent or translucent hydrophilic colloids are typical. For example, proteins such as gelatin, gelatin derivatives, polyvinyl alcohol, cellulose derivatives, natural substances such as starch, polysaccharides such as gum arabic, water-soluble polyvinyl compounds such as dextrin, pullulan, polyvinyl alcohol, polyvinylpyrrolidone, and acrylamide polymers. Synthetic polymeric substances etc. are used. Among these, gelatin and polyvinyl alcohol are particularly effective.

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

Gelatin 28II and benzotriazole 13.2.9'
Dissolve in 300 d of water. The solution is kept at 40C' and stirred. Add 17.9 io of silver nitrate to this solution in water.

Add the solution dissolved in d for 2 minutes.

The pH of the benzotriazole silver emulsion is adjusted and allowed to settle to remove excess salt. Thereafter, the pH was adjusted to 6.30 to obtain a benzotriazole silver emulsion with a yield of 400y.

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

Add 600 d of an aqueous solution containing sodium chloride and potassium bromide to a well-stirred aqueous gelatin solution (containing 20.9 g of gelatin and 3 g of sodium chloride in 1000 d of water, kept at 75 C) and an aqueous solution of silver nitrate (600 11 d of water).
Ij! 0.59 mol of silver nitrate dissolved in the solution) was simultaneously added at an equal flow rate over 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (bromine 50 mol S>) having an average grain size of 0.40 μm was prepared.

After washing with water and desalting, sodium thiosulfate 5WI9 and 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene 201n9 were added to perform chemical sensitization at 60C. The yield of emulsion was 600 II.

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

A well-stirred gelatin aqueous solution (containing gelatin 20II and sodium chloride 3y in 10100O water, 75C
K) 600 d of an aqueous solution containing sodium chloride and potassium bromide and a silver nitrate aqueous solution (600 d of water)
(dissolved 0.59 mol of K silver nitrate) at the same time 40
Added at equal flow rates over a period of 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 parts of sodium thiosulfate and 201 n9 of 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene were added to carry out chemical sensitization at 60C.

The yield of emulsion was 600 g.

Next, a method for preparing a gelatin dispersion of a dye-providing substance will be described.

Using yellow dye-donating substance (A) as 511 surfactant, 0.5 JF of sodium succinate 2-dithylhexyl ester sulfonate,) liisononyl phosphate 1
0. Weigh i9 and add 30d of ethyl acetate to about 60G
Heat to dissolve and make a homogeneous solution. This solution and a 10% solution of lime-treated gelatin (100.9%) were stirred and mixed, and then dispersed using a homogenizer for 10 minutes at 10,000 rpm. This dispersion is called a yellow dye-providing substance dispersion.

A dispersion of a magenta dye-donating substance was prepared in the same manner as above, except that the magenta dye-donating substance (B) was used and 7.5 g of tricresyl phosphate was used as a high-boiling solvent. .

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

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

Dye-donating substance (A) (B) (C) OC16H33(n) (D-1) (D-2) (D-3) Next, the method of making the dye fixing material (A) will be described.

First, the method of preparing the dye fixing layer will be described.

Gelatin hardener H-1 (0,75,l, H-z(
Add o, 2s, l and 160mJl of distilled water to make 10%
Acid-treated gelatin 100! I was added and mixed uniformly.

This mixed solution was uniformly applied to a wet film thickness of 60 μm on a paper support (thickness: 200 μm) laminated with polyethylene in which titanium oxide was dispersed, and then dried. Next, mordant P-1 (tog) and 200 d of distilled water were added, followed by 10% lime-treated gelatin 100J9 and mixed uniformly. This mixture was uniformly applied onto the above-mentioned coating material to form a wet film of 85 μm. This sample was dried and used as a dye fixing layer containing mordant P-1.

Gelatin hardener H-1 CH2-cHsO□CH2C0NH(CH2)2NHc
OCH2SO□CH=CH2 Gelatin hardener H-2 CH2-CH8O2CH2CONH (CH2) 3NH
COCH2So2CH=CH2 mordant p-i Next, the dye fixing layer was coated on a Ni-paper support (thickness 200μ).
A dye-fixing material (A) was prepared by applying a gelatin back layer to one side of the sample to a dry thickness of 8 μm according to the combination of prescriptions below.

Next, a dye fixing material (B) was prepared in exactly the same manner as the dye fixing material (A) except that the gelatin back layer was not provided.

In addition, a paper support (thickness 200μ) for the dye fixing material (A)
A dye fixing material (C) was prepared in exactly the same manner except that the paper support (thickness: 100/I) was used.

Furthermore, a dye fixing material (D) was prepared in exactly the same manner as the dye fixing material (C) except that no gelatin back layer was provided.

G uses a tungsten light bulb in the multi-layered color photosensitive material, and the density changes continuously.

R1 engineering R three-color separation filter (G is 500-600nm
, R is a bandpass filter with a wavelength of 600 to 700 nm, and R is a filter that transmits at least 700 nm.)
Exposure was made for 1 second at 500 lux through the lens.

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

Next, the membrane side 1c11rL2 of the dye fixing material 201n
l! After supplying water, the heat-treated photosensitive coatings were stacked on a fixing material so that the film surfaces were in contact with each other. After heating for 6 seconds on a heat block at 80C, the dye fixing material is peeled off from the photosensitive material, and G, R,
Yellow, magenta, and cyan color images were obtained corresponding to the three-color separation filter of Technique H.

Next, the dye fixing material after fixing the dye was heated to 20% RH,
Table 1 shows the curling height after standing for 1 hour at 40% RH and 5olrRH-c.

In addition, when the dye fixing layer is placed face up on a horizontal table,
+ (plus) if the four corners are above the horizontal surface of the horizontal table, and - ( if the four corners are above the horizontal surface of the horizontal table when placed on the horizontal table with the dye fixing layer facing down) (minus) and shown in the table.

As shown in Table 1, the effect of providing a back layer in maintaining curling balance is clear. By providing the lashes and back layer, it is possible to easily maintain the curl balance in low humidity and high humidity.

It is also clear that this effect is particularly pronounced when the thickness of the support is thin.

Agent: Patent attorney (8107) Kiyotaka Sasaki (and 3 others)

Claims (1)

[Claims] In an image forming method in which mobile dyes distributed in a light-sensitive material are imagewise transferred to a dye-fixing material having a dye-fixing layer, and then the light-sensitive material and the dye-fixing material are peeled off, An image forming method comprising at least one hydrophilic colloid layer on the back surface of the support.