JPH03279956A - Image forming material and production of image forming material - Google Patents

Abstract

PURPOSE:To prevent the adsorption, etc., which are the cause for staining by treating the surfaces in contact with a colored photosensitive layer by a silane coupling agent and/or titanate coupling agent. CONSTITUTION:At least one layer of thermally softened layers and/or release layers are formed between a base and the colored photosensitive layer and at least the surfaces of the thermally softened layers and/or release layers in contact with the colored photosensitive layer are treated by the silane coupling agent and/or titanate coupling agent. The treatment is executed by dissolving the coupling agent in an org. solvent to prepare a dilute soln., and applying this soln. on the surface to be treated, such as intermediate layer of the layer to be treated. The good images free from the staining are obtd. even in the case of provision of the intermediate layer, such as thermally softened layer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an image forming material and a method for producing an image forming material. In particular, the present invention provides an image forming material which prevents scumming from occurring in the transferred image when the image is transferred to an image receiving layer to obtain the transferred image, and a method for producing the same.

[Background of the invention]

When an image forming material having a colored photosensitive layer on a support is exposed and developed to obtain an image, and then transferred to obtain a transferred image, the non-image area becomes smeared on the colored side, etc. Staining may occur.

This is thought to occur due to various reasons, but for example, when a release layer or heat softening layer is provided to efficiently transfer the formed image, the color that forms the colored photosensitive layer in these layers may Agents may get in there, which can cause stains.

For example, an image forming material with a structure in which a heat-softening layer is provided on one side of a support and a colored photosensitive layer (which may be composed of two layers, a colored layer and a photosensitive layer) is further provided on this layer is prepared. When using a heat-softening layer, it is common to form a colored photosensitive layer by coating a colored photosensitive layer coating solution containing a pigment on a support with a heat-softening layer. A heat drying step is required. However, some pigments, especially organic pigments, can be adsorbed to the heat-softened layer when heated, and this can be re-transferred onto the surface of the transfer material such as paper due to heating during the final image transfer, causing background stains. It could be the cause of.

[Problem that the invention seeks to solve]

As described above, conventional image forming materials have had the problem that background smear may occur in the final image.

The present invention is intended to solve this problem, and an object of the present invention is to provide a layer that easily adsorbs the pigment of the colored photosensitive layer, such as a heat softening layer, or Even when using pigments that are easily adsorbed by pigments, it is possible to obtain an image forming material that can prevent the above-mentioned adsorption that causes background smear and obtain good images without background smear. It is also an object to provide a manufacturing method for making such an imaging material.

[Means and effects for solving the problems] The above-mentioned object of the present invention is to have a colored photosensitive layer on a support, the colored photosensitive layer contains a photoreceptor, a binder, and a pigment, and In a colored image-forming material in which an image is obtained by transferring an image obtained by development to an image-receiving layer, at least one heat-softening layer and/or a heat-softening layer is provided between the support and the colored photosensitive layer. Or, image formation characterized in that a release layer is formed, and at least the surface of the heat-softened layer and/or release layer that contacts the colored photosensitive layer is treated with a silane coupling agent and/or a titanate coupling agent. This is achieved through the use of materials.

Further, in a method for producing a colored image forming material in which a colored photosensitive layer coating liquid is applied onto a support to form a colored photosensitive layer, the colored photosensitive layer coating liquid contains a photoreceptor, a binder, and a pigment; And, between the support and the colored photosensitive layer, at least one intermediate layer (such as a heat-softening layer and/or a release layer) is formed using an intermediate layer coating liquid for forming a heat-softening layer and/or a release layer. This can be achieved by a method for producing an image forming material, which further comprises treating at least the surface of the intermediate layer in contact with the colored photosensitive layer with a silane coupling agent and/or a titanate coupling agent.

The present invention was achieved against the following background.

That is, it is thought that one of the causes of background smearing is the adsorption of the pigment to the thermally softened layer during the thermal process. This adsorption can be controlled by manipulating the surface condition of the pigment or by manipulating the surface of an intermediate layer such as a heat softening layer. As a result, out of a huge number of processing methods,
They discovered that treatment with a silane coupling agent and/or a titanate coupling agent met this objective, and completed the present invention.

According to the present invention, by processing the intermediate layer as described above, it has become possible to obtain a final image free of background stains.

The present invention will be explained in more detail below.

The image forming material of the present invention has a colored photosensitive layer on a support. The colored photosensitive layer includes a photoreceptor, a binder, and a pigment.

The photoreceptor functions as a photosensitive substance, and for example, a diazo compound such as orthoquinone diazide can be used. Other preferable photoreceptors that can be used in the present invention will be described in detail later.

The binder is a binding agent in the photosensitive layer, and various polymer compounds can be used.

For example, a preferred binder may include a copolymer of vinyl acetate and vinyl versatate.

Other preferable binders that can be used in the present invention will be described in detail later. In a colored photosensitive layer, a photosensitive layer (for example, consisting of a photoreceptor and a binder) and a colored layer (for example, consisting of a pigment and a binder) are separated. It may be composed of two layers. In that case, the order of the layers is kodan.

In the present invention, the colored photosensitive layer on the support is formed on the support via an intermediate layer such as a heat-softening layer or a release layer. In particular, it is preferable to adopt a structure in which a heat-softening layer is formed on the support (preferably a release layer is further formed thereon), and a colored photosensitive layer is formed thereon. The heat softening layer will be described in detail later, but can be made of, for example, vinyl acetate-ethylene copolymer.

It is preferable to form a back coat layer on the opposite side of the support from the colored photosensitive layer. The back coat layer can be formed of silicone resin or the like.

The support may be made of any material, for example preferably polyethylene terephthalate.

Next, the image forming material of the present invention is image-exposed, developed, and the resulting image is transferred to obtain a transferred image.

For exposure and development, appropriate means can be used depending on the photoreceptor and the like.

The image forming material of the present invention contains a pigment in its colored photosensitive layer.

In the present invention, the term "pigment" refers to a coloring agent for forming a colored image.

Any of various pigments can be used as the coloring agent in the colored photosensitive layer, but in particular, when used for color proofing, the pigments are generally the usual colors required there, i.e., yellow, magenta,
A pigment with a tone that matches cyan and black is required.

Other metal powders, white pigments, fluorescent pigments, etc. can also be used. When the imaging materials of the present invention are used, for example, in color proofing for color image proofing, many pigments known in the art can optionally be used, such as those described below.

(C, I mean color index).

Victoria Pure Blue (C,T 42595) Auramine (C,I 41000) Cathylone Brilliant Flavin (C,I Basic 13) Rhodamine 6GCP (C,I 45160) Rhodamine B (C,I 45170) Safranin OK2O
: 100 (C, I 50240) Erioglaucine Shimla Fast Yellow 8CF (C, I 21105) Benzidine Yellow 4T-564D (C, I 21095) Shimla Fast Yellow 4015 (C, I 12355) Rio/-Luray F 7 B12O3 (C, I 158
30) First Gen Blue TC, RL (C, I 74160) Lionor Blue SM (C0I 26150”) Mitsubishi Carbon Blank MA-100 Mitsubishi Carbon Blank #30. #40. #50 In the practice of the present invention, coloring The content of the pigment in the photosensitive layer can be determined by taking into account the target optical density and the removability of the colored photosensitive layer to the developer.In the present invention, the content of the pigment is 10 to 30% by weight. It is preferable that

Next, the photoreceptor contained in the colored photosensitive layer of the image forming material of the present invention will be explained. Various photosensitive materials can be used as the photoreceptor. For example, when such a photoreceptor is irradiated with actinic rays, its molecular structure undergoes a chemical change in a short period of time, and its solubility in a solvent changes.
It includes all compounds such as monomers, prepolymers, or polymers whose exposed or unexposed portions are dissolved and removed when certain solvents are applied.

Examples of photoreceptors that can be used include photocrosslinkable photosensitive resins, such as those made by esterifying polyvinyl alcohol with cinnamic acid, which are so-called negative-positive type photoreceptors that have reduced correction in the exposed area. There are systems in which diazonium salts and their condensates are mixed with polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, etc., and systems in which aromatic azide compounds are used as photocrosslinking agents and mixed with binders such as cyclized rubber. Photosensitive resins using radical polymerization or photoionic polymerization can also be used.

Furthermore, as a so-called positive-positive type composition that increases the solubility of the exposed area, there is, for example, a photosensitive composition containing 0-quinonediazide as a photosensitizer, and specifically, 1.2-
benzoquinonediazide-4sulfonyl chloride, 1.
Compounds obtained by condensing 2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphthoquinonediazide-6-sulfonyl chloride with a hydroxyl group- and/or amino group-containing compound are preferably used. .

Examples of the hydroxyl group-containing compound include trihydroxybenzophenone, hydroxyanthraquinone, bisphenol A, phenol novolak resin, resorcin benzaldehyde condensation resin, and pyrogallol acetone condensation resin. Examples of amino group-containing compounds include aniline, p-aminodiphenylamine, p-aminobenzophenone, 4,4-diaminobenzophenone, and 4°4-diaminodiphenylamine.

Regarding the above 0-quinonediazide compound, J, K
“Light 5intensive 5ys” written by osar
tea+” (Wiley & 5ons, Nely Y
Ork, 1965) and Kenichi, Inui, “Photosensitive Polymers”
(Kodansha, 1977).

In addition, positive-positive type products include: ■ a compound that can generate an acid when irradiated with actinic rays, ■ a compound that has at least one bond that can be decomposed by an acid, and ■ a novolak resin that contains two or three different types of phenols. A photosensitive composition can also be used.

In the present invention, the content of the photoreceptor in the colored photosensitive layer is preferably 5 to 80% by weight, for example.

Next, the binder contained in the colored photosensitive layer of the image forming material of the present invention will be described.

The binder contained in the colored photosensitive layer can be any binder as long as it can function as a binder, such as a polymer compound that is film-forming and solvent-soluble, and preferably dissolves or swells in an alkaline developer. can be used.

Specific examples of such polymer compounds include the following -
A polymer compound containing a structural unit having an aromatic hydroxyl group represented by the pattern hole (1) in its molecular structure can be mentioned.

General Formula (I) In General Formula (1), RI I and R" each independently represent a hydrogen atom, an alkyl group, or a carboxylic acid group.R"
represents a hydrogen atom, a halogen atom or an alkyl group, and RI4 represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. X represents a divalent organic group that connects to a nitrogen atom and an aromatic carbon atom. n is 0 or 1. , Y represents a phenylene group which may have a substituent or a naphthylene group which may have a substituent.

Specifically, examples of the structural unit forming the structural unit represented by the above-mentioned pattern (1) include N-(4-hydroxyphenyl)-(meth)acrylamide, N-(2-hydroxyphenyl) (meth)acrylamide, N-(4-
Hydroxynaphthyl)-(meth)acrylamide, etc.
Examples include monomers of meth)acrylamides; o-, m- or P-hydroxyphenyl (meth)acrylate monomers; o-, m= or P-hydroxystyrene monomers. Preferably o-, m- or p-hydroxyphenyl (meth)acrylate monomers, N-
(4-hydroxyphenyl)=(meth)acrylamide monomer, more preferably N-(4-hydroxyphenyl)-(meth)acrylamide monomer.

In the present invention, it is preferable to use as a binder a copolymer of Chitsumar and the following Chitsumar, etc., which form the structure represented by the general formula (I).

I5 Alkyl acrylates: CH.

IS C-0R'' I] IS 1 In each of the above formulas, R'' represents a hydrogen atom, an alkyl group, or a halogen atom, and RIth represents an alkyl group, a phenyl group, or a naphthyl group.

When using the above copolymer, the ratio of groups having an aromatic hydroxyl group represented by general formula (1) in the copolymer is preferably 1 to 30 mol%.

The proportion of units formed from the acrylonitriles in the copolymer is preferably 0 to 50 mol%, and more preferably 5 to 40 mol% in consideration of developability. The proportion of structural units formed from the alkyl acrylates is preferably 50 to 95 mol% from the viewpoint of developability with a low alkaline aqueous solution, and most preferably 60 to 95 mol%. Give sex.

In addition to the structural units described above, the above-mentioned acrylic acids such as acrylic acid or methacrylic acid may be copolymerized to form structural units in the polymer compound that is the copolymer, for the purpose of finely adjusting the developability.

In this case, the proportion of the copolymer of acrylic acids in the cough polymer compound is 0, considering the development latitude.
-20 mol% is preferred, and 0-10 mol% is most preferred.

The weight average molecular weight of such a polymer compound is preferably from 1,000 to 100,000, more preferably from 1,000 to 100,000, from the viewpoint of developability or resolution when a low alkaline aqueous solution is used as a developer. A range of 30,000 to 30,000 is preferred. These polymer compounds can be synthesized by a well-known copolymerization method.

Specific examples of such polymer compounds include copolymers having the following structure.

CH3 (weight average molecular weight: 1.000-30,000)! :m2n-(1-25)=(5-40):(50-95) Furthermore, in the image forming material of the present invention, as a binder constituting the colored photosensitive layer, a carboxylic acid represented by the following symbol is used. A polymer compound having vinyl ester polymerized units in its molecular structure can also be preferably used.

RCOQC)I = C)12 However, R represents an alkyl group having 1 to 17 carbon atoms.

Any polymeric compound having the above structure can be used, but as the carboxylic acid vinyl ester monomer for constructing the polymerized unit indicated by the above-mentioned symbol, the following examples are preferable. The name and chemical formula are also shown.

■Vinyl acetate CHzCOOCH=CHz■
Vinyl propionate CH3CHtcOOcH= C
Ht■ Vinyl butyrate CH3(Cut)zcO
OcH=cHz■Vinyl pivalate (CHi)*
CC00CH=CHz■Vinyl caproate CH:+(C
Hz)4COOCH=CHz■Vinyl caprylate
CHz (CHz) bcOOcH= CD z■Vinyl caprate CH3 (CHz) 5cOOcH=
CHz■Vinyl laurate Ch (CHz)
r. C00CH=CHz■Vinyl myristate CH
3 (CHz) +1COOCH=CHz■Vinyl palmitate CH3 (CH2) +4COOC)! =CH
z■Vinyl stearate CHx (CHz) I
6COOCH= CHt@vinyl versatate CHi R' CC00CH=CHz 2 (R1 and R2 are alkyl groups, and the sum of their carbon numbers is 7. That is, R' + R'' = CJti) Carboxylic acid vinyl ester monomer More preferably, the carboxylic acid has 1 to 4 carbon atoms in its main chain.In particular,
Vinyl acetate is preferred.

Note that the above R also includes an alkyl group having a substituent, that is, a vinyl ester of a substituted carboxylic acid is also included in the polymerization unit.

The polymer compound may be a polymer obtained by polymerizing one type of carboxylic acid vinyl ester, a polymer obtained by copolymerizing two or more types of carboxylic acid vinyl esters, or a polymer that can be copolymerized with carboxylic acid vinyl ester. It may be a copolymer with monomers in any composition ratio.

Examples of monomer units that can be used in combination with the polymerized units indicated by the above-mentioned holes include ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene, such as styrene, α-methylstyrene, Styrenes such as p-methylstyrene and p-chlorostyrene, acrylic acids such as acrylic acid and methacrylic acid, unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid, and maleic anhydride, such as diethyl maleate, maleic acid, etc. Diesters of unsaturated dicarboxylic acids such as dibutyl acid, di-2-ethylhexyl maleate, diptylated fumarate, di-2-ethylhexyl fumarate, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic dodecyl acid, 2-chloroethyl acrylate,
α-methylene aliphatic monocarboxylic acid esters such as phenyl acrylate, α-methyl chloroacrylate, methyl methacrylate, and ethyl methacrylate; Nitriles such as acrylonitrile and methacrylonitrile; Amides such as acrylamide; e.g. acrylic anilide, p-chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide, etc., e.g. evamethyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether,
Vinyl ethers such as β-chloroethyl vinyl ether, vinyl chloride, vinylidene chloride, vinylidene cyanide, such as 1-methyl-1-methoxyethylene, 1°1-dimethoxyethylene, 1,2-dimethoxyethylene, 1.
1-dimethoxycarbonylethylene, 1-methyl-1-
Ethylene derivatives such as ditroethylene, such as N-vinylpyrrole, N-vinylcarbazole,
There are vinyl monomers such as N-vinyl compounds such as N-vinylindole, N-vinylpyrrolone, and N-vinylpyrrolidone. These vinyl monomers generally exist in a polymer compound with a structure in which unsaturated double bonds are cleaved.

When using the polymer compound represented by the above-mentioned pattern in the present invention, it is particularly preferable to use a polymer compound having a vinyl acetate polymerization unit in its molecular structure.

Among them, those having 40 to 95-t% of vinyl acetate polymerization units and having a number average molecular weight (MN) of 1,000 to 1
00,000, weight average molecular weight (MW) is s, o
oo to 500.000 is preferred.

More preferably, vinyl acetate polymerized units (especially 40
~95-t%) and polymeric compounds having carboxylic acid vinyl ester polymerized units with a longer chain than vinyl acetate are preferred, especially those with a number average molecular weight (MN) of 2.000 to 60.0
00, weight average molecular weight (MW) is 10,000 to 150
,000 is preferred.

In this case, the monomer that copolymerizes with vinyl acetate to form a polymer compound having vinyl acetate polymerized units may be any monomer that can form a copolymer, such as among the monomers listed above. You can arbitrarily choose from.

Copolymers that can be used as polymer compounds in the present invention are listed below by indicating their monomer components. However, it goes without saying that the invention is not limited to the following examples.

■Vinyl acetate-acrylic acid ester ■Vinyl acetate-maleate ester ■Vinyl acetate-ethylene ■Vinyl acetate-vinyl carboxylate ester ■Vinyl acetate-styrene ■Vinyl acetate-crotonic acid ■Vinyl acetate-maleic acid ■Vinyl acetate-2-ethyl Hexyl acrylate ■ Vinyl acetate-2-ethylhexyl maleate [Phase] Vinyl acetate-methyl vinyl ether ■ Vinyl acetate-vinyl chloride ■ Vinyl acetate-N-vinylpyrrolidone ■ Vinyl acetate-vinyl propionate ■ Vinyl acetate-vinyl pivalate ■ Vinyl acetate louversatic Vinyl acetate ■ Vinyl acetate - Vinyl laurate ■ Vinegar/hinyl acid Vinyl stearate ■ Vinyl acetate - Vinyl versatate - Ethylene [Phase] Vinyl acetate Ruber Versatate - Vinyl 2-ethylhexyl acrylate [Phase] Vinyl acetate Louver Vinyl satic acid - Vinyl laurate ■ Vinyl acetate Rubersatic acid Vinyl crotonic acid @ Vinyl propionate Rubersatic acid Vinyl [Phase] Vinyl propionate Rubersatic acid Crotonic acid @ Pivalic acid - Vinyl stearate - Maleic acid Further, in the present invention, a novolak resin can also be used as the binder.

Novolak resins are generally obtained by polycondensation of at least one type of phenol and an active carbonyl compound, and any of these novolak resins can be used.

The above-mentioned phenols include all compounds in which at least one hydrogen atom bonded to an aromatic ring is substituted with a hydroxyl group, and specific examples of such phenols include, for example:
Phenol, 0-cresol, m-cresol, P-cresol, 3,5 xylenol, 2,4-xylenol, 25 xylenol, carvacrol, thymol, catechol, resorcinol, hydroquinone, pyrogallol, phloroglucin, alkyl group (1 carbon atom ~8) W-converted phenol and the like can be mentioned.

The active carbonyl compounds include, for example, aldehydes and ketones, and specific examples include formaldehyde, acetaldehyde, benzaldehyde, acrolein, furfural, and acetone.

Examples of the novolak resin include phenol formaldehyde novolak resin, m-talesol formaldehyde novolak resin, phenol/m-cresol/formaldehyde copolycondensate resin, phenol/p-cresol/formaldehyde copolycondensate resin, m-cresol/p -cresol/formaldehyde copolycondensate resin,
O-cresol/P-cresol/formaldehyde copolycondensate resin, phenol/0-cresol/m-cresol/formaldehyde copolycondensate resin, phenol/0-cresol/p-cresol/formaldehyde copolycondensate resin, phenol・m-cresol, p-cresol, formaldehyde copolycondensate resin, etc. can be mentioned.

A preferred novolac resin is a phenol formaldehyde novolac resin, which has a weight average molecular weight MW of 3500.
~500, and those with a number average molecular weight MN of 1000 to 200 are preferred.

The molecular weight of the polymer compound in this specification, including the molecular weight of the novolak resin, is measured by GPC (gel permeation chromatography). The number average molecular weight MN and weight average molecular weight MW are calculated by smoothing the peaks in the oligomer region by the method described in Morio Seiji, Tatsuya Miyabayashi, and Masayuki Naka, "Journal of the Chemical Society of Japan," pages 800 to 805 (1972). (Connecting the center of the peak and the center of the valley).

In addition, in the novolac resin, pyrolysis gas chromatography (PGC) is used as a method for confirming the quantitative ratio of different phenols used in the synthesis thereof.

The principle of pyrolysis gas chromatography is
If the equipment and experimental conditions are specified, for example, in the Journal of the Chemical Society of Japan,
New Experimental Chemistry Course” Volume 19, Polymer Chemistry (I) 47
The method for qualitative analysis of novolac resins using pyrolysis gas chromatography is described in pages 4 to 485 (published in 1978), etc., and the method for qualitative analysis of novolac resins using pyrolysis gas chromatography is described in "Analytical Chemistry" No. 18 by Morio Seiji, Takashi Naka, and Masayuki Naka. vol., pages 47-52 (1969).

In the present invention, novolank resin (component (b)
)) and a polymer compound (referred to as component (c)) having a carboxylic acid vinyl ester polymerized unit represented by the above general formula in its molecular structure,
It is preferably contained in a weight ratio range of (b)/(c) = 5/95 to 80/20.

This range is preferable in terms of color reproducibility, thermal deformation (dimensional deviation), and color fastness. Component (b) (c
A particularly preferred ratio of ) is (b)/(c) = by weight
It is in the range of 10/90 to 60/40.

Further, in the present invention, other polymeric compounds that can be used as a binder for the colored photosensitive layer include (meth)
Sulfoalkyl esters of acrylic acid (co)polymers, vinyl acetal (co)polymers, vinyl ether (co)polymers, acrylamide (co)polymers, styrene (co)polymers, cellulose derivatives, etc. may also be mentioned. .

The thickness of the colored photosensitive layer in the image forming material of the present invention can be appropriately determined depending on the target optical density, the type and content of the colorant used in the colored photosensitive layer, and the like. Within the allowable range, the thinner the colored photosensitive layer is, the higher the resolution and the better the image quality. Therefore,
The film thickness is preferably used in the range of 0.1 g/rrf to 5 g/nf.

In the method for producing an image forming material of the present invention, the colored photosensitive layer can generally be formed by coating a colored photosensitive layer coating solution containing a photoreceptor, a binder, and a pigment on a support.

Here, an organic solvent can be used as a solvent to constitute the coating liquid. In carrying out the present invention, any organic solvent can be used as the colored photosensitive layer coating solution, and for example, all of the various known organic solvents can be used.

Examples of organic solvents that can be used include hydrocarbons such as n-hexane, cyclohexane, n-pentane, benzene, toluene, and xylene, methyl alcohol,
Alcohols such as ethyl alcohol, isopropyl alcohol, n-propyl alcohol, t-butyl alcohol, 5ec-butyl alcohol, isobutyl alcohol, n-butyl alcohol, l-pentanol, 2-pentanol, 1-hexanol, acetone, cyclohexanone, Ketones such as methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-〇-butyl ketone, methyl isobutyl ketone, diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, and other methyl lactate, ethyl lactate, Esters such as methyl propionate, methyl butyrate, and ethyl acetate, nitriles such as acetonitrile and propionitrile, and other nitrites such as 1,4-dioxane, dimethylformamide, dimethyl sulfoxide, and methylene chloride, chloroform, and carbon tetrachloride. I can do it. Among these, aromatic hydrocarbons such as benzene, toluene, and xylene, ketones, and esters are preferably used, and particularly preferred are cyclohexanone, toluene, and methyl lactate.

When carrying out the present invention, plasticity and coating properties improvers and the like may be added to the colored photosensitive layer, if necessary.

As plasticizers, various low-molecular compounds such as phthalate esters, triphenyl phosphates, and maleate esters are used, and as agents for improving coating properties, surfactants such as fluorine surfactants, ethyl cellulose polyalkylene ether, etc. are used. Examples include nonionic surfactants.

When constituting the image forming material of the present invention, the colored photosensitive layer can be divided into two layers: a colored layer made of a colored layer and a binder, and a photosensitive layer made of a photosensitive composition. In this case, it does not matter which layer is placed on the support side.

The colored imaging materials of the present invention can be embodied as color proofs.

In this case, the colored photosensitive layer of the colored image-forming material is removed in an imagewise manner by development following imagewise exposure to form a colored image.

Although any support can be used to constitute the image forming material of the present invention, a transparent support is preferably used. As the transparent support, a polyester film, particularly a biaxially oriented polyethylene terephthalate film, is preferred in terms of dimensional stability against water and heat. In addition, acetate film, polyvinyl chloride film, polyethylene film, polypropylene film, polyethylene film, etc. may also be used.

The image forming material can be used to transfer an image to a transfer material.

In the present invention, at least one intermediate layer is formed between the support and the colored photosensitive layer. In order to facilitate the peeling of the body, intermediates such as a release layer (including those whose surface has been subjected to release treatment) between the support and the colored photosensitive layer, or a heat-softening layer are used as intermediates. Provide layers.

The release layer is made of, for example, silicone resin, fluororesin, polyethylene, polypropylene ethylene-α-olefin copolymer, propylene-α-olefin copolymer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene. -Acrylic acid copolymer, ethylene-
It can be formed from polyamide resins such as vinyl acetate copolymers, ionomer resins, waxes, nylons, and copolymerized nylons.

Furthermore, silicone resin or fluororesin may be added to melamine resin or polyacrylate urethane resin.

In addition, polypropylene film, polyethylene film, etc. exhibit good mold release properties without special mold release treatment, so in a preferred embodiment, the film is thinner than the thickness of the support.
A polypropylene layer or a polyethylene layer can be provided as a release layer.

The method for forming a polypropylene layer or polyethylene layer on a support is as follows: (1) A solution of polyvinyl acetate, polyvinyl chloride, epoxy resin, polyurethane resin, natural rubber, synthetic rubber, etc. dissolved in an organic solvent is used as an adhesive. These adhesives are applied to a support, dried by hot air or heating, and then a polypropylene film or a polyethylene film is layered and laminated by pressing under heat.
So-called dry lamination method; (2) Using a copolymer of ethylene and vinyl acetate, a copolymer of ethylene and acrylic ester, polyamide resin, petroleum resin, rosin, wax, or a mixture thereof as an adhesive, these adhesives After applying the material onto a support by a doctor blade method, roll coating method, gravure method, reverse roll method, etc. while keeping it in a molten state by heating it as it is,
The so-called hot-melt lamination method, in which polypropylene or polyethylene films are immediately laminated together and laminated by heating at a high temperature if necessary and then cooling; (3) The polypropylene or polyethylene is kept in a molten state and then extruded. This is the so-called extrusion lamination method, in which the film is extruded into a film, and while it is still in a molten state, a support is bonded and laminated; Examples include a so-called coextrusion method in which a polypropylene layer or a polyethylene layer is formed on a support film by multiple moldings using polypropylene or polyethylene in a molten state.

The thickness of the release layer is suitably in the range of 0.01 to 301 Jm, particularly preferably in the range of 0.1 to 5 μm.

Next, the thermally softened layer will be described.

The thermosoftening layer has a property of softening at the temperature during thermal transfer, and can be formed from a thermoplastic resin. The thermoplastic resin preferably has a softening point of 30"C to 150C. The softening point temperature referred to here is VIC
This is the AT softening point or the value shown by the ring and ball method. In the present invention, specifically, the following resins can be mentioned as preferred resins.

Polyolefins such as polyethylene and polypropylene.

Ethylene copolymers such as ethylene and vinyl acetate, ethylene and acrylic ester, and ethylene and acrylic acid.

PVC.

Vinyl chloride copolymers such as vinyl chloride and vinyl acetate.

Polyvinylidene chloride.

Vinylidene chloride copolymer.

polystyrene.

Styrene copolymers such as styrene and maleic anhydride.

Polyacrylic acid ester.

Polyester resin.

Polyurethane resin.

Acrylic ester copolymers such as acrylic ester and vinyl acetate.

Polymethacrylic acid ester.

Methacrylate ester copolymers such as methyl methacrylate and vinyl acetate, and methyl methacrylate and acrylic acid.

Polyvinyl acetate.

Vinyl acetate copolymer.

Vinyl butyral resin.

Polyamide resins such as nylon, copolymerized nylon, and N-alkoxymethylated nylon.

synthetic rubber.

Petroleum resin.

Chlorinated rubber.

Polyethylene glycol.

Polyvinyl alcohol hydrozine phthalate.

cellulose derivative, cellulose acetate phthalate,
Cellulose acetate succinate.

Schlatsk.

wax.

The heat-softening layer can be provided on the support using a known method.

The thickness of the thermally softened layer is suitably in the range of 1 to 50 pm, particularly preferably in the range of 5 to 30 pm.

The release layer can be provided on the heat-softening layer by applying a solution or emulsion of the release layer resin dissolved in an organic solvent onto the heat-softening layer, or by applying a polypropylene film or a polyethylene film. Examples include a method of laminating on a heat softening layer.

In the present invention, at least the surface of the intermediate layer, particularly the heat-softening layer that contacts the colored photosensitive layer, is treated with a silane coupling agent and/or a titanate coupling agent.

In the present invention, various known silane coupling agents can be used, and specifically, T S
L8308 (vinyltrichlorosilane), T S
L8311 (vinyltriethoxysilane), TSL8
320 (γ-chloropropyltrimethoxysilane)T
SL8395 (T-chloropropylmethyldichlorosilane), TS L8325 CT-chloropropylmethyldimethoxysilane), TS L8326
CT-chloropropylmethyljethoxysilane), T
SL8331 (T-aminopropyltriethoxysilane), TS L8340 (N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane), T
SL8345 (N-(β-aminoethyl)-T-aminopropylmethyldimethoxysilane), TS L83
80 CT-mercaptopropyltrimethoxysilane), TSL8350 (r-glycidoxypropyltrimethoxysilane), TS L8355 (r-glycidoxypropylmethyldimethoxysilane), TS L8
370 CT-methacryloxypropyltrimethoxysilane), TSL8375 (γ-methacryloxypropylmethyldimethoxysilane, manufactured by Toshiba Silicon Corporation), and the like.

In the present invention, the titanate coupling agent includes:
Various known ones can be used, specifically, A
-1 (tetra-1-propoxytitanium), B-1 (tetra-n-butoxytitanium), TOT (tetrakis(2)
-ethylhexyloxy)titanium), TST (tetrastearyloxytitanium), TAA (di-propoxybis(acetylacetonato)titanium), TAT (di-n
-butoxybis(triethanolaminato)titanium),
TLA (dihydroxybis(lactato)titanium), T
OG (titanium-1-propoxyoctylene glycolate), TTS (titanium stearate, manufactured by Nippon Soda Co., Ltd.), El-105 (alkyl titanate type, manufactured by Toyo Morton Co., Ltd.), KRTTS (isoprobyl triisostearoyl titanate 1) -), KR38S (isopro and lutris(dioctylpyrophosphate) titanate), KR44 (isopropyltri(N-aminoethyl-
(aminoethyl) titanate), KR46B (tetraoctylbis(ditridecylphosphite) titanate)
, KR55 (tetra(2,2-diallyloxymethyl-
1-butyl)bis(ditridecyl)phosphite titanate), KR138S (bis(dioctylpyrophosphate)oxyacetate titanate), KR2
38S (bis(dioctylpyrophosphate) ethylene natanate), KR2S (isopropyltrioctanoyl titanate), KR7 (isopropyl dimethacrylylisostearoyl titanate), KR9S (isopropyl tridodecylbenzenesulfonyl titanate),
KRII (isopropyl isostearoyl diacryl titanate), KR12 (isopropyl tri(dioctyl phosphate) titanate), KR34S (isopropyl tricumylphenyl titanate), KR41B (tetraisopropyl bis(dioctyl phosphite) titanate, manufactured by Ajinomoto Co., Ltd.), etc. are used. be able to.

In particular, A-1 and B-1 can be preferably used.

The coupling agent can be treated by dissolving it in an organic solvent to form a dilute solution (for example, a dilute solution of about 1% by weight) and applying this to the surface to be treated, such as the middle of the layer to be treated.

Here, as the solvent for dissolving the coupling agent, any solvent can be used as long as it dissolves the coupling agent used, and various solvents can be used, but organic solvents that can be used For example,
Hydrocarbons such as n-hexane, cyclohexane, n-pentane, benzene, toluene, xylene, methyl alcohol, ethyl alcohol, isopropyl alcohol, n
Propyl alcohol, t-butyl alcohol, 5ec-
7” Hyl alcohol, isobutyl alcohol, n-butyl alcohol, 1-pentanol, 2-pentanol,
Alcohols such as 1-hexanol, ketones such as acetone, cyclohexane, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether Diethylene glycols such as, others 1.
Examples include 4-dioxane, dimethylformamide, dimethyl sulfoxide, methylene chloride, chloroform, and carbon tetrachloride. Preferably used among these are aromatic hydrocarbons and ketones such as benzene, toluene, and xylene, and alcohols such as n-butanol, and particularly preferably cyclohexanone, toluene, and n-butanol. .

The image forming material of the present invention is exposed and developed to form an image area, and at least the formed image area is transferred to a transfer material to obtain a transferred image.

For example, when the method is implemented as a multicolor image forming method, the basic method can be broadly divided into the following methods (1) and (II).

(1) Lay the first colored image-forming material having a colored image-forming layer for the first color on the support onto the transfer material, transfer at least the colored image-forming layer to the transfer material, and peel off the support. do. Next, image exposure is performed through a first color film original corresponding to the first color, and then development processing is performed to form a colored image of the first color on the transfer material.

Next, at least a colored image forming layer of a second colored image forming material having a colored image forming layer of a second color different in tone from the first color is transferred onto the first colored colored image layer on the transfer material. Then, an alignment image of the second color film original corresponding to the second color (generally called a registration mark image is used)
is registered with the first color registration mark image, image exposure is performed through the second color film original, followed by development processing to obtain a two color matched image on the transferred material. Thereafter, similar processing is performed for the third and fourth colors to obtain a multicolor image.

This method is known from Japanese Patent Publication No. 47-27441, Japanese Patent Publication No. 56-501217, etc.

(11) A first color colored image is formed on a first color colored image forming material, at least the colored image is transferred to a transfer material, and the support is peeled off. In addition, a second colored image forming material is added to the second colored image forming material.
After forming a colored image, a second image formed along with this is formed.
While registering the color registration mark image with the first color registration mark image on the transfer material, the second color colored image is transferred onto the first color colored image, and the support is peeled off to align the two colors. get the image. Similarly, colored images of the third color and the fourth color are also transferred onto the transfer material to obtain a multicolor image. In some cases, this multicolor image may be indirectly transferred onto another transfer material to obtain a multicolor image.

This type of method is disclosed in Japanese Patent Application Laid-open Nos. 47-41830, 59-97140, 60-23649 and US Pat. No. 3,775,113.

Imaging materials are typically exposed imagewise through a color separation mask or the like and then developed to form an image.

At this time, an embodiment may be adopted in which only the image portion from the image obtained on the support is directly transferred and laminated onto the transfer material. That is, in one preferred embodiment, only the colored image layer that substantially forms the image is transferred and laminated.

In this case, in order to efficiently transfer the image onto the transfer surface and to facilitate peeling off the support after image transfer, the surface of the support may be subjected to a release treatment using an appropriate oil-repellent substance as described above. ,
Alternatively, it is preferable to provide a release layer on the support.

The image forming material of the present invention can be exposed to appropriate light depending on the colored photosensitive layer, particularly depending on the photoreceptor, and then developed to obtain an image. Any developer can be used as long as it has a developing action to develop the material to be processed. Preferably, a developer containing an alkaline agent and an anionic surfactant is used.

Usable alkaline agents include (1) sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, and lithium hydroxide.

Sodium or ammonium salts of secondary or tertiary phosphates, sodium metasilicate, sodium carbonate.

Inorganic alkaline agents such as ammonia, (2) Mono-, di-, or trimethylamine, mono-, di-,
or triethylamine, mono- or di-isopropylamine, n-butylamine, mono-, di- or triethanolamine, mono-, di- or triisopropylamine, ethyleneimine.

Examples include organic amine compounds such as ethylenediimine.

In addition, as anionic surfactants that can be used, (1)
Higher alcohol sulfate esters (e.g., sodium salt of lauryl alcohol sulfate, ammonium salt of octyl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, sulfuric acid alkyl sulfate, etc.), (2) Salts of aliphatic alcohol phosphate esters (e.g.,
(3) Alkylaryl sulfonate salts (eg, sodium dodecylbenzenesulfonate, sodium isopropylnaphthalenesulfonate, etc.).

dinaphthalenesulfonic acid sodium salt, metanitrobenzenesulfonic acid sodium salt, etc.) (4) Alkylamide sulfonates (5) Sulfonic acid salts of dibasic aliphatic esters (e.g. sodium sulfosuccinate dioctyl ester, sodium sulfosuccinate dihexyl ester, etc.) ) (6) Formaldehyde condensates of alkylnaphthalene sulfonates (for example, formaldehyde condensates of sodium dibutylnaphthalene sulfonate, etc.).

Alkaline agents and anionic surfactants are optional. Can be used in combination with

[Example] Examples of the present invention and comparative examples will be described below.

It should be noted that, as a matter of course, the present invention is not limited only to the embodiments described below, but can take various forms.

Example 1 In order to obtain the image forming material of the present invention, a titanate coupling agent, tetra-i-propoxytitanium (trade name: A -1, manufactured by Nippon Soda Co., Ltd.) in n-butanol was prepared. Further, for color image formation, four colored photosensitive layer dispersions were prepared according to the following formulations.

Color sensation Cyan 1.2-naphthoquinone diazide-4 sulfonic acid-p-cresol formalin ester polymer 2.37g Vinyl acetate-vinyl versatate (80720 parts by weight) copolymer (49.7% methanol solution) Cyanine Blue 4920 (Manufactured by Dainichiseika Chemical) Cyclohexanone 15.36 g 1.10 g 71.47 g Mine) 1.2-naphthoquinonediazide-4-sulfonic acid-p-cresol formalin ester polymer Vinyl acetate-Vinyl versatate (80: 20 weight) Part) Copolymer (49.7% methanol solution) Seika First Carmine 1483 (manufactured by Dainichiseika) Cyclohexanone color Yellow 1.2-naphthoquinonediazide-4-sulfonic acid-P-cresol formalin ester polymer Vinyl acetate-versatic acid Vinyl (80: 20 parts by weight) copolymer 2.37g 15.36g 1.10g 71.47g 2.37g (49.7% methanol solution) 15.3
6 g Seika First Yellow H-7055 (manufactured by Dainichiseika) 1.10 g Cyclohexanone 71.47 g
Black 1.2-naphthoquinonediazide-4-sulfonic acid-p-cresol formalin ester polymer 2.19g Vinyl acetate-vinyl versatate (80: 20 parts by weight) copolymer (49.7% methanol solution) 14.2
1 g Carbon black M A-100 (manufactured by Mitsubishi Kasei) 1.85 g Cyclohexanone 72.05 g In addition, the support shown below was separately prepared.

That is, ethylene-vinyl acetate copolymer (trade name: Evaflex,
(manufactured by DuPont Mitsui Chemical Co., Ltd.) was coated to a thickness of 30 um by an extrusion lamination method, thereby creating a support having a heat-softening layer.

On the support having the heat-softened layer obtained in this way,
It was treated by applying the titanate coupling agent coating solution obtained earlier. Further, the colored photosensitive layer dispersions of the four colors described above were applied to this to a dry film thickness of 1 μm, and then dried.

In this way, colored image forming materials of four colors were created.

Color separation mesh positive films of each color were superimposed on the polyethylene terephthalate film surface of the four-color colored image forming material obtained above, image exposure was performed for 20 seconds from a distance of 50 cm using a 4 kW metal halide lamp, and the following developer was added to Development was performed by dipping for a second to form a four-color colored image.

<Developer> NazCOa 15
g Surfactant (Perex NBL manufactured by Kao Atlas Co., Ltd.) 50 g Distilled water 1000 g Next, the image surface of the yellow image was brought into close contact with the art paper, and the paper was heated at 5 kg/c1il between a pair of nip rolls heated to 80°C. After passing at a speed of 50 cm/min under pressure conditions,
The support was peeled off. Peeling was easy and only the yellow image area was transferred onto the art paper.

Subsequently, colored images were transferred in the order of magenta, cyan, and black, thereby obtaining a color proofing image consisting of four colors on art paper.

The color proofing image obtained in this example is
It was possible to obtain a transferred image with little color cast (background stain) in non-image areas, and the transferred image was extremely close to the actual printed matter.

Example 2 Tetra-n-butoxytitanium (titanium coupling agent solution) was used as a coating solution for treating the intermediate layer of the support.
A 1% by weight n-butanol solution of the product (trade name: B-1, manufactured by Nippon Soda Co., Ltd.) was prepared. In the same manner as in Example 1, a support with a heat-softening layer was treated with this coating solution to coat a colored photosensitive layer, and then exposure, development, and transfer were performed to obtain a color proofing image consisting of four colors. .

The color proofing image obtained in this example is
It was possible to obtain a transferred image with no background smear and excellent image quality, and it was also very similar to the actual printed matter.

Example 3 TSL8311 containing vinyltriethoxysilane, which is a silane coupling agent solution, was used as a coating solution for the intermediate layer treatment of the support, and the rest was as in Example 2.
It was carried out in the same way. As a result, the same effects as in Example 2 were obtained.

Comparative example A colored photosensitive layer dispersion having the following composition was prepared.

Color Cyan 1.2-naphthoquinone diazide-4 sulfonic acid-p-cresol formalin ester polymer 2.37 g Vinyl acetate-vinyl versatate (80: 20 parts by weight) copolymer (49.7% methanol solution) Cyanine blue 4920 (manufactured by Dainichiseika) Cyclohexanone feeling ゝ ゛ (magenta) 1.2-naphthoquinone diazide-4 = sulfonic acid-p-cresol formalin ester polymer Vinyl acetate-vinyl versatate (80720 parts by weight) copolymer (49, 7% methanol solution) Seiki First Carmine 1483 (manufactured by Dainichiseika) Cyclohexanone color Yellow 1.2-naphthoquinonediazide-4 Sulfonic acid-p-cresol formalin ester polymer Vinyl acetate-versatate (80: 20 parts by weight) Copolymer 15.36 g 1.1 g 71.47 g 2.37 g 15.36 g 1.1 g 71.47 g 2.37 g (49.7% methanol solution) 15.3
6g Seiryoku Fast Yellow H-7055 (manufactured by Dainichiseika) 1.1g
Cyclohexanone 71.47 g
1.2-naphthoquinonediazide-4-sulfonic acid-p-cresol formalin ester polymer 2.19 g Vinyl acetate-vinyl versatate (80: 20 parts by weight) copolymer (49.7% methanol solution) ) 14.2
1 g Carbon black MA-100 (manufactured by Mitsubishi Kasei) 1.85 g
Cyclohexanone 72.05g The colored photosensitive layer dispersion obtained here was coated onto the support having the heat-softening layer used in Example 1.2 so that the dry film thickness was 1 μm, and then dried. , four colored image forming materials were prepared.

Example 2 The four colored image forming materials obtained as above were used.
Exposure and development was carried out in the same manner as above, and this was transferred onto art paper to obtain a color proofing image consisting of four colors on art paper.

The color proofing image obtained by this method had background stains in non-image areas and was inferior in color image quality.

〔Effect of the invention〕

As described above, the image forming material of the present invention has the effect that even when an intermediate layer such as a heat softening layer is provided, it is possible to obtain a good image without background smudge. The method for producing an imaging material of the present invention is capable of providing such an advantageous imaging material.

Claims (1)

[Scope of Claims] 1. A colored photosensitive layer is provided on a support, and the colored photosensitive layer contains a photoreceptor, a binder, and a pigment, and the image obtained by image exposure and development is used as an image. In a colored image-forming material that is transferred to an image-receiving layer to obtain an image, at least one heat-softening layer and/or release layer is formed between the support and the colored photosensitive layer, and the heat-softening An image forming material characterized in that at least the surface of the layer and/or the release layer in contact with the colored photosensitive layer is treated with a silane coupling agent and/or a titanate coupling agent. 2. A method for producing a colored image forming material in which a colored photosensitive layer coating liquid is applied onto a support to form a colored photosensitive layer, the colored photosensitive layer coating liquid containing a photoreceptor, a binder, and a pigment; and at least one intermediate layer is formed between the support and the colored photosensitive layer using an intermediate layer coating solution, and furthermore, at least the surface of the intermediate layer in contact with the colored photosensitive layer is coated with a silane coupling agent and/or a titanate. 1. A method for producing an image forming material, the method comprising performing treatment with a coupling agent.