JPH0789254A - Colored image forming material - Google Patents

Abstract

PURPOSE:To provide a colored image forming material which inhibits the generation of a flaw in a transferred image due to the breakdown of a cushion layer and provides colorproof similar to a printed matter. CONSTITUTION:This colored image forming material consists of a cushion layer formed on a support or at the top, and further, at least, one coloring photosensitive layer containing a photosensitive composition and a coloring agent on the cushion layer and a protecting layer formed on the coloring photosensitive layer. A colored image is formed by an image pattern exposure and an image development process, then the colored image is transferred to a transfer medium with a non-image portion exposed to obtain a transferred image. (1) the protecting layer has a solid particle averaging 10mum or less in grain diameter, (2) the solid particle averaging 10mum or less in grain diameter is provided directly on a surface having the protecting layer of the support and on its opposite surface, or a back layer having the solid particle averaging 10mum or less in grain diameter is provided on the surfaces.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored image forming material suitable for producing a color proof or the like for color proofing in color printing, and particularly to a color proof or the like in which a transfer image has no image defect. And a colored image forming material capable of obtaining

[0002]

BACKGROUND OF THE INVENTION It is well known in the art that color sheets (also called color proofs) for color proofing are used to save the labor and time required for proof printing as a pre-step of main printing in multi-color printing. . As a method for producing a multicolor transfer image using a color sheet for color proofing, for example, a direct transfer method described in JP-A-47-41830, in which a colored image is directly transferred and laminated on a final image receiving paper,
The indirect transfer method described in JP-A-59-97140 and JP-A-61-189535, in which a colored image is temporarily transferred onto a temporary (image-receiving) sheet, and JP-A-56-50127.
The method of repeating the step of forming an image after transferring the colored photosensitive layer to the image receiving paper described in JP-A No. 2003-242242 can be mentioned.

In all of these methods, the surface of the material to be transferred on which an image is formed is covered with an organic polymer layer, so that the glossiness of the obtained image surface is too high, which is different from the image quality at the time of actual printing. It had a problem of giving an impression. Particularly, in the technique of JP-A-61-189535, there is a problem that the original gloss and texture cannot be obtained because the non-image area is covered with the organic polymer layer (polymer layer).

In order to solve this problem, therefore, an image-only transfer system has been considered in which only a colored image is transferred and laminated on a material to be transferred to form a multicolor image (JP-A-3-4824).
No. 8). In this method, since the material to be transferred is not covered with the organic polymer layer, it is possible in principle to obtain an image that is extremely close to the image quality at the time of actual printing.

[0005]

However, the colored image-forming material used in the transfer method for transferring only the image portion is
Since only the image is transferred from the cushion layer to the material to be transferred during the heat lamination process, the adhesiveness between the colored photosensitive layer and the cushion layer is lowered (the releasability is increased), and the colored photosensitive layer is provided with adhesiveness or thermal adhesiveness. T of the photosensitive layer to have
It is necessary to lower g. Therefore, it is preferable to apply a colored photosensitive layer on the cushion layer and provide a protective layer after drying. When the colored image-forming material having this protective layer is laminated with a sheet, the back surface (PET surface) and the protective layer are stacked, and even if there is a protective layer, blocking occurs in the storage state over time due to the influence of the colored photosensitive layer having a low Tg. Occurs.

In this respect, in JP-A-3-289660, a surface having a colored photosensitive layer containing an o-quinonediazide compound on a support and having no colored photosensitive layer (back surface) of the support There has been proposed a technique for fixing 300 or more solid particles / cm ² .

Therefore, as a coloring image forming material used in a transfer method for transferring only this image portion, the above-mentioned Japanese Patent Laid-Open No. 3-2 is used.
It was found that the following problems occur when the technique described in No. 89660 is applied. That is, when a large number of colored image-forming materials having solid particles fixed on the back surface side are stacked and placed,
The solid particles may reach the cushion layer through the colored photosensitive layer and destroy the cushion layer. Even if a colored image forming material in which the cushion layer is partially destroyed is exposed to light and developed to obtain a transferred image on the transferred material, an image defect of the transferred image will occur.

The above-mentioned destruction of the cushion layer may occur during vacuum contact when the color separation negative films of the respective colors of the original image are overlapped and exposed. It was also found that this occurs when the solid particles are fixed or contained in the protective layer, not on the back surface side.

It is an object of the present invention to solve the above problems and to provide a colored image-forming material capable of obtaining a color proof similar to a printed matter by suppressing the image loss of the transferred image due to the destruction of the cushion layer. And

[0010]

In order to achieve the above-mentioned object, the present invention 1 has a coloring material which has a cushion layer on or on a support, and which contains a photosensitive composition and a colorant on the cushion layer. An image-forming material having at least one photosensitive layer and a protective layer on the colored photosensitive layer, wherein after the colored image is formed by imagewise exposure and development treatment, the colored image is not transferred to the transfer material. A colored image-forming material, wherein the protective layer contains solid particles having an average particle size of 10 μm or less; An image forming material having a cushion layer on or above, at least one colored photosensitive layer containing a photosensitive composition and a colorant on the cushion layer, and a protective layer on the colored photosensitive layer. The statue In a colored image forming material, which forms a transferred image by forming a colored image by exposure and development and then exposing the non-image portion to a material to be transferred, and a surface having a protective layer of the support. A colored image-forming material, characterized in that a back layer having solid particles having an average particle size of 10 μm or less or having a solid particle having an average particle size of 10 μm or less is provided on the opposite surface.

[0011]

DETAILED DESCRIPTION OF THE INVENTION A preferred embodiment of the present invention is Invention 1; in an image forming material used for image-only transfer, the image forming material comprises a cushion layer, a colored photosensitive layer and a protective layer on a support. A colored image-forming material having in order and solid particles having an average particle diameter of 10 μm or less in the protective layer, the present invention 2; the image-forming material used for transferring only an image, wherein the image-forming material is on one surface of a support. An image forming material having a cushion layer, a colored photosensitive layer, and a protective layer in this order, and a back layer having solid particles having an average particle size of 10 μm or less on the other surface of the support, which is a transparent support; PET, polypropylene film 10-1
Of about 00Myuemu, cushioning layer: ethylene - vinyl acetate copolymer, those ionomer resins 5 to 50 [mu] m, the colored light-sensitive layer; o-quinonediazide and a coloring agent 0.1g ^{/ m 2} ~5g ^/ m 2 of the film Thick, protective layer; water-soluble polymer (PVA, cellulose, etc.) 0.0
1 to 3 μm, and as a specific example, a cushion layer made of ethylene-vinyl acetate resin having a thickness of 30 μm is formed on 75 μm PET, and a colored photosensitive layer (o-quinonediazide + novolak resin) is formed on the cushion layer. , Acrylic resin or vinyl acetate resin), and further, a protective layer [water-soluble polymer (cellulose, polyacrylic acid, modified vinyl acetate resin)] is formed thereon. And the protective layer of the present invention 1 contains a matting agent; solid particles of silicon dioxide (including colloidal silica), aluminum oxide, aluminum silicate, titanium dioxide, calcium carbonate and the like. Then, the present invention 2 has a back layer containing the solid particles on a support opposite to the protective layer.

In the present invention, various kinds of photosensitive compositions can be used as the photosensitive composition contained in the colored photosensitive layer. However, when exposed to actinic rays, the molecular structure of the photosensitive composition is chemically changed in a short time. The compounds include all compounds such as monomers, prepolymers or polymers whose solubility in a solvent is changed and, when a certain kind of solvent is applied, the exposed portion or the unexposed portion is dissolved and removed. Examples of usable photosensitive compositions include a so-called negative / positive type in which the solubility in exposed areas is lowered, and a photocrosslinking type photosensitive agent represented by a polyvinyl alcohol esterified with cinnamic acid. Resin systems; systems in which a diazonium salt or its condensate is condensed with polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, etc .; and systems in which an aromatic azide compound is used as a photocrosslinking agent and combined with a binder such as solidified rubber. A photosensitive resin utilizing radical polymerization or photoionic polymerization can also be used. Further, as a so-called positive / positive type in which the solubility of the exposed portion is increased, for example, a photosensitive resin composition containing o-quinonediazide as a photosensitive substance can be mentioned.

The present invention will be described in more detail below. As the photosensitive composition used in the colored photosensitive layer of the present invention, known positive-type photosensitive compositions / negative-type photosensitive compositions can be used, but as the positive-type photosensitive composition, o- It is preferable to use a photosensitive composition containing a quinonediazide compound. Any o-quinonediazide compound can be used as long as it can function as a photosensitizer. Specifically, for example, 1,2-benzoquinonediazide-4-
Sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphthoquinonediazide-6-sulfonyl chloride and a hydroxyl group and / or an amino group-containing compound are condensed. The compound is preferably used.

Examples of the hydroxyl group-containing compound include trihydroxybenzophenone, dihydroxyanthraquinone, bisphenol A, phenol novolac resin, resorcin benzaldehyde condensation resin and pyrogallol acetone condensation resin. Examples of the amino group-containing compound include aniline, p-aminodiphenylamine,
There are p-aminobenzophenone, 4,4'-diaminodiphenylamine, 4,4'-diaminobenzophenone and the like.

With respect to the quinonediazide compounds, including those mentioned herein, further reference is made to J. Koza (J. Kosa
r) "Light Sensitive System" (Light
Sensitive System (New York City, John Wiley and Sons, 1965), and Nagamatsu and Inui, "Photosensitive Polymer" (Kodansha, 1
1977).

As the negative photosensitive composition, a photopolymerizable photosensitive composition is preferable. Specifically, for example, a generally used photopolymerizable compound can be arbitrarily used. For example, at least one compound arbitrarily selected from the compound group consisting of acrylic acid, methacrylic acid, acrylic acid ester and methacrylic acid ester can be used. For example, ethylene glycol diacrylate, glycerin triacrylate, polyacrylate, ethylene glycol dimethacrylate, 1,3-
Propanediol dimethacrylate, 1,2,4-butanetriol trimethacrylate, polyethylene glycol dimethacrylate, trimethylolethane triacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate Examples include, but are not limited to, acrylate, pentaerythritol tetraacrylate, dipentaerythritol polyacrylate, 1,3-propanediol diacrylate, 1,5-pentanediol dimethacrylate, polyethylene glycol bisacrylate or bismethacrylate. Not something.

The negative photosensitive layer can contain a photopolymerization initiator. In this case, the photopolymerization initiator is optional, but a photopolymerization initiator having less absorption in the visible region is more preferable, and examples of such a photopolymerization initiator include the following compounds. However, it is not limited to these. That is,
Benzophenone, Michler's ketone [4 ', 4'-bis (dimethylamino) benzophenone], 4,4'-bis (diethylamino) benzophenone, 4-methoxy-
Aromatic ketones such as 4'-dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthraquinone, and other aromatic ketones, benzoin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether. , Methylbenzoin, ethylbenzoin and other benzoins, and 2- (o-chlorophenyl)-
4,5-Diphenylimidazole double body, 2- (o-chlorophenyl) -4,5- (m-methoxyphenyl) imidazole double body, 2- (o-fluorophenyl)-
4,5-diphenylimidazole double body, 2- (o-methoxyphenyl) -4,5-diphenylimidazole double body, 2- (p-methoxyphenyl) -4,5-diphenylimidazole double body, 2,4-di (P-Methoxyphenyl) -5-phenylimidazole double body, 2-
(2,4-Dimethoxyphenyl) -4,5-diphenylimidazole duplex, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazole duplex, and U.S. Pat. No. 3,479,185, British Patent 1 , 047,
Mention may be made of 2,4,5-triacryluimidizole duplexes such as the similar duplexes described in US Pat. No. 569 and US Pat. No. 3,784,557.

Other photopolymerizable compounds include 2,4-
Thioxanthones such as diethylthioxanthone can also be used. In this case, known compounds such as p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, N-methyldiethanolamine, and bisdiethylaminobenzophenone can be used as the photopolymerization accelerator.

Next, the photosensitive composition of the present invention may contain a known polymer compound and synthetic resin, and particularly, a high-molecular weight compound having a carboxylic acid vinyl ester polymerization unit represented by the following general formula in its molecular structure. It preferably contains a molecular compound.

[0020]

[Chemical 1]

However, R represents an alkyl group, and also includes an alkyl group having a substituent. Any polymer compound having the above structure can be arbitrarily used, but the following examples are preferable as the carboxylic acid vinyl ester monomer for forming the polymerized unit represented by the above general formula. The name and chemical formula are shown together.

1 vinyl acetate CH ₃ COOCH = CH ₂ 2 vinyl propionate CH ₃ CH ₃ COOCH = C
H ₂ 3 vinyl butyrate CH ₃ (CH ₂ ) ₂ COOCH = CH ₂ 4 vinyl pivalate (CH ₃ ) ₃ COOCH = CH
₂ 5 vinyl caproate CH ₃ (CH _{2) 4} COOCH
= CH ₂ 6 vinyl caprylate CH ₃ (CH ₂ ) ₆ COOCH
= CH ₂ 7 vinyl caprate CH ₃ (CH ₂ ) ₈ COOCH
= CH ₂ 8 vinyl laurate CH ₃ (CH ₂ ) ₁₀ COOCH
= CH ₂ 9 vinyl myristate CH ₃ (CH ₂ ) ₁₂ COOC
H = CH ₂ 10 vinyl palmitate CH ₃ (CH ₂ ) ₁₄ COO
CH = CH ₂ 11 vinyl stearate CH ₃ (CH ₂ ) ₁₆ COO
CH = CH ₂ 12 vinyl versatate

[0023]

[Chemical 2]

The polymer compound (where R ¹ and R ² are alkyl groups and the sum of the carbon atoms thereof is 7; that is, R ¹ + R ² = C ₇ H ₁₆ ) is a carboxylic acid vinyl ester 1 The polymer may be a polymer obtained by polymerizing a seed, or a polymer obtained by copolymerizing two or more kinds of carboxylic acid vinyl ester, and may be any component ratio of the carboxylic acid vinyl ester and another monomer copolymerizable therewith. May be a copolymer of

Examples of the monomer unit that can be used in combination with the polymerized unit represented by the above general formula include ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene and isoprene, for example, styrene and α-methyl. Styrene, p-methylstyrene, p-
Styrenes such as chlorostyrene, acrylic acids such as acrylic acid and methacrylic acid, for example itaconic acid, maleic acid, unsaturated aliphatic dicarboxylic acids such as maleic anhydride, such as diethyl maleate, dibutyl maleate,
Diesters of unsaturated dicarboxylic acids such as di-2-ethylhexyl maleate, dibutyl fumarate, di-2-ethylhexyl fumarate, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid Α such as phenyl, α-methyl chloroacrylate, methyl methacrylate, ethyl ethacrylic acid
-Methylene aliphatic monocarboxylic acid esters, for example, nitriles such as acrylonitrile and methacrylonitrile, amides such as acrylamide, such as acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide, etc. Anilides such as vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether, vinyl chloride, vinylidene chloride, vinylidene cyanide such as 1-methyl-1-methoxyethylene, 1,1-dimethoxyethylene. , 1,2-dimethoxyethylene, 1,1
Ethylene derivatives such as dimethoxycarbonylethylene and 1-methyl-1-nitroethylene, for example, N-vinyl such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidene and N-vinylpyrrolidone There are vinyl monomers such as compounds. These monomer units have a structure in which the unsaturated double bond is cleaved and are present in the polymer compound.

Particularly preferred as the polymer compound used in the present invention is one having a vinyl acetate polymer unit in the molecular structure. Among them, those having 40 to 95% by weight of vinyl acetate polymer units, number average molecular weight (MN)
Is preferably 1,000 to 80,000 and has a weight average molecular weight (MW) of 500 to 200,000.

More preferably, a polymer compound having a vinyl acetate polymer unit (particularly 40 to 95% by weight) and a carboxylic acid vinyl ester polymer unit having a longer chain than vinyl acetate is preferable, and particularly, a number average molecular weight (MN). Is 2,000
0-60,000, weight average molecular weight (MW) is 10.0
It is preferably from 0 to 150,000.

In this case, the monomer constituting the polymer compound having vinyl acetate polymerized units by copolymerization with vinyl acetate may be any monomer as long as it can form a copolymer. You can choose it from your body.

The copolymers that can be used as the polymer compound in the present invention are listed below by showing the monomer components. However, as a matter of course, the present invention is not limited to the following examples.

1 vinyl acetate-ethylene 2 vinyl acetate-styrene 3 vinyl acetate-crotonic acid 4 vinyl acetate-maleic acid 5 vinyl acetate-2-ethylhexyl acrylate 6 vinyl acetate-di-2-ethylhexyl maleate 7 vinyl acetate-methyl vinyl ether 8 Vinyl Acetate-Vinyl Chloride 9 Vinyl Acetate-N-Vinyl Pyrrolidone 10 Vinyl Acetate-Vinyl Propionate 11 Vinyl Acetate-Vinyl Pivalate 12 Vinyl Acetate-Varsatic Acid Vinyl 13 Vinyl Acetate-Vinyl Laurate 14 Vinyl Acetate-Vinyl Stearate 15 Vinyl acetate-vinyl versatate-ethylene 16 Vinyl acetate-vinyl versatate-2-ethylhexyl acrylate 17 Vinyl acetate-vinyl versatate-vinyl laurate 18 Vinyl acetate-bar Vinyl tic acid - crotonic acid 19 vinyl propionate - vinyl versatate 20 vinyl propionate - vinyl versatate - crotonic acid 21 pivalate - vinyl stearate - maleic acid

The photosensitive composition of the present invention can be used as an image forming material. For example, it can be used as a colored image forming material when used as a color proof. In this case, the colored photosensitive layer of the colored image forming material is image-wise removed by imagewise exposure and subsequent development to form a colored image.

Dyes and / or pigments are added as colorants in the colored photosensitive layer. In particular, when used for color proofing, pigments and dyes that have a color tone matching those of the ordinary colors required, that is, yellow, magenta, cyan, and black are required, but other metal powders, white pigments, and fluorescent pigments are also required. Are also used. When applying the present invention to color proofing, many pigments and dyes known in the art can be used, such as:

(C.I means color index). Victoria Pure Blue (CI 42595) Auramine (CI 41000) Catillon Brilliant Flavin (CI Basic 1
3) Rhodamine 6GCP (CI 45160) Rhodamine B (CI 45170) Safranine OK 70: 100 (CI 50240) Erioglaucin X (CI 42080) Fast Black HB (CI 26150) No. 1201 Lionol Yellow (C.I. 2109
0) Lionol Yellow GRO (CI 21090) Shimla First Yellow 8GF (CI 2110)
5) Benzidine Yellow 4T-564D (C.I 2109
5) Shimla Fast Red 4015 (C.I 1235
5) Lionol Red 7B4401 (CI 15830) Fastgen Blue TGR-L (CI 7416)
0) Lionol Blue SM (CI 26150) Mitsubishi Carbon Black MA-100 Mitsubishi Carbon Black # 30, # 40, # 50

When a colorant is used in the present invention, the ratio of the colorant / components other than the colorant in the colored photosensitive layer can be determined by those skilled in the art in consideration of the target optical density and the removability of the colored photosensitive layer from a developer. It can be determined by a known method. The addition amount is not particularly limited, but for example, in the case of a dye, its content is preferably 5% to 75%, and in the case of a pigment, its content is preferably 5% to 90%. .

The film thickness of the colored photosensitive layer is not particularly limited, and is known to those skilled in the art depending on the target optical density, the type of colorant (dye, pigment, carbon black) used in the colored photosensitive layer and the content thereof. The film thickness can be determined by the above method, but the film thickness is preferably 0.1 g / m ^{2 to} 5 g /
m ² .

In carrying out the present invention, a plasticizer, a coatability improver and the like may be further added to the photosensitive composition, if necessary. As plasticizers, various low molecular weight compounds, for example, phthalic acid esters, triphenyl phosphates, maleic acid esters, and as coatability improvers, surfactants such as fluorine-based surfactants and ethyl cellulose polyalkylene ethers are typical. Examples thereof include nonionic activators.

When the photosensitive composition of the present invention is used to form an image forming material, particularly a colored image forming material, the colored photosensitive layer is a colored layer containing a colorant and a binder, and a photosensitive layer containing a photosensitive composition. It can also be divided into two layers. In this case, either layer may be disposed on the support side.

When an image-forming material is formed using the photosensitive composition of the present invention, the support used is arbitrary, but a transparent support is preferably used. As the transparent support, a polyester film, particularly a biaxially stretched polyethylene terephthalate film is preferable from the viewpoint of dimensional stability against water and heat. Besides, an acetate film, a polyvinyl chloride film, a polyethylene film, a polypropylene film, a polyethylene film and the like can be used.

The protective layer of the present invention comprises a layer having a discontinuous phase uniformly or nonuniformly mixed in the continuous phase. In the present invention, a high molecular polymer having good scratch resistance is used for the continuous phase. The high molecular weight polymer preferably used in the present invention is preferably one that provides a coating layer that is substantially transparent to actinic rays, such as polyethylene terephthalate.
Although resins used for various film bases such as polypropylene can be used, those which are soluble in water or the developing solution used are particularly preferable in the present invention. Further, it is desirable to use a high-molecular polymer having appropriate softness and toughness, which does not cause cracks or the like during the drying process or handling after forming the coating layer and has excellent adhesion.
Further, its gas permeability is preferably selected appropriately according to the type of photosensitive composition used. That is, o-
It is preferable to provide a protective layer having high gas permeability in the case of a photosensitive composition that generates gas upon exposure to light such as quinonediazide, and low gas permeability when using a photopolymerization type photosensitive composition. It is preferable to provide a protective layer.

Specific examples of such high molecular weight polymers include polyvinyl alcohol; homopolymers of vinyl ether, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester and the like or copolymers containing them; soluble polyamide; ethyl cellulose, butyl. Examples thereof include cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, hydroxypropyl cellulose and other cellulose derivatives. In addition, polyvinyl acetate, methyl vinyl ether, maleic anhydride copolymer, polyvinylpyrrolidone, gelatin, gum arabic, polyethylene oxide, water-soluble polyester and the like can be mentioned. The thickness is not particularly limited, but preferably 0.001 To 5 μm, particularly preferably 0.01 to 3 μm
m.

The solid particles used in the present invention include polyethylene particles, polypropylene particles, ethylene-propylene copolymer particles, ethylene-vinyl acetate copolymer particles,
Polyethylene terephthalate particles, crosslinked vinyl polymer particles, silicon dioxide (eg colloidal silica),
Diatomaceous earth, zinc oxide, titanium oxide, zirconium oxide, glass, alumina, dextrin, starch (eg rice starch), calcium stearate, zinc stearate, polysaccharide fatty acid ester, polyvinyl acetate, polyvinylidene chloride, polyethylene oxide, polyethylene glycol, Polyacrylic acid, polyacrylamide, polyacrylic acid alkyl ester, polystyrene and polystyrene derivatives, and copolymers using monomers of these polymers, polyvinyl methyl ether, epoxy resin, fusible phenol resin, polyamide, polyvinyl butyral Etc.

In the present invention, the average particle size of 1 from the above solid particles is used.
Those having a particle size of 0 μm or less are used, and these particles may be used alone or as a mixture of two or more kinds.

The method for fixing the solid particles to the protective layer and / or the back layer is not particularly limited, and for example, they may be mixed in the protective layer and / or the back layer coating solution, the powder coating method, or the flow method. The protective layer and / or the back layer are uniformly powdered by a method such as an immersion method, an electrostatic powder spraying method, or an electrostatic fluidized immersion method, and heated to 50 to 130 ° C. using a heat source such as hot air or an infrared heater. Or put it in the designated furnace,
A method of melting the particles through a heating roll may be adopted. At this time, some particles may be integrated with each other, but the particles fixed to the protective layer and / or the back layer have no adverse effect on the colored image-forming material.

The heat fusion method is described in JP-A-55-12.
No. 974, and the dispersion spray method is disclosed in JP-A-57-
No. 34558 can be referred to.

The particle size of the solid particles such as colloidal silica used in the present invention is 10 μm or less, more preferably 0.
1 to 8 μm, particularly 0.5 to 6 μm is preferable.

As a method of providing the back layer and / or the protective layer containing solid particles of colloidal silica or the like, a method of electrostatically adhering and drying droplets of solid particles of colloidal silica or the like can be mentioned.

Copolymer of acrylic acid ester and acrylic acid or methacrylic acid in the liquid of solid particles such as colloidal silica; styrene, acrylic acid ester, copolymer of acrylic acid or methacrylic acid; acrylic acid ester, styrene, acrylonitrile And a copolymer of acrylic acid or methacrylic acid, maleic acid, itaconic acid, etc .; a resin such as polyvinyl alcohol, polyvinyl acetate, polyvinylpyrrolidone or other vinyl-based polymer, and a back layer coating liquid containing such a resin binder. A back layer can be applied.

The thickness of the back layer containing solid particles such as colloidal silica in the second invention is not limited, but
0.0005 to 2 μm is preferable, and more preferably 0.
001 to 1 μm.

The amount of the solid particles in the present invention is preferably 0.001 to ² g / m ² , particularly preferably 0.01 to 1.5 g / m ² in the case of the protective layer, and preferably in the case of the back layer. 0.001 to ² g / m ² , particularly preferably 0.
It is 01 to 1.5 g / m ² .

The image forming material can be used in the form of transferring an image to a material to be transferred. In this case, in order to efficiently perform transfer onto the material to be transferred and to facilitate peeling of the support after image transfer, that is, to improve image transferability and to form a cushion layer and an image forming layer (coloring) with the support. In order to improve releasability between the photosensitive layer and the photosensitive layer, the upper surface of the support may be processed or molded to form a cushion, or a cushion layer may be provided on the surface of the support, which will be described later.

In the present invention, the image forming material of the present invention is exposed and developed to form an image portion, and at least the formed image portion is transferred to a material to be transferred (eg, real paper) to obtain a transferred image. is there.

When the present invention is embodied as a multicolor image forming method, for example, one of the basic methods is as follows.

A colored image of the first color is formed on the colored image forming material of the first color, at least the colored image is transferred to the material to be transferred, and the support is peeled off. Further, after forming the second-color coloring image on the second-color coloring image forming material, the second-color registration mark image formed in association with the second-color coloring image is registered with the first-color registration mark image on the transfer material. , The second colored image is transferred onto the first colored image, and the support is peeled off to obtain a two-color aligned image. Similarly, the colored images of the third color and the fourth color are also transferred onto the material to be transferred to obtain a multicolor image. Also,
In some cases, this multicolor image may be indirectly transferred onto another transfer material to obtain a multicolor image. A method of this kind is disclosed in JP-A-47-41830 and 59-97140.
No. 60-28649 and US Pat. No. 377511.
No. 3 etc.

In the present invention, the image forming material is usually imagewise exposed through a color separation mask or the like and then developed to form an image. At this time, only the image portion of the image obtained on the support is directly transferred and laminated on the material to be transferred. That is, only the colored image layer that substantially forms an image is transferred and laminated. In this case, the upper surface of the support is used as a cushion or a cushion layer is provided on the support in order to efficiently perform the transfer onto the transfer surface and facilitate the peeling of the support after the image transfer. . In the present invention, these are referred to as cushion layers. The thickness of the cushion layer is preferably in the range of 5 μm to 50 μm. The resin used for the cushion layer has a softening point of -30 ° C to 1
It is preferably at 50 ° C. The softening point temperature here is V
It is a value shown by the ICAT softening point or the ring and ball method. In the present invention, specifically, the following may be mentioned as preferable resins.

Polyolefins such as polyethylene and polypropylene. Ethylene copolymers such as ethylene and vinyl acetate, ethylene and acrylic ester, ethylene and acrylic acid. PVC. Vinyl chloride copolymers such as vinyl chloride and vinyl acetate. Polyvinylidene chloride. Vinylidene chloride copolymer. polystyrene. Styrene and styrene copolymers such as maleic anhydride. Polyacrylic ester. Polyester resin. Polyurethane resin. Acrylic ester and acrylic ester copolymers such as vinyl acetate. Polymethacrylic acid ester. Methacrylic acid 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 hydrogen phthalate Cellulose derivative, Cellulose acetate phthalate,
Cellulose acetate succinate. Shellac. wax. Ionomer resin. Among these, ethylene-vinyl acetate copolymer is particularly preferable.

The ethylene-vinyl acetate copolymer resin used in the present invention is preferably one in which the proportion of vinyl acetate in the copolymer resin is in the range of 5% to 33% by weight. The VICAT softening point is preferably 80 ° C. or lower. Further, in the ethylene-vinyl acetate copolymer resin layer of the present invention, various polymers, supercooling substances, surfactants, release agents, etc. are added within the range where the softening point does not substantially exceed 80 ° C. You can

The method for providing the ethylene-vinyl acetate copolymer resin layer on the support is as follows: 1) after coating a solution of the ethylene-vinyl acetate copolymer resin layer in an organic solvent such as toluene on the support. A method of drying to provide an ethylene-vinyl acetate copolymer resin layer. 2) Polyvinyl acetate, polyvinyl chloride, epoxy resin,
A solution of polyurethane resin, natural rubber, synthetic rubber, etc., dissolved in an organic solvent is used as an adhesive, and these adhesives are applied on a support, dried with hot air or heat, and then ethylene-vinyl acetate copolymer A so-called dry laminating method in which resin films are stacked and pressure-bonded under heating to laminate. 3) A mixture of ethylene and vinyl acetate, a copolymer of ethylene and acrylic acid ester, polyamide resin, petroleum resin, rosins and waxes is used as an adhesive, and these adhesives are heated as they are and are supported in a molten state. After applying by doctor blade method, roll coating method, gravure method, reverse roll method, etc. on the body, immediately, ethylene-vinyl acetate copolymer resin film is stuck, if necessary heated to high temperature and then cooled So-called hot melt laminating method. 4) A so-called extrusion laminating method in which the ethylene-vinyl acetate copolymer resin is kept in a molten state and extruded into a film by an extruder, and while the molten state is maintained, the support is pressure-bonded and laminated. 5) When a film serving as a support is formed by the melt extrusion method, a plurality of extruders are used together with a molten ethylene-vinyl acetate copolymer resin to form ethylene-acetic acid on the support film by one-time molding. A so-called coextrusion method for forming a vinyl copolymer resin layer. Etc.

In the image forming method of the present invention, the developer used for developing the image forming material can be arbitrarily used as long as it has a developing action for developing the material to be processed. It is preferable to use a developer containing an alkali agent and an anionic surfactant.

Alkali agents that can be used include (1) sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium or ammonium phosphate dibasic or tertiary acid, sodium metasilicate, Inorganic alkaline agents such as sodium carbonate and ammonia, (2) mono, di, or trimethylamine, mono,
Organic amine compounds such as di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di-, or triethanolamine, mono-, di-, or triisopropanolamine, ethyleneimine, ethylenediimine, and the like can be mentioned.

The anionic surfactants that can be used include (1) higher alcohol sulfates (for example,
Lauryl alcohol sulphate sodium salt, octyl alcohol sulphate ammonium salt, lauryl alcohol sulphate ammonium salt, secondary sodium alkyl sulphate, etc.) (2) Aliphatic alcohol phosphate ester salts (eg cetyl alcohol phosphate sodium salt) Etc.) (3) Alkylaryl sulfonates (for example, sodium dodecylbenzenesulfonate, sodium isopropylnaphthalenesulfonate, sodium dinaphthalenesulfonate, sodium metanitrobenzenesulfonate, etc.) (4) Alkylamidosulfonates

[0061]

[Chemical 3]

(5) Sulfonates of dibasic aliphatic ester (for example, dioctyl sodium sulfosuccinate, dihexyl sodium succinate, etc.)
(6) Formaldehyde condensate of alkylnaphthalene sulfonate (for example, formaldehyde condensate of sodium cibutylnaphthalene sulfonate).

The alkaline agent and the anionic surfactant can be used in any combination.

[0064]

EXAMPLES Examples of the present invention will be illustrated below together with comparative examples. However, the present invention is not limited to the examples described below.

Example 1 On a polyethylene terephthalate film having a thickness of 75 μm, an ethylene-vinyl acetate copolymer (EVAFLEX P-1405 manufactured by Mitsui DuPont Polychemical Co., Ltd .: vinyl acetate content 14% by weight, VICAT softening point 68 ° C.) Was coated by an extrusion laminating method so as to have a thickness of 30 μm, whereby a support I having a cushion layer was prepared. On the support I obtained above, a colored photosensitive layer dispersion having the following composition was applied using a wire bar so as to have a dry film thickness of 1.2 g / m ^2, and dried. Colored Photosensitive Layer Dispersion 1 Photoreceptor QD-1 10 g Vinyl acetate-vinyl versatate (80:20 parts by weight) copolymer Mw = 60000 (50% methanol solution) 70.65 g Vinyl acetate-vinyl versatate-crotonic acid (79: 20: 1 parts by weight) Copolymer Mw = 60,000 (50% methanol solution) 30.28 g Carbon black MA-100 (manufactured by Mitsubishi Kasei) 6.1 g Methyl ethyl ketone 285.54 g

[0066]

[Chemical 4] X / Y = 1/1 /, Mw of resin before reacting Q = 5
00

Next, a protective film having the following composition was formed on the colored photosensitive layer.
Layer coating solution dried to a film thickness of 0.1 g / m ²Painted to be
The cloth was dried and the image forming material samples 1 to 4 were prepared.

TC-5R Hydroxypropyl methylcellulose manufactured by Shin-Etsu Chemical Co., Ltd. 10 g Solid powder particles (described in Table 1) 1 g Water 1000 g

[0069]

[Table 1]

Each of the image-forming material samples obtained as described above was cut into a size of 30 × 25 cm, and each cut into 3 pieces.
Each set has a cross-sectional area of 30 x 2
Place 5cm of 1.2kg weight, 55 ℃, 20% RH
Left for 3 days. Next, the middle sample of each set was taken out and developed with a developer having the following composition at 32 ° C. for 35 seconds, and then each of the samples was placed on art paper by the method described in Example 1 of JP-A-3-228063. Images of the samples were transferred to obtain transfer image samples 1 to 4. The drum temperature is 60 ° C., the pressure roll temperature is 135 ° C., and the roll pressure is 4 kg / cm ² . Table 2 shows the results of measuring the number of image defects in the transfer image samples 1 to 4 thus prepared.

Developer composition Konica PS plate developer SDP-1 (manufactured by Konica Corporation) 20 ml Perex NBL (manufactured by Kao Atlas) 50 ml Water 400 ml

[0072]

[Table 2]

Example 2 The coloring photosensitive layer dispersion liquid of Example 1 was prepared as follows.
The dry film thickness was 1.5 g / m ² . Colored Photosensitive Layer Dispersion 2 Photoconductor QD-1 10 g Vinyl acetate-vinyl versatic acid-Crotonic acid (79: 20: 1 parts by weight) Copolymer Mw = 60000 (50% MeOH solution) 64.5 g Rionol Red 4219X ( Toyo Ink Co., Ltd.) 3.53 g Methyl ethyl ketone 150.87 g Further, the coating solution for the protective layer having the following composition was applied and dried to a film thickness of 0.5 g / m ² after drying.

GL-05 (polyvinyl alcohol manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 10 g Solid powder particles (described in Table 3) Water described in Table 3 500 g

[0075]

[Table 3]

Image forming material samples 5 to 7 were obtained in the same manner as in Example 1 except for the above. Next, transfer image samples 5 to 7 were prepared in the same manner as in Example 1 and image defects were evaluated. The results are shown in Table 4.

[0077]

[Table 4]

Example 3 On one surface of polyethylene terephthalate having a thickness of 75 μm, a coating solution for the back layer having the following composition had a dry thickness of 0.
After coating with a wire bar so as to have a weight of 5 g / m ² , a cushion layer made of an ethylene-vinyl acetate copolymer resin was formed on the surface opposite to the back layer in the same manner as in Example 1 to form a support II. ~ V was formed. Back layer coating liquid 1 Si-coat 900 (manufactured by Daihachi Chemical Co., Ltd.) 100 g BYK-306 (manufactured by Big Kumi Co., Ltd.) 6 g Solid fine powder particles (listed in Table 5) Listed in Table 5 Methyl ethyl ketone 333 g

[0079]

[Table 5]

On the cushion layers of the supports II to V obtained as described above, the colored photosensitive layer dispersion 3 having the following composition was applied using a wire bar so as to have a dry film thickness of 1.1 g / m ² . After drying at 80 ° C. for 2 minutes, a protective layer coating solution having the following composition was applied so that the dry film thickness would be 0.2 g / m ² .
After drying, image forming material samples 8 to 11 were obtained.

Colored Photosensitive Layer Dispersion 3 Photoconductor QD-1 10 g Vinyl acetate-vinyl versatate (80:20 parts by weight) copolymer Mw = 60000 (50% methanol solution) 70.65 g Vinyl acetate-vinyl versatate- Crotonic acid (79: 20: 1 part by weight) Copolymer Mw = 60,000 (50% methanol solution) 30.28 g Rionol blue FG-7330 6.6 g Methyl ethyl ketone 285 g Protective layer coating liquid TC-5R (Shin-Etsu Chemical hydroxy) Propylmethyl cellulose) 10 g Water 500 g Further, the image forming material sample 5 and the colored photosensitive layer coating were prepared in the same manner, and the image forming material sample 12 in which only the protective layer coating liquid was not applied was prepared.

Further, on the support I prepared in Example 1,
After the colored photosensitive layer dispersion liquid 3 was applied and dried in the same manner as above, the protective layer coating liquid was not applied, and the surface of the support opposite to the cushion layer was treated in the same manner as in Example 1 of JP-A-3-289660. As a result, an image forming material sample 13 was prepared by fixing 300 powders / cm ² of solid powder.

Transfer image samples 8 to 13 were prepared from these samples in the same manner as in Example 1 and the number of image defects was measured. The results are shown in Table 6.

[0084]

[Table 6]

Example 4 Image forming material sample 1 was prepared in the same manner as image forming sample 3 of example 3 except that the protective layer coating solution had the following composition.
Created 4. A transfer image sample 14 was prepared from this sample in the same manner as in Example 1 and image defects were evaluated, and the effect of the present invention was obtained.

Protective Layer Coating Liquid GL-05 (Nippon Gosei Kagaku Kogyo Polyvinyl Alcohol) 10 g Syloid 404 (Fuji Silysia Chemical Ltd.) 1 g Water 500 g

[0087]

According to the present invention, it is possible to provide a colored image-forming material capable of suppressing the image loss of the transferred image due to the destruction of the cushion layer and obtaining a color proof similar to a printed matter.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Miyuki Hosoi 1 Sakura-cho, Hino-shi, Tokyo Konica stock company (72) Inventor Kiyoshi Goto 1 Sakura-cho, Hino-shi, Tokyo Konica stock company (72) Inventor Hideaki Mochizuki 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryo Kasei Co., Ltd. (72) Inventor Tetsuya Masuda 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryo Kasei Co., Ltd.

Claims (2)

[Claims] 1. A cushion layer is provided on or above a support, and at least one colored photosensitive layer containing a photosensitive composition and a colorant is provided on the cushion layer, and the colored photosensitive layer is protected. An image forming material having a layer, which forms a colored image by imagewise exposure and development, and then transfers the colored image to the material to be transferred by exposing the non-image portion to obtain a transferred image. 2. The colored image-forming material as described in above, wherein the protective layer has solid particles having an average particle diameter of 10 μm or less. 2. A cushion layer is provided on or above a support, and at least one colored photosensitive layer containing a photosensitive composition and a colorant is provided on the cushion layer, and the colored photosensitive layer is protected. An image forming material having a layer, which forms a colored image by imagewise exposure and development, and then transfers the colored image to the material to be transferred by exposing the non-image portion to obtain a transferred image. In the above, the back surface having the solid particles having an average particle diameter of 10 μm or less is directly provided on the surface of the support opposite to the surface having the protective layer, or the back layer is provided. Characterized colored image forming material.