JPH09230590A - Image forming material and production of release layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the reproducibility for small dots, transfer property and sensitivity and to reduce the production cost by forming the uppermost release layer having photosensitivity or reactivity with a color photosensitive layer during exposure and forming a color photosensitive layer which changes its adhesion property by irradiation with light. SOLUTION: This image forming material has a multilayered release comprising two or more layers, and color photosensitive layers in this order on a base body. The uppermost layer of the release layer is the most distant layer of the two or more layers from the base body. The release layer is obtd. by preparing a resin (matrix resin) having physical properties suitable for the release property, such as thermoplasticity that the resin is softened by heating, and introducing reactive groups which react with radicals produced in the photosensitive layer by exposure or introducing photosensitive groups which produces reactive radicals with the photosensitive layer. As for the photosensitive compsn., a well-known photosensitive compd. which changes its adhesion property by exposure can be used. It is preferable to use a photosensitive compsn. which decreases its adhesion property by exposure.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming material suitable for producing a color proof or the like for color proofing in color printing and a method for producing a release layer thereof, and in particular, small point reproducibility, The present invention relates to an image forming material capable of improving transferability, improving sensitivity and reducing manufacturing cost, and a method for manufacturing a release layer.

[0002]

2. Description of the Related Art Japanese Patent Application No. 6-41292 discloses a release layer which is photosensitive or reactive with a photosensitive layer at the time of exposure and a colored photosensitive layer whose adhesiveness is changed by light irradiation (exposure). An image forming material provided in order is disclosed.
The release layer in the art has a single-layer structure, the release layer has a large film thickness, and the photosensitive or reactive release layer material is expensive. Further, since image exposure is performed through the release layer, particularly in the case of a photosensitive release layer, since the exposure energy is consumed by the thick film release layer, the energy required for image formation increases and However, there is a problem in that the sensitivity is lowered. Furthermore, since the exposed portion and the unexposed portion of the release layer have different cushioning properties (the cushioning property of the exposed portion is weak), there is a problem in that the transferability of small dots decreases and the small dot reproducibility is poor. doing.

Japanese Patent Application No. 62-314170 discloses a multilayer release layer material and a manufacturing method. A two-layer method is described in which a release layer resin is coextruded in order to make the release layer multi-layered. In this method, the film thickness of each layer is 20.
If the thickness is less than μm, a stable film thickness cannot be obtained, and the reproducibility of the transferred image (transferability, resolution, etc.) is poor.

Japanese Patent Application No. 1-190968 discloses a multi-layer release layer material and a manufacturing method. A method is described in which a resin solution for a release layer is applied in multiple layers. However, this technique requires heat retention of the resin solution or the interlayer adhesion is not strong. However, there is a problem in that a good image-forming material having no defects cannot be prepared due to peeling.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above problems, improves small point reproducibility and transferability, and improves the sensitivity and production cost of an image forming material and a release layer. The purpose is to provide a method.

[0006]

The above-mentioned problems of the present invention are as follows. In an image forming material having two or more multi-layered release layers and a colored photosensitive layer on a support in this order, the uppermost release layer is photosensitive or reactive with the colored photosensitive layer at the time of exposure,
An image-forming material, wherein the colored photosensitive layer is a layer whose adhesiveness is changed by light irradiation.

In the method for producing a release layer having a multilayer structure of 2.2 or more, when the release layer is formed into multiple layers, the uppermost release layer is provided on the temporary support, and then the uppermost release layer surface is added. It is achieved by a method for producing a release layer, which comprises pressing to bond the lower release layer provided on the support and peeling off the temporary support to form a multi-layer release layer.

[0008]

The purpose of imparting photosensitivity or reactivity to the release layer is to cause a crosslinking reaction at the interface with the colored photosensitive layer coated on the upper layer during image exposure. Therefore, only the uppermost layer of the release layer needs to be photosensitive or reactive. By using the release layer having this structure, the amount of the photosensitive or reactive material that is expensive in terms of material can be reduced, and the cost can be reduced. Furthermore, since the release layer for reducing the image exposure energy is thin, the sensitivity is not significantly reduced. In addition, the release layer needs to have a cushioning function in consideration of transferability to the uneven surface of the image receiving material. With the configuration of the present invention, the function can be imparted to the lower layer portion of the release layer.

On the other hand, in the case of producing a multi-layered release layer, the uppermost coating solution is generally applied to the lower layer, but in the case of a photosensitive or reactive release layer, a photosensitive or reactivity-imparting agent is used as the lower layer. Since it is necessary to use a solvent that does not permeate into the ink or does not immerse the lower layer, the solvent is limited and the solubility of the photosensitizer or the reactivity-imparting agent is insufficient. The group or reactive group is decomposed. Therefore, the release layer surface as designed cannot be obtained. When coating on a temporary support as in the present invention, the solvent for coating is loosely limited, so that a good solvent for the photosensitivity or reactivity-imparting agent or a solvent with a low boiling point can be selected (drying temperature is low), and the release as designed Layers can be created.

In the present invention, the uppermost layer of the colored photosensitive layer and the release layer is peeled off (the peeling layer is not transferred).

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
In the image forming material of the present invention, an image forming material having a photosensitive composition or the like is subjected to imagewise exposure to form image parts and non-image parts having different tackiness, and the image part having high tackiness is used as a final support ( For example, the transfer image is obtained by transferring to a printing actual paper).

When the image forming material of the present invention is embodied as a multicolor image forming method, the basic method is as follows.

In the case of the direct transfer method, the first color adhesive coloring image is formed on the first color coloring image forming material, the coloring image is transferred onto the final support, and the support is peeled off. Also, the second
After the second color adhesive coloring image is formed on the color coloring image forming material, the second color registration mark image formed therewith is registered with the first color registration mark image of the final support to form the first color. A second color adhesive colored image is transferred onto the colored image and the support is peeled off to obtain a two-color aligned image. Similarly, the third and fourth color adhesive colored images are transferred onto the final support to obtain a multicolor image.

In the image forming material of the present invention, the image forming material is usually imagewise exposed through a color separation mask or the like to form an adhesive image. At this time, only the adhesive image portion formed on the support is directly or indirectly transferred and laminated on the final support. In this case, the release layer according to the present invention is formed on the surface of the support in order to efficiently perform transfer to the final support, facilitate peeling of the support after image transfer, and firmly leave the non-image in the release layer. Is provided.

The uppermost layer of the release layer of the present invention refers to the layer farthest from the support among the release layers composed of two or more layers, and the lower layer is the release layer other than the uppermost layer. Refers to all layers. The uppermost release layer is photosensitive or reactive with the photosensitive layer during exposure.

As the method for providing the lower release layer on the support, (1) a solution prepared by dissolving a resin in an organic solvent is applied on the support, dried by hot air or heating, and then a cover sheet is overlaid. Combined, so-called dry laminating method of laminating by pressure bonding under heating (2) While heating the resin as it is and keeping it in a molten state,
So-called hot melt, which is applied on a support by a doctor blade method, roll coating method, gravure method, reverse roll method, etc., immediately adheres a cover sheet, heats it if necessary at a high temperature, and then cools it. Lamination method (3) While heating the resin as it is and keeping it in a molten state,
Extruded on a support by an extruder, and while this is in a molten state, the cover sheet is pressed and laminated,
So-called extrusion laminating method (4) Using a plurality of extruders or an extruder having a plurality of extrusion ports on a support by the melt extrusion method,
A so-called co-extrusion method in which a layer made of two or more types of resin is formed on a support by one molding, and a cover sheet is similarly pressed and laminated while this is in a molten state. A solution dissolved in a solvent or water is applied on a support and dried by hot air or heating. A so-called solution coating method. (6) The resin is dissolved while heating in an organic solvent that does not dissolve the resin at room temperature, and the resin is cooled. Thus, a method in which a resin solid dispersion in an organic solvent is obtained, coated on a support, dried, and calendered as necessary, thereby fusing the resin solid fine particles to form a layer, etc. As the cover sheet used in (1) to (4), those similar to those used for a support described later can be used.

It is preferable to appropriately select which method is used depending on the properties of the resin. The thickness of the lower layer is preferably 20 to 70 μm, and 25 to 50 μm.
Is more preferable.

In the present invention, a method of providing an uppermost release layer on the upper layer of the lower release layer and forming a multilayer structure of the release layer is as follows. After providing the uppermost release layer on the temporary support, It is carried out by pressing the uppermost release layer surface and adhering it to the lower release layer provided on the support to peel off the temporary support. At this time, the cover sheet in the "support having the lower release layer" obtained in the above (1) to (4) is peeled off.
After being removed, it is bonded to the uppermost release layer surface.

The release layer contained in the image forming material of the present invention is
In the image-forming material according to the present invention, a reactive group that reacts with an active species generated in the photosensitive layer by exposure is used by using a resin (matrix resin) having physical properties suitable for releasability, for example, a resin that is softened by heating. Alternatively, it can be obtained by introducing into the release layer, a photosensitive group that produces an active species that reacts with the photosensitive layer. As a method for introducing the above-mentioned reactive group or photosensitive group into the release layer, a compound having a reactive group or a photosensitive group for the matrix resin, which is introduced during the synthesis of the matrix resin, is introduced. It is possible to apply a method such as chemical modification with, a method of blending a compound having a reactive group or a photosensitive group with a matrix resin, and the like. As the matrix resin, for example, JP-A-4-
The resin forming the heat-softening release layer described in 172351 can be used.

The reactive group introduced into the release layer and reacting with the active species generated in the photosensitive layer upon exposure is not particularly limited as long as it is a group capable of reacting with the active species. Specific examples of the reactive group include a hydroxyl group, a carboxyl group, a sulfo group, an amino group, an epoxy ring group, an epithio ring group, a vinyl group and an onium base. In order to introduce the reactive group into the release layer, a polymer obtained by polymerizing a monomer having such a reactive group by a known method is used as a matrix resin in the release layer, or together with other matrix resin. It may be contained. The polymer is a monomer having the above-mentioned reactive group and ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene and isoprene, such as styrene, α-methylstyrene, p-methylstyrene and p-chlorostyrene. Styrenes such as acrylic acid, acrylic acid such as methacrylic acid, unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid, maleic anhydride, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, Isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, esters of α-methylene aliphatic monocarboxylic acid such as ethyl ethacrylate, For example, acrylonitrile Nitriles methacrylonitrile, etc., for example, amides such as acrylamide, such as acrylic anilide, p
-Anilides such as chloroacrylanilide, m-nitroacrylanilide and m-methoxyacrylanilide; for example, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate and vinyl butyrate; for example, methyl vinyl ether, ethyl vinyl ether and 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-dimethoxy Ethylene derivatives such as carbonylethylene and 1-methyl-1-nitroethylene, for example, N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidene,
It may be used in combination with a vinyl-based monomer such as an N-vinyl compound such as N-vinylpyrrolidone.

As the monomer having a hydroxyl group as a reactive group, vinyl alcohol, 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N- (4-
Hydroxyethylphenyl) methacrylamide, hydroxy-methyl diacetone (meth) acrylamide, N-
(4-hydroxyphenyl) acrylamide, N- (4
-Hydroxyphenyl) methacrylamide, o-, m-
Alternatively, p-hydroxystyrene, o-, m- or p-hydroxyphenyl acrylate or methacrylate and the like can be mentioned.

Examples of the monomer having a carboxyl group or a sulfo group include those having an acryl group or a methacryl group and a carboxyl group or a sulfo group, and examples of such a monomer include the compounds shown below.

[0023]

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[0024]

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Examples of the monomer having an amino group include acrylamide, methacrylamide, 2-aminoethyl vinyl ether, p-aminostyrene and the like.

Examples of the monomer having an epoxy ring include glycidyl acrylate and glycidyl methacrylate, examples of the monomer having an epithio ring include 2,3-epithiopropyl acrylate, 2,3-epithiopropyl methacrylate, and monomers represented by the following general formula. Is mentioned.

[0027]

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Examples of the monomer having a vinyl group include phenyl vinyl ether, CH ₂ ═CH—O—R—O.
_{-Ar-O-CH = CH 2} (Ar is an aromatic ring, R represents an aliphatic group.), Butanediol diacrylate, ethylene glycol dimethacrylate, tetramethylene glycol diacrylate, trimethylol propane triacrylate, tetra Ethylene glycol dimethacrylate, methylene bis acrylamide, methylene bis methacrylamide, divinyl benzene, vinyl methacrylate, vinyl crotonate, vinyl acrylate, vinyl acetylene, trivinyl benzene, glycerin trimethacrylate, ventaerythritol tetramethacrylate, triallyl cyanurate, Divinyl acetylene, divinyl ethane, divinyl sulfide, divinyl sulfone, hexatriene, triethylene glycol dimethacrylate, Arirushianamido, glycol diacrylate, ethylene glycol divinyl ether, diallyl phthalate, divinyl dimethyl silane, glycerol trivinyl ether and the like.

As the monomer having an onium base,
Examples include those represented by the following general formulas (1) to (5).

[0030]

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[0031]

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In the general formulas (1) to (5), X ⁻ represents an anion. That is, halogen ions, sulfate ions,
Phosphate ion, sulfonate ion, acetate ion and the like. Rs bonded to N ⁺ may be the same or different and each R is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, propyl, isobutyl, pentyl, Hexyl, heptyl, decyl groups), alkenyl groups (eg, propenyl, butynyl groups), or aryl groups having 6 to 20 carbon atoms (eg, phenyl, naphthyl groups), alkyl groups (eg, benzyl, Phenethyl and naphthylmethyl groups) or alkaryl groups (eg, tolyl and xylyl groups). Z represents a group of nonmetal atoms necessary for forming an unsaturated heterocyclic ring, and is preferably an imidazole, pyridine, piperidine, pyrrole or morpholine ring. n represents an integer.

As the matrix resin having a hydroxyl group introduced therein, a vinyl polymer having a structural unit having a phenolic hydroxyl group in its molecular structure is preferable. As such a polymer, a carbon-carbon double bond is cleaved, Polymers obtained by polymerization and preferably containing at least one structural unit represented by the following general formulas (6) to (11) are preferably used.

[0034]

[Chemical 6]

In the general formulas (6) to (11), R ₁ and R ₂ each represent a hydrogen atom, an alkyl group or a carboxyl group, and preferably a hydrogen atom. R ₃ represents a hydrogen atom, a halogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group such as a methyl group or an ethyl group. R ₄ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and preferably a hydrogen atom.

A represents an alkylene group which may have a substituent connecting a nitrogen atom or an oxygen atom and an aromatic carbon atom, m represents an integer of 0 to 10, and B represents a substituent. Represents a phenylene group or a naphthylene group which may have a substituent.

The vinyl polymer preferably has a copolymer type structure, and in such a copolymer, the structural unit represented by each of the general formulas (6) to (11) is used. Examples of the monomer that can be copolymerized in combination with at least one kind include ethylene-based unsaturated olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene, such as styrene and α-.
Styrenes such as methylstyrene, p-methylstyrene and p-chlorostyrene, acrylic acids such as acrylic acid and methacrylic acid, and unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid and maleic anhydride, such as acrylic acid. Methyl, ethyl acrylate, acrylic acid n-
Butyl, isobutyl acrylate, dodecyl acrylate,
2-chloroethyl acrylate, phenyl acrylate, α
-Esters of α-methylene aliphatic monocarboxylic acid such as methyl chloroacrylate, methyl methacrylate, ethyl methacrylate, ethyl ethacrylate, nitriles such as acrylonitrile and methacrylonitrile, amides such as acrylamide, such as acryl Anilides such as anilide, p-chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, such as methyl vinyl ether, ethyl vinyl ether. , Isobutyl vinyl ether, vinyl ethers such as β-chloroethyl vinyl ether, vinyl chloride, vinylidene chloride, vinylidene cyanide, for example, 1-methyl-1-methoxyethylene, 1, 1-dimethoxyethylene, 1,2
Ethylene derivatives such as -dimethoxyethylene, 1,1-dimethoxycarbonylethylene, 1-methyl-1-nitroethylene, such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidene, N- There are vinyl monomers such as N-vinyl compounds such as vinylpyrrolidone.

These vinyl monomers are present in the polymer compound with a structure in which the unsaturated double bond is cleaved.

These monomers may be bound to the vinyl polymer in either a block or random state.

The content of the structural unit represented by each of the general formulas (6) to (11) in the vinyl polymer is preferably 5 to 70 mol%, particularly preferably 10 to 40 mol%.

The above-mentioned polymers may be used alone, or two or more kinds may be used in combination in the release layer composition.

Typical specific examples of the vinyl polymer having a hydroxyl group are shown below. In the compounds exemplified below, Mw represents a weight average molecular weight, Mn represents a number average molecular weight, and s, k, l, o, m and n each represent a mol% of a structural unit.

[0043]

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[0044]

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[0045]

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[0046]

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Specific examples of the polymer into which the onium base is introduced include the compounds shown below. (Specific examples of the molar ratio are shown in parentheses.)

[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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Examples of the photosensitive group include the photosensitive groups of the monomers having a photosensitive group shown in Table 6.1 on page 155 of "Photosensitive Polymer" by Mototaro Nagamatsu (Kodansha, 1977). In order to introduce the photosensitive group into the release layer, a polymer obtained by polymerizing the monomer by a known method may be contained in the release layer as a matrix resin or together with another matrix resin. The polymer is a monomer having the above-mentioned reactive group and ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene and isoprene, such as styrene, α-methylstyrene, p-methylstyrene and p-chlorostyrene. Styrenes such as acrylic acid, acrylic acid such as methacrylic acid, unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid, maleic anhydride, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, Isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, esters of α-methylene aliphatic monocarboxylic acid such as ethyl ethacrylate, For example, acrylonitrile Nitriles such as methacrylonitrile, for example, amides such as acrylamide, for example, anilides such as acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide, such as vinyl acetate, vinyl propionate, benzoic acid. Vinyl, vinyl esters such as vinyl butyrate, for example, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, vinyl ethers such as β-chloroethyl vinyl ether, vinyl chloride, vinylidene chloride, vinylidene cyanide, for example, 1-methyl-1-methoxyethylene, 1,1
-Dimethoxyethylene, 1,2-dimethoxyethylene,
1,1-dimethoxycarbonylethylene, 1-methyl-
Ethylene derivatives such as 1-nitroethylene, for example, N-
It may be used in combination with vinyl-based monomers such as N-vinyl compounds such as vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone and N-vinylpyrrolidone.

To chemically modify the matrix resin with a compound having a reactive group or a photosensitive group, for example, when it is desired to introduce a vinyl group into the matrix resin, a matrix resin having a hydroxyl group is prepared, and a vinyl group and a A compound having an epoxy group can be reacted by a known method to bond a hydroxyl group to the epoxy group to synthesize the compound.

A method for blending a compound having a reactive group or a photosensitive group with a matrix resin is described, for example, in JP-A-4-147261, page 2, lower left column, 19th page.
A photopolymerizable composition containing an ethylenically unsaturated compound having a polymerizable unsaturated group, a photopolymerization initiator, and a binder, described in line to page 4, lower right column, line 10 can be applied. .

The material of the support and the temporary support used in the image forming material of the present invention is arbitrary, but a polyester film, particularly a biaxially stretched polyethylene terephthalate film, has strength, dimensional stability against water and heat, economical efficiency, etc. In terms of In addition, an acetate film, a polyvinyl chloride film, a polyethylene film, a polypropylene film or the like can be used. Although the thickness is not particularly limited, it is preferably about 50 to 150 μm when used as a support and about 10 to 50 μm when used as a temporary support from the viewpoints of workability and economy.

In the image forming layer of the image forming material of the present invention, a photosensitive composition having a sensitivity to actinic rays can be used. The structure may be a one-layer structure or a multilayer structure of two or more layers. In the case of a multilayer structure, at least one or more layers may have an image forming ability. Colorants such as dyes can be included.

As the photosensitive composition used in the image forming layer (colored photosensitive layer) of the present invention, a known photosensitive composition whose adhesiveness is changed by exposure can be used, but the adhesiveness is decreased by exposure. Preferred is a photosensitive composition. Photopolymerizable photosensitive compositions are more preferred. Specifically, for example, as the photopolymerizable compound, any of those generally used can be arbitrarily used. For example, at least one selected arbitrarily from the group of compounds consisting of acrylic acid, methacrylic acid, acrylic acid ester and methacrylic acid ester.
A variety of compounds 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, pentaerythritol tetraacrylate, dipentaerythritol polyacrylate, 1,3-propanediol diacrylate,
Examples thereof include 1,5-pentanediol dimethacrylate, polyethylene glycol bisacrylate, bismethacrylate, etc., but are not limited thereto.

A photopolymerization initiator may be contained in the photosensitive composition whose adhesiveness is reduced by exposure. The photopolymerization initiator in this case is optional, 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-4'-dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthra Aromatic ketones such as quinone and other aromatic ketones, benzoin, benzoin methyl ether, benzoin ethers such as benzoin ethyl ether and benzoin phenyl ether, methylbenzoin, ethylbenzoin and other benzoins, and 2-
(O-Chlorophenyl) -4,5-diphenylimidazole duplex, 2- (o-chlorophenyl) -4,5-
(M-Methoxyphenyl) imidazole duplex, 2-
(O-Fluorophenyl) -4,5-diphenylimidazole double body, 2- (o-methoxyphenyl) -4,5
-Diphenylimidazole duplex, 2- (p-methoxyphenyl) -4,5-diphenylimidazole duplex,
2,4-di (p-methoxyphenyl) -5-phenylimidazole double body, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole double body, 2-
(P-Methylmercaptophenyl) -4,5-diphenylimidazole duplex and U.S. Pat. No. 3,479,18.
5, British Patent 1,047,569 and US Patent 3,
Mention may be made of the 2,4,5-triacryluimidizole duplex, such as the similar duplexes described in the respective specifications of 784,557.

As other photopolymerizable initiators, 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 can contain a known polymer compound and synthetic resin, and has a polymer having a carboxylic acid vinyl ester polymerization unit represented by the following general formula in its molecular structure. It is preferable to contain a compound.

[0062]

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

1 vinyl acetate CH ₃ COOCH = CH ₂ 2 vinyl propionate CH ₃ CH ₂ COOCH =
CH ₂ 3 vinyl butyrate CH ₃ (CH ₂ ) ₂ COOCH = C
H ₂ 4 vinyl pivalate (CH ₃ ) ₃ CCOOCH =
CH ₂ 5 vinyl caproate CH ₃ (CH ₂ ) ₄ COOC
H = CH ₂ 6 vinyl caprylate CH ₃ (CH ₂ ) ₆ COOC
H = CH ₂ 7 vinyl caprate CH ₃ (CH ₂ ) ₈ COOC
H = CH ₂ 8 vinyl laurate CH ₃ (CH ₂ ) ₁₀ COO
CH = CH ₂ 9 vinyl myristate CH ₃ (CH ₂ ) ₁₂ CO
OCH = CH ₂ 10 vinyl palmitate CH ₃ (CH ₂ ) ₁₄ C
OOCH = CH ₂ 11 vinyl stearate CH ₃ (CH ₂ ) ₁₆ C
OOCH = CH ₂ 12 Versatic vinylate

[0065]

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(R ¹ and R ² are alkyl groups, and the sum of the number of carbon atoms is 7. That is, R ¹ + R ² = C ₇ H ₁₆ is obtained.) The polymer compound is a carboxylic acid vinyl ester of 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, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid Phenyl, α-methyl methyl acrylate, methyl methacrylate, α-methylene aliphatic monocarboxylic acid esters such as ethyl methacrylate, for example, acrylonitrile, nitriles such as methacrylonitrile, for example, amides such as acrylamide, for example, acrylanilide Anilides such as p-chloroacrylanilide, m-nitroacrylanilide and m-methoxyacrylanilide, for example, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether Vinyl ethers, vinyl chloride, vinylidene chloride, vinylidene cyanide, such as 1-methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1,2-ethylene, 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 polymerized units, number average molecular weight (MN)
However, those having a weight average molecular weight (MW) of 500 to 150,000 are preferred.

More preferably, a polymer compound having a vinyl acetate polymer unit (particularly one having 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) of 10,000
It is preferably from 00 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 example.

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 for use as a color proof. In this case, the image-forming layer of the colored image-forming material, that is, the colored photosensitive layer, changes its tackiness imagewise upon imagewise exposure to form a colored image portion.

Dyes and / or pigments are added as colorants in the colored photosensitive layer. In particular, when used for color proofing, pigments and dyes having the same color as the required ordinary colors, that is, yellow, magenta, cyan, and black are required, but other metal powders, white pigments, and fluorescent pigments are required. Also used. When applying the present invention to a color proof, many pigments and dyes known in the art can be used, as described below.

(C.I means color index). Victoria Pure Blue (CI 42595) Auramine (CI 41000) Katilon 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 (CI 2109
0) Lionol Yellow GRO (CI 21090) Shimla First Yellow 8GF (CI 2110
5) Benzidine Yellow 4T-564D (CI 2109)
5) Shimla Fast Red 4015 (CI 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 may be determined by those skilled in the art in consideration of the target optical density and the image-like tackiness of the colored photosensitive layer. It can be determined by a known method. For example,
In the case of dyes, the content is preferably 5% to 75% by weight.
%, In the case of pigments, the content is preferably 5% by weight.
90% is suitable.

The film thickness of the colored photosensitive layer is determined by a method known to those skilled in the art according to the target optical density, the kind of the coloring agent used in the colored photosensitive layer (dye, pigment, carbon black) and its content. but it is, preferably typically the is used in the range of ^{0.1g / m 2 ~5g / 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. Examples of the plasticizer include various low molecular compounds such as phthalates, triphenyl phosphates and maleates, and examples of the coating improver include surfactants such as a fluorine-based surfactant and ethyl cellulose polyalkylene ether. Nonionic activators and the like.

A protective layer may be used in the image forming material of the present invention, if necessary. Any known protective layer can be used. Specifically, polyvinyl alcohol, celluloses, polyethylene terephthalate, etc. can be used. However, the gas permeability is appropriately selected according to the type of the image forming layer to be used. That is, when a material such as a photopolymerizable photosensitive composition whose image formation is inhibited by oxygen in the air during exposure is used as the image forming layer, a protective layer having low gas permeability may be provided. preferable.

[0080]

EXAMPLES Examples of the present invention will be described below together with comparative examples. However, the present invention is not limited by the examples described below. Example 1 An ethylene-vinyl acetate copolymer (Evaflex, manufactured by Mitsui DuPont Chemical Co., Ltd.) was applied onto a polyethylene terephthalate film having a thickness of 75 μm so as to have a thickness of 30 μm by an extrusion laminating method. On the other hand, thickness 25
On a polyethylene terephthalate film having a thickness of μm, the following coating liquid for the uppermost release layer was applied so as to have a dry film thickness of 0.7 μm.

Coating solution for top layer of release layer Low density polyethylene (Milason, manufactured by DuPont Mitsui Chemicals, Ltd.) 100 parts by weight pentaerythritol triacrylate 100 parts by weight 2,4-diethylthioxanthone 3 parts by weight P-dimethylaminobenzoic acid Ethyl ester 3 parts by weight

The coated surfaces were superposed on each other, and using a fast laminator 8b-700 special type (manufactured by Taisei Laminator Co., Ltd.), pressure 4 kg / cm ² , passing speed 35 cm / min, roller surface temperature 40 ° C. The two layers were bonded together by a nip between the rollers under the conditions, and a release layer having a two-layer structure of low density polyethylene as the uppermost layer was formed.

Next, a coating solution for a colored photosensitive layer having the following composition was applied on the release layer so that the dry film thickness was 3 μm. A 6 μm-thick polyethylene terephthalate film was laminated on the dried colored photosensitive layer to give a cover sheet, thereby obtaining an image forming material.

Colored photosensitive layer solution (cyan) Vinyl acetate-vinyl versatate copolymer (80 parts by weight / 20 parts by weight) 4.0 g Pentaerythritol triacrylate 4.0 g Michler's ketone 0.4 g 2-Ethylanthraquinone 0.4 g Rio Nolblue FG7330 (manufactured by Toyo Ink Co., Ltd.) 0.8 g Methyl ethyl ketone 100 g

The transparent support side of this image-forming material and the plate control wedge (PCW, made by UGRA) were brought into close contact with each other, imagewise exposed by a UV printer, HMW-201KB (made by Oak Manufacturing Co., Ltd.), and then covered. The sheet was peeled off, the image side was overlaid on the art paper, and the pressure was 4 kg / cm ² and the passing speed was 3 using the first laminator 8b-700 special type (Taisei Laminator Co., Ltd.).
When transferred at a nip between rollers under the conditions of a roller surface temperature of 5 cm / min and a roller surface temperature of 80 ° C., the colored image of the unexposed portion was peeled from the uppermost layer of the release layer and transferred onto the art paper with good reproducibility.

Example 2 A transferred image having good reproducibility was obtained in the same manner as in Example 1 except that the coating liquid for the uppermost release layer was changed to the following.

Coating liquid for top layer of release layer LA-544M2 (reactive microgel having a methylol group on the surface, 30% aqueous dispersion, Hoechst Synthesis Co., Ltd.)
Made)

Comparative Example 1 On a polyethylene terephthalate film having a thickness of 75 μm, the following release layer coating solution was applied so as to have a dry film thickness of 30 μm.

Release Layer Coating Liquid Low Density Polyethylene (Mirason, manufactured by Mitsui DuPont Chemicals Ltd.) 100 parts by weight pentaerythritol triacrylate 100 parts by weight 2,4-diethylthioxanthone 3 parts by weight p-dimethylaminobenzoic acid ethyl ester 3 parts by weight

On this release layer, a colored photosensitive layer was applied in the same manner as in Example 1 and a cover sheet was laminated to obtain an image forming material. When the same procedure was performed as in Example 1 below, the results shown in Table 1 were obtained.

Comparative Example 2 The same procedure as in Comparative Example 1 was carried out except that the following releasing layer coating solution was applied onto a polyethylene terephthalate film having a thickness of 75 μm so that the dry film thickness was 30 μm, and the results shown in Table 1 were obtained. It was

Release Layer Coating Liquid LA-544M2 (Reactive microgel having a methylol group on the surface, 30% aqueous dispersion, Hoechst Synthesis Co., Ltd.)
Made)

[0093]

[Table 1]

[0094]

According to the present invention, it is possible to provide an image forming material and a method for producing a release layer which can improve the reproducibility of small dots and the transferability, and can improve the sensitivity and reduce the production cost.

Claims (2)

[Claims] 1. An image forming material having two or more multi-layered release layers and a colored photosensitive layer on a support in this order, wherein the uppermost release layer is photosensitive or reactive with the colored photosensitive layer during exposure. The image forming material, wherein the colored photosensitive layer is a layer whose adhesiveness is changed by light irradiation. 2. A method for producing two or more multi-layered release layers, wherein, when the release layers are multi-layered, the uppermost release layer is provided on a temporary support and then the uppermost release layer surface is added. A method for producing a release layer, comprising applying a pressure layer to a lower release layer provided on a support to peel off the temporary support to form a multi-layer release layer.