JP3191179B2 - Image recording medium and image recording method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image recording medium utilizing photopolymerization. The present invention relates to an image recording method used.

[0002]

2. Description of the Related Art Conventionally, many image forming methods using a photopolymerizable or photocrosslinkable material are known. For example, a photosensitive composition containing a compound capable of addition polymerization or cross-linking and a photopolymerization initiator, and, if necessary, a binder component or a colorant comprising an organic polymer compound or the like is coated on a substrate to form a photosensitive image. As a recording medium, the photosensitive layer is subjected to image exposure of a desired image, the exposed portion is cured, and the unexposed portion is dissolved and removed to form an image composed of an exposed and cured portion, such as a lithographic printing plate or a color proof. How to make a hard copy,
JP 52-9501, JP 52-150104, JP 53-40537, JP 53
As disclosed in -53404 and the like, at least one of the above-described photosensitive compositions is formed between two transparent supports, and a desired image is image-exposed from the transparent support side. Utilizing the resulting change in the adhesive force of the photosensitive composition to a support, a method of forming an image on a support by peeling development, and JP-A-58-88740 and JP-A-62-125358 are disclosed. A photosensitive layer in which a photopolymerizable composition as described above is encapsulated in microcapsules is provided on a substrate, and the photosensitive composition in the microcapsules is imagewise exposed and cured, and then used for an image receiving body or a printing plate. Superimposed on the substrate and pressurized to destroy the unexposed microcapsules and at the same time transfer the photosensitive composition in the microcapsules onto the image receiving body or the printing plate substrate to produce a hard copy or a lithographic printing plate Method
No. 37-18979, JP-A-49-39683, JP-A-60-30400, JP-A-63-1
As disclosed in No. 47162, etc., a photopolymerizable compound and a photopolymerization initiator, and a photosensitive composition containing a binder component and a colorant comprising an organic polymer compound and the like, if necessary, on a substrate. To form a photosensitive image recording medium, image-exposing a desired image to the photosensitive layer, curing the exposed portion, and transferring the unexposed portion onto another substrate by heating and / or pressing. In some cases, an image formed of a photosensitive layer in an exposed portion or an unexposed portion is obtained. In particular, the latter three methods do not use a liquid developer, and are therefore preferable from the viewpoints of environmental pollution, worker safety, and downsizing of the apparatus.

[0003] Peeling development is dry development, but image formation is carried out essentially by utilizing the difference in adhesive strength (adhesive strength) between the exposed and unexposed portions of the photosensitive layer and the printing plate support and release substrate. Therefore, it is difficult to completely remove the unexposed portion, and it is difficult to obtain a high-resolution image.
In the method of encapsulating the photosensitive composition in the microcapsules, it is necessary to reduce the particle size of the microcapsules in order to obtain high resolution. An extremely large force is required for breaking, and a large device is required, which is not preferable. On the other hand, the method of forming an image by transferring an unexposed portion is a method capable of recording an image by a relatively simple process, but in order to sufficiently provide a difference in transferability between the exposed portion and the unexposed portion. However, in the prior art, the polymerization of the exposed portion needs to proceed sufficiently, and the conventional technology requires a very large exposure energy. It has been conventionally known that it is effective to provide an oxygen barrier layer on the photosensitive layer in order to increase the degree of polymerization in the exposed part. However, in the case of dry processing, the oxygen barrier layer is peeled and removed after exposure. And a heavy load is imposed on the device design.

Further, conventionally, since the composition of the photosensitive layer contains a polymerizable compound and a polymer binder as main components, it has been difficult to obtain a high-resolution image during transfer. Therefore, it cannot be applied to high-definition digital recording by laser scanning exposure or the like.

Further, in the conventional image recording medium on which an image is recorded by transferring an unexposed portion, since the unexposed portion of the photosensitive layer has an adhesive property even at room temperature, a protective layer (or a cover) is formed on the photosensitive layer. Sheet) does not have good storage stability at room temperature,
The sheet-like image recording medium could not be wound up and stored for a long period of time.

[0006] In order to solve this problem, a technique of incorporating an extender in a photosensitive layer has been disclosed (Japanese Patent Laid-Open No. 4-17 / 1990).
No. 7253), according to additional tests by the present inventors, although storage stability was improved, no effect could be confirmed with respect to sensitivity and resolution.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a high-sensitivity, high-resolution image recording with a completely dry processing and a simple process. It is to provide an image recording medium that can be used.

[0008]

The above object of the present invention is attained by the following constitutions. That is, (1) the photosensitive layer provided on the support is image-exposed, and an exposed portion and an unexposed portion of the photosensitive layer are caused to have a difference in adhesiveness when heated and / or pressurized. And / or in an image recording medium on which an image is transferred and formed by applying pressure, the photosensitive layer has a polymerizable compound having at least one ethylenically unsaturated bond, a photopolymerization initiator, and an average particle diameter of the photosensitive layer.
An image recording medium characterized by containing a filler larger than the average film thickness .

(2) The image recording medium according to (1), wherein the filler is organic and / or inorganic fine particles.

(3) The photosensitive layer further contains a heat-fusible compound.
Characterized by comprising (1) Symbol placement of the image recording medium.

(4) The image recording medium according to (3), wherein the heat-fusible compound is contained in a dispersed state.

(5) On a support, a polymerizable compound having at least one ethylenically unsaturated bond, a photopolymerization initiator, and a filler having an average particle size larger than the average thickness of the photosensitive layer.
Image-exposing a photosensitive layer of an image recording medium provided with a photosensitive layer containing a material to cause a difference in adhesiveness between an exposed portion and an unexposed portion of the photosensitive layer when heated and / or pressurized. An image recording method for transferring and forming an image by heating and / or pressing.

(6) The photosensitive layer of the image recording medium is further heated.
(5) The image recording method according to (5), containing a fusible compound. Hereinafter, the present invention will be described more specifically.

The image recording medium of the present invention basically comprises a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and a filler having an average particle size larger than the average thickness of the photosensitive layer.
A photosensitive layer containing a material is provided on a support. Further heat melting
It is also preferable to add a neutral compound.

As the support, known materials can be used without any particular limitation as long as they have sufficient mechanical strength, heat resistance and dimensional stability. Specifically, polyester films such as polyethylene terephthalate, polyethylene naphthalate, and aramid resin; cellulose resin films such as cellulose triacetate and cellulose diacetate;
In addition to plastic films such as polyvinyl chloride, polyethylene, polypropylene, polystyrene, polyvinyl alcohol, cellophane, polysulfone, polyimide, polycarbonate, polyamide, polyetheretherketone, polyarylate, ABS, etc., thin paper such as condenser paper, glassine paper, etc. Coated paper, synthetic paper,
Metals, metal foils, various ceramic films, etc. alone,
Alternatively, it can be used as a composite of two or more. Further, it is optional to add a filler, a stabilizer, an additive and the like to these base materials as necessary. The thickness of the support may be in the range of 1 to 500 μm, preferably in the range of 5 to 200 μm.

The polymerizable compound having at least one ethylenically unsaturated bond contained in the photosensitive layer includes:
Known monomers capable of addition polymerization or crosslinking can be used without limitation. Specific compounds include, for example, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydrofuryl Furfuryloxyhexanolide acrete, ε- of 1,3-dioxane alcohol
Monofunctional acrylates such as acrylates of caprolactone adducts and 1,3-dioxolane acrylate, or methacrylic acid, itaconic acid, crotonic acid, and maleic acid ester obtained by replacing these acrylates with methacrylate, itaconate, crotonate, and maleate; ethylene; Glycol diacrylate, triethylene glycol diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcinol diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, diacrylate of neopentyl glycol hydroxypivalate , Neopentylglycol adipate diacrylate, neopentylglycol hydroxypivalate Diacrylate of ε-caprolactone adduct of phenol, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1,3-dioxane diacrylate, tricyclodecane dimethylol acrylate Ε of tricyclodecane dimethylol acrylate
-Caprolactone adducts, bifunctional acrylates such as diacrylate of diglycidyl ether of 1,6-hexanediol, or methacrylic acid, itaconic acid, crotonic acid in which these acrylates are replaced with methacrylate, itaconate, crotonate or maleate , Maleic acid ester; trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate , Dipentaerythritol hexaacrylate ε-caprolactone adduct, pyrogallol Polyacrylates such as acrylate, propionic acid / dipentaerythritol triacrylate, propionic acid / dipentaerythritol tetraacrylate, hydroxypivalaldehyde-modified dimethylolpropane triacrylate, or methacrylates, itaconates of these acrylates, Examples thereof include methacrylic acid, itaconic acid, crotonic acid, and maleic acid ester instead of crotonate and maleate. Among these, acrylate and methacrylate compounds can be particularly preferably used. These compounds can be used alone or in combination of two or more.

In addition, as a compound capable of addition polymerization or cross-linking, a so-called prepolymer obtained by introducing acrylic acid or methacrylic acid into an oligomer having an appropriate molecular weight and imparting photopolymerizability can also be suitably used. These may be used alone or as a mixture of two or more prepolymers, or may be used as a mixture with the above-mentioned monomers.

Examples of the prepolymer include adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, pyromellitic acid, fumaric acid, glutaric acid, Polybasic acids such as pimelic acid, sebacic acid, dodecanoic acid, and tetrahydrophthalic acid, and ethylene glycol, propylene glycol, diethylene glycol, propylene oxide, 1,4-butanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, and glycerin Acrylates in which (meth) acrylic acid has been introduced into a polyester obtained by bonding polyhydric alcohols such as trimethylolpropane, pentaerythritol, sorbitol, 1,6-hexanediol, and 1,2,6-hexanetriol Kind; bisphenol A ·
Epoxy acrylates with (meth) acrylic acid introduced into epoxy resin such as epichlorohydrin / (meth) acrylic acid, phenol novolak / epichlorohydrin / (meth) acrylic acid; ethylene glycol / adipic acid / tolylene diisocyanate / 2-hydroxy Ethyl acrylate, polyethylene glycol tolylene diisocyanate 2-hydroxyethyl acrylate, hydroxyethyl phthalyl methacrylate xylene diisocyanate, 1,2-polybutadiene glycol tolylene diisocyanate 2-hydroxyethyl acrylate,
Urethane acrylate with (meth) acrylic acid introduced into urethane resin like trimethylolpropane, propylene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate; polysiloxane acrylate, polysiloxane diisocyanate-2-hydroxy Silicone resin acrylates such as ethyl acrylate; and alkyd-modified acrylates in which a (meth) acryloyl group is introduced into an oil-modified alkyd resin, and spirane resin acrylates.

As the photopolymerization initiator, known compounds can be used without limitation. For example, one or a combination of two or more of the compounds described on pages 39 to 48 of "Photopolymer Handbook" (edited by the Photopolymer Society, published by the Industrial Research Institute, 1989) can be used.

When a laser light source is used for photopolymerization, especially a semiconductor laser which has recently been remarkably low-priced, has a long life, and has a high output, it is necessary to use a photopolymerization initiator having sensitivity in the red to near infrared. . A borate complex of a cationic dye is preferable as the photopolymerization initiator having sensitivity in red to near infrared.

The borate anion used in the borate complex of the cationic dye is preferably represented by the following general formula (1).

Formula (1) B ⁺ (R ₁ ) (R ₂ ) (R ₃ ) (R ₄ ) In the formula, R ₁ , R ₂ , R ₃ and R ₄ are the same or different. Alkyl groups (eg, ethyl, butyl), aryl groups (eg, phenyl, naphthyl), aralkyl groups (eg, benzyl, phenethyl), alkenyl groups (eg, vinyl, allyl), alkynyl groups (eg, propenyl, butynyl), cycloalkyl Represents a group (for example, cyclopentyl, cyclohexyl), a heterocyclic group (for example, thienyl, pyridyl) or a cyano group, and each group may further have a substituent. Particularly preferably, at least one of R _{1 to} R ₄ is an aryl group, and at least one is an alkyl group.

The aryl group is preferably a phenyl or naphthyl group, and may be substituted with an alkyl group or an alkoxy group. As the alkyl group, an alkyl group having 1 to 12 carbon atoms is preferable, and examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, and decyl. These alkyl groups may be substituted with a halogen atom, an alkoxy group, a hydroxyl group, a cyano group, a phenyl group or the like. Examples of the cationic dye include cationic cyanine, merocyanine, carbocyanine, rhodamine, azomethine, indoaniline, azurenium,
Polymethine, triarylmethane, indoline, thiazine, xanthene, acridine and oxazine dyes.

In order to write an image by scanning exposure using a semiconductor laser as a light source, an infrared-absorbing cationic dye is preferred, and a cyanine-based, azurenium-based, and indoaniline-based dye is particularly preferred. These dyes are described, for example, in Coloring Materials, 61 [4], pp. 215 to 236, and representative specific examples are given below.

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In general, cyanine dyes have a property of discoloring upon exposure (photobleachability), so that the color of the photopolymerization initiator can be eliminated by exposure after image recording. The compound itself is suitable for use as an image recording material.

When a borate complex of a cationic dye is used as a photopolymerization initiator, it is preferable to add a borate anion salt compound as a sensitizer. Preferred borate salt compounds include a quaternary ammonium cation or a quaternary phosphonium cation and the above-mentioned general formula (1)
It is a salt compound which consists of a borate anion represented by these.
As the ammonium cation and the phosphonium cation, tetraalkylammonium and tetraalkylphosphonium are preferable, and as the alkyl group,
Examples thereof include an alkyl group having 1 to 12 carbon atoms (eg, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl). These alkyl groups are halogen atoms, alkoxy groups, hydroxyl groups,
It may be substituted with a cyano group, a phenyl group or the like.

The preferred compounding ratio of the borate complex of the cationic dye to the salt compound of the borate anion as a sensitizer is in the range of 100/1 to 1/20, more preferably 10/1 to 1/20, in terms of molar ratio. The range is 1/10.

As the filler used in the present invention, known fine particles of organic and inorganic compounds can be arbitrarily used as long as they do not excessively deform when an image is transferred and formed.

Specific examples of the compound include inorganic compounds such as silica, titanium oxide, aluminum oxide, zinc oxide, magnesium oxide, zirconium oxide, and aluminum borate; metal carbonates such as calcium carbonate and magnesium carbonate; Metal sulfates such as barium sulfate and magnesium sulfate; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; metal borides such as titanium boride and zirconium boride; titanium carbide, zirconium carbide, niobium carbide and tungsten carbide Metal nitrides; metal nitrides such as titanium nitride, zirconium nitride, and tantalum nitride;
Metal silicides such as titanium silicide, zirconium silicide, molybdenum silicide, other kaolin, clay, talc, diatomaceous earth,
Perlite, bentonite, mica, synthetic mica and the like.

Examples of the organic compound include particles of melamine resin, guanamine resin, styrene-acryl resin, silicone resin, fluorine resin, polymethyl methacrylate, high molecular weight polyethylene and the like.

Particularly preferred compounds include calcium carbonate and silicone resin particles. The color tone of the filler is optional, but when the photosensitive layer contains a dye or pigment and the transferred photosensitive layer is used as a visible image, the filler is substantially colorless, such as an extender. Is preferred.

The shape of the filler is arbitrary and may be irregular, or may be spherical, needle-like, plate-like, column-like, or the like. To spherical are particularly preferred.

The preferred particle size of the filler varies depending on the thickness of the photosensitive layer to be added.
5050 μm (the longest part in the case of irregular shape), more preferably 0.3 to 10 μm. Particularly preferred in the present invention are fine particle fillers having an average particle type of 10 μm or less. The average particle diameter in the present invention is a value obtained by directly measuring the surface of a photosensitive layer provided on a support by observation with an electron microscope.

The relationship between the average particle size of the filler and the film thickness of the photosensitive layer requires that the particle size of the filler be larger than the film thickness of the photosensitive layer. The difference is preferably 10 μm or less, particularly preferably 5 μm or less. As a method of adding a filler to the photosensitive layer, the filler may be directly dispersed in other components constituting the photosensitive layer, or a filler dispersed in an appropriate dispersion medium may be added. Good.

The gist of the present invention is that a filler may be present in a photosensitive layer when an image is transferred and formed. Therefore, the same effect can be obtained even when the image recording medium is formed by coating a filler on a photosensitive layer containing no filler.

The heat-fusible compound preferably used in the present invention is a compound which is solid at room temperature and becomes reversibly liquid when heated. Specific examples of compounds include vegetable waxes such as carnauba wax, candelilla wax, wood wax, ouriculi wax, rice wax, jojoba oil and Espal wax; animal waxes such as beeswax, insect wax, shellac wax and spermaceti wax, and lanolin. Petroleum waxes such as paraffin wax, microcrystalline wax, petrolatum, ester wax and oxidized wax; and mineral waxes such as montan wax, ozokerite and ceresin; Fischer-Tropsch wax, polyethylene wax, montan wax derivatives, paraffin wax derivatives, microcrystalline So-called waxes such as wax derivatives, hardened castor oil, synthetic waxes such as hardened castor oil derivatives, and the like can be mentioned. In addition to these waxes, palmitic acid, stearic acid, margaric acid and benzene Higher alcohols such as palmityl alcohol, stearyl alcohol, behenyl alcohol, marganyl alcohol, myryl alcohol and eicosanol; higher fatty acid esters such as cetyl palmitate, myryl palmitate, cetyl stearate and myryl stearate; acetamide Amides such as amide, propionamide, palmitic amide, stearic amide, behenic amide and amide wax; and higher amines such as stearylamine, behenylamine and palmitylamine are also preferably used. In addition, a low-melting-point thermoplastic resin such as low-molecular-weight polyethylene, polypropylene, polystyrene, polyester, polyamide, and polycaprolactone can also be used.

When the photosensitive layer of the present invention is used for an image recording medium, it is particularly preferable to use a compound having a melting point at 40 to 150 ° C. as the heat-fusible compound. The heat-fusible compound may be dissolved or dispersed in another compound in the photosensitive layer, or may be obtained by dissolving or dispersing the heat-meltable compound in a solvent or a dispersion medium. May be added and mixed in the compound of the above.

In the present invention, it is particularly preferable that the heat-fusible compound is present in a dispersed state in the photosensitive layer. The method of adding the heat-fusible compound in a dispersed state may be such that the heat-fusible compound dispersed in an appropriate dispersion medium by a known method is added and mixed. The average particle size of the dispersed heat-meltable compound is preferably in the range of 0.01 to 20 μm, and more preferably 0.01 to 5 μm.

The amount of the essential components constituting the photosensitive layer of the present invention described above is not particularly limited, but is preferably based on 100 parts by weight of the polymerizable compound having at least one ethylenically unsaturated bond. The photopolymerization initiator is 0.01 to 20 parts by weight, more preferably 0.05 to 10 parts by weight, and the filler is 0.1.
The amount is from 1 to 100 parts by weight, more preferably from 1 to 50 parts by weight, from 5 to 200 parts by weight, more preferably from 10 to 100 parts by weight.

The photosensitive layer of the present invention preferably contains a binder component for the purpose of modifying the present composition and improving the physical properties after curing, in addition to the above components.

As the binder component, an organic high molecular compound is preferable, and this can be appropriately selected according to the purpose of compatibility with other components, tackiness, adhesion, film forming property, developability, printability, improvement, and the like. I just need. Specific compounds include, for example, polymethacrylic acid, polymethyl methacrylate, polyacrylic acid, polyacrylic acid alkyl esters (alkyl groups such as methyl, ethyl and butyl), and acrylic acid alkyl esters (alkyl groups such as methyl, Ethyl, butyl, etc.) and copolymers of acrylonitrile, vinyl chloride, vinylidene chloride, styrene, butadiene, acrylic acid, methacrylic acid, etc .; polyvinyl chloride, vinyl chloride, polyvinylidene chloride, vinylidene chloride, styrene,
Copolymer of styrene-butadiene and acrylonitrile;
Polyacrylonitrile, polyvinyl alcohol, polyvinyl alkyl ether (alkyl groups are methyl, ethyl, propyl, butyl, etc.), polyvinyl alkyl ketone, polystyrene, polybutadiene, polyisoprene, polyamide, polyurethane, polyethylene terephthalate, polyethylene isophthalate; chlorinated polyethylene , Chlorinated polyolefins such as chlorinated polypropylene; chlorinated rubber, cyclized rubber, ethyl cellulose, acetyl cellulose, polyvinyl butyral, polyvinyl formal; other compounds include various itaconic acid copolymers, maleic acid copolymers, and partial esterifications Maleic acid copolymers and the like can be mentioned, and one or more of these compounds can be used in combination. Further, a multicomponent copolymer containing the above compound as a main component in an amount of 30 mol% or more can also be preferably used.

These binder components can be added and mixed in a range of 500 parts by weight or less, more preferably 200 parts by weight or less, based on 100 parts by weight of the polymerizable compound.

The photopolymerizable composition of the present invention may further contain various additives such as a thermal polymerization inhibitor, a coloring agent, a plasticizer, and an oxygen quencher, if necessary.

As the thermal polymerization inhibitor, quinone-based compounds and phenol-based compounds can be used. When a radical polymerization initiator is used, a quinone compound is particularly preferable. Specific compounds include, for example, hydroquinone,
Pyrogallol, p-methoxyphenol, catechol, β
-Naphthol, 2,6-di-t-butyl-p-cresol and the like. Thermal polymerization inhibitor is 10 parts by weight or less, preferably 100 parts by weight of the total amount of the polymerizable compound and the binder, preferably
About 0.01 to 5 parts by weight are added.

As the colorant, carbon black, titanium oxide, iron oxide, phthalocyanine pigment, azo pigment,
Examples include pigments such as anthraquinone pigments, crystal violet, methylene blue, azo dyes, anthraquinone dyes, and cyanine dyes. The coloring agent is based on 100 parts by weight of the total amount of the polymerizable compound and the binder.
0.01 to 50 parts by weight, more preferably 0.01 to 40 parts by weight, is added.

Examples of the plasticizer include phthalic acid esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diisobutyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, isononyl phthalate, dibutyl benzyl phthalate, and diaryl phthalate. Glycol esters such as methyl glycol phthalate, methyl phthalyl ethyl glycolate and methyl phthalyl ethyl glucolate; Phosphate esters such as ricresyl phosphate, triphenyl phosphate, tributyl phosphate and tri-2-ethylhexyl phosphate; butyl Aliphatic monobasic acid esters such as oleate and glycerin monooleate; dibutyl adipate;
Aliphatic dibasic acid esters such as diisobutyl adipate, dioctyl adipate, dioctyl azelate, dibutyl sebacate, dimethyl sebacate, dioctyl sebacate, dibutyl maleate; diethylene glycol dibenzoate, triethylene glycol di-2-ethyl butyrate And other dihydric alcohol esters such as triethyl citrate, glycerin triacetyl ester, and butyl laurate. The plasticizer is preferably used in an amount of 20 parts by weight or less based on 100 parts by weight of the total amount of the polymerizable compound and the binder. Examples of the oxygen quencher include phosphines, phosphonates, phosphites, stannous salt compounds, sulfides,
In addition to disulfides, thiols, thioketones, etc.,
Compounds easily oxidized by oxygen, for example, N, N-dialkylaniline such as N, N-dimethyl-2,6-diisopropylaniline, N, N, 2,4,6-pentamethylaniline, and N-phenylglycine And the like. The addition amount of the oxygen quencher is usually 100% of the total amount of the polymerizable compound and the binder.
It is used in an amount of 20 parts by weight or less based on parts by weight.

The image recording medium of the present invention comprises a photosensitive layer comprising the above-mentioned photopolymerizable composition provided on a support. In order to provide the photopolymerizable composition on the support, the photopolymerizable composition is provided on the support by forming or laminating the support without solvent, or the photopolymerizable composition is dissolved in an appropriate solvent and coated on the support. -The photosensitive layer may be formed by drying. Examples of the solvent for the coating solution include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diisobutyl ketone; esters such as ethyl acetate, butyl acetate, amyl acetate, ethyl propionate, dimethyl phthalate, and ethyl benzoate; Aromatic hydrocarbons such as toluene, xylene, benzene, and ethylbenzene; carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-
Halogenated hydrocarbons such as trichloroethane, monochlorobenzene, chloronaphthalene, and dichloroethane; ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate; and others, dimethylformamide,
Dimethyl sulfoxide, bentoxone and the like can be used.

In the image recording medium of the present invention, in addition to the above-described structure, other layers can be provided as necessary within a range not departing from the object of the present invention.

For example, a layer for controlling the adhesiveness between the support and the photosensitive layer, an oxygen blocking layer on the photosensitive layer, a transport improving layer provided on the side of the support opposite to the surface on which the photosensitive layer is provided. It is also optional to provide an elastic layer or a cushion layer for assisting the adhesion between the photosensitive layer and the image receiving material at the time of transfer, an antistatic layer, and the like.

The layer for controlling the adhesiveness improves the S / N ratio by controlling the transferability of the exposed and unexposed portions of the photosensitive layer during image recording. Specifically, for example, those obtained by treating the surface of a support with a release compound such as a silicone resin, a fluorine resin, or a fluorine-based surfactant, alcohol-soluble polyamide, alcohol-soluble nylon, polyvinyl acetate, polyvinyl chloride, and polyvinyl alcohol A resin obtained by applying a resin such as, on a support can be preferably used.

The image recording medium of the present invention can record an image with a smaller exposure energy than the conventional one without providing an oxygen barrier layer. However, the exposure energy can be further reduced by providing an oxygen barrier layer. Can be done.

The oxygen barrier layer must have low oxygen permeability, have mechanical strength enough to withstand peeling, and have good light transmittance at the photosensitive wavelength of the photopolymerization initiator used (transmittance of 40%).
(Preferably 60% or more)), it is necessary to have high surface smoothness. Specifically, resin films such as polyethylene terephthalate, cellulose triacetate, cellulose diacetate, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, polyethylene, polypropylene, cellophane, polysulfone, polyamide, and polyimide are used alone or in combination of two or more. Can be used as a complex. The thickness of the oxygen barrier layer is 1 to 200 μm, preferably 3 to 50 μm.
Those having a range of μm are preferred.

In order to provide the oxygen barrier layer on the photosensitive layer, a resin film for the oxygen barrier layer is laminated on the photosensitive layer by heating and / or pressing, or the resin for the oxygen barrier layer is dissolved in an appropriate solvent. The solution may be applied and dried on the photosensitive layer. Alternatively, the photosensitive layer may be formed by applying and drying a photosensitive layer on the resin film of the oxygen barrier layer, and then laminating the support on a support by heating and / or pressing.

To perform image recording using the image recording medium of the present invention, after exposing the image from the support side or the oxygen blocking layer side of the image recording medium, the oxygen blocking layer is peeled off if necessary.
The unexposed portion is transferred to the surface of the image receiving material by bringing the photosensitive layer into close contact with the image receiving material and applying heat and / or pressure.
Exposure curing of the formed image is preferable from the viewpoint of improving the fixing property of the image or preventing trapping which is likely to occur when a plurality of colors are transferred in an overlapping manner.

As the image receiving material to which an image is transferred, any material and shape can be used without particular limitation, as long as the material can maintain adhesion to the photosensitive layer at the time of transfer. Typical examples include various papers such as high-quality paper, art paper, coated paper, and synthetic paper (polypropylene, polystyrene or a composite material obtained by laminating them with paper); vinyl chloride resin sheet, ABS resin sheet, polyethylene Single layer of terephthalate film, polyethylene naphthalate film, polyimide film, polyetherimide film, polycarbonate film, polyetheretherketone film, polyarylate film, polysulfone film, polyethersulfone film, etc. Plastic film;
Examples include films formed of various metals, films formed of various ceramics, and the like.

When an image is recorded on an image receiving material having a hydrophilic surface (for example, an aluminum plate or a plastic film subjected to a hydrophilic treatment), it can be used as a planographic printing plate.

If image recording media of different hues (for example, yellow, magenta, cyan, and black) are prepared and sequentially transferred and recorded on the same image receiving material, a full-color image can be formed. The medium can be used as a color proof material or a color print material.

The light source for exposure has a wavelength in an ultraviolet region, a visible light region, or a near infrared region (for example, a certain wavelength range of 200 to 2,000 nm) and generates an electromagnetic wave active to a photopolymerization initiator. Can all be used. For example,
Examples include a laser, a light-emitting diode, a xenon lamp, a halogen lamp, a high-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a tungsten lamp, and a fluorescent tube.

When collective exposure is performed using a xenon lamp, a halogen lamp, a high-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a tungsten lamp, a fluorescent tube, or the like, a negative pattern of a desired exposure image can be formed on an image recording medium by shading. What is necessary is just to overlap and expose the mask material formed of the material.

An array type light source such as a light emitting diode array, a fluorescent tube array, etc., and a light source such as a halogen lamp, a high pressure mercury lamp, a metal halide lamp, a tungsten lamp, a fluorescent tube, etc., are responded to an image signal by an optical shutter material such as a liquid crystal or PLZT. It is also possible to control the exposure. In this case, it is possible to record digital signals by directly writing without using a mask material.

In the case of a laser, light can be converged into a beam and scanning exposure can be performed in accordance with image data. Therefore, the laser is suitable for recording digital signals by directly writing without using a mask material. Further, it is easy to narrow the exposure area to a minute size, and it is possible to form a high-resolution image.

The laser light source used in the present invention may be a solid laser such as a well-known ruby laser, YAG laser, glass laser, etc .; He-Ne laser, He-Xe
Laser, argon laser, krypton laser, nitrogen laser, carbon dioxide laser, carbon monoxide laser,
Other gas lasers such as a discharge excitation molecular laser and an excimer laser; a chemical laser, a dye laser, and a semiconductor laser can be used. In particular, an argon laser, a He-Ne laser, a semiconductor laser and the like are preferably used. Since the oscillation wavelength of the semiconductor laser can be changed by its composition, it is appropriately selected according to the photosensitive wavelength range of the photosensitive composition to be used. Examples of the composition of the semiconductor laser preferably used and its oscillation wavelength range are, for example, InGaP laser (0.65 to 1.0 μm), AlGaAs
Laser (0.7 to 1.0 μm), GaAsP laser (0.7 to 1.0 μm)
m), InGaAs laser (1.0 to 3.5 μm), InAsP laser (1.0 to 3.5 μm), CdSnP ₂ laser (1.01 μm), GaSb laser (1.53 μm) and the like.

[0067]

EXAMPLES The present invention will be described below based on examples, but embodiments of the present invention are not limited to these.

First, an example of the effect of the filler in the present invention will be described.

Example 1 On a transparent polyethylene terephthalate film (Lumilar # 100, manufactured by Toray Industries, Inc.) having a thickness of 100 μm, polyvinyl alcohol (Gosenol GL-05, manufactured by Nippon Synthetic Chemical Company) was used.
Was coated on a support having a thickness of 0.2 μm by a wire bar coating method so as to have a dry film thickness of 1.5 μm to form a photosensitive layer.

Photopolymerizable composition dipentaerythritol hexaacrylate 100 parts by weight (Nippon Kayaku Co., Ltd .: DPHA) Chlorinated polyethylene 50 parts by weight (Sanyo Kokusaku Pulp Co., Ltd .: Supercron 907LTA) Silicone resin particles (Toshiba Silicone Co., Ltd.) : Tospearl 120) 10 parts by weight Magenta pigment (manufactured by Mikuni Dyestuffs Co., Ltd .: MHI-527, 20 parts by weight for process ink methyl ethyl ketone dispersion of magenta pigment) Borate complex of cationic dye (IR-1) 3 parts by weight Organic boron compound (BTPB)・ TBA) 6 parts by weight (tetrabutylammonium salt of butyltriphenylboron) MEK (methyl ethyl ketone) 800 parts by weight The average particle size of Tospearl 120 was observed by microscope.
It was about 2 μm.

A polyethylene terephthalate (PET) film having a thickness of 25 μm was pressed and laminated on this photosensitive layer to prepare an image recording medium according to the present invention (referred to as recording medium-1 of the present invention). A negative mask of a silver halide film on which a negative pattern of a desired image was formed was superimposed on the pressed and laminated PET film of No. 1, and a xenon flash lamp (Xenofax FX180 manufactured by Riso Kagaku Co., Ltd.) was used. Batch exposure was performed at 100 mJ / cm ² . Thereafter, the PET film on the photosensitive layer was peeled off, the photosensitive layer surface was overlaid on art paper (Mitsubishi Paper Corp .: Mitsubishi Tokuyo Art 62.5 kg), and heated and pressed through a hot roll under the following conditions.
The unexposed portion of the photosensitive layer was transferred onto art paper.

Heating / pressing conditions Temperature: 120 ° C. Pressure: 2 kg / cm ² Speed: 2 cm / sec After the sample was cooled to room temperature, the support was peeled off.
The exposed portions of the photosensitive layer were peeled off together with the support, and a uniform magenta image composed of the unexposed portions of the photosensitive layer was formed on the art paper.

The formed image was subjected to batch exposure using the above-described xenon flash lamp with an exposure time of 1 millisecond and an exposure energy of 100 mJ / cm ² , and a magenta image having the same color tone and fixability as the printed matter was obtained. .

Next, after exposing the image recording medium-1 by masking the resolution chart, an image was formed by the above-described processing and observed. As a result, a resolution of 60 lines / mm or more was obtained.

Example 2 Example 1 was repeated except that the photopolymerizable composition was changed to the following composition.
In the same manner as in the above, recording medium-2 of the present invention was prepared.

Photopolymerizable composition diallyl isophthalate prepolymer 50 parts by weight (manufactured by Daiso Corporation: Isodap) dipentaerythritol hexaacrylate (mentioned above: DPHA) 50 parts by weight calcium carbonate (manufactured by Tsuchiya Kaolin Industries: ASP-100) 10 parts by weight 3,3-dimethyl-4-methoxybenzophenone 5 parts by weight Michler's ketone 2 parts by weight Magenta pigment (described above: MHI-527) 15 parts by weight MEK 800 parts by weight The average particle size of calcium carbonate in this example was measured using a microscope. It was about 2.5 μm by observation.

A plate control wedge (manufactured by UGRA) is provided on the pressed and laminated PET film side of the recording medium-2.
And exposed to light of 1000 mJ / cm ^{2 using} a 1.5 kw ultra-high pressure mercury lamp. Thereafter, when an image was transferred and formed on art paper in the same manner as in Example 1, curing was sufficiently advanced up to the sixth wedge step, and the seventh and higher steps were transferred as images.

Examination of the reproducibility of the halftone dots and fine line portions on the same control wedge revealed that 2-98% of halftone dots of 150 lines / inch and a line width of 10 μm were well reproduced.

Example 3 Example 1 was repeated except that the photopolymerizable composition was changed to the following composition.
In the same manner as in the above, recording medium-3 of the present invention was prepared.

Photopolymerizable composition dipentaerythritol hexaacrylate (supra: DPHA) 100 parts by weight Chlorinated polyethylene (supra: Supercron 907LTA) 50 parts by weight Silicone resin particles (Toshiba 130, manufactured by Toshiba Silicone Co., Ltd.) 10 parts by weight Part Magenta pigment (mentioned above: MHI-527) 5 parts by weight Cation dye borate complex (IR-1) 3 parts by weight Organic boron compound (BTPB / TBA) 6 parts by weight 1-phenyl-5-mercaptotetrazole 3 parts by weight N , N, 2,4,6-Pentamethylaniline 3 parts by weight MEK 800 parts by weight Tospearl 130 has an average particle size of about 3 μm.

When the same evaluation as in Example 1 was carried out using the recording medium 3 thus prepared, a magenta image having a color tone equivalent to that of the printed matter and good fixability was obtained.

Next, after exposing the recording medium-3 with the resolution chart as a mask, an image was formed by the above-described processing and observed. As a result, a resolution of 60 lines / mm or more was obtained.

Example 4 On the photosensitive layers of the recording media-1, 2, and 3 prepared in Examples 1 to 3, a 25 μm-released PET film (manufactured by Diafoil Hoechst Ltd .: MRH) was applied. After pressurizing and laminating at 4 ° C. to prepare recording media-4, 5, and 6, image exposure was performed under the same conditions as in Example 1, the laminated PET film was peeled off, and an image was formed in the same manner as in Example 1. As a result of recording, a magenta image having the same color tone and good fixability as the printed matter was obtained.

Next, after exposing these recording media by masking the resolution chart, forming an image by the above-described processing and observing the resolution, all the recording media were 60 lines / mm.
That was all.

Example 5 Recording media 7, 8, and 9 were prepared and evaluated in the same manner as in Example 4 except that the pigment in the photosensitive layer composition was changed to the following. As a result, a uniform yellow image, cyan image, and black image having no color turbidity and excellent fixability were obtained just like the printed matter.

Next, after exposing these recording media by masking the resolution chart, forming an image by the above-described processing and observing them, it was found that all had a resolution of 60 lines / mm or more.

Recording medium-7: MHI-534 (MEK dispersion of yellow pigment manufactured by Mikuni Dye Co., Ltd.) Recording medium-8: MHI-454 (Magenta pigment M manufactured by Mikuni Dye Co., Ltd.)
EK dispersion) Recording medium-9: MA7 (Mitsubishi Kasei carbon black MA # 10)
0 MEK dispersion) Example 6 Recording media-3, 7, 8, 9 prepared in Examples 3 and 5
Then, exposure was performed in the same manner as in Example 1 using four positive films formed by separating the full-color image into four colors of yellow, magenta, cyan, and black as masks.

After the exposed yellow recording medium-7 was transferred onto art paper under the conditions of Example 1, the transferred image was transferred to a xenon flash lamp (see above: Xenofax FX).
180), exposure time 1 millisecond, exposure energy 100mJ
/ Cm ² to obtain a yellow image. A magenta image, a cyan image, and a black image were transferred onto the obtained yellow image by repeating the same method sequentially using recording media-3, 8, and 9. When the four colors were overlaid and transferred with accurate alignment, a full-color image faithful to the original image on which the mask was formed was obtained. The obtained image gave the impression exactly the same as the printed matter.

Example 7 Using the recording mediums 1, 3, 4, 6, 7, 8, and 9 of the present invention, image exposure was performed by laser scanning exposure under the following conditions, and the scanning speed was changed to change the scanning speed. Energy was measured.

Exposure condition Light source: Semiconductor laser (Sharp: LT090MD, output 1)
00mW) Principal wavelength: 830 nm Average energy density of light applied to the photosensitive surface: 50 mJ / cm ² Beam diameter: 8 μm Scanning pitch: 5 μm Comparative Example 1 From the photopolymerizable compositions of Examples 1, 3, 4 and 5, After preparing comparative recording media-1 to 7 except for the filler alone and performing exposure with a semiconductor laser in the same manner as in Example 7, Example 1 was performed.
Image recording was performed under the same conditions as described above. The energy and resolution required for exposure are shown below together with the results of Example 7. Recording medium Exposure energy (mJ / cm ² ) Resolution (lines / mm) Invention 1 40 100 〃 3 15 120 〃 4 3 120 or more ６ 6 2 120 or more ７ 7 3 120 or more ８ 8 2 120 or more ９ 9 4 120 or more Comparison 1 700 55 〃2 320 70 〃3 60 85 〃4 40 80 〃5 40 90 ６6 40 80 ７7 80 75 Comparative Example 2 The filler in the photopolymerizable composition of Example 2 is as follows: The recording media 8 to 10 for comparison were prepared by changing the values, and the same evaluation as in Example 2 was performed.

Comparison -8: 30 parts by weight of talc (FMS), LMS-100, particle size 1 μm, 30 parts by weight Comparison-9: Silica (Nippon Aerosil Co., Ltd .: Aerosil OX50, particle size 0.04 μm) 30 parts by weight Comparison— 10: No filler In all samples, the third or more wedges were transferred as images to art paper. When the reproducibility of halftone dots and thin lines on the same control wedge was examined,
Only 10-93% of dots per line / inch and line width of 40 μm could be reproduced.

Comparative Example 3 A comparative recording medium-11 was prepared by changing the filler of Example 3 to another silicone resin particle (Tosiba Silicone: Tospearl 108, average particle diameter 0.8 μm). Similarly, exposure was performed with a semiconductor laser, and the exposure energy and resolution required for image formation were examined. The results were 320 mJ / cm ² and 90 lines / mm.

Next, examples showing the effects of the heat-fusible compound of the present invention will be described.

Example 8 A photopolymerizable composition having the following composition was dried on a support in which polyvinyl alcohol was provided at a thickness of 0.2 μm on a transparent PET film having a thickness of 100 μm as in Example 1. The photosensitive layer was formed by applying a coating having a thickness of 1.0 μm by a wire bar coating method.

Photopolymerizable composition dipentaerythritol hexaacrylate (supra: DPHA) 100 parts by weight Chlorinated polyethylene (supra: Supercron 907LTA) 50 parts by weight Carnauba wax (MEK dispersion) 50 parts by weight Magenta pigment (previous Source: MHI-527) 20 parts by weight Cation dye borate complex (IR-1) 3 parts by weight Organic boron compound (BTPB / TBA) 6 parts by weight MEK 800 parts by weight Further, a PET film having a thickness of 25 μm is formed on the photosensitive layer. Was pressed and laminated to prepare a recording medium-10 of the present invention.

A negative mask of a silver halide film on which a negative pattern of a desired image was formed was superimposed on the pressed and laminated PET film, and a batch exposure was performed under the same conditions using the same xenon flash lamp as in Example 1.

Thereafter, the PET film on the photosensitive layer was peeled off, the photosensitive layer surface was overlaid on the same art paper as in Example 1, and heated and pressed through a hot roll under the following conditions.
The unexposed portion of the photosensitive layer was transferred onto art paper. Heating / pressurizing conditions Temperature: 85 ° C Pressure: 2 kg / cm ² Speed: 2 cm / sec After the sample was cooled to room temperature, the support was peeled off.
The exposed portions of the photosensitive layer were peeled off together with the support, and a uniform magenta image composed of the unexposed portions of the photosensitive layer was formed on the art paper.

The formed image was subjected to batch exposure using the above-described xenon flash lamp with an exposure time of 1 millisecond and an exposure energy of 100 mJ / cm ² , and a magenta image having the same color tone and fixability as in printing was obtained. .

Next, after exposing the recording medium-10 by masking the resolution chart, an image was formed by the above-described processing and observed. As a result, a resolution of 60 lines / mm or more was obtained.

Example 9 Example 8 was repeated except that the photopolymerizable composition was changed to the following composition.
In the same manner as in the above, recording medium-11 of the present invention was prepared.

Photopolymerizable composition diallyl isophthalate prepolymer (mentioned above: isodap) 50 parts by weight dipentaerythritol hexaacrylate (mentioned above: DPHA) 100 parts by weight carnauba wax (MEK dispersion) 50 parts by weight 3,3- Dimethyl-4-methoxybenzophenone 9 parts by weight Michler's ketone 3 parts by weight Magenta pigment (mentioned above: MHI-527) 20 parts by weight MEK 800 parts by weight A plate control wedge (manufactured by UGRA) )
Exposure equivalent to 1000 mJ / cm ² was performed using a 1.5 kW ultra-high pressure mercury lamp.
Thereafter, when an image was transferred and formed on art paper in the same manner as in Example 8, curing was sufficiently progressed up to the sixth wedge step, and the seventh and higher steps were transferred as images. When the reproducibility of halftone dots and fine line portions on the same control wedge was examined, halftone dots 2 to 9 of 150 lines / inch were examined.
Line widths of 8% and 10 μm were successfully reproduced.

Example 10 Example 8 was repeated except that the photopolymerizable composition was changed to the following composition.
In the same manner as in the above, recording medium-12 of the present invention was prepared.

Photopolymerizable composition dipentaerythritol hexaacrylate (supra: DPHA) 100 parts by weight Chlorinated polyethylene (supra: Supercron 907LTA) 50 parts by weight Carnauba wax (MEK dispersion) 50 parts by weight Magenta pigment (previous Source: MHI-527) 20 parts by weight Borate complex of cationic dye (IR-1) 3 parts by weight Organic boron compound (BTPB / TBA) 6 parts by weight 1-phenyl-5-mercaptotetrazole 3 parts by weight N, N-2, 4,6-Pentamethylaniline 3 parts by weight Methyl ethyl ketone 800 parts by weight Using the recording medium thus prepared, evaluation was performed in the same manner as in Example 8, and a magenta image having a color tone equivalent to that of the printed matter and good fixability was obtained. Was done.

Next, after exposing the recording medium-12 by masking the resolution chart, an image was formed by the above-described processing and observed. As a result, a resolution of 60 lines / mm or more was obtained.

Example 11 Recording media-13 to 19 were prepared and evaluated in the same manner as in Example 1 except that the carnauba wax dispersion contained in the photopolymerizable composition of Example 10 was changed to the following compound. A magenta image having a color tone equivalent to that of the printed matter and good fixability was obtained.

Next, after exposing the recording medium by masking the resolution chart, an image was formed by the above-described processing and the resolution was observed.

Recording Medium-13: MEK dispersion of paraffin wax (Nippon Seiro Co., Ltd .: HNP-10) Recording Medium-14: Polyethylene wax (manufactured by Sanyo Chemical Co., Ltd.)
MEK dispersion of Sunwax 151P) Recording medium-15: Polystyrene (SB-75, manufactured by Sanyo Chemical Industries, Ltd.)
Solution of MEK Recording medium-16: MEK solution of polycaprolactone (manufactured by Daicel Chemical: Plaxel H-1P) Recording medium-17: MEK solution of stearyl alcohol Recording medium-18: Fischer-Tropsch wax (manufactured by Kato Yoko Co., Ltd.) : MEK dispersion of Sasol C1) Recording medium-19: MEK dispersion of behenic acid The results are summarized below.

Recording medium Resolution (lines / mm) Recording medium Resolution (lines / mm) 13 60 or more 17 60 14 60 or more 18 60 or more 15 55 19 60 or more 16 50 Example 12 To the photopolymerizable composition of Example 10, Recording media-20, 21, and 22 of the present invention were prepared and evaluated in the same manner as in Example 8 except that the amount of the carnauba wax dispersion contained was changed as described below. A magenta image having excellent fixability was obtained.

Next, after exposing these recording media by masking the resolution chart, an image was formed by the above-described processing, and the resolution was observed. The results are shown below. Recording medium Carnauba wax addition amount Resolution (book / mm) 205 5 parts by weight 55 21 25 parts by weight 60 or more 22 100 parts by weight 60 or more Example 13 Except that the pigment in the photosensitive layer composition was changed to the following, In the same manner as in Example 10, recording media-23, 24, and 25 were prepared and evaluated. As a result, there is no color turbidity just like printed matter,
In addition, uniform yellow, cyan and black images having excellent fixability were obtained.

Next, after exposing these recording media by masking a resolution chart, forming an image by the above-described processing and observing, a resolution of 60 lines / mm or more was obtained.

Recording Medium-23: MHI-534 (MEK dispersion of yellow pigment manufactured by Mikuni Dye Co., Ltd.) Recording Medium-24: MHI-454 (Magenta pigment M manufactured by Mikuni Dye Co., Ltd.)
EK dispersion) Recording medium-25: MA7 (MEK dispersion of Mitsubishi Carbon) Example 14 Recording medium-12 and 23, 24, 25 prepared in Examples 10 and 13
Each was exposed in the same manner as in Example 8 using four positive films formed by separating a full-color image into four colors of yellow, magenta, cyan, and black. After the exposed yellow recording medium-23 was transferred onto art paper under the conditions of Example 8, the transferred image was collectively exposed under the same exposure conditions using the same xenon flash lamp to obtain a yellow image. A magenta image, a cyan image, and a black image were sequentially transferred onto the obtained yellow image in the same manner using recording media-12, 24, and 25 in the same manner. When the four colors were overlaid and transferred with accurate alignment, a full-color image faithful to the original image on which the mask was formed was obtained. The resulting image gave the exact same impression as the printed matter.

Example 15 Using the recording media of Examples 8 and 10 to 13, image exposure was performed by laser scanning exposure under the following conditions, and the energy required for exposure was measured while changing the scanning speed.

Exposure conditions Light source: Semiconductor laser (Sharp: LT090MD, output 1)
00MW) main wavelength: 830 nm Average irradiated light on the photosensitive surface energy density: 50 mJ / cm ² beam diameter: 8 [mu] m scan pitch: 5 [mu] m also developed by the method described in Example 8 to each of the exposed samples evaluated As a result, magenta, yellow, cyan, and black images having no color turbidity and excellent fixability were obtained in exactly the same manner as the printed matter. In addition, all of the image recording media which had been subjected to scanning exposure with a laser to form an image had a resolution of 120 lines / mm or more.

Example 16 A recording medium 26 was prepared in the same manner as in Example 8, except that the photopolymerizable composition was changed to the following composition (containing a filler and a heat-fusible compound). Evaluation was similarly performed by laser scanning exposure.

Photopolymerizable composition dipentaerythritol hexaacrylate (supra: DPHA) 100 parts by weight Chlorinated polyethylene (supra: Supercron 907LTA) 50 parts by weight Carnauba wax (MEK dispersion) 50 parts by weight Silicone resin particles ( The above: Tospearl 130) 10 parts by weight Magenta pigment (the above: MHI-527) 20 parts by weight Borate complex of cationic dye (IR-1) 3 parts by weight Organic boron compound (BTPB / TBA) 6 parts by weight 1-phenyl- 5-mercaptotetrazole 3 parts by weight N, N, 2,4,6-pentamethylaniline 3 parts by weight MEK 800 parts by weight Comparative Example 4 From the photopolymerizable compositions of Examples 8, 10 and 13, only carnauba wax dispersion Were prepared and exposed with a semiconductor laser in the same manner as in Example 15, and then image recording was performed under the same conditions as in Example 8.

The measurement results of the energy required for exposure and the resolution for Examples 15 and 16 and Comparative Example 4 are shown below.

Recording medium Exposure energy (mJ / cm ² ) Resolution (lines / mm) The present invention 10 6 120 or more 〃 12 2 120 or more 2 13 2 120 or more 2 14 2 120 or more 〃 15 3 120 or more 〃 16 2 120 or more 〃 17 2 120 or more 〃 18 5 100 〃 19 7 95 〃 20 8 110 〃 21 3 120 or more 〃 22 3 120 or more 〃 23 6 100 〃 24 2 120 or more 〃 25 2 120 or more 〃 26 0.4 110 Comparison 12 12 65 Comparative Example 5 A comparative recording medium-17 was prepared in which only the carnauba wax dispersion was removed from the photopolymerizable composition of Example 9, and Example 9 was performed. The same evaluation was performed. The fifth or higher level of the wedge was transferred as an image onto art paper. When the reproducibility of halftone dots and thin lines on the same control wedge was examined,
Only 10-93% of dots per line / inch and line width of 40 μm could be reproduced.

[0118]

According to the present invention, image recording with high sensitivity, high resolution and excellent storability can be performed by a completely dry process and a simple process.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI G03F 7/028 G03F 7/028 7/34 7/34 (56) References JP-A-4-177253 (JP, A) JP JP-A-4-172352 (JP, A) JP-A-4-11245 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F 7/004 G03F 7/027 G03F 7/028 G03F 7 / 34

Claims (6)

(57) [Claims] An image exposure is performed on a photosensitive layer provided on a support, and an exposed portion and an unexposed portion of the photosensitive layer are caused to have a difference in adhesiveness when heated and / or pressurized. And / or in an image recording medium on which an image is transferred and formed by applying pressure, the photosensitive layer has a polymerizable compound having at least one ethylenically unsaturated bond, a photopolymerization initiator, and an average particle.
An image recording medium comprising a filler having a diameter larger than the average thickness of the photosensitive layer . 2. The image recording medium according to claim 1, wherein said filler is organic and / or inorganic fine particles. 3. The photosensitive layer further contains a heat-fusible compound.
Claim 1 Symbol placement of the image recording medium and having. 4. The image recording medium according to claim 3, wherein said heat-fusible compound is contained in a dispersed state. 5. A support, on which a polymerizable compound having at least one ethylenically unsaturated bond, a photopolymerization initiator, and a filler having an average particle size larger than the average thickness of the photosensitive layer.
Image-exposing a photosensitive layer of an image recording medium provided with a photosensitive layer containing a material to cause a difference in adhesiveness between an exposed portion and an unexposed portion of the photosensitive layer when heated and / or pressurized. An image recording method for transferring and forming an image by heating and / or pressing. 6. The method according to claim 1, wherein the photosensitive layer of the image recording medium further comprises a hot melt.
The image recording method according to claim 5, further comprising a fusible compound.