JPH0777812A - Image forming method - Google Patents

Abstract

PURPOSE:To obtain an image forming method by which a high-density high- resolution image can be formed in a simple dry process without losing dimensional stability by laminating a sub base body on a cover sheet or on the back surface of a base body after exposure for imaging and before peeling and development. CONSTITUTION:An image forming material having a photosensitive layer and a cover sheet successively formed in this order on a base material is used for this image forming method. The photosensitive layer contains a polymerizable compd. having at least an ethylene unsatd. bond, photopolymn. initiator, and coloring agent. The cover sheet transmits active rays. In this method, a sub base material is laminated on the cover sheet or the back surface of the base body after exposure for imaging and before peeling and development. As for the base material, paper, synthetic paper, resin film or sheet, plastic film or sheet comprising two or more resin layers, laminated film or sheet comprising paper with a resin layer can be used. As for the sub base body, any material can be selected according to the purpose from those used for the base body or the cover sheet.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method using an image forming material using photopolymerization. More specifically, it relates to an image forming method capable of developing by a dry process which realizes high density, high sensitivity and high resolution image formation.

[0002]

2. Description of the Related Art An image forming material comprising a photopolymerizable composition comprising a polymerizable compound having an ethylenically unsaturated bond, a photoinitiator, a colorant and, if necessary, an organic polymer binder is a colored image such as a color proof. For example, Japanese Patent Application Laid-Open Nos. 61-188537 and 61-286858 disclose such applications. These are used after image-wise exposing the photosensitive layer and then forming and utilizing an image by exposing the unexposed area with a liquid, which is troublesome in maintaining the developing device and treating the developing solution. Was causing.

On the other hand, as a method of forming an image by dry treatment, as disclosed in JP-A-58-24775 and JP-A-4-153658, a transparent support, a photosensitive composition layer, A peeling development method in which a positive image is formed on one support and a negative image is formed on the other support by peeling off the transparent support and the second support after the image is exposed on the material composed of the second support. And, as disclosed in U.S. Pat.Nos. 3,060,023, 3,060,024, 3,060,025, JP-A-63-147154, etc., image formation in which at least a photosensitive composition layer is provided on a support. The image is exposed to the material through a color separation negative or a mask, and the exposed photosensitive composition layer surface is brought into pressure contact while applying heat to the image receptor as necessary to expose the unexposed portion on the image receptor. A transfer development method and the like in which an image is transferred to form an image has been proposed. The image forming method by such a dry process is a preferable method in terms of environmental pollution, safety, and downsizing of the apparatus. Further, in recent years, there has been an increasing demand for a simple and high-definition image forming method by a dry process also in a printing plate making film and a medical image output application.

Generally, these applications require high transmission density, high resolution and high dimensional stability as image quality. However, in order to apply it to the film for printing plate making and medical image output by the peeling development process applying the conventional photopolymerization,
Since it is necessary to perform image exposure through a cover sheet or a base material, there is a drawback that high resolution cannot be obtained. Further, when the cover sheet or the base material is made thin to achieve high resolution, there is a drawback that the cover sheet or the base material is deformed by a mechanical force at the time of peeling and development and the dimensional stability is deteriorated.

[0005]

The present invention has been made based on the above circumstances. That is, an object of the present invention is to provide an image forming material method capable of forming a high density and high resolution image by a simple dry process without impairing dimensional stability.

[0006]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that a polymerizable compound having at least an ethylenically unsaturated bond, a photopolymerization initiator, and In a method for forming an image using a peelable and developable image forming material obtained by laminating a photosensitive layer containing a colorant and an actinic ray transmitting cover sheet in this order,
It has been found that the above object can be achieved by an image forming method characterized by bonding a sub-base material on a cover sheet or on the back surface of a base material after peeling and developing after image exposure.

The image forming material of the present invention will be described in detail.

(1) Image-Forming Material The image-forming material used in the image-forming method of the present invention contains a polymerizable compound having at least an ethylenically unsaturated bond, a photopolymerization initiator and a colorant on a substrate. The photosensitive layer and the actinic ray transparent cover sheet are laminated in this order. Examples of the base material include paper, synthetic paper (for example, synthetic paper containing polypropylene as a main component), resin film or sheet, plastic film or sheet formed by laminating two or more layers of the resin, or various polymer materials. Examples thereof include a film or sheet obtained by laminating the resin layer on paper or the like made of metal, ceramic, wood pulp, cellulose pulp, sulfite pulp, or the like. Further, a base material or the like in which a pigment coating layer having a porous structure is provided on one side or both sides of the above-mentioned film or sheet can be preferably used in the present invention. Examples of the resin constituting the film or sheet of such a resin include acrylic resins such as acrylic acid ester and methacrylic acid ester, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyester resin such as polyacrylate, polychlorinated resin, and the like. Polyolefin resin such as vinyl, polyvinylidene chloride, polyvinylidene fluoride, polyethylene, polypropylene, polystyrene, polyamide resin such as nylon and aromatic polyamide, polyether ether ketone, polysulfone, polyether sulfone, polyimide, polyetherimide, polyparaban Acid, phenoxy resin, epoxy resin, urethane resin, melamine resin, alkyd resin, phenol resin,
Examples thereof include fluororesin and silicone resin. In the present invention, the base material made of a resin is preferably stretched into a sheet or film and heat-set from the viewpoint of dimensional stability. The base material may have no internal microvoids or may have microvoids. Can be appropriately selected according to the application. The paper used in the present invention is preferably a pulp paper made from natural pulp, synthetic pulp, or a mixture thereof, and the paper is made using a Fourdrinier paper machine or the like, and for the purpose of improving smoothness, a machine after paper making is used. It is preferable to perform calendar treatment using a calendar, a super calendar, a thermal calendar, or the like. Further, a base paper coated with a resin layer containing a pigment for improving smoothness can also be preferably used in the present invention. Examples of the paper in the present invention include high-quality paper, art paper, coated paper, single-glossy paper, impregnated paper, paperboard and the like. In addition,
As the paper, when providing a laminated layer of polyolefin resin such as polyethylene and polypropylene containing white fine particles, it is preferable to have Beck smoothness of 50 seconds or more in order to have smoothness, and 100 seconds or more, further 200 It is preferable to have a smoothness of 2 seconds or more. Further, the paper contains additives such as a sizing agent, a fixing agent, a paper strengthening agent, a filler, an antistatic agent, a dye, a pigment, an optical brightener, an antioxidant and an anti-friction agent, if necessary. It may be. The thickness of the substrate in the present invention is usually 2 to 300 μm, preferably 4.5 to 150 μm, and is appropriately selected from such a range. The photosensitive layer contains at least a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator and a colorant.
As the polymerizable compound having such an ethylenically unsaturated bond, known crosslinkable monomers can be used without particular limitation. Specific monomers include, for example, monofunctional acrylic acid esters such as 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, and 2-hydroxypropyl acrylate and their derivatives, or these acrylates replaced with methacrylate, itaconate, crotonate, maleate, and the like. Ε of compounds, polyethylene glycol diacrylate, pentaerythritol diacrylate, bisphenol A diacrylate, neopentyl glycol hydroxypivalate
-Difunctional acrylic acid esters such as diacrylates of caprolactone adducts and their derivatives, or compounds obtained by replacing these acrylates with methacrylates, itaconates, crotonates, maleates, etc., or trimethylolpropane tri (meth) acrylates, dipentaerythritol pentaacrylates. Examples thereof include polyfunctional acrylic acid esters such as dipentaerythritol hexaacrylate and pyrogallol triacrylate and their derivatives, or compounds in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate and the like. As the resin having an ethylenically unsaturated bond, a so-called prepolymer obtained by introducing photopolymerizability by introducing acrylic acid or methacrylic acid into an oligomer having an appropriate molecular weight can be preferably used. In addition, JP-A-58-212994, 61-6649, and 62-4
6688, 62-48589, 62-173295, 62-187092
No. 63-67189, JP-A No. 1-244891, and the like, and the compounds described in “Chemical products of 11290”, Kagaku Kogyo Nipposha, p.286-p.294. ,
The compounds described in “UV / EB Curing Handbook (Raw Materials)”, Kobunshi Kogakukai, pages 11 to 65, and the like can also be preferably used in the present invention. Among these, compounds having two or more acryl or methacryl groups in the molecule are preferable in the present invention, and further, have a molecular weight of 10,000 or less,
It is more preferably 5,000 or less. In the present invention, one of these monomers or prepolymers is used.
One kind or a mixture of two or more kinds can be used. Further, the polymerizable compound having an ethylenically unsaturated bond is usually contained in the photosensitive layer forming composition in an amount of 5% by weight or more, more preferably 15% by weight or more.
It is preferable that the content is at least wt%.

As the photopolymerization initiator used in the photosensitive layer, for example, known photopolymerization initiators described on pages 39 to 56 of Photopolymer Handbook (edited by Photopolymer Handbook, published by Industrial Research Society, 1989) can be used. Although it can be optionally used, spectral sensitization of the photosensitive layer can be easily performed by using a compound represented by the following general formula (1) or (2), and thus image formation can be performed in the ultraviolet to near infrared range. It can be done with any light source in the area. In particular, by imparting sensitivity to red to near infrared, scanning exposure with a semiconductor laser, which has made remarkable progress in recent years, becomes possible, and it can be used as a highly sensitive digital image forming material.

[0010]

[Chemical 1]

In the formula, Dye ⁺ represents a cationic dye and M ^{k +} represents a transition metal coordination complex cation.

R ₁ , R ₂ , R ₃ and R _{4, which} may be the same or different, each represents an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a heterocyclic group or a cyano group, and these alkyl groups, The aryl group, alkenyl group, alkynyl group and heterocyclic group may further have a substituent. However,
At least one of R ₁ , R ₂ , R ₃ and R ₄ is an optionally substituted alkyl group. Also, R ₁ , R ₂ , R ₃ and R ₄ are 2
One or more may combine with each other to form a ring.

R ₅ and R ₆ each represent a hydrogen atom, a halogen atom or a monovalent substituent.

X is a hydroxyl group or --N (R ₇ ) (R ₈ ) group (R ₇ and R ₈ each represent a hydrogen atom or an optionally substituted alkyl group, and R ₅ , R ₆ or R ₇ are M may represent a transition metal atom.

K is 1 to 3, j is 2 or 3, m is 1 to 5,
n represents an integer of 1 to 4, respectively.

Specific examples of the cationic dye represented by Dye ⁺ include JP-A Nos. 62-143044, 63-208036 and 64-842.
Nos. 45, 64-88444, JP-A 1-152108, and 3-202609 can be used. Specific examples of preferable compounds are shown in the compound group A.

<< Compound Group A >>

[0018]

[Chemical 2]

[0019]

[Chemical 3]

[0020]

[Chemical 4]

[0021]

[Chemical 5]

Specific examples of the transition metal coordination complex cation represented by M ^{k +} include those described in JP-A-4-261405 in addition to those listed in the following compound group B.

<< Compound Group B >>

[0024]

[Chemical 6]

M ^{k +} jk X R ₉ R ₁₀ R ₁ R ₂ R ₃ R ₄ Co ²⁺ 2 2 N (C ₂ H ₅ ) ₂ NHCOC ₃ H ₇ (i) CH ₃ Ph Ph Ph Bu Ru ²⁺ 2 2 N (C2H ₅ ) ₂ NHCOC ₃ H ₇ (i) CH ₃ Ph Ph Ph Bu Ru ²⁺ 2 2 N (C ₂ H ₅ ) (C ₂ H ₄ NHSO ₂ CH ₃ ) Cl CH ₃ Ph Ph Ph Bu Ru ^{2 +} 2 2 N (C ₂ H ₅ ) (C ₂ H ₄ NHCOCH ₃ ) H CH ₃ Ph Ph Ph Bu Fe ²⁺ 2 2 N (C ₂ H ₅ ) (C ₂ H ₄ OH) CH ₃ CH ₃ Ph Ph Ph Bu Ir ³⁺ 2 3 N (C ₂ H ₅ ) ₂ NHCOC ₃ H ₇ (i) CH ₃ Ph Ph Ph Bu Ru ²⁺ 2 2 N (C ₂ H ₅ ) ₂ CONHC ₄ H ₉ CH ₃ Ph Ph Ph Bu Ru ²⁺ 2 2 N (C ₂ H ₅ ) ₂ CONHC ₄ H ₉ CH ₃ Ph Ph Ph iPr Co ²⁺ 2 2 N (C ₂ H ₅ ) ₂ NHCOC ₃ H ₇ (i) H Ph Ph Ph Bu Ru ²⁺ 2 2 N (C ₂ H ₅ ) ₂ NHSO ₂ CH ₃ CH ₃ Ph Ph Ph Bu Ru ²⁺ 3 3 N (C ₂ H ₅ ) ₂ NHCOC ₃ H ₇ (i) CH ₃ Ph Ph Ph Bu Ru ^{2 +} 2 2 N (C ₂ H ₅ ) ₂ NHCOC ₃ H ₇ (i) CH ₂ NHSO ₂ CH ₃ Ph Ph Ph Bu Co ²⁺ 2 2 N (C ₂ H ₅ ) ₂ SO ₂ N (C ₂ H ₅ ) ₂ CH ₃ Ph Ph Ph Bu Ru ²⁺ 2 2 N (C ₂ H ₅ ) ₂ NHCOC ₃ H ₇ (i) NHCOCH ₃ Ph Ph Ph Bu Ru ²⁺ 2 2 N (C ₂ H ₅ ) (C ₂ H ₄ NHSO ₂ CH ₃ ) Cl CH ₃ Ph Ph Ph Bu Fe ²⁺ 2 2 N (C ₂ H ₅ ) ₂ NHCONHC ₃ H ₇ (i) CH ₃ Ph Ph P h Bu Ru ²⁺ 2 2 N (C ₂ H ₅ ) ₂ NHCOC ₃ H ₇ (i) CH ₃ Bu Bu Bu Bu Ru ²⁺ 2 2 N (C ₂ H ₅ ) ₂ NHCOC ₃ H ₇ (i) CH ₃ Ph Ph Ph Bz Here, Ph: Phenyl Bu: buthyl iPr: i-propyl Bz: benzyl.

[0026]

[Chemical 7]

[0027]

[Chemical 8]

M ²⁺ R ₁₁ Ru ²⁺ Cl Ru ²⁺ NHCOC ₃ H ₇ (i) Co ²⁺ Cl The photopolymerization initiator represented by the general formula (1) or (2) is a dye anion moiety. In this example, even if this compound is added, a dye having an anion moiety and a borate compound represented by the following general formula (3) are allowed to coexist. The same function can be exhibited even when the compound represented by the general formula (1) is produced by ion exchange in the photosensitive layer or in the coating liquid for the photosensitive layer.
Further, when using the photopolymerization initiator of the general formula (1) or (2), it is preferable to add the borate represented by the general formula (3) for the purpose of improving the sensitivity.

[0029]

[Chemical 9]

In the formula, R ₁ , R ₂ , R ₃ and R ₄ have the same meanings as defined in the general formula (1) or (2), and X ⁺
Is a counter cation (eg, an alkali metal cation,
Periodic table group 5A onium compounds such as ammonium cations and phosphonium cations, and group 6A group onium compounds such as sulfonium and telluronium). Specific examples of the compound are described in JP-A-64-13142 and JP-A-2-4804.

A binder resin is used in the photosensitive layer, if necessary. As the binder resin, polyester resin, polyvinyl acetal resin, polyurethane resin, polyamide resin, cellulose resin, olefin resin, vinyl chloride resin, (meth) acrylic resin, styrene resin, polycarbonate, polyvinyl alcohol , Polyvinylpyrrolidone, polysulfone, polycaprolactone resin, polyacrylonitrile resin, urea resin, epoxy resin, phenoxy resin, rubber resin and the like. Further, a resin having an unsaturated bond in the resin, for example, a diallyl phthalate resin and its derivative,
Chlorinated polypropylene and the like can be polymerized with the above-mentioned compound having an ethylenically unsaturated bond, and thus can be suitably used depending on the application. As the binder resin, one kind or a combination of two or more kinds of the above-mentioned resins can be used. These binder resins are preferably added and mixed in an amount 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 having an ethylenically unsaturated bond.

Examples of the colorant include known colorants used for image formation or precursors thereof. For example, pigments such as carbon black, titanium oxide, iron oxide, phthalocyanine pigments, azo pigments, anthraquinone pigments and quinacridone pigments, and crystal violet, methylene blue, azo dyes, anthraquinone dyes, cyanine dyes and other dyes. Are contained in the photosensitive layer in a combination of one kind or a combination of two kinds or more so as to satisfy the above absorbance.

The amount of the colorant added is preferably 10 to 80% by weight, more preferably 15 to 70% by weight in the photosensitive layer forming composition.

In order to add a colorant to the photosensitive layer, the colorant other than the colorant is added to the photosensitive layer composition by a sand mill, a ball mill, an attritor, an ultrasonic disperser, a jet mill, a homogenizer, a planetary mill. It is possible to disperse and mix using a known apparatus such as the above, and further filter the coating solution as needed before use.

It is also preferable in the image-forming material of the present invention that a part (or one kind) of the colorant is uniformly dissolved and used in the photosensitive layer.

In the photosensitive layer of the present invention, a sensitizer, a thermal polymerization inhibitor, a heat-meltable compound,
The inclusion of other components such as oxygen scavengers and plasticizers is optional.

Examples of the sensitizer include triazine compounds described in JP-A-64-13140, aromatic onium salts and aromatic halonium salts described in JP-A-64-13141, and JP-A-64-1.
Examples thereof include organic peroxides described in Japanese Patent No. 3143, bisimidazole compounds and thiols described in Japanese Patent Publication No. 45-37377 and US Pat. No. 3,652,275. The amount of the sensitizer added is 10 parts by weight or less, preferably about 0.01 to 5 parts by weight, based on 100 parts by weight of the total amount of the polymerizable compound having an ethylenically unsaturated bond and the binder. As the thermal polymerization inhibitor, compounds such as quinone type and phenol type are preferably used. Examples thereof include hydroquinone, pyrogallol, p-methoxyphenol, catechol, β-naphthol, 2,6-di-t-butyl-p-cresol and the like. It is added in an amount of 10 parts by weight or less, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the total amount of the polymerizable compound having an ethylenically unsaturated bond and the binder. The oxygen quencher is preferably N, N dialkylaniline derivative, for example, 11th column 5 of US Pat. No. 4,772,541.
The compounds described in the 8th to 12th columns and the 35th line can be mentioned.

As the plasticizer, phthalic acid esters, trimellitic acid esters, adipic acid esters, other saturated or unsaturated carboxylic acid esters, citric acid esters, epoxidized soybean oil, epoxidized linseed oil,
Epoxy stearic acid epoxies, orthophosphoric acid esters, phosphorous acid esters, glycol esters and the like can be mentioned.

As the heat-fusible compound, a compound which is solid at room temperature and reversibly becomes liquid when heated is used.
Examples of the heat-fusible substances include terpineol, menthol, 1,4-cyclohexanediol, alcohols such as phenol, amides such as acetamide and benzamide,
Coumarin, esters such as benzyl cinnamate, ethers such as diphenyl ether and crown ether, ketones such as camphor and p-methylacetophenone, aldehydes such as vanillin and dimethoxybenzaldehyde, hydrocarbons such as norbornene and stilbene, margarine Higher fatty acids such as acids, higher alcohols such as eicosanol,
Higher fatty acid esters such as cetyl palmitate, higher fatty acid amides such as stearic acid amide, monomolecular compounds represented by higher amines such as behenylamine, beeswax, candelilla wax, paraffin wax, ester wax, montan wax, carnauba wax , Amide wax, polyethylene wax, wax such as microcrystalline wax, ester gum, rosin maleic acid resin, rosin derivative such as rosin phenol resin, phenol resin, ketone resin, epoxy resin, diallyl phthalate resin, terpene hydrocarbon resin, Polymer compounds represented by cyclopentadiene resin, polyolefin resin, polycaprolactone resin, polyolefin oxide such as polyethylene glycol and polypropylene glycol Etc. can be mentioned. Further, if necessary, an antioxidant, a filler, an antistatic agent or the like may be added to the photosensitive layer. As the antioxidant, a chroman compound, a clamane compound, a phenol compound, a hydroquinone derivative, a hindered amine derivative,
Examples thereof include spiroindane compounds, sulfur compounds, phosphorus compounds, and the like, and JP-A-59-182785 and 60-130735.
Japanese Patent Publication No. 61-159644, Japanese Patent Laid-Open No. 1-127387, "1.
Chemical products of 1290 ”, compounds described in Chemical Industry Daily, p.862 to 868, etc., and compounds known to improve durability in photographs and other image recording materials.

Examples of the filler include inorganic fine particles and organic resin particles. Examples of the inorganic fine particles include silica gel, calcium carbonate, titanium oxide, zinc oxide, barium sulfate, talc, clay, kaolin, acid clay, activated clay, alumina and the like, and organic fine particles include fluororesin particles and guanamine resin particles. Resin particles such as acrylic resin particles and silicone resin particles, and as antistatic agents, cationic surfactants, anionic surfactants, nonionic surfactants, polymeric antistatic agents, conductive fine particles, etc. The compounds described in "Chemical products of 11290", Kagaku Kogyo Daily, p.875 to p.876 and the like can also be preferably used.

In the present invention, the photosensitive layer may be formed of a single layer or a plurality of layers of two or more layers.
When it is composed of a plurality of layers, it may be composed of a photosensitive layer having a different composition, and in this case, a photosensitive layer containing no colorant may be contained.

In the present invention, the thickness of the photosensitive layer is 0.1-1.
0 μm is preferable, and 0.3 to 5 μm is more preferable.

The photosensitive layer is prepared by dispersing or dissolving the components of the photosensitive layer in a solvent to prepare a coating solution, and the coating solution is directly laminated on the intermediate layer described later and dried, or on a cover sheet described later. It is formed by coating on and drying.

As the solvent used in the above coating method, water, alcohols (eg ethanol, propanol), cellosolves (eg methyl cellosolve, ethyl cellosolve), aromatics (eg toluene, xylene, chlorobenzene), ketones ( For example, acetone, methyl ethyl ketone), ester solvents (eg ethyl acetate, butyl acetate, etc.), ethers (eg tetrahydrofuran, dioxane), chlorine solvents (eg chloroform, trichloroethylene), amide solvents (eg dimethylformamide, N-methyl). Pyrrolidone), dimethyl sulfoxide and the like.

For the coating, a conventionally known surface sequential coating method using a gravure roll, an extrusion coating method, a wire bar coating method, a roll coating method and the like can be adopted. As the cover sheet, a resin layer provided on the surface of the photosensitive layer by a coating method, a resin layer transferred such as a transfer foil, or a resin film laminated can be appropriately used depending on the application.

As the cover sheet, one having low oxygen permeability and hardly absorbing and / or scattering the wavelength of the exposure light source is used. Particularly, those having a transmittance of 40% or more, preferably 60% or more at a wavelength of about 300 nm to 2000 nm and having high surface smoothness are preferable.

The resin used for the cover sheet is polyvinyl alcohol resin, polyethylene terephthalate,
Polyester resins such as polyethylene naphthalate, polybutylene terephthalate and polycarbonate, acrylic resins such as polymethylmethacrylate and polyacrylic acid ester, polyolefin resins such as polyethylene, polypropylene and polystyrene, polyamide resins such as nylon and aromatic polyamide. , Polyimide resin, polyparabanic acid, phenoxy resin, epoxy resin, urethane resin, melamine resin, alkyd resin, phenol resin,
Examples thereof include fluororesin and silicone resin.

When the cover sheet is formed by laminating a resin film on the surface of the photosensitive layer, polyester resin such as polyethylene terephthalate and polyethylene naphthalate, polyethylene and polypropylene are preferably used as the resin film. It is also preferable to subject the surface of the cover sheet to treatment, and as the method of this surface treatment, corona discharge treatment, flame treatment, ozone treatment, ultraviolet treatment, radiation treatment, surface roughening treatment, chemical treatment, plasma treatment Known resin surface modification techniques such as low temperature plasma treatment, primer treatment, and grafting treatment can be applied as they are. Specifically, you can refer to the methods described in "Basics and Applications of Polymer Surfaces (below)", Chemistry Doujin, Chapter 2 and / or "Handbook of Polymer New Materials" Maruzen, Chapter 8, etc. The above can also be used together. In particular, it is preferable to perform discharge treatment and primer treatment.

The thickness of the cover sheet can be appropriately selected usually in the range of 1 to 200 μm, but when image exposure is carried out through the cover sheet, it is preferably 2 to 50 μm, and particularly preferably 2 to 25 μm. When it is 2 μm or less, it is difficult to uniformly laminate it on the surface of the photosensitive layer, and when it is 50 μm or more, the resolution is remarkably deteriorated due to the film thickness of the cover sheet, and the change of the image area with the exposure amount is remarkably increased. .

A more preferred embodiment of the present invention is to use an image forming material having an intermediate layer provided between the substrate and the photosensitive layer. The intermediate layer is a layer that joins the photosensitive layer and the base material with an appropriate adhesive force, and is formed of all and / or part of the exposed portion of the photosensitive layer by peeling the base material and the cover sheet during image formation. An image should be formed on the cover sheet side, and the adhesiveness should be controlled so that all unexposed portions of the photosensitive layer remain on the adhesive layer.

As the intermediate layer, known pressure-sensitive adhesives and adhesive compositions can be used as long as they satisfy the above relationship of adhesive strength.

Specific examples of the compound preferably used as the pressure-sensitive adhesive and the adhesive composition include natural rubber, natural rubber grafted with methyl methacrylate or styrene or acrylonitrile monomer, cyclized natural rubber, chlorinated natural rubber,
Isoprene rubber, trans polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, chloroprene rubber, acrylonitrile-butadiene rubber, nitrile rubber, butyl rubber, halogenated butyl rubber, ethylene-
Propylene rubber, ethylene-propylene-diene rubber,
Ethylene-vinyl acetate rubber, acrylic rubber, ethylene-
Acrylic rubber, urethane rubber, rubber such as silicone rubber, polystyrene-polybutadiene-polystyrene block copolymer (SBS), polybutadiene of SBS hydrogenated SEBS, polystyrene-polyisoprene-polystyrene block copolymer (SIS) Styrene-based thermoplastic elastomer such as, polyolefin-based thermoplastic elastomer, polyurethane-based thermoplastic elastomer, polyester-based thermoplastic elastomer, polyamide-based thermoplastic elastomer, 1.2-polybutadiene-based thermoplastic elastomer, ethylene-vinyl acetate-based thermoplastic elastomer, poly Vinyl chloride thermoplastic elastomer, natural rubber thermoplastic elastomer, fluororubber thermoplastic elastomer, trans-polyisoprene thermoplastic elastomer, chlorinated polyethylene heat Thermoplastic elastomers such as plastic elastomers, polyester resins, polyurethane resins, polyamide resins, olefin resins, vinyl chloride resins, (meth) acrylic resins, styrene resins, polycarbonate, polycaprolactone resins, epoxies It is a thermoplastic resin such as resin, phenoxy resin, or rubber resin.

The compounds suitably used as the pressure-sensitive adhesive and the adhesive composition can be used alone or in combination of two or more kinds. Further, a mixture of the above compound and a so-called tackifier such as an alicyclic hydrocarbon resin, a rosin resin, or a terpene resin is also preferable. In this case, the tackifier is used in an amount of not more than 50% by weight of the total intermediate layer composition.
If necessary, the intermediate layer further contains an ultraviolet absorber, an antistatic agent,
Antioxidants, fillers, plasticizers and the like can be added.

The intermediate layer is preferably provided on the base material so as to have a dry film thickness of 1 to 80 μm. Particularly preferably 3 to 50 μ
m.

The intermediate layer may be formed by hot-melt extruding the intermediate layer composition on the photosensitive layer formed on the substrate or cover sheet, or by using the intermediate layer composition in water or a suitable organic solvent. A method is used in which it is dispersed or dissolved in and is applied on a substrate or a photosensitive layer formed on a cover sheet and dried to form.

The method for producing the image-forming material of the present invention is to heat and / or laminate the intermediate layer formed on the base material and the photosensitive layer coated and formed on the cover sheet with heating. As the sub-base material used in the present invention, a material suitable for the application can be selected from the same materials as those used for the base material or the cover sheet. In the case of a printing plate-making film or a medical image output application, a polyester resin such as polyethylene terephthalate or polyethylene naphthalate having good light transmittance, or a resin film such as polyethylene or polypropylene is preferably used. A pressure-sensitive adhesive layer or a heat-sensitive adhesive layer can be provided as a sub-base material on the resin film in order to easily bond the sub-base material to the image-forming material after exposure.

Known pressure-sensitive adhesives can be used. For example, acrylic adhesives containing a copolymer of acrylic monomers such as acrylic acid, ethyl acrylate, 2-ethylhexyl acrylate and butyl acrylate as a main component, Examples thereof include rubber-based adhesives containing synthetic rubber and natural rubber as main components. Further, the pressure-sensitive adhesive may contain other resins, surfactants, cross-linking agents, particles or the like for adjusting the initial adhesive strength.

As the heat-sensitive adhesive, known thermoplastic resins can be used, for example, ethylene vinyl acetate copolymer, polyvinyl acetate, polyvinyl alcohol, polyester, polyamide, polyvinyl butyral, polyethylene, polypropylene, phenoxy resin, epoxy. resin,
Acrylic resins and other thermoplastic resins, natural rubber, polybutadiene rubber, styrene-butadiene rubber, chloroprene rubber, acrylonitrile-butadiene rubber, nitrile rubber, urethane rubber, silicone rubber, and other rubbers,
Polystyrene-polybutadiene-polystyrene block copolymer (SBS), polybutadiene of SBS hydrogenated SEBS, polystyrene-polyisoprene-polystyrene block copolymer (SIS) styrene-based thermoplastic elastomer, polyolefin-based thermoplastic elastomer,
Thermoplastic elastomers such as polyurethane-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, etc., so-called tackifiers such as alicyclic hydrocarbon resins, rosin-based resins, terpene-based resins, etc. It is possible to use two or more kinds in combination.

The thickness of the pressure-sensitive adhesive layer and the heat-sensitive adhesive layer is preferably 1 to 100 μm, particularly preferably 2 to 50 μm.
When the film thickness is 1 μm or less, it is difficult to adhere to the image forming material, and when the film thickness is 100 μm or more, the adhesive layer is deformed during peeling and development, which deteriorates the dimensional accuracy of the image. As the method for forming the pressure-sensitive adhesive layer and the heat-sensitive adhesive layer, a method of forming the pressure-sensitive adhesive and the heat-sensitive adhesive on the resin film by hot-melt extrusion, an adhesive composition containing water or a suitable organic compound is used. A method of dispersing or dissolving in a solvent and coating and drying on a resin film to form is used.

On the pressure-sensitive adhesive layer and the heat-sensitive adhesive layer, a primary protective sheet which is made of the same material as the base material and which can be peeled off before being bonded to the image forming material may be laminated. .

In the present invention, in addition to the above-mentioned base material, intermediate layer, photosensitive layer and cover sheet, other layers are provided for the purpose of improving adhesiveness, releasability, adhesiveness, barrier property, storability and the like. Is also good.

(2) Image forming method By combining image exposure on the above-mentioned image forming material having a photosensitive layer and dry treatment by peeling development, environmental problems and waste liquid treatment are required, and it is large. It is possible to easily perform high-concentration and high-resolution image formation at a sufficient speed without performing liquid processing that requires a processing device.

As a light source for forming an image, any light source that generates an active electromagnetic wave with respect to the photopolymerization initiator can be used. For example, a laser, a light emitting diode, a xenon flash lamp, a halogen lamp, a carbon arc lamp, a metal halide lamp, a tungsten lamp, a high pressure mercury lamp, etc. can be mentioned. When performing batch exposure using a xenon lamp, halogen lamp, carbon arc lamp, metal halide lamp, tungsten lamp, high pressure mercury lamp, etc., the negative pattern of the desired exposure image is provided on the cover sheet side of the image forming material as a light shielding material. It suffices to superimpose the mask material formed in step 1 and expose.

When an array type light source such as a light emitting diode array is used, or when a light source such as a halogen lamp, a metal halide lamp or a tungsten lamp is exposed and controlled by an optical shutter material such as liquid crystal or PLZT, an image signal is used. It is possible to carry out digital exposure according to the conditions. In this case, direct writing can be performed without using a mask material.

The laser is suitable for direct writing without using a mask material, since light can be focused into a beam and scanning exposure can be performed according to image data. Further, when a laser is used as a light source, it is easy to narrow the exposure area to a minute size, and high-resolution image formation becomes possible. Argon laser, He-Ne gas laser, YAG laser, semiconductor laser and the like can be used as the laser light source, and in particular, when a photopolymerization initiator having sensitivity in the near-infrared region is used, a comparison is made. A semiconductor laser that is small in size, inexpensive, and easy to obtain a high output can be preferably used. As an example of the composition of the semiconductor laser that is preferably used and its oscillation wavelength range, In
GaP laser (0.65-1.0 μm), AlGaAs laser (0.7
~ 1.0 μm), GaAsP laser (0.7 ~ 1.0 μm), InGaAs
Laser (1.0 to 3.5 μm), InAsP laser (1.0 to 3.5
μm), CdSnP2 laser (1.01 μm), GaSb laser (1.53 μm) and the like.

After image exposure, a sub-base material is attached to the cover sheet side or the base material side of the image forming material. Lamination can be performed by a known method such as a laminator,
The temperature and pressure at the time of bonding may be appropriately selected according to the types of the photosensitive layer, cover sheet and adhesive. When a sub-base material provided with a pressure-sensitive adhesive layer is used, it may be attached by hand.

An image-forming material having a sub-base material bonded thereto can be separated from the cover sheet and the base material after exposure by utilizing the change in adhesiveness between the exposed and unexposed areas of the photosensitive layer to the cover sheet. Thus, an image composed of an exposed portion or an unexposed portion can be stably formed on a cover sheet or a substrate.

The peeling speed and angle are preferably constant speed and constant angle because better image quality can be obtained. Further, it may be peeled off while heating and / or applying pressure as required.

The optimum peeling condition varies depending on the image forming material used, but generally, a large peeling angle of 90 degrees or more is preferable.

If necessary, image post-exposure can be carried out to complete the polymerization of the formed image.

The light irradiated in the post-exposure step is a laser,
Xenon flash lamps, halogen lamps, carbon arc lamps, metal halide lamps, tungsten lamps, infrared lamps, high pressure mercury lamps, fluorescent lamps, sunlight, etc., as long as they act on the photopolymerization initiator added to the photosensitive layer composition. Any known light source can be used. The exposure intensity and the exposure time may be appropriately set depending on the composition and layer configuration of the photosensitive layer and the conditions of the exposure device, as long as they can be cured to such an extent that there is no practical problem as an image forming material. In this case, the same effect can be obtained with either batch exposure or scanning exposure. Further, in the present invention, the photosensitive layer may be heat-treated in these series of steps, if necessary. Regarding the timing of heat treatment of the photosensitive layer, after the photosensitive layer was formed on the cover sheet or other layers by the above various methods, after the image forming material was prepared, the image forming material was subjected to imagewise exposure by the above various methods. The heat treatment can be performed at any timing such as afterward, or the heat treatment may be performed in two or more steps at different timings.

[0072]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1 A 25 μm thick polyethylene terephthalate film (manufactured by Diafoil Hoechst) was coated with an intermediate layer having the following composition by wire bar coating so that the dry film thickness was 15 μm. A base material was created.

Intermediate layer Ethylene / vinyl acetate copolymer 15 parts by weight (Evaflex EV-210 manufactured by Mitsui DuPont Polychemical Co., Ltd.) Toluene 85 parts by weight Corona discharge treatment (80 W / m ² / min) A 15 μm polyethylene terephthalate film (manufactured by Diafoil Hoechst) was used as a cover sheet, and a photosensitive layer composition consisting of the following composition was applied to the corona discharge treated surface of this cover sheet by wire bar coating so that the dry film thickness became 4 μm Was provided with a photosensitive layer. The absorbance of the image-forming material at this time was at least 3.2 in the range of 350 nm to the visible range.

Photosensitive layer composition Dipentaerythritol hexaacrylate 30.0 parts by weight (Nippon Kayaku Co., Ltd. KAYARAD DPHA) Polymethylmethacrylate resin 30.0 parts by weight (Mitsubishi Rayon Co., Ltd. Dianal BR-83) Yellow pigment methyl ethyl ketone Dispersion 12.0 parts by weight as pigment solids (MHI-534 manufactured by Mikuni Dye Co., Ltd.) Magenta pigment methyl ethyl ketone dispersion 12.0 parts by weight as pigment solids (MHI-890 manufactured by Mikuni Dye Co., Ltd.) Methyl ethyl ketone dispersion as cyan pigment 12.0 parts by weight as pigment solids (MHI-454 manufactured by Mikuni Dye Co., Ltd.) 0.6 parts by weight of cyanine (Kayasorb CY-10 manufactured by Nippon Kayaku Co., Ltd.) 1.7 parts by weight of lithium butyl triphenylborate 1-phenyl-5- Mercaptotetrazole 0.9 parts by weight Methyl ethyl ketone 400 parts by weight After the photosensitive layer is dried, the intermediate layer surface of the substrate with the intermediate layer is exposed to light. Superposed layer planes, creating the image forming material is passed between a pair of hot press rolls under the following conditions.

Temperature: 100 ° C. Pressure: 1.2 Kg / cm ²
Transport speed: 10 mm / sec Separately, a heat-sensitive adhesive layer consisting of the following composition was coated on a polyethylene terephthalate film (manufactured by Diafoyhext) with a thickness of 75 μm by wire bar coating to a dry film thickness of 15 μm. A sub-base material with a heat-sensitive adhesive layer was prepared by working.

Heat-sensitive adhesive layer 12 parts by weight of ethylene / vinyl acetate copolymer (Evaflex EV-210 manufactured by Mitsui DuPont Polychemical Co., Ltd.) 3 parts by weight of hydrocarbon resin (Alcon P-90 manufactured by Arakawa Chemical Industry Co., Ltd.) Toluene 85 parts by weight Scanning exposure was performed imagewise from the cover sheet side of the prepared image recording medium under the following conditions.

Light source: LT090MD Sharp Corporation
Output 100 mW, main wavelength 830 nm Optical efficiency: 67% Exposure beam diameter: 10 μm Exposure pitch: 6 μm The sub-base material is placed on the cover sheet side of the image forming material after exposure.
After laminating and pasting at a temperature of 80 ° C, with the base material,
When the cover sheet with the sub-base material attached was peeled at a temperature of 25 ° C. and a speed of 80 cm / sec, an image consisting of an exposed portion was clearly obtained on the cover sheet side with the sub-base material attached,
All unexposed areas were pulled out onto the intermediate layer. The absorbance of the exposed area image obtained as described above was at least 3.2 in the 350 nm to visible region, and the absorbance of the pre-exposure photosensitive layer was retained.
As for the resolution, a line width of 10 μm was reproduced well. The exposure energy required for image formation was 0.8 mJ / cm ² .

Example 2 An intermediate layer having the following composition was coated on a polyethylene terephthalate film substrate having a thickness of 75 μm (T-100 manufactured by Diafoil Hoechst Co., Ltd.) by wire bar coating to give a dry film thickness of 15:
It was coated so as to have a thickness of μm.

Intermediate layer Styrene / butadiene-based copolymer latex 15 parts by weight as solid content (JSR-0548 manufactured by Japan Synthetic Rubber Co., Ltd.) 85 parts by weight of water Next, a photosensitive layer composition having the following composition on the intermediate layer Was coated with a wire bar to form a photosensitive layer having a dry film thickness of 4 μm. The absorbance of the image-forming material at this time was at least 3.2 in the range of 350 nm to the visible range.

Photosensitive layer composition Dipentaerythritol hexaacrylate 30.0 parts by weight (Nippon Kayaku Co., Ltd. KAYARAD DPHA) Polymethylmethacrylate resin 30.0 parts by weight (Mitsubishi Rayon Co., Ltd. Dianarl BR-83) Yellow pigment methyl ethyl ketone Dispersion 12.0 parts by weight as pigment solids (MHI-534 manufactured by Mikuni Dye Co., Ltd.) Magenta pigment methyl ethyl ketone dispersion 12.0 parts by weight as pigment solids (MHI-890 manufactured by Mikuni Dye Co., Ltd.) Methyl ethyl ketone dispersion as cyan pigment 12.0 parts by weight as pigment solids (MHI-454 manufactured by Mikuni Dye Co., Ltd.) 0.6 parts by weight of cyanine (Kayasorb CY-10 manufactured by Nippon Kayaku Co., Ltd.) 1.7 parts by weight of lithium butyl triphenylborate 1-phenyl-5- Mercaptotetrazole 0.9 parts by weight Methyl ethyl ketone 400 parts by weight A cover sheet having the following composition on the intermediate layer Dry film thickness by a wire bar coating creates an image forming material is provided so as to be 6 [mu] m.

Cover sheet Styrene / butadiene copolymer latex 10 parts by weight as solids (JSR-0548 manufactured by Japan Synthetic Rubber Co., Ltd.) Polyvinyl alcohol 5 parts by weight (Gosenol N300 manufactured by Japan Synthetic Chemical Co., Ltd.) Water 85 parts by weight Part polyethylene terephthalate film sub-base material (manufactured by Diafoil Hoechst, thickness 75 μm) and the image-forming material prepared, and image formation was carried out in the same manner as in Example 1. The absorbance of the exposed part image was 350 nm to Minimum 3.2 in the visible range
Therefore, the absorbance of the photosensitive layer before exposure was maintained. As for the resolution, a line width of 10 μm was reproduced well. The exposure energy required for image formation was 0.9 mJ / cm ² .

Example 3 An image recording material was prepared in the same manner as in Example 1 except that the photosensitive layer composition was changed to the following composition and applied to form a dry film thickness of 2.0 μm. The absorbance of this photosensitive layer is 350-
It was at least 4.3 in the visible range.

Photosensitive composition layer Dipentaerythritol hexaacrylate 40.0 parts by weight (Nippon Kayaku Co., Ltd. KAYARAD DPHA) Polymethylmethacrylate resin 45.0 parts by weight (Mitsubishi Rayon Co., Ltd. DIANAR BR-83) Carbon black MEK Dispersion 20.0 parts by weight as solids (DM-022 manufactured by Mikuni Dye Co., Ltd.) 2-Methylanthraquinone 2.0 parts by weight Hydroquinone 0.05 parts by weight Methylethylketone 400 parts by weight Then, the halftone negative was contact exposed from the side of the photosensitive colored sheet support.

Light source: P-627-HA manufactured by Dainippon Screen Co., Ltd. Exposure chart: Plate control wedge UGRA
PCW 82 exposure amount: 25 counts The same sub-base material as in Example 1 was laminated on the cover sheet side of the image recording medium after exposure at a temperature of 80 ° C.
The temperature of the base material and the cover sheet with the sub-base material attached is set to 25
When peeled at 80 ° C. at a speed of 80 cm / sec, an image consisting of an exposed portion was clearly obtained on the cover sheet side to which the sub-base material was attached, and an image consisting of an unexposed portion was formed on the base material side. . The absorbance of the image obtained as above is
It is more than 4.0 in the 350-visible range, and the resolution reproduces the line width of 6 μm well, and 2% to 98% of the halftone dot 150 lines / inch.
Was reproduced well.

Further, when an image formed of the exposed portion of the photosensitive layer formed on the cover sheet side was used as a plate-making film and was subjected to contact printing on a negative PS plate, a good printing plate free from stains on the non-image part was obtained. Was created.

Comparative Example 1 Image formation was carried out in the same manner as in Example 3 except that the sub-base material was not used. The absorbance of the obtained exposed image is 350 n
It was at least 3.2 in the m-visible region and retained the absorbance of the photosensitive layer before exposure. As for the resolution, the line width of 6 μm was reproduced well. However, the interval between fine wires with a width of 20 μm at 100 mm intervals is 100.4 mm.
Therefore, the dimensional accuracy of the image was deteriorated.

Comparative Example 2 Image formation was carried out in the same manner as in Example 3 except that a 75 μm polyethylene terephthalate film was used as the cover sheet and no sub-base material was used. The resulting exposed area image is 10
The dimensional accuracy was good, with a distance of 0 mm and a width of 20 μm of 100.02 mm, but the fine wire could reproduce only a width of 15 μm or more and the resolution was deteriorated.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication location G03F 7/11 503 (72) Inventor Otoyoshi Komamura 1 Sakura-cho, Hino-shi, Tokyo Konica Stock Company In-house

Claims (6)

[Claims] 1. A photosensitive layer containing a polymerizable compound having at least an ethylenically unsaturated bond, a photopolymerization initiator and a colorant, and an actinic ray transparent cover sheet are laminated in this order on a substrate. In the image forming method using the image-forming material capable of peeling and developing, the sub-base material is attached to the cover sheet or the back surface of the base material after image exposure and before peeling and developing. 2. The image forming method according to claim 1, wherein an image forming material having an intermediate layer provided between the substrate and the photosensitive layer is used. 3. The image forming method according to claim 1, wherein the sub-base material is an actinic ray transparent resin film. 4. The image forming method according to claim 1, wherein the sub-base material comprises a pressure-sensitive adhesive layer or a heat-sensitive adhesive layer provided on an actinic ray transparent resin film. 5. The image forming method according to claim 1, wherein the sub-base material comprises a pressure-sensitive adhesive layer or a heat-sensitive adhesive layer provided on an actinic ray transparent resin film. 6. The image forming method according to claim 1, wherein an image forming material using a borate complex of a cationic dye is used as the photopolymerization initiator.