JPH07146548A - Image forming material and image forming method - Google Patents

Abstract

PURPOSE:To provide a dry high-density and high-fineness fine image forming material which maintains a fluctuation in gradation reproducibility with a fluctuation in exposure equal to the fluctuation in gradation reproducibility of a silver salt film and suppresses curling of a fine image forming medium. CONSTITUTION:This image forming material is capable of forming images by peeling a base material and a cover sheet after the material is exposed by active rays. The image forming material described above is constituted by laminating at least an intermediate layer, a coloring agent layer and a cover sheet in this order on the base material. At least the base material is transparent to active rays and the intermediate layer contains at least a polymerizable compd. and polymn. initiator. This image forming method comprises forming the images by exposing the image forming material by the active rays from the base material side, then peeling the base material and the cover sheet.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photopolymerizable image forming material and an image forming method using the same. More specifically, it relates to a high density and high resolution image forming material in a dry process using a photopolymerizable composition and an image forming method using the same.

[0002]

2. Description of the Related Art Conventionally, 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, such as a color proof. Applications for creating colored images are disclosed, for example, in JP-A-61-188537 and 61-286858. However, in these methods, after the colored photosensitive layer is imagewise exposed, the unexposed portion is eluted with a liquid to form an image of only the exposed portion, which is used for maintaining the developing device, treating waste development liquid, etc. The management was complicated.

On the other hand, as a method for forming an image by dry treatment, as disclosed in JP-A-58-24775 and JP-A-4-153658, a transparent support, a colored 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. , U.S. Patents 3,060,023, 3,060,024,
No. 3,060,025, JP-A-63-147154, etc., an image is exposed through a color separation negative or a mask to an image forming material having at least a colored photosensitive composition layer provided on a support. , A transfer developing method in which the surface of the colored photosensitive composition layer after exposure is brought into pressure contact with the image receptor while applying heat as necessary to transfer the unexposed portion onto the image receptor to form an image Is 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. In particular, the peeling development method,
This is a more preferable method because it is simple in process and does not require a transfer device.

Due to such advantages, the application of the dry peeling development system has been attracting attention in recent years, and one of them is an alternative application of a silver salt photographic film such as a plate-making film. In order to substitute silver halide photographic film, it is necessary to achieve high density (transmission density of 3.0 to 3.0 in the ultraviolet to visible light range) and high resolution (reproduction of fine lines of about 10μ).

As an example of the silver salt film substitute material,
As disclosed in JP-B-55-15017, JP-B-60-14339, etc., in a constitution of a thermoplastic elastomer layer, a photosensitive coloring layer, and a cover sheet on a substrate, carbon black has a solid content of 36%. After exposing the contained material to the image from the cover sheet side, the cover sheet is peeled off for high definition
A method has been proposed in which a negative image due to a high-concentration exposed portion is formed on a cover sheet and a positive image due to an unexposed portion is formed on a base material with a thermoplastic elastomer layer interposed therebetween. In the obtained image, only the negative image on the cover sheet is used in view of image strength. For this reason, the cover sheet becomes the final image carrier, so it has the same strength, handling, and
A thickness of 75μ or more is required to maintain the curl property.

Further, in this method, the exposure direction is limited to the cover sheet side due to the filter effect of the colorant. In the close contact analog exposure of a plate-making film or the like, the influence of the film thickness of the cover sheet on the change in the gradation reproducibility with respect to the change in the exposure amount due to light scattering or wraparound is a serious problem. It was difficult to maintain the gradation reproducibility with respect to the change in the exposure amount equivalent to that of the silver salt film.

[0007]

The present invention has been made based on the above circumstances. That is, an object of the present invention is to maintain a change in gradation reproducibility with respect to a change in exposure amount equivalent to a silver salt film, and to suppress curling of a final image carrier, and a dry high density / high definition image forming material and image forming method. To provide.

[0008]

The above object of the present invention is achieved by any one of the following constitutions.

An image-forming material capable of forming an image by peeling off the base material and the cover sheet after exposure to actinic rays, wherein the image-forming material comprises at least an intermediate layer, a colorant layer and a cover sheet on the base material. An image-forming material characterized in that at least the base material is transparent to actinic rays, and the intermediate layer contains at least a polymerizable compound and a polymerization initiator. .

An image-forming material which can be image-formed by peeling off the base material and the cover sheet after exposure to actinic rays, wherein the image-forming material has at least an intermediate layer on the base material and a polymerizable ethylenic monomer. A colored photosensitive layer containing a saturated compound, a polymerization initiator and a colorant as essential components, and a cover sheet laminated in this order,
At least the base material is transparent to actinic rays, and the intermediate layer contains at least a polymerizable compound and a polymerization initiator.

An image-forming material as described in or above, wherein the layer containing a colorant has an absorbance at 350 to 500 nm of 3.0 or more.

At least an intermediate layer, a colorant layer, and
An image comprising a cover sheet laminated in this order, at least the base material being transparent to actinic rays, and the intermediate layer containing at least a polymerizable compound and a polymerization initiator. An image forming method in which an image is formed by exposing a forming material to actinic rays from a base material side and then peeling the base material and a cover sheet.

[0013] At least an intermediate layer, a colored photosensitive layer containing a polymerizable ethylenically unsaturated compound, a polymerization initiator and a colorant as essential components, and a cover sheet are laminated in this order on a substrate. , At least the base material is transparent to actinic rays, and the intermediate layer contains at least a polymerizable compound and a polymerization initiator, exposed to actinic rays from the base material side to the image forming material After that, an image forming method of forming an image by peeling the base material and the cover sheet.

The layer containing a colorant has an absorbance at 350 to 500 nm of 3.0 or more, or after exposing the image forming material described above from the side of the substrate with actinic rays, the substrate and the cover sheet are An image forming method in which an image is formed by peeling.

That is, the inventors of the present invention, as a result of diligent studies, have found that the above-mentioned object can be achieved by configuring the peel-development type image forming material and the image forming method as follows.
That is, it is constituted by laminating at least an intermediate layer, a colorant layer, and a cover sheet on a substrate in this order, at least the substrate is transparent to actinic rays, and the intermediate layer is at least polymerizable. An image forming method in which an image-forming material containing a compound and a polymerization initiator is used to perform image formation by exposing the base material side and a cover sheet after exposing the base material side to actinic rays.

Further, it is constituted by laminating at least an intermediate layer, a colored photosensitive layer containing a polymerizable ethylenically unsaturated compound, a polymerization initiator and a colorant as essential components on a substrate, and a cover sheet in this order. The image forming material is characterized in that at least the substrate is transparent to actinic rays and the intermediate layer contains at least a polymerizable compound and a polymerization initiator. After the exposure, the image formation method that forms the image by peeling the base material and the cover sheet surprisingly makes it possible to design the film thickness of the final image carrier to 75 μm or more and curl is suppressed. It was found that the variation of gradation reproducibility with respect to the variation can be kept equal to that of the silver salt film, and a high density and high resolution dry process image can be formed.

The present invention will be described in detail below.

(1) Image Forming Material The image forming material of the present invention comprises a photosensitive intermediate layer, a photosensitive or non-photosensitive coloring layer, and a cover sheet, which are laminated in this order on an actinic ray permeable substrate. To be done.

As the above-mentioned substrate, a resin layer provided on the surface of the photosensitive intermediate layer by a coating method, a resin foil-transferred resin layer such as a transfer foil, or a resin film-laminated material can be appropriately used depending on the application. However, it is particularly preferable to use a resin film.

As the base material, a material having low oxygen permeability and hardly absorbing and / or scattering the wavelength of the exposure light source is used. Especially, the transmittance is 40 at wavelengths of about 250 nm to 2000 nm.
% Or more, preferably 60% or more, and those having high surface smoothness are preferable.

Examples of the resin constituting the resin film or sheet used as the substrate include polyvinyl alcohol resins, acrylic resins such as acrylic acid ester and methacrylic acid ester, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, Polyester resin such as polyarylate, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polyolefin resin such as polyethylene, polypropylene and polystyrene, polyamide resin such as nylon and aromatic polyamide, polyether ether ketone, polysulfone, poly Ether sulfone, polyimide, polyetherimide, polyparabanic acid, phenoxy resin, epoxy resin, urethane resin, melamine resin, alkyd resin, foam Nord resins, fluorocarbon resins, and silicone resins.

In the present invention, the resin base material is preferably stretched into a sheet or film and heat set, from the viewpoint of dimensional stability.

A release layer forming resin having self-supporting property can also be preferably used in the present invention. It is also preferable to treat the surface of the cover sheet, and as the method of this surface treatment, corona discharge treatment, flame treatment, ozone treatment, ultraviolet treatment, radiation treatment, 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 substrate is usually preferably 75 μm or less,
It is more preferably 0 μm or less.

In the present invention, the intermediate layer has photosensitivity and contains at least a polymerizable compound and a polymerization initiator to balance the adhesive force between the substrate and the colorant layer in the exposed and unexposed areas. It is changing appropriately.

As the polymerizable compound having an ethylenically unsaturated bond, known crosslinkable monomers can be used without particular limitation. Specific monomers include, for example, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, stearyl acrylate, monofunctional acrylic acid esters such as behenyl acrylate and derivatives thereof, or acrylates thereof of methacrylate, itaconate, Compounds replacing crotonate, maleate, etc., polyethylene glycol diacrylate, pentaerythritol diacrylate, bisphenol A diacrylate, hydroxypivalate neopentyl glycol ε
-Difunctional acrylates such as diacrylates of caprolactone adducts and their derivatives, or compounds in which these acrylates are replaced by methacrylates, itaconates, crotonates, maleates, etc., or trimethylolpropane tri (meth) acrylates, dipentaerythritol pentaacrylates Examples thereof include polyfunctional acrylic acid esters such as dipentaerythritol hexaacrylate, pyrogallol triacrylate, and isocyanuric acid 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 to these, Japanese Patent Laid-Open Nos. 58-212994 and 61-6649
No. 62, No. 62-46688, No. 62-48589, No. 62-173295, No. 6
2-187092, 63-67189, compounds described in JP-A 1-244891 and the like, and further, "11290
Chemical products of "Chemical Industry Daily Co., Ltd., compounds described in p.286-p.294," UV / EB curing handbook (raw material edition) "polymer publications, compounds described in p.11-65, etc. Can be preferably used in.

Of these, compounds having two or more acryl or methacryl groups in the molecule are preferable in the present invention, and those having a molecular weight of 10,000 or less, more preferably 5,000 or less are preferable. Further, in the present invention, one kind or a mixture of two or more kinds of these monomers or prepolymers can be used. Further, the polymerizable compound having an ethylenically unsaturated bond is usually contained in the photosensitive intermediate layer forming composition in an amount of 5% by weight or more, more preferably 15% by weight.
The above is preferable.

As the photopolymerization initiator used in the photosensitive intermediate layer, for example, a known photopolymerization initiator described on pages 39 to 56 of the Photopolymer Handbook (Photopolymer Association, published by the Industrial Research Board, 1989) can be optionally used. Although it can be used, spectral sensitization can be easily performed by using the compounds represented by the following general formulas (1) and (2),
Image formation can be performed with any light source in the ultraviolet to near infrared region. For example, since it is possible to perform scanning exposure with a semiconductor laser, which has made remarkable progress in recent years, by providing sensitivity to red to near infrared, it can be used as a highly sensitive digital image forming material.

[0031]

[Chemical 1]

In the formula, Dye ⁺ represents a cationic dye, M ^{K +} represents a transition metal coordination complex cation, and R ₁ , R ₂ , R ₃ and R ₄ may be the same or different, and A substituted or unsubstituted alkyl group, aryl group, alkenyl group, alkynyl group, heterocyclic group or cyano group, and R ₁ ,
At least one of R ₂ , R ₃ and R ₄ is an alkyl group, and two or more of R ₁ , R ₂ , R ₃ and R ₄ 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 a —N (R ₇ ) (R ₈ ) group (R ₇ , R ₈ each represent a hydrogen atom or an optionally substituted alkyl group, and R ₅ , R ₆ or R ₇ are bonded to each other. May form a ring), M represents a transition metal atom. k represents an integer of 1 to 3, l represents 2 or 3, m represents an integer of 1 to 5, and n represents an integer of 1 to 4.

Specific examples of the cationic dye represented by Dye ⁺ include JP-A Nos. 62-143044, 63-208036, and 64-84245.
No. 64-88444, JP-A No. 1-152108, and No. 3-202609 can be used. Specific examples of preferable compounds are shown in the compound group (A).

<< Compound Group (A) >>

[0035]

[Chemical 2]

[0036]

[Chemical 3]

[0037]

[Chemical 4]

[0038]

[Chemical 5]

[0039]

[Chemical 6]

[0040]

[Chemical 7]

Specific examples of the transition metal coordination complex cation represented by M ^{K +} include those listed in the specification of JP-A-4-261405, in addition to those listed in the compound group (B). You can

<< Compound Group (B) >>

[0043]

[Chemical 8]

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 (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 ) (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

[0045]

[Chemical 9]

Where Ph: phenyl Bu: buthyl iPr: i-pr
opyl Bz: represents benzyl.

[0047]

[Chemical 10]

M ²⁺ R ₁₁ Ru ²⁺ Cl Ru ²⁺ NHCOC ₃ H ₇ (i) Co ²⁺ Cl In the photopolymerization initiator represented by the general formulas (1) and (2), the dye anion portion is previously boron-containing. An acid is shown as an example, but even if this compound is added, a dye having an optional anion moiety and a borate compound represented by the following general formula (3) are allowed to coexist in the photosensitive intermediate layer, Alternatively, the same function can be exhibited even when the compound represented by the general formula (1) is produced by ion exchange in the photosensitive intermediate layer coating liquid.

Furthermore, when the initiators of the above general formulas (1) and (2) are used, it is preferable to add a borate represented by the following general formula (3) for the purpose of improving sensitivity.

[0050]

[Chemical 11]

In the formula, R ₁ , R ₂ , R ₃ and R ₄ have the same meanings as defined in the general formula (1), and X ⁺ is a counter cation (for example, alkali metal cation, ammonium cation, phosphonium). 5A group onium compounds such as cations, 6A group onium compounds such as sulfonium and telluronium). Specific examples of the compound are disclosed in JP-A-
64-13142 and JP-A No. 2-4804.

A binder resin is optionally used in the photosensitive intermediate layer. As the binder resin, natural rubber, isoprene-based rubber, butadiene-based rubber, chloroprene rubber, nitrile rubber, butyl rubber, ethylene-based rubber, acrylic rubber, urethane rubber, rubber such as silicone rubber, and polystyrene- Polybutadiene-polystyrene block copolymer (SBS), polybutadiene-hydrogenated SEBS of SBS, polystyrene-polyisoprene-polystyrene block copolymer (SIS) and other styrene-based thermoplastic elastomers, polyolefin-based thermoplastic elastomers, polyurethane-based Thermoplastic elastomer, polyester-based thermoplastic elastomer, polyamide-based thermoplastic elastomer, 1,2-polybutadiene-based thermoplastic elastomer, ethylene-vinyl acetate-based thermoplastic elastomer, polyvinyl chloride-based thermoplastic elastomer, heaven Natural rubber-based thermoplastic elastomers, fluororubber-based thermoplastic elastomers, trans-polyisoprene-based thermoplastic elastomers, chlorinated polyethylene-based thermoplastic elastomers, and other thermoplastic elastomers, polyester-based resins, polyurethane-based resins, polyamide-based resins , Polyvinyl acetate resin, polyolefin resin, vinyl chloride resin,
Thermoplastic resins such as (meth) acrylic resins, styrene resins, polycarbonates, polycaprolactone resins, epoxy resins and phenoxy resins are preferable.

The compounds suitably used as the above-mentioned photosensitive intermediate layer resin may be used alone or in combination of two or more kinds, and these binder resins are 100 parts by weight of the polymerizable compound having the ethylenically unsaturated bond. On the other hand, it is preferable to add and mix it in the range of 500 parts by weight or less, more preferably 200 parts by weight or less.

The photosensitive intermediate layer of the present invention may contain other components such as a sensitizer, a thermal polymerization inhibitor, a heat-fusible compound, an oxygen scavenger and a plasticizer as long as the purpose is not impaired. 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-64-13143. Organic peroxides described, Japanese Patent Publication No. 45-37377 and US Patent No. 3,
Examples thereof include the bisimidazole compounds and thiols described in No. 652,275. The amount of the sensitizer added is the total amount of the polymerizable compound having an ethylenically unsaturated bond and the binder.
10 parts by weight or less, preferably 0.01 to 100 parts by weight
About 5 parts by weight is added.

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.

As the oxygen quencher, N, N dialkylaniline derivatives are preferable, for example, US Pat. No. 4,772,541.
The compounds described in column 11, line 58 to column 12, line 35 of the No.

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-meltable 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, etc. may be added to the photosensitive intermediate layer. Examples of the antioxidant include chroman compounds, clamane compounds, phenol compounds, hydroquinone derivatives, hindered amine derivatives, spiroindane compounds, sulfur compounds, phosphorus compounds and the like.
No. 785, No. 60-130735, No. 61-159644, JP-A-1-12738
No. 7, "Chemical products of 11290", Chemical Industry Daily, p.862-868
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 intermediate layer may be formed of a single layer or plural layers of two or more layers. When it is composed of a plurality of layers, it may be composed of a photosensitive intermediate layer having a different composition.

In the present invention, the thickness of the photosensitive intermediate layer is 50.
It is preferably not more than μm, more preferably not more than 30 μm.

As the method for forming the photosensitive intermediate layer, a method for forming the photosensitive intermediate layer composition by hot melt extrusion directly on the substrate or on the colorant layer formed on the cover sheet, the photosensitive intermediate layer A method in which the composition is dispersed or dissolved in a suitable solvent and directly formed on the substrate, or by coating and drying on the colorant layer formed on the cover sheet to form the composition is used.

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), dimethylsulfoxide, etc., and these may be used alone or in combination of two or more.

The colorant layer is both photosensitive and non-photosensitive and contains at least a colorant and a film forming aid.

As the colorant, carbon black, titanium oxide, iron oxide, phthalocyanine pigment, azo pigment,
Anthraquinone pigments, quinacridone pigments, etc., crystal violet, methylene blue, azo dyes,
The known pigments such as anthraquinone dyes and cyanine dyes and / or 1 to 2 or more kinds of dyes are combined in the colorant layer so that the amount of the colorant added is 10 to 80% by weight in the colorant layer forming composition. % Is preferred, more preferably 15
~ 70% by weight.

In order to add a colorant, a colorant other than the colorant is added to the colorant layer composition by using a publicly-used device such as a sand mill, a ball mill, an attritor, an ultrasonic disperser, a jet mill, a homogenizer or a planetary mill. It may be used by dispersing and mixing, and if necessary, the coating solution may be filtered 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 colorant layer.

As the film forming aid, 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, polyacrylonitrile resin, urea resin, phenoxy resin, rubber resin, terpineol, menthol, 1,4-cyclohexanediol, alcohols such as phenol, amides such as acetamide and benzamide, coumarin, benzyl cinnamate Esters such as, diphenyl ether, ethers such as crown ether, camphor, ketones such as p-methylacetophenone, aldehydes such as vanillin and dimethoxybenzaldehyde, hydrocarbons such as norbornene and stilbene, higher fatty acids such as margaric acid, Monomolecular compounds represented by higher alcohols such as eicosanol, higher fatty acid esters such as cetyl palmitate, higher fatty acid amides such as stearic acid amide, and higher amines such as behenylamine. , Candelilla wax, paraffin wax, ester wax, montan wax,
Waxes such as carnauba wax, amide wax, polyethylene wax, 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 Resins, cyclopentadiene resins, polyolefin-based resins, polycaprolactone-based resins, polymer compounds represented by polyolefin oxides such as polyethylene glycol and polypropylene glycol, and the like can be mentioned. These can be used alone or in combination of two or more. Good.

The amount of these film-forming aids in the colorant layer-forming composition is preferably 10% by weight or more, more preferably 20% by weight or more.

A photosensitive colorant layer is mentioned as one of the preferred embodiments of the present invention. The photosensitive colorant layer contains at least the above-mentioned colorant, a film formation aid, a polymerizable compound and a polymerization initiator.

As the polymerizable compound, all the compounds that can be suitably used as the photosensitive intermediate layer composition can be similarly used.

As the polymerization initiator, all compounds that can be suitably used in the photosensitive intermediate layer composition can be used in the same manner.

The photosensitive colorant layer of the present invention may optionally contain other components such as a sensitizer, a thermal polymerization inhibitor and an oxygen scavenger as long as the purpose is not impaired. As the compound that can be used, the compounds described in the photosensitive intermediate layer composition can be similarly used.

Further, if necessary, an antioxidant, a filler, an antistatic agent, a plasticizer or the like may be added to the colorant layer regardless of the photosensitivity, as long as the purpose is not impaired. As the compound that can be used, the compounds described in the photosensitive intermediate layer composition can be used in the same manner.

In the present invention, the colorant layer has a thickness of 0.2 to 1
The thickness is preferably 0 μm, more preferably 0.5 to 5 μm. Within this film thickness range, the absorbance is at least 3.0 in the wavelength range of at least 500 nm or less.

The colorant layer is prepared by dispersing or dissolving the forming components in a solvent to prepare a coating solution, and the coating solution is directly laminated on the photosensitive intermediate layer and dried, or on a cover sheet described later. It is formed by coating 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, paper, synthetic paper (for example, synthetic paper containing polypropylene as a main component), resin film or sheet, further a plastic film or sheet formed by laminating two or more layers of the resin, or various heights Molecular materials, metals, ceramics or papers made of wood pulp or cellulose pulp, sulfite pulp, and the like, and the like, a film or sheet in which the resin layer is laminated can be mentioned, but it is particularly preferable to use a resin film. is there.

As a resin constituting such a resin film or sheet, a polyvinyl alcohol resin, a polyester resin such as polyethylene terephthalate or polybutylene terephthalate, an acrylic resin such as methyl methacrylate or a polyolefin such as polyethylene or polypropylene. Examples of the resin include a resin and a resin film that can be used as a base material, and a release layer-forming resin having a self-supporting property can be preferably used in the present invention. It is also preferable to subject the surface of the cover sheet to treatment, and as a method of this surface treatment, corona discharge treatment, flame treatment, ozone treatment, ultraviolet treatment, radiation treatment,
Known resin surface modification techniques such as surface roughening treatment, chemical treatment, plasma treatment, low temperature plasma treatment, primer treatment, and grafting treatment can be applied as they are. Specifically, "Fundamental and application of polymer surface (bottom)" Kagaku Dojin, 2
The method described in Chapter and / or "Handbook of New Polymer" Maruzen, Chapter 8, etc. can be referred to, and one kind or two or more kinds thereof can be used in combination. In particular, it is preferable to perform discharge treatment and primer treatment.

The thickness of the cover sheet is usually preferably 25 to 200 μm, more preferably 50 to 150 μm.

The method for producing the image-forming material of the present invention is to laminate a photosensitive intermediate layer formed on a substrate and a colorant layer formed by coating on a cover sheet under heating and / or pressure. .

In the present invention, in addition to the above-mentioned base material, intermediate layer, photosensitive layer, cover sheet, other layers for improving adhesiveness, cushioning property, releasability, adhesion property, barrier property, storability and the like. May be provided.

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

As the light source for forming an image, any light source that generates an active electromagnetic wave with respect to the photopolymerization initiator can be used. Examples thereof include lasers, light emitting diodes, xenon flash lamps, halogen lamps, carbon arc lamps, metal halide lamps, tungsten lamps, high pressure mercury lamps, electrodeless light sources, and the like. When performing batch exposure using a xenon lamp, halogen lamp, carbon arc lamp, metal halide lamp, tungsten lamp, high-pressure mercury lamp, electrodeless light source, etc., provide a negative pattern of the desired exposure image on the base material side of the image forming material. The mask material formed of the light shielding material may be overlapped and exposed.

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, because 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. As the laser light source, it is possible to use an argon laser, a He-Ne gas laser, a YAG laser, a semiconductor laser, etc., for example, in the case of using a photopolymerization initiator having sensitivity in the above-mentioned near infrared region,
A semiconductor laser that is relatively small, inexpensive, and easy to obtain a high output can be preferably used.

The composition of a semiconductor laser that is preferably used and its oscillation wavelength range are shown by way of example. InGaP laser (0.6
5 to 1.0 μm), AlGaAs laser (0.7 to 1.0 μm), GaAsP
Laser (0.7 to 1.0 μm), InGaAs laser (1.0 to 3.5 μm)
μm), InAsP laser (1.0 to 3.5 μm), CdSnP2 laser (1.01 μm), GaSb laser (1.53 μm) and the like.

The image-forming material after exposure utilizes the change in adhesiveness between the exposed portion of the photosensitive intermediate layer and the colorant layer of the unexposed portion to heat the cover sheet and the base material as necessary after exposure. And / or by peeling at a constant speed and a constant angle while applying pressure, an image composed of an exposed portion or an unexposed portion can be stably formed on the cover sheet or the substrate. The optimum peeling condition differs depending on the image forming material used, but generally, a large peeling angle of 90 degrees or more is preferable.

If necessary, post-exposure or post-heating 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 lamp, halogen lamp, carbon arc lamp, metal halide lamp, tungsten lamp, infrared lamp, high pressure mercury lamp, electrodeless light source, fluorescent lamp,
Any known light source that acts on the photopolymerization initiator added to the photosensitive layer composition, such as sunlight, 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.

For post-heat curing, any known heating method can be used. The heating temperature and the heating time may be appropriately set depending on the composition and layer configuration of the photosensitive layer and the conditions of the heating device, as long as the image can be cured to such an extent that there is practically no problem as an image.

[0095]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

In the following, "parts" means "parts by weight as active ingredients" unless otherwise specified.

Example 1 On a transparent polyethylene terephthalate film [T-100 manufactured by Diafoil Hoechst Co., Ltd.] having a thickness of 25 μm, a photosensitive intermediate layer composition having the following composition was formed by a wire bar so as to have a dry film thickness of 10 μm. Coating was performed by a coating method to prepare a base material with a photosensitive intermediate layer.

Photosensitive intermediate layer composition Dipentaerythritol hexaacrylate 100 parts (Nippon Kayaku Co., Ltd. KAYARAD DPHA) Ethylene / vinyl acetate copolymer 100 parts (Mitsui DuPont Polychemical Co., Ltd. Evaflex EV210) ) Bis-imidazole 8 parts Michler's ketone 6 parts Mercaptobenzoxazole 5 parts Toluene 800 parts 100 μm thick transparent polyethylene terephthalate film [T-100 by Diafoil Hoechst Co., Ltd.] Was coated by a wire bar coating method to a dry film thickness of 4 μm to form a colorant layer.

Colorant layer composition Polymethylmethacrylate resin 80 parts (Mitsubishi Rayon Co., Ltd. Dianal BR-83) Carbon black methyl ethyl ketone dispersion 20 parts as pigment solids (Mikuni dye Co., Ltd. DM-022) Methyl ethyl ketone 400 parts After sufficiently drying the photosensitive intermediate layer and the colorant layer, the photosensitive intermediate layer surface and the colorant layer surface are superposed, and an image forming material is prepared by passing between a pair of hot-press rolls under the following conditions. .

Temperature: 100 ° C. Pressure: 1.2 kg / cm ² Conveying speed: 10 mm / sec The image forming material prepared under the above conditions was contact-exposed from the substrate side under the following conditions using a printer for bright room light-sensitive materials. .

Light source: P-627-HA manufactured by Dainippon Screen Co., Ltd. Exposure chart: Plate control wedge UGRA PC
W82 exposure amount: set for each light-sensitive material The substrate with the photosensitive intermediate layer of the image-forming material after exposure and the cover sheet were peeled at a temperature of 25 ° C. and a speed of 80 cm / sec.
The colorant layer was pulled out to the unexposed area on the substrate with the photosensitive intermediate layer, and the colorant layer in the exposed area remained on the cover sheet side and a clear image was obtained.

In the image on the cover sheet side obtained as described above, curling was significantly suppressed, and the halftone dot variation rate due to the change in exposure amount was greatly improved.

Example 2 Example except that the cover sheet was subjected to corona discharge treatment (80 W / m ² / min) to a transparent polyethylene terephthalate film having a thickness of 100 μm (T-100 manufactured by Dia foil Hoechst). An image forming material was prepared in the same manner as in No. 1, and an image was formed in the same manner.

Example 3 An image forming material was prepared in the same manner as in Example 2 except that the base material was changed to a transparent polyethylene terephthalate film [T-100 manufactured by Dia foil Hoechst Co., Ltd.] having a thickness of 15 μm. Formed.

Example 4 An image forming material was prepared in the same manner as in Example 2 except that the composition of the colorant layer was changed as follows, and image formation was carried out in the same manner.

Photosensitive colorant layer composition Dipentaerythritol hexaacrylate 50 parts (Nippon Kayaku Co., Ltd. KAYARAD DPHA) Polymethylmethacrylate resin 75 parts (Mitsubishi Rayon Co., Ltd. Dianal BR-83) Carbon black Methyl ethyl ketone dispersion 30 parts as pigment solids (DM-022 manufactured by Mikuni Dye Co., Ltd.) Bis-imidazole 4 parts Michler's ketone 3 parts Mercaptobenzoxazole 2 parts Methyl ethyl ketone 600 parts Example 5 The composition of the colorant layer is as follows. An image forming material was prepared in the same manner as in Example 2 except that it was changed, and image formation was performed in the same manner.

Photosensitive colorant layer composition 50 parts of dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.) Polymethylmethacrylate resin 75 parts (Dianal BR-83 manufactured by Mitsubishi Rayon Co., Ltd.) Methyl ethyl ketone dispersion 39 parts as pigment solids (MHI-534 manufactured by Mikuni Dye Co., Ltd.) Methyl ethyl ketone dispersion of magenta pigments 39 parts as solid pigment (MHI-890 manufactured by Mikuni Dyes Co., Ltd.) Bis-imidazole 4 parts Michler's ketone 3 Part Mercaptobenzoxazole 2 parts Methyl ethyl ketone 800 parts Example 6 An image forming material was prepared and images were formed in the same manner as in Example 4 except that the composition of the photosensitive intermediate layer was changed as follows.

Photosensitive intermediate layer composition Dipentaerythritol hexaacrylate 100 parts (Nippon Kayaku Co., Ltd. KAYARAD DPHA) Ethylene / vinyl acetate copolymer 100 parts (Mitsui DuPont Polychemical Co., Ltd. Evaflex EV210) ) Cyanine dye 0.6 parts (NK-3212 manufactured by Japan Photosensitive Dye Research Institute Co., Ltd.) Lithium butyl triphenylborate 1.7 parts Tetrahydrofuran 800 parts Example 7 Example 4 except that the composition of the photosensitive intermediate layer was changed as follows. An image forming material was prepared in the same manner as described above, and was used as a material having spectral sensitivity in the infrared.

Photosensitive intermediate layer composition Dipentaerythritol hexaacrylate 100 parts (Nippon Kayaku Co., Ltd. KAYARAD DPHA) Ethylene / vinyl acetate copolymer 100 parts (Mitsui DuPont Polychemical Co., Ltd. Evaflex EV210) ) Cyanine dye 0.6 part (Kayasorb CY-10 manufactured by Nippon Kayaku Co., Ltd.) Lithium butyltriphenylborate 1.7 parts Tetrahydrofuran 800 parts Scanning exposure was performed imagewise on the prepared image forming material from the base material side under the following conditions. .

Light source: LT090MD manufactured by Sharp Corporation
Output 100mW, main wavelength 830nm Optical efficiency: 67% Exposure beam diameter: 10μm Exposure pitch: 6μm After exposure, the substrate with the photosensitive intermediate layer and the cover sheet are at a temperature of 25 ° C and a speed of 80cm / sec. Peeled off.
The colorant layer was pulled out from the unexposed area on the substrate with the photosensitive intermediate layer, and the exposed area of the colorant and the cover sheet was clear, and a clear image was obtained.

In the image on the cover sheet side obtained as described above, curling was significantly suppressed, and the halftone dot variation rate due to changes in the exposure amount was greatly improved. Resolution is
The line width of 10 μm was reproduced well.

Further, the images formed on the cover sheets in Examples 4 to 7 can be further improved in image strength by post-exposure with actinic rays to terminate the reaction. Similarly, in the positive images formed on the base material in Examples 1 to 7, it was possible to improve the image strength by post-exposure with actinic rays.

Comparative Example 1 An image forming material was prepared in the same manner as in Example 4 except that the photosensitive intermediate layer was changed to the following composition to make it non-photosensitive.

Photosensitive intermediate layer composition Ethylene / vinyl acetate copolymer 20 parts (Mitsui DuPont Polychemical Co., Ltd. Evaflex EV210) Toluene 80 parts Comparative Example 2 Comparative Example 2 except that contact exposure is performed from the cover sheet side. An image forming material was prepared in the same manner as in Example 1, and an image was formed in the same manner.

Comparative Example 3 Comparative Example 3 except that the cover sheet was subjected to corona discharge treatment (80 W / m ² / min) and a transparent polyethylene terephthalate film 25 μm thick [T-100 manufactured by Diamond Foil Hoechst] was used. An image forming material was prepared in the same manner as in No. 2 and image formation was performed in the same manner.

The images prepared in Examples 2 to 6 and Comparative Examples 1 to 3 were evaluated.

The dot variation rate (exposure amount dependency) and the curl of the cover sheet with respect to the change in exposure amount of the image formed on the cover sheet were evaluated. The results are shown in Table 1.

[0118]

[Table 1]

[0119]

EFFECT OF THE INVENTION According to the present invention, a dry high-density and high-definition image forming material and image forming in which the fluctuation of gradation reproducibility with respect to the change of exposure amount is kept equal to that of a silver salt film and curling of the final image carrier is suppressed. A method can be provided.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location G03F 7/34 7124-2H (72) Inventor Hiroshi Watanabe 1 Sakura City, Hino City, Tokyo Konica Stock Association In-house (72) Inventor, Otomo Komamura, Konica Stock Company, 1 Sakura-cho, Hino-shi, Tokyo In-house

Claims (6)

[Claims] 1. An image forming material capable of forming an image by peeling off a base material and a cover sheet after exposure to actinic rays, wherein the image forming material comprises at least an intermediate layer, a colorant layer, and An image comprising a cover sheet laminated in this order, at least the base material being transparent to actinic rays, and the intermediate layer containing at least a polymerizable compound and a polymerization initiator. Forming material. 2. An image forming material capable of forming an image by peeling off a base material and a cover sheet after exposure to actinic rays, wherein the image forming material comprises at least an intermediate layer on the base material and a polymerizable ethylene. Of a photosensitive unsaturated compound, a polymerization initiator and a coloring agent as essential components, a colored photosensitive layer, and a cover sheet are laminated in this order,
At least the base material is transparent to actinic rays, and the intermediate layer contains at least a polymerizable compound and a polymerization initiator. 3. The layer containing a colorant has an absorbance at 350 to 500 nm of 3.0 or more.
The image forming material described. 4. At least an intermediate layer, a colorant layer, and
An image comprising a cover sheet laminated in this order, at least the base material being transparent to actinic rays, and the intermediate layer containing at least a polymerizable compound and a polymerization initiator. An image forming method in which an image is formed by exposing a forming material to actinic rays from a base material side and then peeling the base material and a cover sheet. 5. A laminate comprising at least an intermediate layer, a colored photosensitive layer containing a polymerizable ethylenically unsaturated compound, a polymerization initiator and a colorant as essential components, and a cover sheet, which are laminated in this order on a substrate. In the image forming material, at least the base material is transparent to actinic rays, and the intermediate layer contains at least a polymerizable compound and a polymerization initiator. An image forming method in which an image is formed by peeling the base material and the cover sheet after being exposed to light. 6. A base material and a cover sheet after exposing the image-forming material according to claim 1 or 2 from the base material side with an actinic ray, wherein the colorant-containing layer has an absorbance at 350 to 500 nm of 3.0 or more. An image forming method for forming an image by peeling off.