JPH08194310A - Image forming material - Google Patents

Abstract

PURPOSE: To enable handling in a light room and to improve preservability by forming an adhesive layer, a photosensitive layer contg. a polymerizable compd. and a photopolymn. initiator and a peelable cover sheet on a substrate and allowing at least one selected from among the substrate, adhesive layer and cover sheet to have absorption in a wavelength region other than the max. wavelength of absorption of the photopolymn. initiator. CONSTITUTION: This image forming material has an adhesive layer, a photosensitive layer contg. a polymerizable compd. and a photopolymn. initiator and a peelable cover sheet on the substrate and at least one selected from among the substrate, adhesive layer and cover sheet has absorption in a wavelength region other than the max. wavelength of absorption of the photopolymn. initiator. The max. wavelength of absorption of the initiator is <=400nm and the wavelength region of absorption of at least one selected from among the substrate, adhesive layer and cover sheet is >400nm, or the max. wavelength of absorption of the initiator is >=700nm and the wavelength region of absorption of at least one selected from among the substrate, adhesive layer and cover sheet is <700nm.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming material which can be dry-developed, and more particularly to an image forming material which can be handled in a bright room.

[0002]

2. Description of the Related Art An image forming material using a photopolymerizable composition containing at least a polymerizable compound and a photopolymerization initiator is used, for example, for producing a colored image such as a color proof.
-188537, 61-286858, etc. These are used after image-wise exposing the photosensitive layer to elute the unexposed area with a liquid to form an image consisting of the exposed area, and the process of maintaining the developing device and adjusting the developing solution is complicated. In addition, since the development waste liquid needs to be treated, there are many problems in terms of worker safety and environmental suitability.

On the other hand, as a method for forming an image by a dry process, US Pat. Nos. 4,489,154 and 4,282,308, and JP-A-58 are used.
-24775, JP-A-2-66547, JP-A-4-153658 and the like, as disclosed in each publication, a transparent support, a photosensitive composition layer,
After exposing the image to the material comprising the intermediate layer and the second support, the transparent support and the second support are peeled off to form a positive image on one support and a negative image on the other support. Peel development method and U.S. Pat.Nos. 3,060,023 and 3,060,024
No. 3,060,025, JP-A-63-147154, etc., an image is formed on an image-forming material having at least a photosensitive composition layer on a support through a color separation negative or a mask. A transfer development method in which the surface of the photosensitive composition layer that has been exposed and exposed is brought into pressure contact with the image receptor while applying heat to the image receptor and the unexposed portion is transferred onto the image receptor to form an image. Have been proposed.

The image forming method by such dry processing is
This is a preferable method in terms of environmental pollution, safety, and miniaturization of the device. Among them, as in the former, the process that can form an image only by peeling two supports after exposure is
Since it does not require a special developing device, it is excellent as a low-cost image forming material. U.S. Patents 4,489,154 and 4,2
No. 82,308 includes a transparent support, a photosensitive layer, an adhesive intermediate layer,
Although a peel-development type image forming material composed of a base material is disclosed, there is a strong demand for handling it in a bright room from the viewpoint of ease of use as an image forming material, and in the case of a material that forms an image by light, Therefore, the exposure (writing) wavelength is set to a wavelength other than the visible portion, for example, ultraviolet or infrared.

[0005]

With respect to this point, in the image-forming material having a photosensitive layer having at least a polymerizable compound and a photopolymerization initiator, which is the object of the present invention, absorption of a dye serving as a photopolymerization initiator is absorbed. It can be considered that the wavelength can be set to a wavelength other than the visible region, for example, ultraviolet or infrared. However, in the initiator, it is easy to give the absorption maximum to ultraviolet light or infrared light, but it is not easy to prevent even the bottom of the absorption from reaching the visible part. Fogging may occur due to absorption of the hem.

The present invention has been made based on the above circumstances. That is, it is an object of the present invention to allow a dry-developable image forming material to be handled in a bright room (fluorescent lamp: 400 to 700 nm).

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that an adhesive layer on a substrate,
It has a photosensitive layer containing a polymerizable compound and a photopolymerization initiator and a peelable cover sheet, and at least one selected from a substrate, an adhesive layer and a cover sheet is different from the absorption maximum wavelength of the photopolymerization initiator. It has been found that by constructing to have absorption in the wavelength region, it can be handled in a bright room and the storability is improved.

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

<Image-forming material> -Cover sheet The cover sheet may be a resin layer provided on the surface of the photosensitive layer by a coating method, a resin layer such as a transfer foil transferred, or a resin film laminated. The resin film can be used depending on the case, but a resin film is particularly preferable.

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

As the resin used for the cover sheet,
Polyvinyl alcohol resins; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; acrylic resins such as methyl methacrylate; polyolefin resins such as polyethylene and polypropylene; and resin films, self-supporting release materials. A mold layer forming resin can also be preferably used.

It is also preferable to treat the surface of the cover sheet on the photosensitive layer side. As a method of this surface treatment,
Corona discharge treatment, flame treatment, ozone treatment, ultraviolet treatment,
Known resin surface modification techniques such as radiation treatment, surface roughening treatment, chemical treatment, plasma treatment, 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)", Kagaku Dojin, Chapter 2, and "Handbook of New Polymer Materials", Maruzen, Chapter 8, etc., and use one or more of them. Can also be used together. Especially discharge treatment,
It is preferable to place it after a primer treatment.

In order to enable handling in a bright room, the absorption maximum in the photopolymerization initiator is set to ultraviolet (400 nm or less) or infrared (700 nm or more), and the region corresponding to the visible side skirt of the absorption is A colorant having absorption at a wavelength is added to the cover sheet or provided as a separate layer on the cover sheet so that the transmittance is 50% or more at the maximum absorption wavelength of the photopolymerization initiator. At this time, since the cover sheet needs to have high actinic ray transparency, in order to suppress performance deterioration at this point, a coloring agent having high transparency to actinic rays as much as possible, such as indoaniline, azomethine, and spiro compounds, Ferrocene, fluorenone, fulgide, imidazole, perylene, phenazine, phenothiazine, carotene, maleic acid derivative, pyrazolone, stilbene, styryl, dithizone, formazan, acridone, anthanthrone, indanthrene, pyrenodione, violanthrone, indigo, diphenylmethane, fluorane, fluorescein, fluorane, fluorane. Rhodamine, cyanine, pyridinium, pyrylium, quinolinium, rhodanine, acridine, acridinone, carbostyril, coumarin, diphenylamine, quinacridone, quinophthalone, fu Nokisajin, phthaloperinone, porphine, chlorophyll, phthalocyanine, crown, squarylium, a dye such as tetrathiafulvalene is suitable.

As an antistatic measure, various antistatic agents such as ionic, anionic, cationic, amphoteric, and conductive resins are added to the cover sheet or the photosensitive layer of the cover sheet, as long as it does not interfere with the exposure. It can be used by coating on the side opposite to the laminated side.

In order to improve the running property in the exposure / developing apparatus, it is possible to carry out a surface matting treatment on the side opposite to the side where the photosensitive layers are laminated within a range that does not hinder the exposure.

The thickness of the cover sheet is usually preferably 1 to 200 μm, more preferably 5 to 125 μm.

Substrate As the substrate, paper, synthetic paper (for example, synthetic paper containing polypropylene as a main component), resin film or sheet, and further a plastic film or sheet obtained by laminating two or more layers of the resin, Alternatively, a film or sheet in which the above resin layer is laminated on various polymeric materials, metal, ceramics, paper made of wood pulp, cellulose pulp, sulfite pulp, or the like and the above resin layer can be used. Further, a film or sheet provided with a pigment coating layer having a porous structure on one side or both sides can also be preferably used.

As the resin constituting such a resin film or sheet, acrylic resins such as acrylic acid ester and methacrylic acid ester; polyester type resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate and polyarylate. Polyolefin resins such as polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polyethylene, polypropylene and polystyrene; polyamide resins such as nylon and aromatic polyamide; polyether ether ketone, polysulfone, polyether sulfone, polyimide, poly Ether imide, polyparabanic acid, phenoxy resin, epoxy resin, urethane resin, melamine resin, alkyd resin, phenol resin, fluorine resin, silicone resin, etc. And the like.

In the present invention, it is preferable that the resin-made base material is stretched into a sheet or film and heat-set from the viewpoint of dimensional stability, and the base material may have no internal microvoids or microvoids. Even if it exists, it 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 like, and the paper is made by using a rope rope paper machine or the like to improve smoothness. Then, it is preferable to carry out calendering using a machine calender, a super calender, a thermal calender or the like after paper making. Specific examples include high-quality paper, art paper, coated paper, single-glossy paper, impregnated paper, and paperboard. Further, paper coated with a resin layer containing a pigment can be preferably used for improving smoothness. Specific examples thereof include paper provided with a laminate layer of polyolefin resin such as polyethylene and polypropylene containing white fine particles. The base paper used in this case preferably has a Bekk smoothness of 50 seconds or more in order to have smoothness, more preferably 100 seconds or more, and further preferably 200 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 brightening agent, an antioxidant, and an anti-friction agent, if necessary. May be.

In order to enable handling in a bright room, the absorption maximum in the photopolymerization initiator is set to ultraviolet (400 nm or less) or infrared (700 nm or more), and a region corresponding to the skirt portion on the visible side of the absorption is set. A coloring agent having absorption at a wavelength is added to the base material or provided as a separate layer on the base material. At this time, since it is not necessary for the base material to transmit actinic rays, it is not necessary to pay particular attention to transparency, and it is more preferable that the base material is opaque from the viewpoint of shielding light. The colorant may be a dye or a pigment as long as it has an absorption at a wavelength of a region corresponding to at least the visible side skirt of the absorption, but a pigment system in terms of opacity and cost, Carbon black or the like is particularly desirable.

As antistatic measures, various antistatic agents such as ionic, anionic, cationic, amphoteric and conductive resins are added to the base material or coated on the side opposite to the cover sheet side of the base material. Can be used.

To improve the running property in the apparatus, it is possible to perform a surface mat treatment on the side opposite to the cover sheet side.

The thickness of the substrate is usually 2 to 300 μm, preferably 5 to 150 μm, and is appropriately selected from such a range.

Photosensitive Layer The photosensitive layer contains at least a photopolymerizable compound and a photopolymerization initiator.

Typical examples of the photopolymerizable compound include compounds capable of addition polymerization and / or crosslinking, and known monomers can be used without particular limitation. Specific examples of the monomer include 2-ethylhexyl acrylate and 2-ethylhexyl acrylate.
Monofunctional acrylic acid esters such as hydroxyethyl acrylate and 2-hydroxypropyl acrylate and their derivatives, or compounds obtained by replacing these acrylates with methacrylate, itaconate, crotonate, maleate, etc .; polyethylene glycol diacrylate, pentaerythritol diacrylate, bisphenol. A
Diacrylates, difunctional acrylates such as diacrylates of ε-caprolactone adduct of neopentyl glycol hydroxypivalate and their derivatives, or compounds in which these acrylates are replaced with methacrylates, itaconates, crotonates, maleates, etc .; Polyfunctional acrylic acid esters such as tri (meth) acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pyrogallol triacrylate and derivatives thereof,
Alternatively, compounds in which these acrylates are replaced with methacrylates, itaconates, crotonates, maleates and the like can be given.

A so-called prepolymer obtained by introducing photopolymerizability by introducing acrylic acid or methacrylic acid into an oligomer having a suitable molecular weight can also 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, further, "chemical products of 11290" Kagaku Kogyo Nippo, pages 286-294 compounds described The compounds described in “UV / EB Curing Handbook (Raw Materials)”, Kobunshi Kobunkai, pages 11 to 65, and the like can also be preferably used.

Of these, compounds having two or more acryl or methacryl groups in the molecule are preferred in the present invention, and the molecular weight is 10,000 or less, more preferably
It is less than 5,000. Further, in the present invention, one kind or a mixture of two or more kinds of these monomers or prepolymers can be used.

The polymerizable compound having an ethylenically unsaturated bond usually accounts for preferably 5% by weight or more, more preferably 15% by weight or more, in the photosensitive layer forming composition.

As the photopolymerization initiator, for example, any known photopolymerization initiator described on pages 39 to 56 of Photopolymer Handbook (Photopolymer Handbook, published by Industrial Research Institute, 1989) can be arbitrarily used. However, spectral sensitization of the photosensitive layer can be easily performed by using the compound represented by the following general formula (1) or (2), and thus image formation can be performed with any light source in the ultraviolet to near infrared region. It can be carried out. 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.

[0032]

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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 group, aryl group, The 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. In addition, R ₁ , R ₂ ,
Two or more of 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 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 ⁺ , JP-A-62-143044,
63-208036, 64-84245, 64-88444, JP-A-1
-152108, 3-202609, etc. can be used. Specific examples of preferable compounds are shown in the compound group A.

<< Compound Group A >>

[0038]

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[0039]

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[0040]

[Chemical 4]

[0041]

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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 >>

[0043]

[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 (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 Ph Bu Ru ²⁺ 2 2 N (C ₂ H ₅ ) ₂ NHCOC ₃ H ₇ (i) CH ₃ Bu Bu Bu Bu Bu Ru ²⁺ 2 2 N (C ₂ H ₅ ) ₂ NHCOC ₃ H ₇ (i) CH ₃ Ph P
h Ph Bz

[0045]

[Chemical 7]

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

[0047]

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M ²⁺ R ₁₁ Ru2 + Cl Ru2 + NHCOC3H7 (i) Co2 + Cl The photopolymerization initiator represented by the general formula (1) or (2) is, for example, one in which the dye anion part has been changed to boric acid in advance. However, 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 layer or the photosensitive layer coating. Even if the compound represented by the general formula (1) is produced by ion exchange in a working solution, the same function can be exhibited.
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.

[0049]

[Chemical 9]

In the formula, R ₁ , R ₂ , R ₃ and R ₄ have the same meaning 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.

Further, among the photopolymerization initiators used, the following UV-1 to 20 are mentioned as compounds having absorption in the ultraviolet region.

[0052]

[Chemical 10]

[0053]

[Chemical 11]

[0054]

[Chemical 12]

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, such as a diallyl phthalate resin and its derivative, chlorinated polypropylene, etc., can be polymerized with the above-mentioned compound having an ethylenically unsaturated bond, and therefore, it is suitably used depending on the application. be able to. 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 may be 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. preferable.

Examples of the colorant contained in the photosensitive layer of the present invention include carbon black, titanium oxide, iron oxide, phthalocyanine pigments, azo pigments, anthraquinone pigments, quinacridone pigments, crystal violet, methylene blue, and azo. The known pigments and / or dyes such as dyes, anthraquinone dyes, cyanine dyes and the like may be contained alone or in combination of two or more so as to satisfy the above absorbance.

The amount of the colorant added is preferably 1 to 80% by weight, more preferably 4 to 50% by weight in the photosensitive layer forming composition.

In order to add the colorant into the photosensitive layer, the colorant is added to the photosensitive layer composition other than the colorant, such as a sand mill, a ball mill, an attritor, an ultrasonic disperser, a jet mill, a homogenizer, and a planetary mill. It is possible to disperse and mix using a publicly-used device such as the above, and further filter the coating liquid as needed before use. It is also preferable that a part (or one kind) of the colorant is uniformly dissolved and used in the photosensitive layer.

The photosensitive layer may optionally 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.

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 in JP-B-45-37377 and U.S. Pat.
Examples thereof include bisimidazole compounds and thiols described in 3,652,275. The amount of the sensitizer added is 10 parts by weight or less, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the total of the polymerizable compound and the binder.

As the thermal polymerization inhibitor, compounds such as quinone type and phenol type are preferably used, and examples thereof include hydroquinone, pyrogallol, p-methoxyphenol, catechol, β-naphthol, 2,6-di-t-butyl-p. -Examples include cresol. Total of polymerizable compound and binder
10 parts by weight or less based on 100 parts by weight, preferably 0.01-5
About 10 parts by weight is added.

As the oxygen scavenger, N, N-dialkylaniline derivatives are preferable, for example, No. 1 of US Pat. No. 4,772,541.
The compounds described in column 1, line 58 to column 12, line 35 can be mentioned.

As the plasticizer, phthalic acid esters, trimellitic acid esters, adipic acid esters, other saturated or unsaturated carboxylic acid esters, oxalic 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 heat-meltable substances include terpineol, menthol,
Alcohols such as 1,4-cyclohexanediol and phenol; Amides such as acetamide and benzamide; Esters such as coumarin and benzyl cinnamate; Ethers such as diphenyl ether and 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; higher alcohols such as eicosanol; higher fatty acid esters such as cetyl palmitate; stearin Higher fatty acid amides such as acid amides; monomolecular compounds represented by higher amines such as behenylamine; beeswax, candelilla wax, paraffin wax, ester wax, montan wax, carnauba wax, amide wax, polyethylene wax, microcrystalline wax Waxes such as; ester gum, rosin maleic acid resin, rosin phenol resin and other rosin derivatives; phenol resin, ketone resin, epoxy resin, diallyl phthalate resin, terpene carbonization Containing resins, cyclopentadiene resins, polyolefin resins, polycaprolactone resins, polyethylene glycol, high molecular compounds typified polyolefin oxides such as polypropylene glycol and the like.

If necessary, an antioxidant, a filler, an antistatic agent, etc. may be added to the photosensitive layer.

As the antioxidant, a chroman compound,
Claman compounds, phenol compounds, hydroquinone derivatives, hindered amine derivatives, spiroindane compounds, sulfur compounds, phosphorus compounds and the like, JP-A-59-182785, 60-130735, 61-159644, JP-A-1-127387, "Chemical products of 11290" (previously) 862-86
The compounds described on page 8 and the like, and compounds known to improve durability in photographs and other image recording materials can be mentioned.

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 fluorine resin particles and guanamine resin. Examples include particles, resin particles such as acrylic resin particles, and silicon resin particles. Examples of the antistatic agent include cationic, anionic, nonionic surfactants, polymeric antistatic agents, conductive fine particles, and the like, as well as the compounds described in "Chemical products of 11290" pages 875 to 876, etc. 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.
Further, when it is composed of a plurality of layers, it may be composed of photosensitive layers having different compositions, and in this case, a photosensitive layer containing no colorant may be contained.

The thickness of the photosensitive layer is preferably 0.2 to 10 μm,
More preferably, it is 0.5 to 5 μm.

The photosensitive layer is prepared by dispersing or dissolving the forming components in a solvent to prepare a coating solution, and then directly laminating and coating it on the intermediate layer described below, or by coating and drying it on a cover sheet described later. It is formed.

As the solvent used for the coating, 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 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 appropriately adopted.

-Intermediate layer The intermediate layer is a layer for joining the photosensitive layer and the base material with an appropriate adhesive force, and when the image is formed, the base material and the cover sheet are peeled off to expose all / or one of the exposed portions of the photosensitive layer. Image is formed on the cover sheet side, and the adhesiveness is controlled so that all the unexposed areas of the photosensitive layer remain on the adhesive layer, or the photosensitive material is formed by peeling the cover sheet from the base material during image formation. It is necessary to form an image consisting of all / or part of the exposed portion of the layer on the side of the intermediate layer and control the adhesiveness so that all the unexposed portion of the photosensitive layer remains on the cover sheet.

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

Specific examples of the compound suitably 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 /
Rubbers such as acrylic rubber, urethane rubber, silicone rubber; polystyrene / polybutadiene / polystyrene block copolymer (SBS), SEBS obtained by hydrogenating polybutadiene of the SBS, polystyrene / polyisoprene / polystyrene block copolymer (SIS), etc. Styrene-based thermoplastic elastomer, 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, Polyvinyl chloride thermoplastic elastomer, natural rubber thermoplastic elastomer, fluororubber thermoplastic elastomer,
Thermoplastic elastomers such as trans-polyisoprene thermoplastic elastomer and chlorinated polyethylene thermoplastic elastomer; polyester resin, polyurethane resin, polyamide resin, olefin resin, vinyl chloride resin, (meth) acrylic resin , Styrene resin,
Thermoplastic resins such as polycarbonate, polycaprolactone resin, epoxy resin, phenoxy resin, and rubber resin.

The compounds preferably 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.

In order to enable handling in a bright room, the absorption maximum in the photopolymerization initiator is set to ultraviolet (400 nm or less) or infrared (700 nm or more), and at least a region corresponding to the skirt on the visible side of the absorption. A colorant having absorption at the wavelength of is added to the intermediate layer. At this time, since it is not necessary for the intermediate layer to transmit actinic rays, it is not necessary to pay particular attention to transparency, and it is more preferable that the intermediate layer is opaque from the viewpoint of blocking light. The colorant may be a dye or a pigment, as long as it has an absorption at a wavelength of a region corresponding to the skirt portion on the visible side of the absorption,
A pigment system, particularly carbon black or the like is preferable in terms of opacity and cost.

As antistatic measures, various antistatic agents such as ionic, anionic, cationic, amphoteric, and conductive resins can be added to the intermediate layer and used.

To improve the running property in the apparatus, it is possible to perform a surface matting treatment on the side opposite to the cover sheet side.

An ultraviolet absorber, an antioxidant, a filler, a plasticizer and the like can be further added to the intermediate layer, if necessary.

The intermediate layer is preferably provided on the substrate with a dry film thickness of 1 to 80 μm. Particularly preferably 3 to 50 μm
Is.

As the method for forming the intermediate layer, the intermediate layer composition is formed by hot-melt extrusion on the photosensitive layer formed on the substrate or the cover sheet, and the intermediate layer composition is formed with water or a suitable organic compound. A method is used in which it is dispersed or dissolved in a solvent and 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 laminate the base material and the photosensitive layer coated and formed on the cover sheet under heat and / or pressure.

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

<Image Forming Method> As the light source for forming an image, any light source that generates an electromagnetic wave active 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 and high pressure mercury lamps. When performing batch exposure using a xenon lamp, halogen lamp, carbon arc lamp, metal halide lamp, tungsten lamp, high pressure mercury lamp, etc.
A mask material having a negative pattern of a desired exposure image formed of a light-shielding material may be superimposed and exposed on the cover sheet side of the image forming material.

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.

A 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 reduce the exposure area to a minute size, and high-resolution image formation becomes possible. Argon laser,
It is possible to use He-Ne gas laser, YAG laser, semiconductor laser, etc., especially when using the above-mentioned photopolymerization initiator having sensitivity in the near-infrared region, it is relatively small and inexpensive and has high output. A semiconductor laser that is easy to obtain 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 and unexposed portions of the photosensitive layer to the cover sheet, and the cover sheet and the substrate are heated and / or heated after exposure if necessary. Alternatively, 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 a cover sheet or a substrate. The optimum peeling conditions differ depending on the image forming material used, but generally 90
It is preferable that the peeling angle is a large degree or more.

If necessary, image 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,
Any known light source such as a xenon flash lamp, a halogen lamp, a carbon arc lamp, a metal halide lamp, a tungsten lamp, an infrared lamp, a high pressure mercury lamp, a fluorescent lamp, and sunlight, as long as they act on the photopolymerization initiator in the photosensitive layer composition. Can also 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 they are practically usable as an image forming material. In this case, the same effect can be obtained whether it is a batch exposure or a scanning exposure.

For the 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 no practical problem.

[0093]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto. The structure of the dye used here is as follows.

[0094]

[Chemical 13]

Example 1 An intermediate layer having the following composition was coated on a polyethylene terephthalate film containing 20% by weight of carbon black having a thickness of 75 μm by wire bar coating so as to have a dry film thickness of 15 μm. An attached substrate was prepared.

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 Add 20% by weight of 50 μm dye (structural formula A λmax = 645 nm). The polyethylene terephthalate film prepared above was subjected to corona discharge treatment (80 W / m ² / min), and a photosensitive layer composition consisting of the following composition was applied onto the film to obtain a dry film thickness.
The photosensitive layer was provided so as to have a thickness of 3 μm.

Photosensitive Layer Composition Isocyanuric acid EO-modified (n = 3) triacrylate 30.0 parts by weight (Toa Gosei Chemical Industry Co., Ltd. M-315) Polymethylmethacrylate resin 30.0 parts by weight (Mitsubishi Rayon Co., Ltd.) Dyanal BR-83) Methyl ethyl ketone dispersion of black pigment 10.0 parts by weight as pigment solids (MHI-983 manufactured by Mikuni dye Co., Ltd.) 0.6 parts by weight cyanine dye (Kayasorb CY-10 λmax = 780 nm manufactured by Nippon Kayaku Co., Ltd.) Lithium butyl triphenyl borate 1.7 parts by weight 1-phenyl-5-mercaptotetrazole 0.9 parts by weight Methyl ethyl ketone (MEK) 400 parts by weight The intermediate layer surface of the substrate with the intermediate layer and the photosensitive layer surface are superposed,
An image forming material was prepared by passing between a pair of hot-press rolls under the following conditions.

Temperature: 60 ° C. Pressure: 1.2 Kg / cm ² Conveying speed: 10 mm / sec Scanning exposure was performed imagewise from the cover sheet side of the image forming material prepared under the following conditions.

Light source: LT090MD manufactured by Sharp Co., Ltd. Output 100 mW, main wavelength 830 nm Optical efficiency: 67% Exposure beam diameter: 10 μm Exposure pitch: 6 μm The above work was performed in a bright room, and the substrate and cover of the image forming material after exposure When the sheet and the sheet were peeled at a temperature of 25 ° C and a speed of 80 cm / sec, an image consisting of exposed areas was clearly obtained on the cover sheet side, and all unexposed areas were pulled out onto the intermediate layer, causing fogging on the cover sheet. No dirt was generated. still,
The transmittance of the cover sheet at the absorption maximum wavelength of 780 nm of the initiator dye was 78%.

Example 2 A polyethylene terephthalate film having a thickness of 75 μm (T-100 manufactured by Diafoil Hoechst) was coated with an intermediate layer having the following composition by wire bar coating to give a dry film thickness of 15 μm.
Was applied to prepare a substrate with an intermediate layer.

Intermediate layer 15 parts by weight of ethylene / vinyl acetate copolymer (Evaflex EV-210 manufactured by Mitsui DuPont Polychemical Co., Ltd.) MEK dispersion of carbon black 3 parts by weight as solid content (MHI manufactured by Mikuni Pigment Co., Ltd.) # 210) 85 parts by weight of toluene A polyethylene terephthalate film containing 85 parts by weight of 75 μm dye (structural formula C λmax = 465 nm) in an amount of 15% by weight was subjected to corona discharge treatment (80 W / m ² / min), and then a photosensitive composition having the following composition The photosensitive layer composition was coated with a wire bar to form a photosensitive layer so that the dry film thickness was 3 μm.

Photosensitive layer composition Dipentaerythritol hexaacrylate 40.0 parts by weight (Nippon Kayaku Co., Ltd. KAYARAD DPHA) Polymethylmethacrylate resin 40.0 parts by weight (Mitsubishi Rayon Co., Ltd. DIANAR BR-83) Carbon black MEK Dispersion 10.0 parts by weight as solid content (DM-022 manufactured by Mikuni Dye Co., Ltd.) Initiator 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2' -Bisimidazole 2.0 parts by weight (Toshiba Chemical Co., Ltd., λmax = 335 nm) Methyl ethyl ketone 400 parts by weight The intermediate layer surface of the substrate with the intermediate layer and the photosensitive layer surface are overlapped,
An image forming material was prepared by passing between a pair of hot-press rolls under the following conditions.

Temperature: 60 ° C. Pressure: 1.2 Kg / cm ² Conveyance speed: 10 mm / sec The prepared image-forming material was contact-exposed from the cover sheet side with a halftone negative under the following conditions by a printer for light-sensitive room light-sensitive material.

Light source: P-627-HA manufactured by Dainippon Screen Co., Ltd. Exposure amount: 25 counts (about 30 mJ / cm ² ) The above work was performed in a bright room, and a base material and a cover sheet of the image forming material after exposure were used. When peeled off at a temperature of 25 ° C and a speed of 80 cm / sec, an image consisting of exposed areas was clearly obtained on the cover sheet side, all unexposed areas were pulled out onto the intermediate layer, and the cover sheet was not stained by fog. Did not occur. still,
The transmittance of the cover sheet at the absorption maximum wavelength of 340 nm of the initiator dye was 71%.

Example 3 On a polyethylene terephthalate film containing a 50 μm thick black pigment (manufactured by Mikuni Dye Co., Ltd., 20% by weight as a pigment solid content), an intermediate layer having the following composition was coated by a wire bar to give a dry film thickness. Of 15 μm was applied to prepare a substrate with an intermediate layer.

Intermediate layer 15 parts by weight of ethylene / vinyl acetate copolymer (Evaflex EV-210 manufactured by Mitsui DuPont Polychemical Co., Ltd.) 85 parts by weight of toluene 10% by weight of 100 μm dye (structural formula B λmax = 645 nm) was added. Polyethylene terephthalate film (manufactured by DIAFOIL Hoechst) was subjected to corona discharge treatment (80 W / m ² / mi
n) was applied, and a photosensitive layer composition having the following composition was applied thereon by wire bar coating to form a photosensitive layer having a dry film thickness of 4 μm.

Photosensitive layer composition Dipentaerythritol hexaacrylate 60 parts by weight Pentaerythritol / terephthalic acid / acrylate 60 parts by weight (pentaerythritol: terephthalic acid: acrylic acid = 2: 1: 7) Acrylic resin 80 parts by weight (butyl acrylate)・ Ethyl acrylate / maleic anhydride copolymer) Cyanine dye 5 parts by weight (Nippon Kayaku Co., Ltd. Kayasorb CY-10 λmax = 780 nm) Lithium butyl triphenylborate 8 parts by weight 1-phenyl-5-mercaptotetrazole 4 parts by weight Part Methyl ethyl ketone 1000 parts by weight The intermediate layer surface of the substrate with intermediate layer and the photosensitive layer surface are overlapped,
An image forming material was prepared by passing between a pair of hot-press rolls under the following conditions.

Temperature: 60 ° C. Pressure: 1.2 Kg / cm ² Conveying speed: 10 mm / sec Scanning exposure was performed imagewise from the cover sheet side of the prepared image forming material under the following conditions.

Light source: LT090MD manufactured by Sharp Co., Ltd. Output 100 mW, main wavelength 830 nm Optical efficiency: 67% Exposure beam diameter: 10 μm Exposure pitch: 6 μm The above work was performed in a bright room, and the substrate and cover of the image forming material after exposure When the sheet and the sheet were peeled at a temperature of 25 ° C and a speed of 80 cm / sec, an image consisting of exposed areas was clearly obtained on the cover sheet side, and all unexposed areas were pulled out onto the intermediate layer, causing fogging on the cover sheet. No dirt was generated. still,
The transmittance of the cover sheet at the absorption maximum wavelength of 780 nm of the initiator dye was 75%.

Comparative Example 1 A polyethylene terephthalate film having a thickness of 100 μm (T-100 manufactured by Diafoil Hoechst) was coated with an intermediate layer having the following composition by wire bar coating to give a dry film thickness of 15 μm.
Was applied to prepare a substrate with an intermediate layer.

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 Thickness after corona discharge treatment (80 W / m ² / min) 150 μm
On the polyethylene terephthalate film (T-100 manufactured by Diafoyhext), a photosensitive layer composition having the following composition was applied by a wire bar to form a photosensitive layer having a dry film thickness of 4 μm.

Photosensitive layer composition Isocyanuric acid EO-modified (n = 3) triacrylate 30.0 parts by weight (Toa Gosei Chemical Industry Co., Ltd. M-315) Polymethylmethacrylate resin 30.0 parts by weight (Mitsubishi Rayon Co., Ltd. Dianal) BR-83) Methyl ethyl ketone dispersion of black pigment 10.0 parts by weight as pigment solids (MHI-983 manufactured by Mikuni Dye Co., Ltd.) Cyanine dye 0.6 parts by weight (Kayasorb CY-10 λmax = 780 nm manufactured by Nippon Kayaku Co., Ltd.) Lithium Butyltriphenylborate 1.7 parts by weight 1-phenyl-5-mercaptotetrazole 0.9 parts by weight Methylethylketone 400 parts by weight The intermediate layer surface of the substrate with the intermediate layer and the photosensitive layer surface are overlapped,
An image forming material was prepared by passing between a pair of hot-press rolls under the following conditions.

Temperature: 60 ° C. Pressure: 1.2 kg / cm ² Conveying speed: 10 mm / sec Scanning exposure was performed imagewise from the cover sheet side of the image forming material prepared under the following conditions.

Light source: LT090MD manufactured by Sharp Corp. Output 100 mW, main wavelength 830 nm Optical efficiency: 67% Exposure beam diameter: 10 μm Exposure pitch: 6 μm The above work was performed in a bright room, and the base material and cover of the image forming material after exposure When the sheet was peeled off at a temperature of 25 ° C. and a speed of 80 cm / sec, an image consisting of an exposed portion was obtained on the cover sheet side, but the cover sheet was stained by fogging.

Comparative Example 2 A polyethylene terephthalate film having a thickness of 75 μm (T-100 manufactured by Diafoil Hoechst) was coated with an intermediate layer having the following composition by wire bar coating to give a dry film thickness of 15 μm.
Was applied to prepare a substrate with an intermediate layer.

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 Thickness after corona discharge treatment (80 W / m ² / min) A photosensitive layer composition having the following composition was applied onto a 50 μm polyethylene terephthalate film (T-100 manufactured by Diafoil Hoechst) by wire bar coating to form a photosensitive layer having a dry film thickness of 4 μm.

Photosensitive layer composition Dipentaerythritol hexaacrylate 40.0 parts by weight (Nippon Kayaku Co., Ltd. KAYARAD DPHA) Polymethylmethacrylate resin 40.0 parts by weight (Mitsubishi Rayon Co., Ltd. Dianal BR-83) Carbon black MEK Dispersion 10.0 parts by weight as solid content (DM-022 manufactured by Mikuni Dye Co., Ltd.) 2.0 parts by weight 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1 2,2'-Bisimidazole (λmax = 335nm) Methyl ethyl ketone 400 parts by weight Superimposing the intermediate layer surface and the photosensitive layer surface of the substrate with intermediate layer,
An image forming material was prepared by passing between a pair of hot-press rolls under the following conditions.

Temperature: 60 ° C. Pressure: 1.2 Kg / cm ² Conveying speed: 10 mm / sec The prepared image-forming material was contact-exposed from the cover sheet side to the halftone negative from the cover sheet side under the following conditions with a printer for light-sensitive room light-sensitive material.

Light source: P-627-HA manufactured by Dainippon Screen Co., Ltd. Exposure amount: 25 counts (about 30 mJ / cm ² ) The above work was performed in a bright room, and the base material and cover sheet of the image forming material after exposure were used. When peeled at a temperature of 25 ° C. and a speed of 80 cm / sec, an image consisting of an exposed area was obtained on the cover sheet side, but stains due to fog occurred on the cover sheet.

[0120]

According to the present invention, it is possible to obtain an image forming material free from fog even when exposed in a bright room.

Claims (6)

[Claims] 1. An adhesive layer, a photosensitive layer containing a polymerizable compound and a photopolymerization initiator, and a peelable cover sheet are provided on a substrate, and at least selected from the substrate, the adhesive layer and the cover sheet. One of the image forming materials is characterized by having absorption in a wavelength region different from the absorption maximum wavelength of the photopolymerization initiator. 2. The absorption maximum wavelength of the photopolymerization initiator is 400 nm or less, and the absorption wavelength region of at least one selected from the base material, the adhesive layer and the cover sheet is larger than 400 nm. Image forming material. 3. The absorption maximum wavelength of the photopolymerization initiator is 700 nm or more, and the absorption wavelength region of at least one selected from the base material, the adhesive layer and the cover sheet is less than 700 nm. Image forming material. 4. The transmittance of light having a maximum absorption wavelength of the polymerization initiator of the base material, the adhesive layer and the cover sheet having the absorption is 50% or more. Image forming material. 5. The image forming material according to claim 1, wherein at least one outer surface selected from a base material and a cover sheet is subjected to an antistatic treatment. 6. The image forming material according to claim 1, wherein at least one outer surface selected from a base material and a cover sheet is subjected to a runnability improving process.