JP5737573B2 - Release film and method for producing resin laminate - Google Patents

Description

  The present invention relates to a release film and a method for producing a resin laminate.

  Conventionally, in order to protect the surface of an optical member of various displays such as a CRT display device, a liquid crystal television, and a mobile phone, a resin plate having transparency as a display front plate is used on the front surface of the optical member.

  However, since the resin plate having transparency is softer than glass, scratches due to scratching or the like are likely to occur.

  As a method for improving the scratch resistance of the substrate surface, a method of forming a cross-linked film obtained using a polyfunctional monomer such as polyfunctional (meth) acrylate on the substrate surface is known.

  However, in the conventional crosslinked coating, when dirt such as fingerprints, sebum, sweat, and cosmetics adheres, the dirt is easily noticeable and it is difficult to remove the dirt.

  Under such circumstances, the performance of the resin plate often requires not only scratch resistance but also antifouling properties.

  As a technique for improving the scratch resistance and antifouling property, for example, Patent Document 1 discloses a release layer surface and a resin of a release film having a cured film of a specific active energy ray-curable composition as a release layer. A method is proposed in which a plate is cured after being laminated through a specific active energy ray-curable coating composition, and then cured, and then a release film is peeled off to obtain a resin laminate.

  In the above method, when the fluorine-containing monomer in the active energy ray-curable coating composition is cured using a release film having a release layer having a low surface tension, the fluorine-containing portion is applied to the coating surface. By orientation, a resin laminate having a cured film having excellent scratch resistance and antifouling properties can be obtained.

  However, in the release film of Patent Document 1, the curing shrinkage of the release layer forming composition when forming the release layer of the release film is large, and the obtained release film is easily curled and inferior in handleability. There is a tendency. Moreover, it may not be said that the surface tension of the release layer surface is sufficiently low, and the release property when peeling the release film may not be sufficient.

JP 2009-215517 A

  The present invention provides a release film having excellent adhesion between a base film and a release layer of a release film, a release property with a cured coating of a fluorine-containing monomer and water and oil repellency, and curling is suppressed. Provide a method for producing a resin laminate having excellent antifouling properties

The gist of the present invention is that tetrafunctional or higher functional (meth) acrylate (A1), perfluoropolyether (meth) acrylate (B1), organic solvent (C1) , and 2-hydroxy-1- [4- { 4- (2-hydroxy-2-methyl-propionyl) -benzyl} phenyl] -2-methyl-propan-1-one and 2-methyl-1- (4-methylthiophenyl) -2morpholinopropan-1-one After the ultraviolet curable composition (1) containing at least one photopolymerization initiator (D1) selected from is applied onto a film substrate and the organic solvent (C1) in the coating film is volatilized A release film in which a release layer of 0.2 to 1.5 μm obtained by curing by irradiating ultraviolet rays is formed on a film substrate is defined as a first invention.

Moreover, the gist of the present invention is that the active energy ray-curable composition containing perfluoropolyether (meth) acrylate (B2) on the surface of the resin base material, having the following steps (a) to (c). The manufacturing method of the resin laminated body in which the cured film of (2) was laminated | stacked is made into 2nd invention. (I) Tetrafunctional or higher-functional (meth) acrylate (A1), perfluoropolyether (meth) acrylate (B1), organic solvent (C1) , and 2-hydroxy-1- [4- {4- (2-hydroxy 2-methyl-propionyl) -benzyl} phenyl] -2-methyl-propan-1-one and 2-methyl-1- (4-methylthiophenyl) -2morpholinopropan-1-one By applying an ultraviolet curable composition (1) containing the photopolymerization initiator (D1) on the film substrate, volatilizing the organic solvent (C1) in the coating film, and then irradiating with ultraviolet rays The surface of the release layer of the release film in which the release layer having a thickness of 0.2 to 1.5 μm obtained by curing is formed on the film substrate and the resin substrate are combined with perfluoropolyether (meta A) Coating film-containing laminate forming step (b) activity of the active energy ray-curable composition (2) obtained by laminating through the coating film of the active energy ray-curable composition (2) containing the relate (B2) An active energy ray-curable composition (2) in which a coating film-containing laminate of the energy ray-curable composition (2) is irradiated with active energy rays to form a cured film of the active energy ray-curable composition (2). Cured film-containing laminate forming step (c) Peeling step of peeling the release film from the cured film-containing laminate of the active energy ray-curable composition (2)

  The release film of the present invention is excellent in handleability because it is difficult to curl, and has excellent water and oil repellency, so that it has excellent antifouling properties using the release film of the present invention. The excellent resin laminate can be suitably used as a front plate for various displays such as CRTs, liquid crystal televisions, and mobile phones.

Explanatory drawing which shows one example of the manufacturing method of the resin laminated body of this invention

Tetrafunctional or higher (meth) acrylate (A1)

The tetrafunctional or higher functional (meth) acrylate (A1) used in the present invention is one of the components of the ultraviolet curable composition (1) described later.

  Tetrafunctional or higher (meth) acrylate (A1) is a monomer having four or more (meth) acryloyl groups in the molecule.

  Examples of the tetrafunctional or higher functional (meth) acrylate (A1) include ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate. Dipentaerythritol hexa (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, ethylene oxide-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) ) Acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate. These can be used individually by 1 type or in combination of 2 or more types.

  Among these, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate are UV curing compositions (1). It is preferable at the point which is excellent in property and the abrasion resistance of the cured film obtained. Further, dipentaerythritol hexa (meth) acrylate is more preferable from the viewpoint of curability of the ultraviolet curable composition (1).

In the present invention, “(meth) acrylate” means “acrylate” or “methacrylate”, and “(meth) acryloyl group” means “acryloyl group” or “methacryloyl group”, respectively.

Perfluoropolyether (meth) acrylate (B1)

The perfluoropolyether (meth) acrylate (B1) used in the present invention is a component for reducing the surface tension of the release layer of the release film, which will be described later, and improving the water and oil repellency of the release film. In addition, perfluoropolyether (meth) acrylate (B1) reduces the surface tension of the release layer, thereby improving the peelability of the active energy ray-curable composition (2) described later from the cured film. It is also a component of.

  The perfluoropolyether (meth) acrylate (B1) is a monomer having a group having at least one perfluoropolyether unit and at least one (meth) acryloyl group.

The perfluoropolyether units, _{e.g., - [CF 2 CF 2 O} ] -, - [CF 2 O] - and the like.

  The presence of a group having a perfluoropolyether unit imparts water / oil repellency to the surface of the release layer.

  The group having a perfluoropolyether unit in the perfluoropolyether (meth) acrylate (B1) is more on the surface of the release layer of the release film than the fluorinated alkyl group of the fluorinated alkyl (meth) acrylate. It is easy to gather and can impart excellent water and oil repellency to the surface of the release layer.

  On the other hand, the (meth) acryloyl group in the perfluoropolyether (meth) acrylate (B1) is converted into a perfluoropolyether (()) in the release layer by a crosslinking reaction in the curing of the ultraviolet curable composition (1) described later. Immobilization of the (meth) acrylate (B1) unit can be improved, and excellent water and oil repellency can be exhibited even under various storage conditions or use conditions.

  In the present invention, as the perfluoropolyether (meth) acrylate (B1), the fixing of the perfluoropolyether (meth) acrylate (B1) unit in the release layer and the water and oil repellency of the release film are provided. In this respect, those having two or more (meth) acryloyl groups in the molecule are preferred.

  The perfluoropolyether (meth) acrylate (B1) is not particularly limited, and a known perfluoropolyether (meth) acrylate can be used.

Examples of commercially available products of perfluoropolyether (meth) acrylate (B1) include “OPTOOL DAC-HP” (trade name) manufactured by Daikin Industries, Ltd., and “Fluorolink MD500” manufactured by Solvay Solexis Co., Ltd. (Trade name), Fluorolink MD700 "(trade name)," Fluorolink 5105X "(trade name) and" Fluorolink 5101X "(trade name), and" Megafuck RS-75 "(trade name) and" Mega "manufactured by DIC Corporation Fuck RS-76-NS "(trade name). These can be used individually by 1 type or in combination of 2 or more types.

Organic solvent (C1)

Examples of the organic solvent (C1) used in the present invention include non-fluorine solvents such as hydrocarbon solvents and fluorine-containing solvents.

  Specific examples of the non-fluorine solvent include ketones such as methyl ethyl ketone, acetone and methyl isobutyl ketone; monohydric alcohols such as ethanol, 1-propanol, 2-propanol, butanol and 1-methoxy-2propanol, ethylene glycol, diethylene glycol, Alcohols such as polyhydric alcohols such as propylene glycol; esters such as ethyl acetate, butyl acetate and γ-butyrolactone; ethers such as diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, tetrahydrofuran and 1,4-dioxane; toluene, xylene And aromatic amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.

  Specific examples of the fluorine-containing solvent include fluorine-containing alcohols, fluorine-containing ethers, hydrofluorocarbons, and ditrifluoromethylbenzene.

Specific examples of the fluorinated alcohol include H (CF ₂ ) _m (CH ₂ ) _n —OH, F (CF ₂ ) _o (CH ₂ ) _p —OH, F (CF ₂ ) _q CH═CHCH ₂ OH and F _{(CF 2)} a compound represented by _{r CH 2 CH (I) CH} 2 OH and the like. In the above formula, m, n, o, p, q and r each independently represent an integer of 1 to 8.

Specific examples of the fluorine-containing ether include compounds represented by R ²¹ —O—R ²² . In the above formula, R ²¹ and R ²² are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, and at least one of R ²¹ and R ²² contains a fluorine atom.

  Examples of the fluorinated ether include hydrofluoroalkyl ether. Moreover, as a commercial item of fluorine-containing ether, Sumitomo 3M Co., Ltd. product "HE-7100" (brand name) and "HFE-7200" (brand name) are mentioned, for example.

  Specific examples of the hydrofluorocarbon include a hydrofluorocarbon having a chain structure and a cyclic structure.

  Examples of commercially available hydrofluorocarbons include “Bertrel HFC43-10mee” (trade name) manufactured by Mitsui DuPont Fluorochemical Co., Ltd. and “Zeorolla H” (trade name) manufactured by Nippon Zeon Co., Ltd.

  Specific examples of ditrifluoromethylbenzene include o-ditrifluoromethylbenzene, m-ditrifluoromethylbenzene, p-ditrifluoromethylbenzene, and mixtures thereof.

An organic solvent (C1) can be used individually by 1 type or in combination of 2 or more types.

Photopolymerization initiator (D1)

The photopolymerization initiator (D1) used in the present invention is 2-hydroxy-1- [4- {4- (2-hydroxy-2-methyl-propionyl) -benzyl} phenyl] -2-methyl-propane- It is preferably at least one photopolymerization initiator selected from 1-one and 2-methyl-1- (4-methylthiophenyl) -2morpholinopropan-1-one.

  By using the photopolymerization initiator (D1), the curability of the ultraviolet curable composition (1) in the surface layer part forming the surface layer of the release layer of the release film, and the release layer and the active energy of the release film The releasability of the linear curable composition (2) from the cured film and the antifouling property of the cured film of the active energy ray curable composition (2) can be improved.

  In this invention, photoinitiators other than a photoinitiator (D1) can be used together as needed.

Examples of the photopolymerization initiator (D1) include other photopolymerization initiators such as benzophenone, 4,4′-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, and 4-phenylbenzophenone. , Thioxanthones such as t-butylanthraquinone, 2-ethylanthraquinone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone; diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1 Acetophenones such as -one, benzyldimethyl ketal, 1-hydroxycyclohexyl-phenylketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; Benzoin ethers such as tellurium, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine And acylphosphine oxides such as oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; methylbenzoylformate; 1,7-bisacridinylheptane and 9-phenylacridine. These can be used individually by 1 type or in combination of 2 or more types.

UV curable composition (1)

The ultraviolet curable composition (1) used in the present invention is a raw material for forming a release layer of a release film.

  The ultraviolet curable composition (1) contains a tetrafunctional or higher functional (meth) acrylate (A1), a perfluoropolyether (meth) acrylate (B1), an organic solvent (C1), and a photopolymerization initiator (D1).

  As a compounding quantity of the perfluoropolyether (meth) acrylate (B1) in an ultraviolet curable composition (1), 2-5 mass parts is with respect to 100 mass parts of tetrafunctional or more (meth) acrylate (A1). Preferably, 2.5 to 3.5 parts by mass are more preferable. The blending amount of the perfluoropolyether (meth) acrylate (B1) is 2 parts by mass or more, and the peelability between the cured film of the active energy ray-curable composition (2) and the release layer of the release film is improved. Tend to be able to. Moreover, the blending amount of the perfluoropolyether (meth) acrylate (B1) is 4 parts by mass or less, and the curability of the ultraviolet curable composition (1) is improved, and the active energy ray curable composition (2) is improved. There exists a tendency which can make the peelability of a cured film and the release layer of a release film favorable.

  The blending amount of the organic solvent (C1) is preferably 10% by mass or more in the ultraviolet curable composition (1), and the thickness of the coating film after the organic solvent (C1) is volatilized and the load during drying. In the ultraviolet curable composition (1), 99 mass% or less is preferable.

As a compounding quantity of a photoinitiator (D1), with respect to 100 mass parts of tetrafunctional or more than (meth) acrylate (A1) at the point which the hardening acceleration | stimulation effect | action expresses and the productivity of hardened | cured material tends to improve. 0.1 to 10 parts by mass is preferable.

Release layer

In this invention, a mold release layer is obtained by hardening the coating film formed by apply | coating an ultraviolet curable composition (1) on the film base material mentioned later.

  The film thickness of the release layer is 0.2 to 1.5 μm, preferably 0.35 to 1 μm. By making the film thickness of the release layer 0.2 μm or more, the peelability between the cured film of the active energy ray-curable composition (2) and the release layer can be improved. Moreover, curling of the release film can be suppressed by setting the film thickness of the release layer to 1.5 μm or less. Furthermore, by setting the film thickness of the release layer to 0.2 μm or more, the curability of the surface of the release layer is improved, and scratches due to contact with the metal roll during transportation of the obtained release film are improved. Occurrence can be suppressed.

  Examples of the method for applying the ultraviolet curable composition (1) on the film substrate include a casting method, a roller coating method, a bar coating method, a spray coating method, an air knife coating method, a spin coating method, and a flow coating. Method, curtain coating method and dipping method.

  In this invention, after volatilizing the organic solvent (C1) in the coating film of the ultraviolet curable composition (1) on a film base material, it hardens | cures by irradiating an ultraviolet-ray and forms a release layer. Can do.

  The drying temperature for volatilizing the organic solvent (C1) can be arbitrarily set according to the type of the organic solvent (C1) used and the drying time.

  The coating film of the ultraviolet curable composition (1) on the film substrate is cured by ultraviolet rays.

  Examples of the light source include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a fluorescent lamp, and a metal halide lamp.

As the ultraviolet irradiation energy for curing the ultraviolet curable composition (1), the cured level of the surface of the release layer is sufficient, and the cured film and the release layer of the active energy ray curable composition (2) are used. 200 mJ / cm ² or more is preferable and 350 mJ / cm ² or more is more preferable in terms of the integrated light quantity with a wavelength of 320 to 380 nm.

  In the present invention, ultraviolet rays can be irradiated in an inert gas atmosphere as necessary for the purpose of achieving a sufficient curing level on the surface of the release layer.

  As the inert gas, nitrogen gas is preferable because of its low cost. In addition, the oxygen concentration in the ultraviolet irradiation atmosphere is preferably 300 ppm or less.

In the present invention, the contact angle of water on the surface of the release layer is preferably 105 degrees or more, and more preferably 110 degrees or more.

Film base

The film base used in the present invention is a base film for constituting a release film, and a release layer is formed on the surface of the film base.

  The film substrate is not particularly limited, but is preferably one having excellent active energy ray permeability and solvent resistance and low oxygen permeability.

  Specific examples of the film substrate include polyethylene terephthalate film (hereinafter referred to as “PET film”), nylon film, polycarbonate film, acrylic film, polyolefin film such as polypropylene and polyethylene, and cellulose such as diacetyl cellulose and triacetyl cellulose. And a polyvinylidene chloride film. Among these, a PET film is preferable because it has solvent resistance and low oxygen permeability.

  The thickness of the film substrate is preferably 10 μm or more in terms of film strength, and is preferably 200 μm or less in terms of handleability and cost.

  In the present invention, in order to improve the adhesion between the film base and the release layer, the surface of the film base is subjected to an easy adhesion treatment or a film having an easy adhesion layer laminated on the surface of the film base is used. It is preferable to do.

  Examples of the method for easily bonding the surface of the film substrate include chemical treatment methods such as primer treatment, solvent treatment, acid treatment, and alkali treatment, and physical treatment such as corona treatment, plasma treatment, atmospheric pressure plasma treatment, and flame treatment. For example.

  In the present invention, the primer treatment refers to a treatment for forming an easy-adhesion layer with good adhesion to the release layer on the film substrate.

In the present invention, the corona treatment refers to a treatment in which the surface of the film substrate is subjected to a discharge treatment to chemically modify the surface of the film substrate.

Release film

The release film of the present invention is a laminated film in which a release layer is laminated on a film substrate.

Resin base material

The resin base material used by this invention is a base material for obtaining the resin laminated body of this invention mentioned later.

  Examples of the resin base material include sheet-like materials such as polyolefin resin, methacrylic resin, epoxy resin, polyimide resin, phenol resin, polyester resin, and polycarbonate resin, and molded products having various shapes.

In the present invention, the resin of the resin base material is preferably a methacrylic resin from the viewpoint of transparency.

Perfluoropolyether (meth) acrylate (B2)

The perfluoropolyether (meth) acrylate (B2) used in the present invention is a monomer contained in the active energy ray-curable composition (2) described later.

As perfluoropolyether (meth) acrylate (B2), the same thing as perfluoropolyether (meth) acrylate (B1) is mentioned. These can be used individually by 1 type or in combination of 2 or more types.

Active energy ray-curable composition (2)

The active energy ray-curable composition (2) used in the present invention is a composition containing a perfluoropolyether (meth) acrylate compound (B2).

  In the present invention, the active energy ray-curable composition (2) can contain another vinyl monomer (E2).

  Other vinyl monomers (E2) include, for example, tetrafunctional or higher functional (meth) acrylate (E2-a), trifunctional (meth) acrylate (E2-b), and bifunctional (meth) acrylate (E2-c). ), Monofunctional (meth) acrylate (E2-d), and acrylic oligomer (E2-e). These can be used individually by 1 type or in combination of 2 or more types.

  Specific examples of the tetrafunctional or higher (meth) acrylate (E2-a) include those similar to the tetrafunctional or higher (meth) acrylate (A1). These can be used individually by 1 type or in combination of 2 or more types.

  Specific examples of the trifunctional (meth) acrylate (E2-b) include trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, and tris. ((Meth) acryloxyethyl) isocyanurate, caprolactone-modified tris ((meth) acryloxyethyl isocyanurate, pentaerythritol tri (meth) acrylate and alkyl-modified dipentaerythritol tri (meth) acrylate. Can be used alone or in combination of two or more.

  Specific examples of the bifunctional (meth) acrylate (E2-c) include ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth). Acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, ethylene oxide modified trimethylolpropane di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyester di (meth) acrylate, polyethylene glycol di (meth) acrylate, tri Chlodecane dimethylol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, 1,10-decandiol di (meth) acrylate and hydroxypivalate neopentyl glycol di ( And (meth) acrylate. These can be used individually by 1 type or in combination of 2 or more types.

  Specific examples of monofunctional (meth) acrylate (E2-d) include methyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylamide, 7-amino-3,7-dimethyloctyl (meth) acrylate, iso Butoxymethyl (meth) acrylamide, isobornyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, t-octyl (meth) acrylamide, (meth) acryloyl Morpholine, diacetone (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, dicyclopentadiene (meth) Chryrate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydroflur Furyl (meth) acrylate, tetrabromophenyl (meth) acrylate, 2-tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (meth) acrylate, tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl ( (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, phenoxye (Meth) acrylate, butoxyethyl (meth) acrylate, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, bornyl (meth) acrylate, Methyl triethylene diglycol (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-ethylhexyl polyoxy (meth) acrylate, benzyl (meth) acrylate, phenyloxyethyl (meth) acrylate, phenyloxyethyl ( (Meth) acrylate, tricyclodecane mono (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 3-hydroxy-3-fe Noxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate and 2 -Methacryloyloxyethyl-2-hydroxyethylphthalic acid. These can be used individually by 1 type or in combination of 2 or more types.

  Specific examples of the acrylic oligomer (E2-e) include urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, and polyester (meth) acrylate oligomers. These can be used individually by 1 type or in combination of 2 or more types.

  Specific examples of urethane (meth) acrylate oligomers include 1,5-diisocyanatopentane, 1,6-diisocyanatohexane, 1,4-diisocyanatopentane, 1,6-diisocyanato-3,5, 5-trimethylhexane, 1,6-diisocyanato-3,3,5-trimethylhexane, 1,12-diisocyanatododecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanate Natohexane, 1,6,11-triisocyanatoundecane, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphth Diisocyanate, norbornane diisocyanate, decalin diisocyanate, lysine diisocyanate, lysine triisocyanate and other isocyanate compounds, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, polyester polyol Polyol compounds such as polycarbonate diol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) Reacts with hydroxyl-containing (meth) acrylate such as acrylate Urethane (meth) acrylate oligomers; and 1,5-diisocyanatopentane, 1,6-diisocyanatohexane (HDI), 1,4-diisocyanatopentane, 1,6-diisocyanato-3,5, 5-trimethylhexane, 1,6-diisocyanato-3,3,5-trimethylhexane, 1,12-diisocyanatododecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanate Natohexane, 1,6,11-triisocyanatoundecane, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphth 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl to monomers or multimers of isocyanate compounds such as taleenedisocyanate, norbornane diisocyanate, decalin diisocyanate, lysine diisocyanate, lysine triisocyanate Examples include urethane (meth) acrylate oligomers to which hydroxyl group-containing (meth) acrylates such as (meth) acrylates and their caprolactone adducts are added. These can be used individually by 1 type or in combination of 2 or more types.

Specific examples of epoxy (meth) acrylate oligomers include (meth) acrylic acid or derivatives thereof in glycidyl ethers such as phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, bisphenol A type epoxy compounds, and bisphenol F type epoxy compounds. Examples include epoxy poly (meth) acrylate oligomers that have been reacted. These can be used individually by 1 type or in combination of 2 or more types.

  Specific examples of the polyester (meth) acrylate oligomer include polybasic acids such as phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and adipic acid, ethylene glycol, propylene glycol, neopentyl glycol, 1,6-hexanediol, Examples include polyester (meth) acrylate oligomers obtained by reaction of polyhydric alcohols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and bisphenol A with (meth) acrylic acid or derivatives thereof. These can be used individually by 1 type or in combination of 2 or more types.

  Other vinyl monomers (E2) include ditrimethylolpropane in terms of curability of the active energy ray-curable composition (2) and scratch resistance of the cured film of the active energy ray-curable composition (2). Preferred are tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate and trimethylolpropane tri (meth) acrylate. . Further, dipentaerythritol hexa (meth) acrylate is more preferable from the viewpoint of curability of the active energy ray-curable composition (2).

  The total content of the tetrafunctional (meth) acrylate (E2-a) and the trifunctional or higher functional (meth) acrylate (E2-b) in the active energy ray-curable composition (2) is preferably 60 to 95% by mass. 70 to 90% by mass is more preferable. Curability and activity of the active energy ray-curable composition (2) when the total content of the tetrafunctional (meth) acrylate (E2-a) and the trifunctional or higher (meth) acrylate (E2-b) is 60% by mass or more. The cured film of the energy ray curable composition (2) tends to have good transparency, scratch resistance and water / oil repellency. Curing shrinkage of the active energy ray-curable composition (2) when the total content of the tetrafunctional (meth) acrylate (E2-a) and the trifunctional or higher (meth) acrylate (E2-b) is 95% by mass or less. The rate can be lowered, the generation of cracks in the cured film of the active energy ray-curable composition (2) can be suppressed, and the cured film of the active energy ray-curable composition (2) and the resin substrate There exists a tendency which can make favorable adhesiveness of this.

  The content of the bifunctional (meth) acrylate (E2-c) or monofunctional (meth) acrylate (E2-d) in the active energy ray-curable composition (2) is preferably 5 to 40% by mass, 30 mass% is more preferable. A cured film and a resin base material of the active energy ray-curable composition (2) having a bifunctional (meth) acrylate (E2-c) or monofunctional (meth) acrylate (E2-d) content of 5% by mass or more; The adhesion can be made good. Further, the curability and active energy of the active energy ray-curable composition (2) when the content of the bifunctional (meth) acrylate (E2-c) or the monofunctional (meth) acrylate (E2-d) is 40% by mass or less. There is a tendency that the transparency, scratch resistance and water / oil repellency of the cured film of the linear curable composition (2) can be improved.

  In the present invention, the active energy ray-curable composition (2) can contain other compounds as necessary.

  Examples of other compounds include alicyclic epoxy compounds such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and bis- (3,4-epoxycyclohexyl) adipate; modified alicyclic epoxy compounds An aliphatic epoxy compound such as 1,2-epoxycyclodecane; a polyfunctional alicyclic epoxy such as a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a hydrogenated bisphenol A type epoxy compound, or a phenol-novolak type epoxy compound And oxetane compounds such as 3-ethyl-3-hydroxymethyloxetane and 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene.

  In this invention, it is preferable that a photoinitiator (D2) is included in an active energy ray curable composition (2).

  Examples of the photopolymerization initiator (D2) include benzophenone, 4,4′-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoyl benzoate, 4-phenylbenzophenone, t-butylanthraquinone, 2 -Thioxanthones such as ethyl anthraquinone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone; diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Acetophenones such as butanone, 2-hydroxy-1- [4- {4- (2-hydroxy-2-methyl-propionyl) -benzyl} phenyl] -2-methyl-propan-1-one; benzoin methyl ether; Benzoin ethers such as benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, Acylphosphine oxides such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; methylbenzoylformate; 1,7-bisacridinylheptane and 9-phenylacridine. These can be used individually by 1 type or in combination of 2 or more types.

  The content of the photopolymerization initiator (D2) in the active energy ray-curable composition (2) is an active energy ray-curing agent in that a curing promoting effect is exhibited and the productivity of the cured product tends to be improved. 0.1-10 mass parts is preferable with respect to 100 mass parts of sex composition (2).

In the present invention, the active energy ray-curable composition (2) includes a release agent, a lubricant, a plasticizer, an antioxidant, an antistatic agent, a light stabilizer, and an ultraviolet absorber within the range not departing from the gist of the present invention. Various additives such as additives, flame retardants, flame retardant aids, polymerization inhibitors, fillers, pigments, dyes, silane coupling agents, leveling agents, antifoaming agents, fluorescent agents, chain transfer agents, etc. may be added as appropriate. it can.

Cured coating

In the present invention, the cured film is a film obtained by curing a coating film formed by applying the active energy ray-curable composition (2) to the surface of the resin substrate, and is a layer on the surface of the resin laminate described later. It is what forms.

  Examples of the method of applying the active energy ray-curable composition (2) to the surface of the resin substrate include the same method as the method of applying the ultraviolet curable composition (1) to the surface of the film substrate. .

  Examples of the active energy ray for curing the active energy ray-curable composition (2) include ultraviolet rays, electron beams, and X-rays.

When ultraviolet rays are used as the active energy ray, the light source and irradiation energy amount can be the same as the light source and irradiation energy amount for curing the ultraviolet curable composition (1).

Resin laminate

In the present invention, the resin laminate is a laminate in which a cured film of the active energy ray-curable composition (2) is laminated on the surface of a resin substrate.

As a manufacturing method of a resin laminated body, the method which has the process of following (I)-(C) is mentioned, for example.
(A) Active energy ray-curable composition obtained by laminating the surface of the release layer of the release film of the present invention and the resin base material through the coating film of the active energy ray-curable composition (2). Step (2) for forming a coating film-containing laminate (2) of the active energy ray-curable composition (2) Step of forming cured film containing laminate of active energy ray curable composition (2) for forming cured coating (c) Peeling of release film from cured film containing laminate of active energy ray curable composition (2) Process The specific example of the manufacturing method of said resin laminated body is demonstrated with reference to FIG.

  The active energy ray-curable composition (2) (U) is applied to the surface of the release layer (I) of the release film of the present invention in which the release layer (I) is laminated on the surface of the film base (A). Apply.

  Next, the surface of the resin substrate (e) conveyed by the carrier (ke) and the surface of the release layer (ii) of the release film coated with the active energy ray-curable composition (2) are made to face each other. The resin base (E), active energy ray-curable composition (2) (U), release layer (I), and film base (A) are laminated in order by pressing with a press roll. A coating film-containing laminate of the energy beam curable composition (2) is formed.

  The active energy ray-curable composition (2) -coated laminate is irradiated with ultraviolet rays from the film substrate surface side through the film substrate using an ultraviolet irradiation device (), and active energy ray curable. The composition (2) (U) is cured.

  In the present invention, it is preferable to provide a holding time before the irradiation with ultraviolet rays after the coating film-containing laminate of the active energy ray-curable composition (2) is formed.

  The holding time is 0 considering that the perfluoropolyether (meth) acrylate (B2) is transferred to the surface side of the release layer (ii) in the active energy ray-curable composition (2) (U). .5 to 5 minutes are preferred.

  After the cured film-containing laminate of the active energy ray-curable composition (2) formed by curing the active energy ray-curable composition (2) (u) passes through the guide roll (resin), the resin base material The active energy ray-curable composition (2) laminated on the surface of (e) (2) from the cured film (right side of (u) in FIG. 1) to the surface of the film substrate (a) (I) ) Is peeled off to obtain a resin laminate (O) in which the cured film of the active energy ray-curable composition (2) (U) is laminated on the surface of the resin substrate (E). It is done.

In the present invention, the resin laminate (o) is irradiated with ultraviolet rays for the purpose of further improving the scratch resistance of the cured coating on the surface of the resin laminate (o) obtained after peeling the film substrate (a). Can do.

Coating film-containing laminate forming step of active energy ray-curable composition (2)

In the present invention, the coating film-containing laminate forming step of the active energy ray-curable composition (2) is performed by combining the surface of the release layer of the release film and the resin substrate of the present invention with the active energy ray-curable composition ( This is a step of forming a coating film-containing laminate of the active energy ray-curable composition (2) by laminating via the coating film of 2).

Step of forming a cured film-containing laminate of the active energy ray-curable composition (2)

In the present invention, the step of forming the cured film-containing laminate of the active energy ray-curable composition (2) is performed by irradiating the coating-containing laminate of the active energy ray-curable composition (2) with active energy rays. This is a step of forming a cured film-containing laminate of the active energy ray-curable composition (2) by forming a cured film of the curable composition (2).

  In the above step, the surface of the coating film of the active energy ray-curable composition (2) has one surface in contact with the resin substrate and the opposite surface in contact with the release layer of the film substrate. Since the curable composition (2) is cured in an anaerobic atmosphere, the polymerization is not inhibited by oxygen or the like, so that the cured film of the active energy ray-curable composition (2) has antifouling properties and friction durability. Can be improved. In addition, it is possible to eliminate the mixing of bubbles, dust, and the like, which cause a poor finish on the surface of the obtained resin laminate.

  As a method other than the above which makes the surface of the coating film of the active energy ray-curable composition (2) an anaerobic atmosphere, for example, the coating film of the active energy ray-curable composition (2) is formed with a mold and a resin substrate. The method of sandwiching and the method of making the surface of the coating film of the active energy ray-curable composition (2) an anaerobic atmosphere with an inert gas can be mentioned.

  In the method in which the surface of the coating film of the active energy ray-curable composition (2) is made an anaerobic atmosphere using a mold, the repair is required when the mold is damaged, and the active energy ray-curable composition (2 The method of making the surface of the coating film anaerobic atmosphere with an inert gas is also expensive, but in the present invention, the surface of the coating film of the active energy ray-curable composition (2) is made anaerobic with the release film. Since it also serves as an atmosphere, it can be an anaerobic atmosphere at lower cost than other methods.

  In the present invention, as an active energy ray irradiation method for curing the active energy ray-curable composition (2), a method of irradiating from the film substrate side, a method of irradiating from the resin substrate side, or the film substrate side Any of the methods of irradiating from both sides on the resin base material side may be used.

In the present invention, since the active energy ray-curable composition (2) is cured in contact with the release layer surface of the release film, the perfluoropolyether (meth) acrylate (B2) is active energy ray cured. In the conductive composition (2), the concentration is higher on the release layer surface side than on the resin plate side, and a cured film excellent in antifouling property and scratch resistance can be easily formed.

Peeling process

In this invention, a peeling process is a process of peeling a release film from the cured film containing laminated body of an active energy ray curable composition (2).

Hereinafter, the present invention will be described in detail by way of examples. In addition, various evaluation in an Example and a comparative example was implemented with the following method. In the following, “part” and “%” represent “part by mass” and “% by mass”, respectively.
(1) Film thickness The film thickness of the release layer on the film substrate was measured using a table-top film thickness measurement system (manufactured by Filmetrics Co., Ltd., trade name “F-20”).
(2) Adhesiveness Adhesiveness between the film substrate and the release layer was evaluated according to the following criteria using a cross-cut test (JIS K5600-5-6).
“◯”: No peeling of the release layer from the film substrate.
"X": There exists peeling of a release layer from a film base material.
(3) Contact angle In an environment of 23 ° C. and 50% relative humidity, a drop of 0.2 μL of water is dropped on the surface of the release layer of the release film or the surface of the cured film of the resin laminate to carry the portable contact. Using a goniometer (manufactured by Fibro system ab, trade name: “PG-X”), the contact angle with respect to the surface water of the release layer of the release film or the contact angle with respect to the water of the surface of the cured film of the resin laminate is obtained. It was.
(4) Repellency As oil-based ink (black), write "My Name" (trade name, manufactured by Sakura Crepas Co., Ltd.) on the surface of the release layer of the release film or the surface of the cured film of the resin laminate. The repellency of the oil-based ink at that time was visually evaluated on the following criteria to evaluate the repellency of the surface of the release layer of the release film or the surface of the cured film of the resin laminate.
“O”: Oil-based ink repels in a dot-like manner.
“Δ”: The line of oil-based ink becomes thin.
“×”: Oil-based ink does not repel at all.
(5) Curl property The height of the raised edge of the test film is measured when the test film, which is 20 cm square cut off, is placed on a flat surface with the release layer on top. The curl properties of the release film were evaluated according to the following criteria.
“◯”: The height at which the end of the test film is lifted is less than 2 mm.
“Δ”: The height at which the end of the test film is lifted is 2 mm or more and less than 3 mm.
“X”: The height of the lifted edge of the test film is 3 mm or more.
(6) Release property The release film laminated on the surface of the resin laminate is peeled off at a rate of 2.5 m / min so that the peel angle is 90 °, and the cured film of the resin laminate and the release film The releasability with the release layer was evaluated according to the following criteria.
“◯”: Peeled in a state where there was no catch at the time of peeling.
"△": There is a catch at the time of peeling, but peeling is possible.
“X”: A peeling failure is recognized.
[Example 1]
100 parts of dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd., trade name: “M400”) as tetrafunctional or higher functional (meth) acrylate (A1), “OPTOOL” as perfluoropolyether (meth) acrylate compound (B1) DAC-HP "(trade name, manufactured by Daikin Industries, Ltd.) (perfluoropolyether (meth) acrylate 20%, 1,1,2,2,3,3,4-heptafluorocyclopentane, tetrafluoro-1 -Mixture of 50% propanol and 30% propylene glycol monomethyl ether) 15 parts, 960 parts propylene glycol monomethyl ether as organic solvent (C1), 2-methyl-1- (4-methylthiophenyl) as photopolymerization initiator (D1) -2 Morpholinopropan-1-one (BASF Japan Ltd.), trade name: "Irgacure 907") and 5 parts of blended to obtain an ultraviolet-curable composition (1).

  A 100 μm thick PET film (Toyobo Co., Ltd., trade name: “Cosmo Shine A4300”) is used as a film base, and the UV curable composition (1) prepared above is applied to the surface of the film base using a bar coater. Applied.

Next, after drying the PET film coated with the ultraviolet curable composition (1) for 5 minutes in a hot air drying oven at 100 ° C., an integrated light amount of 600 mJ / cm ² (amount of ultraviolet energy at a wavelength of 320 to 380 nm) using a high-pressure mercury lamp. ) Was irradiated to obtain a release film having a release layer with a thickness of 0.5 μm.

  As the perfluoropolyether (meth) acrylate compound (B2), “OPTOOL DAC-HP” (trade name, manufactured by Daikin Industries, Ltd.) (perfluoropolyether (meth) acrylate 20%, 1,1,2,2, 2 parts of 3,3,4-heptafluorocyclopentane, 50% and 30% propylene glycol monomethyl ether), diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide (D2) as photoinitiator (D2) 2 parts of BASF Japan Ltd., trade name: “Lucirin TPO”) and dipentaerythritol hexaacrylate (E2-a) as other vinyl monomer (E2) (trade name: “Toagosei Co., Ltd.”) M400 "), 35 parts, pentaerythritol triacrylate (E2-b) (manufactured by Toagosei Co., Ltd., Product name: “M305”) 15 parts, trimethylolpropane triacrylate (E2-b) (manufactured by Toagosei Co., Ltd., trade name: “M309”) and 1,6-hexanediol diacrylate (E2-c) 10 parts (trade name: “C6DA” manufactured by Osaka Organic Chemical Industry Co., Ltd.) were blended to obtain an active energy ray-curable composition (2).

  Using a methacrylic resin plate “Acrylite MR100” (trade name, manufactured by Mitsubishi Rayon Co., Ltd.) with a thickness of 2 mm as the resin base material, the above adjustment is made on the surface of the methacrylic resin plate on which the hard coat layer is not formed. The active energy ray-curable composition (2) was applied.

  Next, the release film is coated on the surface of the application surface of the active energy ray curable composition (2) so that the release layer of the release film is in contact with the application surface of the ultraviolet curable composition (2). Application of the active energy ray-curable composition (2) by passing it at a speed of 2.5 m / min while pressing with a press roll under the condition that the film thickness of the energy ray-curable composition (2) is 10 μm. A film-containing laminate was formed.

  The coating film containing laminated body of the obtained active energy ray curable composition (2) was hold | maintained for 1 minute.

  Thereafter, the active energy ray-curable composition (2) coating-containing laminate is passed through a position 24 cm below the metal halide lamp with an output of 120 W / cm at a speed of 0.25 m / min. A cured film-containing laminate of product (2) was obtained.

  Subsequently, the release film is peeled from the cured film-containing laminate of the active energy ray-curable composition (2), and the cured film of the active energy ray-curable composition (2) is laminated on the surface of the resin substrate. A laminate was obtained.

  Table 1 shows the evaluation results of the adhesiveness, contact angle, repellency and curling property of the release film.

  Moreover, Table 1 shows the evaluation results on the releasability of the release film and the cured film of the resin laminate using the cured film-containing laminate of the active energy ray-curable composition (2).

  Furthermore, the evaluation result about the contact angle and the repellent property of the surface of the cured film of a resin laminated body is shown in Table 1.

Abbreviations in Table 1 indicate the following compounds.
Cosmo Shine A4300: PET film (manufactured by Toyobo Co., Ltd., trade name: “Cosmo Shine A4300”)
Teijin Tetron Film G2C: PET film (manufactured by Teijin DuPont Films Ltd., trade name: “Teijin Tetron Film G2C”)
Sylphan M1: Polypropylene film (PP film) (Gunze Co., Ltd., trade name: “Sylphan M1”)
M400: Dipentaerythritol hexaacrylate (trade name, manufactured by Toagosei Co., Ltd.)
DAC-HP: Perfluoropolyether (meth) acrylate (manufactured by Daikin Industries, Ltd., trade name: “OPTOOL DAC-HP”)
Fluorolink 5101X: Perfluoropolyether (meth) acrylate (trade name, manufactured by Solvay Solexis Co., Ltd.)
PGME: Propylene glycol monomethyl ether Zeolora H: 1,1,2,2,3,3,4-heptafluorocyclopentane (trade name, manufactured by Nippon Zeon Co., Ltd.)
IRGACURE907: 2-methyl-1- (4-methylthiophenyl) -2morpholinopropan-1-one (trade name, manufactured by BASF Japan Ltd.)
IRGACURE127: 2-Hydroxy-1- [4- {4- (2-hydroxy-2-methyl-propionyl) -benzyl} phenyl] -2-methyl-propan-1-one (trade name, manufactured by BASF Japan Ltd.) )
IRGACURE 184: 1-hydroxycyclohexyl phenyl ketone (trade name, manufactured by BASF Japan Ltd.)
DAROCURE127: 2-hydroxy-2-methyl-1-phenylpropan-1-one (manufactured by BASF Japan Ltd.)
M305: Pentaerythritol triacrylate (trade name, manufactured by Toagosei Co., Ltd.)
16-FDA: 1,10-bis (meth) acryloyloxy-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9, -hexadeca Fluorodecane (trade name, manufactured by Kyoeisha Chemical Co., Ltd.)
[Examples 2 to 5 and Comparative Example 1]
The composition of Table 1 was used as the ultraviolet curable composition (1). Otherwise, a release film, a cured film-containing laminate and a resin laminate of the active energy ray-curable composition (2) were obtained in the same manner as in Example 1. The evaluation results are shown in Table 1. In Comparative Example 1, since no perfluoropolyether (meth) acrylate (B1) was used, the repelling property and the releasability were inferior.
[Examples 6 and 7 and Comparative Examples 2 and 3]
The thickness of the release layer of the release film obtained by curing the ultraviolet curable composition (1) was set to the thickness shown in Table 1. Otherwise, a release film, a cured film-containing laminate and a resin laminate of the active energy ray-curable composition (2) were obtained in the same manner as in Example 1. The evaluation results are shown in Table 1.

In Comparative Example 2, since the film thickness was smaller than the lower limit of the range defined in the present invention, the repellency and releasability were inferior. In Comparative Example 3, the film thickness was larger than the upper limit of the range defined in the present invention, so the curling property was inferior.
[Example 8]
The cumulative amount of ultraviolet light upon curing of the ultraviolet curable composition (1) was 350 mJ / cm ² (the amount of ultraviolet energy having a wavelength of 320 to 380 nm). Otherwise, a release film, a cured film-containing laminate and a resin laminate of the active energy ray-curable composition (2) were obtained in the same manner as in Example 1. The evaluation results are shown in Table 1.
[Example 9]
Using a 50 μm thick PET film (Teijin DuPont Films Co., Ltd., trade name: “Teijin Tetron Film G2C”) with a corona treatment on one side as a film substrate, a release layer is formed on the corona treated surface Except that, a release film, a cured film-containing laminate of the active energy ray-curable composition (2), and a resin laminate were obtained in the same manner as in Example 1. The evaluation results are shown in Table 1.
[Comparative Example 4]
A 30 μm-thick polypropylene film (PP film) (manufactured by Gunze Co., Ltd., trade name: “Sylphan M1”) was used as a release film. Otherwise, a cured film-containing laminate and a resin laminate of the active energy ray-curable composition (2) were obtained in the same manner as in Example 1. The evaluation results are shown in Table 1. In Comparative Example 4, since the release layer of the present invention was not formed, the repellency was inferior.

A: Film base: Release layer: Active energy ray curable composition (2) (before curing) or cured film of active energy ray curable composition (2) (after curing)
E: Resin substrate: Resin laminate: Press roll: Guide roll: Ultraviolet irradiation equipment: Conveyer

Claims (4)

Tetrafunctional or higher functional (meth) acrylate (A1), perfluoropolyether (meth) acrylate (B1), organic solvent (C1) , and 2-hydroxy-1- [4- {4- (2-hydroxy-2- At least one photopolymerization selected from methyl-propionyl) -benzyl} phenyl] -2-methyl-propan-1-one and 2-methyl-1- (4-methylthiophenyl) -2morpholinopropan-1-one An ultraviolet curable composition (1) containing an initiator (D1) is applied onto a film substrate, and the organic solvent (C1) in the coating film is volatilized and then cured by irradiation with ultraviolet rays. A release film in which a release layer having a thickness of 0.2 to 1.5 μm is formed on a film substrate.
  The content of perfluoropolyether (meth) acrylate (B1) in the ultraviolet curable composition (1) is 2 to 4 parts by mass with respect to 100 parts by mass of tetrafunctional or higher (meth) acrylate (A1). Item 2. The release film according to Item 1.   The release film according to claim 1 or 2, wherein the film substrate is a polyethylene terephthalate film having an easy adhesion layer. The cured film of the active energy ray-curable composition (2) containing the perfluoropolyether (meth) acrylate (B-2) is laminated on the surface of the resin base material, which includes the following steps (a) to (c). A method for producing a resin laminate.
(I) Tetrafunctional or higher-functional (meth) acrylate (A1), perfluoropolyether (meth) acrylate (B1), organic solvent (C1) , and 2-hydroxy-1- [4- {4- (2-hydroxy 2-methyl-propionyl) -benzyl} phenyl] -2-methyl-propan-1-one and 2-methyl-1- (4-methylthiophenyl) -2morpholinopropan-1-one By applying an ultraviolet curable composition (1) containing the photopolymerization initiator (D1) on the film substrate, volatilizing the organic solvent (C1) in the coating film, and then irradiating with ultraviolet rays The surface of the release layer of the release film in which the release layer having a thickness of 0.2 to 1.5 μm obtained by curing is formed on the film substrate and the resin substrate are combined with perfluoropolyether (meta A) Coating film-containing laminate forming step (b) activity of the active energy ray-curable composition (2) obtained by laminating through the coating film of the active energy ray-curable composition (2) containing the relate (B2) An active energy ray-curable composition (2) in which a coating film-containing laminate of the energy ray-curable composition (2) is irradiated with active energy rays to form a cured film of the active energy ray-curable composition (2). Cured film-containing laminate forming step (c) Peeling step of peeling the release film from the cured film-containing laminate of the active energy ray-curable composition (2)