JP2005240005A - Curable resin composition, transfer material, and protective layer forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a one-pack type curable resin composition which is excellent in wear resistance and chemical resistance when used as a protecting material for forming a protective layer on the surface of a molded article and has excellent storage stability capable of obtaining the protective layer not causing a crack in the curved surface part of the molded article, to provide a transfer material using the composition, and a protective layer forming method using the curable resin composition. <P>SOLUTION: The protective layer of the molded article is formed by coating a substrate sheet with the curable resin composition and subsequently heating the coated substrate sheet to convert the curable resin composition for transfer material to a B-stage material. After the transfer material, the surface of the protective layer and the molded article are bonded, the bonded one is irradiated with an energy beam to form the protective layer on the molded article. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to a curable resin composition having excellent storage stability and a cured product having excellent wear resistance and chemical resistance. Specifically, coating materials such as plastic, various films, wood, ceramics, glass, quartz fiber for communication, paper, metal, beverage cans, fibers, etc .; resin for optical three-dimensional modeling; sealing material for semiconductors; adhesive for semiconductors A sealing material for organic EL and liquid crystal; an underfill agent; an optical adhesive; a printing plate material and the like, and particularly suitable as a coating material. The present invention relates to a resin composition. The present invention also relates to a transfer material using the curable resin composition and a method for forming a protective layer excellent in wear resistance and chemical resistance.

  In recent years, development of a curable resin composition used for the above-described uses has been promoted, and a positive development has been made on a curable resin composition particularly suitable for a coating material application. Examples of a method for forming a protective layer that covers and protects the surface of a molded product such as plastic or metal include a coating method and a transfer method. For example, the coating method may be performed by spray coating a paint containing an active energy ray-curable resin composition, or by applying a top coat on a molded product using a printing device such as a curtain coater, a roll coater, or a gravure coater. A transfer material having a cured coating film of a paint containing an active energy ray-curable resin composition on a substrate sheet having releasability. Is a transfer method in which a cured coating film is transferred to the surface of the molded product by peeling the substrate sheet after the substrate is adhered to the surface of the molded product, and then a cross-linked coating film is formed by irradiation with active energy rays.

  In particular, with regard to the transfer method, using a paint containing the active energy ray-curable resin composition, it is considered to form a protective layer that is excellent in wear resistance and chemical resistance and that does not crack during transfer. (For example, refer to Patent Document 1).

However, the active energy ray-curable resin composition is a two-component curable composition in which a polymer having a hydroxyl group and a (meth) acryloyl group and a polyfunctional isocyanate are blended immediately before use. Accordingly, the storage stability of the paint containing the active energy ray-curable resin composition is poor, and the viscosity of the remaining coating agent increases when the usage time becomes long or when the painting operation is interrupted. Compared to the first case, it has the disadvantages that it causes fluctuations in the coating thickness or that gels are generated in the coating material, making it unusable.
Japanese Patent Laid-Open No. 10-058895

  The problem to be solved by the present invention is that when used as a protective material for forming a protective layer on the surface of a molded article, a protective layer that is excellent in wear resistance and chemical resistance and does not cause cracks in the curved surface of the molded article is obtained. An object of the present invention is to provide a one-component curable resin composition excellent in storage stability, a transfer material using the composition, and a method for forming a protective layer using the curable resin composition.

Thus, as a result of intensive investigations aimed at the problems as described above, the present inventors have found the following findings (1) to (4) and have completed the present invention.
(1) A resin composition containing a compound (A) having a cyclic ether structure, a compound (B) having a (meth) acryloyl group, a photopolymerization initiator (C) and a thermal cationic polymerization initiator (D) is one liquid. It is a curable resin composition excellent in storage stability in a mold.
(2) After the curable resin composition is applied to a molded article or the like, a cured coating film (protective layer) excellent in wear resistance and chemical resistance is obtained by heating and irradiation with active energy rays.
(3) When the curable resin composition is heated, a cationic polymerization reaction of the cyclic ether in the compound (A) occurs, so that a semi-cured (B-staged) cured coating film can be formed. A transfer material used to form a protective layer on the surface of a molded product is obtained by heating the object after coating the substrate sheet. The semi-cured cured coating film on the transfer material does not have a feeling of adhesion even when it is touched with a finger (no residual tack), so that the transfer material can be wound and stored after being semi-cured.
(4) After bonding the semi-cured cured coating surface of the transfer material to the molded product, it is excellent in wear resistance and chemical resistance by irradiating energy rays, and does not cause cracks in the curved surface during transfer. A protective layer can be formed.

  That is, the present invention is characterized by containing a compound (A) having a cyclic ether structure, a compound (B) having a (meth) acryloyl group, a photopolymerization initiator (C), and a thermal cationic polymerization initiator (D). A curable resin composition is provided.

  The present invention also provides a transfer material comprising the curable resin composition coated on a substrate sheet and then heated to form a B-stage of the curable resin composition.

  Furthermore, the present invention provides a B-staged resin layer and a molded product of a transfer material obtained by coating the curable resin composition on a substrate sheet and then heating to form a B-stage of the curable resin composition. And a method for forming a protective layer of a molded product, which is characterized by irradiating an energy ray after bonding.

  The curable resin composition of the present invention is a one-component curable resin composition excellent in storage stability, and in addition, a protective layer having an expected film thickness can be easily obtained. The protective layer obtained by using the curable resin composition of the present invention is excellent in wear resistance and chemical resistance, and is useful as a protective layer for covering molded articles such as plastics and as an overcoat layer for automobiles, etc. It can use especially preferably as curable resin composition for material manufacture. Further, the transfer material of the present invention is a transfer material having no remaining tack. Furthermore, according to the method for forming a protective layer of the present invention, it is possible to form on the molded product a protective layer that is excellent in wear and chemical resistance and does not cause cracks in the curved surface of the molded product during transfer.

  The present invention is described in detail below. The compound (A) used in the present invention can be used without particular limitation as long as it has a cyclic ether structure. Examples of the compound (A) include a monomer having a cyclic ether structure and a polymer compound having a cyclic ether structure, and a polymer compound having a cyclic ether structure is preferable.

  Examples of the monomer having a cyclic ether structure include epoxy compounds and oxetane compounds.

  Examples of the epoxy compound include phenyl glycidyl ether, pt-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monooxide, Glycidyl ether type epoxy compounds such as 1,2-dodecylene oxide, epichlorohydrin, 1,2-epoxydecane, ethylene oxide, propylene oxide, styrene oxide; cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3- Acryloyloxymethylcyclohexene oxide, 3-vinylcyclohexene oxide, 1,13-tetradecadiene dioxide, limonene dioxide, , 4-epoxycyclohexylmethyl - (3,4-epoxycyclohexyl) carboxylate, di (3,4-epoxycyclohexyl) alicyclic epoxy compounds such as adipate and the like.

  Examples of the oxetane compound include 3,3-dimethyloxetane, 3,3-bis (chloromethyl) oxetane, 2-hydroxymethyloxetane, 3-methyl-3-oxetanemethanol, and 3-methyl-3-methoxymethyloxetane. , 3-ethyl-3-phenoxymethyloxetane, resorcinol bis (3-methyl-3-oxetanylethyl) ether, m-xylylenebis (3-ethyl-3-oxetanylethylether), and the like.

  The monomers having the cyclic ether structure described above may be used alone or in combination of two or more.

  Examples of the polymer compound having a cyclic ether structure include an acrylic resin having a cyclic ether structure, an ester resin having a cyclic ether structure, and a urethane resin having a cyclic ether structure. Among these, acrylic resins having a cyclic ether structure are preferable.

  Examples of the acrylic resin having a cyclic ether structure include (meth) acrylic resins having an epoxy group, (meth) acrylic resins having an oxetane group, and the like. These acrylic resins having a cyclic ether structure may be polymerized with other (meth) acrylic monomers or non- (meth) acrylic monomers as necessary, for example, with a (meth) acrylic monomer having a cyclic ether structure as an essential component. Is obtained.

  Examples of the (meth) acrylic monomer having a cyclic ether structure include a (meth) acrylic monomer having an epoxy group, a (meth) acrylic monomer having an oxetane group, and the like.

  Examples of the (meth) acrylic monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, allyl glycidyl ether, 3,4-epoxycyclohexylmethyl (meth) acrylate, and 2- (1,2 -Epoxy-4,7-methanoperhydroindene-5 (6) -yl) oxyethyl (meth) acrylate, 5,6-epoxy-4,7-methanoperhydroinden-2-yl- (meth) acrylate, 1 , 2-Epoxy-4,7-methanoperhydroinden-5-yl- (meth) acrylate and other (meth) acrylic monomers having a glycidyl ether type epoxy group; 2,3-epoxycyclopentenyl (meth) acrylate, 3 , 4-Epoxycyclohexylmethyl (meth) acrylate, 3,4 Having epoxycyclohexyl methylation polycaprolactone (meth) acrylate alicyclic epoxy group-containing (meth) acrylic monomer. These (meth) acrylic monomers having an epoxy group may be used alone or in combination of two or more.

  Examples of the (meth) acrylic monomer having an oxetane group include 3-methacryloxymethyl-3-ethyloxetane, 3-acryloxymethyl-3-ethyloxetane, α, α-dimethyl-m-isopropenylbenzyl isocyanate, and And an equimolar adduct with 3-ethyl-3-hydroxymethyloxetane. These oxetane compounds may be used alone or in combination of two or more.

  Other (meth) acrylic monomers used as necessary include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid Examples include hexyl, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. Examples of non-acrylic monomers include styrene, vinyl toluene, vinyl acetate, acrylonitrile, and the like. These may be used alone or in combination of two or more.

  In order to produce the acrylic resin having the cyclic ether structure, for example, the (meth) acrylic monomer having the cyclic ether structure is essential, and other acrylic monomers and non-acrylic monomers are used as raw materials as necessary. Add an organic solvent such as methyl ethyl ketone and butyl acetate to the raw material as necessary, and further add a radical initiator such as azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), etc. And a method of reacting in 2 to 15 hours. The amount of the organic solvent used when using the organic solvent is usually 60 to 150 parts by weight with respect to 100 parts by weight of the raw material.

  The compound (A) is preferably a compound having an epoxy group (compound having an epoxy type structure), and more preferably an epoxy compound having an alicyclic structure (compound having an alicyclic epoxy type structure).

  Among the compounds having the alicyclic epoxy type structure, an alicyclic epoxy (meth) acrylic resin obtained by polymerizing 3,4-epoxycyclohexylmethyl (meth) acrylate as an essential component is more preferable.

  The molecular weight of the compound (A) is 500 to 50000 because the hardness of the obtained coating film is high, and the curability, solvent resistance, water resistance and weather resistance of the coating film are good, and the viscosity is not high and easy to use. Is preferable, 1000 to 30000 is more preferable, and 5000 to 25000 is most preferable. Here, when the compound (A) is a polymer compound, the molecular weight is a number average molecular weight.

  The functional group equivalent of the cyclic ether structure of the compound (A) is preferably 80 to 1500 g / eq, more preferably 100 to 1000 g / eq, and most preferably 120 to 500 g / eq.

  The compound (B) used in the present invention can be used without particular limitation as long as it has a (meth) acryloyl group, but a compound having two or more (meth) acryloyl groups in one molecule is preferable. Examples of the compound (B) include a monomer having a (meth) acryloyl group, a polymer compound having a (meth) acryloyl group, and the like, and semi-curing (B-stage) by heat curing for a short time. The polymer compound is preferred for the purpose of expression.

  Examples of the monomer having a (meth) acryloyl group include methyl (meth) acrylate, ethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, butyl (meth) acrylate, botoxyethyl (meth) acrylate, and benzyl. (Meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (Meth) acrylates such as dipropylene glycol (meth) acrylate and 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate; 1,2-ethylene glycol di (meth) acrylate, 1,3-propanediol ( Meta ) Acrylate, diethylene glycol diacrylate, bisphenol A di (meth) acrylate, bisphenol F diacrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, hexane Diol di (meth) acrylate, diacrylate of neopentyl glycol diester of hydroxypivalic acid, 2- (2-hydroxy-1,1'-dimethyl-ethyl) -5-hydroxydimethyl-5-ethyl-1,3-dioxy Acid diacrylate, tricyclodecane dimethylol diacrylate, bisphenol A to ethylene oxide adduct di (meth) acrylate, bisphenol A di (meth) acrylate and its ethylene oxide adduct, Di (meth) acrylates such as Sphenol A di (meth) acrylate and its propylene oxide adduct; glycerol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris ((meth) acryloxyethyl) isocyanurate, Tri (meth) acrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trishydroxyethylisocyanurate tri (meth) acrylate; tetra (meth) such as pentaerythritol tetra (meth) acrylate Acrylate; novolak to ethylene oxide adduct polyacrylate and the like.

  Examples of the polymer compound having the (meth) acryloyl group include epoxy (meth) acrylic resins, urethane (meth) acrylic resins, polyester (meth) acrylic resins, and the like.

  Examples of the epoxy (meth) acrylic resin include those obtained by reacting (meth) acrylic acid with an epoxy resin, preferably an epoxy resin having two or more epoxy groups. Examples of the epoxy resin used here include glycidyl (such as a homopolymer of glycidyl (meth) acrylate, a copolymer with other α, β-unsaturated monomers copolymerizable with glycidyl (meth) acrylate). Epoxy resins obtained by polymerization using meth) acrylate as an essential component can be preferably used. Examples of the α, β-unsaturated monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, isopropyl (meth) acrylate, (meth) Examples include various (meth) acrylic acid esters such as 2-hydroxyethyl crylate and hydroxypropyl (meth) acrylate; styrene; vinyl acetate; acrylonitrile and the like.

  Examples of the urethane (meth) acrylic resin [urethane (meth) acrylate] include, for example, an isocyanate compound having preferably two or more isocyanate groups, and (meth) acryloyl group and hydroxyl group in one molecule. The thing obtained by reacting the unsaturated alcohol which has is mentioned. Examples of the isocyanate compound having two or more isocyanate groups include 4,4'-diphenylmethane diisocyanate (MDI), water-added MDI, 4,4'-biphenyldiisocyanate tridenediisocyanate, isophorone diisocyanate, 1,3 -Xylylene diisocyanate, 1,4-xylene diisocyanate, p-tetramethyl xylene diisocyanate, m-tetramethyl xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthalene diisocyanate, m -Phenylene diisocyanate, p-phenylene diisocyanate, triphenylmethane triisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-tetramethylene diisocyanate Isocyanate, 1,6-hexamethylene diisocyanate, 1,8-octamethylene diisocyanate, L-lysine diisocyanate, 1,6,11-undecane triisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, 2, Polyisocyanate compounds such as 4,4'-biphenyl triisocyanate, 2,4,4'-diphenylmethane triisocyanate, polymethylene phenyl isocyanate, and isocyanurate type polyisocyanates, adduct type polyisocyanates, burette types using these monomers Polyisocyanate etc. are mentioned.

  Examples of the polyester (meth) acrylic resin [polyester (meth) acrylate] include polyester (meth) acrylate obtained by esterifying (meth) acrylic acid, polybasic acid, and polyhydric alcohol under an acid catalyst. It is done. Examples of the polybasic acid include terephthalic acid, isophthalic acid, (anhydrous) phthalic acid, (anhydrous) trimellitic acid, (anhydrous) pyromellitic acid, 2,6-naphthalenedicarboxylic acid, succinic acid, adipic acid, Examples include azelaic acid, sebacic acid, dodecanedioic acid, 1,4-cyclohexanedicarboxylic acid, hexahydro (anhydride) phthalic acid, and the like. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, butanediol 1,3, butanediol 1,4, neopentyl glycol, 2-methylpropanediol 1,3, 3-methylpentanediol 1,5, cyclohexanedimethanol , Hydrogenated bisphenol A, bisphenol A alkylene oxide adduct, glycerin, trimethylolpropane, pentaerythritol and the like.

  Among the polymer compounds having the (meth) acryloyl group, a polymer compound containing a hydroxyl group is preferable. By introducing this hydroxyl group, the hydroxyl group is involved in cationic polymerization, the compound (A) and the compound (B) are crosslinked, and a coating film having a higher density is obtained. The polymer compound containing a hydroxyl group is preferably a hydroxyl group-containing (meth) acrylic resin, more preferably a hydroxyl group-containing epoxy (meth) acrylic resin because it can be easily produced.

  Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprolactone or alkylene oxide adduct of each acrylate, glycerin mono ( (Meth) acrylate, glycerin di (meth) acrylate, glycidyl methacrylate-acrylic acid adduct, trimethylolpropane mono (meth) acrylate, trimethylol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) ) Acrylate, ditrimethylolpropane tri (meth) acrylate, trimethylolpropane-alkylene oxide adduct-di (meth) acrylate, etc. .

  When the polymer compound as described above is used in the present invention, the acid value of the compound (B) reacts with a cyclic ether having cationic polymerizability even when added to the curable resin composition for transfer material of the present invention described later. The acid value of the compound (B) is preferably 2 or less because the storage stability may be deteriorated.

  The molecular weight of the compound (B) used in the present invention is easy to use without increasing the viscosity, does not evaporate at the time of heat-curing, does not reduce the hardness of the coating film, and has solvent resistance, water resistance and weather resistance of the coating film. Is preferably from 500 to 50,000, more preferably from 1,000 to 30,000. More preferably, it is 5000-25000. In addition, when a compound (B) is a high molecular compound, molecular weight says a number average molecular weight.

  The equivalent of the (meth) acryloyl group of the compound (B) is preferably 80 to 1500 g / eq, more preferably 100 to 1000 g / eq, more preferably 100 to 500 g because the weather resistance of the coating film is good and the hardness is high. / Eq is most preferred. In addition, the (meth) acryloyl group in this specification means the molecular weight per double bond.

  A compound (B) may be used individually by 1 type, and may use multiple types together.

  Since the curable resin composition of the present invention has no residual tack after semi-curing and has high hardness, the total number of moles (a) of the cyclic ether structure is more than the number of moles (b) of the (meth) acryloyl group. It is preferable that the number of moles (b) [(b) / (a)] of the (meth) acryloyl group with respect to the total number of moles (a) of the cyclic ether structure is 1 to 10, preferably 1.5 to It is more preferable that it is 8, and it is still more preferable that it is 2-6.

  In the present invention, compounds having both a cyclic ether structure and a (meth) acryloyl group may be used as the compound (A) and the compound (B). Such a compound is, for example, a (meth) acrylic monomer having a cyclic ether structure, for example, glycidyl methacrylate as an essential component, and after polymerizing other acrylic monomers and non-acrylic monomers as necessary, Such an acryloyl group-containing carboxylic acid compound can be reacted at such a ratio that the above amount is within the range [acroyl group / cyclic ether group = 1 to 10] with respect to the number of moles of the cyclic ether group.

  As the photopolymerization initiator (C) used in the present invention, known ones can be used. Specifically, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether; acetophenone, 2, 2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl- Acetophenones such as phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl Aminoacetophenones such as butanone-1, N, N-dimethylaminoacetophenone; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 1-chloroanthraquinone; 2,4- Thioxanthones such as dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -Ketals such as phenylphosphine oxide, acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone such as benzophenone and 4,4'-bisdiethylaminobenzophenone It may be mentioned 2,4,6-trimethylbenzoyl diphenylphosphine oxide, aromatic iodonium salts, sulfonium salts and diazonium salts, a polysilane compound and the like; non-compound or xanthones. These may be used alone or in combination of two or more. Further, a tertiary amine such as triethanolamine and a photopolymerization initiation assistant such as ethyl dimethylaminobenzoate can be used in combination. The photopolymerization initiator (C) is preferably one or more compounds selected from the group consisting of benzoins, acetophenones, and ketals. Moreover, a photoinitiator (C) may be used individually by 1 type, and may use multiple types together.

  The amount of the photopolymerization initiator (C) in the curable resin composition of the present invention can be appropriately adjusted depending on the composition of the curable resin composition. The amount of the compound (C) in the curable resin composition of the present invention is, for example, 0.01 to 10 parts by weight with respect to the total weight of the compound (A) and the compound (B).

The thermal cationic polymerization initiator (D) used in the present invention is, for example, a cationic polymerizable catalyst that is inactive at room temperature but cleaves when heated to reach a critical temperature to generate a cation to initiate cationic polymerization. Examples of such catalysts include antimony hexafluoride ions (SbF ₆ ⁻ ), antimony tetrafluoride ions (SbF ₄ ⁻ ), arsenic hexafluoride ions (AsF ₆ ⁻ ), and phosphorus hexafluoride ions. Nitrogen onium salts, sulfur onium salts, phosphorus onium salts, and iodine onium salts containing (PF ₆ ⁻ ) as an anion component. Specifically, quaternary ammonium salt type compounds, sulfonium salt type compounds, phosphonium salt type compounds, iodonium salt type compounds, and the like can be suitably used.

  Examples of the quaternary ammonium salt type compound include N, N-dimethyl-N-benzylanilinium hexafluoride antimony, N, N-diethyl-N-benzylanilinium boron tetrafluoride, N, N-dimethyl- N-benzylpyridinium hexafluoroantimony, N, N-diethyl-N-benzylpyridinium trifluoromethanesulfonic acid, N, N-dimethyl-N- (4-methoxybenzyl) pyridinium hexafluoromonide, N, N-diethyl- N- (4-methoxybenzyl) pyridinium hexafluoride antimony, N, N-diethyl-N- (4-methoxybenzyl) toluidinium hexafluoride antimony, N, N-dimethyl-N- (4-methoxybenzyl) toluidinium hexa And antimony fluoride.

  Examples of the sulfonium salt type compounds include triphenylsulfonium boron tetrafluoride, triphenylsulfonium hexafluoride antimony, triphenylsulfonium hexafluoride arsenic, tri (4-methoxyphenyl) sulfonium hexafluoride arsenic, and diphenyl (4 -Phenylthiophenyl) sulfonium arsenic hexafluoride

  Examples of the phosphonium salt type compound include ethyltriphenylphosphonium antimony hexafluoride, tetrabutylphosphonium antimony hexafluoride, and the like.

  Examples of the iodonium salt type compound include diphenyliodonium hexafluoride, di-4-chlorophenyliodonium hexafluoride, di-4-bromophenyliodonium hexafluoride, di-p-tolyliodonium hexafluoride And phenyl (4-methoxyphenyl) iodonium arsenic hexafluoride.

  As the thermal cationic polymerization initiator (D), a sulfonium salt compound is preferable.

  The critical temperature of the thermal cationic polymerizable catalyst initiator (D) as described above is usually about 100 to 180 ° C, more preferably 120 to 160 ° C.

  The amount of the thermal cationic polymerization initiator (D) used is such that the curing reaction proceeds sufficiently, it is easy to mix uniformly into the curable resin composition, and the water resistance of the cured coating film does not decrease. The total solid content and the solid content of the compound (B) is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight.

  In the curable resin composition of the present invention, a compound having an active methylene or active methine group causing a Michael addition reaction is added and cured by a Michael addition reaction between a (meth) acryloyl group and an active methylene or active methine group by heating. The resin composition can be semi-cured (B-staged).

  Examples of the compound having an active methylene or active methine group include compounds having an active methylene group such as acetoacetic acid, malonic acid, and cyanoacetic acid, and derivatives thereof; methylmalonic acid, 2-methyl-3-oxobutanoic acid, methylcyano Examples thereof include compounds having an active methine group such as acetic acid and derivatives thereof. Moreover, the compounds shown in the following (1) to (4) can also be used.

(1) a compound obtained by reacting an active methylene group-containing carboxylic acid compound and / or an active methine group-containing carboxylic acid compound with a polyhydric alcohol;
(2) a compound obtained by reacting a polyamine compound with diketene;
(3) A (meth) acrylic monomer having an active methylene group or a (meth) acrylic monomer having an active methine group as an essential component can be obtained by polymerization together with other acrylic monomers or non-acrylic monomers as necessary (meta ) Acrylic resin;
(4) a compound obtained by transesterifying methanetricarboxylic acid trialkyl ester with a polyhydric alcohol;
(5) A compound obtained by an addition reaction between an isocyanate compound and an active methylene group-containing compound.

  The compounds having an active methylene or active methine group as described above may be used alone or in combination of two or more. In addition, it may have only the same type of active methylene group or active methine group, or may have different types of active methylene groups or active methine groups, or an active methylene group and an active methine group. You may have both.

  Moreover, you may use a Michael catalyst in order to accelerate | stimulate a Michael addition reaction as needed. Examples of the Michael catalyst compound include alkali metal hydroxide, alkali metal alkoxide, quaternary ammonium hydroxide, quaternary ammonium carbonate, quaternary ammonium fluoride, quaternary ammonium tetrahydroborate, and tertiary amine. And tertiary phosphine.

  Additives such as organic solvents and colorants may also be added to the cured resin composition of the present invention.

  The organic solvent usually has a boiling point of 50 to 180 ° C. because it has good workability during coating and quick drying before curing. For example, methyl acetate, ethyl acetate, butyl acetate, ethylene glycol mono Examples include ester solvents such as ethyl ether, ethylene glycol monoethyl ether acetate, and ethylene glycol monobutyl ether acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aromatic solvents such as toluene and xylene. The organic solvent may be used alone or in combination of two or more. Although the usage-amount of an organic solvent is not specifically limited, Usually, it is the range from which the solid content concentration of a coating agent will be 5-70 weight%.

  The colorant is not particularly limited. For example, extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments described in the Paint Raw Materials Handbook 1970 edition (edited by the Japan Paint Industry Association) Organic pigments and inorganic pigments such as green pigments, blue pigments, purple pigments, metal powder pigments, luminescent pigments, and pearl pigments, and plastic pigments. A single colorant may be used, or two or more colorants may be used in combination.

  In addition, a compound capable of cationic polymerization may be added to the curable resin composition of the present invention. Examples of the compound capable of cationic polymerization include compounds having a cyclic thioether structure, compounds having a cyclic amine structure, vinyl ether compounds, oxazolines, lactones, and lactams.

A cured coating film (protective layer) using the curable resin composition of the present invention can be obtained, for example, by a method including the following steps.
Step (1): A step of applying the curable paint of the present invention to an object to be coated.
Step (2): A step of performing heating and active energy ray irradiation.

  Examples of the objects to be coated include plastics, various films, wood, ceramics, glass, communication quartz fiber, paper, metal, beverage cans, fibers and the like. Specific examples of plastic and metal include, for example, automobile bodies such as passenger cars, trucks, motorcycles, buses, automobile parts, refrigerators, stereo sets, home appliances such as liquid crystal displays and plasma displays, notebook computers, mobile phones, PDAs, etc. Communication equipment and the like.

  In order to form a cured coating film (protective layer) using the curable resin composition of the present invention, first, as the step (1), the curable resin composition of the present invention is applied to an object to be coated. To do. The application method is not particularly limited, and examples thereof include brush coating, roller coating, air spray coating, airless spray coating, dip coating, flow coating, and the like. In some cases, an air electrostatic spray coating method or a rotary atomizing electrostatic coating method is preferred.

  The solid content in the curable resin composition of the present invention is preferably 30% by weight or more, and more preferably 60% by weight or more. It does not specifically limit as a coating film thickness, According to the use of the coating material obtained, it can set suitably.

  Subsequently, heating and active energy ray irradiation are performed in the second step. By the heating, the cyclic ether structure in the curable resin composition is bonded by a thermal cationic polymerization reaction to form a three-dimensional crosslink, and the curable resin composition is semi-cured (B-staged). When a curable resin composition for transfer material containing an organic solvent is used, the organic solvent is removed from the curable resin composition for transfer material by this heating. The heating conditions can be appropriately selected depending on the composition of the curable resin composition and the coating film pressure, but are usually 55 to 200 ° C, preferably 100 to 180 ° C. The heating time is usually 30 seconds to 40 minutes, preferably 1 to 10 minutes, more preferably 3 to 5 minutes.

Examples of active energy rays include electron beams, ultraviolet rays, and gamma rays. Irradiation conditions can be appropriately selected depending on the composition of the curable resin composition and the coating film thickness, but it is preferable to irradiate so that the integrated light amount is usually 50 to 5000 mj / cm ^2, and the integrated light amount is 500 to 2000 mj. It is more preferable to irradiate so that it may become / cm < ² >.

  Although the heating and active energy ray irradiation in the step (2) may be performed simultaneously, the active energy ray may be irradiated after the heating, or the active energy ray irradiation may be performed after the heating. In order to form a cured coating film (protective layer) using the curable resin composition of the invention, it is preferable to perform irradiation with active energy rays after heating.

  As described above, the curable resin composition of the present invention can be applied to various objects to be coated to obtain a cured coating film (protective layer) excellent in abrasion resistance and solvent resistance. In addition, the curable resin composition of the present invention can be preferably used for producing a transfer material as a curable resin composition for a transfer material. Hereinafter, a transfer material using the curable resin composition of the present invention, a method for producing the transfer material, and a method for forming a protective layer using the transfer material will be described in detail.

  The transfer material of the present invention is obtained by applying the curable resin composition of the present invention on a base sheet and semi-curing (B-stage). The transfer material of the present invention is, for example, a transfer material obtained by coating the curable resin composition of the present invention on a base sheet, and then semi-curing (B-staging) the curable resin composition by heating. Although the transfer material etc. which apply | coat the curable resin composition of this invention on a base material sheet, and irradiate an active energy ray and make curable resin composition B-stage are mentioned, Among these, the present invention is mentioned. A transfer material obtained by coating the curable resin composition on the base sheet and then heating to form a B-stage of the curable resin composition is preferable.

  As the base sheet, those having releasability are preferable. Examples of such a base sheet include a plastic sheet, a metal foil, a cellulose sheet, and a composite of these sheets.

  Examples of the plastic sheet include a polyethylene terephthalate sheet, a polypropylene sheet, a polyethylene sheet, a polycarbonate sheet, a polyolefin sheet, a polystyrene sheet, a polyamide sheet, and a polyester sheet.

  Examples of the metal foil include aluminum foil and copper foil. Examples of the cellulose sheet include glassine paper, coated paper, and cellophane.

  The base sheet is preferably a plastic sheet, and more preferably a polyester sheet.

  In order to produce the transfer material of the present invention, first, the curable resin composition of the present invention is coated on a substrate sheet. This curable resin composition becomes the outermost layer on the surface of the molded product in the method for forming a protective layer described later, and is a layer for protecting the molded product and the pattern layer on the molded product from chemicals and friction. Examples of the method for coating the curable resin composition include a gravure coating method, a roll coating method, a spray coating method, a lip coating method, a coating method such as a comma coating method, a printing method such as a gravure printing method, a screen printing method, etc. Is mentioned. When painting, since the wear resistance and chemical resistance are good, it is preferable to coat so that the thickness of the B-staged resin layer is 0.5 to 30 μm. It is more preferable to paint so that it will be-6 micrometers.

  When using the transfer material of the present invention using the curable resin composition of the present invention, the curable resin composition of the present invention may contain a slip agent. When the slip agent is contained, the protective layer of the transfer material is roughened, so that the transfer material can be easily wound as a sheet and blocking is difficult to occur. In addition, resistance to rubbing and scratching can be increased. Examples of the slip agent include waxes such as polyethylene wax, paraffin wax, synthetic wax and montan wax, and synthetic resins such as silicone and fluorine. The amount of slip agent used is 100 parts by weight of the solid content in the curable resin composition of the present invention in order to sufficiently prevent blocking and frictional scratch resistance and to ensure the transparency of the protective layer. The amount is preferably 0.01 to 15 parts by weight, particularly preferably 0.03 to 6 parts by weight.

  When the protective layer is excellent in releasability from the base sheet, the curable resin composition may be applied so that a B-staged resin layer is directly provided on the base sheet. In order to improve the releasability of the resin layer from the base sheet, the release layer may be formed on the entire surface before providing the B-staged resin layer on the base sheet. In the method for forming a protective layer for a molded product, which will be described later, the release layer is formed when the substrate sheet is peeled from the molded product in order to transfer the B-staged resin layer on the transfer material to the surface of the molded product. The sheet is released from the B-staged resin layer together with the sheet. Examples of the release agent for forming the release layer include melamine resin release agents, silicone resin release agents, fluororesin release agents, cellulose derivative release agents, and urea resin release agents. Polyolefin resin release agents, paraffin release agents, composite release agents thereof, and the like can be used. Examples of the method for forming the release layer include a coating method such as a gravure coating method, a roll coating method, a spray coating method, a lip coating method and a comma coating method, a printing method such as a gravure printing method and a screen printing method.

  It heats, after coating curable resin composition on a base material sheet. By this heating, the cyclic ether structure in the curable resin composition is bonded by a thermal cationic polymerization reaction to form a three-dimensional cross-linking, and the curable resin composition is semi-cured (B-staged). When a curable resin composition containing an organic solvent is used, the organic solvent is removed from the curable resin composition for transfer material by this heating. The heating is usually 55 to 160 ° C, preferably 100 to 140 ° C. The heating time is usually 30 seconds to 30 minutes, preferably 1 to 10 minutes, more preferably 3 to 5 minutes.

  Since the protective layer on the transfer material produced using the curable resin composition of the present invention makes it easy to print another layer on the protective layer or wind up the transfer material, the active energy It is desirable to be in a tack-free state at the stage before irradiation with the line. For this reason, the curable resin composition of this invention combines a compound (A) and a compound (B) so that the protective layer obtained using this may become tack-free in the step before irradiating an active energy ray. It is preferable.

  When manufacturing the transfer material of the present invention, a pattern layer may be formed. The pattern layer is usually formed as a printing layer on the protective layer. As a material for the printing layer, a binder such as a polyvinyl resin, a polyamide resin, a polyester resin, a polyacrylic resin, a polyurethane resin, a polyvinyl acetal resin, a polyester urethane resin, a cellulose ester resin, or an alkyd resin is used as a binder. And a color ink containing an appropriate color pigment or dye as a colorant may be used. As a method for forming the pattern layer, for example, a normal printing method such as an offset printing method, a gravure printing method, a screen printing method, or the like may be used. In particular, the offset printing method and the gravure printing method are suitable for performing multicolor printing and gradation expression. In the case of a single color, a coating method such as a gravure coating method, a roll coating method, a comma coating method, or a lip coating method may be employed. The pattern layer may be provided entirely or partially depending on the pattern to be expressed. The pattern layer may be a metal vapor deposition layer or a combination of a printed layer and a metal vapor deposition layer.

  In addition, when the protective layer and the picture layer have sufficient adhesion to the molded product, the adhesive layer may not be provided, but an adhesive layer may be formed as necessary. An adhesive layer adheres the transfer material which has said each layer to the molded article surface. The adhesive layer is formed on a portion to be adhered on the protective layer or the picture layer. That is, the adhesive layer is formed over the entire surface when the part to be bonded is over the entire surface. Further, if the part to be bonded is partially, an adhesive layer is partially formed. As the adhesive layer, a heat-sensitive or pressure-sensitive resin suitable for the material of the molded product is appropriately used. For example, when the material of the molded product is a polyacrylic resin, a polyacrylic resin may be used. In addition, when the material of the molded product is polyphenylene oxide / polystyrene resin, polycarbonate resin, styrene copolymer resin, polystyrene blend resin, polyacrylic resin, polystyrene resin, polyamide having affinity with these resins A series resin or the like may be used. Furthermore, when the material of the molded product is a polypropylene resin, chlorinated polyolefin resin, chlorinated ethylene-vinyl acetate copolymer resin, cyclized rubber, and coumarone indene resin can be used. Examples of the method for forming the adhesive layer include coating methods such as gravure coating, roll coating, and comma coating, printing methods such as gravure printing, and screen printing.

  The configuration of the transfer material is not limited to the above-described embodiment. For example, when using a transfer material for the purpose of surface protection only, taking advantage of the ground pattern and transparency of the molded product, a base sheet A B-staged resin layer and an adhesive layer can be sequentially formed on the substrate, and the pattern layer can be omitted from the transfer material.

  When the transfer material has a pattern layer or an adhesive layer on the B-staged resin layer, an anchor layer may be provided between these layers. The anchor layer is a resin layer for improving the adhesion between these layers and protecting the molded product and the pattern layer from chemicals. For example, heat is applied to two-component curable urethane resin, melamine resin, epoxy resin, etc. Thermoplastic resins such as curable resins and vinyl chloride copolymer resins can be used. As a method for forming the anchor layer, there are a coating method such as a gravure coating method, a roll coating method and a comma coating method, and a printing method such as a gravure printing method and a screen printing method.

  Next, a method for forming the protective layer of the molded product of the present invention will be described. The method for forming the protective layer of the molded article of the present invention is such that the curable resin composition of the present invention is coated on a base sheet and then heated to form a B-stage of the curable resin composition. -After bonding the staged resin layer and the molded product, the active energy ray is irradiated to cure the B-staged resin layer.

  The material of the molded product is not limited, and examples thereof include a resin molded product, a woodwork product, a metal molded product, and a composite product thereof. These may be transparent, translucent, or opaque. The molded product may be colored or not colored. Examples of the resin include general-purpose resins such as polystyrene resin, polyolefin resin, ABS resin, and AS resin. Also, general engineering resins such as polyphenylene oxide / polystyrene resins, polycarbonate resins, polyacetal resins, acrylic resins, polycarbonate modified polyphenylene ether resins, polyethylene terephthalate resins, polybutylene terephthalate resins, ultrahigh molecular weight polyethylene resins, and polysulfone resins. Super engineering resins such as polyphenylene sulfide resins, polyphenylene oxide resins, polyacrylate resins, polyetherimide resins, polyimide resins, liquid crystal polyester resins, and polyallyl heat-resistant resins can also be used. Furthermore, composite resins to which reinforcing materials such as glass fibers and inorganic fillers are added can also be used.

  As a method for forming the protective layer of the molded article of the present invention, for example, a transfer material is adhered to the surface of the molded article, and then the B-staged resin layer is transferred onto the molded article surface by peeling off the base sheet. After that, the energy beam is cured by irradiating active energy rays to cure the B-staged resin layer (transfer method), or the transfer material is sandwiched in a molding die, and the resin is placed in the cavity. At the same time as injection filling to obtain a resin molded product, a transfer material is adhered to the surface, the base sheet is peeled off, the B-staged resin layer is transferred onto the molded product, and then energy is applied by irradiation with active energy rays. Examples thereof include a method of crosslinking and curing a resin layer that has been B-staged by linear curing (simultaneous molding transfer method).

  The step of cross-linking and curing the B-staged resin layer is transferred to the B-stage by adhering the transfer material to the surface of the molded product as shown in the above method and then peeling the base sheet. After the transferred resin layer is transferred onto the surface of the molded product, an active energy ray irradiation is preferable. However, after the transfer material is adhered to the surface of the molded product, the active energy ray is irradiated from the substrate sheet side. The B-staged resin layer may be cured, and then the base sheet may be peeled off and transferred.

Examples of the active energy ray used in the method for forming the protective layer of the molded article of the present invention include electron beam, ultraviolet ray, and gamma ray. Irradiation conditions are determined according to the composition of the curable resin composition for transfer material used to obtain the protective layer, but it is preferable to irradiate so that the integrated light quantity is usually 50 to 5000 mj / cm ^2. It is more preferable to irradiate so that the amount of light is 500 to 2000 mj / cm ² .

Below, the formation method of the protective layer of the molded article by the said transfer method is demonstrated concretely. First, the transfer material is placed on the molded product with the adhesive layer side down. Next, a heat resistant rubber-like elastic body, for example, a heat transfer rubber set to conditions of a temperature of 80 to 260 ° C. and a pressure of 50 to 200 kg / m ² using a transfer machine such as a roll transfer machine or an up-down transfer machine equipped with silicon rubber. Heat or / and pressure is applied from the substrate sheet side of the transfer material through the elastic body. By doing so, the adhesive layer adheres to the surface of the molded product. Next, when the base sheet is peeled off after cooling, peeling occurs at the interface between the base sheet and the B-staged resin layer. When a release layer is provided on the base sheet, if the base sheet is peeled off, peeling occurs at the boundary surface between the release layer and the B-staged resin layer. Finally, the resin layer transferred to the molded product is completely crosslinked and cured by irradiating with active energy rays. In addition, you may perform the process of irradiating an active energy ray before the process of peeling a base sheet.

  Next, a method for forming a protective layer of a molded product by a simultaneous molding transfer method using injection molding will be specifically described. First, a transfer material is fed into a molding die composed of a movable die and a fixed die with the adhesive layer inside, that is, so that the base sheet is in contact with the fixed die. At this time, a single sheet of transfer material may be fed one by one, or a necessary part of a long transfer material may be intermittently fed. In the case of using a long transfer material, it is preferable to use a feeding device having a positioning mechanism so that the registration of the pattern layer of the transfer material and the molding die coincide. In addition, when the transfer material is intermittently fed, if the transfer material is fixed by the movable mold and the fixed mold after the position of the transfer material is detected by the sensor, the transfer material can always be fixed at the same position. This is convenient because the positional deviation of the pattern layer does not occur. After closing the molding die, molten resin is injected and filled into the die from the gate provided on the movable die, and at the same time as forming the molded product, the transfer material is adhered to the surface. After the resin molded product is cooled, the molding die is opened and the resin molded product is taken out. Finally, after peeling off the base sheet, the resin layer is completely crosslinked and cured by irradiating active energy rays. Further, the substrate sheet may be peeled off after irradiation with active energy rays.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. Parts and percentages in the examples are based on weight. Furthermore, the functional group equivalent of the cyclic ether structure of the compound (A) and the double bond equivalent in terms of solid content of the (meth) acryloyl group-containing compound (B) are theoretical values calculated from the material balance of the raw material.

Synthesis Example 1 [Synthesis of Compound (A) Having Cyclic Ether Structure]
Into a reaction apparatus equipped with a stirrer, a cooling pipe, a dropping funnel and a nitrogen introduction pipe, 463 g of butyl acetate was charged, and the temperature of the system was increased to 110 ° C. while stirring. Next, cyclomer M100 [3,4-epoxycyclohexylmethyl (meth) acrylate, manufactured by Daicel Chemical Industries, Ltd .: purity 96.8%. ] A mixed solution consisting of 463 g and 9.3 g of t-butylperoxy-2-ethylhexanoate (manufactured by Nippon Emulsifier: Perbutyl O) was dropped from the dropping funnel over 2 hours. After dropping, the temperature was maintained at 110 ° C. for 5 hours, then the temperature was raised to 120 ° C., and the reaction was continued at the same temperature for 8 hours. After completion of the reaction, 190 g of butyl acetate was charged to obtain 1,125 g of a compound having a cyclic ether structure. This is called a polymer (A1). The polymer (A1) has a non-volatile content of 41.9%, a Gardner viscosity (25 ° C.): D-E ² , a Gardner color of 1 or less, a styrene-equivalent number average molecular weight by GPC of 9,120, and a solid-equivalent epoxy. Equivalent: 196 mg KOH / g.

Synthesis Example 2 [Synthesis of Compound (B) Having (Meth) Acroyl Group]
A reactor equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introducing tube was charged with 1200 g of butyl acetate, and the temperature was raised until the system temperature reached 110 ° C. while stirring. Next, a mixed solution composed of 1200 g of glycidyl methacrylate and 24 g of perbutyl O was dropped from a dropping funnel over 2 hours. After dropping, the temperature was maintained at 110 ° C. for 7 hours, then the temperature was raised to 120 ° C., and the reaction was continued at the same temperature for 8 hours. Next, nitrogen was changed to dry air, the temperature was lowered to 90 ° C., 1.82 g of methoquinone and 621 g of acrylic acid were charged, 17.7 g of triphenylphosphine was added, the temperature was raised to 100 ° C., and the reaction was continued for 8 hours. Continued. After completion of the reaction, 1160 g of methyl ethyl ketone (MEK) and 730 g of butyl acetate were charged to obtain 4945 g of a compound having an acroyl group. This is referred to as a polymer (B1). The polymer (B1) has a non-volatile content: 37.7%, a Gardner viscosity (25 ° C.): C ² -D, a Gardner color: 1 or less, an acid value: 1.0 mgKOH / g, and a number average molecular weight in terms of styrene by GPC: 11,700, acrylic equivalent in terms of solid content: 218 g / eq, hydroxyl value in terms of solid content: 258 mgKOH / g.

Example 1
The compounds shown in Table 1 were blended to prepare a curable resin composition for transfer materials according to the present invention. This is abbreviated as composition M1. The storage stability of the composition M1 was evaluated as follows. It is shown in Table 3.

<Storage stability test method>
Composition M1 was placed in a sealed container and allowed to stand at 40 ° C. The number of days until the composition M1 gels was measured. The longer the number of days, the better the storage stability.

  A transfer material was produced using the prepared composition M1. Specifically, a polyester resin film having a thickness of 38 μm was used as a base sheet, and a release layer was formed on the film by applying a melamine resin release agent to a thickness of 1 μm by a gravure printing method. The composition M1 was printed on the release layer by a gravure printing method so as to have a thickness of 5 μm. Then, a semi-cured (B-staged) protective layer was obtained by heating at 140 ° C. for 5 minutes.

  Here, the obtained protective layer was touched with a finger (finger touch), and the presence or absence of residual tack was confirmed. The results are shown in Table 3. In Table 3, “O” represents that no tack remains, and “X” represents that tack remains.

  An acrylic ink was printed on the protective layer by a gravure printing method to form a picture layer. An acrylic resin was printed on the pattern layer by a gravure printing method to form a 4 μm thick adhesive layer to obtain a transfer material.

Using this transfer material, transfer and adhere to the surface of the molded product using the simultaneous molding transfer method, and then peel off the base sheet and irradiate ultraviolet rays to completely crosslink and cure the protective layer to form a protective layer on the molded product did. The molding conditions were a resin temperature of 240 ° C., a mold temperature of 55 ° C., and a resin pressure of 300 kg / cm ² . The molded product is a tray-shaped molded product made of acrylic resin and having a length of 95 mm, a width of 65 mm, a rise of 4.5 mm, and a corner of R2.5 mm. The irradiation condition of ultraviolet rays is four times with one 80 w / cm high-pressure mercury lamp, a lamp height of 15 cm, and a conveyor speed of 5 m / min.

  Using the molded article on which the protective layer was formed, a solvent resistance test and an abrasion resistance test were performed, and the presence or absence of cracks on the surface of the protective layer was also observed. Each test and the observation method of the presence or absence of a crack are shown below. The results of each test are shown in Table 3. Table 1 shows the number of moles (b) [(b) / (a)] of the (meth) acryloyl group in the compound (B) relative to the number of moles (a) of the cyclic ether structure in the composition M1.

<Solvent resistance test>
MEK was impregnated into gauze, and the state of the protective layer surface after 50 reciprocating rubbings with a load of (440 g / cm ² ) was visually observed and evaluated according to the following judgment.
A: No change in surface condition.
○: The surface of the protective layer dissolves and scratches occur, but scratches that reach the inside of the protective layer do not occur.
X: The protective layer dissolves and scratches reaching the inside occur.

<Abrasion resistance test>
Using # 0000 steel wool, the degree of damage on the surface of the protective layer after 50 reciprocations with a load (440 g / cm ² ) was visually observed and evaluated according to the following judgment.
A: No change in surface condition.
○: Scratches occur on the surface of the protective layer, but no scratches reach the inside of the protective layer.
X: Scratches reaching the inside occur.

<Presence of cracks>
The state of occurrence of cracks in the protective layer on the curved surface of the molded product was visually judged and evaluated according to the following judgment.
○: Cracks are not observed.
X: Crack generation is observed.

Examples 2 to 4 and Comparative Examples 1 and 2
Compositions M2 to M4, which are curable resin compositions for transfer materials, and comparative compositions M′1 and M′2 were prepared with the formulations shown in Tables 1 and 2. In the same manner as in Example 1, the transfer material was produced and the protective layer of the molded product was formed. The same tests as in Example 1 were performed and the results are shown in Tables 3 and 4.

Example 5
Composition M3 was air-sprayed onto the surface of the molded product to a thickness of 5 μm. Thereafter, it was heated at 120 ° C. for 5 minutes, and further irradiated with ultraviolet rays to obtain a cured coating film. Irradiation conditions are four high-pressure mercury lamps of 80 w / cm, lamp height of 15 cm, and conveyor speed of 5 m / min. Further, the molded product is a tray-shaped molded product made of acrylic resin and having a length of 95 mm, a width of 65 mm, a rise of 4.5 mm, and a corner portion of R2.5 mm.

  The resulting cured coating film was subjected to residual tackiness, solvent resistance test, and abrasion resistance test. The results are shown in Table 5.

Comparative Examples 3 and 4
A cured coating film was obtained in the same manner as in Example 5 except that the comparative composition M′1 or M′2 was used. The resulting cured coating film was subjected to residual tackiness, solvent resistance test, and abrasion resistance test. The results are shown in Table 5.

<Footnotes in Tables 1 and 2>
SH28PA: SH28PA (manufactured by Toray Dow Corning Co., Ltd.), which is a silicone leveling agent, diluted with MEK to a non-volatile content of 10%.
Irgacure 184: Photopolymerization initiator (Ciba Specialty)
SI-110: A sulfonium-based thermal cationic polymerization initiator SI-110 (manufactured by Sanshin Chemical Co., Ltd.) diluted with MEK so as to have a nonvolatile content of 20%.

Claims (14)

A curable resin composition comprising a compound (A) having a cyclic ether structure, a compound (B) having a (meth) acryloyl group, a photopolymerization initiator (C) and a thermal cationic polymerization initiator (D) Stuff. The number of moles (b) [(b) / (a)] of the (meth) acryloyl group in the compound (B) with respect to the number of moles (a) of the cyclic ether structure in the compound (A) is 1 to 10. The curable resin composition according to claim 1. The functional group equivalent (a) of the cyclic ether structure in the compound (A) is 80 to 1500 g / eq, and the equivalent (b) of the (meth) acryloyl group in the compound (B) is 80 to 1500 g / eq. The curable resin composition according to claim 2. The curable resin composition according to claim 2, wherein the compound (A) is a compound having an alicyclic epoxy type structure. The compound having an alicyclic epoxy type structure is an alicyclic epoxy (meth) acrylic resin having a number average molecular weight of 500 to 50,000 obtained by polymerization using 3,4-epoxycyclohexylmethyl (meth) acrylate as an essential component. The curable resin composition according to claim 4. The curable resin composition according to claim 1, wherein the compound (B) is a hydroxyl group-containing (meth) acrylic resin. The hydroxyl group-containing (meth) acrylic resin has a number average molecular weight of 500 to 50,000 and an acid value obtained by reacting an epoxy resin obtained by polymerizing glycidyl (meth) acrylate as an essential component and (meth) acrylic acid. The curable resin composition according to claim 6, which is an epoxy (meth) acrylic resin of 2 or less. The curable resin composition according to claim 1, wherein the photopolymerization initiator (C) is one or more compounds selected from the group consisting of benzoins, acetophenones, and ketals. The curable resin composition according to claim 1, wherein the thermal cationic polymerization initiator (D) is a sulfonium salt compound. The curable resin composition according to any one of claims 1 to 9, which is used for a transfer material. A transfer material obtained by coating the curable resin composition according to any one of claims 1 to 10 on a substrate sheet, and then heating to form a B-stage of the curable resin composition. The transfer material according to claim 11, wherein the base sheet is a plastic sheet. A curable resin composition according to any one of claims 1 to 10 is coated on a substrate sheet, and then heated to be B-staged of a transfer material obtained by B-staging the curable resin composition. A method for forming a protective layer, comprising irradiating an active energy ray after bonding a resin layer and a molded product. The B-staged resin layer of the transfer material is formed by adhering the B-staged resin layer of the transfer material and the molded product, and then peeling the base sheet of the transfer material. The method for forming a protective layer according to claim 13, which is carried out after transfer to the surface of the molded product.