TWI749213B - Active energy ray curable composition and hard coating film - Google Patents

Abstract

The present invention provides an active energy ray curable composition characterized by containing: an active energy ray curable compound (A), selected from hindered amine light stabilizers (B1) containing polymerizable functional groups, and hindered phenols At least one hindered amine-based light stabilizer (B) from the group of hindered amine-based light stabilizers (B2), and a compound selected from the group consisting of a silane coupling agent (c-1) and (meth)acrylamide (c-2) and one or more compounds (C) of the group of polymerizable monomers (c-3) having a tricyclodecane structure. In addition, the present invention provides a hard coating film characterized by being a cured coating film having the active energy ray curable composition on at least one side of a cyclic olefin resin film substrate.

Description

Active energy ray curable composition and hard coating film

The present invention relates to an active energy ray curable composition and a hard coating film.

Cyclic olefin resin films are excellent in transparency, low birefringence, low moisture absorption, heat resistance, electrical insulation, chemical resistance, etc., and are widely used in optical components, medical, packaging films, automobiles, and semiconductor applications. Especially in optical components, it is researched to replace the polyethylene terephthalate (PET), triacetyl cellulose (TAC), etc. used in the past in accordance with the diversification of the units used in liquid crystal displays or touch panels. The use of cyclic olefin resin film with high transparency, low moisture absorption and excellent plastic film.

In addition, the cyclic olefin resin film has insufficient surface hardness, so it may be scratched during processing. In order to improve abrasion resistance and abrasion resistance, it is being studied to provide a curable composition containing active energy rays on the surface. Hard coat and hard coat of the hardened coating film. However, since the main structure of the cyclic olefin resin film is an alicyclic structure, the polarity of the film surface is low, and the water contact angle is as high as about 90°. Therefore, when the active energy ray curable composition is applied, the coating material is difficult to be coated. There is a problem that the adhesion between the surface of the cyclic olefin resin film substrate and the hard coat layer is low when it is widely applied.

As a method to improve the adhesion between the surface of the cyclic olefin resin film substrate and the hard coat layer, it has been proposed to provide a modified olefin resin with a polar group as the main component on the surface of the cyclic olefin resin film substrate. After coating, an ionizing radiation curable resin is applied and cured (for example, refer to Patent Document 1). In this method, although the adhesion between the surface of the cyclic olefin resin film substrate and the hard coat layer can be improved, there are problems in that the steps of applying and drying the primer layer are increased, and the yield is reduced or the production cost is increased. .

In addition, as a method of adhering the hard coat layer to the surface of the cyclic olefin resin film substrate without providing an undercoat layer, a hard coat layer using a curable composition containing a (meth)acrylate having an alicyclic structure has been proposed. The film serves as a hard coat layer (for example, refer to Patent Document 2). In the case of using this curable composition, it is necessary to increase the ratio of (meth)acrylate having an alicyclic structure in order to achieve sufficient adhesion to the surface of the cyclic olefin resin film substrate. However, if the ratio of the (meth)acrylate having an alicyclic structure is increased, the crosslinking density of the cured coating film decreases and the scratch resistance of the cured coating film surface becomes insufficient.

Furthermore, although the cured coating film of the active energy ray curable composition has high adhesiveness (initial adhesiveness) immediately after being formed on the surface of the cyclic olefin resin film substrate, it is exposed to strong light afterwards. This will cause a problem that the adhesiveness (light-resistant adhesiveness) is lowered.

Therefore, it is required to impart high scratch resistance to the surface of the cyclic olefin resin film substrate, and form a cured coating film with excellent adhesion between the surface of the cyclic olefin resin film substrate without a primer layer. And the active energy ray curable composition whose adhesion does not decrease even after exposure to strong light.

Prior art literature Patent literature

Patent Document 1 JP 2004-284158 A

Patent Document 2 JP 2010-89458 A

The problem to be solved by the present invention is to provide an active energy ray curable composition which can impart high scratch resistance to the surface of the substrate and can form an excellent density with the surface of the substrate without a primer layer. Adhesive hardened coating film, and its adhesion will not decrease even after exposure to strong light.

The present invention provides an active energy ray curable composition characterized by containing: an active energy ray curable compound (A), selected from hindered amine light stabilizers (B1) containing polymerizable functional groups, and hindered phenols At least one hindered amine-based light stabilizer (B) from the group of hindered amine-based light stabilizers (B2), and a compound selected from the group consisting of a silane coupling agent (c-1) and (meth)acrylamide (c-2) and one or more compounds (C) of the group of polymerizable monomers (c-3) having a tricyclodecane structure.

In addition, the present invention provides a hard coating film characterized by being a cured coating film having the active energy ray curable composition on at least one side of a cyclic olefin resin film substrate.

The active energy ray curable composition system of the present invention can impart high scratch resistance to the surface of the substrate, and can form a cured coating film with excellent adhesion with the surface of the substrate without a primer layer. Its adhesion will not decrease even after exposure to strong light. Therefore, the active energy ray curable composition of the present invention can be used as an optical film used for liquid crystal displays or touch panel applications.

Form of invention

The active energy ray curable composition system of the present invention contains: an active energy ray curable compound (A), a hindered amine light stabilizer (B1) selected from the group comprising a polymerizable functional group, and a hindered amine system having a hindered phenol group At least one hindered amine-based light stabilizer (B) from the group of light stabilizers (B2), and a compound selected from the group consisting of silane coupling agent (c-1) and (meth)acrylamide (c-2) And one or more compounds (C) of the group of polymerizable monomers (c-3) having a tricyclodecane structure are essential components.

Examples of the active energy ray-curable compound (A) include polyfunctional (meth)acrylate (A1), urethane (meth)acrylate (A2), and the like. These can be used singly or in combination of two or more kinds.

In addition, in the present invention, the so-called "(meth)acrylate" means one or both of acrylate and methacrylate, and the so-called "(meth)acryloyl" means acryloyl One or both of the methacrylic groups.

The aforementioned polyfunctional (meth)acrylate (A1) is a compound having two or more (meth)acrylic groups in one molecule. Specific examples of the polyfunctional (meth)acrylate (A1) include 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol bis(meth) Base) acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylic acid Ester, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethyl Glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate Ester, di(meth)acrylate of ginseng isocyanurate (2-hydroxyethyl) ester, adding more than 4 mol of ethylene oxide or propylene oxide to 1 mol of neopentyl glycol The obtained di(meth)acrylate of the glycol, the di(meth)acrylate of the glycol obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A, three Methylolpropane tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, two -Trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, ginseng isocyanurate (2-(meth)acryloxyethyl) ester , Neopentaerythritol tri(meth)acrylate, Neopentaerythritol tetra(meth)acrylate, Dineopentaerythritol tri(meth)acrylate, Dineopentaerythritol tetra(meth)acrylate , Dineopentaerythritol penta(meth)acrylate, dineopentaerythritol hexa(meth)acrylate, etc. These polyfunctional (meth)acrylate (A1) systems may be used singly or in combination of two or more types. In addition, among these polyfunctional (meth)acrylates (A1), since it can also improve the scratch resistance of the cured coating film of the active energy ray curable composition used in the present invention, dineopentaerythritol six (Meth) acrylate, dineopentyl penta (meth) acrylate, neopentyl erythritol tetra (meth) acrylate, and neopentyl erythritol tri (meth) acrylate are preferred. Tetraol hexa(meth)acrylate and dineopentaerythritol penta(meth)acrylate are more preferable.

The aforementioned urethane (meth)acrylate (A2) is obtained by reacting a polyisocyanate (a2-1) with a (meth)acrylate (a2-2) having a hydroxyl group.

As the aforementioned polyisocyanate (a2-1), aliphatic polyisocyanate and aromatic polyisocyanate can be cited. Since the coloring of the cured coating film of the active energy ray curable composition used in the present invention can be further reduced, the aliphatic polyisocyanate is more good.

The aforementioned aliphatic polyisocyanate is a compound composed of an aliphatic hydrocarbon except for the isocyanate group. Specific examples of the aliphatic polyisocyanate include: aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate; norbornane diisocyanate, isophorone diisocyanate, Methylenebis(4-cyclohexylisocyanate), 1,3-bis(isocyanatomethyl)cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl Alicyclic polyisocyanates such as cyclo-1,5-diisocyanatocyclohexane, etc. In addition, as the aliphatic polyisocyanate, a terpolymer obtained by trimerizing the aforementioned aliphatic polyisocyanate or alicyclic polyisocyanate can also be used. In addition, these aliphatic polyisocyanate systems may be used singly or in combination of two or more kinds.

Among the aforementioned aliphatic polyisocyanates, in order to improve the scratch resistance of the coating film, among the aliphatic polyisocyanates, hexamethylene diisocyanate, which is a linear aliphatic hydrocarbon diisocyanate, and alicyclic diisocyanate are reduced Camphane diisocyanate and isophorone diisocyanate are preferred.

The aforementioned (meth)acrylate (a2-2) is a compound having a hydroxyl group and a (meth)acryloyl group. Specific examples of the (meth)acrylate (a2-2) include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy (meth)acrylate Butyl ester, 4-hydroxybutyl (meth)acrylate, 1,5-pentanediol mono(meth)acrylate, 1,6-hexanediol mono(meth)acrylate, neopentyl glycol mono( Mono(meth)acrylate of diols such as meth)acrylate, neopentyl glycol mono(meth)acrylate, etc.; trimethylolpropane di(meth)acrylate, ring Ethylene oxide (EO) modified trimethylolpropane (meth)acrylate, propylene oxide (PO) modified trimethylolpropane di(meth)acrylate, glycerol di(meth)acrylic acid Mono- or di-(meth)acrylates of triols such as bis(2-(meth)acryloyloxyethyl)hydroxyethyl isocyanurate, or having such alcoholic hydroxyl groups Part of the hydroxyl mono- and di(meth)acrylates modified with ε-caprolactone; neopentylerythritol tri(meth)acrylate, di-trimethylolpropane tri(meth)acrylate, Compounds having monofunctional hydroxyl groups and trifunctional or more (meth)acrylic groups, such as dineopentaerythritol penta(meth)acrylate, or having hydroxyl groups further modified with ε-caprolactone Multifunctional (meth)acrylate; dipropylene glycol mono(meth)acrylate, diethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate ) Acrylates and other (meth)acrylates with alkylene oxide chains; polyethylene glycol-polypropylene glycol mono(meth)acrylate, polyoxybutylene-polyoxypropylene mono(meth)acrylate, etc. Block structure of (meth)acrylates of alkylene oxide chains; poly(ethylene glycol-butylene glycol) mono(meth)acrylate, poly(propylene glycol-butylene glycol) mono(meth)acrylate (Meth)acrylates with random structure of alkylene oxide chains. These (meth)acrylate (a2-2) systems may be used singly or in combination of two or more kinds.

Among the aforementioned urethane (meth)acrylates (A2), in order to improve the scratch resistance of the cured coating film of the active energy ray curable composition used in the present invention, there are 4 or more ( The meth)acryloyl group is preferred. In order to make the aforementioned urethane (meth)acrylate (A2) have 4 or more (meth)acrylic acid groups in one molecule, as the aforementioned (meth)acrylate (a2-2), It is preferable to have 2 or more (meth)acryloyl groups. As such (meth)acrylate (a2-2), for example, trimethylolpropane di(meth)acrylate, ethylene oxide modified trimethylolpropane di(meth)acrylic acid Ester, propylene oxide modified trimethylolpropane di(meth)acrylate, glycerol di(meth)acrylate, bis(2-(meth)acryloyloxyethyl) hydroxyethyl iso Cyanuric acid ester, neopentylerythritol tri(meth)acrylate, di-trimethylolpropane tri(meth)acrylate, dineopentaerythritol penta(meth)acrylate, etc. For these (meth)acrylates (a2-2), one type may be used with respect to one type of the aforementioned aliphatic polyisocyanate, or two or more types may be used in combination. In addition, among these (meth)acrylates (a2-2), neopentylerythritol tri(meth)acrylate and dineopentaerythritol penta(meth)acrylate can improve scratch resistance. Better.

The reaction of the aforementioned polyisocyanate (a2-1) and the aforementioned (meth)acrylate (a2-2) can be carried out by a urethane reaction of a conventional method. Furthermore, in order to promote the progress of the urethane reaction, it is preferable to perform the urethane reaction in the presence of a urethane catalyst. Examples of the aforementioned carbamate catalyst include: amine compounds such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine; triphenylphosphine, triethylphosphine, etc. Phosphorus compounds; organic tin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin diacetate, tin octylate, and organic compounds such as zinc octylate Zinc compounds, etc.

In addition, as necessary, as active energy ray-curable compounds (A) other than the above-mentioned polyfunctional (meth)acrylate (A1) and urethane (meth)acrylate (A2), (A) (Meth)acrylate (A3) of relatively high molecular weight such as epoxy acrylate, polyester (meth)acrylate, and polyether (meth)acrylate. As the aforementioned epoxy (meth)acrylate, for example, it can be obtained by reacting (meth)acrylic acid with bisphenol-type epoxy resin, novolak-type epoxy resin, polyglycidyl methacrylate, etc., and esterifying it. By. In addition, as the aforementioned polyester (meth)acrylate, for example, it can be exemplified by reacting (meth)acrylic acid with a polyester having hydroxyl groups at both ends obtained by polycondensing a polyhydric carboxylic acid and a polyhydric alcohol, and esterifying it. Obtained, or obtained by reacting (meth)acrylic acid with polycarboxylic acid and adding alkylene oxide and esterifying it. Furthermore, as the aforementioned polyether (meth)acrylate, for example, one obtained by reacting (meth)acrylic acid with a polyether polyol and esterifying it can be cited. Moreover, the said (meth)acrylate (A3) may be used independently, and may use 2 or more types together.

Furthermore, in the active energy ray curable composition used in the present invention, in addition to (A1) to (A3) exemplified as the active energy ray curable compound (A), if blended with a phosphoric acid group (former The base) acrylate (A4) is better because the adhesion to the substrate is improved. The aforementioned (meth)acrylate (A4) having a phosphoric acid group is a (meth)acrylate having at least one phosphoric acid group in one molecule. As the (meth)acrylate (A4) having a phosphoric acid group, for example, (meth)acryloyloxyethyl phosphoric acid, di(meth)acryloyloxyethyl phosphate, tris(methyl) phosphate ) Acrylic oxyethyl, caprolactone-modified phosphoric acid (meth) acryloxyethyl, etc., and compounds having 2 or more (meth)acryloxy groups per molecule may also be used. Moreover, these (meth)acrylate (A4) systems which have a phosphoric acid group may be used individually by 1 type, and may use 2 or more types together.

When the active energy ray curable composition used in the present invention is blended with the aforementioned (meth)acrylate (A4) having a phosphoric acid group, the blending amount is improved due to the improved adhesion performance with the substrate, and the curing The scratch resistance of the surface of the coating film can also be further improved. In the active energy ray curable compound (A), 0.1-30% by mass is preferred, and 0.5-20% by mass is more preferred.

Next, the aforementioned hindered amine-based light stabilizer (B) will be described.

As said light stabilizer (B1), the hindered amine type light stabilizer which has a polymerizable functional group, such as a (meth)acryl group and a vinyl group, is mentioned, for example. More specifically, (meth)acrylate 2,2,6,6-tetramethyl-4-piperidinate, (meth)acrylate 1,2,2,6,6-pentamethyl-4 -Piperidinate etc. These light stabilizers (B1) may be used singly or in combination of two or more kinds.

As said light stabilizer (B2), the hindered amine type light stabilizer which has hindered phenolic groups, such as 3,5-di-tributyl-4-hydroxyphenyl, etc. is mentioned, for example. More specifically, a compound represented by the following formula (1) and the like can be mentioned. This light stabilizer (B2) can also be used in combination with the aforementioned light stabilizer (B1).

As the content of the hindered amine-based light stabilizer (B), since the adhesion to the cyclic olefin resin is improved, the adhesion even after exposure to strong light can be suppressed (hereinafter referred to as "light-resistant adhesion" The reduction of the “performance”) is preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 2 parts by mass relative to 100 parts by mass of the active energy ray-curable compound (A).

Next, the aforementioned compound (C) will be described. The aforementioned compound (C) must be selected from the group consisting of a silane coupling agent (c-1), a (meth)acrylamide compound (c-2) and a tricyclodecane structure in order to obtain excellent light resistance adhesion. One or more compounds in the group of polymerizable monomers (c-3).

The aforementioned silane coupling agent (c-1) is capable of obtaining excellent light resistance adhesion due to the covalent bond formed at the substrate interface of the adherend. Specific examples of the aforementioned silane coupling agent (c-1) include: vinyl trimethoxysilane, vinyl triethoxy silane, and other vinyl-containing silane coupling agents; 2-(3,4-epoxy Cyclohexyl) ethyl trimethoxy silane, 3-glycidoxy propyl methyl dimethoxy silane, 3-glycidoxy propyl trimethoxy silane, 3-glycidoxy propyl Silane coupling agents with epoxy groups such as methyldiethoxysilane and 3-glycidoxypropyltriethoxysilane; silane coupling agents with styryl groups such as p-styryltrimethoxysilane Mixture; 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyl Silane coupling agents with (meth)acryloyl groups such as methyl diethoxysilane, 3-(meth)acryloyloxypropyl triethoxysilane, etc.; N-2-(aminoethyl )-3-Aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene) propylamine, N-(vinylbenzyl)-2- Aminoethyl-3-aminopropyltrimethoxysilane hydrochloride and other silane coupling agents with amine groups; 3-ureidopropyltrialkoxysilane and other ureido silane coupling agents; Silane coupling agents with mercapto groups such as 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc.; thioethers such as bis(triethoxysilylpropyl) tetrasulfide, etc. -Based silane coupling agent; silane coupling agent with isocyanurate skeleton such as -(trimethoxysilylpropyl) isocyanurate; alkoxysilane compound with methyl group and phenyl group , Silane coupling agents with alkyl and phenyl groups, such as alkoxysilane compounds with propyl and phenyl groups; alkoxysilane compounds with acryloyl and phenyl groups, and methacryloyl and phenyl groups Silane coupling agents having (meth)acrylic acid groups and phenyl groups such as alkoxysilane compounds; silane coupling agents having isocyanate groups such as 3-isocyanate propyltriethoxysilane; methyl trimethoxysilane, Silane coupling agents having alkyl groups such as ethyl trimethoxysilane, propyl trimethoxysilane, butyl trimethoxysilane, hexyltrimethoxysilane, and decyltrimethoxysilane. These silane coupling agents can be used alone, or two or more of them can be used in combination. Among them, from the viewpoint of maintaining excellent scratch resistance and improving light resistance adhesion, one or more selected from the group consisting of alkyl groups, phenyl groups, and (meth)acrylic groups are used. The functional group of the silane coupling agent is preferred.

As the silane coupling agent having an alkyl group and a phenyl group, and a silane coupling agent having a (meth)acryloyl group and a phenyl group are used as the aforementioned silane coupling agent (c-1), the content of the alkoxy group is more From the viewpoint of excellent light resistance and adhesion, the range of 5 to 30% by mass in the silane coupling agent is preferable, the range of 10 to 25% by mass is more preferable, and the range of 13 to 22% by mass is more preferable.

The aforementioned (meth)acrylamide compound (c-2) causes erosion of the substrate and promotes the hydrogen abstraction reaction of the photopolymerization initiator (D). Therefore, by curing at the interface of the substrate, an excellent Light resistance and adhesion.

啉、N-[3-(N’,N’-二甲基胺基丙基)(甲基)丙烯醯胺、3-(丙烯醯基胺基)丙基三甲基氯化銨等的二甲基胺基丙基(甲基)丙烯醯胺的4級鹽、異丙基(甲基)丙烯醯胺、二乙基(甲基)丙烯醯胺、N-(2-羥乙基)(甲基)丙烯醯胺、2-(甲基)丙烯醯胺-2-甲基丙烷磺酸、(3-(甲基)丙烯醯胺丙基)三甲基三甲基氯化銨、3-丙烯醯基-2-

唑啶、丙烯醯胺己酸、三級丁基丙烯醯胺、丁氧基甲基丙烯醯 胺、N,N’-(1,2-二羥基伸乙基)雙丙烯醯胺、十二烷基丙烯醯胺、N,N’-伸乙基雙丙烯醯胺、N,N’-亞甲基雙丙烯醯胺、羥基甲基(甲基)丙烯醯胺、苯基丙烯醯胺等。此等(甲基)丙烯醯胺可單獨使用，亦可併用2種以上。此等之中，從維持優異的耐擦傷性，並且能更加提升耐光密合性之觀點，使用選自包含N-[3-(N’,N’-二甲基胺基丙基)(甲基)丙烯醯胺、3-(丙烯醯基胺基)丙基三甲基氯化銨、及N-(2-羥乙基)(甲基)丙烯醯胺之群組的1種以上之化合物為較佳。 Specific examples of the aforementioned (meth)acrylamide compound (c-2) include (meth)acrylamide, dimethyl(meth)acrylamide, and acrylamide

Morpholine, N-[3-(N',N'-dimethylaminopropyl)(meth)acrylamide, 3-(acrylamide)propyltrimethylammonium chloride, etc. The quaternary salt of methylaminopropyl(meth)acrylamide, isopropyl(meth)acrylamide, diethyl(meth)acrylamide, N-(2-hydroxyethyl)( (Meth)acrylamide, 2-(meth)acrylamide-2-methylpropanesulfonic acid, (3-(meth)acrylamide propyl)trimethyltrimethylammonium chloride, 3- Acryl-2-

Zolidine, acrylamide caproic acid, tertiary butyl acrylamide, butoxy methacrylamide, N,N'-(1,2-dihydroxyethylene) bisacrylamide, dodecane Alkylacrylamide, N,N'-ethylenebisacrylamide, N,N'-methylenebisacrylamide, hydroxymethyl(meth)acrylamide, phenylacrylamide, etc. These (meth)acrylamides may be used alone, or two or more of them may be used in combination. Among these, from the viewpoint of maintaining excellent abrasion resistance and improving light resistance adhesion, use selected from the group consisting of N-[3-(N',N'-dimethylaminopropyl) (former Yl)acrylamide, 3-(acrylamide)propyltrimethylammonium chloride, and N-(2-hydroxyethyl)(meth)acrylamide group of one or more compounds For better.

In addition, in the present invention, the "(meth)acrylamide" refers to acrylamide and/or methacrylamide.

The aforementioned polymerizable monomer (c-3) having a tricyclodecane structure is one that can obtain excellent light resistance adhesion, especially when a cyclic olefin resin film substrate is used as the substrate, by virtue of its approximation The affinity caused by the structure of the product can obtain more excellent light resistance adhesion.

As specific examples of the aforementioned polymerizable monomer (c-3), dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentyl (meth)acrylate, and dicyclopentyl (meth)acrylate can be used. Group) monomers having one radical polymerizable group such as acrylate; dimethylol tricyclodecane di(meth)acrylate, tricyclodecanediol di(meth)acrylate, tricyclic Monomers having two radically polymerizable groups such as decane dimethanol di(meth)acrylate and the like. These polymerizable monomers may be used alone or in combination of two or more kinds. Among these, from the viewpoint of obtaining more excellent light resistance adhesion, it is preferable to use the aforementioned monomer having two radically polymerizable groups, which is selected from the group consisting of dimethylol tricyclodecane bis(formaldehyde). One or more polymerizable monomers from the group of methacrylate, tricyclodecanediol di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate are more preferable.

The content of the compound (C) is preferably in the range of 1 to 50 parts by mass relative to 100 parts by mass of the active energy ray curable compound (A) from the viewpoint of obtaining more excellent light resistance adhesion. The range of 1.5-40 parts by mass is more preferable, and the range of 2-25 parts by mass is more preferable.

In terms of the content of the silane coupling agent (c-1) used alone as the compound (C), from the viewpoint of obtaining more excellent light resistance adhesion, it is 100% compared to the active energy ray-curable compound (A). Parts by mass are preferably in the range of 1-50 parts by mass, more preferably in the range of 1.5-40 parts by mass, and more preferably in the range of 2-25 parts by mass.

Regarding the content of the case where the aforementioned (meth)acrylamide compound (c-2) is used alone as the aforementioned compound (C), from the viewpoint of obtaining more excellent light resistance adhesion, compared to the aforementioned active energy ray curability 100 parts by mass of the compound (A) is preferably in the range of 3-50 parts by mass, more preferably in the range of 5-40 parts by mass, and more preferably in the range of 7-25 parts by mass.

Regarding the content of the case where the polymerizable monomer (c-3) is used alone as the compound (C), from the viewpoint of obtaining a longer light resistance adhesion, compared to the active energy ray curable compound (A ) 100 parts by mass, preferably in the range of 1-50 parts by mass, more preferably in the range of 1.5-40 parts by mass, more preferably in the range of 2-25 parts by mass, and particularly preferably 11-20 parts by mass.

In addition, the active energy ray curable composition of the present invention can be applied to a substrate and then irradiated with active energy rays to form a cured coating film. The so-called active energy rays refer to ionizing radiation such as ultraviolet rays, electron rays, α rays, β rays, and γ rays. In the case of irradiating ultraviolet rays as active energy rays to form a cured coating film, it is preferable to add a photopolymerization initiator (D) described later to the active energy ray curable composition of the present invention to improve the curability. In addition, if necessary, a photosensitizer (E) may be further added to improve the curability. On the other hand, in the case of using ionizing radiation such as electron beams, α rays, β rays, and γ rays, it can be cured quickly without using photopolymerization initiator (D) or photosensitizer (E), so There is no need to particularly add the photopolymerization initiator (D) or photosensitizer (E).

啉基(4-甲硫基苯基)丙烷-1-酮、2-苯甲基-2-二甲基胺基-1-(4-

啉基苯基)-丁酮等的苯乙酮系化合物；苯偶姻、苯偶姻甲基醚、苯偶姻異丙基醚等的苯偶姻系化合物；2,4,6-三甲基苯偶姻二苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦等的醯基氧化膦系化合物；苯甲基(二苯甲醯)、甲基苯基乙醛酯、羥苯基乙酸2-(2-羥基乙氧基)乙基酯、羥苯基乙酸2-(2-側氧基-2-苯基乙醯氧基乙氧基)乙基酯等的苯甲基系化合物；二苯甲酮、鄰苯甲醯基苯甲酸甲基-4-苯基二苯甲酮、4,4’-二氯二苯甲酮、羥基二苯甲酮、4-苯甲醯基-4’-甲基-二苯基硫化物、丙烯醯化二苯甲酮、3,3’,4,4’-四(三級丁基過氧羰基)二苯甲酮、3,3’-二甲基-4-甲氧基二苯 甲酮、2,4,6-三甲基二苯甲酮、4-甲基二苯甲酮等的二苯甲酮系化合物；2-異丙基噻噸酮、2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、2,4-二氯噻噸酮等的噻噸酮系化合物；米其勒酮、4,4’-二乙基胺基二苯甲酮等的胺基二苯甲酮系化合物；10-丁基-2-氯吖啶酮、2-乙基蒽醌、9,10-菲醌、樟腦醌、1-[4-(4-苯甲醯基苯基氫硫基)苯基]-2-甲基-2-(4-甲基苯基磺醯基)丙烷-1-酮等。此等光聚合起始劑(C)可以1種使用，亦可併用2種。 As the aforementioned photopolymerization initiator (D), for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, and oligo{2-hydroxy-2 -Methyl-1-[4-(1-methylvinyl)phenyl]acetone}, benzyl dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2- Methyl propane-1-one, 4-(2-hydroxyethoxy) phenyl-(2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-

Linyl (4-methylthiophenyl) propane-1-one, 2-benzyl-2-dimethylamino-1-(4-

Acetophenone-based compounds such as linylphenyl)-butanone; benzoin-based compounds such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; 2,4,6-trimethyl Benzoin diphenyl phosphine oxide, bis(2,4,6-trimethylbenzyl)-phenyl phosphine oxide and other phenyl phosphine oxide compounds; benzyl (dibenzoyl), Methyl phenylacetaldehyde ester, 2-(2-hydroxyethoxy) ethyl hydroxyphenylacetate, 2-(2-side oxy-2-phenylacetoxyethoxy) hydroxyphenylacetate ) Benzyl compounds such as ethyl ester; benzophenone, phthalate methyl-4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxy two Benzophenone, 4-benzyl-4'-methyl-diphenyl sulfide, acrylic benzophenone, 3,3',4,4'-tetra(tertiary butylperoxycarbonyl) ) Benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, etc. Benzophenone compounds; thioxanthones such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, etc. Ketone compounds; aminobenzophenone compounds such as Michelone and 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethyl Anthraquinone, 9,10-phenanthrenequinone, camphorquinone, 1-[4-(4-benzylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl) (Alkyl) propan-1-one and the like. These photopolymerization initiators (C) may be used singly or in combination of two types.

In addition, as the aforementioned photosensitizer (E), for example, tertiary amine compounds such as diethanolamine, N-methyldiethanolamine, and tributylamine, urea compounds such as o-toluenethiourea, and diethyldiethanolamine Sulfur compounds such as sodium thiophosphate and s-benzylisothiourea p-toluenesulfonate.

The usage amount of the aforementioned photopolymerization initiator (D) and photosensitizer (E) is relative to the aforementioned active energy ray curable compound (A) and the aforementioned compound ( The total of 100 parts by mass of B) is preferably 0.05-20 parts by mass, and more preferably 0.5-10 parts by mass.

In the active energy ray curable composition of the present invention, in addition to the above-mentioned active energy ray curable compound (A), hindered amine-based light stabilizer (B), compound (C), etc., it can be blended according to the application or required characteristics. Combine organic solvents, polymerization inhibitors, surface modifiers, antistatic agents, defoamers, viscosity modifiers, light stabilizers, weather stabilizers, heat stabilizers, ultraviolet absorbers, antioxidants, leveling agents, organic pigments, Additives for inorganic pigments, pigment dispersants, organic beads, etc.; inorganic fillers for silica (silica particles), alumina, titania, zirconia, antimony pentoxide, etc. These other blend systems may be used singly, or two or more of them may be used in combination.

By blending silica particles with the aforementioned inorganic filler, the scratch resistance of the cured coating film surface of the active energy ray curable composition of the present invention can be further improved, and the adhesion to the substrate can also be improved. As the aforementioned silica particles, the surface of the silica particles may be modified with organic bases, or those without surface modification. In addition, the aforementioned silica particles can further improve the transparency of the cured coating film and the scratch resistance of the surface of the active energy ray curable composition of the present invention. Therefore, nano-sized silica particles are preferred, and colloidal particles are preferred. Silica is better. The average particle diameter of the aforementioned silica fine particles is preferably in the range of 5 to 200 nm, and more preferably in the range of 5 to 100 nm. In addition, the average particle size is a value measured by a dynamic light scattering method.

In the case of blending the aforementioned inorganic filler, since the scratch resistance of the cured coating film surface of the active energy ray curable composition of the present invention can be further improved, the adhesion to the substrate can also be further improved. Based on 100 parts by mass of the active energy ray curable compound (A), preferably 1 to 150 parts by mass, and more preferably 5 to 100 parts by mass.

The aforementioned organic solvents are useful for appropriately adjusting the solution viscosity of the active energy ray curable composition of the present invention, and especially for thin film coating, it is easy to adjust the film thickness. As the organic solvent that can be used here, for example, aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, isopropanol, and tertiary butanol; ethyl acetate, butyl acetate, propylene glycol mono Esters such as methyl ether acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. These solvents may be used singly, or two or more of them may be used in combination.

As a method of forming a cured coating film from the active energy ray curable composition of the present invention, for example, a method of applying the active energy ray curable composition to a base material and then irradiating the active energy ray is exemplified.

Examples of the aforementioned substrate include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polypropylene, polyethylene, and polyethylene. Polyolefin resins such as pentene-1; cellulose acetate (diacetyl cellulose, triacetyl cellulose, etc.), cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, Cellulose resins such as cellulose acetate and nitrocellulose phthalate; acrylic resins such as polymethyl methacrylate; vinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride; polyvinyl alcohol; Ethylene-vinyl acetate copolymer; polystyrene; polyamide; polycarbonate; polysulfide; polyether sulfide; polyether ether ketone; polyimine, polyetherimine, and other polyimide-based resins ; Cyclic olefin resin film substrate, etc. The active energy ray curable composition of the present invention can obtain excellent transparency, scratch resistance, and light resistance adhesion regardless of which of these substrates are used, and is particularly suitable for use in the aforementioned ring, which has increased in demand in recent years. Shape olefin resin film substrate.

As the said cyclic olefin resin film base material, what is necessary is just what polymerized a cyclic olefin, it may be a homopolymer or a copolymer, and it can use it without a restriction|limiting in particular. Examples of commercially available cyclic olefin resins include "ZEONOR (registered trademark)" and "ZEONEX (registered trademark)" manufactured by ZEON Co., Ltd.; and "ARTON (registered trademark)" manufactured by JSR Co., Ltd. ; "TOPAS (registered trademark)" manufactured by Polyplastics Co., Ltd., etc.

The aforementioned cyclic olefin resin film base material is obtained by molding a cyclic olefin resin on a film. In addition, the surface of the cyclic olefin resin film substrate is treated with surface roughening, such as sandblasting, solvent treatment, etc., in order to improve the adhesion between the active energy ray curable composition used in the present invention and the cured coating film. Electric treatment (corona discharge treatment, atmospheric piezoelectric slurry treatment), chromic acid treatment, flame treatment, hot air treatment, ozone. Ultraviolet rays. Electron beam irradiation treatment, oxidation treatment, etc. are preferred. Among these, corona discharge treatment, atmospheric pressure slurry treatment, etc., are subjected to electrical treatment.

In addition, the thickness of the aforementioned cyclic olefin resin film substrate is preferably in the range of 1 to 200 μm, more preferably in the range of 5 to 100 μm, and more preferably in the range of 10 to 50 μm. By setting the thickness of the film base material within this range, even when the cured coating film of the active energy ray curable composition of the present invention is provided on one side of the cyclic olefin resin film base material, curling can be easily suppressed.

The hard coat film of the present invention is obtained by coating the active energy ray curable composition on at least one surface of a cyclic olefin resin film substrate, and then irradiating the active energy ray to form a cured coating film. As a method of coating the aforementioned active energy ray curable composition on the cyclic olefin resin film substrate, for example, die coating, micro-gravure coating, gravure coating, roll coating, cut-off wheel coating, air knife coating, and contact coating can be mentioned. (kiss coat), spray coating, bridging coating, dip coating, spin coating, wheel coating (wheeler coating), brush coating, full plate coating by screen printing, wire rod coating, flow coating, etc.

In addition, in order to harden the active energy ray curable composition, when ultraviolet rays are used as the active energy rays, as the device for irradiating ultraviolet rays, for example, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and electrodeless lamps (Fusion lamp), chemical lamp, black light lamp, mercury-xenon lamp, short arc lamp, helium cadmium laser, argon laser, sunlight, LED, etc.

In addition to excellent optical properties, dimensional stability, heat resistance, transparency, and light resistance, the hard coat film of the present invention has excellent scratch resistance on its surface and can be used in various applications, especially as liquid crystals. Optical films used in image display parts of image display devices such as displays (LCD) and organic EL displays (OLED) are useful. In particular, even if it is thin, it has excellent scratch resistance, so it can be suitable as a portable electronic notebook, mobile phone, smart phone, portable audio player, mobile computer, tablet terminal, etc. that requires miniaturization or thinning. Used for the optical film of the image display part of the image display device of the electronic terminal. Moreover, when it is used as an optical film, it can be used as a protective film used on the outermost surface of the image display part of an image display device, and a base material for a touch panel. Furthermore, in the case of use as a protective film, for example, in an image display device composed of a transparent panel for protecting the image display module provided on the upper part of an image display module such as an LCD module or an OLED module, by It is used by being attached to the surface or back of the transparent panel, and it is effective for preventing scratches or preventing scattering when the transparent panel is damaged.

[Example]

The following examples illustrate the present invention in more detail.

(Example 1)

A mixture of 100 parts by mass of dineopentaerythritol hexaacrylate (hereinafter referred to as "DPHA") and dineopentaerythritol pentaacrylate (hereinafter referred to as "DPPA") (DPHA/DPPA=65/35 (Mass ratio)), 26 parts by mass of silica fine particles ("MEK-ST40" manufactured by Nissan Chemical Industry Co., Ltd., with an average particle size of 10-20 nm, 40% by mass of organosilica gel (colloidal silica) Ethyl ketone dispersion) (silica fine particles), 0.5 parts by mass of hindered amine light stabilizer having a methacrylic acid group (ADEKA STAB (registered trademark) LA-87" manufactured by ADEKA Co., Ltd.; 2,2,6,6-tetramethyl-4-piperidinyl acrylate), and 6 parts by mass of 1-hydroxycyclohexyl phenyl ketone ("IRGACURE (registered trademark) 184" manufactured by BASF Japan Co., Ltd.) , 20 parts by mass of methyl trimethoxysilane ("KBM-13" manufactured by Shin-Etsu Chemical Co., Ltd.) is uniformly stirred, and then diluted with methyl ethyl ketone to prepare active energy ray hardening with 40% by mass of non-volatile content Sexual composition (1).

(Example 2)

Except that the blending amount of ADEKA STAB LA-87 was changed from 0.5 part by mass to 0.1 part by mass, the same procedure as in Example 1 was carried out to prepare an active energy ray curable composition (2).

(Example 3)

Except that the blending amount of ADEKA STAB LA-87 was changed from 0.5 part by mass to 1 part by mass, the same procedure as in Example 1 was carried out to prepare an active energy ray curable composition (3).

(Example 4)

Except that the blending amount of KBM-13 was changed from 20 parts by mass to 5 parts by mass, the same procedure as in Example 1 was carried out to prepare an active energy ray curable composition (4).

(Example 5)

Except that the ADEKA STAB LA-87 used in Example 1 was changed to a hindered amine light stabilizer having a methacrylic acid group (ADEKA Co., Ltd. "ADEKA STAB (registered trademark) LA-82"; methacrylic acid 1 ,2,2,6,6-pentamethyl-4-piperidinate), in the same manner as in Example 1, the active energy ray curable composition (5) was prepared.

(Example 6)

Except that the ADEKA STAB LA-87 used in Example 1 was changed to a hindered amine-based light stabilizer with a hindered phenol group ("TINUVIN (registered trademark) PA144" manufactured by BASF Japan Co., Ltd.; shown in the following formula (1) Except for the compound), the same procedure as in Example 1 was carried out to prepare an active energy ray curable composition (6).

(Example 7)

A mixture of 100 parts by mass of dineopentaerythritol hexaacrylate (hereinafter referred to as "DPHA") and dineopentaerythritol pentaacrylate (hereinafter referred to as "DPPA") (DPHA/DPPA=65/35 (Mass ratio)) 0.5 parts by mass of hindered amine light stabilizer having a methacrylic acid group (ADEKA STAB (registered trademark) LA-87" manufactured by ADEKA Co., Ltd.; methacrylic acid 2,2,6, 6-tetramethyl-4-piperidinate), and 6 parts by mass of 1-hydroxycyclohexyl phenyl ketone ("RUNTECURE (registered trademark) 1104" manufactured by BASF Japan Co., Ltd.), and 15 parts by mass of N-[ 3-(N',N'-Dimethylaminopropyl)acrylamide (hereinafter referred to as "DMAPAA") is uniformly stirred and diluted with methyl ethyl ketone to prepare a 40% by mass non-volatile content Active energy ray curable composition (7).

(Example 8)

Except that the blending amount of ADEKA STAB LA-87 was changed from 0.5 part by mass to 1 part by mass, the same procedure as in Example 1 was carried out to prepare an active energy ray curable composition (8).

(Example 9)

Except that the blending amount of DMAPAA was changed from 15 parts by mass to 10 parts by mass, the same procedure as in Example 1 was carried out to prepare an active energy ray curable composition (9).

(Example 10)

Except that 3-(acrylamido)propyltrimethylammonium chloride (hereinafter referred to as "DMAPAA-Q") was used instead of DMAPAA, the active energy ray curable composition (10 ).

(Example 11)

Except having used 2-hydroxyethyl acrylamide (hereinafter, abbreviated as "HEAA") instead of DMAPAA, the same procedure as in Example 1 was carried out to prepare an active energy ray curable composition (11).

(Example 12)

Except that the ADEKA STAB LA-87 used in Example 1 was changed to a hindered amine light stabilizer having a methacrylic acid group (ADEKA Co., Ltd. "ADEKA STAB (registered trademark) LA-82"; methacrylic acid 1 , 2,2,6,6-pentamethyl-4-piperidinate), in the same manner as in Example 1, the active energy ray curable composition (12) was prepared.

(Example 13)

Except that the ADEKA STAB LA-87 used in Example 1 was changed to a hindered amine-based light stabilizer with a hindered phenol group ("TINUVIN (registered trademark) PA144" manufactured by BASF Japan Co., Ltd.; shown in the following formula (1) Except for the compound), the same procedure as in Example 1 was carried out to prepare an active energy ray curable composition (13).

(Example 14)

A mixture of 94 parts by mass of dineopentaerythritol hexaacrylate (hereinafter referred to as "DPHA") and dineopentaerythritol pentaacrylate (hereinafter referred to as "DPPA") (DPHA/DPPA=65/35 (Mass ratio)), 6 parts by mass of 1-hydroxycyclohexyl phenyl ketone ("RUNTECURE 1104" manufactured by BASF Co., Ltd.), 0.5 parts by mass of 2,2,6,6-tetramethyl-4 -Piperidinate (manufactured by ADEKA Co., Ltd., reactive hindered amine "ADEKA STAB LA-87"), 10 parts by mass of silica particles (manufactured by Nissan Chemical Industry Co., Ltd. "MEK-ST40", average particle size 10~ 20nm, 40% by mass methyl ethyl ketone dispersion of organosilica gel) (silica fine particles are 4 parts by mass), 15 parts by mass of dimethylol tricyclodecane diacrylate (Kyoeisha Chemical Co., Ltd. "LIGHT ACRYLATE DCP-A" manufactured by Co., Ltd.) After uniformly stirring, it was diluted with methyl ethyl ketone to prepare an ultraviolet curable composition (14) with a non-volatile content of 40% by mass.

(Example 15)

Except that the blending amount of dimethylol tricyclodecane diacrylate was changed from 15 parts by mass to 10 parts by mass, the same procedure as in Example 1 was carried out to prepare an active energy ray curable composition (15).

(Example 16)

Except that the ADEKA STAB LA-87 used in Example 1 was changed to a hindered amine-based light stabilizer with a hindered phenol group ("TINUVIN (registered trademark) PA144" manufactured by BASF Japan Co., Ltd.; shown in the following formula (1) Except for the compound), the same procedure as in Example 1 was carried out to prepare an active energy ray curable composition (16).

(Comparative example 1)

Except that ADEKA STAB LA-87 used in Example 1 was not used, the same procedure as in Example 1 was carried out to prepare an active energy ray curable composition (R1).

(Comparative example 2)

-2-基)-4,7-二氮雜癸烷-1,10-二胺的質量比1：1的混合物)以外，與實施例1同樣地進行，調製活性能量線硬化性組成物(R2)。 Except that the ADEKA STAB LA-87 used in Example 1 was changed to a hindered amine light stabilizer ("TINUVIN (registered trademark) 111FDL" manufactured by BASF Japan Co., Ltd.; dimethyl succinate and 4-hydroxy-2, 2,6,6-Tetramethyl-1-piperidine ethanol polymer with N,N',N”,N”'-four-(4,6-bis-(butyl-(N-methyl) -2,2,6,6-Tetramethylpiperidin-4-yl)amino)-tri

-2-yl)-4,7-diazadecane-1,10-diamine with a mass ratio of 1:1), the same procedure as in Example 1 was carried out to prepare an active energy ray curable composition ( R2).

(Comparative example 3)

Except that the ADEKA STAB LA-87 used in Example 1 was changed to a hindered amine light stabilizer ("TINUVIN (registered trademark) 770DF" manufactured by BASF Japan Co., Ltd.; bis(2,2,6,6-tetramethyl) Except for 4-piperidinyl) sebacate), the same procedure as in Example 1 was carried out to prepare an active energy ray curable composition (R3).

(Comparative example 4)

Except that the ADEKA STAB LA-87 used in Example 1 was changed to a hindered amine light stabilizer (ADEKA Co., Ltd. "ADEKA STAB (registered trademark) LA-81"; bis(1-undecyloxy-2) , 2,6,6-Tetramethylpiperidin-4-yl)carbonate), in the same manner as in Example 1, to prepare an active energy ray curable composition (R4).

(Comparative Example 5)

Except that the ADEKA STAB LA-87 used in Example 1 was changed to a hindered amine light stabilizer ("TINUVIN (registered trademark) 123" manufactured by BASF Japan Co., Ltd.; sebacic acid bis{2,2,6,6- Except for tetramethyl-1-(octyloxy)piperidin-4-yl ester}), the same procedure as in Example 1 was carried out to prepare an active energy ray curable composition (R5).

(Comparative Example 6)

Except that the ADEKA STAB LA-87 used in Example 1 was changed to a hindered amine light stabilizer ("TINUVIN (registered trademark) 5100" manufactured by BASF Japan Co., Ltd.; double (2,2,6,6-tetramethyl) -1-octyloxypiperidin-4-yl)-1,10-sebacate and 1,8-bis[{2,2,6,6-tetramethyl-4-((2,2, 6,6-Tetramethyl-1-octyloxypiperidin-4-yl)-decane-1,10-diyl)piperidin-1-yl}oxy]octane mixture), and implementation In the same manner as in Example 1, an active energy ray curable composition (R6) was prepared.

(Comparative Example 7)

Except that the ADEKA STAB LA-87 used in Example 1 was changed to a hindered amine light stabilizer ("TINUVIN (registered trademark) 292" manufactured by BASF Japan Co., Ltd.; double (1,2,2,6,6-五) Methyl-4-piperidinyl) sebacate 70~80% by mass and methyl-1,2,2,6,6-pentamethyl-4-piperidinyl sebacate 20~30% by mass Except for the mixture), the same procedure as in Example 1 was carried out to prepare an active energy ray curable composition (R7).

(Comparative Example 8)

Except that the ADEKA STAB LA-87 used in Example 1 was changed to a hindered amine light stabilizer (ADEKA STAB (registered trademark) LA-52" manufactured by ADEKA Co., Ltd.; 4 (1,2,2,6,6) Except for -pentamethyl-4-piperidinyl)butane-1,2,3,4-tetracarboxylic acid ester), the same procedure as in Example 1 was carried out to prepare an active energy ray curable composition (R8).

(Comparative Example 9)

Except that the ADEKA STAB LA-87 used in Example 1 was changed to an ultraviolet absorber ("TINUVIN (registered trademark) 400" manufactured by BASF Japan Co., Ltd.), the same procedure was carried out as in Example 1, and the active energy ray curability was prepared. Composition (R9).

(Comparative Example 10)

Except that the ADEKA STAB LA-87 used in Example 1 was changed to an ultraviolet absorber ("TINUVIN (registered trademark) 384-2" manufactured by BASF Japan Co., Ltd.), the same procedure as in Example 1 was carried out to prepare active energy rays Curable composition (R10).

(Comparative Example 11)

Except that the ADEKA STAB LA-87 used in Example 1 was changed to antioxidant ("IRGANOX (registered trademark) 1010" manufactured by BASF Japan Co., Ltd.), the same procedure as in Example 1 was carried out to prepare an active energy ray curable composition物(R11).

(Comparative Example 12)

Except not using KBM-13 used in Example 1, the same procedure as in Example 1 was carried out to prepare an active energy ray curable composition (R12).

[Method of Making Hard Coating Film]

The active energy ray curable composition obtained in the examples and comparative examples was applied to a ring shape which had been previously electrically treated (corona discharge treatment; output 100W, speed 1.0m/min) using a wire bar On an olefin resin film substrate ("ZEONOR (registered trademark) film PT14-080" made by Japan's ZEON Co., Ltd., thickness 25μm), heated at 60°C for 90 seconds, placed in an air environment for 60 seconds, and irradiated with ultraviolet rays Device ("MIDN-042-C1" manufactured by Eyegraphics Co., Ltd., lamp: 120W/cm, high-pressure mercury lamp), ^{irradiates ultraviolet rays with an irradiation light quantity of 0.22 J/cm 2 to} obtain a hard coat film (1 )~(16), and (R1)~(R12).

[Evaluation of scratch resistance]

For the surface of the hard coating film obtained above, use a clock-type counter type friction tester (a 1.0cm diameter round friction roller, steel wool #0000, load 500g, 10 round trips) to test, visually observe the test The surface of the later cured coating film was evaluated for scratch resistance using the following criteria.

A: No scars.

B: The number of shallow scars is 5 or less.

C: The number of scars is 5 or less.

D: There are many scars.

E: There are many significant and deep scars.

[Evaluation of initial adhesion]

On the surface of the cured coating film of the hard coating film obtained above, 11 vertical and horizontal notches were scored at 1 mm intervals to make 100 squares. Next, the transparent tape ("Cellotape (registered trademark) CT-18" manufactured by Nichiban Co., Ltd.) was brought into close contact with the surface, immediately peeled off, and the operation was repeated twice. The ratio of the residual area remaining from peeling was evaluated by the following criteria to evaluate the initial adhesion. In addition, the evaluators of D to F based on the following criteria were judged as unqualified.

A: The residual area ratio is 100%.

B: The residual area ratio is 95% or more and 99% or less.

C: The residual area ratio is 85% or more and 95% or less.

D: The residual area ratio is 50% or more and 84% or less.

E: The residual area ratio is 35% or more and 49% or less.

F: The residual area ratio is 34% or less.

[Evaluation of the adhesion (light resistance) after the light resistance test]

The hard coat film obtained above was subjected to an accelerated weather resistance test using a sunlight weather tester (according to JIS L0891: 2007, the test conditions are as follows), and after the test, the initial adhesion was evaluated in the same manner as the above-mentioned initial adhesion. , And evaluate the light resistance adhesion.

Light source: continuous sunlight carbon arc lamp

Temperature: 63°C

Relative humidity: 50%RH

Irradiation time: 50 hours, 100 hours, 150 hours

Rain cycle and time: not set

The composition of the active energy ray curable composition of the Examples and Comparative Examples and the evaluation results of the hard coat films obtained above are shown in Tables 1 to 3. In addition, the composition systems in Tables 1 to 3 are all listed in terms of non-volatile content, and the mass parts are values rounded off to the first decimal place.

From the evaluation results shown in Tables 1 to 3, the active energy ray-curable composition system of the present invention has excellent scratch resistance on the surface of the cured coating film, and also has high initial adhesion to the cyclic olefin resin film substrate. The light resistance adhesion (adhesion after the light resistance test) is also excellent.

On the other hand, Comparative Examples 1 to 11 shown in Tables 4 and 5 use the active energy ray curable composition that does not contain the hindered amine-based light stabilizer (B) used in the present invention, but has scratch resistance , At least one of the initial adhesion and light resistance adhesion is insufficient, and there is a problem in practicality. In addition, in Comparative Example 12, an active energy ray curable composition containing no compound (C) was used, but the light-resistant adhesiveness was insufficient.

Claims (11)

An active energy ray curable composition characterized by containing: an active energy ray curable compound (A), a hindered amine light stabilizer (B1) selected from the group comprising a polymerizable functional group and a hindered amine having a hindered phenol group A hindered amine-based light stabilizer (B) of at least one type of the group of light stabilizers (B2), and a compound selected from the group consisting of a silane coupling agent (c-1) and (meth)acrylamide (c-2) ) And at least one compound (C) of the group of a polymerizable monomer (c-3) having a tricyclodecane structure, wherein the active energy ray-curable compound (A) contains a polyfunctional (methyl) Acrylate (A1), the multifunctional (meth)acrylate (A1) is selected from the group consisting of dineopentaerythritol hexa(meth)acrylate, dineopentaerythritol penta(meth)acrylate, new At least one of the group of pentaerythritol tetra(meth)acrylate and neopentaerythritol tri(meth)acrylate. According to the active energy ray curable composition of claim 1, wherein the light stabilizer (B1) is selected from the group consisting of 2,2,6,6-tetramethyl-4-piperidinate (meth)acrylate and (a Yl) at least one of the group of 1,2,2,6,6-pentamethyl-4-piperidinyl acrylate. The active energy ray curable composition of claim 1, wherein the light stabilizer (B2) is a compound represented by the following formula (1),

The active energy ray curable composition of claim 1, wherein the content of the hindered amine-based light stabilizer (B) is in the range of 0.05 to 5 parts by mass relative to 100 parts by mass of the active energy ray curable compound (A) . The active energy ray curable composition of claim 1, wherein the silane coupling agent (c-1) has one or more selected from the group consisting of an alkyl group, a phenyl group, and a (meth)acryloyl group Functional silane coupling agent. The active energy ray curable composition of claim 1, wherein the (meth)acrylamide compound (c-2) is selected from the group consisting of N-[3-(N',N'-dimethylaminopropyl (Meth)acrylamide, 3-(acrylamido)propyltrimethylammonium chloride, and N-(2-hydroxyethyl)(meth)acrylamide group 1 More than kind of compounds. The active energy ray curable composition of claim 1, wherein the polymerizable monomer (c-3) having a tricyclodecane structure is selected from the group consisting of dimethylol tricyclodecane di(meth)acrylate One or more polymerizable monomers in the group of tricyclodecanediol di(meth)acrylate and tricyclodecane dimethanol di(meth)acrylate. The active energy ray curable composition of claim 1, wherein the content of the compound (C) is in the range of 1 to 50 parts by mass relative to 100 parts by mass of the active energy ray curable compound (A). The active energy ray curable composition according to any one of claims 1 to 8, wherein the active energy ray curable composition system further contains an inorganic filler. The active energy ray curable composition of claim 9, wherein the inorganic filler is silica particles. A hard coat film, which is characterized by the cyclic olefin resin film substrate One side less, with a cured coating film of the active energy ray curable composition according to any one of claims 1 to 10.