TW201843249A - Active energy ray-curable composition and hard coat film - Google Patents

Abstract

The present invention provides an active energy ray-curable composition which is characterized by containing: an active energy ray-curable compound (A); at least one hindered amine light stabilizer (B) that is selected from the group consisting of hindered amine light stabilizers (B1) having a polymerizable functional group and hindered amine light stabilizers (B2) having a hindered phenol group; and one or more compounds (C) that are selected from the group consisting of silane coupling agents (c-1), (meth)acrylamide compounds (c-2) and polymerizable monomers (c-3) having a tricyclodecane structure. The present invention also provides a hard coat film which is characterized by having a cured coating film of the active energy ray-curable composition on at least one surface of a cyclic olefin resin film substrate.

Description

   Active energy ray hardening composition and hard coating film   

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

Cyclic olefin resin films are excellent in transparency, low birefringence, low moisture absorption, heat resistance, electrical insulation, and chemical resistance, and are widely used in optical members, medical, packaging films, automobiles, and semiconductor applications. Especially in optical components, in accordance with the diversification of units used in liquid crystal displays or touch panels, research is being conducted to replace conventional polyethylene terephthalate (PET), triethyl cellulose (TAC), etc. Cyclic olefin resin film with high transparency and low hygroscopicity.

In addition, the cyclic olefin resin film has insufficient surface hardness, so there is a possibility of scarring during processing. In order to improve abrasion resistance and scratch resistance, it is being studied to provide an active energy ray-curable composition on the surface. Hard coating of hard coatings, etc. However, since the cyclic olefin resin film has an alicyclic structure as its main structure, the film surface has low polarity, and the water contact angle is as high as about 90 °. Therefore, when an active energy ray-curable composition is applied, it is difficult to coat the coating material. The problem of wide application, low adhesion between the surface of the cyclic olefin resin film substrate and the hard coat layer.

As a method for improving the adhesion between the surface of the cyclic olefin resin film substrate and the hard coat layer, it is proposed to provide a modified olefin resin having a polar group as the main component on the surface of the cyclic olefin resin film substrate. A method of applying and curing a radiation-curable resin after coating (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 undercoat layer are increased, the yield is reduced, or the cost is increased. .

In addition, as a method for adhering a hard coat layer to the surface of a cyclic olefin resin film substrate without providing an undercoat layer, a hard coat using a hardening 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). When using this curable composition, in order to make the adhesiveness with the surface of a cyclic olefin resin film base material sufficient, it is necessary to increase the ratio of the (meth) acrylate which has an alicyclic structure. However, if the ratio of the (meth) acrylic acid ester which has an alicyclic structure is raised, there exists a problem that the crosslinking density of a hardened coating film will fall, and the scratch resistance of the hardened coating film surface will become insufficient.

In addition, although the hardened coating film of the active energy ray-curable composition has high adhesion (initial adhesion) immediately after it is formed on the surface of the cyclic olefin resin film substrate, it is subsequently exposed to strong light. A problem arises in that its adhesiveness (light-resistant adhesiveness) is reduced.

Therefore, it is required to provide high scratch resistance to the surface of the cyclic olefin resin film substrate, to form a hardened coating film with excellent adhesion to the surface of the cyclic olefin resin film substrate without a primer layer, And an active energy ray-curable composition that does not decrease in adhesion even when exposed to strong light.

Prior art literature Patent literature

Patent Document 1 Japanese Patent Laid-Open No. 2004-284158

Patent Document 2 Japanese Patent Application Publication No. 2010-89458

The problem to be solved by the present invention is to provide an active energy ray-curable composition capable of imparting high scratch resistance to the surface of a substrate and forming an excellent dense bond with the surface of the substrate without a primer layer. The hardened coating film, and its adhesion will not decrease even after being exposed to strong light.

The present invention provides an active energy ray-curable composition, which is characterized in that it contains an active energy ray-curable compound (A), and is selected from the group consisting of a hindered amine light stabilizer (B1) containing a polymerizable functional group and a hindered phenol. Group of hindered amine-based light stabilizers (B2) based on a 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.

The present invention also provides a hard coating film comprising at least one surface of a cyclic olefin resin film base material, the hard coating film having the active energy ray-curable composition.

The active energy ray-curable composition system of the present invention can impart high scratch resistance to the surface of a substrate, and can form a hardened coating film with excellent adhesion to the surface of the substrate without a primer layer. Its adhesion does not decrease even when exposed to strong light. Therefore, the active-energy-ray-curable composition of the present invention can be used as an optical film used in liquid crystal display or touch panel applications.

Embodiment of the invention

The active energy ray-curable composition system of the present invention contains an active energy ray-curable compound (A), and is selected from the group consisting of a hindered amine light stabilizer (B1) having a polymerizable functional group and a hindered amine system having a hindered phenol group. A hindered amine light stabilizer (B) of at least one of the group of light stabilizers (B2), and a compound selected from the group consisting of a silane coupling agent (c-1), (meth) acrylamide compound (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 a polyfunctional (meth) acrylate (A1), a urethane (meth) acrylate (A2), and the like. These may be used singly or in combination of two or more kinds.

In the present invention, the "(meth) acrylate" means one or both of an acrylate and a methacrylate, and the "(meth) acryl" refers to an acryl With one or both of methacrylfluorenyl.

The polyfunctional (meth) acrylate (A1) is a compound having two or more (meth) acrylfluorenyl groups in one molecule. Specific examples of the polyfunctional (meth) acrylate (A1) include 1,4-butanediol di (meth) acrylate and 3-methyl-1,5-pentanediol bis (methyl) 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) acrylic acid Ester, di (meth) acrylate of ginseng (2-hydroxyethyl) isocyanurate, and ethylene oxide or propylene oxide added to 4 mol or more in 1 mol of neopentyl glycol Di (meth) acrylate of diol obtained, di (meth) acrylate of diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A, Methylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate Propylene oxide modified trimethylolpropane tri (meth) acrylate, di-trimethylolpropane tri (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, isotris Polycyanate (2- (meth) propenyloxyethyl), neopentaerythritol tri (meth) acrylate, neopentaerythritol tetra (meth) acrylate, dipentaerythritol tri (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. These polyfunctional (meth) acrylates (A1) may be used singly or in combination of two or more kinds. Among these polyfunctional (meth) acrylates (A1), since the scratch resistance of the cured coating film of the active energy ray-curable composition used in the present invention can also be improved, dipentaerythritol six (Meth) acrylate, dipentaerythritol penta (meth) acrylate, neopentaerythritol tetra (meth) acrylate, neopentaerythritol tri (meth) acrylate are preferred, and dineopentyl Tetraol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate are more preferred.

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

Examples of the polyisocyanate (a2-1) include an aliphatic polyisocyanate and an aromatic polyisocyanate. Since the coloration 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 suitable. good.

The aliphatic polyisocyanate is a compound composed of an aliphatic hydrocarbon at a site other than 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, and the like. Methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl Cycloaliphatic polyisocyanate, etc., such as -1, 5- diisocyanato cyclohexane. In addition, a terpolymer obtained by trimerizing the aliphatic polyisocyanate or the alicyclic polyisocyanate may be used as the aliphatic polyisocyanate. These aliphatic polyisocyanates may be used singly or in combination of two or more kinds.

Among the aforementioned aliphatic polyisocyanates, in order to improve the abrasion resistance of the coating film, among the aliphatic polyisocyanates, hexamethylene diisocyanate, which is a diisocyanate that is a linear aliphatic hydrocarbon, and alicyclic diisocyanate, which is a degradation of the aliphatic polyisocyanate. Phenane diisocyanate and isophorone diisocyanate are preferred.

The (meth) acrylate (a2-2) is a compound having a hydroxyl group and a (meth) acrylfluorenyl group. Specific examples of the (meth) acrylate (a2-2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 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) acrylates of diols such as meth) acrylates, hydroxytrimethylacetate neopentyl glycol mono (meth) acrylates; trimethylolpropane di (meth) acrylates, cyclic 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 esters, bis (2- (meth) acrylfluorenyloxyethyl) hydroxyethyl isocyanurates, or the like having alcoholic hydroxyl groups Mono- and di (meth) acrylates of which a part of the hydroxyl group is modified with ε-caprolactone; neopentaerythritol tri (meth) acrylate, di-trimethylolpropane tri (meth) acrylate, Monofunctional hydroxyl groups such as dipentaerythritol penta (meth) acrylate and 3 A polyfunctional (meth) acrylate having a higher (meth) acrylfluorenyl group, or a hydroxyl group further modified with ε-caprolactone; dipropylene glycol mono (meth) acrylate, (Meth) acrylates having an oxyalkylene chain, such as ethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and polyethylene glycol mono (meth) acrylate; polyethylene glycol -Polypropylene glycol mono (meth) acrylate, polyoxybutylene-polyoxypropylene mono (meth) acrylate, etc. (meth) acrylates having a block structure of an oxyalkylene chain; poly (ethylene glycol- Butyl glycol) mono (meth) acrylate, poly (propylene glycol-butylene glycol) mono (meth) acrylate, and the like (meth) acrylates having an oxyalkylene chain having a random structure. These (meth) acrylates (a2-2) 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, 4 or more (1 Meth) acrylfluorenyl is preferred. In order that the urethane (meth) acrylate (A2) has four (meth) acrylfluorenyl groups in one molecule, as the (meth) acrylate (a2-2), It is preferable that the (meth) acrylfluorenyl group has two or more. Examples of such a (meth) acrylate (a2-2) include trimethylolpropane di (meth) acrylate and ethylene oxide modified trimethylolpropane di (meth) acrylic acid. Ester, propylene oxide modified trimethylolpropane di (meth) acrylate, glycerol di (meth) acrylate, bis (2- (meth) propenyloxyethyl) hydroxyethyl isopropyl Tricyanate, neopentaerythritol tri (meth) acrylate, di-trimethylolpropane tri (meth) acrylate, dinepentaerythritol penta (meth) acrylate, and the like. These (meth) acrylic acid esters (a2-2) may be used alone or in combination of two or more kinds with respect to one of the aforementioned aliphatic polyisocyanates. Among these (meth) acrylates (a2-2), neopentyltetraol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are formed because they can improve scratch resistance. Better.

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

If necessary, as the active energy ray-curable compound (A) other than the above-mentioned polyfunctional (meth) acrylate (A1) and urethane (meth) acrylate (A2), (formaldehyde (Meth) acrylate epoxy ester, polyester (meth) acrylate, polyether (meth) acrylate, and the like having a relatively high molecular weight (meth) acrylate (A3). Examples of the (meth) acrylic epoxy ester include (meth) acrylic acid and bisphenol-type epoxy resin, novolac-type epoxy resin, polyglycidyl methacrylate, and the like, which are obtained by esterification. By. Examples of the polyester (meth) acrylate include (meth) acrylic acid and esterified by reacting (meth) acrylic acid with a polyester having hydroxyl groups at both ends obtained by polycondensation of a polycarboxylic acid and a polyol. Obtained or obtained by reacting (meth) acrylic acid with an alkylene oxide added to a polycarboxylic acid and esterifying it. Furthermore, examples of the polyether (meth) acrylate include those obtained by reacting (meth) acrylic acid with a polyether polyol and esterifying the polyether (meth) acrylate. Moreover, the said (meth) acrylate (A3) can be used individually or in combination of 2 or more types.

In addition, in the active-energy-ray-curable composition used in the present invention, in addition to (A1) to (A3) exemplified as the above-mentioned active-energy-ray-curable compound (A), if (A) having a phosphate group is blended Base) acrylate (A4) is more preferable because the adhesion performance with the substrate is further improved. The (meth) acrylate (A4) having a phosphate group is a (meth) acrylate having at least one phosphate group in one molecule. Examples of the (meth) acrylate (A4) having a phosphate group include (meth) acrylfluorenyloxyethyl phosphate, di (meth) acrylfluorenyloxyethyl phosphate, and tris (methyl) phosphate ) Acrylomethyloxyethyl, caprolactone modified (meth) acrylomethyloxyethyl phosphate, and the like, compounds having 2 or more (meth) acrylomethyl groups in one molecule may be used. These (meth) acrylates (A4) having a phosphate group may be used alone or in combination of two or more.

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 thereof is further improved due to the adhesion performance with the base material, and hardened. The abrasion resistance of the surface of the coating film can also be further improved. Among the aforementioned active energy ray-curable compounds (A), 0.1 to 30% by mass is preferable, and 0.5 to 20% by mass is more preferable.

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

Examples of the light stabilizer (B1) include a hindered amine light stabilizer having a polymerizable functional group such as a (meth) acrylfluorenyl group or a vinyl group. More specifically, (meth) acrylic acid 2,2,6,6-tetramethyl-4-piperidinyl ester, (meth) acrylic acid 1,2,2,6,6-pentamethyl-4 -Piperidine esters and the like. These light stabilizers (B1) may be used alone or in combination of two or more.

Examples of the light stabilizer (B2) include a hindered amine light stabilizer having a hindered phenol group such as 3,5-di-tertiary butyl-4-hydroxyphenyl. More specific examples include compounds represented by the following formula (1). This light stabilizer (B2) may be used in combination with the light stabilizer (B1).

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

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

The silane coupling agent (c-1) has a covalent bond formed at the substrate interface of the adherend, and thus excellent light-resistant adhesiveness can be obtained. Specific examples of the silane coupling agent (c-1) include vinyl-based silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; 2- (3,4-epoxy) (Cyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Epoxy-based silane coupling agents such as methyldiethoxysilane and 3-glycidoxypropyltriethoxysilane; styrene-based silane coupling agents such as p-styryltrimethoxysilane Mixture; 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyl Silyl coupling agents having (meth) acrylfluorenyl groups, such as methylmethyldiethoxysilane, 3- (meth) propenyloxypropyltriethoxysilane; N-2- (aminoethyl ) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-bis Silane coupling agents having an amine group, such as hydrochloride of methylene-butylene) propylamine, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, and the like; Urea-based silane coupling agents such as 3-ureidopropyltrialkoxysilane; mercapto-containing silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane Mixtures; thioether group-containing silane coupling agents such as bis (triethoxysilylpropyl) tetrasulfide; iso-trimerization including quino- (trimethoxysilylpropyl) isocyanurate Silane coupling agents with cyanate ester skeletons; silane coupling agents with alkyl groups and phenyl groups, such as alkoxysilane compounds having methyl and phenyl groups, alkoxysilane compounds having propyl groups and phenyl groups; Alkyl and phenyl alkoxysilane compounds, methacryl groups and phenyl alkoxysilane compounds, etc., and (meth) acryl groups and phenyl-based silane coupling agents; 3-isocyanatepropyltriphenyl Isocyanate-containing silane coupling agents such as ethoxysilane; methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethyl Silane group, butyl trimethoxy Silane, hexyl trimethoxy Silane, decyl trimethoxy silane-having alkyl group such as a silane-coupling agents. These silane coupling agents may be used alone or in combination of two or more kinds. Among these, from the viewpoint of maintaining excellent scratch resistance and further improving light adhesion resistance, one or more members selected from the group consisting of an alkyl group, a phenyl group, and a (meth) acrylfluorenyl group are used. The functional group is preferably a silane coupling agent.

The content of the alkoxy group in the case where a silane coupling agent having an alkyl group and a phenyl group and a silane coupling agent having a (meth) acrylfluorenyl group and a phenyl group is used as the silane coupling agent (c-1) is further obtained. From the viewpoint of excellent light-resistant adhesiveness, a range of 5 to 30% by mass is preferable, a range of 10 to 25% by mass is more preferable, and a range of 13 to 22% by mass is more preferable.

The (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 fastness.

Specific examples of the (meth) acrylamide compound (c-2) include (meth) acrylamide, dimethyl (meth) acrylamide, and acrylamide Phenol, N- [3- (N ', N'-dimethylaminopropyl) (meth) acrylamide, 3- (propenylamino) propyltrimethylammonium chloride, etc. 4th-order salt of methylaminopropyl (meth) acrylamide, isopropyl (meth) acrylamide, diethyl (meth) acrylamide, N- (2-hydroxyethyl) ( (Meth) acrylamidonium, 2- (meth) acrylamido-2-methylpropanesulfonic acid, (3- (meth) acrylamidopropyl) trimethyltrimethylammonium chloride, 3- Allyl-2- Amidazol, acrylamide caproic acid, tertiary butylacrylamide, butoxymethacrylamide, N, N '-(1,2-dihydroxylethyl) bisacrylamide, dodecane Acrylamide, N, N'-ethylidenebisacrylamide, N, N'-methylenebisacrylamide, hydroxymethyl (meth) acrylamide, phenylacrylamide, and the like. These (meth) acrylamide can be used alone or in combination of two or more kinds. Among these, from the viewpoint of maintaining excellent scratch resistance and further improving light adhesion resistance, a material selected from the group consisting of N- [3- (N ', N'-dimethylaminopropyl) (methyl One or more compounds of the group acrylamide, 3- (propenylamino) propyltrimethylammonium chloride, and N- (2-hydroxyethyl) (meth) acrylamido Is better.

In the present invention, the "(meth) acrylamide" means acrylamide and / or methacrylamide.

The aforementioned polymerizable monomer (c-3) having a tricyclodecane structure is one capable of obtaining excellent light-resistant adhesiveness, and particularly when a cyclic olefin resin film substrate is used as the substrate, the approximate With the affinity due to the structure, more excellent light-resistant adhesion can be obtained.

Specific examples of the polymerizable monomer (c-3) include dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and dicyclopentyl (methyl) Monomer) having one radical polymerizable group such as acrylate; dimethylol tricyclodecane di (meth) acrylate, tricyclodecanediol di (meth) acrylate, tricyclic A monomer having two radical 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-resistant adhesiveness, it is preferable to use the aforementioned monomer having two radically polymerizable groups, and it is selected from the group consisting of dimethyloltricyclodecanebis (methyl One or more types of polymerizable monomers in the group of acrylate) acrylate, tricyclodecanediol di (meth) acrylate, and tricyclodecanedimethanol di (meth) acrylate are more preferred.

The content of the compound (C) is preferably in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the active energy ray-curable compound (A) from the viewpoint of obtaining more excellent light-resistant adhesiveness. The range of 1.5 to 40 parts by mass is more preferred, and the range of 2 to 25 parts by mass is even more preferred.

The content of the case where the silane coupling agent (c-1) is used alone as the compound (C) is, from the viewpoint of obtaining more excellent light-resistant adhesiveness, compared to the active energy ray-curable compound (A) 100 The mass part is preferably in the range of 1 to 50 parts by mass, more preferably in the range of 1.5 to 40 parts by mass, and even more preferably in the range of 2 to 25 parts by mass.

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-resistant adhesion, it is harder than the active energy ray. 100 parts by mass of the compound (A) is preferably in a range of 3 to 50 parts by mass, more preferably in a range of 5 to 40 parts by mass, and even more preferably in a range of 7 to 25 parts by mass.

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

In addition, the active energy ray-curable composition of the present invention can be irradiated with an active energy ray after being applied to a substrate to form a hardened coating film. The so-called active energy rays refer to free radiation such as ultraviolet rays, electron rays, α rays, β rays, and γ rays. When an ultraviolet ray is irradiated as an active energy ray to form a cured coating film, a photopolymerization initiator (D) described later is added to the active energy ray-curable composition of the present invention to improve the hardenability. If necessary, a photosensitizer (E) may be further added to improve the hardenability. On the other hand, in the case of using free radiation such as electron rays, α rays, β rays, and γ rays, since the photopolymerization initiator (D) or the photosensitizer (E) can be rapidly cured without using a photopolymerization initiator (D) or a photosensitizer, There is no need to add a photopolymerization initiator (D) or a photosensitizer (E) in particular.

Examples of the photopolymerization initiator (D) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, and oligo {2-hydroxy-2 -Methyl-1- [4- (1-methylvinyl) phenyl] acetone}, benzyldimethylketal, 1- (4-isopropylphenyl) -2-hydroxy-2- Methylpropane-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2- (4-Methylthiophenyl) propane-1-one, 2-benzyl-2-dimethylamino-1- (4- Acetophenone-based compounds such as phenylphenyl) -butanone; benzoin-based compounds such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; 2,4,6-trimethyl Benzylphosphine oxide compounds such as phenylbenzoin diphenylphosphine oxide, bis (2,4,6-trimethylbenzylfluorenyl) -phenylphosphine oxide; benzyl (dibenzofluorene), Methylphenylacetaldehyde, 2- (2-hydroxyethoxy) ethyl hydroxyphenylacetate, 2- (2-sideoxy-2-phenylacetamidooxyethoxy) hydroxyphenylacetate ) Benzyl compounds such as ethyl esters; benzophenone, o-benzophenylacetic acid methyl-4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxydione Benzophenone, 4-benzylidene-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3 ', 4,4'-tetrakis (tert-butylperoxycarbonyl) ) Dibenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, etc. Benzophenone-based compounds; 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, thioxanthone such as 2,4-dichlorothioxanthone Ketone compounds; Michelin, 4,4'-diethylaminobenzophenone, etc. Aminobenzophenone-based compounds; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, 1- [4- (4-benzophenone Phenylhydrothio) phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propane-1-one and the like. These photopolymerization initiators (C) may be used alone or in combination.

Examples of the photosensitizer (E) include tertiary amine compounds such as diethanolamine, N-methyldiethanolamine, and tributylamine; urea compounds such as o-toluthiourea; and diethyldiamine. Sulfur compounds such as sodium thiophosphate, s-benzyl isothiourea p-toluenesulfonate, and the like.

The amounts of the photopolymerization initiator (D) and photosensitizer (E) used are relative to the active energy ray-curable compound (A) and the compound ( B) A total of 100 parts by mass, preferably 0.05 to 20 parts by mass, and more preferably 0.5 to 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 may be blended in accordance with the use or required characteristics. Combining 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 such as inorganic pigments, pigment dispersants and organic beads; inorganic fillers such as silica (silica particles), alumina, titania, zirconia, antimony pentoxide, etc. These other blends may be used singly or in combination of two or more kinds.

By blending silica particles in the inorganic filler, the scratch resistance of the hardened 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. The silica particles may be those whose surface is modified with an organic surface, or those whose surface is not modified. In addition, since the aforementioned silica particles can further improve the transparency and scratch resistance of the hardened coating film of the active energy ray-curable composition of the present invention, nanometer-sized silica particles are preferred, and they are in a colloidal state. Silica is better. The average particle diameter of the silica fine particles is preferably in a range of 5 to 200 nm, and more preferably in a range of 5 to 100 nm. The average particle diameter is a value measured by a dynamic light scattering method.

In the case where the aforementioned inorganic filler is blended, the scratch resistance of the hardened 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 be further improved. Of 100 parts by mass of the active energy ray-curable compound (A), 1 to 150 parts by mass is more preferred, and 5 to 100 parts by mass is even more preferred.

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

As a method of forming a hardened 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 substrate and then irradiating the active energy ray is mentioned.

Examples of the substrate include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polypropylene, polyethylene, and polymethylmethacrylate. Polyolefin resins such as pentene-1; cellulose acetate (diacetyl cellulose, triethyl cellulose, etc.), cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, Cellulose resins such as cellulose phosphophthalate and nitrocellulose; acrylic resins such as polymethyl methacrylate; vinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride; polyvinyl alcohol; Ethylene-vinyl acetate copolymer; polystyrene; polyfluorene; polycarbonate; polyfluorene; polyetherfluorene; polyetheretherketone; polyfluorene imine, polyetherfluorine, etc. ; Cyclic olefin resin film substrate and the like. The active energy ray-curable composition of the present invention can obtain excellent transparency, abrasion resistance, and light adhesion regardless of which substrate is used, and is particularly suitable for use in the aforementioned ring that has increased in demand in recent years. Olefin resin film substrate.

The cyclic olefin resin film substrate may be a polymer obtained by polymerizing a cyclic olefin, and may be a homopolymer or a copolymer, and may be used without particular limitation. Examples of commercially available cyclic olefin resins include "ZEONOR (registered trademark)" and "ZEONEX (registered trademark)" made by Japan Zeon Corporation; and "ARTON (registered trademark)" made by JSR Corporation. ; "TOPAS (registered trademark)" made by Polyplastics Corporation.

The cyclic olefin resin film substrate is obtained by molding a cyclic olefin resin on a film. In addition, the surface of the cyclic olefin resin film substrate is subjected to surface unevenness treatment by a sandblasting method, a solvent treatment method, or the like in order to improve the adhesion between the active energy ray-curable composition used in the present invention and the cured coating film. Electrical treatment (corona discharge treatment, atmospheric piezoelectric slurry treatment), chromic acid treatment, flame treatment, hot air treatment, ozone. UV. An electron beam irradiation treatment, an oxidation treatment, and the like are more preferable, and among them, a corona discharge treatment, an atmospheric piezoelectric slurry treatment, and the like are electrically treated.

The thickness of the 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 substrate within this range, even when a 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 substrate, curling can be easily suppressed.

The hard coating film of the present invention is obtained by applying the active energy ray-curable composition to at least one side of a cyclic olefin resin film substrate, and then irradiating the active energy ray to form a hardened coating film. Examples of a method for applying the active energy ray-curable composition to a cyclic olefin resin film substrate include die coating, microgravure coating, gravure coating, roll coating, corner wheel coating, air knife coating, and contact coating. (kiss coat), spray coating, bridge coating, dip coating, spin coating, wheel coat, brush coating, full-plate coating using screen printing, wire rod coating, flow coating, and the like.

In addition, in order to harden the active energy ray-curable composition, when ultraviolet rays are used as the active energy rays, examples of the means for irradiating ultraviolet rays include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halogen 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 the excellent optical properties, dimensional stability, heat resistance, transparency, and light resistance, the hard coating film of the present invention is suitable for various applications due to its excellent scratch resistance on the surface, especially as a liquid crystal An optical film used in an image display portion of an image display device such as a display (LCD) or an organic EL display (OLED) is useful. In particular, it has excellent scratch resistance even if it is thin, so it can be used as a portable device that requires miniaturization or thinness, such as electronic notebooks, mobile phones, smartphones, portable audio players, mobile computers, and tablet terminals. An optical film used in an image display section of an image display device of an electronic terminal. Moreover, when it is used as an optical film, it can be used as a protective film used for the outermost surface of the image display part of an image display device, and a base material of a touch panel. When used as a protective film, for example, an image display device having a transparent panel for protecting the image display module is provided on the upper part of an image display module such as an LCD module or an OLED module. It is used by being attached to the front or back surface of the transparent panel, and is effective for preventing scratches or scattering when the transparent panel is damaged.

    [Example]    

Hereinafter, the present invention will be described more specifically with reference to examples.

(Example 1)

100 parts by mass of a mixture of dipentaerythritol hexaacrylate (hereinafter referred to as "DPHA") and dipentaerythritol 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 to 20 nm, 40% by mass of organic silica gel (colloidal silica) Methyl ethyl ketone dispersion) (for silica fine particles), 0.5 parts by mass of a hindered amine light stabilizer having a methacryl group ("ADEKA STAB (registered trademark) LA-87" manufactured by ADEKA Corporation); 2,2,6,6-tetramethyl-4-piperidinyl acrylate) and 6 parts by mass of 1-hydroxycyclohexylphenyl ketone ("IRGACURE (registered trademark) 184" manufactured by BASF Japan Co., Ltd.) 20 parts by mass of methyltrimethoxysilane ("KBM-13", manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was uniformly stirred, and then diluted with methyl ethyl ketone to prepare 40% by mass of active energy ray hardening Sexual composition (1).

(Example 2)

An active energy ray-curable composition (2) was prepared in the same manner as in Example 1 except that the blending amount of ADEKA STAB LA-87 was changed from 0.5 parts by mass to 0.1 part by mass.

(Example 3)

An active energy ray-curable composition (3) was prepared in the same manner as in Example 1 except that the blending amount of ADEKA STAB LA-87 was changed from 0.5 parts by mass to 1 part by mass.

(Example 4)

An active energy ray-curable composition (4) was prepared in the same manner as in Example 1 except that the blending amount of KBM-13 was changed from 20 parts by mass to 5 parts by mass.

(Example 5)

In addition to changing ADEKA STAB LA-87 used in Example 1 to a hindered amine light stabilizer having a methacryl group ("ADEKA STAB (registered trademark) LA-82" manufactured by ADEKA Corporation); methacrylic acid 1 Except for 2,2,6,6-pentamethyl-4-piperidinyl ester), the same procedure as in Example 1 was performed to prepare an active energy ray-curable composition (5).

(Example 6)

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

(Example 7)

100 parts by mass of a mixture of dipentaerythritol hexaacrylate (hereinafter referred to as "DPHA") and dipentaerythritol pentaacrylate (hereinafter referred to as "DPPA") (DPHA / DPPA = 65/35 (Mass ratio)), 0.5 parts by mass of a hindered amine light stabilizer having a methacryl group ("ADEKA STAB (registered trademark) LA-87" manufactured by ADEKA Co., Ltd.); 6-tetramethyl-4-piperidine ester), 6 parts by mass of 1-hydroxycyclohexylphenyl ketone ("RUNTECURE (registered trademark) 1104" manufactured by BASF Japan Co., Ltd.), and 15 parts by mass of N- [ 3- (N ', N'-dimethylaminopropyl) acrylamide (hereinafter, simply referred to as "DMAPAA") was stirred uniformly, and then diluted with methyl ethyl ketone to prepare a 40% by mass nonvolatile component. Active energy ray-curable composition (7).

(Example 8)

An active energy ray-curable composition (8) was prepared in the same manner as in Example 1 except that the blending amount of ADEKA STAB LA-87 was changed from 0.5 parts by mass to 1 part by mass.

(Example 9)

An active energy ray-curable composition (9) was prepared in the same manner as in Example 1 except that the blending amount of DMAPAA was changed from 15 parts by mass to 10 parts by mass.

(Example 10)

An active energy ray-curable composition (10) was prepared in the same manner as in Example 1 except that 3- (propenylaminoamino) propyltrimethylammonium chloride (hereinafter, simply referred to as "DMAPAA-Q") was used instead of DMAPAA. ).

(Example 11)

An active energy ray-curable composition (11) was prepared in the same manner as in Example 1 except that 2-hydroxyethylpropenamide (hereinafter, simply referred to as "HEAA") was used instead of DMAPAA.

(Example 12)

In addition to changing ADEKA STAB LA-87 used in Example 1 to a hindered amine light stabilizer having a methacryl group ("ADEKA STAB (registered trademark) LA-82" manufactured by ADEKA Corporation); methacrylic acid 1 Except for 2,2,6,6-pentamethyl-4-piperidinyl ester), the same procedure as in Example 1 was performed to prepare an active energy ray-curable composition (12).

(Example 13)

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

(Example 14)

A mixture of 94 parts by mass of dipentaerythritol hexaacrylate (hereinafter referred to as "DPHA") and dipentaerythritol pentaacrylate (hereinafter, referred to as "DPPA") (DPHA / DPPA = 65/35 (Mass ratio)), 6 parts by mass of 1-hydroxycyclohexylphenyl ketone ("RUNTECURE 1104" manufactured by BASF Co., Ltd.), 0.5 parts by mass of methacrylic acid 2,2,6,6-tetramethyl-4 -Piperidine ester (made by ADEKA Corporation, reactive hindered amine "ADEKA STAB LA-87"), 10 parts by mass of silica particles ("MEK-ST40" manufactured by Nissan Chemical Industry Co., Ltd., average particle size 10 ~ 20nm, 40% by mass methyl ethyl ketone dispersion of an organic silica gel (4 parts by mass of silica fine particles), 15 parts by mass of dimethylol tricyclodecane diacrylate (Kyoeisha Chemical Co., Ltd. "LIGHT ACRYLATE DCP-A" by Co., Ltd.) was uniformly stirred, and then diluted with methyl ethyl ketone to prepare a UV-curable composition (14) having a non-volatile content of 40% by mass.

(Example 15)

An active energy ray-curable composition (15) was prepared in the same manner as in Example 1 except that the blending amount of the dimethyloltricyclodecane diacrylate was changed from 15 parts by mass to 10 parts by mass.

(Example 16)

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

(Comparative example 1)

An active energy ray-curable composition (R1) was prepared in the same manner as in Example 1 except that ADEKA STAB LA-87 used in Example 1 was not used.

(Comparative example 2)

In addition to changing the ADEKA STAB LA-87 used in Example 1 to a hindered amine light stabilizer ("TINUVIN (registered trademark) 111FDL" manufactured by BASF Japan Co., Ltd .; dimethyl succinate and 4-hydroxy-2, Polymer of 2,6,6-tetramethyl-1-piperidine ethanol with N, N ', N ", N'''-H- (4,6-bis- (butyl- (N-methyl -2,2,6,6-tetramethylpiperidin-4-yl) amino) -tri Except for -2-yl) -4,7-diazadecane-1,10-diamine (mixture of 1: 1), the same procedure as in Example 1 was performed to prepare an active energy ray-curable composition ( R2).

(Comparative example 3)

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

(Comparative Example 4)

In addition to changing the ADEKA STAB LA-87 used in Example 1 to a hindered amine light stabilizer ("ADEKA STAB (registered trademark) LA-81" manufactured by ADEKA Corporation); bis (1-undecyloxy-2 Except that 2,2,6,6-tetramethylpiperidin-4-yl) carbonate) was carried out in the same manner as in Example 1 to prepare an active energy ray-curable composition (R4).

(Comparative example 5)

In addition to changing the ADEKA STAB LA-87 used in Example 1 to a hindered amine-based 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}), an active energy ray-curable composition (R5) was prepared in the same manner as in Example 1.

(Comparative Example 6)

In addition to changing the ADEKA STAB LA-87 used in Example 1 to a hindered amine light stabilizer ("TINUVIN (registered trademark) 5100" manufactured by BASF Japan Co., Ltd.); bis (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) other than Example 1 was performed in the same manner to prepare an active energy ray-curable composition (R6).

(Comparative Example 7)

In addition to changing the ADEKA STAB LA-87 used in Example 1 to a hindered amine-based light stabilizer ("TINUVIN (registered trademark) 292" manufactured by BASF Japan Co., Ltd.); double (1,2,2,6,6-five (Methyl-4-piperidinyl) sebacate 70 to 80% by mass and methyl-1,2,2,6,6-pentamethyl-4-piperidinylsebacate 20 to 30% by mass The mixture was prepared in the same manner as in Example 1 except that the active energy ray-curable composition (R7) was prepared.

(Comparative Example 8)

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

(Comparative Example 9)

Except changing the ADEKA STAB LA-87 used in Example 1 to an ultraviolet absorber ("TINUVIN (registered trademark) 400" manufactured by BASF Japan Co., Ltd.), it was performed in the same manner as in Example 1 to adjust the active energy ray hardenability. Composition (R9).

(Comparative Example 10)

Except changing the ADEKA STAB LA-87 used in Example 1 to an ultraviolet absorber ("TINUVIN (registered trademark) 384-2" manufactured by BASF Japan Co., Ltd.), it was performed in the same manner as in Example 1 to prepare an active energy ray. Hardening composition (R10).

(Comparative Example 11)

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

(Comparative Example 12)

An active energy ray-curable composition (R12) was prepared in the same manner as in Example 1 except that KBM-13 used in Example 1 was not used.

    [Manufacturing method of hard coating film]    

The active energy ray-curable compositions obtained in the examples and comparative examples were coated with a wire bar on a ring having an electric treatment (corona discharge treatment; output 100W, speed 1.0m / min) in advance. Olefin resin film substrate ("ZEONOR (registered trademark) film PT14-080", manufactured by Japan Zeon Corporation, thickness 25 μm), heated at 60 ° C for 90 seconds, and left in air for 60 seconds, and then irradiated with ultraviolet rays Device ("MIDN-042-C1" manufactured by Eyegraphics Co., Ltd., lamp: 120 W / cm, high-pressure mercury lamp), irradiated with ultraviolet light at a light intensity of 0.22 J / cm ^{2 to} obtain a hard coating film having a hardened coating film having a thickness of 2 μm (1 ) ~ (16), and (R1) ~ (R12).

    [Evaluation of Scratch Resistance]    

The surface of the hard coating film of the hard coating film obtained above was tested using a watch type counter type friction tester (1.0 cm diameter circular friction roller, steel wool # 0000, load 500 g, 10 round trips), and the test was visually observed The hardened coating film surface was evaluated for abrasion resistance using the following criteria.

A: No scars.

B: There are 5 or less scars.

C: The number of flaws is 5 or less.

D: There are many scars.

E: There are many significantly 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 scores were scored at intervals of 1 mm to make 100 squares. Next, after the transparent tape ("Cellotape (registered trademark) CT-18" manufactured by Nichiban Co., Ltd.) was adhered to the surface, it was immediately peeled off and the operation was repeated twice. The residual area ratio remaining from the unpeeling was evaluated for initial adhesion using the following criteria. In addition, the evaluators of D to F based on the following criteria were judged to be unacceptable.

A: The residual area ratio is 100%.

B: The residual area ratio is 95% to 99%.

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

D: The residual area ratio is 50% to 84%.

E: The residual area ratio is 35% to 49%.

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

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

The hard coating film obtained as described above was subjected to a weather resistance promotion test using a weather resistance tester (according to JIS L0891: 2007, the test conditions are as described below), and after the test was evaluated in the same manner as the initial adhesion described above. And evaluate light fastness.

Light source: continuous sunlight arc arc lamp

Temperature: 63 ℃

Relative humidity: 50% RH

Exposure time: 50 hours, 100 hours, 150 hours

Rainfall period and time: not set

The compositions of the active energy ray-curable compositions of Examples and Comparative Examples and the evaluation results of the hard coating films obtained above are shown in Tables 1 to 3. In addition, all the composition systems in Tables 1 to 3 are described in terms of the amount of non-volatile components. For the mass parts, the values are rounded to the nearest decimal place.

From the evaluation results shown in Tables 1 to 3, the active energy ray-curable composition 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, and furthermore, Light resistance (adhesion after light resistance test) was also excellent.

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

Claims (13)

    An active energy ray-curable composition comprising: an active energy ray-curable compound (A); and a hindered amine having a hindered phenol group and a hindered amine having a polymerizable functional group. At least one hindered amine light stabilizer (B) in the group of light stabilizers (B2), and selected from the group consisting of a silane coupling agent (c-1) and a (meth) acrylamide compound (c-2 ) And one or more compounds (C) in the group of polymerizable monomers (c-3) having a tricyclodecane structure.         The active energy ray-curable composition according to claim 1, wherein the light stabilizer (B1) is selected from the group consisting of (meth) acrylic acid 2,2,6,6-tetramethyl-4-piperidine ester and (methyl Group) at least one of the group of 1,2,2,6,6-pentamethyl-4-piperidinyl acrylate.     The active energy ray-curable composition according to claim 1 or 2, wherein the light stabilizer (B2) is a compound represented by the following formula (1),     The active energy ray-curable composition according to any one of claims 1 to 3, wherein the content of the hindered amine light stabilizer (B) is 0.05 with respect to 100 parts by mass of the active energy ray-curable compound (A). ~ 5 parts by mass.         The active energy ray-curable composition according to any one of claims 1 to 4, wherein the silane coupling agent (c-1) has a group selected from the group consisting of an alkyl group, a phenyl group, and a (meth) acryl group. Silane coupling agent of one or more functional groups of the group.         The active energy ray-curable composition according to any one of claims 1 to 5, wherein the (meth) acrylamido compound (c-2) is selected from the group consisting of N- [3- (N ', N'- Dimethylaminopropyl) (meth) acrylamide, 3- (propenylamino) propyltrimethylammonium chloride, and N- (2-hydroxyethyl) (meth) acrylamine One or more compounds of the amine group.         The active energy ray-curable composition according to any one of claims 1 to 6, wherein the polymerizable monomer (c-3) having a tricyclodecane structure is selected from the group consisting of dimethyloltricyclodecanedi One or more polymerizable monomers in the group of (meth) acrylate, tricyclodecanediol di (meth) acrylate, and tricyclodecanedimethanol di (meth) acrylate.         The active energy ray-curable composition according to any one of claims 1 to 7, wherein the content of the compound (C) is 1 to 50 parts by mass based on 100 parts by mass of the active energy ray-curable compound (A). range.         The active energy ray-curable composition according to any one of claims 1 to 8, wherein the active energy ray-curable compound (A) is a polyfunctional (meth) acrylate (A1).         The active energy ray-curable composition according to claim 9, wherein the polyfunctional (meth) acrylate (A1) is selected from the group consisting of dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta ( At least one of the group of meth) acrylate, neopentaerythritol tetra (meth) acrylate, and neopentaerythritol tri (meth) acrylate.         The active energy ray-curable composition according to any one of claims 1 to 10, wherein the active energy ray-curable composition further contains an inorganic filler.         The active energy ray-curable composition according to claim 11, wherein the inorganic filler is silica particles.         A hard coating film comprising a cyclic olefin resin film substrate on at least one side thereof, and a hard coating film having the active energy ray-curable composition according to any one of claims 1 to 12.