TWI722040B - Cyclic olefin resin film - Google Patents

Abstract

The present invention provides a cyclic olefin resin film characterized by a cured coating film having an active energy ray curable composition on at least one side of a cyclic olefin resin film substrate, the active energy ray curable composition containing active energy ray A curable compound (A) and a hindered amine-based light stabilizer (B) are essential components, and the hindered amine-based light stabilizer (B) is selected from hindered amine-based light stabilizers having a polymerizable functional group (B1) and at least one of the group of hindered amine-based light stabilizers (B2) having hindered phenol groups. It also provides a cyclic olefin resin film which can impart high scratch resistance to the surface of the cyclic olefin resin film substrate and can be formed between the surface of the cyclic olefin resin film substrate without a priming coat. A cured coating film with excellent adhesion, and a cured coating film of active energy ray curable composition whose adhesion does not decrease even after strong light exposure.

Description

Cyclic olefin resin film

The present invention relates to a cyclic olefin resin film having a cured coating film of an active energy ray curable composition having high scratch resistance and excellent adhesion to a cyclic olefin resin film substrate.

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, semiconductor applications, etc. . In particular, in optical components, the diversification of units that are used in liquid crystal displays or touch panels is being explored to replace the previously used polyethylene terephthalate (PET) and triacetylcellulose (TAC). ) And other plastic films, and cyclic olefin resin films with high transparency and low moisture absorption are used.

In addition, the cyclic olefin resin film has insufficient surface hardness and may be damaged during processing. In order to improve abrasion resistance and scratch resistance, it is being explored to provide a curable composition containing active energy rays on its surface. Protective layer such as hard coat of coating film. However, because 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 about 90°. Therefore, it is difficult to coat the active energy ray curable composition. The problem that the material is spread and the adhesion between the surface of the cyclic olefin resin film substrate and the hard coat layer is low.

As a method to improve the adhesion between the surface of the cyclic olefin resin film substrate and the hard coat layer, it is proposed to install a modified olefin resin having a polar group as the main component on the surface of the cyclic olefin resin film substrate. After the primer layer is applied, an ionizing radiation curable resin is applied and cured (for example, refer to Patent Document 1). In this method, the adhesion between the surface of the cyclic olefin resin film substrate and the hard coat layer can be improved, but the steps of applying and drying the primer layer are added, which further has the problem of reduced productivity and increased cost.

In addition, as a method of attaching a hard coat layer to the surface of a cyclic olefin resin film substrate without providing an undercoat layer, a hard coat film containing a curable composition containing a (meth)acrylate having an alicyclic structure has been proposed. It is used as a hard coat layer (for example, refer to Patent Document 2). In the case of using this curable composition, in order to achieve sufficient adhesion to the surface of the cyclic olefin resin film substrate, it is necessary to increase the ratio of the (meth)acrylate having an alicyclic structure. 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.

In addition, the adhesion (initial adhesion) of the cured coating film of the active energy ray curable composition just after the formation of the cyclic olefin resin film substrate surface is high, but afterwards, it adheres to strong light. The deterioration of the resistance (light resistance) becomes a problem.

Here, it is sought to have a cured coating film that can impart high scratch resistance to the surface of the cyclic olefin resin film substrate and can form an excellent adhesion with the surface of the cyclic olefin resin film substrate without a primer layer. It is a cyclic olefin resin film that is a hardened coating film of an active energy ray curable composition whose adhesion does not decrease even after exposure to strong light.

Advanced technical literature Patent literature

Patent Document 1 JP 2004-284158 A

Patent Document 2 JP 2010-89458 A

Summary of the invention

The problem to be solved by the present invention is to provide a cyclic olefin resin film that can impart high scratch resistance to the surface of the cyclic olefin resin film substrate and can be applied to the surface of the cyclic olefin resin film substrate without a primer. A hardened coating film with excellent adhesion is formed therebetween, and a hardened coating film of an active energy ray curable composition whose adhesion does not decrease after exposure to strong light.

The inventors of the present invention have made diligent studies to solve the above-mentioned problems, and found that by using a specific light stabilizer in the active energy ray curable composition as the material of the hardened coating film formed on the surface of the cyclic olefin resin film substrate , Can impart high scratch resistance to the surface of the cyclic olefin resin film substrate, can form a cured coating film with excellent adhesion between the surface of the cyclic olefin resin film substrate without a primer, and its adhesion After being exposed to strong light, it will not decrease, thus completing the present invention.

That is, the present invention relates to a cyclic olefin resin film characterized by having a cured coating film of an active energy ray curable composition on at least one side of a cyclic olefin resin film substrate, the active energy ray curable composition Contains active energy ray curable compound (A) and hindered amine light stabilizer (B) as essential components, and the hindered amine light stabilizer (B) is selected from hindered amines containing polymerizable functional groups It is at least one of the group of light stabilizers (B1) and hindered amine light stabilizers (B2) having hindered phenol groups.

The cyclic olefin resin film of the present invention has a high scratch resistance due to the hardened coating film of the active energy ray curable composition formed on its surface. Moreover, the hardened coating film is combined with the cyclic olefin resin as the base material. High adhesion, after exposure to strong light, its high adhesion will not be reduced. Therefore, the cyclic olefin resin film of the present invention can be used as an optical film for liquid crystal displays and touch panel applications.

The form used to implement the invention

The cyclic olefin resin film of the present invention is a cyclic olefin resin film substrate having a cured coating film of an active energy ray curable composition, the active energy ray curable composition containing active energy ray curable Compound (A) and hindered amine-based light stabilizer (B) as essential components, the hindered amine-based light stabilizer (B) is selected from hindered amine-based light stabilizers (B1) containing polymerizable functional groups and At least one of the group of hindered phenol-based hindered amine-based light stabilizers (B2).

As said active energy ray curable compound (A), a polyfunctional (meth)acrylate (A1), a urethane (meth)acrylate (A2), etc. are mentioned, for example. One type of these may be used, or two or more types may be used in combination.

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

The aforementioned polyfunctional (meth)acrylate (A1) is a compound having two or more (meth)acryloyl groups in one molecule. As specific examples of this multifunctional (meth)acrylate (A1), 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, tricyclodecane dimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, Diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate and other dihydric alcohols (Meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, di(meth)acrylic acid of (2-hydroxyethyl) isocyanurate Ester, the di(meth)acrylate of the glycol obtained by adding more than 4 mol of ethylene oxide or propylene oxide to 1 mol of neopentyl glycol, to 1 mol Di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide modified by adding 2 moles of ethylene oxide or propylene oxide to bisphenol A Methylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tri(meth)acrylate, di-trimethylol Propane tetra(meth)acrylate, ginseng (2-(meth)acryloyloxyethyl) isocyanurate, neopentylerythritol tris(meth) Acrylate, neopentyl erythritol tetra (meth) acrylate, dine pentaerythritol tri (meth) acrylate, dine pentaerythritol tetra (meth) acrylate, dine pentaerythritol five (meth) ) Acrylate, dineopentaerythritol hexa(meth)acrylate, etc. One type of these polyfunctional (meth)acrylates (A1) may be used, or two or more types may be used in combination. In addition, among these polyfunctional (meth)acrylates (A1), from the viewpoint of improving the scratch resistance of the cured coating film of the active energy ray curable composition used in the present invention, di-neo-pentylene four Alcohol hexa(meth)acrylate, dineopentaerythritol penta(meth)acrylate, neopentaerythritol tetra(meth)acrylate, neopentaerythritol tri(meth)acrylate, more preferably Dineopentaerythritol hexa(meth)acrylate is used in combination with dineopentaerythritol penta(meth)acrylate. In addition, as a mass ratio in the case of using dineopentaerythritol hexa(meth)acrylate in combination with dineopentaerythritol penta(meth)acrylate, in terms of improving the scratch resistance of the cured coating film, it is more It is preferably in the range of 40/60 to 80/20, more preferably in the range of 50/50 to 75/25, and still more preferably in the range of 60/40 to 70/30.

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 exemplified, but from the viewpoint that the coloration of the cured coating film of the active energy ray curable composition used in the present invention can be further reduced, it is more It is preferably an aliphatic polyisocyanate.

The aforementioned aliphatic polyisocyanate is a compound composed of an aliphatic hydrocarbon except for the isocyanate group. As specific examples of this aliphatic polyisocyanate, hexamethylene diisocyanate, ionic Aliphatic polyisocyanates such as amino acid diisocyanate and lysine triisocyanate; norbornane diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate), 1,3-bis(isocyanate) (Methyl)cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane and other alicyclic polyisocyanates Wait. In addition, a ternary body obtained by terminating the aforementioned aliphatic polyisocyanate or alicyclic polyisocyanate can also be used as the aforementioned aliphatic polyisocyanate. Moreover, these aliphatic polyisocyanates may use 1 type, and may use 2 or more types together.

Among the aforementioned aliphatic polyisocyanates, in order to improve the scratch resistance of the coating film, among the aliphatic polyisocyanates, preferably: hexamethylene diisocyanate, which is a diisocyanate of linear aliphatic hydrocarbon, is alicyclic The diisocyanates are norbornane diisocyanate and isophorone diisocyanate.

The aforementioned (meth)acrylate (a2-2) is a compound having a hydroxyl group and a (meth)acryloyl group. As specific examples of this (meth)acrylate (a2-2), 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl ( Meth) acrylate, 4-hydroxybutyl (meth)acrylate, 1,5-pentanediol mono(meth)acrylate, 1,6-hexanediol mono(meth)acrylate, neopentyl Glycol mono(meth)acrylate, hydroxytrimethylacetate neopentyl glycol mono(meth)acrylate and other diol mono(meth)acrylates; trimethylolpropane bis(meth) Acrylate, ethylene oxide (EO) modified trimethylolpropane (meth)acrylate, propylene oxide (PO) modified trimethylolpropane di(meth)acrylate, glycerol di( Meth) acrylate, bis(2-(meth)acryloyloxyethyl)hydroxyethyl isocyanurate and other triol mono- or di(meth)acrylates, or Mono- and di-(meth)acrylates having hydroxyl groups modified with ε-caprolactone as part of the alcoholic hydroxyl groups; neopentyl erythritol tri(meth)acrylate, di-trimethylolpropane tri( Meth) acrylate, dineopentaerythritol penta (meth) acrylate, and other compounds having a monofunctional hydroxyl group and a trifunctional or more (meth)acrylic acid group, or the compound is further used as ε-hexyl Multifunctional (meth)acrylate with hydroxyl group modified by lactone; dipropylene glycol mono(meth)acrylate, diethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, poly (Meth)acrylates with oxyalkylene chain such as ethylene glycol mono(meth)acrylate; polyethylene glycol-polypropylene glycol mono(meth)acrylate, polyoxybutylene-polyoxyethylene Propylene mono(meth)acrylate and other (meth)acrylates with block structure of oxyalkylene chain; poly(ethylene glycol-tetramethylene glycol) mono(meth)acrylate, poly(meth)acrylate (Propylene glycol-butylene glycol) Mono(meth)acrylates and other (meth)acrylates having random structure of alkylene oxide chains. One type of these (meth)acrylates (a2-2) may be used, or two or more types may be used in combination.

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, it is preferably in one molecule Those with four or more (meth)acrylic groups. In order to make the aforementioned urethane (meth)acrylate (A2) into one having four or more (meth)acrylic groups in one molecule, as the aforementioned (meth)acrylate (a2-2), Preferably, it has two or more (meth)acrylic acid groups. As such (meth)acrylate (a2-2), for example, trimethylolpropane di(meth)acrylate, ethylene oxide modified trimethylolpropane di(meth)acrylic acid Ester, epoxy propylene Alkane modification trimethylolpropane di(meth)acrylate, glycerol di(meth)acrylate, bis(2-(meth)acryloxyethyl) hydroxyethyl isocyanuric acid Esters, neopentylerythritol tri(meth)acrylate, di-trimethylolpropane tri(meth)acrylate, dineopentylerythritol 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 conventional urethane reaction. Moreover, 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; phosphorus compounds such as triphenylphosphine and triethylphosphine ; Dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin diacetate, tin octoate and other organotin compounds, zinc octoate and other organozinc compounds.

If necessary, as the active energy ray curable compound (A) other than the above-mentioned polyfunctional (meth)acrylate (A1) and urethane (meth)acrylate (A2), epoxy can be used (Meth)acrylates, polyester (meth)acrylates, polyether (meth)acrylates and other relatively high molecular weight (meth)acrylates (A3). As the epoxy (meth)acrylate, for example, a combination of bisphenol type epoxy resin, novolac type epoxy resin, polyglycidyl methacrylate, etc. with (meth) acrylic acid The result of the reaction and esterification. In addition, as the aforementioned polyester (meth)acrylate, for example, a polyester obtained by polycondensing a polycarboxylic acid and a polyol with a hydroxyl group at both ends is reacted with (meth)acrylic acid. Those obtained by esterification, or those obtained by adding alkylene oxide to a polycarboxylic acid, reacted with (meth)acrylic acid and esterified. In addition, as the aforementioned polyether (meth)acrylate, for example, a polyether polyol and (meth)acrylic acid are reacted to be esterified. 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 above-mentioned active energy ray-curable compound (A), if ( The meth)acrylate (A4) is preferable in terms of improving the adhesion to the substrate. 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 (Meth)acryloyloxyethyl, caprolactone-modified phosphoric acid (meth)acryloyloxyethyl, etc., and compounds having two or more (meth)acryloyl groups in one molecule can also be used. Moreover, these (meth)acrylates (A4) which have a phosphoric acid group may use 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 can further improve the adhesion to the substrate and also In terms of improving the scratch resistance of the cured coating film surface, it is preferably 0.1 to 30% by mass in the active energy ray curable compound (A), and more preferably 0.5 to 20% by mass.

The active energy ray curable composition used in the present invention contains, as essential components, the above-mentioned active energy ray curable compound (A) and is selected from hindered amine light stabilizers (B1) containing polymerizable functional groups And a hindered amine-based light stabilizer (B) of at least one of the group of hindered amine-based light stabilizers (B2) having a hindered phenol group.

As said light stabilizer (B1), the hindered amine type light stabilizer which has polymerizable functional groups, such as a (meth)acryl group and a vinyl group, is mentioned, for example. More specifically, (meth)acrylic acid-2,2,6,6-tetramethyl-4-piperidinate, (meth)acrylic acid-1,2,2,6,6-pentamethyl 4-piperidinyl ester and so on. One type of these light stabilizers (B1) may be used, or two or more types may be used in combination. Among these, in terms of improving the adhesion to the cyclic olefin resin and suppressing the adhesion after strong light exposure (hereinafter referred to as "light resistance adhesion"), it is preferable to use (Meth) acrylate 2,2,6,6-tetramethyl-4-piperidinate.

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, the compound etc. represented by following formula (1) are mentioned. This light stabilizer (B2) can also be used in combination with the aforementioned light stabilizer (B1).

The blending amount of the hindered amine-based light stabilizer (B) in the active energy ray curable composition used in the present invention can further suppress the decrease in the initial adhesion to the cyclic olefin resin and the light resistance adhesion. , Relative to 100 parts by mass of the active energy ray curable compound (A), preferably 0.05 to 5 parts by mass, more preferably 0.1 to 2% by mass, and still more preferably 0.3 to 1.5% by mass.

In addition, the active energy ray curable composition used in the present invention can be formed into a cured coating film by applying active energy rays to the ring-shaped substrate. The so-called active energy rays refer to ionizing radiation such as ultraviolet rays, electron rays, α rays, β rays, and γ rays. When irradiating ultraviolet rays as an active energy ray to form a cured coating film, it is preferable to add a photopolymerization initiator (C) described later to the active energy ray curable composition of the present invention to improve the curability. In addition, if necessary, a photosensitizer (D) 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 hardens quickly even if the photopolymerization initiator (C) and photosensitizer (D) are not used. Therefore, there is no need to add the photopolymerization initiator (C) and the photosensitizer (D).

啉基(4-硫甲基苯基)丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-

啉基苯基)-丁酮等之苯乙酮系化合物；安息香、安息香甲基醚、安息香異丙基醚等之安息香系化合物；2,4,6-三甲基安息香二苯基膦氧化物、雙(2,4,6-三甲基苯甲醯基)-苯膦氧化物等之醯基膦氧化物系化合物；二苯乙二酮(聯苯甲醯)、甲基苯基乙醛酸酯、氧基苯基乙酸2-(2-羥乙氧基)乙酯、氧基苯基乙酸2-(2-側氧-2-苯基乙醯氧基乙氧基)乙酯等之二苯乙二酮系化合物；二苯基酮、o-苯甲醯基安息香酸甲基-4-苯二苯基酮、4,4’-二氯二苯基酮、羥二苯基酮、4-苯甲醯基-4’-甲基-二苯基硫化物、丙烯酸化二苯基酮、3,3’,4,4’-四(三級丁基過氧羰基)二苯基酮、3,3’-二甲基-4-甲氧基二苯基酮、2,4,6-三甲基二苯基酮、4-甲基二苯基酮等之二苯基酮系化合物；2-異丙基噻噸酮(2-isopropylthioxanthone)、2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、2,4-二氯噻噸酮等之噻噸酮系化合物；米其勒酮、4,4’-二乙基胺基二苯基酮等之胺基二苯基酮系化合物；10-丁基-2-氯吖啶酮、2-乙基蒽醌、9,10-菲醌、莰醌(camphorquinone)、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)可使用一種，亦可併用兩種以上。 Examples of the aforementioned photopolymerization initiator (C) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, and oligo{2-hydroxy-2 -Methyl-1-[4-(1-methylvinyl)phenyl]acetone}, diphenylethylenedione dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy- 2-Methylpropane-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2 -

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

Acetophenone compounds such as linylphenyl)-butanone; benzoin compounds such as benzoin, benzoin methyl ether, benzoin isopropyl ether, etc.; 2,4,6-trimethylbenzoin diphenylphosphine oxide , Bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide and other phosphine oxide compounds; diphenylethylenedione (biphenylmethyl), methylphenylacetaldehyde Ester, 2-(2-hydroxyethoxy)ethyl oxyphenylacetate, 2-(2-oxo-2-phenylacetoxyethoxy)ethyl oxyphenylacetate, etc. Benzophenone compounds; benzophenone, o-benzoylbenzoic acid methyl-4-benzenediphenylketone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-Benzyl-4'-methyl-diphenyl sulfide, acrylated diphenyl ketone, 3,3',4,4'-tetra(tertiary butylperoxycarbonyl) diphenyl ketone , 3,3'-Dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone and other diphenyl ketone compounds ; 2-isopropylthioxanthone (2-isopropylthioxanthone), 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and other thioxanthones Ketone compounds; amino benzophenone compounds such as Michelone, 4,4'-diethylamino benzophenone, etc.; 10-butyl-2-chloroacridone, 2-ethyl Anthraquinone, 9,10-phenanthrenequinone, camphorquinone, 1-[4-(4-benzylphenylsulfanyl)phenyl]-2-methyl-2-(4-methyl Phenylsulfonyl) propan-1-one and the like. One type of these photopolymerization initiators (C) may be used, or two or more types may be used in combination.

In addition, as the aforementioned photosensitizer (D), 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, s-benzylisothiuronium-p-toluenesulfonate, etc.

The usage amount of the above-mentioned photopolymerization initiator (C) and photosensitizer (D) is relative to the active energy ray curable compound (A) and the above compound (B) in the active energy ray curable composition of the present invention A total of 100 parts by mass of, preferably 0.05-20 parts by mass, more preferably 0.5-10% 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), etc., depending on the application and required characteristics, an organic solvent, Polymerization inhibitors, surface treatment agents, antistatic agents, defoamers, viscosity modifiers, light stabilizers, weather stabilizers, heat stabilizers, ultraviolet absorbers, antioxidants, leveling agents, organic pigments, inorganic pigments, pigments Additives for dispersants, organic beads, etc.; inorganic fillers for silica (silica particles), alumina, titania, zirconia, antimony pentoxide, etc. One type of these other blends may be used, or two or more types may be used in combination.

Among the aforementioned inorganic fillers, by blending silica particles, the scratch resistance of the surface of the cured coating film of the active energy ray curable composition used in 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 groups, or they may be unmodified. In addition, the aforementioned silica particles further improve the performance of the cured coating film of the active energy ray curable composition used in the present invention. In terms of transparency and surface abrasion resistance, nanometer order size silica particles are preferred, and colloidal silica is more preferred. 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 the value measured by the dynamic light scattering method.

In the case of blending the aforementioned inorganic filler, the blending amount can further improve the scratch resistance of the hardened coating film surface of the active energy ray curable composition used in the present invention, and also improve the adhesion to the substrate. Specifically, it is preferably 1 to 150 parts by mass, and more preferably 5 to 100 parts by mass with respect to 100 parts by mass of the active energy ray curable compound (A).

The aforementioned organic solvent is used to appropriately adjust the solution viscosity of the active energy ray curable composition used in the present invention, and especially for film coating, it becomes easy to adjust the film thickness. Examples of organic solvents that can be used 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. Esters such as monomethyl ether acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. One type of these solvents may be used, or two or more types may be used in combination.

The cyclic olefin resin film substrate used in the cyclic olefin resin film of the present invention is not particularly limited as long as it is formed by polymerizing a cyclic olefin, and a homopolymer or a copolymer may be used. 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 preferably made by sandblasting, solvent treatment, etc., in order to improve the adhesion to the cured coating film of the active energy ray curable composition used in the present invention. Convex treatment, electric treatment (corona discharge treatment, atmospheric pressure plasma treatment), chromic acid treatment, flame treatment, hot air treatment, ozone, ultraviolet rays, electron beam irradiation treatment, oxidation treatment, etc. Among these, it is more preferable to perform electrical treatment such as corona discharge treatment and atmospheric pressure slurry 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 still more preferably in the range of 10 to 50 μm. By setting the thickness of the film substrate to this range, even when the cured coating film of the active energy ray curable composition used in the present invention is provided on one side of the cyclic olefin resin film, curling is easily suppressed .

The cyclic olefin resin film of the present invention is obtained by coating an 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. Examples of methods for applying the active energy ray curable composition to the cyclic olefin resin film include die coating, micro-gravure coating, gravure coating, roll coating, comma coating, and pneumatic knife coating ( air knife coat, kiss coat, spray cloth, pass-over coating, dip coating, spinner coating, wheeler coat, brush coating, screen coating ( For silk screen, solid coat, wire bar coat, flow coat, etc.

In addition, when ultraviolet rays are used as active energy rays in order to harden the active energy ray curable composition, examples of devices that irradiate ultraviolet rays include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and Electrode lamp (fusion lamp), chemical lamp (chemical lamp), black light lamp, mercury-xenon lamp, short arc lamp, helium cadmium laser, argon laser, sunlight, LED, etc.

The cyclic olefin resin film of the present invention is suitable for various applications due to the excellent optical properties, dimensional stability, heat resistance, transparency, and scratch resistance of the surface of the substrate. (LCD), organic EL display (OLED) and other image display device of the image display part of the optical film is particularly useful. In particular, because it has excellent scratch resistance even if it is thin, it can be suitably used for miniaturization, for example, e-notebooks, mobile phones, smart phones, mobile audio players, mobile computers, tablet terminals, etc. Or thinner optical film for the image display part of the image display device of the portable electronic terminal equipment. 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 the board|substrate of a touch panel. Furthermore, in the case of using as a protective film, for example, in an image display device in which a transparent panel for protecting the image display module is provided on top of an image display module such as an LCD module, an OLED module, etc., Used by being attached to the surface or inner surface of the transparent panel, it effectively prevents scratches and prevents scattering when the transparent panel is damaged.

Example

The following examples illustrate the present invention in more detail.

(Preparation Example 1)

A mixture of dineopentaerythritol hexaacrylate (hereinafter, referred to as "DPHA".) and dineopentaerythritol pentaacrylate (hereinafter referred to as "DPPA".) (DPHA/DPPA=65/35 (mass) Ratio)) 100 parts by mass, silica particles ("MEK-ST40" manufactured by Nissan Chemical Industry Co., Ltd., average particle size of 10-20nm, 40% by mass methyl ethyl ketone dispersion of organosilica sol (silica gel) Liquid) 25 parts by mass (10 parts by mass in terms of silica fine particles), hindered amine light stabilizer having a methacrylic acid group (ADK STAB (registered trademark) LA-87" manufactured by ADEKA Co., Ltd.; (2,2,6,6-tetramethyl-4-piperidinyl acrylate) 1 part by mass, and 1-hydroxycyclohexyl phenyl ketone ("IRGACURE (registered trademark) 184" manufactured by BASF JAPAN Co., Ltd.) After 6 parts by mass were uniformly stirred, it was diluted with methyl ethyl ketone to prepare an active energy ray curable composition (1) having a non-volatile content of 50% by mass.

(Preparation Example 2)

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

(Preparation Example 3)

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

(Preparation Example 4)

Except that the blending amount of ADK STAB LA-87 was changed from 1 part by mass to 2 parts by mass, the same procedure as in Preparation Example 1 was carried out to prepare an active energy ray curable composition (4).

(Preparation Example 5)

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

(Preparation Example 6)

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

(Comparative Preparation Example 1)

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

(Comparative Preparation Example 2)

-2-基)-4,7-二氮雜癸烷(diazadecane)-1,10-二胺的質量比1：1的混合物)以外，與製備例1同樣地進行，製備活性能量線硬化性組成物(R2)。 Except that ADK STAB LA-87 used in Preparation Example 1 was changed to 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 and N,N',N”,N”'-four-(4,6-bis-(butyl-(N-methyl- 2,2,6,6-Tetramethylpiperidin-4-yl)amino)-tris

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

(Comparative Preparation Example 3)

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

(Comparative Preparation Example 4)

Except that the ADK STAB LA-87 used in Preparation Example 1 was changed to a hindered amine light stabilizer (ADK STAB (registered trademark) LA-81" manufactured by ADEKA Co., Ltd.; carbonic acid bis(1-undecyloxy- Except for 2,2,6,6-tetramethylpiperidin-4-yl)ester), the same procedure was performed as in Preparation Example 1 to prepare an active energy ray curable composition (R4).

(Comparative Preparation Example 5)

Except that ADK STAB LA-87 used in Preparation Example 1 was changed to hindered amine light stabilizer (made by BASF JAPAN Co., Ltd.) "TINUVIN (registered trademark) 123"; Same as Preparation Example 1 except for sebacic acid bis{2,2,6,6-tetramethyl-1-(octyloxy)piperidin-4-yl ester}) Proceed to prepare an active energy ray curable composition (R5).

(Comparative Preparation Example 6)

Except that ADK STAB LA-87 used in Preparation Example 1 was changed to a hindered amine light stabilizer ("TINUVIN (registered trademark) 5100" manufactured by BASF JAPAN Co., Ltd.; 1,10-sebacic acid bis(2,2, 6,6-tetramethyl-1-octyloxypiperidin-4-yl) ester (bis(2,2,6,6-tetramethyl-1-octyloxypiperidin-4-yl)-1,10-decanedioate) and 1,8-Bis[{2,2,6,6-Tetramethyl-4-((2,2,6,6-tetramethyl-1-octyloxypiperidin-4-yl)-decane Except the mixture of -1,10-diyl)piperidin-1-yl}oxy]octane), it was carried out in the same manner as in Preparation Example 1 to prepare an active energy ray curable composition (R6).

(Comparative Preparation Example 7)

Except that ADK STAB LA-87 used in Preparation Example 1 was changed to hindered amine light stabilizer ("TINUVIN (registered trademark) 292" manufactured by BASF JAPAN Co., Ltd.; Sebacic acid bis (1,2,2,6, 6-Pentamethyl-4-piperidinyl) ester 70~80% by mass and sebacic acid methyl-1,2,2,6,6-pentamethyl-4-piperidyl ester 20~30% by mass Except for the mixture), the same procedure as in Preparation Example 1 was carried out to prepare an active energy ray curable composition (R7).

(Comparative Preparation Example 8)

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

(Comparative Preparation Example 9)

Except that the ADK STAB LA-87 used in Preparation Example 1 was changed to an ultraviolet absorber ("TLNUVIN (registered trademark) 400" manufactured by BASF JAPAN Co., Ltd.), the same procedure as in Preparation Example 1 was carried out to prepare active energy ray curable Composition (R9).

(Comparative Preparation Example 10)

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

(Comparative Preparation Example 11)

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

(Example 1)

Using a wire bar (Wire Bar), the active energy ray curable composition (1) obtained in Preparation Example 1 is coated on the surface which has been subjected to electrical treatment (corona discharge treatment; output 100W, speed 1.0m/min) Cyclic olefin resin film substrate ("ZEONOR (registered trademark) film ZF16-100" manufactured by Zeon Co., Ltd., thickness 100μm) is heated at 60°C for 90 seconds, and then an ultraviolet irradiation device (EYE GRAPHICS) is used in an air environment. "MIDN-042-C1" manufactured by Co., Ltd., lamp: 120W/cm, high-pressure mercury lamp), ^{irradiated with ultraviolet light at 0.4J/cm 2 of} irradiation light to obtain a cyclic olefin resin film with a cured coating film of 2μm in thickness (1) .

[Evaluation of scratch resistance]

For the surface of the hardened coating film of the cyclic olefin resin film (1) obtained above, a crockmeter type friction tester (a 1.0cm diameter circular friction element, steel wool #0000 (Steel wool # 0000), load 500g, 10 round trips), the test was performed, the surface of the cured coating film after the test was visually observed, and the scratch resistance was evaluated according to the following criteria.

A: No scars.

B: 5 or less shallow scars.

C: 5 or less scars.

D: Many scars.

E: Multiple obvious deep scars.

[Evaluation of initial adhesion]

On the surface of the cured coating film of the cyclic olefin resin film (1) obtained above, 11 longitudinal and transverse slits were cut at 1 mm intervals to make 100 squares. Next, cellophane tape ("Cellotape (registered trademark) CT-18" manufactured by NICHIBAN Co., Ltd.) was attached to the surface and peeled off in one go, and this operation was repeated twice. From the ratio of the remaining area remaining without peeling, the initial adhesion was evaluated by the following criteria. In addition, those evaluated as 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% or more and 99% or less.

C: The residual area ratio is 85% or more and 94% 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 adhesion (light resistance) after light resistance test]

For the cyclic olefin resin film (1) obtained above, an accelerated weathering test (accelerated weathering test) using Sunshine Weather-O-Meter (according to JIS L0891, the test conditions are as follows.) The initial adhesion evaluation was carried out in the same manner, and the light resistance adhesion was evaluated.

Light source: sunlight carbon arc (sunshine carbon arc) lamp continuous irradiation

Temperature: 63°C

Relative humidity: 50%RH

Irradiation time: 48 hours

Rain cycle and time: not set

(Examples 2 to 6 and Comparative Examples 1 to 11)

Except for using the active energy ray curable compositions (2) to (6) and (R1) to (R11) obtained from the above preparation examples 2 to 6 and comparative preparation examples 1 to 11, it is the same as in Example 1, Cyclic olefin resin films (2)~(6) and (R1)~(R11) with respective cured coating films were prepared, and the scratch resistance, initial adhesion, and light adhesion resistance were evaluated for the obtained cyclic olefin resin film Sex.

Tables 1 to 3 show the composition of the active energy ray curable composition prepared by the above-mentioned Preparation Examples 1 to 6 and Comparative Preparation Examples 1 to 11, and the evaluation results of the cyclic olefin resin film obtained above. In addition, the compositions in Tables 1 to 3 are all described in terms of non-volatile content.

According to the evaluation results shown in Table 1, the examples 1 to 6 of the cyclic olefin resin film of the present invention have excellent scratch resistance on the surface of the cured coating film of the active energy ray curable composition of the film, and The initial adhesion of the cyclic olefin resin film substrate is also high, and 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 2 and 3 are cyclic olefin resin films having a cured coating film of an active energy ray curable composition that does not contain the hindered amine-based light stabilizer used in the present invention. At least one of the scratch resistance, initial adhesion, and light adhesion resistance of these cyclic olefin resin films is insufficient, and there is a problem of practicality.

Claims (4)

A cyclic olefin resin film having a cured coating film of an active energy ray curable composition on at least one side of a cyclic olefin resin film substrate, the active energy ray curable composition containing an active energy ray curable compound (A) With hindered amine-based light stabilizer (B) as an essential component, the hindered amine-based light stabilizer (B) is selected from hindered amine-based light stabilizers (B1) containing polymerizable functional groups and those having hindered At least one of the group of phenol-based hindered amine light stabilizers (B2), wherein the active energy ray curable compound (A) is a multifunctional (meth)acrylate (A1) and/or urethane Ester (meth)acrylate (A2), the multifunctional (meth)acrylate (A1) is selected from the group consisting of dineopentaerythritol hexa(meth)acrylate, dineopentaerythritol penta(meth) At least one of the group of acrylate, neopentyl erythritol tetra (meth) acrylate and neopentyl erythritol tri (meth) acrylate, the urethane (meth) acrylate (A2) is Neopentyl erythritol tri(meth)acrylate and dineopentaerythritol penta(meth)acrylate are used as raw materials, and the light stabilizer (B1) is selected from the group consisting of (meth)acrylic acid-2,2,6, At least one of the group of 6-tetramethyl-4-piperidinyl ester and (meth)acrylate-1,2,2,6,6-pentamethyl-4-piperidinyl ester, the light stabilizer (B2 ) Is a compound represented by the following formula (1),

The cyclic olefin resin film 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 cyclic olefin resin film according to claim 1, wherein the active energy ray-curable compound (A) contains a polyfunctional (meth)acrylate (A1). The cyclic olefin resin film according to any one of claims 1 to 3, wherein the active energy ray curable composition further contains an inorganic filler.