TWI663229B - Active energy ray-curable composition and film using the same - Google Patents

Abstract

The present invention provides an active energy ray-curable composition and a film using the active energy ray-curable composition. The active energy ray-curable composition contains an active energy ray-curable compound (A) and has the following general formula (1): Resin (B) of the 4th ammonium salt shown. The active energy ray-curable composition of the present invention can form a hardened coating film having antistatic performance equal to or more than that of a conventional one without using halogen such as chloride ion, that is, without halogen.

(In the formula, R ¹ to R ³ each independently represent an alkyl group or a phenyl group, and R ⁴ represents an alkyl group, an alkoxy group, a phenyl group, or an oxyphenyl group.)

Description

Active energy ray-curable composition and film using the same

The present invention relates to an active energy ray-curable composition capable of forming a hard coat layer having a high antistatic property on the surface of a film by coating and hardening the surface of the film, and a film using the same.

Various resin films are used for anti-damage films on the surface of flat panel displays (FPD) such as liquid crystal displays (LCD), organic EL displays (OLED), plasma displays (PDP), automotive interior and exterior decorative films (sheets), and windows Low-reflection film or heat ray cutting film. However, since the surface of a resin film is soft and has low abrasion resistance, in order to supplement this, a hard coating agent containing a UV-curable composition or the like is generally applied to the surface of the film and hardened to provide a hard coating layer on the surface of the film. on. If the steps for setting the hard coat layer are briefly described, the film material rolled into a roll is output to a coating machine, a hard coating agent is applied, and the hard coat layer is hardened by irradiating ultraviolet rays, and then re-rolled into a roll. Cylindrical.

In the winding step F, static electricity is generated on the film surface due to the friction between the films. Therefore, when the film is pulled out from the roll during reprocessing, there may be problems of film adhesion to each other, or dust due to static electricity. The problem of easy adhesion to the film surface.

In order to suppress the generation of static electricity on the surface of this film, The method of blending antistatic agent in hard coating agent. For example, a method of blending a polymer containing a level 4 ammonium salt group as an antistatic agent in a hard coating agent has been proposed (for example, refer to Patent Document 1). However, the relative anion of the quaternary ammonium salt of the quaternary ammonium salt-containing polymer used herein is chloride, which is not good in consideration of the environment.

Therefore, there is a demand for an active energy ray-curable composition that does not use halogens such as chloride ions, that is, can form a hardened coating film having antistatic properties equal to or higher than that of a known person in the absence of halogens.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2007-332181

The problem to be solved by the present invention is to provide an active energy ray-curable composition and a film using the same. The active energy ray-curable composition can be formed without using halogen such as chloride ion, that is, can be formed without halogen. Hardened coating film with antistatic performance equal to or higher than that of a conventional person.

In order to solve the above-mentioned problems, the inventors of the present invention have made strenuous research results and found that by mixing a specific resin containing "a quaternary ammonium salt having no halogen" into the active energy ray-curable composition, it is possible to eliminate the use of chloride ions, etc. Halogen, that is, a halogen-free, hardened coating film having antistatic properties equal to or higher than those of a conventional person can be formed, and the present invention has been completed.

That is, the present invention relates to an active energy ray sclerosis A composition and a film using the same, the active energy ray-curable composition is characterized by containing an active energy ray-curable compound (A) and a resin having a fourth-order ammonium salt represented by the following general formula (1) (B).

(In the formula, R ¹ to R ³ each independently represent an alkyl group or a phenyl group, and R ⁴ represents an alkyl group, an alkoxy group, a phenyl group, or an oxyphenyl group.)

The active energy ray-curable composition of the present invention is halogen-free, and is an environmentally friendly material that can be formed on the surface of a resin film by coating and curing the surface of the resin film with a hard coat layer having high antistatic properties. Therefore, the hardened coating film of the active energy ray-curable composition of the present invention can prevent the generation of static electricity on the film surface, and can prevent the adhesion of various resin films and the adhesion of dust and the like caused by static electricity. Therefore, the film having the hardened coating film of the active energy ray-curable composition of the present invention is environmentally friendly, and problems such as adhesion and adhesion of dust and the like can be avoided when rolled up into a roll shape and when withdrawn from the roll. , And can provide a film excellent in subsequent operations.

In addition, a thin film having a hard coat layer including a hardened coating film of the active energy ray-curable composition of the present invention can be used in flat-panel displays such as liquid crystal displays (LCD), organic EL displays (OLED), and plasma displays (PDP). (FPD) film for surface damage prevention or touch panel protection film, decorative film (sheet) for interior and exterior of automobiles, low reflection film or hot wire for windows Various applications such as cut-off film. Furthermore, when used in these applications, it also has excellent antistatic properties and can suppress adhesion of dust and the like.

[Form of Implementing Invention]

The active energy ray-curable composition of the present invention includes an active energy ray-curable compound (A) and a resin (B) having a quaternary ammonium salt represented by the following general formula (1).

(In the formula, R ¹ to R ³ each independently represent an alkyl group, a phenyl group, and R ⁴ represents an alkyl group, an alkoxy group, a phenyl group, or an oxyphenyl group.)

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

In addition, in the present invention, "(meth) acrylate" means one or both of acrylate and methacrylate, and "(meth) acrylfluorenyl" means acrylfluorenyl and methacrylfluorene One or both.

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 di ( (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 2-butane 2-ethyl-1,3-propanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di Di (meth) acrylates of dihydric alcohols such as (meth) acrylates, triethylene glycol di (meth) acrylates, dipropylene glycol di (meth) acrylates, and tripropylene glycol di (meth) acrylates , Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ginseng (2-hydroxyethyl) isotricyanate di (meth) acrylate, to 1 mole Bis (meth) acrylate of diol obtained by adding ethylene oxide or propylene oxide to 4 mol or more of neopentyl glycol, and 1 mol of bisphenol A Diol (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylol obtained by adding 2 moles of ethylene oxide or propylene oxide Propane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (Meth) acrylate, di-trimethylolpropane tri (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, ginseng (2- (meth) acryloxyethyl) Group) isotricyanate, neopentaerythritol tri (meth) acrylate, neopentaerythritol tetra (meth) acrylate, dinepentaerythritol tri (meth) acrylate, dinepentaerythritol Alcohol tetra (meth) acrylate, dinepentaerythritol penta (meth) acrylate, dinepentaerythritol hexa (meth) acrylate, and the like. These polyfunctional (meth) acrylates (A1) can be used singly or in combination of two or more kinds. 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 of the present invention, dipentaerythritol hexa ( (Meth) acrylic acid esters, dinepentaerythritol penta (meth) acrylate, neopentaerythritol tetra (meth) acrylic acid Ester, neopentaerythritol tri (meth) acrylate.

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 aliphatic polyisocyanates and aromatic polyisocyanates. However, from the viewpoint of reducing the color of the cured coating film of the active energy ray-curable composition of the present invention, fats are preferred. Family of polyisocyanates.

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

Among the aforementioned aliphatic polyisocyanates, in order to improve the scratch resistance of the coating film, among the aliphatic polyisocyanates, hexamethylene diisocyanate of a diisocyanate of a linear aliphatic hydrocarbon and norbornane of an alicyclic diisocyanate are preferred. Diisocyanate, isophorone diisocyanate.

The (meth) acrylate (a2-2) is a compound having a hydroxyl group and a (meth) acrylfluorenyl group. As this (meth) acrylate (a2-2) Specific examples include 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, neopentyl hydroxytrimethylacetate Mono (meth) acrylates of dihydric alcohols such as diol mono (meth) acrylates; trimethylolpropane di (meth) acrylate, ethylene oxide (EO) modified trimethylolpropane (Meth) acrylate, propylene oxide (PO) modified trimethylolpropane di (meth) acrylate, glycerol di (meth) acrylate, bis (2- (meth) acrylic acid) Mono- or di (meth) acrylates of trihydric alcohols such as hydroxyethyl) hydroxyethyl isocyanurate, or a modification of some of these alcoholic hydroxyl groups with ε-caprolactone Mono and di (meth) acrylates with hydroxyl groups; neopentaerythritol tri (meth) acrylate, bis (trimethylolpropane) tri (meth) acrylate, dinepentaerythritol penta (methyl) ) Monofunctional hydroxyl groups such as acrylic esters and (meth) acrylfluorenyl groups with trifunctional or higher functionality A compound, or a polyfunctional (meth) acrylate having a hydroxyl group, which is further modified with ε-caprolactone; dipropylene glycol mono (meth) acrylate, diethylene glycol mono (methyl) ) (Meth) acrylates with polyoxyalkylene chains, such as acrylates, polypropylene glycol mono (meth) acrylates, and polyethylene glycol mono (meth) acrylates; polyethylene glycol-polypropylene glycol Mono (meth) acrylates, such as mono (meth) acrylates, polyoxybutylene-polyoxypropylene mono (meth) acrylates, and other (meth) acrylates with an oxyalkylene chain having a block structure; poly (ethylene glycol) -Tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate, etc. (meth) acrylates with random structured oxyalkylene chains, etc. . These (meth) acrylates (a2-2) may be used alone or in combination of two or more.

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 of the present invention, it is preferable to have 4 or more in one molecule ( (Meth) acrylfluorenyl. In order that the urethane (meth) acrylate (A2) has four or more (meth) acrylfluorenyl groups in one molecule, the (meth) acrylate (a2-2) is preferably used. Those having two or more (meth) acrylfluorenyl groups. 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 singly or in combination of two or more kinds with respect to one type of the aliphatic polyisocyanate. Among these (meth) acrylates (a2-2), neopentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are more effective because of their improved scratch resistance. Good.

The reaction between the polyisocyanate (a2-1) and the (meth) acrylate (a2-2) can be carried out by a urethane reaction in a general method. In addition, in order to promote the urethanization reaction, it is preferable to perform the urethanization reaction in the presence of a urethanization catalyst. Examples of the urethane catalyst include amine compounds such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine; phosphorus compounds such as triphenylphosphine and triethylphosphine; and dilauric acid Organotin compounds such as dibutyltin, octyltin trilaurate, octyltin diacetate, dibutyltin diacetate, tin octoate, Organic zinc compounds such as zinc octoate.

If necessary, as the active energy ray-curable compound (A) other than the polyfunctional (meth) acrylate (A1) and the urethane (meth) acrylate (A2), epoxy (formaldehyde) can be used. Group) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, and the like. Examples of the epoxy (meth) acrylate include, for example, the reaction of a (meth) acrylic acid with a bisphenol-type epoxy resin, a phenol-type epoxy resin, a poly (propylene methacrylate), and the like. The winner. Further, as the polyester (meth) acrylate, for example, a (meth) acrylic acid is reacted and esterified with a polyester having hydroxyl groups at both ends obtained by polycondensing a polycarboxylic acid and a polyhydric alcohol, and Obtained, or obtained by reactive esterification of (meth) acrylic acid with alkylene oxide added to a polycarboxylic acid. Examples of the polyether (meth) acrylate include those obtained by reactively esterifying a polyether polyol with (meth) acrylic acid.

The resin (B) is one having a fourth-order ammonium salt represented by the following general formula (1).

(In the formula, R ¹ to R ³ each independently represent an alkyl group, a phenyl group, and R ⁴ represents an alkyl group, an alkoxy group, a phenyl group, or an oxyphenyl group.)

R ¹ to R ³ in the general formula (1) are each independently an alkyl group or a phenyl group, but in the case of an alkyl group, it is preferably one having 1 to 6 carbon atoms, more preferably 1 to 3, Even more preferred is methyl. In the case of a phenyl group, it may be a substituent having a benzene ring, and examples thereof include alkyl-substituted phenyl groups such as tolyl and ethylphenyl. On the other hand, R ⁴ is an alkyl group, an alkoxy group, a phenyl group, or an oxyphenyl group, but in the case of an alkyl group or an alkoxy group, it is preferably one having 1 to 6 carbon atoms, and more preferably 1 to 3 of them. In the case of a phenyl or oxyphenyl group, a substituent on the benzene ring may be used. For example, an alkyl-substituted phenyl group such as tolyl, ethylphenyl, etc. may be mentioned as the phenyl group. Examples of the oxyalkyl-substituted phenyl group include oxymethylphenyl and oxyethylphenyl.

In addition, R ¹ to R ³ in the general formula (1) are preferably alkyl groups, and more preferably all are methyl groups. In addition, R ⁴ in the general formula (1) is preferably a phenyl group or an alkyl-substituted phenyl group.

Examples of the method for producing the resin (B) include, for example, a polymerizable monomer (b1) having a quaternary ammonium salt represented by the following general formula (1) as an essential component, and the polymerizable monomer ( b1) A method of copolymerizing with a polymerizable polymerizable monomer (b2).

Specific examples of the polymerizable monomer (b1) include 2- (methacrylfluorenyloxy) ethyltrimethylammonium toluenesulfonate and 2- (methacrylfluorenyloxy) methanesulfonic acid. Ethyltrimethylammonium, 3- (methacryloxy) propyltrimethylammonium tosylate, 3- (methacryloxy) propyltrimethylammonium mesylate, methanesulfonic acid 2- (Methacrylamidooxy) ethyltrimethylammonium, 3- (methacrylamido) propyltrimethylammonium mesylate, and the like.

Examples of the polymerizable monomer (b2) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, ( Isobutyl (meth) acrylate, n-amyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) acrylic acid N-heptyl, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, etc. (Meth) acrylic acid alkyl esters; cyclohexyl (meth) acrylate, isoamyl (meth) acrylate, etc. (meth) acrylic acid esters having an alicyclic structure; methoxypolyethylene glycol mono ( (Meth) acrylate, octyloxy polyethylene glycol. Polypropylene glycol mono (meth) acrylate, dodecyloxypolyethylene glycol mono (meth) acrylate, octadecyloxyethylene glycol mono (meth) acrylate, phenoxy polyethylene Alcohol mono (meth) acrylate, phenoxy polyethylene glycol. Polyalkylene glycol such as polypropylene glycol mono (meth) acrylate, nonylphenoxy polypropylene glycol mono (meth) acrylate, nonylphenoxy poly (ethylene glycol. Propylene glycol) mono (meth) acrylate, etc. Mono (meth) acrylates of diols and the like. These can be used singly or in combination of two or more kinds.

Among the aforementioned polymerizable monomers (b2), from the viewpoint of further improving the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention, the mono (methyl) of polyalkylene glycol is preferred. The acrylate is more preferably a methoxypolyethylene glycol mono (meth) acrylate.

Among the mono (meth) acrylates of the polyalkylene glycol, the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved. The number average molecular weight of the poly (alkylene glycol) as the raw material of the mono (meth) acrylate is preferably in the range of 500 to 8,000, more preferably in the range of 1,000 to 6,000, and even more preferably in the range of 2,000 to 5,000.

The ratio of the polymerizable monomer (b1) in the raw material of the resin (B) is preferably in the range of 40 to 90% by mass, more preferably in the range of 50 to 80% by mass, and even more preferably 60 to 70% by mass. % Range. Again, making In the case where the mono (meth) acrylate of the polyalkylene glycol is used as the polymerizable monomer (b2), the poly (meth) acrylate of the poly (alkylene glycol) in the raw material of the resin (B) is The ratio is preferably in the range of 10 to 60% by mass, more preferably in the range of 20 to 50% by mass, and even more preferably in the range of 30 to 40% by mass.

The blending amount of the resin (B) is more preferably in the range of 1 to 30 parts by mass, relative to 100 parts by mass of the active energy ray-curable compound (A), in terms of improving antistatic properties. The range is 2 to 20 parts by mass, and even more preferably 3 to 15 parts by mass.

In addition, after the active energy ray-curable composition of the present invention is applied onto a substrate, the active energy ray can be irradiated into a cured coating film. This active energy ray refers to free radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. In the case where a hardened coating film is formed by irradiating ultraviolet rays as active energy rays, it is preferable to add a photopolymerization initiator (C) to the active energy ray-curable composition of the present invention to improve hardenability. If necessary, a photosensitizer (D) may be further added to improve the curability. On the other hand, in the case of using free radiation such as an electron beam, an alpha ray, a beta ray, and a γ ray, it is not necessary because the photo-curing initiator (C) or the photosensitizer (D) does not need to be rapidly cured. In particular, a photopolymerization initiator (C) or a photosensitizer (D) is added.

Examples of the photopolymerization initiator (C) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and oligomeric {2-hydroxy- 2-methyl-1- [4- (1-methylvinyl) phenyl] acetone}, benzyldimethylketal, 1- (4-isopropylphenyl) -2-hydroxy-2- Methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2- Phenyl (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4- Acetophenone-based compounds such as phenyl phenyl) -butanone; benzoin-based compounds such as benzoin, benzoin methyl ether, benzoin isopropyl ether; and 2,4,6-trimethyl oxide Benzoyl diphenylphosphine, bis (2,4,6-trimethylbenzylidene) -phenylphosphine oxide and other phosphonium oxide based compounds; benzil (biphenyl Formamidine), methyl phenyl glyoxy ester, 2- (2-hydroxyethoxy) ethyl hydroxyphenylacetate, 2- (2-oxo-2- Diphenylethylene diketone compounds such as phenylacetoxyethoxy) ethyl ester; diphenyl ketone, o-benzyl benzoic acid methyl-4-phenyldiphenyl ketone, 4,4 '-Dichlorodiphenyl ketone, hydroxydiphenyl ketone, 4-benzylidene-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3', 4,4'-tetrakis (tertiary butoxycarbonyl) diphenyl ketone, 3,3'-dimethyl-4-methoxydiphenyl ketone, 2,4,6-trimethyldiphenyl Diphenyl ketone compounds such as ketones, 4-methyldiphenyl ketone; 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone Tonone, 2,4-dichlorothioxanthone, etc. Ketone compounds; Amino diphenyl ketone compounds such as Michler's Ketone, 4,4'-diethylamino diphenyl ketone; 10-butyl-2-chloroacridone, 2 -Ethyl anthraquinone, 9,10-phenanthrenequinone, camphorquinone, 1- [4- (4-benzylidenephenylsulfanyl) phenyl] -2-methyl-2 -(4-Tolylsulfonyl) propan-1-one and the like. These photopolymerization initiators (C) may be used alone or in combination of two or more.

Examples of the photosensitizer (D) include tertiary amine compounds such as diethanolamine, N-methyldiethanolamine, and tributylamine; urea compounds such as o-toluenethiourea; and diethyldithio Sulfur such as sodium phosphate, s-benzyl isothiuronium-p-toluenesulfonate Compounds etc.

The amounts of the photopolymerization initiator (C) and photosensitizer (D) used are 100% by mass of the active energy ray-curable compound (A) and the active energy ray-curable compound in the active energy ray-curable composition of the present invention. The compound (B) is preferably 0.05 to 20 parts by mass, and more preferably 0.5 to 10% by mass.

In addition to the above-mentioned active energy ray-curable compound (A) and the resin (B) having a level 4 ammonium salt, the active energy ray-curable composition of the present invention may be blended in accordance with applications and required characteristics: organic solvents, Polymerization inhibitor, surface conditioner, antistatic agent, defoaming agent, viscosity modifier, light stabilizer, weathering stabilizer, heat resistance stabilizer, ultraviolet absorber, antioxidant, leveling agent, organic pigment, inorganic pigment, pigment Additives such as dispersants, silica beads, organic beads, etc .; inorganic fillers such as silica, alumina, titania, zirconia, antimony pentoxide, etc. These other blends may be used singly or in combination of two or more kinds.

The organic solvent is useful for appropriately adjusting the solution viscosity of the active energy ray-curable composition of the present invention, and is particularly intended to facilitate adjustment of the film thickness when performing film coating. Examples of the organic solvent that can be used here include alcohols such as methanol, ethanol, isopropanol, and tertiary butanol; ester compounds such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; Ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; aromatic hydrocarbons such as toluene and xylene. These organic solvents can be used singly or in combination of two or more kinds.

The aforementioned substrate film used in the film of the present invention may be in the form of a film or a sheet, and its thickness is preferably in the range of 20 to 500 μm. also, The material of the substrate film is preferably a resin with high transparency, and examples thereof include polymers such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Ester-based resins; Polyolefin-based resins such as polypropylene, polyethylene, and polymethylpentene-1; cellulose acetate (cellulose diacetate, cellulose triacetate, etc.), cellulose acetate propionate, cellulose acetate butyrate Cellulose resins such as cellulose, cellulose acetate propionate butyrate, cellulose acetate phthalate, and nitrocellulose; acrylic resins such as polymethyl methacrylate; polyvinyl chloride, polyvinylidene chloride And other vinyl chloride resins; polyvinyl alcohol; ethylene / vinyl acetate copolymers; polystyrene; polyfluorene; polycarbonate; polyfluorene; polyetherfluorene; polyetheretherketone; polyimide, polyether Polyimide-based resins such as aryleneimide; norbornene-based resins (for example, "ZEONOR" manufactured by Zeon Corporation of Japan); modified norbornene-based resins (for example, "ARTON" manufactured by JSR Corporation); An olefin copolymer (for example, "APEL" manufactured by Mitsui Chemicals Corporation). Alternatively, two or more substrates containing these resins may be bonded together.

The thickness of the resin film is preferably in a range of 20 to 200 μm, more preferably in a range of 30 to 150 μm, and even more preferably in a range of 40 to 130 μm. By setting the thickness of the film base material within this range, even when a hard coat layer is provided on one side of the cycloolefin resin film by the active energy ray-curable composition of the present invention, curling can be easily suppressed.

The film of the present invention is obtained by coating the active energy ray-curable composition of the present invention on at least one side of the film, and then irradiating the active energy ray to form a cured coating film. Examples of a method for applying the active energy ray-curable composition of the present invention to a film include, for example, : Die coating, micro gravure coating, gravure coating, roller coating, comma coating, air knife coating, kiss coating, spray coating, pass-over coating, dip coating , Spinner coating, wheeler coating, brush coating, solid coating using screen printing, wire rod coating, flow coating, etc.

In the case where the active energy ray-curable composition of the present invention contains an organic solvent, the organic solvent is volatilized after the active energy ray-curable composition is applied to a substrate film and before the active energy ray is irradiated. The resin (B) is segregated on the surface of the coating film, and is preferably heated or dried at room temperature. The conditions for heating and drying are not particularly limited as long as the organic solvent is volatilized, but it is usually preferred to be heating and drying within a range of a temperature of 50 to 100 ° C and a time of 0.5 to 10 minutes.

In addition, in order to harden the active energy ray-curable composition, examples of the means for irradiating ultraviolet rays include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and electrodeless lamps (fusion lamps (fusion lamps ( fusion lamp)), chemical lamp, black light lamp, mercury-xenon lamp, short arc lamp, helium cadmium laser, argon laser, sunlight, LED lamp, etc.

In addition to the high anti-blocking property, the film of the hardened coating film having the active energy ray-curable composition of the present invention is also excellent in abrasion resistance on the surface, so it can be applied to various applications, but it is particularly useful. An optical film used as an image display portion of an image display device such as a liquid crystal display (LCD) or an organic EL display (OLED). In particular, it is suitable for use as, for example, an electronic notebook, a mobile phone, a smart phone, and a portable audio player because it has excellent scratch resistance even if it is thin. Optical film of the image display part of the image display device of the portable electronic terminal, such as mobile computer, tablet terminal, etc., which is highly demanding for miniaturization and thickness reduction. When used as an optical film, it is possible to use a protective film as the outermost surface of an image display portion of an image display device or a base material of a touch panel. In addition, in the case of using as a protective film, for example, an image display device having a structure in which 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 stuck on the surface or inside of the transparent panel, which is effective for preventing damage or scattering when the transparent panel is broken.

[Example]

Hereinafter, the present invention will be described in more detail through examples.

(Synthesis Example 1: Synthesis of Resin (1) with Grade 4 Ammonium Salt)

In a flask equipped with a stirring device, a reflux cooling tube, and a nitrogen introduction tube, 87.5 parts by mass of 2- (methacryloxy) ethyltrimethylammonium tosylate (hereinafter referred to as "DMS") 80 was added. Mass% aqueous solution (70 parts by mass for DMS), 30 parts by mass of methoxypolyethylene glycol methacrylate ("BLEMMER PME-4000" manufactured by NOF CORPORATION; number of repeating units n ≒ 90, molecular weight 4,000) , 94.5 parts by mass of methanol, 9.45 parts by mass of propylene glycol monomethyl ether, and 1.08 parts by mass of a polymerization initiator (azobisisobutyronitrile), and reacted at 80 ° C for 6 hours in a nitrogen environment. Next, methanol was added and diluted to obtain a 45% by mass solution of the resin (1) having a fourth-order ammonium salt (sulfonate). The weight average molecular weight of the obtained resin was 10,000.

(Synthesis Example 2: Synthesis of Resin (2) with Grade 4 Ammonium Salt)

Burner equipped with stirring device, reflux cooling tube and nitrogen introduction tube To the bottle was added 87.5 parts by mass of an 80% by mass aqueous solution of 2- (methacryloxy) ethyltrimethylammonium toluenesulfonate (hereinafter referred to as "DMS") (in terms of DMS, 70 parts by mass). 30 parts by mass of methoxypolyethylene glycol methacrylate ("BLEMMER PME-1000" manufactured by NOF Corporation; number of repeating units n ≒ 23, molecular weight 1,000), 94.5 parts by mass of methanol, and 9.45 parts by mass of propylene glycol monomer Methyl ether and 1.08 parts by mass of a polymerization initiator (azobisisobutyronitrile) were reacted at 80 ° C. for 6 hours under a nitrogen atmosphere. Next, methanol was added and diluted to obtain a 45% by mass solution of the resin (2) having a fourth-order ammonium salt (sulfonate). The weight average molecular weight of the obtained resin was 10,000.

(Preparation example 1: Preparation of matrix resin of active energy ray-curable composition)

36.64 parts by mass of neo-pentaerythritol tetra (tri) acrylate ("Aronix M305" manufactured by Toa Synthesis Co., Ltd., a mixture of neo-pentaerythritol tetra-acrylate and neo-pentaerythritol triacrylate), 9.16 parts by mass Trimethylolpropane triacrylate ("MIRAMER M3150" from MIWON Corporation), 37.2 parts by mass of a solvent (mixture of acetone / methoxypropanol = 1/1), 7 parts by mass of a photopolymerization initiator (BASF Japan Co., Ltd. "IRGACURE 184"; 1-hydroxycyclohexylphenyl ketone) is uniformly mixed to prepare a matrix resin of an active energy ray-curable composition.

(Example 1)

90 parts by mass of the matrix resin (45.8 parts by mass in terms of resin content) obtained in Preparation Example 1 and 4.1 parts by mass of Synthesis Example 1 were obtained as a resin (1) having a fourth-order ammonium salt (sulfonate). 45% by mass of solution (1.8 parts by mass in terms of resin) are uniformly mixed to obtain an active energy ray-curable composition 物 (1).

(Example 2)

90 parts by mass of the matrix resin (45.8 parts by mass with respect to the resin component) obtained in Preparation Example 1 and 10.2 parts by mass of the resin (1) having a fourth-order ammonium salt (sulfonate) obtained in Synthesis Example 1 The 45% by mass solution (4.6 parts by mass in terms of resin) was uniformly mixed to obtain an active energy ray-curable composition (2).

(Example 3)

90 parts by mass of the matrix resin (45.8 parts by mass with respect to the resin component) obtained in Preparation Example 1 and 10.2 parts by mass of the resin (2) having a fourth-order ammonium salt (sulfonate) obtained in Synthesis Example 2 The 45% by mass solution (4.6 parts by mass in terms of resin) was uniformly mixed to obtain an active energy ray-curable composition (3).

(Synthesis Example 3: Synthesis of Resin (R1) with Grade 4 Ammonium Salt)

A flask equipped with a stirring device, a reflux cooling tube, and a nitrogen introduction tube was charged with 87.5 parts by mass of 80-80 parts by mass of 2- (methacryloxy) ethyltrimethylammonium chloride (hereinafter referred to as "DMC"). Mass% aqueous solution (70 parts by mass for DMC), 30 parts by mass of methoxypolyethylene glycol methacrylate ("BLEMMER PME-1000" manufactured by NOF CORPORATION; number of repeating units n ≒ 23, molecular weight 1,000) , 94.5 parts by mass of methanol, 9.45 parts by mass of propylene glycol monomethyl ether, and 1.08 parts by mass of a polymerization initiator (azobisisobutyronitrile), and reacted at 80 ° C for 6 hours in a nitrogen environment. Next, methanol was added and diluted to obtain a 45% by mass solution of a resin (R1) having a fourth-order ammonium salt (hydrochloride). The weight average molecular weight of the obtained resin was 10,000.

(Comparative example 1)

90 parts by mass of the matrix resin (45.8 parts by mass in terms of resin content) obtained in Preparation Example 1 and 4.1 parts by mass of the resin (1) having a fourth-order ammonium salt (hydrochloride) obtained in Synthesis Example 3 45% by mass of the solution (1.8 parts by mass in terms of resin) were uniformly mixed to obtain an active energy ray-curable composition (R1).

Using the active energy ray-curable compositions (1) to (3) and (R1) obtained in Examples 1 to 3 and Comparative Example 1, the following tests and evaluations were performed.

[Halogen-free evaluation of coatings]

It evaluated by whether the component in the active-energy-ray-curable composition obtained above contains a halogen.

○: Halogen-free.

×: Halogen-containing.

[Evaluation of paint appearance]

The appearance of the active energy ray-curable composition obtained above was visually observed, and the appearance of the coating film was evaluated according to the following criteria.

○: No cloudiness or precipitation.

△: There was very little cloudiness or precipitation.

×: Cloudiness or precipitation.

[Preparation of evaluation samples]

The active energy ray-curable composition was applied to a 80 μm-thick cellulose triacetate (TAC) film (manufactured by Fujifilm Corporation) with a bar coater so that the film thickness became 5 μm, and dried at 60 ° C. for 2 minutes. A high-pressure mercury lamp was irradiated with an irradiation light amount of 1.5 kJ / m ² to obtain a TAC film with a cured coating film as a sample for evaluation.

[Evaluation of coating film appearance]

The appearance of the cured coating film of the evaluation sample obtained above was visually observed, and the appearance of the coating film was evaluated according to the following criteria.

○: No whitening.

△: Very little whitening.

×: There is whitening.

[Measurement of surface resistance value (evaluation of antistatic property)]

The surface of the hardened coating film of the evaluation film obtained above was measured for surface resistance using a digital ultra-high resistance / microampere meter ("R8340A" manufactured by Advantest Co., Ltd.) at an applied voltage of 500V.

The evaluation or measurement results are shown in Table 1.

From the evaluation results shown in Table 1, it can be seen that the active energy ray-curable compositions of the present invention of Examples 1 to 3 are halogen-free and environmentally friendly materials, and have excellent coating appearance. It is also known that the hardened coating film system of the active energy ray-curable composition of the present invention has excellent appearance, and its surface resistance value is also from the 9th to the 10th order of 10, and has high antistatic performance.

On the other hand, Comparative Example 1 is an example in which a material having a quaternary ammonium salt containing chloride ions is used. Although the appearance of the coating, the appearance of the coating film, and the surface resistance value are satisfactory levels, there is a problem that it is not halogen-free.

Claims (4)

An active-energy-ray-curable composition comprising: an active-energy-ray-curable compound (A); and a resin (B) having a quaternary ammonium salt represented by the following general formula (1), wherein the resin ( B) is further having a polyoxyalkylene chain; (In the formula, R ¹ to R ³ each independently represent an alkyl group or a phenyl group, and R ⁴ represents an alkyl group, an alkoxy group, a phenyl group, or an oxyphenyl group.) For example, the active energy ray-curable composition of claim 1, wherein the blending amount of the resin (B) is within a range of 1 to 30 parts by mass relative to 100 parts by mass of the active energy ray-curable compound (A). . A hardened product characterized by hardening an active energy ray-curable composition as claimed in claim 1 or 2. A film characterized by a hardened coating film having an active energy ray-curable composition as claimed in claim 1 or 2.