KR20210055685A - Active energy ray-curable composition and film using same - Google Patents

Abstract

The present invention is characterized in that in an active energy ray-curable composition containing an active energy ray-curable compound (A) and an antistatic agent (B), the antistatic agent (B) has a cation moiety represented by formula (1). It provides an active energy ray-curable composition, and a film using the active energy ray-curable composition. This active energy ray-curable composition can form a hard coat layer having excellent anti-glare properties and antistatic properties.

Description

Active energy ray-curable composition and film using same

The present invention relates to an active energy ray-curable composition capable of forming a hard coat layer and a film using the same.

Resin film is a film for preventing scratches on the surface of flat panel displays (FPD) such as liquid crystal displays (LCD), organic EL displays (OLED), plasma displays (PDP), etc., decorative films for interior and exterior of automobiles (sheets), low reflection for windows It is used in various applications such as films and hot wire cut films. However, since the surface of the resin film is flexible and has low scratch resistance, for the purpose of supplementing this, it is recommended to apply and cure a hard coat agent containing an active energy ray-curable composition on the film surface to provide a hard coat layer on the film surface. It is generally done.

In addition, in these applications, in recent years, the demand for low cost and high precision is increasing, but when a hard coat agent is applied at a high speed, it is easy to peel off and charge, and there is a problem that a coating film defect is caused by adsorbing floating foreign substances in the air, resulting in a decrease in yield. . Therefore, as a measure to suppress such a decrease in yield, a method of imparting antistatic properties is widely used, and in particular, an inexpensive and highly transparent quaternary ammonium salt-based antistatic agent is frequently used (for example, Patent Documents 1 and 2 See.).

On the other hand, as resin films used in the manufacture of FPDs, triacetyl cellulose (TAC) films and cycloolefin polymer (COP) films have been mainstream until now, but they are relatively inexpensive due to the flow of cost reduction, and have low moisture permeability and high dimensions. The use rate of a film with a hard coat layer using a polymethyl methacrylate substrate having stability as a supporting substrate is increasing.

Although an anti-glare hard coat is used for a polarizing plate, with the increase in the use of polymethyl methacrylate substrates in recent years, it is required to further impart antistatic properties. However, it was very difficult to achieve both low haze and antistatic properties required for the expression of anti-glare properties because the process of particle agglomeration and the process of antistatic expression were mixed when drying the coating film of the hard coat composition.

Japanese Patent Laid-Open Publication No. 2004-143303 Japanese Patent Laid-Open Publication No. 2004-123924

The problem to be solved by the present invention is to provide an active energy ray-curable composition capable of forming a hard coat layer having excellent anti-glare properties and antistatic properties, and a film using the same.

The present invention is characterized in that in an active energy ray-curable composition containing an active energy ray-curable compound (A) and an antistatic agent (B), the antistatic agent (B) has a cation moiety represented by the following formula (1). It is to provide an active energy ray-curable composition and a film using the same.

(In formula (1), X represents a phosphorus atom or a nitrogen atom, R ¹ to R ⁴ each independently represent an alkyl group or alkenyl group having 1 to 20 carbon atoms, and the total number of carbon atoms is 10 or more. )

The active energy ray-curable composition of the present invention is capable of forming a hard coat layer excellent in coating stability, coating film appearance, anti-glare property and antistatic property on various substrates including a polymethyl methacrylate substrate.

Accordingly, a film having a hard coat layer including a cured coating film of the active energy ray-curable composition of the present invention is applied to a flat panel display (FPD) such as a liquid crystal display (LCD), an organic EL display (OLED), and a plasma display (PDP). It can be suitably used as an optical film to be used.

The active energy ray-curable composition of the present invention contains an active energy ray-curable compound (A) and an antistatic agent (B) as essential components.

As the active energy ray-curable compound (A), for example, urethane (meth)acrylate (A1), epoxy (meth)acrylate (A2), the urethane (meth)acrylate (A1), and the epoxy (meth) Polyfunctional (meth)acrylate other than acrylate (A2) (hereinafter, abbreviated as "other polyfunctional (meth)acrylate (A3)"), polyester (meth)acrylate, polyether (meth)acrylic Rate, styrene, etc. can be used. These active energy ray-curable compounds (A) may be used alone or in combination of two or more. In addition, among these, from the viewpoint of obtaining even more excellent hard coat properties, the group consisting of urethane (meth)acrylate (A1), epoxy (meth)acrylate (A2) and other polyfunctional (meth)acrylates (A3) It is preferable to use at least one compound selected from.

In addition, in the present invention, "(meth)acrylate" refers to one or both of acrylate and methacrylate, and "(meth)acryloyl" refers to one or both of acryloyl and methacryloyl. In other words, "(meth)acrylic" means one or both of acrylic and methacrylic.

As said urethane (meth)acrylate (A1), it is used for the purpose of adjustment of abrasion resistance and flexibility, For example, of polyisocyanate (a1-1) and (meth)acrylate (a1-2) having a hydroxyl group. Reactant (A1X); It is a reaction product (A1Y) of a polyisocyanate (a1-1) and a (meth)acrylate (a1-2) having a hydroxyl group and a polyol (a1-3), and at least one (meth)acryloyl group, preferably 2 to You can use those having six.

Examples of the polyisocyanate (a1-1) 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- Alicyclic polyisocyanates such as methyl-1,5-diisocyanatocyclohexane; Aromatic polyisocyanates, such as toluene diisocyanate, xylene diisocyanate, and diphenylmethane diisocyanate, etc. can be used. These polyisocyanates may be used alone or in combination of two or more.

As the polyisocyanate (a1-1), it is preferable to use an aliphatic polyisocyanate and/or an alicyclic polyisocyanate from the viewpoint of reducing the coloring of the cured coating film of the active energy ray-curable composition, among the above, At least one polyisocyanate selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate is more preferable, and hexamethylene diisocyanate and/or isophorone diisocyanate is still more preferable.

The (meth)acrylate (a1-2) has a hydroxyl group and a (meth)acryloyl group, and, for example, 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)acrylates of dihydric alcohols such as mono(meth)acrylate and hydroxypivalate neopentyl glycol mono(meth)acrylate; Trimethylolpropanedi (meth)acrylate, ethylene oxide (EO) modified trimethylolpropane (meth)acrylate, propylene oxide (PO) modified trimethylolpropanedi (meth)acrylate, glycerindi (meth)acrylate, bis Mono or di(meth)acrylate of a trihydric alcohol such as (2-(meth)acryloyloxyethyl)hydroxyethyl isocyanurate, or a hydroxyl group in which a part of these alcoholic hydroxyl groups is modified with ε-caprolactone Mono and di(meth)acrylates having; Monofunctional hydroxyl groups and trifunctional groups such as pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, etc. The compound having the above (meth)acryloyl group, or a polyfunctional (meth)acrylate having a hydroxyl group obtained by further modifying the compound with ε-caprolactone; (Meth)acrylates having oxyalkylene chains such as dipropylene glycol mono(meth)acrylate, diethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and polyethylene glycol mono(meth)acrylate ; (Meth)acrylates having block-structured oxyalkylene chains such as polyethylene glycol-polypropylene glycol mono(meth)acrylate and polyoxybutylene-polyoxypropylene mono(meth)acrylate; Poly(ethylene glycol-tetramethylene glycol) mono(meth)acrylate, poly(propylene glycol-tetramethylene glycol) mono(meth)acrylate, and the like (meth)acrylates having an oxyalkylene chain having a random structure. have. These (meth)acrylates (a1-2) may be used alone or in combination of two or more. Among these, in the case of using a type (A1X) that does not use a polyol (a1-3) as the urethane (meth)acrylate (A2), since even more excellent scratch resistance is obtained, pentaerythritol tri(meth) ) It is preferable to use at least one compound selected from the group consisting of acrylate, dipentaerythritol penta (meth) acrylate, and tripentaerythritol hepta (meth) acrylate. In addition, in the case of using a type (A1Y) in which a polyol (a1-3) is used as the urethane (meth)acrylate (A2), since even more excellent flexibility is obtained, 2-hydroxyethyl (meth)acrylate It is preferable to use.

Examples of the polyol (a1-3) include polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; Polyester polyol, polycarbonate polyol, etc. can be used. These polyols may be used alone or in combination of two or more. Among these, it is preferable to use polyether polyol, and polytetramethylene glycol is more preferable from the viewpoint of obtaining even more excellent flexibility.

Reaction of the polyisocyanate (a1-1) and the (meth)acrylate (a1-2), and the polyisocyanate (a1-1) and the (meth)acrylate (a1-2) and the polyol (a1- For the reaction of 3), urethanization reaction of a conventional method can be used. Moreover, when performing a urethanization reaction, you may use a urethanization catalyst as needed. Examples of the urethanization catalyst include amine compounds such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine; Phosphorus compounds such as triphenylphosphine and triethylphosphine; Organic tin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin diacetate, and tin octylate, and organic zinc compounds such as octylate zinc can be used.

As the urethane (meth)acrylate (A2), the number average molecular weight of the urethane (meth)acrylate in the case of using a type (A1Y) using a polyol (a1-3) is further excellent in flexibility and resistance to friction. It is preferable that it is a range of 800 to 6,000, and a range of 1,000 to 4,000 is more preferable from the viewpoint of obtaining similarity. In addition, the number average molecular weight of the urethane (meth)acrylate represents a value measured by a gel permeation column chromatography (GPC) method (eluent; tetrahydrofuran, polystyrene conversion).

When (A1X) and (A1Y) are used in combination as the urethane (meth)acrylate (A1), the mass ratio [(A1X)/(A1Y)] of 10 It is preferably in the range of /90 to 90/10, and more preferably in the range of 30/70 to 70/30.

As the epoxy (meth)acrylate (A2), it is used for the purpose of improving antistatic properties and anti-glare properties, and for example, an addition reaction product of an unsaturated monocarboxylic acid and an epoxy compound can be used.

As said unsaturated monocarboxylic acid, (meth)acrylic acid, crotonic acid, cinnamic acid, etc. can be used, for example. These compounds may be used alone or in combination of two or more. Among these, it is preferable to use (meth)acrylic acid in terms of scratch resistance and antistatic properties.

Examples of the epoxy compound include epoxy compounds having a bisphenol A skeleton such as bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and brominated bisphenol A diglycidyl ether; Epoxy compounds having a bisphenol F skeleton such as bisphenol F diglycidyl ether; Epoxy compounds having a hydrogenated phthalic acid skeleton; Compounds having an epoxy group and a (meth)acryloyl group such as glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, and 3,4-epoxycyclohexylmethyl (meth) acrylate can be used. I can. These compounds may be used alone, or two or more may be used in combination, or a polymer of these compounds may be used. Among these, from the viewpoint of scratch resistance and antistatic properties, it is preferable to use an epoxy group and a (meth)acrylic compound, and it is more preferable to use a polymer of glycidyl (meth)acrylate.

In using the polymer of the epoxy compound as a raw material for the epoxy (meth)acrylate (A2), a solvent may be used in combination from the viewpoint of adjusting the viscosity. As the solvent, for example, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, or the like can be used. These solvents may be used alone or in combination of two or more. The content in the case of using the solvent is preferably in the range of 50 to 150 parts by mass based on 100 parts by mass of the epoxy (meth)acrylate (A2).

In the case of using a polymer of the epoxy compound as a raw material of the epoxy (meth)acrylate (A2), the viscosity of the epoxy (meth)acrylate (A2) containing a solvent when forming a hard coat layer The range of 100 to 3,000 mPa·s is preferable, and the range of 150 to 2,000 mPa·s is more preferable because the coating stability of can be further improved. In addition, the said viscosity represents a value measured using a B-type viscometer.

As said other polyfunctional (meth)acrylate (A3), it is used in order to obtain a hard coat property, and other than the said (A1) and (A2), the (meth)acryloyl group in 1 molecule is preferably 2 to It represents a compound having 8, more preferably 3 to 6. Examples of the other polyfunctional (meth)acrylate (A3) include 1,4-butanedioldi(meth)acrylate, 3-methyl-1,5-pentanedioldi(meth)acrylate, and 1,6- Hexanedioldi(meth)acrylate, neopentylglycoldi(meth)acrylate, 2-methyl-1,8-octanedioldi(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol Di(meth)acrylate, tricyclodecanedimethanoldi(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene Di(meth)acrylates of dihydric alcohols such as glycol di(meth)acrylate and tripropylene glycol di(meth)acrylate; Polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, di(meth)acrylate of tris(2-hydroxyethyl)isocyanurate, 4 mol or more of ethylene oxide per 1 mol of neopentyl glycol Or di(meth)acrylate of diol obtained by adding propylene oxide; Di(meth)acrylate of diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A; Trimethylolpropane tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylol Propanetetra(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol Tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hexa(meth)acrylate , Tripentaerythritol hepta (meth)acrylate, tripentaerythritol octa (meth)acrylate, and the like can be used. These compounds may be used alone or in combination of two or more.

As the other polyfunctional (meth)acrylate (A3), from the viewpoint of obtaining even more excellent scratch resistance among the above, tripentaerythritol octa (meth)acrylate, tripentaerythritol hepta (meth)acrylate, One selected from the group consisting of dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, and pentaerythritol tri(meth)acrylate It is more preferable to use the above compounds, and pentaerythritol tetra(meth)acrylate and pentaerythritol tri(meth)acrylate are more preferable.

As the active energy ray-curable compound (A), urethane (meth)acrylate (A1), epoxy (meth)acrylate (A2) and others are obtained from the viewpoint of obtaining even more excellent antistatic properties, anti-glare properties and scratch resistance. A combination of a functional (meth)acrylate (A3) or a combination of an epoxy (meth)acrylate (A2) and other polyfunctional (meth)acrylates (A3) is preferred.

When all of (A1) to (A3) are used as the active energy ray-curable compound (A), the amount of the urethane (meth)acrylate (A1) is further excellent in scratch resistance, antistatic property, and anti-glare property. From the viewpoint of obtaining this, in the active energy ray-curable compound (A), it is preferably in the range of 1 to 50% by mass, and more preferably in the range of 5 to 30% by mass. In addition, the amount of the epoxy (meth)acrylate (A2) used is in the range of 10 to 80% by mass in the active energy ray-curable compound (A) from the viewpoint of obtaining even more excellent scratch resistance, antistatic property and anti-glare property. It is preferable, and the range of 20-60 mass% is more preferable.

In the case of using a combination of epoxy (meth)acrylate (A2) and other polyfunctional (meth)acrylate (A3) as the active energy ray-curable compound (A), the polyfunctional (meth)acrylate (A1 ) And the mass ratio [(A2)/(A3)] of the epoxy (meth)acrylate (A3) is preferably in the range of 20/80 to 90/10 from the viewpoint of obtaining even more excellent scratch resistance and antistatic properties. And the range of 40/60 to 80/20 is more preferable.

As the active energy ray-curable compound (A), in addition to the above (A1) to (A3), if necessary, polyester (meth)acrylate, polyether (meth)acrylate, styrene, or the like can be used. These compounds may be used alone or in combination of two or more. The total mass of the (A1) to (A3) in the active energy ray-curable compound (A) is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more. .

As the antistatic agent (B), in order to achieve both excellent anti-glare properties and antistatic properties, it is essential to use an ionic liquid having a cation moiety represented by the following formula (1).

(In formula (1), X represents a phosphorus atom or a nitrogen atom, R ¹ to R ⁴ each independently represent an alkyl group or alkenyl group having 1 to 20 carbon atoms, and the total number of carbon atoms is 10 or more. )

Since the antistatic agent (B) has a long-chain hydrocarbon in the cation portion, it is estimated that the three-dimensional structure is larger and the hydrophobicity is higher than that of the conventionally used antistatic agent, so that excellent anti-glare properties and antistatic properties can be achieved.

As the antistatic agent (B), for example, in the formula (1), X is a phosphorus atom or a nitrogen atom, R ¹ to R ⁴ are each independently an alkyl group or alkenyl group having 1 to 20 carbon atoms, and a carbon atom An ionic liquid (B1) having a sum of 10 or more and less than 30, wherein X is a phosphorus atom or a nitrogen atom in the formula (1), and R ¹ to R ⁴ are each independently an alkyl group or alke with 3 to 20 carbon atoms. It is a nil group, and an ionic liquid (B2) etc. in which the total number of carbon atoms is 30 or more can be used.

As the ionic liquid (B1), since further excellent anti-glare properties and antistatic properties are obtained, each of R ¹ to R ⁴ in the formula (1) independently has preferably 1 to 16 carbon atoms, more preferably Preferably, it represents an alkyl group of 1 to 14, and the total number of carbon atoms is preferably in the range of 15 to 28, more preferably in the range of 20 to 26.

As the ionic liquid (B2), since further excellent anti-glare properties and antistatic properties are obtained, it is preferable that X in the formula (1) represents a phosphorus atom, and R ¹ to R ⁴ are each independently a carbon atom It is preferable to use those having an alkyl group having the number of preferably 4 to 18, more preferably 5 to 16, and the total number of carbon atoms is preferably in the range of 30 to 40, more preferably in the range of 31 to 36 Do.

As the anion part of the antistatic agent (B), for example ^{Br -, Cl -, I -} , BF 4 -, PF 6 -, FeCl 4 -, AlCl 4 -, Al 2 Cl 7 -, NO 3 -, ClO _{^{4 -, HSO 4 -, CH}} 3 SO 4 -, CH 3 SO 3 -, CF 3 SO 3 -, C 6 H 4 CH 3 SO 3 -, C 4 F 7 SO 3 -, CH 3 CH 2 OSO 3 - _{^{, CH 3 COO -, CF 3}} COO -, C 3 F 7 COO -, (NC) 2 N -, (CF 3 SO 2) 2 N -, (C 2 F 5 SO 2) 2 N -, (CF 3 _{SO 2) (CF 3 CO)} N -, Tf 2 N -, SCN -, (CF 3 SO 2) 3 C -, AsF 6 -, SbF 6 -, NbF 6 -, TaF 6 -, C (CN) 3 ^- it can be used.

The content of the antistatic agent (B) is preferably in the range of 0.01 to 20% by mass in the active energy ray-curable composition, and in the range of 0.05 to 5% by mass, from the viewpoint of obtaining even more excellent anti-glare property and antistatic property. It is more preferable.

As an active energy ray-curable composition of this invention, it is preferable to contain a solvent (C) in order to improve coatability.

Examples of the solvent (C) include methanol, ethanol, propanol, butanol, diacetone alcohol, diacetone alcohol, dimethylcarbitol, methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, Acetylacetone, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether, and the like can be used. These solvents may be used alone or in combination of two or more. Among these, it is preferable to use ethanol from the viewpoint of obtaining even more excellent antistatic properties.

When using the said solvent (C), it is preferable that it is in the range of 40-80 mass% in an active energy ray-curable composition from a point of coatability etc. as a usage-amount.

The active energy ray-curable composition of the present invention can be formed into a cured coating film by irradiating an active energy ray after coating a substrate. This active energy ray refers to ionizing radiation such as ultraviolet rays, electron rays, α rays, β rays, and γ rays. When making a cured coating film by irradiating ultraviolet rays as an active energy ray, it is preferable to add a photoinitiator (D) to the active energy ray-curable composition of this invention to improve curability. Further, if necessary, a photosensitizer (E) may be further added to improve curability. On the other hand, when ionizing radiation such as electron beam, α-ray, β-ray, and γ-ray is used, it cures quickly without using a photoinitiator (D) or a photosensitizer (E). It is not necessary to add a sensitizer (E).

Examples of the photoinitiator (D) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and oligo{2-hydroxy-2-methyl-1-[4- (1-methylvinyl)phenyl]propanone}, benzyldimethylketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy) Phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2- Acetophenone compounds such as dimethylamino-1-(4-morpholinophenyl)-butanone; Benzoin compounds such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; Acylphosphine oxide-based compounds such as 2,4,6-trimethylbenzoindiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; Benzyl, such as benzyl (dibenzoyl), methylphenylglyoxyester, oxyphenylacetic acid 2-(2-hydroxyethoxy)ethyl ester, and oxyphenylacetic acid 2-(2-oxo-2-phenylacetoxyethoxy)ethyl ester System compound; Benzophenone, o-benzoylbenzoate methyl-4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, acrylated benzophenone, 3,3 ',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, etc. Benzophenone compounds of; Thioxanthone compounds, such as 2-isopropyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, and 2,4-dichloro thioxanthone; Aminobenzophenone compounds such as Michler's ketone and 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, 1-[4-(4-benzoylphenylsulfonyl)phenyl]-2-methyl-2- (4-methylphenylsulfonyl)propan-1-one and the like can be used. These photopolymerization initiators (D) may be used alone or in combination of two or more.

In addition, examples of the photosensitizer (E) include tertiary amine compounds such as diethanolamine, N-methyldiethanolamine, and tributylamine, urea compounds such as o-tolylthiourea, and sodium diethyldithiophosphate. and sulfur compounds such as s-benzyl isothiouronium-p-toluenesulfonate, and the like.

When using the photoinitiator (D) and photosensitizer (E), the amount used is preferably in the range of 0.05 to 20 parts by mass, respectively, based on 100 parts by mass of the active energy ray-curable compound (A), and 0.5 to The range of 10 parts by mass is more preferable.

The active energy ray-curable composition of the present invention contains the active energy ray-curable compound (A) and the antistatic agent (B) as essential components, but may contain other additives as necessary.

Examples of the other additives include polymerization inhibitors, surface modifiers, antistatic agents other than (B), defoaming agents, viscosity modifiers, light stabilizers, weather stabilizers, heat stabilizers, ultraviolet absorbers, antioxidants, leveling agents, organic pigments, Additives such as inorganic pigments, pigment dispersants, and fine particles; Inorganic fillers, such as silicon oxide, aluminum oxide, titanium oxide, zirconia, and antimony pentoxide, etc. can be used. These additives may be used alone or in combination of two or more.

As the fine particles, inorganic fine particles and organic fine particles can be used, and it is preferable to use a transparent one. Plastic polymer beads may be used as the organic fine particles, for example, styrene beads (refractive index 1.60), melamine beads (refractive index 1.57), acrylic beads (refractive index 1.49 to 1.535), acrylic-styrene beads (refractive index 1.54 to 1.58 ), benzoguanamine-formaldehyde beads, polycarbonate beads, polyethylene beads, and the like. As the inorganic fine particles, for example, spherical silica, amorphous silica, or the like can be used. Among these, it is preferable to use organic fine particles, and since the cohesive force is high and compatibility with the antistatic agent (B) is good, and further excellent antistatic properties and anti-glare properties are obtained, acrylic beads and/or acrylic-styrene-based It is preferable to use beads, and acrylic beads are more preferable.

The particle size of the fine particles is preferably in the range of 0.5 to 5.0 µm, more preferably in the range of 0.8 to 3.5 µm, and more preferably in the range of 1.0 to 2.5 µm from the viewpoint of high cohesiveness and further excellent antistatic properties and anti-glare properties. The range is more preferred. In addition, the particle diameter of the organic fine particles represents the particle diameter when the integrated amount occupies 50% in the integrated particle amount curve of the particle size distribution measurement result in the particle size distribution.

In the case of using the fine particles, from the viewpoint of obtaining even more excellent antistatic properties and anti-glare properties, it is preferably in the range of 0.5 to 15% by mass in the active energy ray-curable composition, and the range of 1 to 7% by mass is It is more preferable.

The film of the present invention is obtained by coating the active energy ray-curable composition of the present invention on at least one surface of a film substrate, and then irradiating with an active energy ray to obtain a cured coating film.

The material of the film substrate used in the film of the present invention is preferably a resin having high transparency, and examples thereof include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; Polyolefin resins such as polypropylene, polyethylene, and polymethylpentene-1; Cellulose resins, such as cellulose acetate (diacetyl cellulose, triacetyl cellulose, etc.), cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, cellulose acetate phthalate, and cellulose nitrate; Acrylic resins such as polymethyl methacrylate; Vinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride; Polyvinyl alcohol; Ethylene-vinyl acetate copolymer; polystyrene; Polyamide; Polycarbonate; Polysulfone; Polyethersulfone; Polyetheretherketone; Polyimide resins such as polyimide and polyetherimide; Norbornene resin (e.g., ``Zeonoa'' manufactured by Nippon Xeon Corporation), modified norbornene resin (e.g., ``Atone'' manufactured by JSR Corporation), cyclic olefin copolymer (e.g., Mitsui Chemical Co., Ltd. ``Apel'') and the like. Moreover, you may use the thing which bonded two or more types of base materials containing these resins.

In addition, in the present invention, by using the active energy ray-curable composition, even when polymethyl methacrylate is used as the film substrate, a hard coat layer having excellent anti-glare properties and antistatic properties can be formed.

The polymethyl methacrylate substrate (hereinafter, abbreviated as “PMMA”) is a substrate made of a polymer containing polymethyl methacrylate as a main component (preferably 100% by mass), for example, Sumitomo Chemical ``Technology S014G'', ``Technoloy S001G'', ``Technoloy S000'' manufactured by Mitsubishi Chemical Co., Ltd.``Acriflen HBS006'', ``Acriflen HBXN47'', ``Acriflen HBS010'', D "Fanlight Film PC-2151" manufactured by Jin Kasei Co., Ltd. can be obtained as a commercial item.

The film substrate may be in the form of a film or a sheet, and the thickness thereof is in the range of, for example, 20 to 500 µm. Further, when using a film-like base film, the thickness thereof is preferably in the range of 20 to 200 µm, more preferably in the range of 30 to 150 µm, and even more preferably in the range of 40 to 130 µm. By making the thickness of a film base material into the said range, even when a hard coat layer is provided on one side of a film by the active energy ray-curable composition of this invention, it becomes easy to suppress curl.

As a method of coating the active energy ray-curable composition of the present invention on the film substrate, for example, die coat, microgravure coat, gravure coat, roll coat, comma coat, air knife coat, kiss coat, spray coat, dip coat, Spinner coat, brush application, solid coat by silk screen, wire bar coat, flow coat, etc. are mentioned.

After applying the active energy ray-curable composition to the base film, it is preferable to heat or dry it at room temperature in order to volatilize the solvent (C) before irradiating the active energy ray. As the conditions for heat drying, for example, heating and drying in a temperature range of 50 to 100°C and a time range of 0.5 to 10 minutes are exemplified.

As the active energy rays for curing the active energy ray-curable composition of the present invention, as described above, ionizing radiation such as ultraviolet rays, electron rays, α rays, β rays, and γ rays. Here, in the case of using ultraviolet rays as the active energy ray, examples of the device for irradiating the ultraviolet rays include low pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, electrodeless lamps (fusion lamps), chemical lamps, Black light lamps, mercury-xenon lamps, short arc lamps, helium-cadmium lasers, argon lasers, sunlight, LED lamps, etc. are mentioned.

When forming the cured coating film of the active energy ray-curable composition of the present invention on the film substrate, the film thickness of the cured coating film should be sufficient to have the hardness of the cured coating film, and suppress curling of the film due to curing shrinkage of the coating film. From the point of view, the range of 1 to 30 µm is preferable, the range of 3 to 15 µm is more preferable, and the range of 4 to 10 µm is still more preferable.

As described above, the active energy ray-curable composition of the present invention is capable of forming a hard coat layer having excellent coating stability, coating appearance, anti-glare property and antistatic properties on various substrates including a polymethyl methacrylate substrate.

Accordingly, a film having a hard coat layer including a cured coating film of the active energy ray-curable composition of the present invention is applied to a flat panel display (FPD) such as a liquid crystal display (LCD), an organic EL display (OLED), and a plasma display (PDP). It can be suitably used as an optical film to be used.

Example

The present invention will be described in more detail by examples below.

[Example 1]

40 parts by mass of an equivalent mixture of pentaerythritol tetraacrylate (hereinafter abbreviated as "PETTA") and pentaerythritol triacrylate (hereinafter abbreviated as "PETA"), urethane acrylate (1) (dipentaeryth) A reaction product of ritolpentaacrylate and isophorone diisocyanate, solid content 100% by mass, hereinafter abbreviated as ``UA (1).) 20 parts by mass, urethane acrylate (2) (polytetramethylene glycol and isophorone diisocyanate and Reaction product of 2-hydroxyethyl acrylate, number average molecular weight: 1,600, solid content 100% by mass, hereinafter abbreviated as ``UA (2)''), epoxy acrylate (1) (polyglycidyl methacrylate and acrylic acid Methyl isobutyl ketone solution, solid content 50% by mass, viscosity 1,000 mPa·s, hereinafter abbreviated as “EA (1)”) 40 parts by mass, ethanol 144 parts by mass, 1-hydroxycyclohexylphenyl ketone 5 After sufficiently mixing the mass parts, antistatic agent (B) (in formula (1), X represents a phosphorus atom, R ¹ to R ³ represent an alkyl group having 6 carbon atoms, and R ⁴ represents an alkyl group having 14 carbon atoms. a represents, that is, the total number of carbon atoms 32, the anion portion _{(CF 3 SO 2) 2 N} -.) 3 parts by weight of organic beads (Sekisui addition Hing high as to whether or manufactured crosslinked acrylic fine particles, the particle size of the 1.5㎛ , Refractive index 1.495) 3.5 parts by mass were mixed, and the mixture was stirred with a dispersion stirrer for 30 minutes to prepare an active energy ray-curable composition.

[Examples 2 to 16, Comparative Examples 1 to 6]

An active energy ray-curable composition was prepared in the same manner as in Example 1, except that the type and amount of the active energy ray-curable compound (A) and the antistatic agent (B) to be used were changed as shown in Tables 1 to 4.

[Production of sample for evaluation]

The active energy ray-curable composition obtained in Examples and Comparative Examples was coated on a polymethyl methacrylate film having a thickness of 60 μm to a film thickness of 5 μm using a bar coater, dried at 60° C. for 1 minute, and then in a nitrogen atmosphere. Under an ultraviolet irradiation apparatus (manufactured by Eye Graphics Co., Ltd., a high pressure mercury lamp), it was irradiated twice at an irradiation amount of 75 mJ/m 2, and a polymethyl methacrylate film having a cured coating film was obtained as a sample for evaluation.

[An evaluation method of anti-glare property]

(1) Haze evaluation

The obtained sample for evaluation was based on JIS K7136:2000, and the haze was measured using a haze meter ("NDH4000" manufactured by Nippon Denshoku Co., Ltd.).

(2) Evaluation of transmission sharpness

The obtained sample for evaluation was based on JIS K7374:2007, using an image-sharpness measuring instrument ("ICM-IT" manufactured by Suga Shikki Co., Ltd.), and an optical comb width; It measured at four points of 0.125, 0.5, 1.0, and 2.0 mm. For evaluation, the total value of the measured 4 points was used.

From the above, a haze of 4 or less and a transmission sharpness of 375% or less were judged to be excellent in anti-glare properties.

[Evaluation method of antistatic property]

About the surface of the cured coating film of the obtained evaluation sample, according to JIS test method C2139:2008, using a high resistivity meter ("Hyresta UP MCP-HT450" manufactured by Mitsubishi Chemical Analytech Co., Ltd.), applied voltage ; 500V, measuring time; The surface resistance value was measured in 10 seconds. A surface resistance value (Ω/□) of 10 ^-13 or less was judged to be excellent in antistatic properties.

The abbreviations in Table 4 are as follows

-"Pyridine-based antistatic agent"; "1-Butyl-4-methylpyridinium bis(trifluoromethanesulfonyl)imide" manufactured by Tokyo Kasei Kogyo Co., Ltd.

-"Imidazole-based antistatic agent"; "1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide" manufactured by Tokyo Kasei Kogyo Co., Ltd.

From the evaluation results shown in Tables 1 to 4, it can be seen that the cured coating films of the active energy ray-curable compositions of the present invention of Examples 1 to 16 have excellent antistatic properties and anti-glare properties. Further, as the amount of the antistatic agent (B) increased, the transmission clarity decreased, the antiglare property was obtained, and the antistatic property was also improved.

Comparative Examples 1 to 2 shown in Table 4 are an embodiment in which the antistatic agent (B) is not contained, the transmission clarity is increased, and the antistatic property is also poor. In Comparative Examples 3 to 5, other antistatic agents were used instead of the antistatic agent (B) used herein, but the antistatic properties were poor.

Claims (9)

In an active energy ray-curable composition containing an active energy ray-curable compound (A) and an antistatic agent (B),
The active energy ray-curable composition, characterized in that the antistatic agent (B) has a cation moiety represented by the following formula (1).

(In formula (1), X represents a phosphorus atom or a nitrogen atom, R ¹ to R ⁴ each independently represent an alkyl group or alkenyl group having 1 to 20 carbon atoms, and the total number of carbon atoms is 10 or more. ) The active energy ray-curable composition according to claim 1, wherein the content of the antistatic agent (B) is in the range of 0.01 to 20% by mass. The method according to claim 1, wherein the active energy ray-curable compound (A) is composed of urethane (meth)acrylate (A1), epoxy (meth)acrylate (A2) and other polyfunctional (meth)acrylate (A3). At least one compound selected from the group, active energy ray-curable composition. The active energy ray-curable composition according to claim 1, wherein R ¹ to R ⁴ in Formula (1) are each independently an alkyl group or alkenyl group having 1 to 20 carbon atoms, and the total number of carbon atoms is 10 or more and less than 30. . The active energy ray-curable composition according to claim 1, wherein R ¹ to R ⁴ in Formula (1) are each independently an alkyl group or alkenyl group having 3 to 20 carbon atoms, and the total number of carbon atoms is 30 or more. The active energy ray-curable composition according to claim 1, wherein the active energy ray-curable composition further contains a solvent (C). The active energy ray-curable composition according to claim 6, wherein the solvent (C) contains ethanol. A cured product of the active energy ray-curable composition according to any one of claims 1 to 7. A film comprising a cured coating film of the active energy ray-curable composition according to any one of claims 1 to 7.