TW202413450A - Active energy ray-curable composition, cured product and film - Google Patents

Abstract

The problem to be solved by the present invention is to provide an active energy ray-curable composition, a cured product, and a film that can form a cured coating film with excellent anti-glare properties and transparency. The present invention provides an active energy ray-curable composition, a cured product, and a film using the same, wherein the active energy ray-curable composition contains: epoxy (meth)acrylate (A), other multifunctional (meth)acrylate (B), and organic microparticles (C), and the active energy ray-curable composition is characterized in that: the multifunctional (meth)acrylate (B) contains at least one of a compound (B1) having a urate skeleton in the molecule or a compound (B2) having a carboxyl group in the molecule.

Description

Active energy ray-curable composition, cured product and film

The present invention relates to an active energy ray-curable composition, a cured product and a film capable of forming a hard coating layer.

Resin films can be used in various applications such as anti-scratch films on the surface of flat panel displays (FPD) such as liquid crystal displays (LCD), organic electroluminescence displays (OLED), plasma displays (plasma display panels (PDP)), decorative films (sheets) for interior and exterior decoration of automobiles, low-reflection films for windows, or heat-ray cut-off films. However, since the surface of the resin film is soft and has low scratch resistance, in order to compensate for the above disadvantages, the following operation is usually performed: a hard coating agent containing an active energy ray-curable composition is applied to the film surface and hardened to form a hard coating layer on the film surface.

In the field of optical parts represented by display applications, if the glossiness of the display surface is high, the light on the product surface will be reflected too much, which may cause problems. Therefore, it is required to arrange an anti-glare film or an anti-glare anti-reflection film with an anti-glare function on the outermost surface of the display. As an anti-glare film, the following technology is known: using an active energy ray-curable composition containing particles with an average particle size of micrometers, the surface of the coating obtained after curing is formed with appropriate concavities and convexities, thereby diffusing light.

As such an anti-glare film, there is known a film obtained by curing a coating liquid containing microparticles (surface convex particles) and a resin, wherein the microparticles (surface convex particles) are fine particles fixed to the surface of core particles and have a convex surface shape. (Patent Document 1)

The surface convex particles described in Patent Document 1 use inorganic fine particles in at least one of the core particles and the microparticles, so it is believed that there are problems with the affinity between the cured resin layer and the particle interface or the transparency of the film. Therefore, an active energy ray-curable resin composition that can provide excellent anti-glare properties by using organic fine particles and has little reduction in transparency or adhesion to the substrate has been developed. (Patent Document 2)

However, the minimum haze value of the cured coating obtained from the composition described in the embodiment of Patent Document 2 is 2.4%, and the transparency is not disclosed. Therefore, there are further issues in terms of balancing transparency and anti-glare properties. [Prior Art Document] [Patent Document]

[Patent document 1] Japanese Patent Publication No. 2005-4163 [Patent document 2] Japanese Patent Publication No. 2005-272582

[The problem that the invention wants to solve]

The problem to be solved by the present invention is to provide an active energy ray-curable composition, a cured product and a film capable of forming a cured coating film having excellent anti-glare properties and transparency. [Means for solving the problem]

The inventors of the present invention have conducted intensive research to solve the above-mentioned problems and have found that an active energy ray-curable composition capable of forming a cured coating having excellent anti-glare properties and transparency can be obtained by blending a compound having a specific structure with organic microparticles, thereby completing the present invention. That is, the present invention relates to the inventions described in [1] to [7] below. The present invention includes the following contents. [1] An active energy ray-curable composition comprising: an epoxy (meth)acrylate (A), another multifunctional (meth)acrylate (B), and organic microparticles (C), wherein the multifunctional (meth)acrylate (B) contains at least one of a compound (B1) having a urate skeleton in the molecule or a compound (B2) having a carboxyl group in the molecule. [2] The active energy ray-curable composition according to [1], wherein the epoxy (meth)acrylate (A) is a reaction product of polyglycidyl methacrylate and acrylic acid. [3] The active energy ray-curable composition according to [1] or [2], wherein the polyfunctional (meth)acrylate (B) further comprises a compound (B3) having three or more (meth)acryloyl groups in the molecule, and the compound (B3) is different from the compound (B1) and the compound (B2). [4] The active energy ray-curable composition according to any one of [1] to [3], wherein the average primary particle size of the organic microparticles (C) is in the range of 0.5 μm to 3 μm. [5] An active energy ray-curable composition according to any one of [1] to [4], wherein the content of the organic fine particles (C) is in the range of 1 to 10 parts by mass relative to 100 parts by mass of the total of the epoxy (meth)acrylate (A) and the multifunctional (meth)acrylate (B). [6] A cured product, which is a cured product of the active energy ray-curable composition according to any one of [1] to [5]. [7] A film, characterized in that it comprises a cured coating film of the active energy ray-curable composition according to any one of [1] to [5]. [Effect of the invention]

The active energy ray-curable composition of the present invention can form a cured coating film having excellent coating stability, coating appearance, anti-glare properties and transparency on various substrates including triacetyl cellulose substrates.

Therefore, a film having a hard coating layer including a cured coating film of the active energy ray-curable composition of the present invention can be suitably used as an optical film used in flat panel displays (FPD) such as liquid crystal displays (LCDs), organic EL displays (OLEDs), and plasma displays (PDPs).

<Active energy ray-curable composition> The active energy ray-curable composition of the present invention (hereinafter, sometimes referred to as "composition") contains epoxy (meth)acrylate (A), other multifunctional (meth)acrylate (B), and organic fine particles (C) as essential components. In addition, in the present invention, "(meth)acrylate" refers to one or both of acrylate and methacrylate, "(meth)acryl" refers to one or both of acryl and methacryl, and "(meth)acrylic group" refers to one or both of acrylic group and methacrylic group. In addition, epoxy (meth)acrylate (A) is sometimes referred to as (A) component, and the same applies to other components. Furthermore, the compounds having a (meth)acryl group in the active energy ray-curable composition including the epoxy (meth)acrylate (A) and the other multifunctional (meth)acrylate (B) are sometimes collectively referred to as "radical polymerizable compounds".

[Epoxy (meth)acrylate (A)] As epoxy (meth)acrylate (A), for example, an addition reaction product of an unsaturated monocarboxylic acid and an epoxy compound can be used.

As the unsaturated monocarboxylic acid, for example, (meth)acrylic acid, crotonic acid, cinnamic acid, etc. can be used. These compounds can be used alone or in combination of two or more. Among these, (meth)acrylic acid is preferably used in terms of scratch resistance.

As the epoxy compound, for example, 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 (meth)acrylate glycidyl ether, 4-hydroxybutylacrylate glycidyl ether, and (meth)acrylate 3,4-epoxyhexylmethyl ester, etc. can be used. These compounds can be used alone, two or more of them can be used in combination, and polymers of these can also be used. Among these, from the viewpoint of abrasion resistance, it is preferred to use a compound having an epoxy group and a (meth)acryl group, and it is more preferred to use a polymer of glycidyl (meth)acrylate.

When the polymer of the epoxy compound is used as the raw material of the epoxy (meth) acrylate (A), a solvent may be used in combination for adjusting the viscosity. As the solvent, for example, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, etc. may be used. These solvents may be used alone or in combination of two or more. When the solvent is used, the content is preferably in the range of 50 to 150 parts by mass relative to 100 parts by mass of the epoxy (meth) acrylate (A).

When the polymer of the epoxy compound is used as the raw material of the epoxy (meth) acrylate (A), the viscosity of the epoxy (meth) acrylate (A) including the solvent is preferably in the range of 100 mPa·s to 3,000 mPa·s, and more preferably in the range of 150 mPa·s to 2,000 mPa·s, from the viewpoint of further improving the coating stability when forming the hard coating layer. The viscosity is a value measured using a B-type viscometer.

The content of epoxy (meth)acrylate (A) is preferably in the range of 10% to 80% by mass, more preferably in the range of 15% to 50% by mass, and particularly preferably in the range of 20% to 40% by mass, relative to the total amount of the radical polymerizable compound in the active energy ray-curable composition. By setting the content in the above range, the transparency and anti-glare properties of the cured coating can be improved in a well-balanced manner.

[Other multifunctional (meth)acrylates (B)] The multifunctional (meth)acrylate (B) is different from the epoxy (meth)acrylate (A) and is a compound having two or more (meth)acryloyl groups in the molecule, or a mixture containing a plurality of these compounds. In the present invention, the multifunctional (meth)acrylate (B) contains at least one of a compound (B1) having a urate skeleton in the molecule or a compound (B2) having a carboxyl group in the molecule.

[Compounds (B1) having a urate skeleton in the molecule] Examples of the compound (B1) having a urate skeleton in the molecule include isocyanuric acid derivatives such as tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, bis(2-hydroxyethyl)isocyanurate di(meth)acrylate, and compounds obtained by changing the starting material of these compounds, i.e., hydroxyethyl (meth)acrylate, to ethylene oxide (EO), propylene oxide, or ε-caprolactone-modified products of hydroxyethyl (meth)acrylate. In addition, compounds obtained by reacting the above-mentioned isocyanuric acid derivatives, polyisocyanates, and compounds having a polymerizable unsaturated group and a hydroxyl group at the terminal can also be listed. Examples of the polyisocyanates include toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, hexylene diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, Ester, trans-cyclohexane 1,4-diisocyanate, lysine diisocyanate, tetramethylxylene diisocyanate, lysine triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyl octane, 1,3,6-hexane triisocyanate, dicycloheptane triisocyanate, trimethylhexane diisocyanate and other polyisocyanates. Examples of the compound having a polymerizable unsaturated group and one hydroxyl group at the terminal include compounds obtained by reacting 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethylphthalic acid, pentaerythritol tri(meth)acrylate, 3-acryloyloxyglycerol mono(meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-1-(meth)acryloyloxy-3-(meth)acryloyloxypropane, glycerol di(meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polyε-caprolactone mono(meth)acrylate, 4-hydroxybutyl (meth)acrylate, ε-caprolactone mono(meth)acrylate, and the like. These compounds can be used alone or in combination of two or more. Among these, compound (B1) is preferably a compound having a hydroxyl group, and tris(2-hydroxyethyl)isocyanurate di(meth)acrylate is particularly preferred.

The content of the compound (B1) having a urate skeleton in the molecule is preferably in the range of 1 mass % to 60 mass %, more preferably in the range of 5 mass % to 50 mass %, and particularly preferably in the range of 10 mass % to 40 mass % relative to the total amount of the free radical polymerizable compound in the active energy ray-curable composition. By setting the content in the above range, the abrasion resistance and anti-glare properties of the cured coating can be improved in a well-balanced manner.

[Compounds (B2) having a carboxyl group in the molecule] The compound (B2) having a carboxyl group in the molecule is not particularly limited as long as it has at least one carboxyl group and at least one (meth)acryl group in the molecule. For example, it can be exemplified by: carboxyl-containing (meth)acrylates, reaction products of hydroxyl-containing (meth)acrylates and acid anhydrides, carboxyl-containing urethane (meth)acrylates, carboxyl-containing polyester (meth)acrylates, carboxyl-containing polyether (meth)acrylates, polyacrylates obtained by copolymerizing carboxyl-containing vinyl monomers with (meth)acryl-containing vinyl monomers, and the like. The reaction product of the hydroxyl-containing (meth)acrylate and anhydride can be obtained by reacting succinic anhydride, 1-dodecenylsuccinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetramethylmaleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endometrimethyltetrahydrophthalic anhydride, methylendometrimethyltetrahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, chlorendic anhydride, metaphthalic anhydride, Acid anhydrides such as benzenetricarboxylic anhydride react with pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, or ethylene oxide-modified products of (di)pentaerythritol penta(meth)acrylate, propylene oxide-modified products, oligomers of dipentaerythritol penta(meth)acrylate, etc. in the presence of a catalyst such as N,N-dimethylbenzylamine, triethylamine, tributylamine, triethylenediamine, benzyltrimethylammonium chloride, benzyltriethylammonium bromide, tetramethylammonium bromide, cetyltrimethylammonium bromide, zinc oxide, etc. Among these, the compound obtained by reacting pentaerythritol tri(meth)acrylate or dipentaerythritol tri(meth)acrylate with succinic anhydride is more preferred. Examples of commercially available products include "Aronix" (manufactured by Toagosei Co., Ltd.) M510 or M520. These compounds may be used alone or in combination of two or more.

The content of the compound (B2) having a carboxyl group in the molecule is preferably in the range of 1 mass % to 60 mass %, more preferably in the range of 5 mass % to 50 mass %, and particularly preferably in the range of 10 mass % to 40 mass % relative to the total amount of the radical polymerizable compound in the active energy ray-curable composition. By setting the content in the above range, the abrasion resistance and anti-glare properties of the cured coating can be improved in a well-balanced manner.

The multifunctional (meth)acrylate (B) may further contain a compound (B3) having three or more (meth)acryl groups in the molecule, wherein the compound (B3) does not have a urate skeleton and/or a carboxyl group in the molecule.

[Compounds (B3) having three or more (meth)acryloyl groups in the molecule] As compounds (B3) having three or more (meth)acryloyl groups in the molecule, for example, urethane (meth)acrylate (B3-1), multifunctional (meth)acrylate (B3-2), polyester (meth)acrylate, polyether (meth)acrylate, etc. can be used. These can be used alone or in combination of two or more. Among these, in terms of obtaining better hard coating properties, it is preferred to use one or more compounds selected from the group consisting of urethane (meth)acrylate and multifunctional (meth)acrylate.

The urethane (meth)acrylate (B3-1) may be, for example, a reaction product of a polyisocyanate and a (meth)acrylate having a hydroxyl group; or a reaction product of a polyisocyanate, a (meth)acrylate having a hydroxyl group and a polyol. A compound having 3 or more, preferably 3 to 6 (meth)acryloyl groups may be used.

As the polyisocyanate, for example, aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate; alicyclic polyisocyanates such as norbornane diisocyanate, isophorone diisocyanate, dimethylbis(4-cyclohexyl isocyanate), 1,3-bis(isocyanatomethyl)cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, and 2-methyl-1,5-diisocyanatocyclohexane; aromatic polyisocyanates such as toluene diisocyanate, xylene diisocyanate, and diphenylmethane diisocyanate can be used. These polyisocyanates can be used alone or in combination of two or more.

As the polyisocyanate, among the above compounds, aliphatic polyisocyanates and/or alicyclic polyisocyanates are preferably used in terms of reducing the coloring of the cured coating film of the active energy ray-curable composition. More preferably, at least one polyisocyanate selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate is used. Hexamethylene diisocyanate and/or isophorone diisocyanate is more preferably used.

The (meth)acrylate having a hydroxyl group is a compound having a hydroxyl group and a (meth)acryl group, for example, trihydroxymethylpropane di(meth)acrylate, ethylene oxide (EO)-modified trihydroxymethylpropane (meth)acrylate, propylene oxide (PO)-modified trihydroxymethylpropane di(meth)acrylate, glycerol di(meth)acrylate; compounds having a monofunctional hydroxyl group and a trifunctional or higher (meth)acryl group such as pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di-trihydroxymethylpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, or a multifunctional (meth)acrylate having a hydroxyl group obtained by further modifying the compound with ε-caprolactone; dipropylene glycol mono(meth)acrylate, diethylene glycol mono(meth)acrylate, dipropylene ... (meth)acrylates having an oxyalkylene chain such as (meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate; (meth)acrylates having an oxyalkylene chain having a block structure such as polyethylene glycol-polypropylene glycol mono(meth)acrylate, polyoxybutyl-polyoxypropyl mono(meth)acrylate; (meth)acrylates having an oxyalkylene chain having a random structure such as poly(ethylene glycol-tetramethylethylene glycol) mono(meth)acrylate, poly(propylene glycol-tetramethylethylene glycol) mono(meth)acrylate, etc. These (meth)acrylates (b1-2) may be used alone or in combination of two or more. Among these, when no polyol is used as the raw material of the urethane (meth)acrylate (B3-1), it is preferred to use one or more compounds selected from the group consisting of pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and tripentaerythritol hepta(meth)acrylate in order to obtain better abrasion resistance.

As the polyol, for example, polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; polyester polyols, polycarbonate polyols, etc. can be used. These polyols can be used alone or in combination of two or more. Among these, polyether polyols are preferably used, and polytetramethylene glycol is more preferably used in terms of obtaining better bendability.

The reaction of the polyisocyanate with the (meth)acrylate having a hydroxyl group, and the reaction of the polyisocyanate with the (meth)acrylate and the polyol can be carried out by a conventional urethanization reaction. In addition, a urethanization catalyst can be used as needed during the urethanization reaction. As the urethanization catalyst, for example, 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 octoate; organic zinc compounds such as zinc octoate, etc. can be used.

When a polyol is used as a raw material of the urethane (meth) acrylate (B3-1), the number average molecular weight of the urethane (meth) acrylate (B3-1) is preferably in the range of 800 to 6,000, and more preferably in the range of 1,000 to 4,000, in order to obtain more excellent flexibility and scratch resistance. The number average molecular weight of the urethane (meth) acrylate refers to a value measured by gel permeation column chromatography (gel permeation chromatography, GPC) (eluent: tetrahydrofuran, polystyrene conversion).

The multifunctional (meth)acrylate (B3-2) is a compound other than the epoxy (meth)acrylate (A) and the urethane (meth)acrylate (B3-1) having three or more (meth)acryl groups in one molecule, preferably a compound having 3 to 8 (meth)acryl groups. As the multifunctional (meth)acrylate (B3-2), for example, trihydroxymethylpropane tri(meth)acrylate, ethylene oxide-modified trihydroxymethylpropane tri(meth)acrylate, propylene oxide-modified trihydroxymethylpropane tri(meth)acrylate, di-trihydroxymethylpropane tri(meth)acrylate, di-trihydroxymethylpropane tetra(meth)acrylate, 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, etc. can be used. These compounds can be used alone or in combination of two or more.

As the above (B3-2), in terms of obtaining better scratch resistance, it is more preferred to use one or more compounds selected from the group consisting of tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate and pentaerythritol tri(meth)acrylate, and more preferably pentaerythritol tetra(meth)acrylate and pentaerythritol tri(meth)acrylate. These compounds may be used alone or in combination of two or more.

The content of the compound (B3) having three or more (meth)acryloyl groups in the molecule is preferably in the range of 10% to 80% by mass, more preferably in the range of 15% to 70% by mass, and particularly preferably in the range of 30% to 60% by mass, relative to the total amount of the radical polymerizable compound in the active energy ray-curable composition. By setting the content in the above range, the transparency and anti-glare properties of the cured coating can be improved in a well-balanced manner.

[Compound (B4) having two (meth)acryloyl groups in the molecule] The composition of the present invention may also contain a compound (B4) having two (meth)acryloyl groups in the molecule. Wherein, compound (B4) is a compound that does not correspond to any of (A), (B1), and (B2). Examples of the compound (B4) having two (meth)acryloyl groups in the molecule include: 1,4-butanediol di(meth)acrylate, 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-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, Di(meth)acrylates of diols such as acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, and tripropylene glycol di(meth)acrylate; di(meth)acrylates of polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and tri(2-hydroxyethyl)isocyanurate; di(meth)acrylates of diols obtained by adding 4 or more mols of ethylene oxide or propylene oxide to 1 mol of neopentyl glycol; di(meth)acrylates of diols obtained by adding 2 mols of ethylene oxide or propylene oxide to 1 mol of bisphenol A, etc.

[Organic fine particles (C)] The organic fine particles (C) used in the present invention are used to impart anti-glare properties to the surface of the cured coating film by generating irregularities. The organic fine particles (C) are not particularly limited as long as they are insoluble in either the solvent or the radical polymerizable compound in the active energy ray-curable composition of the present invention and have a lower affinity for water than the radical polymerizable compound. In particular, in terms of having a low affinity for either the radical polymerizable compound or water and having the aggregates of the polymerized resin fine particles uniformly dispersed in the radical polymerizable compound, preferably, the polymerized resin fine particles are a dispersion of polymerized resin fine particles obtained by polymerization in water in the presence of a surfactant such as a dispersant, a stabilizer, or an emulsifier, or polymerized resin fine particles having a surfactant attached to the surface of particles obtained by separating and drying the dispersion. The polymer resin microparticles obtained by these methods generally have the surfactant washed away, but it cannot be completely washed away and remains on the surface of the particles, so the affinity for water is lower than that of free radical polymerizable compounds.

As the organic microparticles (C), for example, spherical microparticles formed by crosslinked polymers such as polyurethane microparticles, (meth)acrylic resin microparticles, styrene resin microparticles, benzoguanine resin microparticles, melamine resin microparticles, and formaldehyde resin microparticles can be used. Among them, (meth)acrylic microparticles are preferred due to their excellent solvent resistance and hardness.

In the present invention, since the organic fine particles (C) aggregate into secondary particles and form a concavoconvex surface, the average primary particle size is not particularly limited as long as it is less than the film thickness of the cured coating containing the composition of the present invention. In particular, when the cured film thickness is considered, it is 0.1 μm to 30 μm, but when the cured film thickness is assumed to be a normal cured film thickness, such as a cured film thickness of about 5 μm to 30 μm, it is preferably 0.1 μm to 15 μm, more preferably 0.2 μm to 10 μm, and most preferably 0.5 μm to 3 μm. By setting the average primary particle size to these ranges, it is possible to form tiny and finely spaced concavoconvex surfaces, so that an active energy ray-curable composition capable of forming a cured coating with excellent transparency and anti-glare properties can be obtained. In addition, the organic fine particles (C) may be transparent fine particles, cloudy fine particles, colored fine particles, etc. as needed. In addition, even when the film thickness of the cured coating film containing the active energy ray-curable composition is thinner than the average particle size of the organic fine particles (C), the organic fine particles having a particle size smaller than the film thickness of the cured coating film will aggregate into secondary particles and appear on the surface of the coating film, thereby enhancing the effect of making the coating film surface uneven and reducing the reduction in transparency.

In the present invention, the average primary particle size of the organic fine particles (C) refers to an average primary particle size measured by a laser diffraction particle size distribution measuring device using a laser analysis scattering method.

The active energy ray-curable composition of the present invention can improve both anti-glare and transparency by adjusting the balance of the hydrophilicity of each component. For example, component (A) has a hydroxyl group derived from an epoxy group, compound (B1) contains a urate skeleton, and compound (B2) contains a carboxyl group, so components (A) and (B) are hydrophilic. On the other hand, component (C) is hydrophobic. Therefore, it is believed that the active energy ray-curable composition of the present invention undergoes phase separation due to the difference in hydrophilicity of each component, and component (C) easily aggregates into secondary particles, thereby improving the transparency and anti-glare of the cured coating.

Therefore, the content of the organic fine particles (C) is preferably in the range of 1 to 10 parts by mass, more preferably in the range of 2 to 8 parts by mass, and particularly preferably in the range of 3 to 5 parts by mass, relative to 100 parts by mass of the total of the epoxy (meth)acrylate (A) and the multifunctional (meth)acrylate (B). By setting the content in these ranges, an appropriate concavoconvex shape is obtained, and an active energy ray-curable composition capable of forming a cured coating film having excellent transparency and anti-glare properties can be obtained.

[Other components] The active energy ray-curable composition of the present invention must contain components (A) to (C), but may also contain a photopolymerization initiator, a photosensitizer, a monofunctional (meth)acrylate compound that is not compatible with component (A), other additives, etc., as necessary.

The active energy ray-curable composition of the present invention can be formed into a cured coating by irradiating active energy rays after being applied to a substrate. The active energy rays refer to ionizing rays such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When the cured coating is formed by irradiating ultraviolet rays as active energy rays, it is preferred to add a photopolymerization initiator to the active energy ray-curable composition of the present invention to improve the curability. In addition, if necessary, a photosensitizer may be further added to improve the curability. On the other hand, when ionizing rays such as electron beams, α rays, β rays, and γ rays are used, the composition will cure quickly even without using a photopolymerization initiator or photosensitizer, so there is no need to specifically add a photopolymerization initiator or photosensitizer.

As the photopolymerization initiator, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, oligo{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone}, benzyl dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-oxo-1-[4-(1-methylvinyl)phenyl]propanone, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 2-methyl-2-oxo-1-[4-(1-methylvinyl)phenyl]propanone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-oxo-1-[4-(1-methylvinyl)phenyl]propanone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1- ...1-hydroxycyclohexylphenyl ketone, 1-hydroxycyclohexylphenyl ketone, 1-hydroxycyclohexylphenyl ketone, 1-hydroxycyclohexylphenyl ketone, 1-hydroxycyclohexylphenyl ketone, 1-hydroxycyclohexylphenyl ketone, 1- Acetophenone compounds such as benzoin, benzoin methyl ether, benzoin isopropyl ether, etc.; acyl phosphine oxide compounds such as 2,4,6-trimethylbenzoin diphenylphosphine oxide and bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide; benzoyl (biphenylformyl), methylphenyl glyoxylate, oxyphenylacetic acid 2-(2-hydroxyethoxy)ethyl ester, oxyphenylacetic acid benzoyl compounds such as 2-(2-oxo-2-phenylacetyloxyethoxy)ethyl ester; benzophenone, 4-phenylbenzoylbenzoylmethyl-4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, Benzophenone compounds such as benzophenone; 2-isopropylthiothione, 2,4-dimethylthiothione, 2,4-diethylthiothione, 2,4-dichlorothiothione; aminobenzophenone compounds such as michler's ketone and 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, 1-[4-(4-benzoylphenylthio)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propane-1-one, etc. These photopolymerization initiators may be used alone or in combination of two or more.

In addition, as the photosensitizer, for example, tertiary amine compounds such as diethanolamine, N-methyldiethanolamine, and tributylamine, urea compounds such as o-tolylthiourea, sulfur compounds such as diethyldithiophosphate, and s-benzylisothiouronium-p-toluenesulfonate, etc. can be used.

The amount of the photopolymerization initiator and photosensitizer used is preferably in the range of 0.05 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the total amount of the radical polymerizable compound in the active energy ray-curable composition.

Examples of the monofunctional (meth)acrylate compound include benzyloxyethyl (meth)acrylate, benzyl (meth)acrylate, phenylethyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-phenyl-2-(4-acryloxyphenyl)propane, 2-phenyl-2-(4-(meth)acryloxyphenyl)propane, 2-phenyl-2-(4-(meth)acryloxyethoxyphenyl)propane, 2-phenyl-2-(4-(meth)acryloyloxypropoxyphenyl)propane, chlorophenyl (meth)acrylate, bromophenyl (meth)acrylate, chlorobenzyl (meth)acrylate, bromobenzyl (meth)acrylate, chlorophenyl ethyl (meth)acrylate, bromophenyl ethyl (meth)acrylate, chlorophenoxyethyl (meth)acrylate, bromophenoxyethyl (meth)acrylate, 2,4,6-trichlorophenyl (meth)acrylate, 2,4,6-tribromophenyl (meth)acrylate, 2,4,6-trichlorobenzyl (meth)acrylate Monofunctional (meth)acrylates having an aromatic ring such as 2,4,6-tribromobenzyl (meth)acrylate, 2,4,6-trichlorophenoxyethyl (meth)acrylate, 2,4,6-tribromophenoxyethyl (meth)acrylate, o-phenylphenol (poly)ethoxy (meth)acrylate, and p-phenylphenol (poly)ethoxy (meth)acrylate; cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tetrahydrofuran (meth)acrylate (Meth)acrylates having an alicyclic alkyl group such as furfuryl ester and glycidyl cyclocarbonate (meth)acrylate; (meth)acrylates having an alkyl group having 1 to 22 carbon atoms such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, and stearyl (meth)acrylate; styrene compounds such as styrene, α-methylstyrene, and chlorostyrene, etc.

As the other additives, for example, solvents, polymerization inhibitors, surface conditioners, antistatic agents, defoamers, viscosity adjusters, light stabilizers, weather stabilizers, heat stabilizers, ultraviolet absorbers, antioxidants, leveling agents, organic pigments, inorganic pigments, pigment dispersants, additives other than component (C), such as microparticles; inorganic fillers such as silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, antimony pentoxide, etc. These additives can be used alone or in combination of two or more. Among these, microparticles are preferably used in terms of obtaining a better anti-glare property.

As the fine particles, for example, inorganic fine particles such as spherical silica and amorphous silica can be used.

The particle size of the microparticles is preferably in the range of 0.5 μm to 5 μm, more preferably in the range of 0.8 μm to 3.5 μm, and further preferably in the range of 1.0 μm to 2.5 μm, in terms of high cohesion and better anti-glare properties. In addition, the particle size of the microparticles indicates the particle size when the cumulative amount accounts for 50% in the cumulative particle amount curve of the particle size distribution measurement result in the particle size distribution.

The amount of the fine particles used is preferably in the range of 0.5% by mass to 15% by mass, more preferably in the range of 1% by mass to 7% by mass in the active energy ray-curable composition in order to obtain a more excellent anti-glare property.

As the solvent, for example, methanol, ethanol, propanol, butanol, diacetone alcohol, isopropyl alcohol, diacetone alcohol, dimethyl carbitol, methyl acetate, ethyl acetate, propyl acetate, dimethyl carbonate, methyl ethyl ketone, methyl isobutyl ketone, acetone, acetylacetone, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether, toluene, etc. can be used. These solvents can be used alone or in combination of two or more. Among these, isopropyl alcohol is preferably used in terms of obtaining better transparency and anti-glare properties.

When the solvent is used, the amount used is preferably in the range of 40% by mass to 80% by mass in the active energy ray-curable composition from the viewpoint of coating properties and the like.

<Cured Product> The cured product of the present invention is obtained by irradiating the active energy ray-curable composition of the present invention with active energy rays to cure it, and may be in any shape such as a film or a three-dimensional object.

As mentioned above, the active energy rays for curing the active energy ray-curable composition of the present invention are ionizing rays such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Here, when ultraviolet rays are used as the active energy rays, the devices for irradiating the ultraviolet rays include, for example, 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, solar light, and light emitting diode (LED) lamps.

<Film> The film of the present invention is obtained by applying the active energy ray-curable composition of the present invention to at least one side of a film substrate and then irradiating the film with active energy rays to form a cured coating.

The material of the film substrate used in the film of the present invention is preferably a highly transparent resin, for example, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.; polyolefin resins such as polypropylene, polyethylene, polymethylpentene-1, etc.; cellulose resins such as cellulose acetate (diacetyl cellulose, triacetyl cellulose, etc.), cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, cellulose acetate phthalate, cellulose nitrate, etc.; acrylic resins such as polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, etc. Vinyl chloride resins such as ethylene; polyvinyl alcohol; ethylene-vinyl acetate copolymers; polystyrene; polyamide; polycarbonate; polysulfone; polyethersulfone; polyetheretherketone; polyimide resins such as polyimide and polyetherimide; norbornene resins (e.g., "Zeonor" manufactured by ZEON Co., Ltd. of Japan), modified norbornene resins (e.g., "Arton" manufactured by JSR Co., Ltd.), cyclic olefin copolymers (e.g., "Apel" manufactured by Mitsui Chemicals Co., Ltd.), etc. Furthermore, a substrate formed by laminating two or more substrates containing these resins may also be used.

Furthermore, in the present invention, by using the active energy ray-curable composition, even when triacetyl cellulose is used as the film substrate, a hard coating layer having excellent anti-glare properties and transparency can be formed.

The film substrate may be in the form of a film or a sheet, and its thickness is, for example, in the range of 20 μm to 500 μm. In addition, when a film-shaped substrate film is used, its thickness is preferably in the range of 20 μm to 200 μm, more preferably in the range of 30 μm to 150 μm, and further preferably in the range of 40 μm to 130 μm. By setting the thickness of the film substrate in the above range, even when a hard coating layer is provided on one side of the film using the active energy ray-curable composition of the present invention, curling can be easily suppressed.

Examples of methods for applying the active energy ray-curable composition of the present invention to the film substrate include die coating, micro-gravure coating, gravure coating, roller coating, notch wheel coating, air knife coating, kiss coating, spray coating, dip coating, rotary coating, brush coating, full screen coating using a wire mesh, wire rod coating, and flow coating.

In order to volatilize the solvent after applying the active energy ray-curable composition on the substrate film and before irradiating the active energy ray, it is preferably dried by heating or at room temperature. As the conditions for heat drying, for example, the temperature ranges from 50°C to 100°C and the time ranges from 0.5 minutes to 10 minutes.

In order to make the hardness of the cured coating film sufficient and to suppress the curling of the film due to the curing shrinkage of the coating film, the film thickness of the cured coating film when the cured coating film of the active energy ray-curable composition of the present invention is formed on the film substrate is preferably in the range of 1 μm to 30 μm, more preferably in the range of 3 μm to 15 μm, and further preferably in the range of 4 μm to 10 μm.

As described above, the active energy ray-curable composition of the present invention can form a hard coating layer excellent in coating stability, coating film appearance, anti-glare property and transparency on various substrates including polymethyl methacrylate substrates.

Therefore, a film having a hard coating layer including a cured coating film of the active energy ray-curable composition of the present invention can be suitably used as an optical film used in flat panel displays (FPD) such as liquid crystal displays (LCDs), organic EL displays (OLEDs), and plasma displays (PDPs).

[Example] The present invention will be described in more detail below through examples.

[Example 1] 40 parts by mass of a multifunctional monomer (a mixture of pentaerythritol tetraacrylate and pentaerythritol triacrylate), 80 parts by mass of epoxy acrylate (a methyl isobutyl ketone solution of a reaction product of polyglycidyl methacrylate and acrylic acid, solid content 50%), 152.5 parts by mass of isocyanuric acid EO-modified diacrylate, a mixed solvent (dimethyl carbonate/MIBK/IPA/propyl acetate/1-butanol/toluene/acetone = 27.9/4.5/47.1/12.5/5.0/25.4/30.1), and 5 parts by mass of a photoinitiator (1-hydroxycyclohexyl phenyl ketone) were fully mixed, and then 3.3 parts of organic microparticles were added to prepare an active energy ray-curable composition having a non-volatile component content of 36% by mass.

[Example 2 to Example 4 and Comparative Example 1 to Comparative Example 5] Except for changing the formulation to that shown in Table 1, the same procedure as in Example 1 was followed to prepare an active energy ray-curable composition, and then an evaluation film was prepared and evaluated.

[Preparation of evaluation samples] The active energy ray-curable composition was applied to a 60 μm thick triacetyl cellulose film (manufactured by Fuji Film Co., Ltd.) using a bar coater to a film thickness of 5 μm. After drying at 60°C for 1 minute, the film was irradiated twice in a nitrogen atmosphere using an ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd., high-pressure mercury lamp) at an irradiation dose of 75 mJ/ ^m2 to obtain a triacetyl cellulose film with a cured coating as an evaluation sample.

[Evaluation of haze] The obtained evaluation film was measured using a haze meter ("NDH4000" manufactured by Nippon Denshoku Co., Ltd.) under D65 light source in accordance with Japanese Industrial Standards (JIS) K7136. The smaller the haze value, the better the anti-glare property, and the range of 1.0±0.5% was set as acceptable.

[Evaluation of total light transmittance] The obtained evaluation film was measured in accordance with JIS K7361-1. The higher the total light transmittance, the higher the transparency, and 90% or more was considered acceptable.

[Evaluation of transparency] In accordance with JIS K7374, the obtained evaluation film was measured at four points of light comb width: 0.125 mm, 0.5 mm, 1.0 mm, and 2.0 mm using an image measuring instrument ("ICM-1T" manufactured by Suga Testing Instruments Co., Ltd.). The total value of the measured four points was used for evaluation. If the total value is high, the anti-glare property is too weak, and if it is low, the anti-glare property is too strong and the visibility of the screen is reduced, so the range of 310%-340% is set as acceptable.

[Evaluation results] The results are shown in Table 1.

[Table 1] Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Comparison Example 1 Comparison Example 2 Comparison Example 3 Comparison Example 4 Comparison Example 5 Photopolymerization initiator 5 5 5 5 5 5 5 5 5 (A) Ingredients Epoxy Acrylate (1) 40 35 20 20 20 20 20 20 20 (B) Ingredients Compound (B1) M215 20 10 40 Compound (B2) M510 40 Compound (B3) M305 40 55 40 40 40 40 40 40 40 M309 40 M360 40 M408 40 MT3547 40 M450 40 Organic microparticles 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 Reviews Fog (%) 1.3 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Total light transmittance (%) 92.1 92.1 92.1 92.1 92.1 92.1 92.1 92.1 92.1 Transparent clarity (%) 310 335 315 325 363 352 360 348 356

The abbreviations in the table are as follows. R-1104: 1-Hydroxycyclohexylphenyl ketone, manufactured by RUNTEC Chemical under the trade name "RUNTECURE 1104" [(A) component] Epoxy acrylate (1): Methyl isobutyl ketone solution of the reaction product of poly(glycidyl methacrylate) and acrylic acid (solid content 50%), viscosity 1000 mPa·s [(B) component] M215: Isocyanuric acid EO-modified diacrylate, manufactured by Toagosei under the trade name "Aronix M-215" M510: Polyacid-modified acrylic acid oligomer (containing carboxyl group), acid value 80 mgKOH/g-120 mgKOH/g, manufactured by Toagosei under the trade name "Aronix M-510" M305: Pentaerythritol tetraacrylate (containing 55%-63% pentaerythritol triacrylate), manufactured by Toa Gosei Co., Ltd. under the trade name "Aronix M-305" M309: Trihydroxymethylpropane triacrylate, manufactured by Toa Gosei Co., Ltd. under the trade name "Aronix M-309" M360: Trihydroxymethylpropane EO-modified triacrylate (EO modification number n=2), manufactured by Toa Gosei Co., Ltd. under the trade name "Aronix M-360" M408: Di-trihydroxymethylpropane tetraacrylate, manufactured by Toa Gosei Co., Ltd. under the trade name "Aronix M-408" MT3547: Glycerol triacrylate, manufactured by Toa Gosei Co., Ltd. under the trade name "Aronix MT-3547" M450: Pentaerythritol tetraacrylate, manufactured by Toa Gosei Co., Ltd. under the trade name "Aronix M-450" [(C) ingredient] Organic microparticles: cross-linked acrylic acid monodisperse particles, average primary particle size 1.5 nm, refractive index 1.49

From the evaluation results shown in Table 1, it was found that the cured coating films of the active energy ray-curable composition of the present invention in Examples 1 to 4 had excellent transparency and anti-glare properties.

On the other hand, Comparative Examples 1 to 5 shown in Table 1 are in a form that does not contain either the compound (B1) or the compound (B2), and although the transmission clarity is improved, the anti-glare property is poor.

without

without.

without.

Claims (7)

An active energy ray-curable composition comprising: epoxy (meth)acrylate (A), other multifunctional (meth)acrylate (B), and organic microparticles (C), The multifunctional (meth)acrylate (B) contains at least one of a compound (B1) having a urate skeleton in the molecule or a compound (B2) having a carboxyl group in the molecule. The active energy ray-curable composition according to claim 1, wherein the epoxy (meth)acrylate (A) is a reaction product of polyglycidyl methacrylate and acrylic acid. The active energy ray-curable composition as described in claim 1, wherein the multifunctional (meth)acrylate (B) further contains a compound (B3) having three or more (meth)acryloyl groups in the molecule, the compound (B3) is different from the compound (B1) and the compound (B2). The active energy ray-curable composition according to claim 1, wherein the average primary particle size of the organic fine particles (C) is in the range of 0.5 μm to 3 μm. The active energy ray-curable composition according to claim 1, wherein the content of the organic fine particles (C) is in the range of 1 to 10 parts by mass relative to 100 parts by mass of the total of the epoxy (meth)acrylate (A) and the multifunctional (meth)acrylate (B). A cured product is a cured product of the active energy ray-curable composition according to any one of claims 1 to 5. A film characterized by comprising a cured coating film of the active energy ray-curable composition according to any one of claims 1 to 5.