KR20240043703A - 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 capable of forming a cured coating film having excellent anti-glare properties and transparency.
The present invention contains an organic fine particle dispersion (A) and an epoxy (meth)acrylate (B), and the organic fine particle dispersion (A) includes organic fine particles (a-1) and a dispersant (a-2). and an active energy ray-curable composition in which the dispersant (a-2) is an alkanolamine-based compound, a cured product using the same, and a film are provided.

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 coat layer.

Resin films are used to prevent damage to the surface of flat panel displays (FPDs) such as liquid crystal displays (LCDs), organic EL displays (OLEDs), and plasma displays (PDPs), decorative films (sheets) for the interior and exterior of automobiles, and films for windows. It is used for various purposes such as reflective film and heat cut film. However, since the surface of the resin film is soft and has low scratch resistance, in order to compensate for this, it is generally common to form a hard coat layer on the film surface by coating and curing a hard coat agent made of an active energy ray curable composition or the like on the film surface. It is being done.

Particularly in the field of optical components typically used for displays, if the glossiness of the display surface is high, the reflection of light from the product surface may be too large, causing inconvenience. Therefore, it is required to place an anti-glare film or an anti-glare anti-reflection film having an anti-glare function on the outermost surface of the display. As an anti-glare film, there is a known technique of diffusing light by using an active energy ray-curable composition containing particles with an average particle size of microns and forming appropriate irregularities on the surface of the coating film obtained after curing.

As such an anti-glare film, it is known that a coating liquid containing microparticles having a convex shape on the surface (convex surface particles) and a resin, etc., in which microparticles are adhered to the surface of the core particle, is cured (Patent Document 1).

Since the surface convex-shaped particles described in Patent Document 1 use inorganic fine particles for at least one of the core particles and the fine particles, problems in affinity between the cured resin layer and the particle interface and transparency of the film were considered. Therefore, an active energy ray-curable resin composition was developed that can provide excellent anti-glare properties by using organic fine particles and further reduces transparency and adhesion to the substrate with little decrease (Patent Document 2).

However, the cured coating film obtained from the composition described in the example of Patent Document 2 has a minimum haze value of 2.4%, and transmission clarity is not disclosed. Therefore, there was another challenge in achieving both transparency and anti-glare properties.

Japanese Patent Publication No. 2005-4163 Japanese Patent Publication No. 2005-272582

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.

As a result of intensive research to solve the above problems, the present inventors discovered that by mixing a compound having a specific structure and organic fine particles, an active energy ray-curable composition capable of forming a cured coating film with excellent anti-glare properties and transparency was obtained. , completed the present invention.

That is, the present invention relates to the inventions described in [1] to [8] below.

[1] Contains organic fine particle dispersion (A) and epoxy (meth)acrylate (B),

The organic fine particle dispersion (A) contains organic fine particles (a-1) and a dispersant (a-2),

An active energy ray-curable composition wherein the dispersant (a-2) is an alkanolamine-based compound.

[2] The active energy ray-curable composition according to [1], wherein the organic fine particles (a-1) have an average primary particle diameter in the range of 0.5 to 3 μm.

[3] The active energy ray-curable composition according to [1] or [2], wherein the dispersant (a-2) has an amine value of 80 mgKOH/g or more.

[4] The active energy ray-curable composition according to any one of [1] to [3], wherein the epoxy (meth)acrylate (B) is a reaction product of polyglycidyl methacrylate and acrylic acid.

[5] The active energy ray-curable composition according to any one of [1] to [4], further comprising a polyfunctional (meth)acrylate (C) different from the epoxy acrylate (B).

[6] The active energy ray-curable composition according to [5], wherein the polyfunctional (meth)acrylate (C) is a compound having a nurate skeleton in the molecule.

[7] A cured product of the active energy ray curable composition according to any one of [1] to [6].

[8] A film characterized by having a cured coating film of the active energy ray curable composition according to any one of [1] to [6].

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

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

<Active energy ray curable composition>

The active energy ray-curable composition (hereinafter sometimes simply referred to as “composition”) of the present invention contains organic fine particle dispersion (A) and epoxy (meth)acrylate (B) as essential components.

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. , “(meth)acrylic” refers to one or both of acrylic and methacrylic. In addition, the organic fine particle dispersion (A) is sometimes simply referred to as component (A), and the same applies to other components.

＜＜Organic fine particle dispersion (A)＞＞

The organic fine particle dispersion (A) in the composition of the present invention contains at least organic fine particles (a-1) and a dispersant (a-2), and the dispersant (a-2) is an alkanolamine-based compound.

＜＜＜Organic fine particles (a-1)＞＞＞

The organic fine particles (a-1) used in the present invention are used to create irregularities on the surface of the cured coating film and provide anti-glare properties, and are insoluble in both the solvent and the radical polymerizable compound in the active energy ray curable composition of the present invention. ), and is not particularly limited, as long as it is an organic fine particle with a lower affinity for water than the radical polymerizable compound, but among them, a dispersion of polymerized resin fine particles obtained by polymerizing in water in the presence of surfactants such as dispersants, stabilizers, and emulsifiers. However, the polymerized resin fine particles obtained by separating and drying from this dispersion and having a surfactant attached to the particle surface have low affinity for both the radical polymerizable compound and water, and the aggregates of the polymerized resin fine particles are uniformly dispersed in the radical polymerizable compound. It is desirable in that respect. Polymerized resin fine particles obtained by these methods are generally washed to remove the surfactant, but since the surfactant cannot be completely washed away and remains on the particle surface, it has a lower affinity for water than a radically polymerizable compound.

Examples of the organic fine particles (a-1) include spherical cross-linked polymers such as polyurethane-based fine particles, (meth)acrylic resin-based fine particles, styrene resin-based fine particles, benzoguanine resin-based fine particles, melamine resin-based fine particles, and formaldehyde resin-based fine particles. Fine particles, etc. can be used, and among them, (meth)acrylic fine particles are preferable from the viewpoint of excellent solvent resistance and hardness.

In the present invention, since the organic fine particles (a-1) are aggregated into secondary particles to form an uneven surface, the average primary particle size may be less than or equal to the film thickness of the cured coating film made of the composition of the present invention and is not particularly limited. However, especially when considering the case where the cured film thickness is thick, it is 0.1 to 30 μm, but when assuming a normal cured film thickness, for example, about 5 to 30 μm, 0.1 to 15 μm is preferable, and more preferably 0.2 to 10 μm, most preferably 0.5 to 3 μm. By setting the average primary particle size within these ranges, an active energy ray-curable composition capable of forming a cured coating film with excellent transparency and anti-glare properties can be obtained.

In addition, the organic fine particles (a-1) may be transparent, cloudy, colored, etc., as needed. Furthermore, even when the film thickness of the cured coating film made of the active energy ray-curable composition is thinner than the average particle diameter of the organic fine particles (a-1), organic fine particles with a particle size smaller than the film thickness of the cured coating film aggregate and secondary particles form. Since it comes out on the surface of the coated film, the effect of causing irregularities on the surface of the coated film is improved and the decrease in transparency can also be reduced.

In the present invention, the average primary particle size of the organic fine particles (a-1) refers to the average primary particle size measured by a laser diffraction particle size distribution measuring device using a laser analysis scattering method.

Therefore, the content of the organic fine particles (a-1) is preferably in the range of 0.5 to 20% by mass, more preferably in the range of 1 to 15% by mass, and 3 to 10% by mass in the solid content of the composition. It is particularly preferable that By setting these ranges, an active energy ray-curable composition capable of forming a cured coating film excellent in transparency and anti-glare properties can be obtained.

In addition, the solid content of the composition refers to the total of all components other than the solvent in the composition.

＜＜＜Dispersant (a-2)＞＞＞

The dispersant (a-2) is not particularly limited as long as it is an alkanolamine-based compound containing all of an alkyl group, a hydroxyl group, and an amino group in one molecule, and various known compounds can be used.

As the dispersant (a-2), for example, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, methylethanolamine, methylisopropanolamine, methyldiethanolamine, methyldiethanolamine. Isopropanolamine, diethanolisopropanolamine, diisopropanolethanolamine, tetrahydroxyethylethylenediamine, N,N-bis(2-hydroxyethyl)2-propanolamine, N,N-bis(2-hydroxypropyl)- N-(hydroxyethyl)amine, N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine, N,N,N',N'-tetrakis(2-hydroxy Propyl) Alkanolamines such as ethylenediamine and tris(2-hydroxybutyl)amine; Alkanolamines having an amide bond that is a reaction product between any alkanolamine and an unsaturated fatty acid; Alkanes such as polymers having a skeleton of triisopropanolamine Alkanolamines with a structure in which part of the amine is bonded to a polymer; (meth)acrylic acid, crotonic acid, phosphoric acid ester, vinyl sulfonate, (meth)allyl sulfonate, 2-methylpropanesulfonic acid (meth)acrylamide, styrene Alkanolamine salts such as sulfonic acids (for example, alkanolamine salts such as ethanolamine salts, diethanolamine salts, triethanolamine salts, dibutylaminoethanol salts, and triisopropanolamine salts).

The amine value of the dispersant (a-2) is preferably 80 mgKOH/g or more and 200 mgKOH/g or less, more preferably 85 mgKOH/g or more and 180 mgKOH/g or less, and especially preferably 90 mgKOH/g or more and 150 mgKOH/g or less. By setting these ranges, an active energy ray-curable composition capable of forming a cured coating film excellent in transparency and anti-glare properties can be obtained.

The active energy ray-curable composition of the present invention was able to improve both anti-glare properties and transparency by adjusting the balance of hydrophilicity of each component. More specifically, phase separation is promoted between the hydrophobic organic fine particles (a-1) and the dispersant (a-2), which is a hydrophilic alkanolamine-based compound, and the organic fine particles (a-1) aggregate into secondary particles. It is thought that the transparency and anti-glare properties of the cured coating film are improved by the adsorption of the dispersant (a-2) on the surface of the secondary aggregate.

＜＜Epoxy (meth)acrylate (B)＞＞

As epoxy (meth)acrylate (B), 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 may be used individually or two or more types may be used in combination. Among these, it is preferable to use (meth)acrylic acid from the viewpoint of scratch resistance.

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 dil ether; Epoxy compounds having a hydrogenated phthalic acid skeleton; glycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl Compounds having an epoxy group such as (meth)acrylate and a (meth)acryloyl group can be used. These compounds may be used individually, two or more types may be used in combination, and polymers thereof may be used. Among these, from the viewpoint of scratch resistance, it is preferable to use an epoxy group and a (meth)acrylic compound, and it is more preferable to use polyglycidyl (meth)acrylate, which is a polymer of glycidyl (meth)acrylate.

When using a polymer of the epoxy compound as a raw material for the epoxy (meth)acrylate (B), a solvent may be used together from the viewpoint of viscosity adjustment. As the solvent, for example, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, etc. can be used. These solvents may be used individually or two or more types may be used in combination. The content when using the solvent is preferably in the range of 50 to 150 parts by mass with respect to 100 parts by mass of epoxy (meth)acrylate (B).

In the case of using a polymer of the above-mentioned epoxy compound as a raw material of the above-mentioned epoxy (meth)acrylate (B), the viscosity of the above-mentioned epoxy (meth)acrylate (B) containing a solvent is equal to the viscosity at the time of forming the hard coat layer. From the point that coating stability can be further improved, the range of 100 to 3,000 mPa·s is preferable, and the range of 150 to 2,000 mPa·s is more preferable. Additionally, the viscosity represents the value measured using a B-type viscometer.

The content of epoxy (meth)acrylate (B) is preferably in the range of 10 to 80% by mass, and preferably in the range of 15 to 50% by mass, relative to the total amount of radically polymerizable compounds in the active energy ray curable composition. And it is particularly preferable that it is in the range of 20 to 40 mass%. By setting it within this range, both transparency and anti-glare properties of the cured coating film can be improved in a good balance.

The active energy ray-curable composition of the present invention may contain polyfunctional (meth)acrylate (C) other than epoxy (meth)acrylate (B).

＜＜Multifunctional (meth)acrylate (C)＞＞

By containing polyfunctional (meth)acrylate (C), the hardness of the cured product is improved.

As polyfunctional (meth)acrylate (C), trimethylolpropane tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, and ditrimethyl. All-propane tri(meth)acrylate, ditrimethylolpropane 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.

Also, as the polyfunctional (meth)acrylate (C), for example, urethane (meth)acrylate can be used. Examples of urethane (meth)acrylate include reaction products of polyisocyanate and (meth)acrylate having a hydroxyl group.

Examples of the polyisocyanate include aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate; norbornane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexylisocyanate), 1,3 -Alicyclic polyisocyanates such as bis(isocyanatomethyl)cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, and 2-methyl-1,5-diisocyanatocyclohexane; toluenedi Aromatic polyisocyanates such as isocyanate, xylene diisocyanate, and diphenylmethane diisocyanate can be used. These polyisocyanates may be used individually or two or more types may be used in combination.

The (meth)acrylate having a hydroxyl group is one having a hydroxyl group and a (meth)acryloyl group, for example, trimethylolpropane di(meth)acrylate, ethylene oxide (EO) modified trimethylolpropane (meth)acrylate. Trivalent compounds such as trimethylolpropane di(meth)acrylate, propylene oxide (PO)-modified trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, and bis(2-(meth)acryloyloxyethyl)hydroxyethyl isocyanurate. Mono- or di(meth)acrylates of alcohols, or mono- and di(meth)acrylates with hydroxyl groups obtained by modifying some of these alcoholic hydroxyl groups into ε-caprolactone; pentaerythritol tri(meth)acrylate, pentaerythate Compounds having a monofunctional hydroxyl group and a trifunctional or higher (meth)acryloyl group such as ritol tetra(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, or , polyfunctional (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, polypropylene glycol mono(meth)acrylate ) Acrylate, (meth)acrylate having an oxyalkylene chain, such as polyethylene glycol mono(meth)acrylate; polyethylene glycol-polypropylene glycol mono(meth)acrylate, polyoxybutylene-polyoxypropylene mono(meth) (meth)acrylate having an oxyalkylene chain in a block structure such as acrylate; poly(ethylene glycol-tetramethylene glycol) mono(meth)acrylate, poly(propylene glycol-tetramethylene glycol) mono(meth)acrylate, etc. (meth)acrylate having an oxyalkylene chain of random structure, etc.

In addition to polyisocyanate and (meth)acrylate having a hydroxyl group, urethane (meth)acrylate may use polyol as a reaction raw material.

As the polyol, for example, polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; polyester polyol, polycarbonate polyol, etc. can be used. These polyols may be used individually or two or more types may be used in combination.

Among polyfunctional (meth)acrylates (C), compounds having a nurate skeleton can also be used. For example, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, bis(2-hydroxyethyl) Isocyanurate di(meth)acrylate, and hydroxyethyl(meth)acrylate, which is the starting material for these compounds, are reacted with ethylene oxide (EO), propylene oxide, or ε-capro of hydroxyethyl(meth)acrylate. Isocyanuric acid derivatives such as compounds changed to lactone modifications, urethane (meth)acrylate having a nurate skeleton, etc. are included. Among them, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate is particularly preferable. Since tris(2-hydroxyethyl)isocyanurate di(meth)acrylate has a polar structure of a hydroxyl group and a nurate skeleton, it promotes aggregation of hydrophobic organic fine particles (a-1) and provides anti-glare properties. can be further improved.

These polyfunctional (meth)acrylates (C) may be used individually or two or more types may be used in combination.

The content of polyfunctional (meth)acrylate (C) is preferably in the range of 20 to 85% by mass, and 30 to 80% by mass, relative to the total amount of radically polymerizable compounds in the active energy ray-curable composition. It is preferable, and it is especially preferable that it is in the range of 50 to 70 mass%. By setting it within this range, both transparency and anti-glare properties of the cured coating film can be improved in a good balance.

[Other ingredients]

In addition to components (A) to (C), the active energy ray-curable composition of the present invention may contain a photopolymerization initiator, a photosensitizer, a monofunctional (meth)acrylate compound, other additives, etc., as needed.

The active energy ray-curable composition of the present invention can be formed into a cured coating film by applying it to a substrate and then irradiating it with active energy rays. These active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, α-rays, β-rays, and γ-rays. When forming a cured coating film by irradiating ultraviolet rays as an active energy ray, it is preferable to add a photopolymerization initiator to the active energy ray curable composition of the present invention to improve curability. Additionally, if necessary, a photosensitizer may be added to improve curability. On the other hand, when using ionizing radiation such as electron beams, α-rays, β-rays, and γ-rays, it is cured quickly without using a photopolymerization initiator or photosensitizer, so there is no need to add a photopolymerization initiator or photosensitizer in particular.

Examples of the photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 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-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino - Acetophenone-based compounds such as 1-(4-morpholinophenyl)-butanone; Benzoin-based compounds such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; 2,4,6-trimethylbenzoindiphenyl Acylphosphine oxide-based compounds such as phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; benzyl(dibenzoyl), methylphenylglyoxyester, oxyphenylacetic acid 2-(2-hydroxy) Benzyl-based compounds such as ethoxy)ethyl ester and oxyphenylacetic acid 2-(2-oxo-2-phenylacetoxyethoxy)ethyl ester; benzophenone, o-benzoylbenzoic acid methyl-4-phenylbenzophenone, 4,4 '-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone , Benzophenone compounds such as 3,3'-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, and 4-methylbenzophenone; 2-isopropylthioxanthone, 2,4-dimethyl Thioxanthone-based compounds such as thioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone; aminobenzophenones such as Michler's ketone and 4,4'-diethylaminobenzophenone Compounds; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl- 2-(4-methylphenylsulfonyl)propan-1-one, etc. can be used. These photopolymerization initiators may be used individually or two or more types may be used in combination.

In addition, examples of the photosensitizer include tertiary amine compounds such as diethanolamine, N-methyldiethanolamine, and tributylamine, urea compounds such as o-tolylthiourea, sodium diethyldithiophosphate, Sulfur compounds such as s-benzylisothiuronium-p-toluenesulfonate can be used.

When using the above photopolymerization initiator and photosensitizer, the usage amount is preferably in the range of 0.05 to 20 parts by mass, respectively, when the total amount of radically polymerizable compounds in the active energy ray curable composition is 100 parts by mass, and 0.5 to 10 parts by mass. The range of mass parts is more preferable.

Monofunctional (meth)acrylate compounds include benzoyloxyethyl (meth)acrylate, benzyl (meth)acrylate, phenylethyl (meth)acrylate, phenoxyethyl (meth)acrylate, and phenoxydiethylene glycol (meth)acrylate. Acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-phenyl-2-(4-acryloyloxyphenyl)propane; 2-phenyl-2-(4-(meth)acrylate 1oxyphenyl)propane, 2-phenyl-2-(4-(meth)acryloyloxyethoxyphenyl)propane, 2-phenyl-2-(4-(meth)acryloyloxypropoxyphenyl)propane, etc. , Chlorophenyl (meth)acrylate, Bromophenyl (meth)acrylate, Chlorobenzyl (meth)acrylate, Bromobenzyl (meth)acrylate, Chlorophenyl ethyl (meth)acrylate, Bromophenylethyl (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, 2,4,6-tribromobenzyl (meth)acrylate, 2,4,6-trichlorophenoxyethyl (meth) ) Acrylate, 2,4,6-tribromophenoxyethyl (meth)acrylate, o-phenylphenol (poly)ethoxy (meth)acrylate, p-phenylphenol (poly)ethoxy (meth)acrylate Monofunctional (meth)acrylate having an aromatic ring such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth) (meth)acrylate having an alicyclic alkyl group such as acrylate, tetrahydrofurfuryl (meth)acrylate, glycidylcyclocarbonate (meth)acrylate; methyl (meth)acrylate, ethyl (meth)acrylate , propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, (meth)acrylates having an alkyl group of 1 to 22 carbon atoms, such as stearyl (meth)acrylate; styrene-based compounds such as styrene, α-methylstyrene, and chlorostyrene, etc. are mentioned.

Examples of the other additives mentioned above include solvents, polymerization inhibitors, surface conditioners, antistatic agents, anti-foaming agents, viscosity modifiers, light-resistant stabilizers, weather-resistant stabilizers, heat-resistant stabilizers, ultraviolet absorbers, antioxidants, leveling agents, organic pigments, and inorganic pigments. , pigment dispersant, and fine particles other than component (a-2); inorganic fillers such as silicon oxide, aluminum oxide, titanium oxide, zirconia, antimony pentoxide, etc. can be used. These additives may be used individually or two or more types may be used in combination. Among these, it is preferable to use fine particles from the viewpoint of obtaining even more excellent anti-glare properties.

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

The particle size of the fine particles is preferably in the range of 0.5 to 5 μm, more preferably in the range of 0.8 to 3.5 μm, and still more preferably in the range of 1.0 to 2.5 μm, from the viewpoint of high cohesion and excellent anti-glare properties. do. In addition, the particle size of the fine particles represents the particle size when the integrated amount accounts for 50% of the integrated particle amount curve of the particle size distribution measurement result.

The amount used when using the above-mentioned fine particles is preferably in the range of 0.5 to 15% by mass, and more preferably in the range of 1 to 7% by mass, based on the active energy ray curable composition, from the viewpoint of obtaining even more excellent anti-glare properties.

Examples of the solvent include 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 may be used individually or two or more types may be used in combination. Among these, it is preferable to use isopropyl alcohol from the viewpoint of obtaining even more excellent transparency and anti-glare properties.

The amount used when using the solvent is preferably in the range of 40 to 80 mass% of the active energy ray curable composition from the viewpoint of coatability and the like.

＜Hardened product＞

The cured product of the present invention is obtained by curing the active energy ray curable composition of the present invention by irradiating active energy rays, and may have any shape such as a film or a three-dimensional sculpture.

As mentioned above, the active energy rays that cure the active energy ray curable composition of the present invention are ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Here, when using ultraviolet rays as active energy rays, examples of devices that irradiate 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, Examples include black light lamps, mercury-xenon lamps, short arc lamps, helium/cadmium lasers, argon lasers, solar lights, and LED lamps.

＜Film＞

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 a film substrate, and then irradiating the active energy ray to form a cured coating film.

As the material of the film base used in the film of the present invention, a resin with high transparency is preferable, and examples include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polypropylene, polyethylene, Polyolefin resins such as polymethylpentene-1; cellulose acetate (diacetylcellulose, triacetylcellulose, etc.), cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, cellulose acetate phthalate, cellulose nitrate, etc. Cellulose resin; Acrylic resin such as polymethyl methacrylate; Vinyl chloride resin such as polyvinyl chloride and polyvinylidene chloride; Polyvinyl alcohol; Ethylene-vinyl acetate copolymer; Polystyrene; Polyamide; Polycarbonate; Polysulfone ；Polyether sulfone; Polyether ether ketone; Polyimide-based resin such as polyimide and polyetherimide; Norbornene-based resin (for example, “ZEONOR” manufactured by ZEON CORPORATION), modified norbornene-based resin (for example, "ARTON" manufactured by JSR CORPORATION), a cyclic olefin copolymer (for example, "APEL" manufactured by Mitsui Chemicals, Inc.), etc. are mentioned. Additionally, you may use a combination of two or more types of substrates made of these resins.

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

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 Co. ., Ltd. “Technolloy S014G”, “Technolloy S001G”, “Technolloy S000” manufactured by Mitsubishi Chemical Corporation, “ACRYPLEN HBS006”, “ACRYPLEN HBXN47”, “ACRYPLEN HBS010” manufactured by Teijin Chemicals Ltd. Products such as “Panlite film PC-2151” are available as commercial products.

The film substrate may be in a film shape or a sheet shape, and its thickness is in the range of 20 to 500 μm, for example. Moreover, when using a film-shaped base film, the thickness is preferably in the range of 20 to 200 μm, more preferably in the range of 30 to 150 μm, and still more preferably in the range of 40 to 130 μm. By setting the thickness of the film base material to this range, curling becomes easy to suppress even when a hard coat layer is formed on one side of the film with the active energy ray curable composition of the present invention.

Methods for coating the active energy ray curable composition of the present invention on the film substrate include, for example, die coat, microgravure coat, gravure coat, roll coat, comma coat, air knife coat, kiss coat, spray coat, and dip coat. , spinner coat, brushing, solid coat by silk screen, wire bar coat, flow coat, etc.

After applying the active energy ray-curable composition to a base film, it is preferable to heat or dry at room temperature to volatilize the solvent before irradiating the active energy ray. Conditions for heat drying include, for example, heat drying at a temperature of 50 to 100°C and a time of 0.5 to 10 minutes.

When forming a 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 is such that the hardness of the cured coating film is sufficient and curling of the film due to curing shrinkage of the coating film is suppressed. In that, 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 more preferable.

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

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

Example

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

[Example 1]

55 parts by mass of polyfunctional monomer [mixture of pentaerythritol tetraacrylate and pentaerythritol triacrylate], epoxy acrylate [reaction product of polyglycidyl methacrylate and acrylic acid, solid content 50%, diluted with methyl isobutyl ketone] 70 parts by mass, isocyanuric acid EO-modified diacrylate urethane acrylate (“ARONIX M215” manufactured by TOAGOSEI CO., Ltd.), 10 parts by mass, dispersant (a-1) (“DISPERBYK-109” manufactured by BYK-Chemie) ), 3.0 parts by mass, mixed solvent (dimethyl carbonate/MIBK/IPA/propyl acetate/methyl acetate/1,3 dioxolane=20.1/22.6/65.4/39.0/9.7/4.5), 161.3 parts by mass, photoinitiator (1-hydroxy After sufficiently mixing 5 parts by mass of cyclohexyl phenyl ketone), an active energy ray curable composition with a non-volatile content of 36.8% by mass was prepared by mixing 4.4 parts by mass of organic fine particles (polymethyl methacrylate composition fine particles, refractive index 1.51, average particle diameter 2.0 μm). did.

[Examples 2 to 4 and Comparative Examples 2 to 4]

Except for changing the formulation shown in Table 1, the same procedure as in Example 1 was performed to adjust the active energy ray-curable composition, and then a film for evaluation was produced and evaluated.

[Production of samples for evaluation]

The active energy ray-curable composition was applied to a PMMA film with a thickness of 60 μm using a bar coater to a film thickness of 5 μm, dried at 60°C for 1 minute, and then irradiated with an ultraviolet irradiation device (manufactured by EYE GRAPHICS Co., Ltd., high pressure) under a nitrogen atmosphere. It was irradiated twice at an irradiation amount of 75 mJ/m ² using a mercury lamp, and a PMMA film with a cured coating film was obtained as a sample for evaluation.

[Hayes’ evaluation]

The film for evaluation obtained above was measured using a haze meter (“NDH4000” manufactured by NIPPON DENSHOKU INDUSTRIES Co., Ltd.) under a D65 light source in accordance with JIS K7136. The smaller the haze value, the better the anti-glare properties, and those within the range of 2.0 to 3.0% were considered acceptable.

[Evaluation of total light transmittance]

The evaluation film obtained above was measured according to JIS K7361-1. The higher the total light transmittance, the higher the transparency, and 90% or more was considered passing.

[Evaluation of transmission clarity]

The evaluation film obtained above was measured using an image quality measuring device (“ICM-1T” manufactured by Suga Test Instruments Co., Ltd.) according to JIS K7374, with an optical comb width of 0.125, 0.5, 1.0, and 2.0 mm. Measured at 4 points. For evaluation, the total value of the four measured points was used. If this total value is high, the anti-glare property is weak, and if this total value is low, the anti-glare property is too strong and the visibility of the screen decreases. Therefore, those in the range of 310 to 355% were judged as passing.

[Evaluation results]

The results are shown in Table 1.

The abbreviations in the table are as follows.

Organic fine particles (a-1): fine particles composed of polymethyl methacrylate, average primary particle diameter 2.0 μm, refractive index 1.51

DISPERBYK-109: Alkylolaminoamide, manufactured by BYK-Chemie.

DISPERBYK-180: Alkylol ammonium salt of a copolymer containing an acid group, manufactured by BYK-Chemie.

DISPERBYK-U100: Salt of unsaturated polyaminoamide and low molecular weight polyester acid, manufactured by BYK-Chemie.

DISPERBYK-102: Copolymer with an acidic group, manufactured by BYK-Chemie.

DISPERBYK-103: Copolymer with affinity for pigments, manufactured by BYK-Chemie.

Epoxy (meth)acrylate (B): Methyl isobutyl ketone solution of the reaction product of polyglycidyl methacrylate and acrylic acid (50% solid content), viscosity 1000 mPa·s.

M305: Pentaerythritol tetraacrylate (contains 55 to 63% of pentaerythritol triacrylate), TOAGOSEI CO., Ltd. Manufacturing brand name “ARONIX M-305”

M215: Isocyanuric acid EO modified diacrylate, TOAGOSEI CO., Ltd. Product name "ARONIX M-215" of manufacture

R-1104: 1-hydroxycyclohexylphenyl ketone, brand name “RUNTECURE 1104” manufactured by RUNTEC Chemical.

From the evaluation results shown in Table 1, it was found that the cured coating film 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 Example 1 shown in Table 1 did not contain the dispersant (a-2), and the transparency of the cured coating film decreased.

In addition, Comparative Examples 2 to 4 shown in Table 1 were embodiments in which an alkanolamine-based compound was not used as a dispersant, and the transparency of the cured coating film also decreased.

Claims (8)

Contains organic fine particle dispersion (A) and epoxy (meth)acrylate (B),
The organic fine particle dispersion (A) contains organic fine particles (a-1) and a dispersant (a-2),
An active energy ray-curable composition wherein the dispersant (a-2) is an alkanolamine-based compound. In claim 1,
An active energy ray-curable composition wherein the average primary particle diameter of the organic fine particles (a-1) is in the range of 0.5 to 3 μm. In claim 1,
An active energy ray-curable composition wherein the dispersant (a-2) has an amine value of 80 mgKOH/g or more. In claim 1,
An active energy ray-curable composition in which the epoxy (meth)acrylate (B) is a reaction product of polyglycidyl methacrylate and acrylic acid. In claim 1,
An active energy ray-curable composition further containing a polyfunctional (meth)acrylate (C) different from the epoxy acrylate (B). In claim 5,
An active energy ray-curable composition wherein the polyfunctional (meth)acrylate (C) is a compound having a nurate skeleton in the molecule. A cured product of the active energy ray curable composition according to any one of claims 1 to 6. A film characterized by having a cured coating film of the active energy ray curable composition according to any one of claims 1 to 6.