TW202003711A - Photosensitive resin composition and anti-glare film - Google Patents

Abstract

The present invention relates to a photosensitive resin composition for an anti-glare film which comprises a polyfunctional (meth) acrylate (A) having at least three (meth)acryloyl groups in the molecule, a photopolymerization initiator (C), polystyrene particles (D), and silica (E); and a cured anti-glare film thereof.

Description

Photosensitive resin composition and anti-glare film

The present invention relates to a novel anti-glare property applicable to image display devices such as liquid crystal display devices (LCD), plasma display devices (PDP), electroluminescent display devices (ELD), cold cathode tube display devices (CRT), etc. A photosensitive resin composition for a film, an antiglare film formed by curing the photosensitive resin composition, an optical member such as a polarizing plate having an antiglare film, and an image display device.

In recent years, image display devices such as liquid crystal display devices, plasma display devices, and electroluminescence display devices have become larger and higher in resolution. Since these display devices have high image quality, light or objects are on the display screen section The reflection has a greater impact on the appearance of the image.

As a method for preventing the reflection of the display screen, there is a method in which an inorganic filler or an organic filler dispersed in a photosensitive resin is coated on a film to make the surface uneven to produce anti-glare properties, which scatters light incident from the outside This can prevent the visibility of the display from being reduced.

However, due to the higher resolution of the image display device, there is a problem that the brightness distribution phenomenon is disturbed by the irregularities on the surface of the anti-glare film, and glare (sparkling) appears on the screen due to the brightness distribution, resulting in reduced visibility . Although attempts have been made to set a refractive index difference between the photosensitive resin and the filler, and scatter light by internal haze to suppress glare, there is no one that meets all requirements for anti-glare performance, image sharpness, and contrast.

Patent Document 1 describes an anti-glare hard coating film provided with a transparent hardened resin layer as a first hard coat layer on a transparent plastic film or a plate-like substrate, and a hardened resin containing inorganic or organic fine particles The film serves as the second hard coat.

Patent Document 2 describes an anti-glare hard coat film, which is an anti-glare hard coat film provided with at least one anti-glare hard coat layer on at least one surface of a transparent plastic film, the internal haze of which is 0.5% or less, and the surface Haze/internal haze is 2.0 or more.

Patent Document 3 describes an anti-glare film in which the haze of the anti-glare layer is 5% or less, the ten-point average height of the surface of the anti-glare layer is 0.15 μm or more and 1.0 μm or less, and the anti-glare layer is provided with particles. Concavo-convex surface of convex parts and concave parts with no binder but only adhesive matrix, the average interval of concave-convex is 10μm or more and 150μm or less, anti-glare layer contains particles in the binder matrix, and the refractive index (nA) and adhesion of the particles The refractive index difference (|nA-nM|) of the refractive index (nM) of the agent matrix is 0.00 or more and 0.04 or less.

Patent Document 4 describes an anti-glare film formed by laminating a transparent base film and an anti-glare layer, wherein the anti-glare layer is prepared with a light-transmitting resin with a particle size of 0.5 to 2.0 μm The first light-transmitting fine particles having a difference in refractive index of 0.04 to 0.20 and the second light-transmitting fine particles having a difference in refractive index from the light-transmitting resin of 0.3 or less and protruding from the surface of the anti-glare layer by 0.1 to 0.3 μm Mixed and constructed.

Patent Document 5 describes a method for manufacturing a surface uneven sheet, which includes: a first step of mixing an organic resin material with a material that is incompatible with the organic resin material to prepare a coating liquid; the coating liquid is formed after coating The second step of the coating film having a phase-separated structure in which the organic resin material and the incompatible material are phase-separated; after the coating film is hardened to cure the organic resin material and solidify the phase-separated structure, the hardened The third step of removing incompatible materials from the coating film to form a hardened resin layer with a surface uneven structure.

Patent Literature 6 describes a light diffusing substrate in which a light diffusing sheet formed of a resin film layer having a fine uneven surface on at least one surface of a transparent substrate is formed, wherein the light diffusing sheet Has a haze of 40% or more, and the image sharpness measured with an optical comb of 0.5 mm width according to JIS K 7105 is 35 or more.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2000-912

[Patent Document 2] JP 2007-58204

[Patent Document 3] JP 2011-59481

[Patent Document 4] JP 2000-121809

[Patent Document 5] JP 2006-116533

[Patent Document 6] JP 2002-107512

The object of the present invention is to provide a photosensitive resin composition for a new type of anti-glare film that can be applied to image display devices such as liquid crystal display devices, plasma display devices, electroluminescence display devices, cold cathode tube display devices, etc. And an anti-glare film formed by curing the photosensitive resin composition, an optical member such as a polarizing plate having the anti-glare film, and an image display device.

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, they have found that the above-mentioned object can be achieved by a photosensitive resin composition having the following structure, and the present invention has been completed.

The present invention is as follows.

[Invention 1] A photosensitive resin composition for an anti-glare film, comprising: a polyfunctional (meth)acrylate (A) having at least 3 (meth)acryloyl groups in the molecule, and photopolymerization Starter (C), polystyrene particles (D) and silica (E).

[Invention 2] The photosensitive resin composition according to Invention 1, wherein when the total amount of the resin components of the photosensitive resin composition is 100% by weight, component A is 10 to 95% by weight and component C is 0.5 to 10% by weight, and with respect to the total amount of the resin components of the photosensitive resin composition, the D component is 1 to 30% by weight, and the E component is 0.1 to 10% by weight.

[Invention 3] The photosensitive resin composition according to Invention 1 or 2, wherein the average particle diameter of the component D is 1 μm to 5 μm.

[Invention 4] The photosensitive resin composition according to any one of Inventions 1 to 3, wherein the difference between the refractive index of the component A and the refractive index of the component D is 0.05 to 1.5.

[Invention 5] The photosensitive resin composition according to any one of Inventions 1 to 4, wherein the average particle diameter of the component E is 1 μm to 5 μm.

[Invention 6] The photosensitive resin composition according to any one of Inventions 1 to 5, wherein the total haze of the antiglare film formed by curing the photosensitive resin composition is 15% to 35%.

[Invention 7] The photosensitive resin composition according to any one of Inventions 1 to 6, wherein the internal haze of the anti-glare film obtained by curing the photosensitive resin composition is 10% or more.

[Invention 8] An anti-glare film obtained by curing the photosensitive resin composition according to any one of Inventions 1 to 7.

[Invention 9] An optical member having a layer obtained by curing the photosensitive resin composition according to any one of Inventions 1 to 7.

[Invention 10] A polarizing plate having a layer obtained by curing the photosensitive resin composition according to any one of Inventions 1 to 7.

[Invention 11] An image display device having a layer obtained by curing the photosensitive resin composition according to any one of Inventions 1 to 7.

According to the present invention, a novel anti-glare film can be provided. In one aspect, the anti-glare film of the present invention imparts good visibility, anti-glare, anti-scratch properties, scratch resistance, and/or pencil hardness. In addition, applying the layer hardened from the photosensitive resin composition of the present invention to an image display device or the like has the advantage of having anti-glare properties in the image display device or the like. In one aspect, the image display device of the present invention has good visibility. In one aspect, the image display device of the present invention has good visibility and/or suppresses the occurrence of glare. In one aspect, the anti-glare film of the present invention can simultaneously form a surface uneven shape for scattering incident light and a region mainly responsible for internal scattering of light.

The photosensitive resin composition for the antiglare film of the present invention contains: a polyfunctional (meth)acrylate (A) having at least 3 (meth)acryloyl groups in the molecule, and photopolymerization initiation Agent (C), polystyrene particles (D) and silica (E).

In the present invention, the "total amount of the resin components of the photosensitive resin composition" refers to the total amount of both the A component and the C component described above. In addition, when other thermally polymerizable or photopolymerizable monomers are contained as the component B, it means the total amount of the above three components A, C, and B. In addition, "the total amount of resin components with respect to the photosensitive resin composition" means the weight% when the total amount is 100% by weight. For example, when the total amount of component A, component B, and component C is 100 parts by weight, the total amount of components other than component A, component B, and component C relative to the resin component of the photosensitive resin composition is 10% by weight. It is 10 parts by weight, and the total amount of the photosensitive resin composition is 110 parts by weight.

Hereinafter, each of these components will be described.

In addition, the terms (meth)acrylate, (meth)acrylic acid, and (meth)acryloyl group described in this specification refer to methacrylate or acrylate, methacrylic acid, or acrylic acid, respectively, and The meaning of methacryloyl or acryloyl.

The polyfunctional (meth)acrylate of the component A of the present invention has a (meth)acryloyl group, and preferably has an acryloyl group. In the molecule, the (meth)acryloyl group contains at least 3 or more, preferably 3 to 10, more preferably 3 to 7, even more preferably 3 to 6. The polyfunctional (meth)acrylate may further contain functional groups having active hydrogen such as hydroxyl groups or amine groups, urethane groups, halogen and other functional groups.

Examples of the polyfunctional (meth)acrylate include, for example, neopentaerythritol tri(meth)acrylate, neopentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(methyl). Acrylate, dipentaerythritol hexa(meth)acrylate, trineopentaerythritol hepta(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane polyethoxylate Base tri(meth)acrylate, bistrimethylolpropane tetra(meth)acrylate, tripentaerythritol octa(meth)acrylate and other polyester acrylates; tri(acryloyloxyethyl) ) Trimeric isocyanate, epichlorohydrin (ECH) modified glycerin tri(meth)acrylate, ethylene oxide (EO) modified glycerin tri(meth)acrylate, propylene oxide (PO) modified glycerin triglyceride (Meth)acrylate, EO modified tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, EO modified trimethylolpropane tri(methyl) Acrylic ester, PO modified trimethylolpropane tri(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, neopentaerythritol ethoxytetra(meth)acrylic acid Ester, polysiloxane hexa(meth)acrylate, polyurethane polyfunctional (meth)acrylate which is a reactant of diol and polyisocyanate and polyfunctional (meth)acrylate having hydroxyl group, A polyfunctional urethane (meth)acrylate, etc., which is a reactant of a polyfunctional (meth)acrylate having an active hydrogen (hydroxyl group, amine group, etc.) and a polyisocyanate compound. In addition, these may be used alone or in combination of two or more.

Preferred examples of the polyfunctional (meth)acrylate of the present invention include: polyfunctional (meth)acryloyl groups having 3 to 7 (preferably 3 to 6) (meth)acryloyl groups in the molecule. ) Acrylic ester; polyfunctional acrylate having 3 to 7 (preferably 3 to 6) acryl groups in the molecule; having 3 to 7 (preferably 3 to 6) in the molecule (methyl ) Acryl-based polyester-type multifunctional (meth)acrylate; 3 to 7 (preferably 3 to 6) acryl-based polyester-type multifunctional acrylate in the molecule.

Examples of the above-mentioned polyfunctional (meth)acrylates having active hydrogen include polyfunctional (meth)acrylates having a hydroxyl group or an amine group, for example: neopentaerythritol tri(meth)acrylate, dineopentyl Tetraol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, etc. Pentaerythritol; methanol such as trimethylolpropane tri(meth)acrylate; epoxy acrylate such as bisphenol A diepoxy acrylate. Among them, preferred are neopentaerythritol triacrylate and dipentaerythritol pentaacrylate. These polyfunctional (meth)acrylates having active hydrogen may be used alone or in combination of two or more.

As the polyisocyanate, a polyisocyanate composed of a chain aliphatic hydrocarbon, a cyclic aliphatic hydrocarbon (alicyclic type), or an aromatic hydrocarbon can be used. Examples of the "aliphatic hydrocarbon" include saturated and unsaturated aliphatic hydrocarbons. Examples of such polyisocyanates include, for example, chain saturated hydrocarbon polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate; and isophor Cyclic saturated hydrocarbons such as ketone diisocyanate, dicyclohexylmethane diisocyanate, methylene bis (4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate (alicyclic) Polyisocyanate; 2,4-toluene diisocyanate, 1,3-xylene diisocyanate, terephthalic diisocyanate, 3,3'-dimethyl-4,4'-diisocyanate, 6-isopropyl-1, Aromatic polyisocyanates such as 3-phenyl diisocyanate and 1,5-naphthalene diisocyanate. Among them, isophorone diisocyanate and hexamethylene diisocyanate are preferred. These polyisocyanates may be used alone or in combination of two or more.

The polyfunctional urethane (meth)acrylate mentioned above is obtained, for example, by reacting the polyfunctional (meth)acrylate having active hydrogen with the polyisocyanate. The amount of polyisocyanate used is usually in the range of 0.1 to 50 equivalents based on the equivalent of isocyanate groups, preferably 0.1 to 10 equivalents, relative to 1 equivalent of active hydrogen groups in the polyfunctional (meth)acrylate with active hydrogen. range. The reaction temperature is usually 30 to 150°C, preferably 50 to 100°C. The end point of the reaction may be, for example, when the residual isocyanate is reacted with excess n-butylamine, and the polyisocyanate calculated by the back titration method with 1N hydrochloric acid becomes 0.5% by weight or less.

In order to shorten the reaction time for preparing the above polyfunctional urethane (meth)acrylate, a catalyst may be added. As the catalyst, either a basic catalyst or an acid catalyst can be used. Examples of the basic catalyst include amines such as triethylamine, diethylamine, dibutylamine, and ammonia; phosphines such as tributylphosphine and triphenylphosphine; pyridine and pyrrole. Examples of the acid catalyst include, for example, metal salts such as copper naphthenate, cobalt naphthenate, zinc naphthenate, tributoxyaluminum, tetrabutoxytrititanium, and tetrabutoxyzirconium; aluminum chloride, etc. Lewis acids; 2-ethyl hexane tin, octyl tin trilaurate, dibutyl tin dilaurate, octyl tin diacetate and other tin compounds. When using such catalysts, the amount of the catalyst added is usually about 0.1 to 1 part by weight relative to 100 parts by weight of polyisocyanate.

In addition, it is preferable to use a polymerization inhibitor (eg, methoxyphenol, hydroquinone, methylhydroquinone, phenothiazine, etc.) in order to prevent polymerization during the reaction while reacting. The use amount thereof is about 0.01 to 1% by weight relative to the reaction mixture, preferably about 0.05 to 0.5% by weight.

The reaction temperature of the above reaction is 60 to 150°C, preferably 80 to 120°C.

A commercially available product can also be used as the multifunctional (meth)acrylate of the present invention. Examples of commercially available products include: KAYARADPET 30 (manufactured by Nippon Kayaku Co., Ltd.), LIGHT ACRYLATE PE-3A, LIGHT ACRYLATE PE-4A, LIGHT ACRYLATE DPE-6A, LIGHT ACRYLATE TMP-A (the above are all common (Produced by Rong Chemical Co., Ltd.), SR444, SR315S, SR350 (all of which are manufactured by Sartomer Japan Co., Ltd.), etc.

In the present invention, the use amount of the multifunctional (meth)acrylate component is usually 10 to 95% by weight of the total resin component of the photosensitive resin composition of the present invention, preferably 30 to 90% by weight, and 60 to 90% by weight, 30 to 80% by weight, or 60 to 80% by weight.

In the present invention, in addition to the polyfunctional (meth)acrylate as required, other thermally polymerizable or photopolymerizable monomers (B) may be added. Examples of the polymerizable monomer include, for example, (meth)acrylate having at least 2 or 1 (meth)acryloyl group in the molecule, and (meth)acrylate having 1 or more epoxy groups. Base) acrylate, etc.

Specific examples of the bifunctional (meth)acrylate containing two (meth)acryloyl groups include ethylene glycol di(meth)acrylate and diethylene glycol di(meth)acrylate. , Triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, 1,2-propanediol di(meth)acrylate, 1, 3-propanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di( Meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate , 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth) Acrylate, neopentyl glycol di(meth)acrylate, 2,2,4-trimethyl-1,6-hexanediol di(meth)acrylate, 2,4,4-trimethyl- 1,6-hexanediol (meth)acrylate, 2,4-diethyl-1,5-pentanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, etc. In addition, these may be used alone or in combination of two or more.

Specific examples of the above-mentioned monofunctional (meth)acrylate containing one (meth)acryloyl group include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, and 2-propyl (meth)acrylate Ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, (meth) 2-ethylhexyl acrylate, n-dodecyl (meth) acrylate, isolauryl (meth) acrylate, n-octadecyl (meth) acrylate, isostearyl (meth) acrylate , Benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, glycidyl (meth)acrylate, N,N-dimethyl Amino (meth)acrylate, N,N-diethylamino (meth)acrylate, morpholine (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth) 2-Hydroxypropyl acrylate, 4-hydroxybutyl (meth)acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth) Acrylate, 2-methoxyethyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylenedioxide Alcohol (meth)acrylate, 2-butoxyethyl (meth)acrylate, butoxytriethylene glycol (meth)acrylate, 2-ethoxyethyl (meth)acrylate, (meth) Group) 2-(2-ethoxyethoxy) ethyl acrylate, ethoxy polyethylene glycol (meth) acrylate, 4-nonylphenoxy ethylene glycol (meth) acrylate, tetra Hydrofurfuryl (meth)acrylate, caprolactone modified tetrahydrofurfuryl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylic acid 2 -Hydroxy-3-propoxypropyl ester, cyclohexyl methyl (meth)acrylate, cyclohexyl ethyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentyl (meth)acrylate Oxyethyl, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, p-phenylphenyl (meth)acrylate, o-phenylphenyl (meth) Group) acrylate, 2-(p-phenylphenoxy)ethyl (meth)acrylate, 2-(o-phenylphenoxy)ethyl (meth)acrylate, 2-(2-(p Phenylphenoxy)ethoxy)ethyl (meth)acrylate, 2-(2-(o-phenylphenoxy)ethoxy)ethyl (meth)acrylate, 2-(2- (2-(p-phenylphenoxy)ethoxy)ethoxy)ethyl (meth)acrylate, 2-(2-(2-(o-phenylphenoxy)ethoxy)ethoxy Group) ethyl (meth)acrylate, 2-(2-(2-(2-(p-phenylphenoxy)ethoxy)ethoxy)ethoxy)ethyl (meth)acrylate , 2-(2-(2-(2-(o-phenylphenoxy)ethoxy)ethoxy)ethoxy)ethyl (meth)acrylate, etc. In addition, these may be used alone or in combination of two or more.

Examples of the (meth)acrylate having one or more epoxy groups include the ring prepared by reacting a compound having one or more epoxy groups with (meth)acrylic acid. Oxygen (meth)acrylate. The structure of the epoxy (meth)acrylate is not particularly limited, but the compound having an epoxy group as a raw material for preparing the epoxy (meth)acrylate includes, for example, bisphenol A type and bisphenol S type, bisphenol F type, epoxidized oil type, phenol novolak type, alicyclic type or those obtained by modifying these. Specific examples include: acrylate obtained by reacting the adduct of bisphenol A and epichlorohydrin with acrylic acid, acrylate obtained by reacting phenol novolak with epichlorohydrin and then reacted with acrylic acid, and bisphenol S and The acrylate obtained by reacting the adduct of epichlorohydrin with acrylic acid, the acrylate obtained by reacting epoxidized soybean oil with acrylic acid, etc. are not limited thereto. In addition, these may be used alone or in combination of two or more.

Preferred examples of the above-mentioned epoxy (meth)acrylates include: epoxy (meth)acrylates prepared by reacting compounds having two or three epoxy groups with (meth)acrylic acid; Bisphenol A epoxy (meth)acrylate prepared by reaction of oxidized bisphenol A with (meth)acrylic acid; bisphenol A epoxy acrylate prepared by reaction of epoxidized bisphenol A with acrylic acid; epoxidized phenol Phenol novolak epoxy (meth)acrylate prepared by reaction of novolak and (meth)acrylic acid; phenol novolak epoxy epoxy ester prepared by reaction of epoxidized phenol novolak and acrylate.

A commercially available product may be used as the above-mentioned epoxy (meth)acrylate. Commercially available products include, for example, epoxy ester 3000A, epoxy ester MK (made by Kyoeisha Chemical Co., Ltd.), CN104, CN104NS, CN151 (all of which are made by Sartomer Japan Co., Ltd.), HITALOID 7851, HITALOID 7663 (All of the above are manufactured by Hitachi Chemical Co., Ltd.) etc.

In the present invention, the use amount of the component B is usually 1 to 70% by weight, preferably 5 to 50% by weight, and more preferably 5 to 30% by weight in the total amount of the resin components of the photosensitive resin composition of the present invention %, especially good is 10 to 30% by weight.

In the present invention, examples of the photopolymerization initiator include, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, and the like; acetophenone, 2,2-diethoxy -2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexylbenzene Acetone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-1-one and other acetophenones; 2-ethylanthraquinone, 2-tert-butyl Anthraquinones, 2-chloroanthraquinone, 2-pentylanthraquinone and other anthraquinones; 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone Thioxanthones; acetophenone dimethyl ketal, benzyl dimethyl ketal and other ketals; benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide Ether, 4,4'-dimethylaminobenzophenone and other benzophenones; 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,4,6- Phosphine oxides such as trimethylbenzyl)-phenylphosphine oxide. In addition, these may be used alone or in combination of two or more.

A commercially available product can also be used as the above-mentioned photopolymerization initiator. Examples of commercially available products include Irgacure 184 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Irgacure 907, Irgacure 369, Irgacure 379, and the like manufactured by BASF.

In the photosensitive resin composition of the present invention, the use amount of the photopolymerization initiator is 0.5 to 10% by weight, preferably 1 to 7% by weight in the total amount of the resin components of the photosensitive resin composition of the present invention.

In the present invention, a hardening accelerator may also be used. Examples of the hardening accelerator that can be used include, for example: triethanolamine, diethanolamine, N-methyldiethanolamine, 2-methylaminoethyl benzoate, dimethylaminoacetophenone, p-dimethyl Isoamyl aminobenzoate, amines such as EPA, and hydrogen donors such as 2-mercaptobenzothiazole. When the solid content of the resin composition of the present invention is 100% by weight, the amount of the curing accelerator used is usually 0 to 5% by weight.

In the present invention, examples of polystyrene particles include non-crosslinked polystyrene particles, crosslinked polystyrene particles, crosslinked methyl methacrylate-styrene copolymer particles, crosslinked acrylic acid-styrene Translucent particles such as copolymer particles. In addition, there is no need for special surface treatment, but surface-treated particles can also be used. The shape of the polystyrene particles is not particularly limited. For example, a spherical shape, a cylindrical shape, etc. are mentioned. Among them, spherical ones are preferred. Tejia is spherical and consistent in shape.

The average particle diameter of the polystyrene particles is preferably 1 to 5 μm, and commercially available products can be used. Examples of commercially available products include: SX series manufactured by Zongyan Chemical Co., Ltd., Techpolymer series manufactured by Sekisui Chemical Products Co., Ltd., and 3000 series, 4000 series, and 2000 series manufactured by Moritex Co., Ltd.

The average particle size is measured by, for example, a particle size distribution meter (for example, ELSZ-2000, manufactured by Otsuka Electronics Co., Ltd.) using a static light scattering method (photon correlation method).

The average particle diameter of the polystyrene particles is preferably 1 to 5 μm, and more preferably 2 to 4 μm. If it is less than 1 μm, it tends to fail to obtain sufficient anti-glare property, and if it exceeds 5 μm, glare easily occurs due to the unevenness of the surface, and penetration may be reduced.

Regarding the refractive index of the polystyrene particles of the present invention, the refractive index of the above polyfunctional (meth)acrylate or a mixture of the polyfunctional (meth)acrylate and epoxy (meth)acrylate, which is The difference in refractive index of the ethylene particles is preferably 0.05 to 1.5.

The refractive index of the polyfunctional (meth)acrylate or the refractive index of the mixture of the polyfunctional (meth)acrylate and the epoxy (meth)acrylate can be, for example, a multi-wavelength Abbe refractometer (DR-M2, Atago Co., Ltd.) to measure.

As a mixture of neopentaerythritol triacrylate and epoxy acrylate, those having a refractive index of 1.482 to 1.493 can be used. The refractive index of neopentaerythritol triacrylate is 1.477.

The refractive index of the polystyrene particles can be measured by any method. For example, the mixing ratio of any two solvents different in refractive index selected from diiodomethane, 1,2-dibromopropane, and n-hexane can be changed. In a solvent that changes the refractive index, the light-transmitting particles are dispersed in equal amounts and the turbidity is measured, and the refractive index of the solvent when the turbidity becomes minimum is measured using an Abbe refractometer.

In the photosensitive resin composition of the present invention, the amount of polystyrene particles used is preferably 1 to 30% by weight, and more preferably 5 to 25% by weight relative to the total amount of the resin components of the photosensitive resin composition.

In the present invention, the shape of silicon dioxide is not particularly limited. For example, a spherical shape, a needle shape, a convex-concave shape, an elliptical shape, a bead shape, a hammer shape, a rod shape, a spindle shape, and other non-spherical shapes can be cited. Examples of silicon dioxide include NIPSIL series manufactured by Tosoh Silica Co., Ltd., and Excelica series manufactured by Tokuyama Co., Ltd., and the like. In addition, organic silica sol series and Snowtex series manufactured by Nissan Chemical Industry Co., Ltd. dispersed in a solvent, Quotron PL series manufactured by Fuso Chemical Industry Co., Ltd., and Sea Hoster KE series manufactured by Japan Catalyst Co., Ltd. can also be used. The OSCAL series manufactured by Nikon Catalyst Chemical Industry Co., Ltd.

The average particle diameter of the silicon dioxide is preferably 1 to 5 μm. If it exceeds 5 μm, glare is easily generated due to surface irregularities, and the sharpness and penetration rate of the penetrating image may be reduced. If it is less than 1.0 μm, it may be difficult to obtain anti-glare properties and the anti-glare properties are poor.

In addition, the average particle diameter of the above-mentioned polystyrene particles and the average particle diameter of silica can be independently selected, but it is preferable to reduce the average particle diameter of silica.

In the photosensitive resin composition of the present invention, the amount of silica used is usually 0.1 to 10% by weight, preferably 0.1 to 5% by weight, and more preferably the total amount of the resin components of the photosensitive resin composition 0.1 to 2% by weight, particularly preferably 0.3 to 2% by weight.

In addition, leveling agents, defoamers, ultraviolet absorbers, light stabilizers, etc. may be added to the photosensitive resin composition of the present invention as necessary to impart various target functions. Examples of the leveling agent include, for example, fluorine-based compounds, silicone compounds, acrylic compounds, and the like, and examples of ultraviolet absorbers include, for example, benzotriazole-based compounds, benzophenone-based compounds, and trivalent compounds. Examples of light stabilizers such as azine-based compounds include hindered amine-based compounds and benzoate-based compounds.

A diluent can be used in the photosensitive resin composition of the present invention. Examples of diluents that can be used include, for example, alcohols (eg, methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, etc.), lactones (eg, γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptanolide, α-acetyl-γ-butyrolactone, ε-caprolactone, etc.), ethers (for example, dioxane, 1,2 -Dimethoxymethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, triethylene glycol dimethyl ether, triethylene glycol Alcohol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, etc.), carbonates (such as ethyl carbonate, propyl carbonate, etc.), ketones (such as acetone, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone, diacetone alcohol, acetophenone, etc.), phenols (such as phenol, cresol, xylenol, etc.), esters (such as ethyl acetate, propyl acetate, butyl acetate Ester, ethyl lactate, ethylcellulose acetate, butylcellulose acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol mono Ether acetate, etc.), hydrocarbons (such as toluene, xylene, diethylbenzene, cyclohexane, etc.), halogenated hydrocarbons (such as trichloroethane, tetrachloroethane, monochlorobenzene, etc.), petroleum solvents Organic solvents such as petroleum ether and naphtha, hydrofluoroethers such as 2H,3H-tetrafluoropropanol and other fluorine-based alcohols, perfluorobutyl methyl ether, perfluorobutyl ethyl ether Wait). These can be used alone or in combination of two or more.

In the photosensitive resin composition of the present invention, the concentration of the solid content (total amount of component A to E) of the photosensitive resin composition of the present invention is usually 10 to 80% by weight as an example of the amount of diluent used %, preferably 20 to 80% by weight, more preferably 20 to 60% by weight, particularly preferably 30 to 60% by weight.

The method for producing the anti-glare film of the present invention will be explained.

The anti-glare film of the present invention can be produced by forming a coating film layer on a base film using the resin composition of the present invention, and then irradiating the coating film layer with active energy rays to form an anti-glare layer. The active energy rays are not particularly limited, and examples thereof include ultraviolet rays, electron beams, and the like. In the case of curing by ultraviolet light, it is preferable to use a xenon lamp, a high-pressure mercury lamp, or a metal halide lamp as the light source, and adjust the light amount, the arrangement of the light source, etc. as necessary. The temperature condition is not particularly limited, but it is preferably 10 to 30°C, and more preferably 15 to 25°C. The irradiation time is preferably such that the antiglare layer is fully exerted to the extent that the base film is not damaged, and is preferably 5 to 30 seconds.

Regarding the conditions at the time of curing, it is more preferable to perform curing by irradiating an active energy ray in an environment in which an inert gas is replaced. The oxygen concentration is preferably 1% by volume or less, and more preferably 0.5% by volume or less. The inert gas used is preferably nitrogen.

The base film used may be a transparent film, and examples thereof include polyester, polypropylene, polyethylene, polyacrylate, polycarbonate, cellulose triacetate, polyether sulfone, and cycloolefin-based polymers. Wait. The base film may be a sheet having a certain thickness. The substrate film used may be a substrate film having a color or an easily adhesive layer, or a substrate film subjected to surface treatment such as corona treatment.

The thickness of the base film may be selected from the range of 5 to 2000 μm, preferably 20 to 200 μm.

The thickness of the anti-glare film of the present invention must be set in the range of 1.0 to less than 25.0 μm, preferably 1.5 to 20 μm, and more preferably 2.0 to 15.0 μm. When the thickness of the anti-glare film is less than 1.0 μm, irregularities of polystyrene particles are formed on the surface of the anti-glare film, glare easily occurs, and scratch resistance, pencil hardness, etc. are poor. When the thickness is 25.0 μm or more, curling easily occurs. In addition, it cannot cope with the thinning of the display device.

Examples of the coating method of the photosensitive resin composition include bar coater coating, wire bar coating, pneumatic blade coating, gravure coating, reverse gravure coating, micro-gravure coating, and reverse coating. Micro-gravure coating, die coater coating, vacuum die coating, lip die coating, dip coating, cast coating, spin coating, etc.

In the anti-glare film of the present invention, in order to simultaneously form the surface unevenness shape for scattering incident light and the region mainly responsible for internal scattering of light, it is preferable to balance the composition of the resin, the particle size of the dispersed particles, the refractive index, Designed for decentralization.

The internal haze and the surface haze in the present invention are obtained by the following method.

Internal haze = (haze of anti-glare film with surface haze set to 0)-(haze of base film)

Surface haze = (haze of anti-glare film)-(haze of anti-glare film with surface haze set to 0)

In addition, the haze value of the film can be measured by the following method.

That is, the total haze value (full Hz) of the obtained film was measured according to JIS K7136. As the measuring device, for example, a haze meter HM-150 manufactured by Murakami Color Technology Research Institute Co., Ltd. can be used.

The total haze of the anti-glare film is preferably 15 to 35%. When a film with a total haze of less than 15% is applied to a high-resolution display of 100 ppi or more, glare easily occurs. When the total haze exceeds 35%, although glare is less likely to occur, the transmittance and color reproduction Sex and contrast may be reduced.

The internal haze of the anti-glare film is preferably 10% or more. When the internal haze is less than 10%, if it is used for a high-resolution display of 100 ppi or more, glare may easily occur.

The surface haze of the anti-glare film is preferably 1 to 15%, and more preferably 1 to 10%. When the surface haze is less than 1%, the anti-glare effect of external light is reduced due to the uneven structure of the surface, and there is a problem that it is difficult to improve visibility. When a film with a surface haze of more than 15% is used for a high-resolution display of 100 ppi or more, there is a problem that glare easily occurs due to the uneven structure of the surface.

In the present invention, in order to reduce the surface reflectance, an anti-reflection layer may be formed on the anti-glare film. The material forming the anti-reflection layer uses a material having a lower refractive index than the anti-glare film. Examples of the material for forming the anti-reflection layer include, for example, ultraviolet or thermosetting acrylic resin-based materials containing fluorine or silicon in the molecule, mixed materials in which inorganic fine particles such as colloidal silica are dispersed in the resin, tetraethoxy Sol-gel-based materials using metal alkoxides such as silanes and titanium tetraethoxide. By coating the anti-reflective layer forming material so that the film thickness after drying becomes 0.05 to 0.15 μm (the film is set so that the wavelength showing the minimum value of reflectance is preferably 500 to 700 nm, and more preferably 520 to 650 nm Thickness), and after drying, irradiating active energy rays such as ultraviolet rays, electron beams, etc. to form a hardened film, an anti-reflection layer can be obtained.

The anti-glare film of the present invention is suitable for a liquid crystal display device, a plasma display device, a rear projection display device, an organic EL display device, a SED, a flexible display device, a CRT, etc., and is particularly high resolution of 100 ppi or more The display surface of the display device. In addition, the anti-glare film of the present invention is also suitable for use in optical members such as polarizing plates.

[Example]

Hereinafter, the present invention will be described more specifically through examples, but the present invention is not limited to the examples.

Example 1

76 parts by weight of neopentaerythritol triacrylate (KAYARAD PET 30, manufactured by Nippon Kayaku Co., Ltd.) as multifunctional (meth)acrylate, epoxy acrylate as epoxy (meth)acrylate ( Epoxy ester 3000A, manufactured by Kyoeisha Chemical Co., Ltd.) 19 parts by weight, Irgacure 184 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, 5 parts by weight, Techpolymer XX-01JH (poly Styrene particles, average particle diameter 2.0 μm, refractive index 1.595, manufactured by Sekisui Chemical Products Co., Ltd.) 15 parts by weight, NIPSIL SS-50F as silicon dioxide (average particle size 1.1 μm, manufactured by Tosoh Silica Co., Ltd.) 0.575 parts by weight was blended to form a photosensitive resin composition, and the composition was diluted with toluene to a solid content concentration of 50%. The obtained diluted solution of the photosensitive resin composition was applied on a cellulose triacetate film (80 μm) so that the film thickness became about 6 μm, and dried at 80° C. By using an ultraviolet irradiation device (UV transport device, Eyegraphics) (Manufactured by a company limited by shares) It was cured under irradiation conditions of 120 mJ/cm ² to obtain an anti-glare film.

Example 2

95 parts by weight of neopentaerythritol triacrylate (KAYARAD PET 30, manufactured by Nippon Kayaku Co., Ltd.) as a multifunctional (meth)acrylate, and Irgacure 184 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator ) 5 parts by weight of Techpolymer XX-01JH (polystyrene particles, average particle diameter 2.0 μm, refractive index 1.595, manufactured by Sekisui Chemical Products Co., Ltd.) as polystyrene particles 15 parts by weight of NIPSIL as silicon dioxide SS-50F (average particle diameter 1.1 μm, manufactured by Tosoh Silica Co., Ltd.) 0.575 parts by weight was prepared to form a photosensitive resin composition, and the composition was diluted with toluene to a solid content concentration of 50%. The obtained diluted solution of the photosensitive resin composition was applied to triacetyl cellulose film (80 μm) so as to have a film thickness of about 6 μm, and dried at 80° C. with an ultraviolet irradiation device (UV transport device, Eyegraphics (Manufactured by a company limited by shares) It was cured under irradiation conditions of 120 mJ/cm ² to obtain an anti-glare film.

Example 3

An anti-glare film was obtained in the same manner as in Example 1 except that the ratio of neopentaerythritol triacrylate and epoxy acrylate was changed as described in 5 in Table 1.

Example 4

It is the same as Example 1 except that the ratio of neopentaerythritol triacrylate and epoxy acrylate is changed as described in Table 1, and the amount of polystyrene particles is changed from 15 parts by weight to 17 parts by weight. Coating and film hardening to obtain an anti-glare film.

Example 5

Except that the amount of neopentaerythritol triacrylate and epoxy acrylate was changed as described in Table 1, and the amount of polystyrene particles was changed from 15 parts by weight to 13 parts by weight, the rest was the same as Example 2. Coating and film hardening were performed in the same manner to obtain an anti-glare film.

Example 6

In addition to changing NIPSIL SS-50F of Example 1 to NIPSILSS-178B (average particle size 2.9 μm, manufactured by Tosoh Silica Co., Ltd.) as silicon dioxide, and changing the formulation amount of 0.575 parts by weight to 0.375 parts by weight, the remaining Coating and film hardening were performed in the same manner as in Example 1 to obtain an anti-glare film.

Example 7

Except that the epoxy ester 3000A described in Example 1 was changed to CN-104NS (epoxy acrylate, manufactured by Sartomer Japan Co., Ltd.) as the epoxy acrylate, and the formulation amount of NIPSILSS-50F was changed to 1.15 parts by weight, The rest was coated and film-hardened in the same manner as in Example 1 to obtain an anti-glare film.

Example 8

Except that XX-01JH described in Example 1 was changed to XX-02JH (manufactured by Sekisui Chemical Co., Ltd., polystyrene particles, average particle diameter 3.0 μm, refractive index 1.595), the remaining In the same manner as in Example 1, coating and film hardening were performed to obtain an anti-glare film.

Example 9

In addition to changing the amount of neopentyl alcohol triacrylate as described in Table 1, and changing the polystyrene particles from XX-01JH to XX-02JH (manufactured by Sekisui Chemical Products Co., Ltd.), and the amount Other than changing from 15 parts by weight to 10 parts by weight, the rest was applied in the same manner as in Example 2 and the film was cured to obtain an anti-glare film.

Example 10

Except that the method of changing neopentaerythritol triacrylate described in Example 1 to dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.), the rest was coated and filmed in the same manner as in Example 1. After hardening, an anti-glare film is obtained.

Comparative example 1

Except for changing the polystyrene particles from XX-01JH described in Example 1 to XX-05JH (manufactured by Sekisui Chemical Co., Ltd., polystyrene particles, average particle diameter 2.5 μm, refractive index 1.525), the remaining In the same manner as in Example 1, coating and film hardening were performed to obtain an anti-glare film.

Comparative example 2

Except that the neopentaerythritol triacrylate described in Example 1 was set to 66.5 parts by weight, and 28.5 parts by weight of epoxy ester 3000A was blended, and silicon dioxide was not added, the rest was coated in the same manner as in Example 1. The film is hardened to obtain an anti-glare film.

Comparative Example 3

Except that the dipentaerythritol hexaacrylate described in Example 8 was set to 95 parts by weight, and epoxy ester 3000A and SS-50F were not added, the rest was coated and film hardened in the same manner as in Example 1. An anti-glare film is obtained.

The formulations of Examples and Comparative Examples are shown in Table 1.

In Table 1, "PET-30" represents neopentaerythritol triacrylate (KAYARAD PET 30, manufactured by Nippon Kayaku Co., Ltd.), and "DPHA" represents dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd. Company), "3000A" means epoxy acrylate (epoxy ester 3000A, manufactured by Kyoeisha Chemical Co., Ltd.), "CN-104 NS" means epoxy acrylate (CN-104 NS, Sartomer Japan Co., Ltd. ), "184 D" means a photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals), "XX-01JH" means polystyrene particles (Techpolymer XX-01JH, average particle diameter 2.0 μm, refractive index 1.595, (Made by Sekisui Chemical Products Co., Ltd.), "XX-02JH" means polystyrene particles (Techpolymer XX-02JH, average particle diameter 3.0 μm, refractive index 1.595, manufactured by Sekisui Chemical Products Co., Ltd.), "XX-05JH ”Indicates polystyrene particles (Techpolymer XX-05JH, average particle size 2.5 μm, refractive index 1.525, manufactured by Sekisui Chemical Products Co., Ltd.), “SS-50F” indicates silicon dioxide (NIPSIL SS-50F, average particle size 1.1 μm, manufactured by Tosoh Silica Co., Ltd.), “SS-178B” means silicon dioxide (NIPSIL SS-178B, average particle diameter 2.9 μm, manufactured by Tosoh Silica Co., Ltd.).

The total light transmittance (Tt) is measured by a haze meter HM-150 manufactured by Murakami Color Technology Research Institute Co., Ltd.

The total haze (total Hz) is measured by a haze meter HM-150 manufactured by Murakami Color Technology Research Institute Co., Ltd.

The internal haze (internal Hz) and surface haze (surface Hz) are the hazes manufactured by Murakami Color Technology Research Institute Co., Ltd. after the antiglare layer forming surface is laminated to the glass with an adhesive to eliminate surface haze. Measured by HM-150.

In terms of reflectance (Y), 5° specular reflection is measured by a spectrophotometer U-4000 manufactured by Hitachi, Ltd.

Regarding glare, three test groups were used to visually evaluate the occurrence of glare by the 300 LPI Ronchi-Ruling according to the following criteria to determine a consistent view.

◎: No glare.

○: There is glare but not obvious.

△: State with glare.

X: State where glare is very noticeable.

The sharpness of the through image was evaluated by an image measuring device ICM-1 (manufactured by Suga Testing Machine Co., Ltd.).

The evaluation results of each item are shown in Table 2.

In Example 1, good results were obtained in any of reflectance, glare, and sharpness of the transmitted image. In Example 2 in which the epoxy ester 3000A was removed in Example 1, as in Example 1, good results were obtained in any of reflectance, glare, and sharpness of the transmitted image. In Example 3 where the ratio of pentaerythritol triacrylate and epoxy acrylate 3000A was changed, although glare was slightly worse than Example 1, good film characteristics were obtained. In Examples 4 and 5 in which the amount of polystyrene particles was changed, good results were obtained in terms of reflectance and glare. In Example 6 where the type of silica is changed, Example 7 where the type of epoxy acrylate is changed, Examples 8 and 9 where the particle size of polystyrene particles is changed, and when the polyfunctional acrylate is changed from neopentyl alcohol In Example 10 in which the triacrylate was changed to dipentaerythritol hexaacrylate, good results were also obtained in terms of glare and the like.

In Comparative Example 1, since the refractive index of the polystyrene particles was changed from 1.595 to 1.525, the internal haze and surface haze were greatly reduced. Although the glare is good, the reflectance is worse than in Example 1. Not suitable as an anti-glare film. In Comparative Example 2, because SS-50F was excluded from Example 3 and formed to change the unevenness of the surface, it was inferior in glare. In Comparative Example 3, since the composition was changed from neopentaerythritol triacrylate to dipentaerythritol hexaacrylate and the epoxy acrylates 3000A and SS-50F were removed, the glare was significantly worse than Example 1. And as a result, the reflectance is also worse than Example 1.

[Industry availability]

The photosensitive resin composition for the anti-glare film of the present invention is composed of a polyfunctional (meth)acrylate having three or more (meth)acryloyl groups, a photopolymerization initiator, polystyrene particles and It is composed of silicon dioxide and acts as an anti-glare film.

The anti-glare film of the present invention can be provided with anti-glare properties by being attached to image display devices such as cathode-ray tube display devices, plasma display device panels, liquid crystal display devices, organic electroluminescence display devices, etc. The industry has industrial availability.

In one form, the anti-glare film of the present invention imparts good visibility, anti-glare, anti-scratch properties, scratch resistance, and/or pencil hardness.

Claims (11)

A photosensitive resin composition for anti-glare film, comprising: a multifunctional (meth)acrylate (A) having at least 3 (meth)acryloyl groups in the molecule, and a photopolymerization initiator ( C), polystyrene particles (D) and silicon dioxide (E). The photosensitive resin composition according to item 1 of the patent application scope, wherein, when the total amount of the resin components of the photosensitive resin composition is 100% by weight, the component A is 10 to 95% by weight and the component C is 0.5 to 10% by weight, and with respect to the total amount of the resin components of the photosensitive resin composition, the D component is 1 to 30% by weight, and the E component is 0.1 to 10% by weight. The photosensitive resin composition as described in item 1 or 2 of the patent application, wherein the average particle diameter of the component D is 1 μm to 5 μm. The photosensitive resin composition according to any one of claims 1 to 3, wherein the difference between the refractive index of component A and the refractive index of component D is 0.05 to 1.5. The photosensitive resin composition according to any one of items 1 to 4 of the patent application range, wherein the average particle diameter of the component E is 1 μm to 5 μm. The photosensitive resin composition according to any one of claims 1 to 5, wherein the total haze of the antiglare film formed by curing the photosensitive resin composition is 15% to 35%. The photosensitive resin composition according to any one of claims 1 to 6, wherein the internal haze of the anti-glare film formed by curing the photosensitive resin composition is 10% or more. An anti-glare film is obtained by curing the photosensitive resin composition described in any one of the patent application items 1 to 7. An optical member having a layer obtained by curing the photosensitive resin composition described in any one of claims 1 to 7 of the patent application. A polarizing plate has a layer formed by curing the photosensitive resin composition according to any one of the patent application items 1 to 7. An image display device having a layer obtained by curing the photosensitive resin composition according to any one of claims 1 to 7 of the patent application.