JP2010276870A - Anti-glare film, polarizing plate, and liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an anti-glare film having high hardness, low curling properties, and high visibility. <P>SOLUTION: In this anti-glare film, at least one side of a cyclic olefin-based resin substrate has a first cured film with a thickness of 1-20 μm obtained by curing a first curable composition and a second cured film with a thickness of 1-20 μm obtained by curing a second curable composition. The first curable composition contains (B1) compound containing three or more (meta)acryloyl groups in a molecule, and (A1) inorganic oxide particles with a particle size of 5-200 nm modified with a silane coupling agent containing an ethylenic unsaturated group. The second curable composition contains (B2) compound containing three or more (meta)acryloyl groups in a molecule, and (C) particles with a number-average particle size of 0.3-20 μm. The sum of the first cured film and second cured film is 2-30 μm. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an antiglare film having a laminated structure, a polarizing plate provided with the antiglare film, and a liquid crystal display device using the polarizing plate.

  In a display device such as a liquid crystal display device, a light diffusion layer is generally provided on the surface thereof. Such a light diffusing layer functions as an anti-glare (anti-glare) layer that diffuses the surface reflected light, and visibility is hindered by a ghost phenomenon in which an external environment such as fluorescent light or illumination light such as sunlight is reflected on the screen. For the purpose of prevention. As the light diffusion layer, a layer having a fine concavo-convex structure provided on the surface by sandblasting or roughening by mixing transparent particles is known (for example, Patent Document 1).

  On the other hand, with the widespread use of liquid crystal display devices, they are often used in places with high temperatures and high humidity such as in the interior of automobiles, and liquid crystal display devices with excellent heat resistance are required. However, the conventional liquid crystal display device uses a highly permeable triacetyl cellulose film for the protective film of the polarizing element, and neither heat resistance nor moisture resistance is sufficient.

JP-A-9-265004

  The present invention has been made in view of the above problems, and an object thereof is to provide a high heat resistance and low curl antiglare film, a polarizing plate using the antiglare film, and a liquid crystal display device. .

  As a result of intensive studies to achieve the above object, the present inventors have found that an antiglare film capable of satisfying the above various properties can be obtained by using a specific layer structure. Was completed.

That is, the present invention provides the following film, polarizing plate and liquid crystal display device.
[1] Curing the first curable film having a thickness of 1 to 20 μm and the second curable composition obtained by curing the first curable composition on at least one surface of the cyclic olefin-based resin substrate And a second cured film having a thickness of 0.5 to 20 μm obtained in this order, and the first curable composition was modified with (A1) an ethylenically unsaturated group-containing silane coupling agent. Inorganic oxide particles having a number average particle size of 5 to 200 nm, and (B1) a compound having 3 or more (meth) acryloyl groups in the molecule, the second curable composition is (B2) A compound having three or more (meth) acryloyl groups in the molecule, and (C) a particle having a number average particle size of 0.3 to 20 μm, the first cured film and the second cured film The antiglare film is characterized in that the total is 2 to 30 μm.
[2] The antiglare film according to 1, wherein the second curable composition further comprises (A2) inorganic oxide particles having a particle size of 5 to 200 nm modified with an ethylenically unsaturated group-containing silane coupling agent. .
[3] The antiglare film according to 1, wherein the inorganic oxide particles of the component (A1) are silica particles.
[4] The antiglare film according to 2, wherein the inorganic oxide particles of the component (A2) are silica particles.
[5] The antiglare film according to any one of 1 to 3, wherein the component (C) is acrylic resin particles.
[6] The antiglare film according to any one of 1 to 5, wherein the component (C) has a number average particle diameter of 0.3 to 2 times the film thickness of the second cured film.
[7] The antiglare film according to any one of 1 to 6, wherein a total film thickness of the first cured film and the second cured film is 3 to 20 μm.
[8] A polarizing plate comprising the antiglare film according to any one of 1 to 7.
[9] A liquid crystal display device comprising the polarizing plate according to 8.

  According to the present invention, an antiglare film having high heat resistance, scratch resistance and high hardness can be provided.

It is the schematic diagram which showed one Embodiment of this invention.

  The antiglare film of the present invention will be described below.

<Anti-glare film>
The antiglare film of the present invention has a transparent substrate and a structure in which first and second cured films are laminated on at least one surface of the transparent substrate.
The antiglare film of the present invention will be described below.

<Transparent substrate>
As the transparent substrate used in the present invention, a film of a cyclized olefin resin is used. Since the cyclized olefin resin is transparent and has high heat resistance and low moisture permeability, high heat resistance and durability are imparted when a liquid crystal display device is manufactured using the antiglare film of the present invention. can do. Here, the term “transparent” means that a film that is actually used can be used practically as long as it has a transmittance of 80% or more in the visible region (wavelength 400 to 800 nm), and has a transmittance of 90% or more. It is preferable. Moreover, it is preferable that heat resistance has Tg higher than the heating temperature for volatilizing the solvent of a curable composition. Specifically, it is preferable to use a cyclized olefin resin having a Tg of 100 ° C. or higher, preferably 120 ° C. or higher.

  Such a cyclic olefin-based resin is preferably any of the following (1) to (6), and is any of the following (2), (3), (5), and (6). Is more preferable.

［上記式（Ｉ）中、aおよびｂは独立に０または１を示し、ｃおよびｄは独立に０〜２の整数を示し、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²およびＲ¹³はそれぞれ独立に、水素原子；ハロゲン原子；酸素原子、硫黄原子、窒素原子またはケイ素原子を含む連結基を有してもよい置換または非置換の炭素数１〜４０の炭化水素基；または極性基を示し、Ｒ¹⁰とＲ¹¹、またはＲ¹²とＲ¹³とは一体化して２価の炭化水素基を形成してもよく、Ｒ¹⁰またはＲ¹¹と、Ｒ¹²またはＲ¹³とは相互に結合して炭素環または複素環（これらの炭素環または複素環は単環構造でもよいし、他の環が縮合した多環構造でもよい。）］
（１）上記一般式（Ｉ）で表される環状オレフィン系単量体に由来する構造単位を有する開環(共)重合体
（２）上記一般式（Ｉ）で表される環状オレフィン系単量体に由来する構造単位を有する開環（共）重合体を水素添加して得られる開環(共)重合水添体
（３）上記（１）または（２）の開環（共）重合体または開環(共)重合水添体をフリーデルクラフト反応により環化したのち、水素添加して得られる開環（共）重合水添体
（４）上記一般式（Ｉ）で表される環状オレフィン系単量体の付加(共)重合体
（５）上記一般式（Ｉ）で表される環状オレフィン系単量体とエチレンまたは１置換エチレンとの付加共重合体
（６）上記一般式（Ｉ）で表される環状オレフィン系単量体、ビニル系環状炭化水素系単量体およびシクロペンタジエン系単量体からなる群より選ばれる少なくとも１種の単量体の付加型（共）重合体またはその水添体

[In the above formula (I), a and b independently represent 0 or 1, c and d independently represent an integer of 0 to 2, and R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^{9, R 10, R 11,} R 12 and R ¹³ are each independently a hydrogen atom, a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom or silicon atom linking group which may substituted or unsubstituted with a containing A hydrocarbon group having 1 to 40 carbon atoms; or a polar group, and R ¹⁰ and R ¹¹ , or R ¹² and R ¹³ may be integrated to form a divalent hydrocarbon group, R ¹⁰ or R ¹¹ and R ¹² or R ¹³ are bonded to each other to form a carbocyclic or heterocyclic ring (the carbocyclic or heterocyclic ring may be a monocyclic structure or a polycyclic structure in which other rings are condensed)]
(1) Ring-opening (co) polymer having a structural unit derived from the cyclic olefin monomer represented by the general formula (I) (2) Cyclic olefin monomer represented by the general formula (I) Ring-opening (co) polymerized hydrogenated product obtained by hydrogenating a ring-opening (co) polymer having a structural unit derived from a monomer (3) Ring-opening (co) polymerization of (1) or (2) above A ring-opened (co) polymerized hydrogenated product obtained by cyclization of a coalescence or ring-opened (co) polymerized hydrogenated product by Friedel-Craft reaction and hydrogenation (4) represented by the above general formula (I) Addition (co) polymer of cyclic olefin monomer (5) Addition copolymer of cyclic olefin monomer represented by general formula (I) and ethylene or monosubstituted ethylene (6) General formula Cyclic olefin monomer, vinyl cyclic hydrocarbon monomer and cyclopentadiene monomer represented by (I) At least one monomer of the addition type selected from the group consisting of (co) polymer or a hydrogenated derivative

  A well-known method can be used for manufacture of a transparent base material. Specific examples include a method of dissolving the above resin in a solvent, casting the film on a film such as PET, and drying by heating, and a method of forming a film by heating the resin and extruding it from a slit. Further, it may be a film that is formed by the above method and then stretched while being heated. The thickness of the film used as the substrate can be appropriately adjusted in consideration of operability and the like, and for example, a film having a thickness of 40 to 150 μm can be used.

  The transparent substrate can be subjected to various surface treatments before forming a first cured film described later. Examples of the surface treatment include plasma treatment, corona discharge treatment, alkali treatment, and coating treatment. Among these, it is preferable to perform corona discharge treatment.

<First cured film>
A 1st cured film is a cured film layer with a film thickness of 1-20 micrometers formed directly on the said transparent base material or through another layer. The first cured film includes (A1) inorganic oxide particles having a number average particle diameter of 5 to 200 nm modified with an ethylenically unsaturated group-containing silane coupling agent, and (B1) three or more (meth) in the molecule. It can be formed using a first curable composition containing a compound having an acryloyl group.
In the antiglare film of the present invention, the first cured film has an effect of increasing the hardness of the film.

<Second cured film>
The second cured film is a cured film layer having a film thickness of 0.5 to 20 μm formed on the first cured film. The second cured film has (B2) a compound having 3 or more (meth) acryloyl groups in the molecule, and (C) a number average particle size of 0.3 to 20 μm and a film thickness of the second cured film. The 2nd curable composition containing the particle | grains which are 0.3-2 times can be hardened | cured and formed. In addition, the film thickness of the 2nd cured film in case a component (C) protrudes from a cured film points out the film thickness in the center point of two protruding components (C).
In the antiglare film of the present invention, the second cured film has an effect of imparting antiglare property to the film.

  By making the cured film formed on the base material into a plurality of layers, it becomes possible to relieve the shrinkage stress and reduce the curl of the antiglare film. The thickness of each of the first cured film and the second cured film can be appropriately determined depending on the required performance of the antiglare film. For example, the thickness of the first cured film is 1 to 20 μm, preferably 5 to 15 μm. The film thickness of the second cured film is 0.5 to 20 μm, preferably 0.7 to 12 μm, and more preferably 0.9 to 10 μm. By setting the film thickness of the first cured film within the above range, a film having high hardness and low curl can be obtained. By setting the film thickness of the second cured film in the above range, a high-definition antiglare film can be obtained. The sum total of the film thickness of a 1st cured film and a 2nd cured film is 3-30 micrometers. If the total film thickness is less than 3 μm, the hardness of the film surface may be insufficient, and if it exceeds 30 μm, the cured film tends to crack, making it difficult to handle the film. The total thickness of the first cured film and the second cured film can be appropriately changed according to the required surface hardness.

<First curable composition>
The 1st curable composition (henceforth the 1st composition) used by this invention may contain the following component (A1), (B1), and (D1)-(F1). Among these components, (A1) and (B1) are essential components, and (D1) to (F1) are optional components that can be added as necessary.
(A1) Inorganic oxide particles having a number average particle size of 5 to 200 nm modified with an ethylenically unsaturated group-containing silane coupling agent (B1) Compound (D1) radical having 3 or more (meth) acryloyl groups in the molecule Polymerization initiator (E1) Organic solvent (F1) Other additives These components will be described below.

(A1) Inorganic oxide particles having a number average particle size of 5 to 200 nm modified with an ethylenically unsaturated group-containing silane coupling agent The number average particle size modified with an ethylenically unsaturated group-containing silane coupling agent used in the present invention By blending 5 to 200 nm inorganic oxide particles (hereinafter referred to as “reactive particles”), the hardness of the film of the present invention can be increased and curling of the film can be suppressed.

(1) Inorganic oxide particles The inorganic oxide particles contained in the cured film of the present invention are silicon, aluminum, zirconium, titanium, zinc, germanium, from the viewpoint of non-coloring of the cured film of the resulting resin composition. It is an oxide particle of at least one element selected from the group consisting of indium, tin, antimony and cerium. Examples of these oxides include silica, aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, and cerium oxide. Among these, silica, aluminum oxide, zirconia, and antimony oxide are preferable from the viewpoint of high hardness. These can be used singly or in combination of two or more. Furthermore, the oxide particles of such elements are preferably in the form of powder or solvent dispersion sol. In the case of a solvent dispersion sol, the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. Examples of such organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, and γ-butyrolactone. Esters such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone it can. Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.

  The first and second cured films of the present invention contain inorganic oxide particles having a number average particle diameter of 5 to 200 nm. If the number average particle diameter of the inorganic oxide particles exceeds 200 nm, the curl of the cured product may be increased or the definition may be reduced. On the other hand, if the number average particle size is smaller than 5 nm, the hardness may be inferior. In the present invention, the number average particle diameter of the inorganic oxide particles means an average value of 50 particle diameters measured with a transmission electron microscope.

  As a product marketed as silicon oxide particles, for example, silica particles, for example, colloidal silica, manufactured by Nissan Chemical Industries, Ltd., trade names: methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA- ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL and the like can be mentioned. Moreover, as a powder silica, Nippon Aerosil Co., Ltd. product name: Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, Asahi Glass Co., Ltd. Product name: Sildex H31, H32, H51, H52, H121 H122, manufactured by Nippon Silica Kogyo Co., Ltd., trade names: E220A, E220, manufactured by Fuji Silysia Co., Ltd., trade name: SYLYSIA470, manufactured by Nippon Sheet Glass Co., Ltd.

Moreover, as an aqueous dispersion product of alumina, product name manufactured by Nissan Chemical Industries, Ltd .: As an aqueous dispersion product of alumina sol-100, -200, -520, zinc antimonate powder, product name manufactured by Nissan Chemical Industries, Ltd. : Cellulax, Alumina, Titanium oxide, Tin oxide, Indium oxide, Zinc oxide powder and solvent-dispersed products are manufactured by CI Kasei Co., Ltd. Product name: Nanotech, antimony-doped tin oxide aqueous dispersion sol is Ishihara Product name manufactured by Sangyo Co., Ltd .: SN-100D, ITO powder includes products manufactured by Mitsubishi Materials Corporation, and examples of the cerium oxide aqueous dispersion include product names manufactured by Taki Chemical Co., Ltd. it can. The oxide particles have a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fiber shape, or an indefinite shape, and preferably a spherical shape. The specific surface area of oxide particles (by BET method using nitrogen) is preferably 10 to 1000 m ² / g, more preferably 100 to 500 m ² / g. These oxide particles can be used in a dry powder, or dispersed in water or an organic solvent. For example, a dispersion of fine oxide particles known in the art as a solvent dispersion sol of the above oxide can be used directly. In particular, use of a solvent-dispersed sol of an oxide is preferable in applications that require excellent transparency in a cured product.

(2) Ethylenically unsaturated group-containing silane coupling agent The inorganic oxide particles are surface-treated with an ethylenically unsaturated group-containing silane coupling agent, so that (B) 3 or more (meta ) Compatibility with a compound having an acryloyl group is improved, and it becomes possible to co-crosslink with another curable composition at the time of curing, and the scratch resistance of the cured film can be improved. The ethylenically unsaturated group-containing silane coupling agent is not particularly limited as long as it is a compound having an ethylenically unsaturated group and a hydrolyzable silyl group. Examples of the ethylenically unsaturated group include a vinyl group and a (meth) acryloyl group. The hydrolyzable silyl group is a group that reacts with water to produce a silanol (Si-OH) group. For example, one or more methoxy groups, ethoxy groups, n-propoxy groups, isopropoxy groups on silicon. A group, an alkoxy group such as an n-butoxy group, an aryloxy group, an acetoxy group, an amino group, or a halogen atom is bonded. As such an ethylenically unsaturated group-containing silane coupling agent, a commercially available product such as methacryloyloxypropyltrimethoxysilane can be used. For example, a compound described in International Publication No. WO97 / 12942 can be used. It can also be used.

The amount of component (A1) added is not particularly limited, but is usually 30 to 80% by mass when the total of components excluding the organic solvent in the composition of the present invention is 100% by mass. . The reason for this is that when the amount added is less than 30% by mass, the curl of the obtained film may become large. On the other hand, when the amount added exceeds 80% by mass, the hardness of the cured product may decrease. There is.
For this reason, the amount of component (A1) added is more preferably 40 to 80% by mass.

(B1) Compound having 3 or more (meth) acryloyl groups in the molecule Compound having 3 or more (meth) acryloyl groups in the molecule (hereinafter also referred to as polyfunctional (meth) acrylate) is a curable composition Used to increase the hardness and scratch resistance of a cured product obtained by curing the product.

  Examples of the compound having three or more (meth) acryloyl groups include tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, and trimethylol. Propane tri (meth) acrylate, ethylene oxide (hereinafter referred to as “EO”) modified trimethylolpropane tri (meth) acrylate, propylene oxide (hereinafter referred to as “PO”) modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri ( (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Examples include tetratetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and phenol novolac polyglycidyl ether (meth) acrylate. can do.

  Commercially available products of these polyfunctional (meth) acrylates include, for example, SA1002 (manufactured by Mitsubishi Chemical Corporation), biscoat 195, biscoat 230, biscoat 260, biscoat 215, biscoat 310, biscoat 214HP, biscoat 295, biscoat. 300, biscoat 360, biscoat GPT, biscoat 400, biscoat 700, biscoat 540, biscoat 3000, biscoat 3700 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), Kayarad R-526, HDDA, NPGDA, TPGDA, MANDA, R- 551, R-712, R-604, R-684, PET-30, GPO-303, TMPTA, THE-330, DPHA, DPHA-2H, DPHA-2C, DPHA-2I, DPHA-40H, D- 10, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, T-1420, T-2020, T-2040, TPA-320, TPA-330, RP-1040, RP-2040, R-011, R-300, R-205 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-220, M-233, M-240, M- 215, M-305, M-309, M-310, M-315, M-325, M-400, M-6200, M-6400 (manufactured by Toagosei Co., Ltd.), light acrylate BP-4EA, BP-4PA, BP-2EA, BP-2PA, DCP-A (above, manufactured by Kyoeisha Chemical Co., Ltd.), New Frontier BPE-4, BR-42M, GX-8345 (above, first Kogyo Seiyaku Co., Ltd.), ASF-400 (above, Nippon Steel Chemical Co., Ltd.), lipoxy SP-1506, SP-1507, SP-1509, VR-77, SP-4010, SP-4060 (above And NK ester A-BPE-4 (manufactured by Shin-Nakamura Chemical Co., Ltd.). Said compound can be used individually by 1 type or in combination of 2 or more types.

The amount of component (B1) added is not particularly limited, but is usually 15 to 70 masses when the total amount of components excluding the organic solvent in the first composition of the present invention is 100 mass%. %. The reason for this is that when the addition amount is less than 20% by mass, the scratch resistance of a cured product obtained by curing the curable composition may be lowered, whereas when the addition amount exceeds 70% by mass. The hardness of the cured product of the curable composition may be reduced.
For this reason, the amount of component (B1) added is more preferably 20 to 60% by mass.

(D1) Radical polymerization initiator In the first composition and the second of the present invention, it is preferable to blend (D1) a radical polymerization initiator.
As such (D1) radical polymerization initiator, for example, a compound that thermally generates active radical species (thermal polymerization initiator) and a compound that generates active radical species by radiation (light) irradiation (photopolymerization initiation) In general, a photopolymerization initiator is preferable because it can be cured in a short time.

  Specific examples of the photopolymerization initiator include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, Triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropyl Phenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, -Isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl)- 2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), 4-benzoyl-4′-methyldiphenyl sulfide, etc. be able to.

  Examples of commercially available photopolymerization initiators include Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, Darocur 1116, manufactured by Ciba Specialty Chemicals Co., Ltd. 1173, BASF's Lucillin TPO, 8893UCB's Ubekrill P36, Fratelli Lamberti's Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B, Nippon Kayaku Kogyo Co., Ltd., KAYACURE BMS, etc. be able to.

  Examples of the thermal polymerization initiator include peroxides and azo compounds. Specific examples include benzoyl peroxide, t-butyl-peroxybenzoate, and azobisisobutyronitrile.

  The content of the (D1) radical polymerization initiator used as necessary in the present invention is 0.01 to 20% by mass when the total amount of components excluding the solvent in the composition is 100% by mass. It is preferably 0.1 to 10% by mass. When the amount is less than 0.01% by mass, the added effect is not sufficiently exhibited. When the amount exceeds 20% by mass, the hardness may be inferior when a cured product is obtained.

(E1) Organic solvent The composition of this invention can contain the organic solvent in order to adjust the thickness of a coating film or to improve coating property. For example, the viscosity (25 ° C.) when used for the purpose of the present invention is usually 0.1 to 50,000 mPa · sec, and preferably 0.5 to 10,000 mPa · sec.

  Specific examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and methyl amyl ketone, esters such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methanol and ethanol. , Sec-butanol, t-butanol, alcohols such as 2-propanol and isopropanol, aromatics such as benzene, toluene and chlorobenzene, aliphatics such as hexane and cyclohexane, or a combination of two or more Is mentioned. Among these, ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, methyl amyl ketone, esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methanol, ethanol, sec-butanol , T-butanol, 2-propanol, isopropanol and the like are preferable, and methyl isobutyl ketone, methyl amyl ketone, methyl ethyl ketone, t-butanol, and propylene glycol monomethyl ether are used alone or in combination of two or more.

  (E1) The total addition amount of the organic solvent is not particularly limited, but it is preferably 50 to 100,000 parts by mass with respect to 100 parts by mass in total of components other than the organic solvent. The reason for this is that when the addition amount is less than 50 parts by mass, it may be difficult to adjust the viscosity of the curable composition, while when the addition amount exceeds 100,000 parts by mass, the curable composition. This is because the storage stability of the resin may be reduced, or the solid content may be reduced too much to reduce the coating uniformity.

(F1) Additive The composition of the present invention includes a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, a wettability improver, and a surfactant as long as the objects and effects of the present invention are not impaired. It is also preferable to further contain additives such as a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, a silane coupling agent, a pigment, a dye, and a slip agent.

  The coating method of the first composition and the second composition on the substrate is a usual coating method such as dipping coating, spray coating, flow coating, shower coating, roll coating, spin coating, brush coating. Etc.

<Second curable composition>
The 2nd curable composition (henceforth the 2nd composition) used by this invention may contain the following component (A2)-(F2). Among these components, (B2) and (C) are essential components, and (A2) and (D2) to (F2) are optional components that can be added as necessary.
(A2) Number of compounds (C) having three or more (meth) acryloyl groups in the molecule (B2) inorganic oxide particles modified with an ethylenically unsaturated group-containing silane coupling agent and having a number average particle size of 5 to 200 nm Particles having an average particle diameter of 0.3 to 20 μm (D2) Radical polymerization initiator (E2) Organic solvent (F2) Other additives These components will be described below.

(B2) Compound having 3 or more (meth) acryloyl groups in the molecule The component (B2) used in the second composition can be the same as the component (B1) described above, and detailed description thereof is omitted. .

  The amount of component (B2) added is not particularly limited, but is usually 15 to 95 masses when the total amount of components excluding the organic solvent in the second composition of the present invention is 100 mass%. %, And more preferably 20 to 90% by mass.

(C) Particles having a number average particle size of 0.3 to 20 μm The second composition used in the present invention has a number average particle size of 0 for the purpose of imparting antiglare properties to the second cured film. 3 to 20 μm particles (hereinafter also referred to as “anti-glare particles”) are blended. The particle size of the antiglare particles refers to the number average particle size measured by a dynamic light scattering method.

  The anti-glare particles can be used without particular limitation as long as they are transparent particles having the above particle diameters. For example, silica particles, zirconia particles, acrylic resin particles, acrylic-styrene resin particles, styrene resin particles. Etc.

  The kind of particle | grains used as (C) component in a 2nd composition can be suitably determined according to the required characteristic of an anti-glare film. Moreover, the particle diameter of (C) component can use the particle | grains of a number average particle diameter 0.3 to 2 times the film thickness of a 2nd cured film. When the number average particle diameter of the component (C) is 0.3 to 1 times the film thickness of the second cured film, the refractive index of the material constituting the component (C) is from components other than the component (C). It is preferable to select a cured film having a refractive index different from that of 0.03 or more. Here, “refractive index” represents a refractive index of 589 nm at 25 ° C. When the number average particle size of component C) is 1 to 2 times the film thickness of the second cured film, the antiglare particles protrude from the surface of the second cured film. It can be set arbitrarily.

  The amount of component (C) added is not particularly limited, but is 0.3 to 20 when the total amount of components excluding the organic solvent in the second composition of the present invention is 100% by mass. It is preferable that it is mass%, and it is more preferable to set it as 0.5-15 mass%.

(A2) Inorganic oxide particles having a number average particle size of 5 to 200 nm modified with an ethylenically unsaturated group-containing silane coupling agent The (A2) component optionally used in the second composition is Since the same thing can be used, detailed description is abbreviate | omitted.

  The amount of component (A2) added is not particularly limited, but is 30 to 80% by mass when the total of components excluding the organic solvent in the second composition of the present invention is 100% by mass. It is preferable that it is preferable to set it as 35-80 mass%.

  In addition, since (D2), (E2), and (F2) that can be optionally added can be the same as (D1), (E1), and (F1), detailed description thereof is omitted.

<Formation of cured film>
The composition of the present invention can be cured by heat and / or radiation (light). When using heat, as the heat source, for example, an electric heater, an infrared lamp, hot air, or the like can be used. In the case of radiation (light), the radiation source is not particularly limited as long as the composition can be cured in a short time after coating. For example, as an infrared radiation source, a lamp, a resistance heating plate, Commercially available lasers, etc., as visible ray sources, sunlight, lamps, fluorescent lamps, lasers, etc., ultraviolet ray sources, mercury lamps, halide lamps, lasers, etc., and electron beam sources Using thermionic electrons generated from the tungsten filament, cold cathode method for generating metal through a high voltage pulse, and secondary electron method using secondary electrons generated by collision of ionized gaseous molecules with metal electrodes Can be mentioned. Examples of the source of alpha rays, beta rays, and gamma rays include fission materials such as ⁶⁰ Co. For gamma rays, a vacuum tube that collides accelerated electrons with the anode can be used. These radiations can be irradiated alone or in combination of two or more at a certain time.

The cured product of the present invention can be obtained by coating and curing the curable composition on various substrates, for example, plastic substrates. Specifically, it can be obtained as a coated molded body by coating the composition and preferably drying the volatile component at 20 to 200 ° C. and then performing a curing treatment with heat and / or radiation. The preferable curing conditions in the case of heat are 20 to 150 ° C., and are performed within a range of 10 seconds to 24 hours. When using radiation, it is preferable to use ultraviolet rays or electron beams. In such a case, the preferable irradiation amount of ultraviolet rays is 0.01 to 10 J / cm ² , more preferably 0.1 to ² J / cm ² . Further, the preferable electron beam irradiation conditions are an acceleration voltage of 10 to 300 kV, an electron density of 0.02 to 0.30 mA / cm ² , and an electron beam irradiation amount of 1 to 10 Mrad.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, the scope of the present invention is not limited to description of these Examples. “Part” and “%” mean “part by mass” and “% by mass” unless otherwise specified. Further, in the present invention, the “solid content” means a part obtained by removing volatile components such as a solvent from the composition, and specifically, obtained by drying the composition on a hot plate at a predetermined temperature for 1 hour. It means a residue (nonvolatile component).
Production Example 1
Synthesis of silane coupling agent (Ab)
To a solution consisting of 221 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyltin dilaurate in dry air, 222 parts of isophorone diisocyanate was added dropwise over 1 hour at 50 ° C. with stirring, followed by heating and stirring at 70 ° C. for 3 hours. This is composed of NK ester A-TMM-3LM-N (manufactured by Shin-Nakamura Chemical Co., Ltd.) comprising 60% by mass of pentaerythritol triacrylate and 40% by mass of pentaerythritol tetraacrylate. 549 parts were added dropwise at 30 ° C. over 1 hour, and then heated and stirred at 60 ° C. for 10 hours to obtain an organic compound (Ab) containing a polymerizable unsaturated group. When the amount of residual isocyanate in the product was analyzed by FT-IR, it was 0.1% or less, indicating that the reaction was almost quantitatively completed. Infrared absorption spectrum of the product disappeared absorption peaks characteristic 2260 cm ^-1 to the absorption peak and the raw material isocyanate compounds characteristic 2550 cm ^-1 mercapto group in the raw material, new urethane bond and S (C = O) NH- peaks characteristic 1720 cm ^-1 to a peak and an acryloxy group of characteristic 1660 cm ^-1 based on observed, acryloxy group and -S (C = O as a polymerization unsaturated group) NH-, It was shown that an acryloxy group-modified alkoxysilane having a urethane bond was formed. As a result, a total of 773 parts of organic compounds (Abs) represented by the formulas (14) and (15) and 220 parts of pentaerythritol tetraacrylate were obtained.

Production Example 2
Production of Reactive Particle 1 8.84 parts of composition produced in Production Example 1 (containing 6.88 parts of silane coupling agent (Ab)), silica particle dispersion (silica concentration 31.6%, manufactured by ADEKA AT- 20Q was replaced with MEK by ultrafiltration) 89.9 parts, 0.12 part of ion exchange water, 0.03 part of 0.1N sulfuric acid, and 0.01 part of p-hydroxyphenyl monomethyl ether After stirring at 60 ° C. for 4 hours, 1.38 parts of orthoformate methyl ester was added, and the mixture was further stirred at the same temperature for 1 hour to obtain a dispersion of reactive particles. 2 g of this dispersion was weighed in an aluminum dish, dried on a hot plate at 175 ° C. for 1 hour, and weighed to determine the solid content, which was 36.4%.

Production Example 3
Production of Reactive Particles 2 0.73 parts of methacryloxypropyltrimethoxysilane (SZ6030; manufactured by Toray Dow Corning), silica particle dispersion (silica concentration 30%, AT-20QB manufactured by Adeka) was replaced with MEK by ultrafiltration A mixture of 97.7 parts, 0.12 parts of ion-exchanged water, 0.03 part of 0.1N sulfuric acid, and 0.01 part of p-hydroxyphenyl monomethyl ether was stirred at 60 ° C. for 4 hours, and then ortho 1.38 parts of formic acid methyl ester was added, and the mixture was further heated and stirred at the same temperature for 1 hour to obtain a dispersion of reactive particles. 2 g of this dispersion was weighed on an aluminum dish, dried on a hot plate at 175 ° C. for 1 hour, and weighed to determine the solid content, which was 30.0%.

Preparation of Curable Composition 1 135.7 parts (40.8 parts as reactive particles) of reactive particle dispersion 2 produced in Production Example 3 above, polyfunctional urethane acrylate (manufactured by Nippon Kayaku Co., Ltd., DPHA-40H) ) 33.9 parts, 22.5 parts of isocyanuric acid EO-modified triacrylate (manufactured by Toagosei Co., Ltd., Aronix M315), 1.4 parts of 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals, Irgacure 184), 1.4 parts of 4-benzoyl-4'-methyldiphenyl sulfide (manufactured by Nippon Kayaku Co., Ltd., KAYACURE BMS) and 114 parts of propylene glycol monomethyl ether (PGME) were placed in a flask and stirred for 30 minutes at room temperature to uniformly 308.8 parts A liquid mixture was obtained. Thereafter, the solvent was distilled off using an evaporator at a reduced pressure of 80 mmHg, and the mixture was concentrated until the total amount became 249.8 parts, whereby the intended composition 1 was obtained.

Preparation of Curable Composition 2 214.6 parts of reactive silica particle dispersion 1 produced in Production Example 2 above (78.1 parts as reactive silica particles), dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., DPHA) 20.1 parts, 1-hydroxycyclohexyl phenyl ketone 1.8 parts (Ciba Specialty Chemicals, Irgacure 184), 4-benzoyl-4'-methyldiphenyl sulfide (Nippon Kayaku Co., Ltd., KAYACURE BMS) 1.4 parts and 13 parts of methyl ethyl ketone (MEK) were placed in a flask and stirred at room temperature for 30 minutes to obtain 249.5 parts of Composition 2.

Preparation of curable composition 3 27.8 parts of pentaerythritol triacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD PET-30), 18.6 parts of trimethylolpropane triacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., Biscoat # 295), 46.4 parts of polyfunctional acrylate (Osaka Organic Chemical Co., Ltd., biscoat # 802), 7.2 parts of 1-hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals), 150 parts of methyl ethyl ketone (MEK) The mixture was placed in a flask and stirred at room temperature for 30 minutes to obtain 250 parts of composition 3.

Preparation of curable compositions 4-6 1 part of acrylic particles (MX-180 average particle size 1.9 μm, manufactured by Soken Chemical Co., Ltd.) were added to 100 parts of the solids of compositions 1-3 above, and The mixture 4-6 was obtained by stirring for 30 minutes.
Table 1 shows the solid content compositions of Compositions 1 to 6, respectively.
Show.

The contents of the commercially available products described in Table 1 are shown below.
DPHA: dipentaerythritol hexaacrylate; Aronix M315 manufactured by Nippon Kayaku Kogyo Co., Ltd .: Isocyanuric acid EO-modified triacrylate: manufactured by Toagosei Co., Ltd. DPHA-40H: reaction product of dipentaerythritol pentaacrylate and hexamethylene diisocyanate; Nippon Kayaku Kogyo Co., Ltd. Viscoat # 802: Multifunctional acrylate; Osaka Organic Chemical Industry Co., Ltd. PET-30: Pentaerythritol triacrylate; Nippon Kayaku Kogyo Co., Ltd. Biscoat # 295: Trimethylolpropane triacrylate; Osaka Irgacure 184: 1-hydroxycyclohexyl phenyl ketone manufactured by Organic Chemical Industry Co., Ltd .; manufactured by Ciba Specialty Chemicals Co., Ltd.
KAYACURE BMS: 4-benzoyl-4′-methyldiphenyl sulfide; manufactured by Nippon Kayaku Co., Ltd. MX180TA: acrylic particles having an average particle size of 1.9 μm; manufactured by Soken Chemical Co., Ltd.

Production of laminated body 1 (Example 1)
The production procedure of the laminate 1 is shown below.
An 80 μm-thick cyclic olefin polymer film (manufactured by JSR, ARTON R5000) was treated using a corona surface treatment apparatus (manufactured by Kasuga Denki, AGF-012) at a discharge amount of 320 W · min / m ² . . On the treated film, curable composition 1 was applied as a younger layer using a 30 mil bar coater, placed in an oven at 80 ° C. for 3 minutes, dried, and 400 mJ / cm in a high pressure mercury lamp. ^The coating film was hardened by irradiating ² ultraviolet rays. The film thickness of the obtained younger brother layer was 12 μm. Subsequently, a curable composition 4 was overcoated as a second layer on the film with a hard coat using a 3 mil bar coater, which was put into an oven at 80 ° C. for 3 minutes, dried, and then a high pressure mercury lamp. The laminated body 1 was produced by irradiating with 400 mJ / cm ² ultraviolet rays. The film thickness of the second layer was 1.2 μm.

Preparation of laminated bodies 2-8 (Examples 2-4, Comparative Examples 1-4)
Laminates 2 to 6 were respectively produced in the same manner as the laminate 1 except that the curable composition described in Table 2 was used. Table 2 shows the thickness of the first and second layers of each laminate.

Various physical properties of the laminates 1 to 8 were measured or evaluated as follows. The evaluation results are shown in Table 2.

(1) Pencil hardness The measurement load was 500 g and the measurement method evaluated pencil hardness based on JIS K5600-5-4.
(2) Adhesiveness The adhesiveness of the cured film formed on the substrate is 1 mm square in terms of the remaining film ratio in a total of 100 grids in accordance with the cross cellophane tape peeling test in JIS K5600-5-6. The adhesion was evaluated according to the following criteria.
○: Remaining film ratio is 100 to 90%
Δ: Remaining film ratio is less than 90 to 50%
X: Remaining film ratio is less than 50 to 0%

(3) Antiglare property A fluorescent lamp (total luminous flux: 3520 lm) was projected on the film, and the degree of blurring of the outline of the fluorescent lamp was visually evaluated according to the following criteria.
○: The outline of the fluorescent lamp is not known at all.
Δ: The outline of the fluorescent lamp is slightly known.
X: The outline of the fluorescent lamp can be clearly seen.
(4) Haze Using a color haze meter manufactured by Suga Seisakusho Co., Ltd., the haze value (%) was measured according to ASTM D1003 and evaluated as a value including a base film.

(5) Curl property The film formed on the base material was cut into a size of 10 cm x 10 cm, the curl value was calculated as an average value of four corners, and evaluated according to the following evaluation criteria.
○: Curl value is less than 0.5 cm Δ: Curl value is 0.5 cm or more and less than 1 cm ×: Curl value is 1 cm or more

Production Example 4
Production of TAC film 100 parts by weight of cellulose acetate (oxidation degree 60.8%), 12 parts by weight of triphenyl phosphate, 300 parts by weight of methylene chloride and 50 parts by weight of methanol are put into a sealed container and kept at 80 ° C. under pressure. It dissolved completely with stirring. The solution was then filtered, cooled and kept at 30 ° C., and applied to a PET film affixed to a crow substrate with a 15 mil applicator. After standing in this state for 5 minutes, drying was further terminated in an oven at 100 ° C. for 1 hour to obtain a TAC film having a thickness of 80 μm.

Manufacture of laminated body 9 Except having used the TAC film manufactured in the manufacture example 4, the operation similar to Example 1 was performed and the laminate 9 was produced.

Production Example 5
Production of PVA Film A dyeing solution was prepared by dissolving 20 parts by weight of boric acid, 0.2 parts by weight of iodine, and 0.5 parts by weight of potassium iodide in 480 parts by weight of water. A PVA film (Vinylon film # 40, manufactured by Aicello) was immersed in this dyeing solution for 30 seconds, and then the film was stretched twice in one direction and dried to prepare a PVA film having a thickness of 30 μm.
Production Example 6
Production of UV-curable adhesive 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (Daicel, Celoxide 2021P) 39.4 parts, poly [(3-methyl-1,5- (Pentanediol) / (adipic acid)] (manufactured by Kuraray Co., Ltd., Kuraray polyol P-1010) 11.6 parts, diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate (manufactured by Sun Apro, CPI-110A) 5 parts, 38.4 parts of neopentyl glycol diglycidyl ether (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., SR-NPG) and 8.1 parts of polyoxypropylene glyceryl ether (manufactured by Sanyo Chemical Industries, Ltd., Sanniks GP-400) The mixture was stirred for 4 hours and mixed uniformly. Thereafter, it was allowed to stand for 24 hours to obtain an ultraviolet curable adhesive.

Example 5
The UV curable adhesive was coated on a cyclic olefin polymer film (manufactured by JSR, ARTON R5000) using a wire bar coater # 3, and the PVA film of Production Example 5 was coated with defects such as bubbles. Bonding was done so as not to enter. Next, an ultraviolet curable adhesive was applied onto the laminate 1 using a wire bar coater # 3, and was bonded onto the PVA of the bonded film so that no defects such as bubbles would enter. On the glass plate, the four sides are fixed with tape so that the laminate 1 is on top, and light is irradiated from the laminate 1 side with a metal halide lamp (illuminance 220 mW / cm ² , irradiation light quantity 1,000 mJ / cm ² ), A polarizing plate 1 was produced.

Comparative Example 5
In Example 5, the same operation was performed except that the TAC film of Production Example 4 was used instead of the cyclic olefin polymer film, and the laminate 9 was used instead of the laminate 1, and the polarizing plate 2 was produced.

(6) Wet heat resistance test The polarizing plates 1 and 2 are 50 mm × using a super dumbbell cutter (SSK-12862-06, manufactured by Dumbbell) and an SD-type lever-type sample cutter (SDL-200, manufactured by Dumbbell). Punched to a size of 80 mm. The punched polarizing plate was fixed to 7 mm-thick non-alkali glass with a heat-resistant adhesive and exposed to an environment of 85 ° C. and 85% RH (relative humidity) for 250 hours. As a result, the polarizing plate 1 could not be confirmed after the wet heat resistance test, but the polarizing plate 2 was changed to yellow due to the loss of the color of the polarizer.

  The antiglare film of the present invention has excellent heat resistance, and can be suitably used for a liquid crystal display device used in a place where the temperature is particularly high.

DESCRIPTION OF SYMBOLS 1 ... Anti-glare film 10 ... Transparent base material 21 ... 1st cured film 22 ... 2nd cured film

Claims (9)

Obtained by curing the first cured film having a film thickness of 1 to 20 μm and the second curable composition obtained by curing the first curable composition on at least one surface of the cyclic olefin-based resin substrate. Having a second cured film with a thickness of 0.5 to 20 μm in this order,
The first curable composition comprises (A1) inorganic oxide particles having a number average particle diameter of 5 to 200 nm modified with an ethylenically unsaturated group-containing silane coupling agent, and (B1) three or more in the molecule. Containing a compound having a (meth) acryloyl group of
The second curable composition contains (B2) a compound having 3 or more (meth) acryloyl groups in the molecule, and (C) particles having a number average particle size of 0.3 to 20 μm,
The antiglare film, wherein the total of the first cured film and the second cured film is 2 to 30 μm.   The antiglare film according to claim 1, wherein the second curable composition further comprises (A2) inorganic oxide particles having a particle diameter of 5 to 200 nm modified with an ethylenically unsaturated group-containing silane coupling agent.   The antiglare film according to claim 1, wherein the inorganic oxide particles of the component (A1) are silica particles.   The antiglare film according to claim 2, wherein the inorganic oxide particles of the component (A2) are silica particles.   The anti-glare film according to any one of claims 1 to 3, wherein the component (C) is acrylic resin particles.   The antiglare film according to any one of claims 1 to 5, wherein the component (C) has a number average particle size of 0.3 to 2 times the film thickness of the second cured film.   The anti-glare film according to any one of claims 1 to 6, wherein a total film thickness of the first cured film and the second cured film is 3 to 20 µm.   A polarizing plate comprising the antiglare film according to claim 1.   A liquid crystal display device comprising the polarizing plate according to claim 8.

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