JP2008062539A - Glare shielding film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a glare shielding film which keeps a protective layer capable of demonstrating curability, abrasion resistance, hardness, adhesiveness, transparency, etc., and additionally a superior glare shielding effect overlying the surface of a transparent film made of a cycloolefin resin. <P>SOLUTION: In the glare shielding film, a particle-containing protective layer overlies the surface of the transparent film made of a cycloolefin resin. The protective layer is obtained by photocuring a protective layer forming composition containing an active energy ray curable composition [containing (A) 40-60 wt.% of a polyfunctional monomer having a surface tension of 37 mN/m or below and at least three acryloyl groups, (B) 10-60 wt.% of a polymer obtained by bringing acrylic acid addition reaction with a glycidyl (meth)acrylate polymer, and (C) optionally 0-50 wt.% of another acrylic oligomer] and particles with a mean particle size of 50-600 nm. The glare shielding film has a maximum height surface roughness Ry of 1.0-3.2 μm and an image clarity of at least 5%. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an antiglare film, and more particularly to a laminated antiglare film in which a protective layer is adhered to a transparent film made of a cyclic olefin resin.

Conventionally, polycarbonate (PC), polymethylmethacrylate (PMMA), etc. have been widely used as molding materials for optical applications, but PC has a large birefringence, PMMA has a high water absorption, and heat resistance is insufficient. Therefore, there is a demand for the development of new molding materials with improved performance.
Therefore, in recent years, cyclic olefin-based resins have attracted attention and are being widely used. However, the cyclic olefin-based resin film has low birefringence, low moisture absorption, high transparency, and high heat resistance, but has a problem that the surface is slightly brittle and easily scratched.

In general, in order to impart hard coat properties to various plastic materials, the surface of the plastic material is coated with an active energy ray curable resin.
Therefore, it is conceivable to apply the active energy ray-curable resin to the surface of the cyclic olefin resin film, but a general-purpose resin has a problem that the adhesiveness to the cyclic olefin resin film is insufficient.

  In contrast, a method of containing a non-reactive component polymer in the active energy ray-curable coating agent (for example, Patent Document 1), a method of blending an alicyclic (meth) acrylic compound as a polymerizable compound (for example, Patent Document 2), methods using a specific photopolymerization initiator (for example, Patent Document 3), and the like have been proposed, and the adhesiveness can be improved by these methods.

  However, in these methods, the addition of these polymers and the like reduces the crosslink density of the active energy ray-curable coating agent, reduces the scratch resistance of the resulting cured film, causes curling, and further There are problems such as insufficient hardness of the cured film on the cyclic olefin-based resin film.

  In addition, the molding material for optical use displays a clearer image particularly in application to various displays such as a liquid crystal display device such as a plasma display device, a mobile phone, a PDA (personal digital assistant), and a video camera, Suppresses glare that occurs in the display image due to reflection or scattering of light that enters or exits the screen, and also causes rainbow-colored moire called so-called Newton's ring that occurs due to light interference caused by the display image. There is a strict demand for higher performance, such as preventing the occurrence of problems.

Various antireflection treatments, antiglare treatments, and the like have been taken for such high performance, but the present situation has yet to be obtained that satisfies all of these requirements.
JP-A-8-12787 JP-A-5-306378 JP 2002-275392 A

  The object of the present invention is to provide a protective layer capable of exhibiting an excellent antiglare effect on its surface in addition to properties such as curability, scratch resistance, hardness, adhesion, and transparency in a transparent film made of a cyclic olefin resin. It aims at providing the anti-glare film formed by.

  The present inventors have conducted extensive research on the characteristics of various optical molding materials such as so-called antireflection films and antiglare films. As a result, the basics of low birefringence, low moisture absorption, high transparency, high heat resistance, etc. In addition to ensuring a certain characteristic, partial display unevenness such as so-called white blur and / or black floating, or unclear display of background image, non-uniform display such as glare and / or glare, Newton ring We found that there are mainly three types of defects called light interference, and it is necessary to eliminate them in a well-balanced manner. Furthermore, a specific resin composition containing specific particles on the surface of a transparent film made of cyclic polyolefin The protective layer is coated with an object, and the average particle diameter of the particles constituting the protective layer is adjusted to display a clear image, and the maximum height roughness R on the surface of the protective layer It has also been found that three problems that are in a trade-off relationship with each other, such as preventing interference of light by adjusting, and preventing uneven display such as glare by adjusting image clarity, can be solved. The present invention has been completed.

That is, according to the present invention, the antiglare film is configured by laminating a particle-containing protective layer on the transparent film surface,
The transparent film is made of a cyclic olefin resin,
The protective layer is a layer obtained by photocuring a protective layer forming composition containing an active energy ray-curable resin composition and particles having an average particle size of 50 to 600 nm,
The active energy ray-curable resin composition has a maximum height roughness Ry of 1.0 to 3.2 μm on its surface and a mapping property of 5% or more. Is 40 to 60% by weight of a polyfunctional monomer having an acryloyl group of 3 or more, and (B) a polymer obtained by addition reaction of acrylic acid with a glycidyl (meth) acrylate polymer. And (C) 0 to 50% by weight of any other acrylic oligomer (provided that the total of the respective components is 100% by weight).

  According to the present invention, basic characteristics such as low birefringence, low moisture absorption, high transparency, and high heat resistance can be ensured by using a transparent film made of a cyclic olefin resin. In addition, by forming the protective layer using specific particles in combination with a specific resin composition, it is possible to improve the adhesion and impart a hard coat function to the transparent film described above. Furthermore, transparency is ensured by using particles having a specific average particle diameter, and light that is likely to be generated when transparency is increased while preventing partial display unevenness such as so-called white blur and black floating. It is possible to satisfy all of the characteristics that are in a trade-off relationship with each other, such as effectively preventing Newton's ring due to interference and sufficiently exhibiting good image clarity that prevents the phenomenon of image flickering and glare.

The antiglare film of the present invention is mainly constituted by laminating a transparent film and a protective layer.
The transparent film is mainly composed of a cyclic olefin resin. Examples of the cyclic olefin resin include the following (co) polymers. (1) A ring-opening polymer of a cyclic olefin represented by the following formula (I) (hereinafter referred to as “specific monomer”). (2) A ring-opening copolymer of a specific monomer and a copolymerizable monomer. (3) A hydrogenated (co) polymer of the ring-opening (co) polymer of (1) or (2) above. (4) A (co) polymer obtained by cyclizing the ring-opening (co) polymer of (1) or (2) by Friedel-Craft reaction and then hydrogenating it. (5) A saturated copolymer of a specific monomer and an unsaturated double bond-containing compound. (6) Addition type (co) polymers of one or more monomers selected from specific monomers, vinyl cyclic hydrocarbon monomers and cyclopentadiene monomers and their hydrogenated (co) heavy Coalescence. (7) An alternating copolymer of a specific monomer and an acrylate.

[Wherein, R ^{1 to} R ⁴ are the same or different and each represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or another monovalent organic group, and R ¹ and R ² or R ³ and R ⁴ may be combined to form a divalent hydrocarbon group, and R ¹ or R ² and R ³ or R ⁴ are bonded to each other to form a monocyclic or polycyclic structure. May be. m is 0 or a positive integer, and p is 0 or a positive integer. ]

<Specific monomer>
Specific examples of the specific monomer include the following compounds, but the present invention is not limited to these specific examples.
Bicyclo [2.2.1] hept-2-ene,
Tricyclo [4.3.0.1 ^2,5 ] -8-decene,
Tricyclo [4.4.0.1 ^2,5 ] -3-undecene,
Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
Pentacyclo ^{[6.5.1.1 3,6 .0 2,7 .0 9,13]} -4- pentadecene,
5-methylbicyclo [2.2.1] hept-2-ene,
5-ethylbicyclo [2.2.1] hept-2-ene,
5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-cyanobicyclo [2.2.1] hept-2-ene,
8 methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-ethoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-n-propoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8 isopropoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-n-butoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,

8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-methyl-8-ethoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-methyl -8-n-propoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-methyl-8-isopropoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-methyl -8-n-butoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
5-ethylidenebicyclo [2.2.1] hept-2-ene,
8 ethylidene tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
5-phenylbicyclo [2.2.1] hept-2-ene,
8-phenyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
5-fluorobicyclo [2.2.1] hept-2-ene,
5-fluoromethylbicyclo [2.2.1] hept-2-ene,
5-trifluoromethylbicyclo [2.2.1] hept-2-ene,

5-pentafluoroethylbicyclo [2.2.1] hept-2-ene,
5,5-difluorobicyclo [2.2.1] hept-2-ene,
5,6-difluorobicyclo [2.2.1] hept-2-ene,
5,5-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5-methyl-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5,5,6-trifluorobicyclo [2.2.1] hept-2-ene,
5,5,6-tris (fluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrafluorobicyclo [2.2.1] hept-2-ene,

5,5,6,6-tetrakis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5-difluoro-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-fluoro-5-pentafluoroethyl-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5-heptafluoro-iso-propyl-6-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-chloro-5,6,6-trifluorobicyclo [2.2.1] hept-2-ene,
5,6-dichloro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-trifluoromethoxybicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-heptafluoropropoxybicyclo [2.2.1] hept-2-ene,
8-fluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-fluoro-methyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8 difluoromethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8 pentafluoroethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,

8,8-difluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,9-difluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-methyl-8-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9- trifluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9- tris (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9,9- tetrafluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9,9- tetrakis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,

8,8-difluoro-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,9-difluoro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9- trifluoro-9-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9- trifluoro-9-trifluoromethoxy-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,

8,8,9- trifluoro-9-pentafluoro propoxy tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-Fluoro-8-pentafluoroethyl-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,9-difluoro-8-heptafluoro-iso- propyl-9-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-Chloro -8,9,9- trifluoro tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,

8,9-dichloro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8- (2,2,2-trifluoroethoxy-carbonyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
, And the like 8-methyl-8- (2,2,2-trifluoroethoxy-carbonyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene. These can be used alone or in combination of two or more.

Among the specific monomers, in the above formula (1), R ¹ and R ³ are each a hydrogen atom or a hydrocarbon group having 1 to 10, more preferably 1 to 4, particularly preferably 1 to 2 carbon atoms. Each of R ² and R ⁴ is a hydrogen atom or a monovalent organic group, and at least one of R ² and R ⁴ represents a polar group having a polarity other than a hydrogen atom and a hydrocarbon group; An integer of 3 and p is an integer of 0 to 3, more preferably m + p = 0 to 4, more preferably 0 to 2, particularly preferably m = 1 and p = 0. The specific monomer with m = 1 and p = 0 is preferred in that the cyclic olefin resin obtained has a high glass transition temperature and excellent mechanical strength.

  Examples of the polar group of the specific monomer include a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, an allyloxycarbonyl group, an amino group, an amide group, and a cyano group, and these polar groups are connected via a linking group such as a methylene group. It may be bonded. In addition, a hydrocarbon group in which a divalent organic group having a polarity such as a carbonyl group, an ether group, a silyl ether group, a thioether group, or an imino group is bonded as a linking group can also be exemplified. Among these, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, or an allyloxycarbonyl group is preferable, and an alkoxycarbonyl group or an allyloxycarbonyl group is particularly preferable.

Furthermore, a monomer in which at least one of R ² and R ⁴ is a polar group represented by the formula — (CH ₂ ) _n COOR is obtained by using a cyclic olefin-based resin having a high glass transition temperature, a low hygroscopic property, and various materials. It is preferable at the point from which it has the outstanding adhesiveness. In the formula relating to the specific polar group, R is a hydrocarbon group having 1 to 12 carbon atoms, more preferably 1 to 4, particularly preferably 1 to 2, and preferably an alkyl group. In addition, n is usually 0 to 5, but the smaller the value of n, the higher the glass transition temperature of the resulting cyclic olefin resin, which is preferable, and the specific monomer having n of 0 is It is preferable in that the synthesis is easy.

In the above formula (I), R ¹ or R ³ is preferably an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, particularly preferably a methyl group, In particular, the fact that this alkyl group is bonded to the same carbon atom as the carbon atom to which the specific polar group represented by the formula — (CH ₂ ) _n COOR is bonded is the moisture absorption of the resulting cyclic olefin resin. It is preferable at the point which can make property low.

<Copolymerizable monomer>
Specific examples of the copolymerizable monomer include cycloolefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, and dicyclopentadiene. The number of carbon atoms of the cycloolefin is preferably 4-20, and more preferably 5-12. These can be used alone or in combination of two or more.
A preferred use range of the specific monomer / copolymerizable monomer is 100/0 to 50/50, more preferably 100/0 to 60/40, in weight ratio.

<Ring-opening polymerization catalyst>
In the present invention, (1) a ring-opening polymer of a specific monomer, and (2) a ring-opening polymerization reaction for obtaining a ring-opening copolymer of a specific monomer and a copolymerizable monomer are metathesis It is carried out in the presence of a catalyst. This metathesis catalyst includes (a) at least one selected from W, Mo and Re compounds, (b) Deming periodic table group IA elements (for example, Li, Na, K, etc.), IIA group elements (for example, , Mg, Ca, etc.), group IIB elements (eg, Zn, Cd, Hg, etc.), group IIIA elements (eg, B, Al, etc.), group IVA elements (eg, Si, Sn, Pb, etc.), or group IVB A catalyst comprising a combination of at least one element selected from compounds having elements (for example, Ti, Zr, etc.) and having at least one element-carbon bond or the element-hydrogen bond. In this case, in order to increase the activity of the catalyst, an additive (c) described later may be added.

Representative examples of W, Mo or Re compounds suitable as component (a) include WCl ₆ , MoCl ₆ , ReOCl _3, etc. JP-A-1-132626, page 8, lower left column, line 6 to page 8, upper right page. The compounds described in column 17th line can be mentioned.
Specific examples of the component (b) include n-C ₄ H ₉ Li, (C ₂ H ₅ ) ₃ Al, (C ₂ H ₅ ) ₂ AlCl, (C ₂ H ₅ ) _1.5 AlCl _1.5 , (C ₂ H ₅ ) AlCl ₂ , methylalumoxane, LiH and the like, the compounds described in JP-A-1-132626, page 8, upper right column, line 18 to page 8, lower right column, line 3 can be mentioned. As typical examples of the component (c) which is an additive, alcohols, aldehydes, ketones, amines and the like can be suitably used, but further, JP-A-1-132626, page 8, lower right column, The compounds shown in line 16 to page 9, upper left column, line 17 can be used.

  The amount of the metathesis catalyst used is a range in which “(a) component: specific monomer” is usually 1: 500 to 1: 50,000 in terms of the molar ratio of the component (a) to the specific monomer. The range is preferably 1: 1,000 to 1: 10,000. The ratio of the component (a) to the component (b) is such that (a) :( b) is 1: 1 to 1:50, preferably 1: 2 to 1:30 in terms of metal atomic ratio. The ratio of the component (a) to the component (c) is such that the molar ratio (c) :( a) is in the range of 0.005: 1 to 15: 1, preferably 0.05: 1 to 7: 1. The

<Solvent for polymerization reaction>
Examples of the solvent used in the ring-opening polymerization reaction (solvent constituting the molecular weight modifier solution, solvent for the specific monomer and / or metathesis catalyst) include alkanes such as pentane, hexane, heptane, octane, nonane and decane. , Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene Halogenated alkanes such as chloroform and tetrachloroethylene, aryl halides; saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate, and dimethoxyethane; Ether, tetrahydrofuran, and the like can be illustrated ethers such as dimethoxyethane, it can be used singly or in combination. Of these, aromatic hydrocarbons are preferred.
As the amount of the solvent used, “solvent: specific monomer (weight ratio)” is usually in an amount of 1: 1 to 10: 1, preferably in an amount of 1: 1 to 5: 1. The

<Molecular weight regulator>
The molecular weight of the resulting ring-opening (co) polymer can be adjusted by the polymerization temperature, the type of catalyst, and the type of solvent. In the present invention, the molecular weight is adjusted by allowing the molecular weight regulator to coexist in the reaction system. To do.
Here, suitable molecular weight regulators include, for example, α-olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and the like. Styrene can be mentioned, and among these, 1-butene and 1-hexene are particularly preferable. These molecular weight regulators can be used alone or in admixture of two or more.
The amount of the molecular weight regulator used is 0.005 to 0.6 mol, preferably 0.02 to 0.5 mol, per 1 mol of the specific monomer subjected to the ring-opening polymerization reaction.

(2) In order to obtain a ring-opening copolymer, a specific monomer and a copolymerizable monomer may be subjected to ring-opening copolymerization in the ring-opening polymerization step, and further, polybutadiene, polyisoprene, etc. In the presence of unsaturated hydrocarbon polymers such as conjugated diene compounds, styrene-butadiene copolymers, ethylene-nonconjugated diene copolymers, polynorbornene and the like containing two or more carbon-carbon double bonds in the main chain. The specific monomer may be subjected to ring-opening polymerization.
The ring-opening (co) polymer obtained as described above can be used as it is, but obtained by hydrogenating an olefinically unsaturated bond in the molecule of this (co) polymer (3) Hydrogenated (co) polymers are preferred because they are excellent in heat resistance colorability and light resistance and can improve the durability of the retardation film.

<Hydrogenation catalyst>
For the hydrogenation reaction, a method of hydrogenating a normal olefinically unsaturated bond can be applied. That is, by adding a hydrogenation catalyst to the ring-opening polymer solution and allowing hydrogen gas at normal pressure to 300 atm, preferably 3 to 200 atm, to act at 0 to 200 ° C., preferably 20 to 180 ° C. Done.
As a hydrogenation catalyst, what is used for the hydrogenation reaction of a normal olefinic compound can be used. Examples of the hydrogenation catalyst include a heterogeneous catalyst and a homogeneous catalyst.

  Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst material such as palladium, platinum, nickel, rhodium, and ruthenium is supported on a carrier such as carbon, silica, alumina, and titania. In addition, homogeneous catalysts include nickel naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, chlorotris (triphenylphosphine) rhodium. Dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium, and the like. The form of the catalyst may be powder or granular.

These hydrogenation catalysts are used in such a ratio that the ring-opening (co) polymer: hydrogenation catalyst (weight ratio) is 1: 1 × 10 ⁻⁶ to 1: 2.
The hydrogenation rate of the hydrogenated (co) polymer is 50% or more, preferably 90% or more, more preferably 98% or more, and most preferably 99% or more, as measured by 500 MHz and ¹ H-NMR. The higher the hydrogenation rate, the better the stability to heat and light. When used as the transparent film of the present invention, stable characteristics can be obtained over a long period of time.
In addition, when the ring-opening (co) polymer molecule has an aromatic group, the aromatic group is less likely to deteriorate the heat resistance coloring property and light resistance, and conversely, optical characteristics such as refractive index and wavelength dispersion. The optical properties such as the above or heat resistance may be brought about, and hydrogenation is not necessarily required.

  The ring-opening (co) polymer obtained as described above contains known antioxidants such as 2,6-di-t-butyl-4-methylphenol and 2,2′-dioxy-3,3. '-Di-t-butyl-5,5'-dimethyldiphenylmethane, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane; UV absorber, eg 2,4 -It can be stabilized by adding dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone or the like. Further, additives such as a lubricant can be added for the purpose of improving processability.

The hydrogenated (co) polymer used as the cyclic olefin-based resin used in the present invention preferably has a gel content contained in the hydrogenated (co) polymer of 5% by weight or less, Further, it is particularly preferably 1% by weight or less.
In addition, as the cyclic olefin resin used in the present invention, (4) the ring-opening (co) polymer of the above (1) or (2) is cyclized by Friedel-Craft reaction and then hydrogenated (co) heavy Merges can also be used.

<Cyclization by Friedel-Craft reaction>
The method for cyclizing the ring-opening (co) polymer of (1) or (2) by Friedel-Craft reaction is not particularly limited, but the acidic compound described in JP-A-50-154399 is used. The publicly known method used can be adopted. Specifically, Lewis acids such as AlCl ₃ , BF ₃ , FeCl ₃ , Al ₂ O ₃ , HCl, CH ₃ ClCOOH, zeolite, activated clay, and Bronsted acid are used as the acidic compound.
The cyclized ring-opening (co) polymer can be hydrogenated in the same manner as the ring-opening (co) polymer of (1) or (2) above.
Further, as the cyclic olefin resin used in the present invention, (5) a saturated copolymer of the specific monomer and the unsaturated double bond-containing compound can also be used.

<Unsaturated double bond-containing compound>
As an unsaturated double bond containing compound, ethylene, propylene, butene etc., Preferably it is C2-C12, More preferably, C2-C8 olefin type compound can be mentioned.
The preferred use range of the specific monomer / unsaturated double bond-containing compound is 90/10 to 40/60, more preferably 85/15 to 50/50, in weight ratio.
In the present invention, in order to obtain a saturated copolymer of (5) a specific monomer and an unsaturated double bond-containing compound, a usual addition polymerization method can be used.

<Addition polymerization catalyst>
As the catalyst for synthesizing the above (5) saturated copolymer, at least one selected from a titanium compound, a zirconium compound and a vanadium compound and an organoaluminum compound as a promoter are used.

  Here, examples of the titanium compound include titanium tetrachloride and titanium trichloride, and examples of the zirconium compound include bis (cyclopentadienyl) zirconium chloride and bis (cyclopentadienyl) zirconium dichloride.

Furthermore, as the vanadium compound, the general formula VO (OR) _a X _b or V (OR) _c X _d [wherein R is a hydrocarbon group, X is a halogen atom, and 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ (a + b) ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 3 ≦ (c + d) ≦ 4. Or an electron-donating adduct of these compounds.

  Examples of the electron donor include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, acid amides, acid anhydrides, oxygen-containing electron donors such as alkoxysilanes, ammonia, amines, Examples thereof include nitrogen-containing electron donors such as nitrile and isocyanate.

  Furthermore, as the organoaluminum compound as the promoter, at least one selected from those having at least one aluminum-carbon bond or aluminum-hydrogen bond is used.

  In the above, for example, when the vanadium compound is used, the ratio of the vanadium compound to the organoaluminum compound is such that the ratio of aluminum atom to vanadium atom (Al / V) is 2 or more, preferably 2 to 50, particularly preferably 3 to 20. Range.

  As the solvent for the polymerization reaction used for the addition polymerization, the same solvent as that used for the ring-opening polymerization reaction can be used. Moreover, adjustment of the molecular weight of the (5) saturated copolymer obtained is normally performed using hydrogen.

  Furthermore, as the cyclic olefin-based resin used in the present invention, (6) one or more monomers selected from the above-mentioned specific monomer and a vinyl-based cyclic hydrocarbon-based monomer or a cyclopentadiene-based monomer. Addition copolymers and their hydrogenated copolymers can also be used.

<Vinyl cyclic hydrocarbon monomer>
Examples of the vinyl cyclic hydrocarbon monomer include vinyl cyclopentene monomers such as 4-vinylcyclopentene and 2-methyl-4-isopropenylcyclopentene, 4-vinylcyclopentane, 4-isopropenylcyclopentane and the like. Vinylated 5-membered hydrocarbon monomers such as vinylcyclopentane monomers, 4-vinylcyclohexene, 4-isopropenylcyclohexene, 1-methyl-4-isopropenylcyclohexene, 2-methyl-4-vinyl Vinylcyclohexene monomers such as cyclohexene and 2-methyl-4-isopropenylcyclohexene, vinylcyclohexane monomers such as 4-vinylcyclohexane and 2-methyl-4-isopropenylcyclohexane, styrene, α-methylstyrene, 2-methylstyrene, 3- Styrenic monomers such as styrene styrene, 4-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-phenylstyrene, p-methoxystyrene, d-terpene, 1-terpene, diterpene, d-limonene, 1- Terpene monomers such as limonene and dipentene, vinylcycloheptene monomers such as 4-vinylcycloheptene and 4-isopropenylcycloheptene, 4-vinylcycloheptane, 4-isopropenylcycloheptane, etc. And vinyl cycloheptane monomers. Styrene and α-methylstyrene are preferable. These can be used alone or in combination of two or more.

<Cyclopentadiene monomer>
(6) Examples of cyclopentadiene monomers used as addition copolymer monomers include cyclopentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene, 2-ethylcyclopentadiene, and 5-methyl. Examples include cyclopentadiene, 5,5-methylcyclopentadiene, and the like. Cyclopentadiene is preferred. These can be used alone or in combination of two or more.

The addition type (co) polymer of at least one monomer selected from the above specific monomer, vinyl cyclic hydrocarbon monomer and cyclopentadiene monomer is the above (5) specific monomer. It can be obtained by the same addition polymerization method as the saturated copolymer of the unsaturated double bond-containing compound.
The hydrogenated (co) polymer of the addition type (co) polymer can be obtained by the same hydrogenation method as the hydrogenated (co) polymer of the above (3) ring-opening (co) polymer. .
Further, as the cyclic olefin resin used in the present invention, (7) an alternating copolymer of the specific monomer and acrylate can also be used.

<Acrylate>
(7) Examples of the acrylate used for the production of the alternating copolymer of the specific monomer and the acrylate include, for example, straight chain having 1 to 20 carbon atoms such as methyl acrylate, 2-ethylhexyl acrylate, and cyclohexyl acrylate, C2-C20 heterocyclic group-containing acrylate such as branched or cyclic alkyl acrylate, glycidyl acrylate, 2-tetrahydrofurfuryl acrylate, C6-C20 aromatic ring group-containing acrylate such as benzyl acrylate, iso Examples thereof include acrylates having a polycyclic structure having 7 to 30 carbon atoms such as boronyl acrylate and dicyclopentanyl acrylate.

  In the present invention, (7) In order to obtain an alternating copolymer of the specific monomer and acrylate, when the total of the specific monomer and acrylate is 100 mol in the presence of Lewis acid, The specific monomer is 30 to 70 mol, the acrylate is 70 to 30 mol, preferably the specific monomer is 40 to 60 mol, and the acrylate is 60 to 40 mol, particularly preferably the specific monomer. The body undergoes radical polymerization at a rate of 45 to 55 mol and acrylate at a rate of 55 to 45 mol.

  (7) The amount of Lewis acid used to obtain the alternating copolymer of the specific monomer and acrylate is 0.001 to 1 mol per 100 mol of acrylate. Also, known organic peroxides or azobis radical polymerization initiators that generate free radicals can be used, and the polymerization reaction temperature is usually -20 ° C to 80 ° C, preferably 5 ° C to 60 ° C. . Moreover, the same solvent as used for the ring-opening polymerization reaction can be used as the solvent for the polymerization reaction.

  The “alternate copolymer” as used herein refers to a structure in which the structural unit derived from the specific monomer is not adjacent, that is, the structural unit derived from the acrylate is always adjacent to the structural unit derived from the specific monomer. It means a copolymer having a structure as a unit, and does not deny a structure in which structural units derived from acrylate are adjacent to each other.

The preferred molecular weight of the cyclic olefin resin used in the present invention is an intrinsic viscosity [η] _inh. 0.2 to 5 dl / g, more preferably 0.3 to 3 dl / g, particularly preferably 0.4 to 1.5 dl / g, and the number in terms of polystyrene measured by gel permeation chromatography (GPC). The average molecular weight (Mn) is 8,000 to 100,000, more preferably 10,000 to 80,000, particularly preferably 12,000 to 50,000, and the weight average molecular weight (Mw) is 20,000 to 300. It is preferable to use those having a molecular weight of 30,000, more preferably 30,000 to 250,000, particularly preferably 40,000 to 200,000.

Inherent viscosity [η] _inh , number average molecular weight and weight average molecular weight are in the above ranges, so that the heat resistance, water resistance, chemical resistance, mechanical properties of the cyclic olefin resin and the antiglare film of the present invention are used. The balance with the stability of the optical characteristics is good.

  The glass transition temperature (Tg) of the cyclic olefin resin used in the present invention is usually 120 ° C. or higher, preferably 120 to 350 ° C., more preferably 130 to 250 ° C., and particularly preferably 140 to 200 ° C. This is to stabilize the change in optical properties of the obtained cyclic olefin resin film and prevent thermal deterioration of the resin when heated to near Tg and processed, such as stretching.

  The saturated water absorption at 23 ° C. of the cyclic olefin resin used in the present invention is preferably 2% by weight or less, more preferably 0.01 to 2% by weight, and particularly preferably 0.1 to 1% by weight. . If the saturated water absorption is within this range, the optical characteristics are uniform, the adhesiveness between the obtained cyclic olefin resin film and other optical members and adhesives is excellent, and peeling does not occur during use. Moreover, it is excellent in compatibility with an antioxidant and the like, and can be added in a large amount. The saturated water absorption is a value obtained by immersing in 23 ° C. water for 1 week and measuring the increased weight according to ASTM D570.

The cyclic olefin resin used in the present invention has a photoelastic coefficient (C _P ) of 0 to 100 (× 10 ⁻¹² Pa ⁻¹ ) and a stress optical coefficient (C _R ) of 1,500 to 4. Those satisfying 1,000 (× 10 ⁻¹² Pa ⁻¹ ) are preferably used. Here, for the photoelastic coefficient (C _P ) and the stress optical coefficient (C _R ), various documents (Polymer Journal, Vol. 27, No, 9 pp 943-950 (1995), Journal of the Japan Rheological Society, Vol. 19, No. 2, p93-97 (1991), Photoelastic Experimental Method, Nikkan Kogyo Shimbun, 7th edition of 1975. The former is the degree of phase difference caused by stress in the glassy state of the polymer. In contrast, the latter represents the degree of occurrence of the phase difference due to stress in the flow state.

The large photoelastic coefficient (C _P ) means that stress generated from external factors or strain generated from freezing strain when the cyclic olefin resin film is used in combination with another optical member or adhesive. For example, in the case where a protective layer is laminated as in the present invention and when it is used by being fixed to another optical member, residual strain at the time of bonding or It means that an unnecessary phase difference is likely to be generated due to a minute stress generated by the shrinkage of the material accompanying a temperature change or a humidity change. Therefore, it is better that the photoelastic coefficient (C _P ) is as small as possible.

On the other hand, a large stress optical coefficient (C _R ) means that, for example, a desired retardation can be obtained with a small stretch ratio when imparting retardation to a cyclic olefin-based resin film. There is a great merit that it is easy to obtain a film capable of imparting a phase difference, and that when the same phase difference is desired, the film can be thinned as compared with a film having a small stress optical coefficient (C _R ).

From the above viewpoint, the photoelastic coefficient (C _P ) is preferably 0 to 100 (× 10 ⁻¹² Pa ⁻¹ ), more preferably 0 to 80 (× 10 ⁻¹² Pa ⁻¹ ), and particularly preferably 0. To 50 (× 10 ⁻¹² Pa ⁻¹ ), more preferably 0 to 30 (× 10 ⁻¹² Pa ⁻¹ ), and most preferably 0 to 20 (× 10 ⁻¹² Pa ⁻¹ ). Minimize unnecessary phase difference due to stress generated when the protective layer is laminated, stress generated when the antiglare film is fixed to other optical members, phase change caused by environmental changes during use, etc. It is to stop.

  The cyclic olefin resin used in the present invention includes the above (1) to (2) ring-opening (co) polymer, (3) to (4) hydrogenated (co) polymer, and (5) saturated copolymer. It is composed of a polymer, (6) an addition type (co) polymer, or a hydrogenated (co) polymer thereof, or (7) an alternating copolymer, which includes known antioxidants, ultraviolet absorbers, etc. Can be further stabilized. Moreover, in order to improve workability, the additive used in conventional resin processings, such as a lubricant, can also be added.

  The cyclic olefin resin used in the present invention is a known antioxidant, such as 2,6-di-t-butyl-4-methylphenol, 2,2′-dioxy-3,3′-di-t-butyl. -5,5'-dimethyldiphenylmethane, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, UV absorbers such as 2,4-dihydroxybenzophenone, 2-hydroxy It may be stabilized by adding -4-methoxybenzophenone or the like. Moreover, additives such as a lubricant may be added for the purpose of improving processability.

  The cyclic olefin resin film used in the antiglare film of the present invention is produced by manufacturing the above cyclic olefin resin into a film or sheet by a known method such as a melt molding method or a solution casting method (solvent casting method). Can be used. Of these, the solvent casting method is preferred from the viewpoint of good film thickness uniformity and surface smoothness. From the viewpoint of production cost, the melt molding method is preferable.

  The thickness of the cyclic olefin resin film used in the present invention is usually 1 to 500 μm, preferably 1 to 300 μm, more preferably 10 to 250 μm, and particularly preferably 50 to 200 μm. This is to ensure good handling and facilitate winding into a roll.

The thickness distribution of the cyclic olefin resin film used in the present invention is usually within ± 20%, preferably within ± 10%, more preferably within ± 5%, particularly preferably within ± 3% relative to the average value. is there. The thickness variation per 1 cm is usually 10% or less, preferably 5% or less, more preferably 1% or less, and particularly preferably 0.5% or less. By performing such thickness control, unevenness in the antiglare film surface can be prevented.
Specifically, trade name “Arton” manufactured by JSR Co., Ltd. and the like can be mentioned.

  As the cyclic olefin-based resin film used in the antiglare film of the present invention, a stretched one is preferably used as necessary. Specifically, it can be produced by a known uniaxial stretching method or biaxial stretching method. That is, a horizontal uniaxial stretching method by a tenter method, a compression stretching method between rolls, a longitudinal uniaxial stretching method using rolls with different circumferences, a biaxial stretching method in which horizontal uniaxial and longitudinal uniaxial are combined, a stretching method by an inflation method, etc. Can be used.

  In the case of the uniaxial stretching method, the stretching speed is usually 1 to 5,000% / min, preferably 50 to 1,000% / min, more preferably 100 to 1,000% / min, Particularly preferred is 100 to 500% / min.

  In the case of the biaxial stretching method, stretching may be performed in two directions at the same time, or the stretching may be performed in a direction different from the first stretching direction after uniaxial stretching. In these cases, the intersection angle of the two stretching axes is usually in the range of 120 to 60 degrees. The stretching speed may be the same or different in each stretching direction, and is usually 1 to 5,000% / min, preferably 50 to 1,000% / min, and more preferably Is from 100 to 1,000% / min, particularly preferably from 100 to 500% / min.

  The stretching temperature is not particularly limited, but is usually Tg ± 30 ° C., preferably Tg ± 10 ° C., more preferably Tg based on the glass transition temperature (Tg) of the cyclic olefin resin of the present invention. It is in the range of −5 to Tg + 10 ° C. Within the above range, it is possible to suppress the occurrence of phase difference unevenness, and control of the refractive index ellipsoid is facilitated, which is preferable.

  The draw ratio is not particularly limited because it is determined by desired properties, but is usually 1.01 to 10 times, preferably 1.1 to 5 times, and more preferably 1.1 to 3.5 times. When the draw ratio exceeds 10 times, it may be difficult to control the phase difference.

  The stretched film may be cooled as it is, but it should be allowed to stand in a temperature atmosphere of Tg-20 ° C. to Tg for at least 10 seconds, preferably 30 seconds to 60 minutes, more preferably 1 minute to 60 minutes. Is preferred. Thereby, the retardation film which consists of a stable cyclic olefin resin film with little change with time of retardation characteristics is obtained.

Moreover, the linear expansion coefficient of the cyclic olefin resin film used in the present invention is preferably 1 × 10 ⁻⁴ (1 / ° C.) or less, more preferably 9 × 10, in the temperature range of 20 ° C. to 100 ° C. ⁻⁵ (1 / ° C.) or less, particularly preferably 8 × 10 ⁻⁵ (1 / ° C.) or less, and most preferably 7 × 10 ⁻⁵ (1 / ° C.) or less. In the case of a retardation film, the difference in linear expansion coefficient between the stretching direction and the direction perpendicular thereto is preferably 5 × 10 ⁻⁵ (1 / ° C.) or less, more preferably 3 × 10 ⁻⁵ (1 / ° C.). ) Or less, particularly preferably 1 × 10 ⁻⁵ (1 / ° C.) or less. By setting the linear expansion coefficient within the above range, when the retardation film composed of the cyclic olefin resin film is used as the antiglare film of the present invention, a stress change caused by the temperature and humidity during use is exerted. Changes in retardation and antiglare properties are suppressed, and long-term stability can be obtained when used as an antiglare film of the present invention.

The film stretched as described above is oriented with molecules by stretching and gives a phase difference to transmitted light. This phase difference is the retardation value of the film before stretching, the stretching ratio, the stretching temperature, the stretching orientation. It can be controlled by the thickness of the later film. Here, the phase difference is defined by the product (Δnd) of the refractive index difference (Δn) of birefringent light and the thickness (d).
A protective layer is a layer obtained by photocuring the composition for protective layer formation containing the active energy ray curable resin composition and the particle | grains which have an average particle diameter of 50-600 nm.

  The active energy ray-curable resin composition is preferably (A) a polyfunctional monomer having a surface tension of 37 mN / m or less and having 3 or more acryloyl groups (hereinafter referred to as component (A)), (B) glycidyl ( Addition reaction of acrylic acid to (meth) acrylate polymer (hereinafter referred to as “component (B)”) and (C) optionally other acrylic oligomer (hereinafter referred to as “component (C)”) in a specific amount Do it. In particular, the component (A) is a component that can impart the hardness of a protective layer obtained from the active energy ray-curable resin composition, adhesion to a transparent film, and the like. The component (B) is a component that can impart further improvement in the hardness of the protective layer, curability, reduction in curling during curing, and the like. By blending the component (B), the component (B) has a high molecular weight and has many hydroxyl groups in the molecule, so the compatibility with the highly hydrophobic component (A) decreases. (B) It is thought that it is because it transfers to the surface of the surface protective film from which a component is obtained. (C) component is an arbitrary component which can provide toughness etc.

The surface tension of the component (A) is suitably in the range of 37 mN / m or less, more preferably 30 mN / m or more, from the viewpoint that sufficient hardness and adhesion can be obtained. The surface tension is measured by a vertical plate method (wilhemy method) using a Kyowa CBVP surface tension meter.
Specific examples of the component (A) include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, triacrylate of glycerin propylene glycol adduct, triacrylate of trimethylolpropane propylene glycol adduct, and the like. Is high in hardness, trimethylolpropane triacrylate and ditrimethylolpropane tetraacrylate are preferable.
The compounding amount of the component (A) in the active energy ray-curable resin composition is 40 to 60% by weight (however, the total of the components (A), (B), and (C) is 100% by weight). It is appropriate that it is 50 to 60% by weight.

  As described above, the component (B) is a polymer acrylate obtained by adding acrylic acid to a glycidyl (meth) acrylate polymer. The addition amount of acrylic acid to the epoxy group is suitably about 1: 1 to 1: 0.8 because unreacted epoxy adversely affects the stability of the composition, and 1: 1 to 1: 0.9. The degree is preferred.

  Examples of the glycidyl (meth) acrylate polymer include homopolymers of glycidyl (meth) acrylate, copolymers of glycidyl (meth) acrylate and various α, β-unsaturated monomers not containing a carboxyl group, and the like. It is done. Examples of the α, β-unsaturated monomer not containing the carboxyl group include various (meth) acrylic acid esters, styrene, vinyl acetate, acrylonitrile and the like. When glycidyl (meth) acrylate and an α, β-unsaturated monomer not containing a carboxyl group are copolymerized to obtain a glycidyl (meth) acrylate polymer, crosslinking occurs during the reaction. Therefore, high viscosity and gelation can be effectively prevented. The molecular weight of the glycidyl (meth) acrylate polymer is a weight average molecular weight of about 5,000 to 100,000 and 10,000 to 50 from the viewpoint of curling reduction during curing and prevention of gelation during the acrylic addition reaction. About 1,000 is preferable. (B) 70 weight% or more is suitable for the usage-amount of the glycidyl (meth) acrylate in a component in consideration of the hardness of a protective layer, the transferability of a polymer, etc., and 75 weight% or more is preferable.

A known copolymerization method can be applied to the production of the component (B). The production of the glycidyl (meth) acrylate polymer is carried out by charging this monomer, a polymerization initiator, and, if necessary, a chain transfer agent and a solvent into a reaction vessel, under a nitrogen stream at 80 to 90 ° C. for about 3 to 6 hours. It is appropriate to do in The resulting glycidyl (meth) acrylate polymer and acrylic acid can be subjected to a ring-opening esterification reaction to obtain the component (B). Usually, in order to prevent polymerization of acrylic acid itself, The reaction temperature is suitably 100 to 120 ° C., and the reaction time is suitably about 5 to 8 hours.
The blending amount of the component (B) in the active energy ray-curable resin composition is 10 to 60% by weight (however, the total of the components (A), (B) and (C) is 100% by weight). It is suitable and 20 to 50% by weight is preferred.

  Specific examples of the component (C) include polyfunctional polyester acrylate, polyfunctional urethane acrylate, and epoxy acrylate. Of these, polyfunctional urethane acrylates are preferred from the viewpoints of scratch resistance and toughness of the cured coating film. For example, (a) a urethane reaction product of (meth) acrylate having a hydroxyl group and an isocyanate compound having two or more isocyanate groups in the molecule, and (b) an isocyanate compound having two or more isocyanate groups in the molecule. Examples include a reaction product obtained by reacting a polyol, polyester or polyamide-based diol to synthesize an adduct, and then adding a (meth) acrylate having a hydroxyl group to the remaining isocyanate group (for example, JP-A-2002-275392). Issue).

  The polyfunctional urethane acrylate is a urethane reaction product composed of a (meth) acrylate having a hydroxyl group and a polyvalent isocyanate compound having two or more isocyanate groups. As the (meth) acrylate having a hydroxyl group, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like are preferable.

The blending amount of the component (C) in the active energy ray-curable resin composition is 0 to 50% by weight (however, the sum of the components (A), (B) and (C) is 100% by weight). Is suitable.
The active energy ray-curable resin composition can be blended with an organic solvent in order to adjust the viscosity according to the individual application. As the organic solvent, those which do not dissolve the cyclic olefin resin film, which is a transparent film, are suitable. For example, ester solvents, alcohol solvents, and ketone solvents are preferable.

  As the active energy ray used for curing the active energy ray-curable resin composition, for example, any of ultraviolet rays and electron beams may be used. When the resin composition is cured with an electron beam or the like, a photopolymerization initiator is not required, but when cured with ultraviolet rays, the photopolymerization initiator is usually 1 to 15 weights per 100 parts by weight of the resin composition. About parts can be contained. As the photopolymerization initiator, various known ones such as Darocur 1173, Irgacure 651, Irgacure 184, Irgacure 907, Irgacure 754 (all manufactured by Ciba Specialty Chemicals) and benzophenone can be used. If necessary, various additives other than those described above, for example, a polymerization inhibitor, an antioxidant, an ultraviolet absorber, an antistatic agent, a light stabilizer, a solvent, an antifoaming agent, and a leveling agent may be blended.

  The particles contained in the protective layer are not particularly limited, but may be any of those usually used as fillers, such as carbon black, copper, nickel, silver, iron, or a composite powder thereof; zinc oxide, tin oxide , Metal oxides such as titanium oxide, tin monoxide, calcium oxide, magnesium oxide, beryllium oxide, aluminum oxide, silica (fumed silica, fused silica, precipitated silica, ultra fine powder amorphous silica, crystalline silica, anhydrous silicic acid, etc.) Metal carbonates such as calcium carbonate, potassium carbonate, sodium carbonate, magnesium carbonate, barium carbonate; metal nitrides such as boron nitride, silicon nitride, and aluminum nitride; metal carbides such as SiC; aluminum hydroxide, magnesium hydroxide, etc. Metal hydroxides: aluminum borate, barium titanate, calcium phosphate , Calcium silicate, clay, gypsum, barium sulfate, mica, diatomaceous earth, white clay, talc, zeolites, pigments, and the like. Of these, silica is preferable. Specifically, Aerosil 50, 90G, 130, 200, 200V, 200CF, 300, 380, R972, R972V, R974, RX200, R202, R805, R812S, OX50 manufactured by Nippon Aerosil Co., Ltd. MX020W, MX030W, MX050W, MX100W, Eposter MA1002, Seahoster KE-E10, KE-E30, KE-E40, KE-E50, KE-E70, MX series manufactured by Soken Chemical Co., Ltd. (MX-150, MX-180TA, MX- 300), MR series, MP series and the like.

  The primary average particle diameter of the particles used for forming the protective layer is not particularly limited, and is generally a particle having a size called a nanoparticle, specifically about 1 nm to 100 nm, about 1 nm to 50 nm, and Those of about 1 nm to 25 nm are suitable. In addition to these, depending on the method for forming the protective layer, the type of particles used, etc., the above-mentioned particles such as those having an average particle size of about 50 to 800 nm, so-called microparticles of about 100 nm to 3 μm, etc. You may use together the particle | grains of a different magnitude | size group. When forming the protective layer, for example, the microparticles are used in combination at about 0.1 to 30% by weight, further about 0.2 to 20% by weight, and about 0.5 to 10% by weight with respect to the nanoparticles. It is preferable. This is because the desired average particle diameter and surface roughness can be easily obtained.

  On the other hand, the particles in the protective layer after formation may show the form of secondary, tertiary or higher aggregated particles, but depending on the formation method, the primary particles do not aggregate and show a dispersed form in which they are completely dispersed. Alternatively, primary particles and aggregated particles of secondary particles or more may be mixed. In particular, it is more preferable that the nanoparticles are completely dispersed in the state of primary particles or in a state close thereto, and particles having a relatively large size coexist in the state of primary particles. This is because it becomes easy to control the average particle diameter and the maximum height roughness on the surface of the protective layer. The average particle size is preferably about 50 to 600 nm, particularly about 50 to 400 nm, and more preferably about 50 to 200 nm. By having such an average particle diameter, the transparency of the resin composition can be secured and the haze value can be adjusted to an appropriate value. As a result, when the antiglare film of the present invention is arranged on the surface of a black background image such as so-called white blur or black float, it is possible to effectively prevent the occurrence of a blurred whitish portion on the black background image. The background image can be projected clearly.

The protective layer is usually stirred and mixed so that the particles are mixed in the above-mentioned active energy ray-curable resin composition in a liquid or suspension state, and the particles are uniformly dispersed. At this time, by adjusting the agitation method, agitation speed, agitation force, agitation time, etc., it is possible to control the distribution and agglomeration state of the particles, and to disperse the primary particles used as raw materials almost completely as primary particles. And forming aggregated particles such as secondary particles having a predetermined particle size different from the primary particles used as a raw material, and further, part of the secondary particles are partially collapsed or aggregated, It can be formed into tertiary particles and the like. In the present invention, it is preferable that the average particle size is in the above-described range in the state where the protective layer is completed, regardless of the particle size of the particles before and during the formation of the protective layer. However, here, the average particle diameter in the active energy ray-curable resin composition is regarded as the average particle diameter in a state where the protective layer is completed. At this time, the average particle diameter (d: hydrodynamic diameter) means a value obtained by a cumulant method from an autocorrelation function obtained by a photon correlation method. The autocorrelation function can be obtained directly from the temporal change of the scattering intensity, and the secondary autocorrelation function G2 (τ) is expressed by the following equation.
G ₂ (τ) = 1 + β | G ₁ (τ) | ²
(Where G ₁ (τ) is a first-order autocorrelation function and β is a constant)

When the particles are monodisperse, G ₁ (τ) becomes a single exponential decay curve and is expressed as follows using the decay constant Γ.
G ₁ (τ) = exp (−Γτ)
ln (G ₁ (τ)) = − Γτ

Further, Γ is expressed as follows using the diffusion coefficient D.
Γ = q ² D
q = (4πn ₀ / λ ₀ ) · sin (θ / 2)
(Where q is the scattering vector, n ₀ is the refractive index of the solvent, and λ ₀ is the wavelength of the laser light)

The average particle diameter d can be obtained from the diffusion coefficient D using the Einstein-Stokes equation.
d = kT / 3πη ₀ D
(Where d is the average particle size, k is the Boltzmann constant, T is the absolute temperature, and η ₀ is the viscosity of the solvent)
This average particle diameter can be measured by, for example, FPAR-1000 manufactured by Otsuka Electronics.

  Any method known in the art can be used to disperse / stir the particles. However, depending on the strength of the dispersion / stirring force, the length of the dispersion / stirring time, etc. It is suitable to appropriately select the primary particle size. In particular, in order to obtain particles in a form in which primary particles and agglomerated particles of secondary particles or more are mixed, the particles are referred to as so-called nanoparticles because they are stirred while being pulverized so that the particles do not aggregate. In order to disperse / stir the particles on the other hand, it is preferable to select a particle having a relatively large particle diameter called a so-called microparticle and to mix them.

  In addition, since the particles have a small average particle diameter in the protective layer after formation, transparency in the protective layer can be ensured, while relatively large particles are dispersed in some places to effectively make Newton rings. While preventing, glare can be minimized. In particular, when applied to a display device such as a touch panel and a film or the like is further laminated on the surface of the antiglare film of the present invention, Newton's rings generated by contact with the film can be more effectively prevented.

  In the protective layer, the particles are preferably contained in an amount of about 10 to 30%, more preferably 17 to 22%, based on the total weight of the protective layer. As a result, unevenness such as white blurring and black floating can be prevented, and the background image can be clearly displayed. In addition, anti-Newton ring properties and glare can be prevented, and the three types of balance can be adjusted appropriately.

  It is preferable that the maximum height roughness Ry (μm) of the surface of the protective layer is usually set to about 1.0 to 3.2, and particularly about 1.8 to 3.2, 2.0 to About 3.2 and about 2.0 to 2.6 are more preferable. By adjusting to such a maximum height roughness, the anti-Newton ring property can be effectively exhibited in combination with the above-mentioned average particle diameter of particles and / or the content ratio of relatively large particles. The surface height roughness Ry is the sum of the maximum value of the peak height of the contour curve and the maximum value of the valley depth at the reference length specified in JIS B0601'94. The maximum height roughness Ry can be measured using, for example, a surface roughness shape measuring machine, Handy Surf E-35A (manufactured by Tokyo Seimitsu Co., Ltd.).

  For example, in order to realize the above-mentioned surface height roughness (Ry), for example, in the protective film after formation, the maximum particle size Rm is usually about 30 μm or less, preferably about 20 μm or less, particularly about 10 μm or less. It is preferable. From another viewpoint, it is preferable that the particles having a particle diameter of 1300 nm or more are 1.5 to 7% by weight, 1.5 to 6.2% by weight, 1% It is preferable that they are 0.5 to 5.5 weight%, 1.5 to 5 weight%, and also 2.0 to 5 weight%. In this case, the particles having a particle size of 1300 nm or more are preferably primary particles. This is because it becomes easy to control the average particle diameter and the maximum height roughness on the surface of the protective layer, and the long-term stability of the coating liquid prepared for forming the protective layer can be ensured. As described above, the generation of the Newton ring described above can be more reliably prevented by containing a specific relatively large particle diameter within this range. Further, particles having a relatively large particle size are effective for preventing glare, which will be described later. However, if too many particles are contained, glare may be manifested. Therefore, the balance can be achieved so that the effects of anti-Newton ring and glare prevention can be maximized.

  Further, the protective layer preferably has an image clarity of about 5% or more, about 7% or more, about 8% or more, about 10% or more, about 13% or more, about 15% or more, or about 18% or more. % Or more, about 30% or more, particularly about 40% or more, about 43% or more, preferably about 45% or more. Here, the image clarity is a so-called glare, that is, an index representing the degree of discomfort caused to the observer due to light scattering, etc. When this value is large, the image clarity is good and the glare, etc. Means that it is hard to occur. Specifically, it indicates the ratio of light passing through a slit in an optical comb having a slit (interval) of a predetermined width, and for example, it is measured using a clarity measuring machine ICM-1T (manufactured by Suga Test Instruments). Can do. In the present invention, an optical comb having an interval of 0.5 mm is used. This glare is likely to appear when a protective layer is formed by interspersing particles having a relatively large particle size among particles having a uniform particle size. Therefore, in order to prevent this, it is conceivable to uniformly disperse particles having a small particle size without including particles having a relatively large particle size. However, in this case, Newton rings are likely to occur. Therefore, it is necessary to balance parameters so as to minimize the occurrence of both. In the present invention, by adjusting the image clarity together with the average particle diameter of the particles and the maximum height roughness Ry in the protective layer, All the factors that are trade-offs to each other can be satisfied.

  The protective layer preferably has a haze value of about 12% or less, more preferably about 10% or less, and particularly preferably 5% or less. The haze value is also called haze value, and represents the degree of haze and the degree of diffusion. By setting this value in the above-described range, so-called white blur can be prevented. The haze value is related to the average particle size, particle size distribution, etc. of the particles contained in the protective layer. Therefore, the background image can be displayed more clearly in combination with the average particle diameter and / or the content ratio of relatively large particles.

  As described above, the protective layer of the present invention is prepared by mixing particles with a resin composition, and optionally preparing a liquid or suspension using an appropriate organic solvent, etc., and applying / drying this to a transparent film. It can be formed by irradiating with active energy rays. As the coating method of the active energy ray-curable resin composition, bar coater coating, air knife coating, gravure coating, gravure reverse coating, reverse roll coating, lip coating, die coating, dip coating, Various methods such as offset printing, flexographic printing, and screen printing can be employed. Irradiation of active energy rays is not particularly limited, and may be appropriately adjusted depending on the composition of the resin composition to be used, the type of active energy rays, the thickness of the resin composition, etc., by the method of cultivated land in the field. Can do. Although the film thickness of a protective layer is not specifically limited, Usually, it is preferable about 1-20 micrometers, it is more preferable that it is about 1-10 micrometers, More preferably, it is about 1-5 micrometers.

In the antiglare film of the present invention, the active energy ray-curable resin composition (which may optionally contain the filler described above) is further provided on the surface opposite to the surface on which the particle-containing protective layer of the transparent film is formed. It is preferable that the back surface protective layer which consists of is formed. In this case, the film thickness of the back surface protective layer is not particularly limited, and examples thereof include the same film thickness as the above protective layer. Thus, by providing a protective layer on both surfaces, warping of the film can be prevented.
In addition, the surface of the protective layer preferably has 10 or less scratches generated when it is rubbed 10 times with steel wool at a load of 500 g, and it is particularly preferable in terms of surface hardness that no scratches are generated.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the following, “part” is based on weight.

(B) Production of component In a reactor equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introducing tube, 250 parts of glycidyl methacrylate (hereinafter referred to as GMA), 1.3 parts of lauryl mercaptan, 1,000 parts of butyl acetate And 2,2′-azobisisobutyronitrile (hereinafter referred to as AIBN) 7.5 parts, the temperature was raised to about 90 ° C. over about 1 hour under a nitrogen stream, Incubated for 1 hour. Next, from a dropping funnel previously charged with a mixed solution consisting of 750 parts of GMA, 3.7 parts of lauryl mercaptan and 22.5 parts of AIBN, the mixed liquid was dropped into the system in about 2 hours under a nitrogen stream. After incubating at the temperature for 3 hours, 10 parts of AIBN was charged, and the mixture was incubated for 1 hour. Then, it heated up at 120 degreeC and heat-retained for 2 hours. The weight average molecular weight of the obtained acrylic polymer was 19,000 (styrene conversion by GPC). After cooling to 60 ° C, the nitrogen inlet tube was replaced with an air inlet tube, 507 parts of acrylic acid (hereinafter referred to as AA), 2.0 parts of methoquinone and 5.4 parts of triphenylphosphine were charged and mixed, and then under air bubbling The temperature was raised to 110 ° C. After incubating at the same temperature for 8 hours, 1.4 parts of methoquinone was charged and cooled, and ethyl acetate was added so that the non-volatile content was 50% to obtain varnish B1.

  As the component (B), in the above-mentioned production examples, the amount of monomer used in the initial charge was 175 parts GMA, 75 parts of methyl methacrylate (hereinafter referred to as MMA), the amount of monomer used in the subsequent charge was 525 parts of GMA, and MMA225. The varnish B2 having a non-volatile content of 50% was obtained in the same manner as in the production example described above except that the amount of AA used was changed to 355 parts. The weight average molecular weight of the acrylic polymer before the AA reaction was 20,000.

  In addition, as the component (B), in the above-described production example, the amount of monomer used in the initial charge was changed to 125 parts GMA, 125 parts of methyl methacrylate MMA, and the amount of monomer used in the subsequent charge was changed to 375 parts of GMA and 375 parts of MMA. Except that the amount used was changed to 254 parts, the reaction was carried out in the same manner as in the production example described above to obtain varnish B3 having a non-volatile content of 50%. The weight average molecular weight of the acrylic polymer before the AA reaction was 23,000.

Preparation of active energy ray-curable resin composition (A) 50 parts of trimethylolpropane triacrylate (surface tension 36.2 mN / m),
(B) 25 parts of the above varnish B1,
(C) 25 parts of polyfunctional urethane acrylate was mixed and adjusted to 50% solid content with ethyl acetate, and 1-hydroxy-cyclohexyl phenyl ketone (Ciba Specialty Chemicals Co., Ltd.) was used as a photopolymerization initiator. (Trade name “Irgacure 184”) was added at 5% with respect to the solid content of the blend and dissolved to prepare an ultraviolet curable composition.
In addition, all the compounding quantities of (B) component are solid content conversion. The surface tension of the component (A) was measured by a vertical plate method (wilhemy method) using a Kyowa CBVP surface tension meter. The polyfunctional urethane acrylate of component (C) was manufactured by Arakawa Chemical Industries, Ltd., and trade name “Beam Set 557”.

Example 1
UV curable composition (adjusted to 80% solids with ethyl acetate, adjusted to 70% solids with MEK) 65.1 parts methyl ethyl ketone (MEK) 10.0 parts silica (Aerosil R-974) (Average particle size: about 12 nm, manufactured by Nippon Aerosil Co., Ltd.) 9.17 parts The above ingredients were passed through a roll mill disperser three times. Thereafter, it was diluted with MEK to obtain a coating material A for a protective layer having a solid content of 48%.

Also,
Ultraviolet curable composition (adjusted to 80% solids with ethyl acetate and adjusted to 70% solids with MEK) 57.1 parts acrylic particles (MX-180TA (average particle size: about 1. 8 μm), manufactured by Soken Chemicals Co., Ltd.) 1.25 parts Acrylic particles (MA-1002 (average particle size: about 2.5 μm), manufactured by Nippon Shokubai Co., Ltd.) 0.25 parts (About 40 cm, inner height: 58 cm) and stirred with a wing having a diameter of about 11 cm for 150 minutes. Then, it diluted with MEK and obtained the coating material B for protective layers with a solid content of 48%.

95 parts of the obtained paint A and 25 parts of paint B are mixed and applied to a transparent film made of cyclic olefin resin, Arton (registered trademark) (film thickness 100 μm) by gravure reverse method. did. The film was dried at 70 ° C. for 40 seconds, irradiated with ultraviolet rays of 300 mJ / cm ² and cured to form an antiglare film having a protective layer having a thickness of 1.7 μm.

Example 2
UV curable composition (adjusted to 80% solids with ethyl acetate, adjusted to 70% solids with MEK) 50.0 parts MEK 10 parts silica (K-500 (average particle size: approx. 2.0 μm), manufactured by Tosoh Silica Co., Ltd.) 10 parts The above components were passed through a roll mill disperser three times. Then, it diluted with MEK and obtained the coating material C for protective layers with a solid content of 48%.
125 parts of the paint A obtained in Example 1 and 5 parts of the paint C are mixed, and a transparent film made of a cyclic olefin-based resin, Arton (registered trademark) (manufactured by JSR Corporation, film thickness) by the gravure reverse method. 100 μm). The film was dried at 70 ° C. for 40 seconds, irradiated with ultraviolet rays of 300 mJ / cm ² and cured to form an antiglare film having a protective layer having a thickness of 3.0 μm.

Example 3
6. UV curable composition (adjusted to 80% solid content with ethyl acetate) 65.1 parts Methyl ethyl ketone (MEK) 25.8 parts Silica (Aerosil (average particle size: about 12 nm), manufactured by Nippon Aerosil Co., Ltd.) 17 parts The above ingredients were blended in an open drum for stirring (inner diameter of about 40 cm, inner height of 58 cm) and stirred with a wing having a diameter of about 11 cm for 150 minutes. Then, it diluted with MEK and obtained the coating material for protective layers of 40% of solid content.

The obtained paint was applied by a gravure reverse method to a transparent film made of a cyclic olefin resin, Arton (registered trademark) (manufactured by JSR Corporation, film thickness 100 μm). The film was dried at 80 ° C. for 60 seconds, irradiated with ultraviolet rays of 150 mJ / cm ² and cured to form an antiglare film having a protective layer with a thickness of 4 μm.
Moreover, as shown in Table 2, a resin composition was formed in the same manner as in the preparation of the active energy ray-curable resin composition described above except that the formulation was changed, and particles were formed according to the method of the following examples. Films 1-4 containing no

Comparative Example 1
A paint was obtained in the same manner as in Example 1 except that the ingredients of Example 1 were stirred with a dispersion for 30 to 45 minutes, and an antiglare film having a protective layer having a thickness of 4 μm was formed using this paint.

Comparative Example 2
A paint was obtained in the same manner as in Example 1 except that the ingredients of Example 1 were stirred with a dispersion for 210 minutes, and an antiglare film having a protective layer having a thickness of 4 μm was formed using this paint.
The following evaluation was performed about the obtained anti-glare film and films 1-4. The results are shown in Table 1 and Table 2, respectively.

(Average particle size)
It measured using FPAR-1000 made from Otsuka Electronics, and calculated the average particle diameter by the cumulant analysis. (Maximum particle size)
It measured using FPAR-1000 made from Otsuka Electronics, and calculated the maximum particle size by cumulant analysis. (Measurement of haze value)
Based on JIS-K7361-1 (ISO13468-1), it measured using the Nippon Denshoku Industries Co., Ltd. NDH2000 haze meter, and computed with the following formula | equation.
Haze value (%) = diffuse transmittance (%) / total light transmittance (%)

(White blur evaluation)
Black tape is pasted on the back side of the protective layer, visually observed with a three-wavelength fluorescent lamp, ◎ has almost no whiteness on the surface, ○ has little whiteness on the surface, but there is no practical problem, △ indicates the surface Rated as clearly white. (Measurement of maximum height roughness Ry)
Based on JIS B0601'94, it measured using the maximum height roughness shape measuring machine (HANDYSURF E-35A by Tokyo Seimitsu Co., Ltd.).

(Anti-Newton ring evaluation)
Place a glass plate on a black mount under a three-wavelength fluorescent lamp and visually observe the interference unevenness when the coating surface is pressed with a finger. ◎ indicates no interference unevenness, ○ indicates interference unevenness Was evaluated as having a slight interference, and Δ indicating that interference unevenness was visible. (Evaluation of image clarity)
An optical comb having an interval of 0.5 mm was applied to an image clarity measuring instrument ICM-1T (manufactured by Suga Test Instruments Co., Ltd.), and light (%) transmitted from the optical comb interval was measured.

(Glare evaluation)
The glare evaluation was performed by visually observing the glare of the image using a display having a resolution, horizontal of 1280 dots, and vertical of 1024 lines, and evaluated that there was almost no glare, ○ had little glare, and Δ had glare. . (Adhesion evaluation)
According to the JIS grid pattern method (25 grid pattern), 25 square grids of 2 mm square were formed on the protective layer using a cutter, the area was peeled off with cellophane tape, and the number of grids remaining was evaluated. ○ was 25/25, and x was 23/25 or less. (Steel wool resistance evaluation)
Apply a load of 500 g to 1 cm square # 0000 steel wool, visually observe the degree of scratching on the surface after 10 reciprocations at a movable distance of 2 cm, ○ indicates no scratch on the surface, or about one scratch, Δ indicates It evaluated that there existed 2 or 3 flaws and x had four or more flaws.

  The present invention relates to various optical devices, specifically, various displays such as word processors, computers, televisions, display panels, mobile phones, etc., the surfaces of polarizing plates used in liquid crystal display devices, etc., sunglasses lenses made of transparent plastics It can be used as an anti-glare film for optical lenses such as prescription eyeglass lenses, camera finder lenses, display portions of various instruments, window glass for automobiles, trains, etc., optical filters, functional films and the like.

Claims (10)

It is an antiglare film configured by laminating a particle-containing protective layer on the transparent film surface,
The transparent film is made of a cyclic olefin resin,
The protective layer is a layer obtained by photocuring a protective layer forming composition containing an active energy ray-curable resin composition and particles having an average particle size of 50 to 600 nm,
The active energy ray-curable resin composition has a maximum height roughness Ry of 1.0 to 3.2 μm on its surface and a mapping property of 5% or more. Is 40 to 60% by weight of a polyfunctional monomer having an acryloyl group of 3 or more, and (B) a polymer obtained by addition reaction of acrylic acid with a glycidyl (meth) acrylate polymer. And (C) 0 to 50% by weight of any other acrylic oligomer (however, the total of the respective components is 100% by weight). The cyclic olefin-based resin has the following formula (I)

[Wherein, R ^{1 to} R ⁴ are the same or different and each represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or another monovalent organic group, and R ¹ and R ² or R ³ and R ⁴ may be combined to form a divalent hydrocarbon group, and R ¹ or R ² and R ³ or R ⁴ are bonded to each other to form a monocyclic or polycyclic structure. May be. m is 0 or a positive integer, and p is 0 or a positive integer. ]
The antiglare film according to claim 1, which is a film made of a resin obtained by (co) polymerizing a monomer containing at least one compound represented by the formula:   The antiglare film according to claim 1, wherein the protective layer exhibits a haze value of 12% or less.   The antiglare film according to any one of claims 1 to 3, wherein the protective layer is formed by containing particles having a particle diameter of 1300 nm or more in an amount of 1.5 to 7% by weight based on all particles.   The antiglare film according to claim 4, wherein the particles having a particle size of 1300 nm or more are primary particles.   The antiglare film according to any one of claims 1 to 5, wherein the protective layer is formed by containing particles in an amount of 10 to 30% by weight with respect to the total protective layer.   The anti-glare film according to any one of claims 1 to 6, wherein the polyfunctional monomer as component (A) is trimethylolpropane triacrylate and / or ditrimethylolpropane tetraacrylate.   The glycidyl (meth) acrylate polymer as the component (B) is composed of glycidyl (meth) acrylate with 70% by weight or more of all the constituent monomers. Anti-glare film.   The acrylic oligomer which is (C) component is polyfunctional urethane acrylate, The anti-glare film as described in any one of Claims 1-8.   The back surface protective layer which consists of the said active energy ray curable resin composition is further formed in the surface on the opposite side to the surface in which the particle-containing protective layer of the transparent film is formed. The anti-glare film as described in 2.