KR100852562B1 - Hard-coated antiglare film, method of manufacturing the same, optical device, polarizing plate, and image display - Google Patents

Abstract

It provides an anti-glare hard coating film excellent in hardness, scratch resistance and anti-glare. The anti-glare hard coating film of the present invention comprises a transparent plastic film base material, a hard coating layer containing fine particles is formed on at least one side of the transparent plastic base material, the hard coating layer has a thickness in the range of 15 to 30㎛ The fine particles have a weight average particle diameter in the range of 30 to 75% of the thickness of the hard coating layer, and the average inclination angle θ _a of the uneven shape on the surface of the hard coating layer is in the range of 0.4 to 1.5 degrees, and the hard coating layer is specified in three types. It is formed using the resin for hard coat formation containing a resin component.

Description

Anti-glare hard coating film, manufacturing method of anti-glare hard coating film, optical element, polarizing plate and image display device {HARD-COATED ANTIGLARE FILM, METHOD OF MANUFACTURING THE SAME, OPTICAL DEVICE, POLARIZING PLATE, AND IMAGE DISPLAY}

BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which shows the structure of an example of the anti-glare hard coat film of this invention.

It is a cross-sectional schematic diagram which shows the structure of the other example of the anti-glare hard coat film of this invention.

3 is a schematic diagram illustrating an example of a relationship between an illuminance curve, a height h, and a reference length L. FIG.

The present invention relates to an anti-glare hard coat film, a method for producing an anti-glare hard coat film, an optical element, a polarizing plate, and an image display device.

With the recent advances in technology, image display apparatuses have been developed and put into practice in addition to conventional CRTs (Cathode Ray Tubes), liquid crystal displays (LCDs), plasma displays (PDPs), electroluminescent displays (ELDs), and the like. Among them, LCDs have been changed from notebook personal computers and monitors to televisions according to technological innovations related to high viewing angle, high resolution, high-speed response, color reproducibility, and the like. The basic configuration of the LCD is that the flat glass substrates each having a transparent electrode are disposed to face each other through spacers so as to have a predetermined gap therebetween, and a liquid crystal material is injected and sealed between the glass substrates to form a liquid crystal cell. It is the structure which provided the polarizing plate in the outer side surface of a pair of glass substrate, respectively. Conventionally, a cover plate made of glass or plastic is attached to the surface of the liquid crystal cell to prevent scratches on the polarizing plate attached to the surface of the liquid crystal cell. However, mounting the cover plate is disadvantageous in terms of cost and weight. Therefore, hard coating treatment has gradually been performed on the surface of the polarizing plate. In the hard coating process, an anti-glare hard coating film is generally used to serve as prevention of reflection of a light source on the LCD and the like.

The anti-glare hard coat film is obtained by forming a thin hard coat layer of about 2 to 10 탆 on one or both surfaces of the transparent plastic film base material using resins such as thermosetting resins and ultraviolet curable resins and fine particles. The surface of the hard coat layer is concave-convex by the fine particles, whereby antiglare property is exhibited. When the said resin is coated on glass and a hard coat layer is provided, hardness of 4H or more is shown by pencil hardness. However, when the base is the transparent plastic film base material, if the thickness of the hard coat layer is not sufficient, it is generally affected by the transparent plastic film base material, and the pencil hardness is generally lowered to 3H or less.

By shifting the use of LCDs to home televisions, users of ordinary home televisions can easily assume the same handling as conventional televisions using glass CRTs, even if they are televisions using LCDs. The pencil hardness of the said glass CRT is about 9H. For this reason, the improvement of hardness is calculated | required with respect to the anti-glare hard coat film used for LCD.

Improvement of the hardness of an anti-glare hard coat film becomes possible by increasing the layer thickness of a hard coat layer. However, when the layer thickness is increased, the particles contained in the hard coat layer are completely embedded in the hard coat layer, and there is a fear that sufficient anti-glare property cannot be exhibited. In order to solve this problem, there is also a method of increasing the amount of the fine particles added, but in this case, there is also a problem that the number of particles in the layer direction increases and, as a result, the haze value increases. As for the high hardness of the anti-glare hard coating film and the problems of anti-glare property and haze value, Japanese Patent Laid-Open No. 1999-286083, Japanese Patent Laid-Open No. 2000-326447 and Japanese Patent Laid-Open No. 2001-194504 And Japanese Patent Laid-Open No. 2001-264508 have been proposed.

Japanese Patent Application Laid-Open No. 1999-286083 discloses an anti-glare hard coating comprising a hard coating layer mainly composed of particles having an average particle diameter of 0.6 to 20 µm, particles having an average particle diameter of 1 to 500 nm, and a hard coating resin on a transparent substrate film. The film is disclosed. The publication also discloses that the thickness of the hard coat layer is not more than the particle size of the particles, preferably not more than 80% of the average particle size (specifically, 16 µm or less).

Japanese Patent Laid-Open No. 2000-326447 discloses a hard coat film formed by forming at least one hard coat layer on at least one side of a plastic substrate film. The publication also discloses that the thickness of the hard coat layer is 3 to 30 µm, and that inorganic fine particles having a secondary particle diameter of 20 µm or less are added to the hard coating layer. The publication also discloses providing the anti-glare property by making the surface of the hard coat layer into an irregular shape.

Japanese Patent Application Laid-Open No. 2001-194504 discloses an antireflection film formed by laminating a hard coat coating layer, an anti-reflective thin film layer composed mainly of a metal alkoxide and a hydrolyzate thereof on at least one surface of a plastic film, which is less than a breakdown deformation of the hard coat layer An antireflection film having an elastic modulus of from 0.7 to 5.5 GPa is disclosed. The publication also discloses that the film thickness of the hard coat layer is 0.5 µm or more and 20 µm or less, and the average particle diameter of the fine particles contained in the hard coating layer is 0.01 to 10 µm.

Japanese Patent Application Laid-Open No. 2001-264508 discloses an anti-glare hard coating layer containing particles having an average particle diameter of 1 to 10 탆 on a transparent support, inorganic fine particles having an average particle diameter of 0.001 to 0.2 탆, and a photocurable organosilane. An anti-glare antireflection film in which a layer of low refractive index having a refractive index in the range of 1.35 to 1.49 is sequentially laminated from a decomposition product and / or a partial condensate thereof and a composition containing a fluorine-containing polymer, having a haze value of 3 to 20%. The anti-glare anti-reflective film which exists in the range of and whose average reflectance of 450 nm-650 nm is 1.8% or less is disclosed. The publication also discloses that the anti-glare hard coat layer has a film thickness of 1 to 10 m.

However, in these conventional anti-glare hard coat films, the problem of both hardness and anti-glare cannot be said to be fully solved. In Japanese Patent Laid-Open No. 1999-286083, there is a problem that sufficient hardness cannot be exhibited if the thickness of the hard coat layer is about the above. In Japanese Patent Application Laid-Open No. 2000-326447, in the above-described configuration, when the surface roughness of the surface of the hard coating layer is not considered at all, and the inorganic fine particles are completely embedded in the hard coating layer, However, there is a problem in that it cannot exhibit sufficient anti-glare property. The antireflection film described in Japanese Patent Application Laid-Open No. 2001-194504 improves in terms of hardness and scratch resistance, but, for example, when fine particles having an average particle diameter of about 1.8 μm are added to a hard coating layer having a film thickness of about 20 μm, There is a problem that the fine particles are completely embedded in the hard coat layer, so that sufficient anti-glare property cannot be exhibited. Although the anti-glare antireflection film of Unexamined-Japanese-Patent No. 2001-264508 aims at the improvement of abrasion resistance, anti-glare, etc., there exists a problem that sufficient hardness is not obtained.

An object of the present invention is to provide an anti-glare hard coat film having excellent hardness, scratch resistance and anti-glare property, an optical element, a polarizing plate, an image display device and an anti-glare hard coat film using the same.

In order to achieve the above object, the anti-glare hard coating film of the present invention comprises a transparent plastic film base material, a hard coating layer containing fine particles is formed on at least one side of the transparent plastic film base material, the hard coating layer is 15 To 30 μm, the fine particles have a weight average particle diameter in the range of 30 to 75% of the thickness of the hard coating layer, and the average inclination angle θ _a of the uneven shape on the surface of the hard coating layer is in the range of 0.4 to 1.5 degrees. A hard coat layer is formed using the resin for hard coat layer formation containing the following (A) component, (B) component, and (C) component.

(A) component: At least one of urethane acrylate and urethane methacrylate

Component (B): at least one of polyol acrylate and polyol methacrylate

Component (C): A polymer or copolymer formed from at least one of the following (C1) and the following (C2), or a mixed polymer of the polymer and the copolymer

(C1): alkyl acrylate having an alkyl group having at least one of a hydroxyl group and acryloyl group

(C2): Alkyl methacrylate which has an alkyl group which has at least one group of a hydroxyl group and acryloyl group.

The manufacturing method of the anti-glare hard coat film of this invention is a manufacturing method of the anti-glare hard coat film in which the hard coat layer containing microparticles | fine-particles was formed in at least one surface of the transparent plastic film base material, The resin for hard-coat layer formation, and the said hard coat layer. Preparing a hard coat layer forming material comprising fine particles having a weight average particle diameter in the range of 30 to 75% of the thickness, and a solvent; coating the hard coat layer forming material on at least one side of the transparent plastic film substrate to form a coating film And hardening the coating film to form a hard coating layer having _a thickness in the range of 15 to 30 µm and having an average inclination angle θ _a of the uneven surface of the surface in the range of 0.4 to 1.5 degrees. Resin for coating layer formation contains the following (A) component, (B) component, and (C) component.

(A) component: At least one of urethane acrylate and urethane methacrylate

Component (B): at least one of polyol acrylate and polyol methacrylate

Component (C): A polymer or copolymer formed from at least one of the following (C1) and the following (C2), or a mixed polymer of the polymer and the copolymer

(C1): alkyl acrylate having an alkyl group having at least one of a hydroxyl group and acryloyl group

(C2): Alkyl methacrylate which has an alkyl group which has at least one group of a hydroxyl group and acryloyl group.

The optical element of this invention contains an optical member, and the anti-glare hard coat film of this invention is formed in at least one surface of the said optical member.

The polarizing plate of this invention contains a polarizer and the anti-glare hard coat film of the said invention.

The image display device of the present invention includes the anti-glare hard coat film of the present invention.

Another image display device of the present invention includes the optical element of the present invention.

Another image display device of the present invention includes the polarizing plate of the present invention.

In the anti-glare hard coat film of the present invention, since the thickness of the hard coat layer is within the predetermined range, the hardness is sufficient. In the anti-glare hard coat film of the present invention, since the particle diameter of the fine particles is within the predetermined range, and the average inclination angle θ _a of the concave-convex shape on the surface of the hard coating layer is within the predetermined range, the anti-glare property is excellent. It is also excellent in scratch resistance. Therefore, the image display apparatus to which the anti-glare hard coat film of this invention is applied is excellent in image display characteristic, since a screen is appropriately protected, excellent in handleability, and excellent in anti-glare property. In the anti-glare hard coat film of the present invention, since the hard coat layer is formed by using the hard coat layer-forming resin containing the three components, the hardness is further improved, and the crack of the hard coat layer is prevented, and the hard Curl generation due to cure shrinkage of the coating layer is effectively prevented. Such a high-performance anti-glare hard coat film of the present invention can be produced by the production method of the present invention. However, the anti-glare hard coat film of this invention may be manufactured by another manufacturing method.

Best Mode for Carrying Out the Invention

In the anti-glare hard coat film of the present invention and a method for producing the same, the component (B) preferably contains at least one of pentaerythritol triacrylate and pentaerythritol tetraacrylate. This is because the hardness can be more improved, and the curling can be prevented more effectively while maintaining the flexibility.

The anti-glare hard coat film of the present invention may be an aspect in which an antireflection layer is formed on the hard coat layer. It is preferable that the said antireflection layer contains hollow and spherical silicon oxide ultrafine particles.

In the anti-glare hard coat film of the present invention, the glossiness according to JIS K 7105 is preferably in the range of 50 to 95. The glossiness means 60 degree mirror surface glossiness of JIS K 7105 (1981 edition).

In the manufacturing method of the anti-glare hard coat film of this invention, it is preferable that the said solvent contains ethyl acetate. This is because in the obtained anti-glare hard coat film, the adhesion between the hard coat layer and the transparent plastic film base material can be improved, and peeling of the hard coat layer can be prevented. It is preferable that the content rate of the said ethyl acetate is 20 weight% or more with respect to the said whole solvent.

Next, this invention is demonstrated concretely. However, this invention is not restrict | limited by the following description.

The anti-glare hard coat film of the present invention has a hard coat layer on one or both sides of the transparent plastic film substrate.

The transparent plastic film base material is not particularly limited. It is preferable that the said transparent plastic film base material is excellent in the light transmittance of visible light (preferably 90% or more of light transmittance), and excellent in transparency (preferably haze value 1% or less). The formation material of the said transparent plastic film base material contains a polyester polymer, a cellulose polymer, a polycarbonate polymer, an acrylic polymer, etc., for example. The polyester polymer includes, for example, polyethylene terephthalate, polyethylene naphthalate and the like. The cellulose polymers include, for example, diacetyl cellulose, triacetyl cellulose (TAC) and the like. The said acrylic polymer contains polymethyl methacrylate etc., for example. The forming material of the transparent plastic film base material also includes, for example, a styrene polymer, an olefin polymer, a vinyl chloride polymer, an amide polymer, and the like. The styrene polymer includes, for example, polystyrene, acrylonitrile-styrene copolymer, and the like. The olefin polymer includes, for example, polyethylene, polypropylene, polyolefin containing cyclic structure, polyolefin containing norbornene structure, ethylene-propylene copolymer and the like. The amide polymer includes, for example, nylon, aromatic polyamide, and the like. The material for forming the transparent plastic film base material may be, for example, an imide polymer, a sulfone polymer, a polyether sulfone polymer, a polyether ether ketone polymer, a polyphenylene sulfide polymer, a vinyl alcohol polymer, or vinylidene chloride. Polymers, vinyl butyral polymers, allylated polymers, polyoxymethylene polymers, epoxy polymers, blends of the above polymers, and the like. Of these, those having a low optical birefringence are suitably used. The anti-glare hard coat film of this invention can also be used for a polarizing plate, for example as a protective film. In this case, as said transparent plastic film base material, the film formed from triacetyl cellulose, a polycarbonate, an acrylic polymer, the polyolefin containing a cyclic structure, the polyolefin containing a norbornene structure, etc. is preferable. In the present invention, the transparent plastic film base may be the polarizer itself. With such a configuration, a protective layer made of TAC or the like is not required and the structure of the polarizing plate can be simplified. Thereby, the number of manufacturing processes of a polarizing plate or an image display apparatus can be reduced, and production efficiency can be improved. Moreover, if it is such a structure, a polarizing plate can be thinned more. When the transparent plastic film base material is a polarizer, the hard coating layer serves as a conventional protective layer. With such a configuration, the anti-glare hard coat film also serves as a cover plate mounted on the surface of the liquid crystal cell.

In the present invention, the thickness of the transparent plastic film base material is not particularly limited. The thickness is preferably in the range of 10 to 500 µm, more preferably in the range of 20 to 300 µm, considering the point of workability such as strength, handleability, thinness, and the like, and most preferably 30 to It is the range of 200 micrometers. The refractive index of the transparent plastic film base material is not particularly limited. The refractive index is, for example, in the range of 1.30 to 1.80, preferably in the range of 1.40 to 1.70.

As mentioned above, the said hard coat layer is formed using the resin for hard-coat layer formation containing the following (A) component, (B) component, and (C) component, for example.

(A) component: At least one of urethane acrylate and urethane methacrylate

Component (B): at least one of polyol acrylate and polyol methacrylate

Component (C): A polymer or copolymer formed from at least one of the following (C1) and the following (C2), or a mixed polymer of the polymer and the copolymer

(C1): alkyl acrylate having an alkyl group having at least one of a hydroxyl group and acryloyl group

(C2): Alkyl methacrylate which has an alkyl group which has at least one group of a hydroxyl group and acryloyl group.

As said urethane acrylate and urethane methacrylate which are said (A) component, what contains acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, a polyol, and diisocyanate as a component is used. At least one of the urethane acrylate and the urethane methacrylate is, for example, at least one monomer of acrylic acid, methacrylic acid, acrylic acid ester and methacrylic acid ester and a hydroxyl having at least one hydroxyl group using a polyol. It can manufacture by making at least one of the hydroxy acrylate and the hydroxy methacrylate which has one or more hydroxyl groups, and reacting this with diisocyanate. In the said (A) component, the said urethane acrylate and the said urethane methacrylate may be used individually by 1 type. In the said (A) component, the said urethane acrylate and the said urethane methacrylate can also use 2 or more types together.

The acrylic acid ester includes, for example, alkyl acrylate, cycloalkyl acrylate and the like. The alkyl acrylates include, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate and the like. The cycloalkyl acrylate includes, for example, cyclohexyl acrylate. The methacrylic acid ester includes, for example, alkyl methacrylate, cycloalkyl methacrylate, and the like. The alkyl methacrylates include, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, butyl methacrylate and the like. The cycloalkyl methacrylate includes, for example, cyclohexyl methacrylate.

The polyol is a compound having at least two hydroxyl groups. The polyol is, for example, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3- Butanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, 2,2,4-trimethyl- 1,3-pentanediol, 3-methyl-1,5-pentanediol, hydroxypivalic acid neopentyl glycol ester, tricyclodecane dimethylol, 1,4-cyclohexane diol , Spiroglycol, tricyclodecane dimethylol, hydrogenated bisphenol A, ethylene oxide added bisphenol A, propylene oxide added bisphenol A, trimethylolethane, trimethylolpropane, glycerin, 3-methylpentane- 1,3,5-triol, pentaerythritol, dipentaerythritol, tripentaerythritol, glucose, and the like.

As said diisocyanate, various diisocyanates of aromatic, aliphatic or alicyclic can be used, for example. The diisocyanate is, for example, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 2,4-tolylene diisocyanate, 4,4-di Phenyl diisocyanate, 1,5-naphthalene diisocyanate, 3,3-dimethyl-4,4-diphenyl diisocyanate, xylene diisocyanate, trimethylhexamethylene dia Isocyanate, 4,4-diphenylmethane diisocyanate, and the like, and hydrogenated materials thereof.

The blending ratio of the component (A) is not particularly limited. By use of the said (A) component, the softness of the hard coat layer formed and adhesiveness with respect to a transparent plastic film base material can be improved. From the viewpoint of these points and the hardness of the hard coat layer, etc., the blending ratio of the component (A) is, for example, in the range of 15 to 55% by weight relative to the entire resin component in the hard coat layer forming material, preferably 25 to 45% by weight. Range. The whole said resin component means the quantity which added together the total amount of the said three components, and the total amount of the said resin component, when using the total amount of (A) component, (B) component, and (C) component, or another resin component, The same applies to the following.

The (B) component is, for example, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, 1,6-hexanediol acrylate, pentaerythrate Lithol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, 1,6-hexanediol methacrylate, and the like. These may be used alone. These can also use two or more types together. For example, as said polyol acrylate, the monomer component which consists of a polymer of pentaerythritol triacrylate and pentaerythritol tetraacrylate, and the mixed component containing pentaerythritol triacrylate and pentaerythritol tetraacrylate are preferable.

The blending ratio of the above (B) is not particularly limited. For example, the blending ratio of the component (B) is preferably in the range of 70 to 180% by weight with respect to the component (A), and more preferably in the range of 100 to 150% by weight. When the compounding ratio of the said (B) component is 180 weight% or less with respect to the said (A) component, hardening shrinkage of the hard coat layer formed can be prevented effectively. As a result, the curl of the anti-glare hard coat film can be prevented, and the fall of bendability can be prevented. If the compounding ratio of the said (B) component is 70 weight% or more of the said (A) component, the hardness of the hard coat layer formed can be improved more, and it becomes possible to improve scratch resistance.

In the component (C), the alkyl groups of (C1) and (C2) are not particularly limited. The alkyl group is, for example, an alkyl group having 1 to 10 carbon atoms. The alkyl group may be linear. The alkyl group may be branched. As said (C) component, the polymer, copolymer, or mixture of the said polymer and the said copolymer containing the repeating unit of following General formula (1) is mentioned, for example.

In Formula 1, R ¹ is -H or -CH ₃ , R ² is -CH ₂ CH ₂ OX or a group represented by the formula (2), wherein X is -H or acryl represented by the formula (3) It is a diary.

In Formula 2, X is -H or an acryloyl group represented by Formula 3 below, and X may be the same or different.

Examples of the component (C) include 2,3-dihydroxypropyl acrylate, 2,3-diacryloyloxypropyl acrylate, 2-hydroxy-3-acryloyloxypropyl acrylate, and 2-acrylic. Royloxy-3-hydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, 2,3-diacryloyloxypropyl methacrylate, 2-hydroxy-3-acryloyloxypropyl Methacrylate, 2-acryloyloxy-3-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-acryloyloxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-acrylic Polymers, copolymers or mixtures of such polymers and copolymers formed from at least one monomer selected from the group consisting of royloxy methacrylates.

The blending ratio of the component (C) is not particularly limited. For example, the mixing ratio of the component (C) is preferably in the range of 25 to 110% by weight, more preferably in the range of 45 to 85% by weight based on the component (A). If the compounding ratio of the said (C) component is 110 weight% or less, the coating property of a hard coat layer forming material will become excellent. When the compounding ratio of the said (C) component is 25 weight% or more, hardening shrinkage of the hard coat layer formed can be prevented. As a result, curl generation can be prevented in an anti-glare hard coat film.

The said hard coat layer contains microparticles | fine-particles in order to provide anti-glare property by making the surface structure into an uneven structure. Examples of the fine particles include inorganic fine particles and organic fine particles. The said inorganic fine particle is not specifically limited. The inorganic fine particles include silicon oxide fine particles, titanium oxide fine particles, aluminum oxide fine particles, zinc oxide fine particles, tin oxide fine particles, calcium carbonate fine particles, barium sulfate fine particles, talc fine particles, kaolin fine particles, calcium sulfate fine particles and the like. The said organic fine particle is not specifically limited. The organic fine particles are, for example, polymethyl methacrylate resin powder (PMMA fine particles), silicone resin powder, polystyrene resin powder, polycarbonate resin powder, acrylic-styrene resin powder, benzoguanamine resin powder, melamine resin powder And polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, polyfluoroethylene resin powder and the like. These inorganic fine particles and organic fine particles may be used alone. These inorganic fine particles and organic fine particles can also use 2 or more types together.

The weight average particle diameter of the fine particles is in the range of 30 to 75% of the film thickness of the hard coat layer, and preferably in the range of 30 to 50%. If the weight average particle diameter of the said microparticles | fine-particles is 30% or more, sufficient uneven | corrugated shape can be formed in the surface of the said hard coat layer, and sufficient anti-glare function can be provided. If the weight average particle diameter of the said microparticles | fine-particles is 75% or less, the difference in the unevenness | corrugation of a surface can be made into an appropriate magnitude | size, an external appearance can be made favorable and scattering of reflected light can be made suitable.

The weight average particle diameter of the said microparticles | fine-particles can be measured, for example by the method as described in the Example mentioned later.

The shape of the fine particles is not particularly limited. The shape of the fine particles may be, for example, a substantially spherical bead. The shape of the fine particles may be in an amorphous form such as powder. In this invention, it is preferable that the said microparticles | fine-particles are plural types of microparticles | fine-particles whose average particle diameter is two or more types. In this case, the fine particles means that there are two or more groups (particulate particles) in which a plurality of fine particles having one weight average particle diameter are collected. As mentioned above, as said microparticles | fine-particles, a substantially spherical thing is preferable, More preferably, it is a substantially spherical fine particle whose aspect ratio is 1.5 or less. If the aspect ratio is 1.5 or less, the average inclination angle θ _a can be more preferably controlled in the concave-convex shape on the surface of the hard coat layer.

The blending ratio of the fine particles is not particularly limited. The blending ratio of the fine particles can be appropriately set. The blending ratio of the fine particles is, for example, in the range of 2 to 70 parts by weight, preferably in the range of 4 to 50 parts by weight, and more preferably in the range of 15 to 40 parts by weight based on 100 parts by weight of the total resin component.

The average inclination angle θ _a in the uneven shape of the surface of the hard coat layer is in the range of 0.4 to 1.5 degrees. If the said average inclination-angle (theta) _a is 0.4 degree or more, anti-glare property is excellent. Haze value can be made into an appropriate range as the said average inclination-angle (theta) _a is 1.5 degrees or less. In the present invention, the average inclination angle θ _a is preferably in the range of 0.5 to 1.2 degrees, more preferably in the range of 0.6 to 1.1 degrees. In the present invention, the average inclination angle θ _a can be adjusted by appropriately selecting, for example, the kind of the resin for forming the hard coat layer, the thickness of the hard coating layer, the kind of the fine particles, the average particle diameter of the fine particles, and the like. It is possible to set the average inclination angle θ _a in the predetermined range of the present invention without trial and error.

In the present invention, the average inclination angle θ _a is a value defined by Equation 1 below. The said average inclination-angle (theta) _a is _a value measured by the method as described in the Example mentioned later, for example.

In the above Equation 1, Δ _a is the vertex and the valley of the peak (neighboring peak) at the reference length L of the roughness curve specified in JIS B 0601 (1994 edition), as shown in the following Equation 2 The sum (h1 + h2 + h3 ... + hn) of the difference (height h) of the lowest point of trough) is obtained by dividing the reference length L. The illuminance curve is a curve obtained by removing a surface wave component longer than a predetermined wavelength from the cross-sectional curve with a phase difference compensation type high pass filter. The cross-sectional curve is a contour appearing in the cross section when the target surface is cut in a plane perpendicular to the target surface. An example of the said roughness curve, height h, and reference line L is shown in FIG.

In the concavo-convex shape of the hard coat layer, arithmetic mean roughness Ra (arithmetic mean surface roughness Ra), which is one of surface roughness, is, for example, in the range of 0.05 to 0.3 µm, preferably in the range of 0.07 to 0.2 µm, more preferably Is in the range of 0.09 to 0.15 µm. The arithmetic mean surface roughness Ra is defined in JIS B 0601 (1994 version). The arithmetic mean surface roughness Ra is measured by the method of the Example mentioned later, for example. In the present invention, the arithmetic mean surface roughness Ra can be adjusted by appropriately selecting, for example, the kind of the resin for forming the hard coat layer, the thickness of the hard coat layer, the kind of the fine particles, the weight average particle diameter of the fine particles, and the like. Ramen arithmetic average surface roughness Ra of the said predetermined range can be used without trial and error of ramen excessive.

It is preferable to reduce the difference in refractive index between the fine particles and the hard coating layer from the viewpoint of preventing light scattering or interference fringes occurring at the interface between the fine particles and the hard coating layer. The interference fringe is a phenomenon in which the reflected light of external light incident on the hard coat film exhibits the color of iridescent light. In recent years, three-wavelength fluorescent lamps excellent in clarity have been used in offices and the like. Under the three-wavelength fluorescent lamps, interference fringes appear remarkably. Since the refractive index of the hard coat layer is generally in the range of 1.4 to 1.6, fine particles having a refractive index close to the range of this refractive index are preferable. The difference in refractive index between the fine particles and the hard coat layer is preferably less than 0.05.

When the difference between the refractive index of the transparent plastic film base material and the refractive index of the hard coat layer is d, the d is preferably 0.04 or less. If d is 0.04 or less, interference fringes can be suppressed. As for said d, it is more preferable that it is 0.02 or less.

The hard coating layer has a thickness in the range of 15 to 30 μm, preferably in the range of 18 to 25 μm. If the thickness is within the predetermined range, the hardness of the hard coat layer is also sufficient (for example, 4H or more in pencil hardness). If the thickness is within the predetermined range, curling can also be prevented more effectively.

The anti-glare hard coat film of the present invention, for example, to prepare a hard coating layer forming material containing the three components, the hard coating layer forming material containing the fine particles and a solvent, the hard coating layer forming material is the transparent plastic film substrate It can be manufactured by coating on at least one surface of and forming a coating film, and hardening the said coating film to form the said hard coat layer.

The solvent is not particularly limited. The solvent is, for example, dibutyl ether, dimethoxymethane, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1,3-dioxolane, 1,3,5-tri Oxane, tetrahydrofuran, acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, ethyl formic acid, formic acid propyl, formic acid n-pentyl, Methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, n-pentyl acetate, acetylacetone, diacetone alcohol, methyl acetoacetate, ethyl acetoacetate, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2 Butanol, 1-pentanol, 2-methyl-2-butanol, cyclohexanol, isobutyl acetate, methyl isobutyl ketone (MIBK), 2-octanone, 2-pentanone, 2-hexanone, 2 -Heptanone, 3-heptanone, ethylene glycol And the like furnace ethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether. These can also be used individually by 1 type. These can also use two or more types together. From the viewpoint of improving the adhesion between the transparent plastic film base material and the hard coat layer, the solvent preferably contains ethyl acetate in a proportion of 20% by weight or more of the whole, and more preferably in a proportion of 25% by weight or more of the whole. It contains ethyl acetate and optimally contains ethyl acetate in the ratio of 30 to 70 weight% of the whole. If the ratio of ethyl acetate in the said solvent is 70 weight% or less, the volatilization rate of a solvent can be made moderate and it becomes possible to prevent coating nonuniformity and dry nonuniformity effectively. The kind of solvent used together with ethyl acetate is not specifically limited. The solvent includes, for example, butyl acetate, methyl ethyl ketone, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and the like.

Various leveling agents may be added to the hard coat layer forming material. Examples of the leveling agent include fluorine or silicon leveling agents, and are preferably silicon leveling agents. The silicone leveling agent includes, for example, reactive silicone, polydimethylsiloxane, polyether modified polydimethylsiloxane, polymethylalkylsiloxane, and the like. Of these silicone-based leveling agents, the reactive silicones are particularly preferred. By adding the reactive silicone, lubricity is imparted to the surface so that the scratch resistance lasts for a long time. When using the thing which has a hydroxyl group as said reactive silicone, when the thing containing a siloxane component as an antireflection layer (low refractive index layer) was formed on the said hard coat layer, the adhesiveness of the said antireflection layer and the said hard coat layer improves.

The blending amount of the leveling agent is, for example, 5 parts by weight or less, preferably 0.01 to 5 parts by weight based on 100 parts by weight of the total resin component.

If necessary, pigments, fillers, dispersants, plasticizers, ultraviolet absorbers, surfactants, antioxidants, thixotropic agents and the like may be added to the hard coat layer forming material in a range that does not impair performance. The said additive may be used individually by 1 type. The said additive can also use 2 or more types together.

As the hard coat layer forming material, a conventionally known photopolymerization initiator can be used. Examples of the photopolymerization initiator include 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone , Benzoin propyl ether, benzyl dimethyl ketal, N, N, N ', N'-tetramethyl-4,4'-diaminobenzophenone, 1- (4-isopropylphenyl) -2-hydroxy-2 -Methylpropan-1-one etc. can be mentioned, In addition, a thioxanthone type compound etc. can be used.

As a method of coating the hard coat layer forming material on a transparent plastic film base material, for example, coating methods such as a fountain coating method, a die coating method, a spin coating method, a spray coating method, a gravure coating method, a roll coating method and a bar coating method It is available.

The hard coat layer forming material is coated to form a coating film on the transparent plastic film base material, and the coating film is cured. Prior to the curing, it is preferable to dry the coating film. The drying may be, for example, natural drying, drying in blown air, heat drying, or a combination thereof.

The hardening means of the coating film of the said hard coat layer forming material is not specifically limited. The curing means is preferably ionizing radiation curing. Various activation energy can be used for the said hardening means. The active energy is preferably ultraviolet light. As the energy source, for example, a source such as a high pressure mercury lamp, a halogen lamp, a xenon lamp, a metal halide lamp, a nitrogen laser, an electron beam accelerator, or a radioactive element is preferable. As for the irradiation amount of the said energy source, 50-5000mJ / cm <^2> is preferable as integrated exposure amount in an ultraviolet-ray wavelength 365nm. When the said irradiation amount is 50 mJ / cm <^2> or more, hardening becomes more enough and the hardness of the hard coat layer formed becomes more enough. When the said irradiation amount is 5000 mJ / cm <^2> or less, coloring of the hard coat layer formed can be prevented, and transparency can be improved.

As described above, the anti-glare hard coat film of the present invention can be produced by forming the hard coat layer on at least one surface of the transparent plastic film base material. In addition, the anti-glare hard coat film of this invention can also be manufactured by manufacturing methods other than the method mentioned above. The hardness of the anti-glare hard coat film of the present invention has a hardness of, for example, 4H or more in pencil hardness.

An example of the anti-glare hard coat film of this invention is shown in the cross-sectional schematic diagram of FIG. As shown in the figure, in the anti-glare hard coat film 4 of this example, the hard coat layer 2 including the fine particles 3 is formed on one surface of the transparent plastic film base 1. This invention is not limited to the structure of FIG. 1, The anti-glare hard-coating film in which the hard-coating layer 2 was formed in both surfaces of the transparent plastic film base material 1 may be sufficient. The hard coat layer 2 of this example is a single layer. However, this invention is not limited to this. The hard coat layer 2 may have a multilayer structure in which two or more layers are laminated.

In the anti-glare hard coat film of the present invention, an antireflection layer (low refractive index layer) may be disposed on the hard coat layer. An example of the anti-glare hard coat film of the present invention including the antireflection layer is shown in a cross-sectional schematic diagram of FIG. 2. As shown, in the anti-glare hard coat film 6 of this example, a hard coat layer 2 containing fine particles 3 is formed on one side of the transparent plastic film base 1, and on the hard coat layer 2. The antireflection layer 5 is formed in the structure. When light enters an object, it repeats the phenomenon of reflection at its interface, absorption in the inside, and scattering, and passes through the back of the object. For example, when the anti-glare hard coat film is attached to the image display device, one of the factors that lower the visibility of the image is the reflection of light at the interface between the air and the hard coat layer. The antireflection layer reduces surface reflection. In the anti-glare hard coat film 6 shown in FIG. 2, the hard coat layer 2 and the antireflection layer 5 are formed on one side of the transparent plastic film base 1. However, this invention is not limited to this. In the anti-glare hard coat film of the present invention, the hard coat layer 2 and the antireflection layer 5 may be formed on both surfaces of the transparent plastic film base 1. In the anti-glare hard coat film 6 shown in FIG. 2, the hard coat layer 2 and the antireflection layer 5 are single layers, respectively. However, this invention is not limited to this. The hard coat layer 2 and the antireflection layer 5 may each have a multilayer structure in which two or more layers are stacked.

In the present invention, the antireflection layer is formed by stacking two or more layers of the optical thin film or the optical thin film in which thickness and refractive index are strictly controlled. The antireflection layer exhibits an antireflection function by canceling the inverted phases of the incident light and the reflected light with each other by using the interference effect of light. The wavelength region of visible light for expressing the antireflection function is, for example, 380 to 780 nm, and the wavelength region with high visibility is particularly in the range of 450 to 650 nm, and it is preferable to design the antireflection layer to minimize the reflectance of its central wavelength of 550 nm. desirable.

In the design of the antireflection layer based on the interference effect of light, as a means for improving the interference effect, for example, there is a method of increasing the refractive index difference between the antireflection layer and the hard coating layer. In general, in a multilayer antireflection layer having a structure in which two to five optical thin layers (thin films with tight control of thickness and refractive index) are laminated, a plurality of components having different refractive indices are formed by a predetermined thickness, thereby providing an optical design of the antireflection layer. The degree of freedom increases, and the antireflection effect can be further improved, and the spectral reflection characteristic can also be made uniform (flat) in the visible light region. In the above optical thin film, since high thickness precision is required, the formation of each layer is generally performed by dry deposition, vacuum deposition, sputtering, CVD, or the like.

The multilayer antireflection layer is preferably a two-layer structure in which a silicon oxide layer having a low refractive index (refractive index: about 1.45) is laminated on a titanium oxide layer having a high refractive index (refractive index: about 1.8), and more preferably a titanium oxide layer. The silicon oxide layer is laminated on the layer, the titanium oxide layer is laminated on the silicon oxide layer, and the silicon oxide layer is laminated on the titanium oxide layer. By forming these two-layer antireflection layers or four-layer antireflection layers, it is possible to uniformly reduce the reflection in the wavelength region of visible light (for example, in the range of 380 to 780 nm).

It is also possible to express the antireflection effect by forming a single optical thin film (antireflection layer) on the hard coat layer. Generally, the coating method of the wet type fountain coating, die coating, spin coating, spray coating, gravure coating, roll coating, bar coating etc. is employ | adopted for formation of a single layer antireflection layer.

The material for forming the single-layer antireflection layer is, for example, a resin material such as an ultraviolet curing acrylic resin, a hybrid material in which inorganic fine particles such as colloidal silica are dispersed in the resin, and metal alkoxides such as tetraethoxysilane and titanium tetraethoxide. Sol-gel materials and the like. In the above-mentioned forming material, it is preferable to contain a fluorine group for imparting antifouling properties to the surface. In the forming material, a forming material having a high inorganic component content is preferable for reasons of scratch resistance and the like, and more preferably the sol-gel material. The sol-gel material may be used by partial condensation.

As said antireflection layer (low refractive index layer), the fluorine compound which has the siloxane oligomer of the range of ethylene glycol conversion number average molecular weights 500-10000, the polystyrene conversion number average molecular weight 5000 or more, and has a fluoroalkyl structure and a polysiloxane structure. It is preferable that it is formed from a material containing the material (the material described in Japanese Patent Laid-Open No. 2004-167827) because of its compatibility with scratch resistance and low reflection.

The antireflection layer (low refractive index layer) may contain an inorganic sol in order to improve film strength. The inorganic sol is not particularly limited. The inorganic sol includes, for example, silica, alumina, magnesium fluoride and the like. Of these, silica sol is preferred. The mixing ratio of the inorganic sol is, for example, in the range of 10 to 80 parts by weight based on 100 parts by weight of the total solid of the antireflection layer forming material. The particle diameter of the inorganic fine particles in the inorganic sol is preferably in the range of 2 to 50 nm, and more preferably in the range of 5 to 30 nm.

The material for forming the antireflection layer preferably contains hollow, spherical silicon oxide ultrafine particles. It is preferable that an average particle diameter is about 5-300 nm, and, as for the said silicon oxide ultrafine particle, the range of 10-200 nm is more preferable. The silicon oxide ultrafine particles are hollow spheres in which a cavity is formed inside an outer shell having pores, and contain at least one of a solvent and a gas during preparation of the silicon oxide ultrafine particles in the cavity. In addition, it is preferable that a precursor material for forming the cavity of the silicon oxide ultrafine particles remains in the cavity. The thickness of the outer shell is in the range of about 1 to 50 nm, and preferably in the range of 1/50 to 1/5 of the average particle diameter of the silicon oxide ultrafine particles. It is preferable that the said outer shell is formed by the some coating layer. In the silicon oxide ultrafine particles, the pores are preferably blocked, and the cavity is sealed by the outer shell. This is because the porous or cavities of the ultrafine silicon oxide particles are held in the antireflection layer, so that the refractive index of the antireflection layer can be further reduced. As a method for producing such hollow, spherical silicon oxide ultrafine particles, for example, a method for producing silica-based fine particles disclosed in Japanese Patent Laid-Open No. 2000-233611 is suitably employed.

The temperature of drying and curing at the time of forming the antireflection layer (low refractive index layer) is not particularly limited. The temperature of the said drying and hardening is a range of 60-150 degreeC, for example, Preferably it is the range of 70-130 degreeC. The time of the said drying and hardening is a range of 1 to 30 minutes, for example, and when considering productivity, the range of 1 to 10 minutes is preferable. Further, after the drying and curing, heat treatment is further performed to obtain a high hardness anti-glare hard coat film having an antireflection layer. The temperature of the heat treatment is not particularly limited. The temperature of the said heat processing is the range of 40-130 degreeC, for example, Preferably it is the range of 50-100 degreeC. The heat treatment time is not particularly limited. As for the said heat processing time, it is more preferable to carry out 10 hours or more from a viewpoint of 1 minute-100 hours and abrasion resistance improvement, for example. The heat treatment can be performed by a method using a hot plate, an oven, a belt furnace or the like.

When the anti-glare hard coat film including the anti-reflection layer is mounted on the image display device, the frequency of the anti-reflection layer becoming the outermost layer is high. For this reason, the antireflection layer is susceptible to contamination from the external environment. The antireflection layer is more prone to contamination as compared to a simple transparent plate. For example, the antireflection layer may have a change in surface reflectance due to adhesion of contaminants such as fingerprints, fingerprints, sweats, haircut materials, or the like. In order to prevent adhesion of the contaminants and to improve the ease of removal of the adhered contaminants, it is preferable to laminate an antifouling layer formed from a fluorine group-containing silane compound or a fluorine group-containing organic compound on the antireflection layer.

In the anti-glare hard coat film of the present invention, it is preferable to perform surface treatment on at least one of the transparent plastic film base material and the hard coat layer. When surface-treating the said transparent plastic film base material surface, adhesiveness with the said hard coat layer, a polarizer, or a polarizing plate further improves. Surface treatment of the surface of the hard coat layer further improves adhesion to the antireflection layer, the polarizer or the polarizing plate. Examples of the surface treatment include low pressure plasma treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, or acid or alkali treatment. As surface treatment in the case of using a triacetyl cellulose film as said transparent plastic film base material, alkali treatment is preferable. This alkali treatment can be performed by, for example, contacting the triacetyl cellulose film surface with an alkaline solution, followed by washing with water and drying. As the alkaline solution, for example, a potassium hydroxide solution or a sodium hydroxide solution can be used. The prescribed concentration (molar concentration) of hydroxide ions in the alkali solution is preferably in the range of 0.1 to 3.0 N (mol / L), more preferably in the range of 0.5 to 2.0 N (mol / L).

In the anti-glare hard coat film in which the hard coat layer is formed on one surface of the transparent plastic film base material, a solvent treatment may be performed on the other surface in order to prevent curling. The solvent treatment can be carried out by bringing the transparent plastic film base material into contact with a soluble solvent or a swellable solvent. By the said solvent process, the force which wants to curl is provided also to the said other surface, and the curling generation can be prevented by canceling the force to curl by formation of the said hard coat layer by this. Similarly, in the anti-glare hard coat film in which the hard coat layer is formed on one side of the transparent plastic film substrate, in order to prevent curling, a transparent resin layer may be formed on the other side. As said transparent resin layer, the layer which has a thermoplastic resin, a radiation curable resin, a thermosetting resin, or other reactive resin as a main component is mentioned, for example. Among these, especially the layer which has a thermoplastic resin as a main component is preferable.

The anti-glare hard coat film of this invention can be normally bonded to the said transparent plastic film base material side to the optical member used for LCD and ELD through an adhesive or an adhesive agent. In this bonding, the surface treatments described above may be performed on the surface of the transparent plastic film base material.

As said optical member, a polarizer or a polarizing plate is mentioned, for example. The polarizing plate includes a polarizer, and a transparent protective film is generally used on one side or both sides of the polarizer. When providing a transparent protective film on both surfaces of the said polarizer, the transparent protective film of front and back may be the same material, and may be a different material. The polarizing plate is usually disposed on both sides of the liquid crystal cell. The said polarizing plates are arrange | positioned so that the absorption axes of two polarizing plates may be substantially orthogonal to each other.

Next, the polarizing plate is demonstrated as an example about the optical member which laminated | stacked the anti-glare hard-coating film of this invention. The polarizing plate which has the function of this invention can be obtained by laminating | stacking the anti-glare hard coat film of this invention with a polarizer or a polarizing plate using an adhesive agent, an adhesive, etc.

The polarizer is not particularly limited. As said polarizer, a dichroic substance, such as an iodine or a dichroic dye, is made to adsorb | suck to hydrophilic polymer films, such as a polyvinyl alcohol-type film, a partially foamed polyvinyl alcohol-type film, and an ethylene vinyl acetate copolymerization partial saponification film, for example. And polyene oriented films such as uniaxially stretched, dehydrated products of polyvinyl alcohol, and dehydrochloric acid treated products of polyvinyl chloride. Among these, the polarizer which consists of a divinyl substance, such as a polyvinyl alcohol-type film and iodine, is preferable because it has a high polarization dichroic ratio. The thickness of the polarizer is not particularly limited. The thickness of the polarizer is, for example, about 5 to 80 µm.

The polarizer which uniaxially stretched the polyvinyl alcohol-type film by iodine can be produced by dyeing the polyvinyl alcohol-type film by immersing it in the aqueous solution of iodine, and extending | stretching 3 to 7 times the original length, for example. The aqueous solution of iodine may contain boric acid, zinc sulfate, zinc chloride or the like as necessary. In addition, the polyvinyl alcohol-based film may be immersed in an aqueous solution containing boric acid, zinc sulfate, zinc chloride or the like. If necessary, the polyvinyl alcohol-based film may be dipped in water and washed with water before dyeing. By washing the polyvinyl alcohol-based film with water, the contamination of the surface of the polyvinyl alcohol-based film and the antiblocking agent can be washed. In addition, the polyvinyl alcohol-based film is swollen to prevent the nonuniformity such as unevenness of dyeing. Stretching may be performed after staining with iodine, stretching may be performed while dyeing, or dyeing with iodine after stretching. It can extend | stretch also in aqueous solution, such as a boric acid and potassium iodide, or in a water bath.

As a transparent protective film provided in the single side | surface or both surfaces of the said polarizer, it is preferable that it is excellent in transparency, mechanical strength, thermal stability, moisture shielding property, stability of retardation value, etc. As a material which forms the said transparent protective film, the same thing as the said transparent plastic film base material is mentioned, for example.

As said transparent protective film, the polymer film of Unexamined-Japanese-Patent No. 2001-343529 (WO 01/37007) is mentioned. The polymer film described in the above publication is, for example, a thermoplastic resin having at least one imide group of a substituted imide group and an unsubstituted imide group in the (A) side chain, and at least one phenyl group of the substituted phenyl group and an unsubstituted phenyl group in the (B) side chain. And a polymer film formed from a resin composition containing a thermoplastic resin having a nitrile group. As a polymer film formed from the said resin composition, the polymer film formed from the resin composition containing the alternating copolymer which consists of isobutylene and N-methyl maleimide, and an acrylonitrile- styrene copolymer is mentioned, for example. The said polymer film can be manufactured by extrusion molding the said resin composition into a film form. Since the said polymer film has a small phase difference and a small photoelastic coefficient, when applied to protective films, such as a polarizing plate, defects, such as a nonuniformity by a deformation | transformation, can be eliminated. The polymer film is excellent in humidification durability because of its low moisture permeability.

As for the said transparent protective film, the film made of cellulose resins, such as triacetyl cellulose, and the film made of norbornene-type resin are preferable from a point of polarization characteristic, durability, etc. As a commercial item of the said transparent protective film, a brand name "FUJITAC" (made by Fuji Photo Film Co., Ltd.), a brand name "ZEONOA" (Nippon Zeon, for example) are mentioned. Co., Ltd.), a brand name "ARTON" (made by JSR Corporation), etc. are mentioned.

The thickness of the transparent protective film is not particularly limited. The thickness of the transparent protective film is, for example, in the range of 1 to 500 µm in terms of workability such as strength, handleability, thinness, and the like. If it is the said range, a polarizer will be mechanically protected and a polarizer will not shrink even if it is exposed to high temperature, high humidity, and can maintain stable optical characteristics. The thickness of the said transparent protective film becomes like this. Preferably it is the range of 5-200 micrometers, More preferably, it is the range of 10-150 micrometers.

The structure of the polarizing plate which laminated | stacked the anti-glare hard coat film is not specifically limited. The said polarizing plate may be the structure which laminated | stacked the transparent protective film, the polarizer, and the transparent protective film in this order, for example on the anti-glare hard-coating film. The said polarizing plate may be the structure which laminated | stacked the polarizer and the transparent protective film in this order, for example on the anti-glare hard-coating film.

Various optical members, such as the anti-glare hard coat film of this invention and the polarizing plate using this, can be used suitably for various image display apparatuses, such as a liquid crystal display device. The liquid crystal display device of this invention is the same structure as the conventional liquid crystal display device except using the anti-glare hard coat film of this invention. The liquid crystal display device of the present invention can be manufactured by, for example, assembling a drive circuit by appropriately assembling each component such as an optical member such as a liquid crystal cell, a polarizing plate, and an illumination system (backlight, etc.) as necessary. The liquid crystal cell is not particularly limited, and various types such as TN type, STN type, and π type can be used.

In the present invention, the configuration of the liquid crystal display device is not particularly limited. The liquid crystal display device of the present invention includes, for example, a liquid crystal display device in which the optical member is disposed on one side or both sides of the liquid crystal cell, a liquid crystal display device using a backlight or a reflecting plate in an illumination system, and the like. In these liquid crystal display devices, the optical member of the present invention can be disposed on one side or both sides of the liquid crystal cell. When arrange | positioning an optical member on both sides of the said liquid crystal cell, they may be same or different. In the liquid crystal display, for example, various optical members and optical components such as a diffusion plate, an antiglare layer, an antireflection layer, a protective plate, a prism array, a lens array sheet, a light diffusion plate, a backlight, and the like may be disposed.

Example

Next, the Example of this invention is described with a comparative example. However, the present invention is not limited by the following examples and comparative examples.

Example 1

Resin raw material (Dinipon) which contains the resin component containing (A) component, (B) component, and (C) component shown below, and a photoinitiator in solid content concentration 66weight% in the following mixed solvent of ethyl acetate and butyl acetate Ink company (Dainippon Ink And Chemicals, Incorporated), a brand name GRANDIC PC1071) was prepared. 30 weight part of PMMA particles (weight average particle diameter, refractive index 1.49) and 0.5 weight part of leveling agents were added to 100 weight part of this resin raw materials. Then, the resin raw material which added the said PMMA particle | grains and a leveling agent was acetic acid so that butyl acetate: ethyl acetate (weight ratio) = 55: 45 (45 weight% of ethyl acetate with respect to all the solvent), and a solid content concentration might be 55 weight%. Diluted with ethyl. In this way, a hard coat layer forming material was prepared. The leveling agent is a copolymer copolymerized in a molar ratio of dimethylsiloxane: hydroxypropyl siloxane: 6-isocyanate hexyl isocyanuric acid: aliphatic polyester = 6.3: 1.0: 2.2: 1.0.

(A) component: urethane acrylate consisting of pentaerythritol-based acrylate and hydrogenated xylene diisocyanate (100 parts by weight)

(B) component: 49 parts by weight of dipentaerythritol hexaacrylate (hereinafter referred to as component B1 (monomer)), 41 parts of pentaerythritol tetraacrylate (hereinafter referred to as component B4 (monomer)) and pentaerythritol triacrylate ( Hereinafter, 24 weight part of B5 component (monomer))

Component (C): a polymer, a copolymer having a repeating unit represented by the formula (1) or a mixture of the polymer and copolymer (59 parts by weight)

Photopolymerization initiator: 3 parts by weight of Irgacure 184 (produced by Chiba Specialty Chemicals)

Mixed solvent: Butyl acetate: ethyl acetate (weight ratio) = 89: 11

The hard coat layer forming material was coated on a transparent plastic film substrate (80 탆 thick triacetyl cellulose film, refractive index: 1.48) using a bar coater to form a coating film. The said coating film was dried by heating at 100 degreeC for 1 minute after the said coating. The said coating film after drying was hardened | cured by irradiating the ultraviolet-ray of accumulated light quantity 300mJ / cm <^2> with a metal halide lamp, and the hard coat layer of 20 micrometers in thickness was formed. Thus, the anti-glare hard coating film according to the present embodiment was produced.

Example 2

In the present Example, the anti-glare hard coat film was produced by the method similar to Example 1 except having changed the addition amount of PMMA particle into 15 weight part.

Example 3

In the present Example, 30 weight part of PMMA particles (refractive index 1.49) of 15 micrometers of weight average particle diameters were added, and the anti-glare hard-coating film was carried out similarly to Example 1 except having changed solid content concentration to 35%. Made.

Example 4

In the present Example, 30 weight part of PMMA particles (refractive index 1.49) of 8 micrometers of weight average particle diameters were added, and the anti-glare hard-coating was performed by the same method as Example 1 except having changed the film thickness of the hard-coat layer into 16 micrometers. The film was produced.

Example 5

In the present Example, the anti-glare hard coat film was produced by the method similar to Example 1 except having changed the film thickness of the hard coat layer into 16 micrometers.

Example 6

In the present Example, the anti-glare hard coat film was produced by the method similar to Example 1 except having changed the film thickness of the hard coat layer into 29 micrometers.

Example 7

In the present Example, 30 weight part of PMMA particles (refractive index 1.49) of 15 micrometers of weight average particle diameters were added, and the anti-glare hard-coating was carried out similarly to Example 1 except having changed the film thickness of the hard-coat layer to 23 micrometers. The film was produced.

Example 8

In the present Example, the anti-glare hard coat film was produced by the method similar to Example 1 except having provided the antireflective layer on the hard coat layer.

The antireflection layer was formed as follows. First, as a material for forming the antireflection layer, a siloxane oligomer (Colcoat N103 (Colcoat Co., Ltd.) product, solid content) having an average molecular weight of 500 to 10,000 in terms of ethylene glycol 2% by weight)). Next, the number average molecular weight of the said siloxane oligomer was measured. As a result, the number average molecular weight was 950. Subsequently, the brand name Opstar JTA105 (made by JSR Corporation, 5 weight% of solid content) was prepared as a fluorine compound whose number average molecular weight by polystyrene conversion is 5000 or more, and has a fluoroalkyl structure and a polysiloxane structure. . Next, the number average molecular weight of the fluorine compound was measured. As a result, the number average molecular weight in terms of polystyrene was 8000. As a hardening | curing agent, the brand name JTA105A (made by JSR Corporation, 5 weight% of solid content) was prepared.

Subsequently, 100 parts by weight of the Opstar JTA105, 1 part by weight of the JTA105A, 590 parts by weight of the Colcot N103 and 151.5 parts by weight of butyl acetate were mixed to prepare the antireflection layer forming material. The antireflection layer forming material was coated on the hard coat layer by die coating so as to have the same width as the hard coat layer. After the coating, the mixture was dried and cured by heating at 120 ° C. for 3 minutes to form an antireflection layer (low refractive index layer, 0.1 μm in thickness, and a refractive index of 1.43).

Example 9

In this example, an antireflection layer was formed on the hard coat layer of the antiglare hard coat film obtained in Example 1 to produce an antiglare antireflection hard coat film.

The antireflection layer was formed as follows. That is, 100 parts by weight of a dipentaerythritol acrylate, 15 parts by weight of a silicone polymer having a methacryloxypropyl group and a butyl group, 2.5 parts by weight of hexanediol acrylate, 6 parts by weight of a lucirin type photopolymerization initiator, And a hollow, spherical silicon oxide ultrafine particle having a diameter of 60 nm and hydrophobized by surface treatment with a silane coupling agent having an acryl group, in a mixed solvent (IPA / MIBK / butyl cellosolve / toluene (80/9 / 10.5 / 0.5)). The dispersion was adjusted so that the solid content was 3% by weight to obtain an antireflection layer forming material. Using this antireflection layer forming material, an antireflection layer was formed on the hard coat layer by the same method as in Example 7.

Example 10

First, the anti-glare hard coat film which concerns on a present Example was produced like Example 1. Subsequently, the coating liquid mentioned later was applied to the non-hard-coating surface (surface opposite to the formation surface of a hard-coating layer) of a triacetyl cellulose film so that the thickness at the time of wet may be set to 20 micrometers with a wire bar, and the coating film was formed. After the coating, the coating film was subjected to drying treatment at 80 ° C. for 1 minute. As the coating solution, a mixed solvent of acetone: ethyl acetate: IPA (isopropyl alcohol) = 37: 58: 5 (weight ratio) was used.

Example 11

First, the anti-glare hard coat film which concerns on a present Example was produced like Example 1. Subsequently, the coating liquid mentioned later was applied to the non-hard-coating surface (surface opposite to the formation surface of a hard-coating layer) of a triacetyl cellulose film so that the thickness at the time of wet may be set to 20 micrometers with a wire bar, and the coating film was formed. After the coating, the coating film was subjected to drying treatment at 80 ° C. for 1 minute. As said coating liquid, what mix | blended diacetyl cellulose so that solid content concentration might be 0.5weight% with respect to the mixed solvent of acetone: ethyl acetate: IPA (isopropyl alcohol) = 37: 58: 5 (weight ratio) was used.

Example 12

In this Example, the anti-glare hard coat film was produced by the method similar to Example 1 except not having used a leveling agent.

Comparative Example 1

100 parts by weight of urethane acrylate-based UV-curable resin, 15 parts by weight of polystyrene particles having a weight average particle diameter of 3.5 μm (refractive index: 1.59), leveling agent (trade name; MEGAFAC F-470N, Dainippon Ink and Chemicals Co., Ltd.) Ltd.) 0.5 part by weight, 2.5 parts by weight of synthetic smectite, 5 parts by weight of a photopolymerization initiator (trade name; Irgacure 907, Chiba Specialty Chemicals Co., Ltd.), a mixed solvent of butyl acetate and toluene (butyl acetate: toluene = 13: 87, weight ratio) so as to obtain a solid content concentration of 35% by weight to prepare a material for forming a hard coat layer.

Subsequently, the material for forming the hard coat layer was coated on a transparent plastic film substrate (a triacetyl cellulose film having a thickness of 80 µm, with a refractive index of 1.48) with a bar coater to form a coating film. After the said coating, the said coating film was heated and dried at 100 degreeC for 1 minute. After the drying, the coating film was irradiated with a UV light having a cumulative amount of light of 300 mJ / cm ^{2 using} a metal halide lamp to form a hard coating layer having a thickness of 5 μm. This produced the anti-glare hard coat film which concerns on this comparative example.

Comparative Example 2

In this comparative example, the anti-glare hard coat film which concerns on this comparative example was obtained by the method similar to Example 1 except having changed the addition amount of PMMA particle into 3 weight part.

Comparative Example 3

In this comparative example, the anti-glare hard coat film which concerns on this comparative example was obtained by the same method as Example 1 except having changed the addition amount of PMMA particle into 70 weight part.

Comparative Example 4

In this comparative example, the anti-glare hardening according to this comparative example was carried out in the same manner as in Comparative Example 1 except that the fine particles were PMMA particles having a weight average particle diameter of 3 μm (refractive index: 1.49), and the addition amount thereof was changed to 30 parts by weight. A coating film was obtained.

evaluation

Various characteristics in each Example and each comparative example were evaluated or measured by the following method.

(Thickness of hard coating layer)

The total thickness of the anti-glare hard coat film was measured using a microgauge thickness gauge manufactured by Mitsutoyo Corporation. The thickness of the transparent plastic film base material was subtracted from the said overall thickness. This calculated the thickness of the hard coat layer. The results are shown in Table 1 below.

(Thickness of the antireflection layer)

The thickness of the antireflection layer was calculated from the waveform of the interference spectrum using MCPD2000 (trade name), which is an instantaneous multi-photometric system manufactured by Otsuka Electronics Co., Ltd ..

(Haze)

Haze was measured using the brand name haze meter HR300 (Murakami Color Research Laboratory) according to the haze of JISK7136 (1981 edition). The results are shown in Table 1 below.

(Glossiness)

The glossiness was measured at 60 °, and according to JIS K 7105 (1981 edition), using the trade name digital variable gloss meter UGV-5DP (manufactured by Suga Test Instrument Co., Ltd.). Measured. The results are shown in Table 1 below.

(Pencil hardness)

The anti-glare hard coat film was mounted on the glass plate with the surface where the hard coat layer was not formed face down. Then, the pencil hardness was measured about the surface of the said hard coat layer according to the pencil hardness test of JISK-5400 (but load 500g). The results are shown in Table 1 below.

(Scratch resistance)

The scratch resistance of the anti-glare hard coat film was evaluated by the following test contents. The results are shown in Table 1 below.

(1) The sample was cut | disconnected to the magnitude | size more than width 25mm and length 100mm or more, and this was mounted on the glass plate.

(2) The steel wool # 0000 was uniformly affixed on the smooth cross section of the circumference of 25 mm in diameter, and the sample surface was reciprocated 30 at a speed of about 100 mm per second at a load of 1.5 kg. Then, it determined by visual evaluation by the following indicators.

A: There are no scratches.

B: There is a scratch, but it does not affect visibility.

C: Clear scratches damage the visibility.

(Arithmetic mean surface roughness Ra and mean tilt angle θ _a )

On the surface where the hard coating layer of the anti-glare hard coating film was not formed, a glass plate (1.3 mm) made by Matsunami Glass Ind., Ltd. was bonded with an adhesive, and a high-precision fine shape measuring instrument (brand name; The surface shape of the hard coat layer was measured using a Surfcoder ET4000, manufactured by Kosaka Laboratory Ltd., to obtain the arithmetic average surface roughness Ra value and the average tilt angle θ _a value. The results are shown in Table 1 below. The high-precision microshape automatically calculates the arithmetic mean surface roughness Ra and the average tilt angle θ _a .

(reflectivity)

The anti-glare hard coating is formed by bonding a black acrylic plate (thickness 2.0 mm, manufactured by Mitsubishi Rayon Co., Ltd.) to an adhesive layer having a thickness of about 20 μm on a surface where the hard coating layer of the anti-glare hard coating film is not formed. We lost reflection of the back of the film. About this anti-glare hard coat film, the reflectance of the hard coat layer surface was calculated | required. The reflectance was measured using a brand name UV2400PC (with an 8 ° inclination sphere) spectrophotometer manufactured by Shimadzu Corporation, and measured the spectral reflectance (mirror reflectance + diffuse reflectance), thereby measuring the total length of the C light source / 2 ° field of view. The reflectance (Y value) was calculated by calculation. The results are shown in Table 1 below.

(Refractive Index of Hard Coating Layer)

The refractive index of the hard coat layer was measured using a multi-wavelength Abbe refractometer (Atago Co., Ltd. product, brand name: DR-M2 / 1550). The results are shown in Table 1 below.

(Refractive index of fine particles)

The microparticles | fine-particles were mounted on the slide glass, the refractive index standard liquid was dripped on the microparticles | fine-particles, and the cover glass was covered and the sample was produced. The sample was observed under a microscope, and the refractive index of the refractive index standard solution in which the outline of the fine particles was most difficult at the interface with the refractive index standard solution was defined as the refractive index of the fine particles. The results are shown in Table 1 below.

(Adhesiveness)

The adhesiveness with respect to the transparent plastic film base material of a hard coat layer was evaluated by performing the board | substrate peeling test of JISK5400. That is, 100 peel tests were performed, the number which the hard-coat layer peeled from the film base material was counted, and it was shown by peeling number / 100. The results are shown in Table 1 below.

(Weight average particle diameter of fine particles)

A particle size distribution analyzer (brand name: Coulter multisizer, Beckman Coulter, Inc.) using a pore electrical resistance method by Coulter count method By measuring the electrical resistance of the electrolyte solution corresponding to the volume of the fine particles when the fine particles passed through the pores, the number and volume of the fine particles were measured to measure the weight average particle diameter of the fine particles.

As shown in Table 1, the anti-glare hard coat film of the present Example was excellent in all properties of hardness, scratch resistance, anti-glare and adhesion. In contrast, the anti-glare hard coat film of Comparative Example 1 had insufficient hardness, the anti-glare hard coat film of Comparative Example 2 was poor in anti-glare, and the anti-glare hard coat films of Comparative Examples 3 and 4 had scratch resistance. Lagged behind.

Those skilled in the art will clearly appreciate that many changes can be made in the above detailed description of the preferred embodiments of the invention. Accordingly, the scope of the invention should be determined by the appended claims.

In the anti-glare hard coat film of the present invention, since the thickness of the hard coat layer is within the predetermined range, the hardness is sufficient. In the anti-glare hard coat film of the present invention, since the particle diameter of the fine particles is within the predetermined range, and the average inclination angle θ _a of the concave-convex shape on the surface of the hard coating layer is within the predetermined range, the anti-glare property is excellent. It is also excellent in scratch resistance. Therefore, the image display apparatus to which the anti-glare hard coat film of this invention is applied is excellent in image display characteristic, since a screen is appropriately protected, excellent in handleability, and excellent in anti-glare property. In the anti-glare hard coat film of the present invention, since the hard coat layer is formed by using the resin for forming the hard coat layer containing the three components, the hardness is further improved, and cracking of the hard coat layer is prevented, and Curl generation due to cure shrinkage of the hard coat layer is effectively prevented.

Claims (14)

As anti-glare hard coating film, Including a transparent plastic film substrate, On at least one side of the transparent plastic film base material, a hard coat layer containing fine particles is formed, The hard coating layer has a thickness in the range of 15 to 30㎛, The fine particles have a weight average particle diameter in the range of 30 to 75% of the thickness of the hard coat layer, The average inclination angle θ _a of the uneven shape of the surface of the hard coating layer is in the range of 0.4 to 1.5 degrees, An anti-glare hard coating film wherein the hard coating layer is formed using a resin for forming a hard coating layer containing the following components (A), (B) and (C): (A) component: At least one of urethane acrylate and urethane methacrylate Component (B): at least one of polyol acrylate and polyol methacrylate Component (C): A polymer or copolymer formed from at least one of the following (C1) and the following (C2), or a mixed polymer of the polymer and the copolymer (C1): alkyl acrylate having an alkyl group having at least one of a hydroxyl group and acryloyl group (C2): Alkyl methacrylate which has an alkyl group which has at least one group of a hydroxyl group and an acryloyl group. The method of claim 1, The anti-glare hard coat film in which the said (B) component contains at least one of pentaerythritol triacrylate and pentaerythritol tetraacrylate. The method of claim 1, An anti-glare hard coating film having an anti-reflection layer formed on the hard coating layer. The method of claim 3, wherein The anti-reflection layer is an anti-glare hard coating film containing ultra-fine silicon oxide fine particles of hollow. The method of claim 1, Anti-glare hard coating film whose glossiness according to JIS K 7105 is in the range of 50 to 95. As a manufacturing method of the anti-glare hard coat film in which the hard coat layer containing microparticles | fine-particles was formed in at least one surface of the transparent plastic film base material, Preparing a hard coat layer forming material comprising a hard coat layer forming resin, fine particles having a weight average particle diameter in the range of 30 to 75% of the thickness of the hard coat layer, and a solvent, Coating the hard coat layer forming material on at least one surface of the transparent plastic film base material to form a coating film, and Hardening the said coating film, the thickness is the range of 15-30 micrometers, and the process of forming the hard-coating layer whose average inclination-angle (theta) _a of the uneven | corrugated shape of the surface is a range of 0.4-1.5 degree, Method for producing an anti-glare hard coating film wherein the hard coating layer-forming resin comprises the following (A) component, (B) component and (C) component: (A) component: At least one of urethane acrylate and urethane methacrylate Component (B): at least one of polyol acrylate and polyol methacrylate Component (C): A polymer or copolymer formed from at least one of the following (C1) and the following (C2), or a mixed polymer of the polymer and the copolymer (C1): alkyl acrylate having an alkyl group having at least one of a hydroxyl group and acryloyl group (C2): Alkyl methacrylate which has an alkyl group which has at least one group of a hydroxyl group and an acryloyl group. The method of claim 6, The manufacturing method of the anti-glare hard-coating film whose said (B) component contains at least one of pentaerythritol triacrylate and pentaerythritol tetraacrylate. The method of claim 6, Method for producing an anti-glare hard coating film wherein the solvent comprises ethyl acetate. The method of claim 8, A method of producing an anti-glare hard coat film in which the content ratio of ethyl acetate is 20% by weight or more based on the entire solvent. Including an optical member, An optical element, wherein the anti-glare hard coat film according to claim 1 is disposed on at least one side of the optical member. A polarizer comprising a polarizer and an anti-glare hard coat film according to claim 1. An image display device comprising the anti-glare hard coat film according to claim 1. An image display device comprising the optical element according to claim 10. An image display device comprising the polarizing plate according to claim 11.

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