CN100476455C - Anti-glare hard-coated film and manufacturing method thereof - Google Patents

Abstract

The invention provides a hard-coated antiglare film which includes a transparent film substrate and a hard-coating layer that contains fine particles and is formed on at least one side of the transparent film substrate, wherein the hard-coating layer has a thickness of 15 mum to 30 mum, the fine particles have an average particle size of 30% to 75% of the thickness of the hard-coating layer, and the fine particles form unevenness with a thetaa value of 0.4 DEG to 1.5 DEG according to JIS B 0601. In this way, the invention provides a hard-coated antiglare film with high hardness, high scratch resistance and good antiglare properties, a method of manufacturing the film, an optical element using the film, and an image display including the film or the optical element.

Description

Anti-glare hard-coated film and manufacturing method thereof

technical field

The present invention relates to an anti-glare hard-coated film in which a hard-coat layer is provided on at least one surface of a transparent film substrate and a method for producing the same. More specifically, it relates to optical elements such as polarizers, and image display devices such as CRT (Cathode Ray Tube), liquid crystal display (LCD), plasma display (PDP), and electroluminescent display (ELD). Hard coating film and its manufacturing method.

Background technique

There is LCD as one of various image display devices, but along with technological innovations related to LCD's high viewing angle, high definition, high-speed response, color reproducibility, etc., the application of LCD is also changing from notebook type personal Computer or monitor changes to TV. The basic structure of the LCD is that flat glass substrates respectively equipped with transparent electrodes are arranged to face each other through a spacer in a manner of forming a gap at a certain interval, a liquid crystal material is injected between the glass substrates, and sealed to form a liquid crystal cell, and then Polarizers are respectively provided on the outer surfaces of the pair of glass substrates. In the past, a cover made of glass or plastic was installed on the surface of the liquid crystal cell to prevent damage to the polarizing plate attached to the surface of the liquid crystal cell. However, it is disadvantageous in terms of cost and weight when the cover plate is attached, followed by hard-coating the surface of the polarizing plate.

A hard-coated film that has been hard-coated on a transparent plastic film substrate is usually formed on a transparent plastic film substrate with a thickness of about 2 to 10 μm using a power radiation curable resin such as a thermosetting resin or an ultraviolet curable resin. obtained from a hard coating. When the above-mentioned resin is applied to form a hard coat layer on glass, it shows characteristics of 4H or more in terms of pencil hardness. However, when the substrate is a transparent plastic film substrate, if the thickness of the hard coat layer is not sufficient, it is usually affected. Under the influence of the transparent plastic film substrate, the pencil hardness is reduced to below 3H.

By transferring the application of LCD to home TVs, users of general home TVs can easily imagine that even TVs using LCDs can perform the same operations as TVs using conventional glass-made CRTs. . The pencil hardness of the glass CRT is about 9H, which is quite different from the pencil hardness characteristics of conventional hard coat films. For this reason, even if the pencil hardness is less than 9H, further improvement in hardness of the hard coat film is required.

In order to increase the hardness of the hard coat film, the layer thickness of the hard coat layer can be increased. However, an increase in the layer thickness has a problem that sufficient anti-glare properties cannot be exhibited if the particles contained in the hard coat layer are completely embedded in the hard coat layer. In order to improve the antiglare property, there is also a method of increasing the amount of particles added, but in this case, the number of particles in the layer direction increases, and as a result, there is a problem that the haze value also increases. Therefore, in recent years, the disadvantages that have occurred are the result of solving the realization of high hardness of the hard coat film, that is, the increase of the anti-glare property or the haze value. As a method for solving the above-mentioned problems, the following JP-A 11- 286083-4 Proposal.

In Japanese Patent Application Laid-Open No. 11-286083, it is disclosed that on a transparent base film, particles with an average particle diameter of 0.6 to 20 μm, fine particles with an average particle diameter of 1 to 500 nm, and a hard coat resin are formed as main components. sex film. In addition, it is described 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, not more than 16 μm). However, when the thickness of a hard-coat layer is this level, sufficient hardness cannot be exhibited.

JP-A-2000-326447 discloses a hard-coated film in which at least one hard coat layer is formed on at least one surface of a plastic substrate film, and it is described that the thickness of the hard coat layer is 3 to 30 μm. , and furthermore, inorganic fine particles having a secondary particle size of 20 μm or less are added to the hard coat layer. Furthermore, it is also described that the surface of the hard coat layer is concavo-convex to impart anti-glare properties, but if it is such a structure, the surface roughness of the hard coat surface is completely ignored, and the inorganic particles are completely embedded in the hard coat layer. In the case of such a structure inside a coating layer, sufficient anti-glare property cannot be exhibited.

In Japanese Unexamined Patent Publication No. 2001-194504, an antireflection film is disclosed, which is formed by laminating a hard coat film layer and an antireflection film layer mainly composed of a metal alkoxide and its hydrolyzate on at least one surface of a plastic film. As a result, the elastic modulus below the fracture deformation of the hard coating is 0.7 to 5.5 GPa. In addition, it is described that the film thickness of the hard coat layer is not less than 0.5 μm and not more than 20 μm, and that the average particle diameter of the fine particles contained in the hard coat layer is 0.01 to 10 μm. However, according to the invention described in Japanese Unexamined Patent Publication No. 2001-194504, although the hardness and scratch resistance are improved, for example, adding fine particles with an average particle diameter of 1.8 μm to a hard coat layer with a film thickness of about 20 μm In the case of medium, the fine particles are completely embedded in the hard coat layer, and sufficient anti-glare property cannot be exhibited.

In Japanese Patent Laid-Open No. 2001-264508, an anti-glare anti-reflection film is disclosed, which is an anti-glare hard coating layer with particles having an average particle diameter of 1 to 10 μm sequentially laminated on a transparent support, and composed of Compositions containing inorganic fine particles with an average particle diameter of 0.001 to 0.2 μm, photocurable organosilane hydrolyzates and/or partial condensates thereof, and fluorine-containing polymers have a refractive index in the range of 1.35 to 1.49 For the low refractive index layer, the haze value of the antiglare and antireflection film is in the range of 3 to 20%, and the average reflectance at 450 μm to 650 μm is 1.8% or less. In addition, it is described that the film thickness of the antiglare hard coat layer is 1 to 10 μm. The object of the invention described in Japanese Unexamined Patent Application Publication No. 2001-264508 is to improve scratch resistance, anti-glare properties, etc., but there is a problem that sufficient hardness cannot be obtained.

Contents of the invention

The present invention has been accomplished in view of the above-mentioned problems, and its object is to provide an anti-glare hard-coated film with high hardness, scratch resistance, and anti-glare properties, its manufacturing method, an optical element using it, and a their image display devices.

In order to solve the above-mentioned conventional problems, the inventors of the present invention have intensively studied an antiglare hard-coat film, a method for producing the same, an optical element using the same, and an image display device including them. As a result, they found that the above-mentioned object can be achieved by adopting the following constitution, and completed the present invention.

That is, in order to solve the above-mentioned problems, the anti-glare hard-coated film of the present invention has a hard-coat layer containing particles on at least one surface of a transparent film substrate, the film thickness of the above-mentioned hard-coat layer is not less than 15 μm and not more than 30 μm, and The average particle diameter of the above-mentioned fine particles is 30% to 75% of the film thickness of the hard coat layer, and the θa of the uneven shape formed by the above-mentioned fine particles according to JIS B 0601 is 0.4° to 1.5°.

According to the above configuration, since the film thickness of the hard coat layer is 15 to 30 μm, it is a structure in which insufficient hardness is suppressed. In addition, the particles used are such that the average particle size of the particles contained in the hard coat layer is 30 to 75% of its film thickness, and the θa of the uneven shape formed by the particles is 0.4° to 1.5°, which is comparable to the film thickness of the hard coat layer. larger than particle size. Therefore, at least a part of the fine particles can be exposed from the surface layer of the hard coat layer, so that the anti-glare property can be improved. In addition, it is also possible to suppress a decrease in scratch resistance that occurs when fine particles of a small particle size that are less affected by gravitational sedimentation are used. That is, according to the above-mentioned constitution, an antiglare hard-coat film having excellent hardness, antiglare property, and scratch resistance can be provided.

The material for forming the hard coat layer preferably contains urethane acrylate, polyol (meth)acrylate, and a (meth)acrylic polymer having two or more hydroxyl groups.

By containing urethane acrylate as a forming material of the hard coat layer as in the above configuration, elasticity and flexibility can be imparted to the hard coat layer. Moreover, hardening of a hard-coat layer can be made high by containing a polyol (meth)acrylate. Furthermore, by containing the (meth)acrylic polymer which has a 3-hydroxypropyl group, cure shrinkage is moderated and the hard coat layer which suppressed curling generation can be obtained.

The above-mentioned polyol (meth)acrylate preferably comprises pentaerythritol triacrylate and pentaerythritol tetraacrylate.

According to the above configuration, the occurrence of curling can be further suppressed while maintaining high hardness and good flexibility.

In addition, it is preferable to provide at least one antireflection layer on the above-mentioned hard coat layer.

When an antireflection layer is provided on the outer surface of the hard coat layer as in the above configuration, reflection of light at the interface between the hard coat layer and air can be reduced. Thereby, when the antiglare hard-coat film of the said structure is applied to an image display apparatus etc., for example, the fall of the visibility of the image of a display screen can be suppressed.

In addition, it is preferable to contain hollow and spherical silicon oxide ultrafine particles in the antireflection layer.

In addition, in the above-mentioned hard-coated antiglare film, it is preferable that the glossiness according to JIS K 7105 is 50 or more and 95 or less. In addition, the above-mentioned "glossiness" refers to the 60-degree warp surface glossiness based on JIS K 7105 (1981 edition).

In addition, the method for producing an antiglare hard-coated film of the present invention is a method for producing an antiglare hard-coated film in which a hardcoat layer is formed on at least one surface of a transparent film substrate in order to solve the above-mentioned problems, including : The process of preparing the forming material of the hard coat layer, that is, the process of adding particles having an average particle diameter of 30% to 75% of the film thickness of the hard coat layer to the forming material and preparing the forming material; coating the above forming material A step of forming a coating film on at least one surface of the above-mentioned film substrate; curing the above-mentioned coating film to form a concave-convex shape with a film thickness of 15 μm or more and 30 μm or less, and the θa of JIS B 0601 passing JIS B 0601 is 0.4 ° above 1.5° below the hard coating process.

According to the method described above, a hard coat layer having a film thickness of 15 μm to 30 μm is formed, so an antiglare hard coat film having sufficient hardness can be produced. In addition, since particles having an average particle size of 30 to 75% of the film thickness of the hard coat layer are used, even if most of the particles are buried in the hard coat layer, at least a part of the particles can be exposed. Comes out of the hard coat of the structure. Furthermore, since a hard coat layer is formed so that θa is 0.4° to 1.5°, a layer excellent in anti-glare property can be obtained. In addition, the use of fine particles having a relatively large particle diameter compared to the film thickness of the hard coat layer can also suppress the reduction in scratch resistance that occurs when fine particles that are less prone to gravity sedimentation are used. That is, according to the above-mentioned method, a hard-coated antiglare film having good hardness, antiglare and scratch resistance can be produced.

It is preferable to use a solvent containing ethyl acetate as a diluting solvent for the forming material of the hard-coat layer.

Thereby, it is possible to form a hard coat layer which is excellent in adhesion to the film base material and can reduce peeling from the film base material.

Moreover, it is preferable that content of the said ethyl acetate is 20 weight% or more. Thereby, a hard-coat layer with more excellent adhesiveness with a film base material can be formed.

In addition, in order to solve the above-mentioned problems, the optical element of the present invention is provided with the above-mentioned antiglare hard coat film on at least one surface of the optical member.

Moreover, the polarizing plate of this invention is equipped with the antiglare hard-coat film mentioned above in order to solve the said subject.

In addition, in order to solve the above-mentioned problems, the polarizing plate of the present invention is provided with the above-mentioned antiglare hard-coat film on at least one surface of the polarizer.

Moreover, in order to solve the above-mentioned problems, the image display device of the present invention includes the above-mentioned anti-glare hard-coat film, the above-mentioned optical element, or the above-mentioned polarizing plate.

The present invention exerts effects as described below by means explained above.

That is, according to the present invention, a hard-coated anti-glare film having high hardness, excellent anti-glare properties and scratch resistance can be provided, so when the hard-coated anti-glare film is used in, for example, various optical elements or image display devices , while preventing damage to these devices, it can have a good anti-glare effect and prevent the reflection of external light.

Description of drawings

FIG. 1 is a schematic cross-sectional view showing an outline of an anti-glare hard-coat film according to one embodiment of the present invention.

2 is a schematic cross-sectional view showing the outline of an antiglare antireflection hard coat film according to another embodiment of the present invention.

Detailed ways

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing the outline of an anti-glare hard-coat film according to this embodiment.

As shown in FIG. 1 , the hard-coated anti-glare film 4 has a hard-coat layer 2 on one side of a transparent film substrate 1 . In addition, although not shown in FIG. 1 , the hard coat layer 2 may also be provided on both surfaces of the film substrate 1 . In addition, in FIG. 1 , the case where the hard coat layer 2 is a single layer is illustrated, but as long as it has the structure of the hard coat layer of this invention, these may be two or more layers.

The above-mentioned film substrate 1 is not particularly limited as long as it has excellent visible light transmittance (preferably 90% or more light transmittance) and excellent transparency (preferably a haze value of 1% or less). Specifically, for example, polyester-based polymers such as polyethylene terephthalate or polyethylene naphthalate; cellulose-based polymers such as diacetyl cellulose or triacetyl cellulose; ; Polycarbonate-based polymers; Films made of transparent polymers such as polymethyl methacrylate and other acrylic polymers. In addition, styrene-based polymers such as polystyrene and acrylonitrile-styrene copolymer (AS resin), polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, ethylene-propylene Olefin-based polymers such as copolymers; vinyl chloride-based polymers; films made of transparent polymers such as nylon or aramid-based polymers. In addition, there are also imide-based polymers; sulfone-based polymers; polyethersulfone-based polymers; polyether-etherketone-based polymers; polyphenylene sulfide-based polymers; vinyl alcohol-based polymers, Vinylidene chloride-based polymers; polyvinyl butyral-based polymers; arylate-based polymers; polyoxymethylene-based polymers; epoxy-based polymers; or films made of transparent polymers such as mixtures of the above polymers, etc. . In particular, it is suitable to use a thin film with little optical birefringence. When the anti-glare hard-coated film 4 of this embodiment is used as a protective film for a polarizer, as the film substrate 1, triacetyl cellulose, polycarbonate, acrylic polymer, cyclic or norbornene-containing Structured polyolefins, etc. In addition, the film substrate 1 may be a polarizer itself which will be described later. With such a configuration, the structure of the polarizing plate can be simplified without a protective layer made of TAC or the like, so that the number of manufacturing steps can be reduced and production efficiency can be improved. In addition, the thickness of the polarizing plate can be further reduced. In addition, when the film substrate 1 is a polarizer, the hard coat layer 2 functions as a conventional protective layer. In addition, as a hard coat film, it may also serve as a cover plate attached to the surface of a liquid crystal cell.

The thickness of the film substrate 1 can be appropriately determined, and is generally 10 to 500 μm in consideration of workability such as strength and handleability, and thin layer properties. Especially preferably, it is 20-300 micrometers, More preferably, it is 30-200 micrometers. Furthermore, the refractive index of the film substrate 1 is not particularly limited, but is usually about 1.30 to 1.80, and particularly preferably about 1.40 to 1.70.

The above-mentioned hard coat layer 2 is made of urethane acrylate (A), polyol (meth)acrylate (B), and (meth)acrylic polymer (C) having an alkyl group containing two or more hydroxyl groups. formed of materials.

As said urethane acrylate (A), what contains (meth)acrylic acid and/or its ester, a polyhydric alcohol, and a diisocyanate as a structural component is used. For example, it is possible to use a substance prepared by making (meth)acrylic acid and/or its ester, and a polyhydric alcohol into a hydroxy (meth)acrylate having at least one hydroxyl group by reacting it with a diisocyanate. produced in response.

(Meth)acrylic acid means acrylic acid and/or methacrylic acid, and (meth)acrylic acid means the same thing in this invention. These constituent components may be used alone or in combination of two or more.

Examples of esters of (meth)acrylic acid include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylic acid Alkyl (meth)acrylates such as butyl esters, cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylates, and the like.

The above polyhydric alcohol is a compound having at least two hydroxyl groups, for example, ethylene glycol, 1,3-propanediol, 1,2-propanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol, Diol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, 2,2,4-trimethyl-1,3-pentane Diol, 3-methyl-1,5-pentanediol, neopentyl glycol trimethylacetate, cyclohexanedimethylol, 1,4-cyclohexanediol, spirocyclodiol, Tricyclodecane Hydroxymethyl, Hydrogenated Bisphenol A, Ethylene Oxide Added Bisphenol A, Propylene Oxide Added Bisphenol A, Trimethylolethane, Trimethylolpropane, Glycerin, 3-Methylol Pentaerythritol-1,3,5-triol, pentaerythritol, dipentaerythritol, tripentaerythritol, sugars, etc.

As the above-mentioned diisocyanate, various aromatic, aliphatic or aromatic diisocyanates can be used, for example, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 2, 4-tolyl diisocyanate, 4,4-diphenyl diisocyanate, 1,5-naphthyl diisocyanate, 3,3-dimethyl-4,4-diphenyl diisocyanate, xylene diisocyanate, three Methylhexamethylene diisocyanate, 4,4-diphenylmethane diisocyanate, etc., and these hydrogenated products, etc. are further mentioned.

When the addition amount of the said urethane acrylate (A) is too small, the flexibility and adhesiveness of the obtained hard-coat layer will fall, and when it is too large, the hardness of the hard-coated layer after hardening will fall. For this reason, the urethane acrylate (A) is preferably 15% to the total resin components of the hard coat forming material (the total amount of components A to C, or the total amount when there is an added resin material, etc.). % by weight to 55% by weight, more preferably 25% by weight to 45% by weight. When the addition amount of a urethane acrylate (A) exceeds 55 weight% with respect to the total resin component of a hard-coat forming material, hard-coat performance may fall and it is unpreferable. Also, when blended in a ratio of less than 15% by weight, flexibility and adhesiveness may not be improved, which may not be preferable.

Examples of the constituents of the polyol (meth)acrylate (B) include pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, hexa(meth)acrylate, Dipentaerythritol meth)acrylate, 1,6-hexanediol (meth)acrylate, and the like. In addition, it is preferable to contain a monomer component composed of a polymer of pentaerythritol triacrylate and pentaerythritol tetraacrylate. Furthermore, a mixed component containing pentaerythritol triacrylate and pentaerythritol tetraacrylate is also particularly preferable.

The compounding quantity of a polyol (meth)acrylate (B) is preferably 70 weight% - 180 weight% with respect to a urethane acrylate (A), More preferably, it is 100 weight% - 150 weight%. When the ratio of polyol (meth)acrylate (B) to urethane acrylate (A) exceeds 180% by weight, the cure shrinkage of the hard coat layer increases, and as a result, the hard coat film Since curling increases or flexibility decreases, it may not be preferable. Moreover, when a ratio is less than 70 weight%, since hard-coat property, ie, hardness and scratch resistance fall, it may not be preferable. Moreover, it is preferable that it exists in the range of 0-0.7 from a practical viewpoint about scratch resistance, and it is more preferable that it exists in the range of 0-0.5. Scratch resistance can be set in the said range by making the compounding quantity of a polyol (meth)acrylate (B) into the said range. Here, the calculation of the above-mentioned scratch resistance will be described in Examples described later.

As said (meth)acryl polymer (C), the (meth)acryl polymer which has an alkyl group containing 2 or more hydroxyl groups can be used. More specifically, for example, a (meth)acrylic polymer having a 2,3-dihydroxypropyl group represented by the following chemical formula (1), or a polymer having the following chemical formula (1) in the molecule A (meth)acrylic polymer having a 2-hydroxyethyl group and a 2,3-dihydroxypropyl group having a repeating structural unit and a structural unit represented by the following chemical formula (2).

The amount of the (meth)acrylic polymer (C) having an alkyl group containing two or more hydroxyl groups is preferably 25% by weight to 110% by weight, more preferably 45% by weight, relative to the urethane acrylate (A). % by weight to 85% by weight. When the compounding amount exceeds 110% by weight, coatability may decrease, which is not preferable in some cases. Moreover, when the compounding quantity is less than 25 weight%, generation|occurence|production of curling will increase remarkably, and it may be unpreferable.

In addition, in the present invention, by containing the (meth)acrylic polymer (C), curing shrinkage of the hard coat layer 2 can be suppressed, and as a result, generation of curling can be prevented. From the viewpoint of producing a hard coat film, etc., it is preferable to suppress curling within at least 30 mm. By suppressing curling within this range, workability and productivity can be further improved.

Fine particles 3 are contained in the above-mentioned hard coat layer 2 . The microparticles 3 mainly function as antiglare microparticles for imparting antiglare properties. The fine particles 3 are classified into inorganic fine particles and organic fine particles. The above-mentioned inorganic fine particles are not particularly limited, and examples thereof include silicon oxide, titanium oxide, aluminum oxide, zinc oxide, tin oxide, calcium carbonate, barium sulfate, talc, kaolin, and calcium sulfate. In addition, the organic fine particles are not particularly limited, for example, polymethacrylic acid methacrylate resin powder, silicone resin powder, polystyrene resin powder, polycarbonate resin powder, acryl styrene resin powder , benzomelamine-based resin powder, melamine-based resin powder, polyolefin-based resin powder, polyester-based resin powder, polyamide-based resin powder, polyimide-based resin powder, polyfluorinated Vinyl resin powder, etc. These inorganic fine particles and organic fine particles may be used in combination of two or more.

The average particle diameter of the fine particles 3 is 30% to 75% of the film thickness of the hard coat layer 2 , more preferably 30% to 50% inclusive. When the average particle diameter is less than 30%, sufficient unevenness cannot be formed on the surface, and a sufficient antiglare function cannot be imparted. On the other hand, when the average particle diameter exceeds 75%, the unevenness of the surface becomes too large, the appearance deteriorates, and the scattering of reflected light increases, resulting in whitening.

The compounding amount of the above-mentioned fine particles 3 is not particularly limited, and can be appropriately set. Specifically, it is preferably 2 to 70 parts by weight, more preferably 4 to 50 parts by weight, and particularly preferably 15 to 40 parts by weight with respect to 100 parts by weight of the hard coat forming material.

In order to suppress as much as possible the scattering of light generated at the cross-sections of the microparticles 3 and the hard coat layer 2 , it is necessary to reduce the refractive index of the microparticles 3 and the hard coat layer 2 . The refractive index of the hard-coat layer 2 is normally 1.4-1.6. Therefore, as the fine particles 3 , it is preferable to use organic fine particles having a refractive index similar to that of the hard coat 2 or inorganic fine particles composed of silicon oxide. When the refractive index is 0.05 or more, scattering of light is enhanced. As a result, for example, when it is applied to an image display device, there may be a problem that the displayed content is not clear.

The shape of the microparticles 3 is not particularly limited, and may be bead-like, substantially spherical, or amorphous. One or more of these fine particles can be appropriately selected and used. As the fine particles 3, substantially spherical fine particles having an aspect ratio of 1.5 or less are preferably used. When substantially spherical particles or polygonal particles having an aspect ratio exceeding 1.5 are used, it may sometimes become difficult to control θa of the concavo-convex shape formed by the microparticles 3 .

The average inclination angle θa of the hard coat layer 2 needs to be not less than 0.4° and not more than 1.5°. When θa is less than 0.4°, sufficient anti-glare properties cannot be exhibited, and reflections on the appearance and the like appear. On the other hand, when θa exceeds 1.5°, the haze value increases. When it is within the above-mentioned range, the anti-glare effect of the hard coat layer 2 can be improved, and the reflection of external light etc. can be prevented favorably. In addition, the average inclination angle is a value obtained by a method based on JIS B0601.

When the difference between the refractive index of the film substrate 1 and the hard coat layer 2 is d, d is preferably 0.04 or less, more preferably 0.02 or less. As the film substrate 1, when polyethylene terephthalate is used, by adding about 35% of titanium oxide to the total resin component of the hard coat forming material in ultrafine particles with a particle diameter of 100 nm or less, it can be relatively Since the refractive index of polyethylene terephthalate film is about 1.64, controlling d below 0.02 can suppress the generation of interference fringes.

As the film substrate 1, when a triacetyl cellulose film is used, by adding about 40% of silicon oxide to the total resin component of the hard coat forming material in ultrafine particles with a particle diameter of 100 nm or less, it can be used in the same manner as above. The refractive index of the triacetyl cellulose film is about 1.48, and d is controlled below 0.02, which can suppress the generation of interference fringes.

The thickness of the above-mentioned hard coat layer 2 is preferably 15 to 30 μm, more preferably 18 to 25 μm. Since the lower limit of the thickness is 15 μm, since the hard coat layer 2 contains polyol (meth)acrylate (B), the hardness can be maintained at a certain value or more (for example, 4H or more in pencil hardness). In addition, in order to further increase the hardness, the upper limit of the thickness is set to 25 μm, because the hard coat layer 2 contains urethane acrylate (A) and a (meth)acrylic polymer (C) having a 3-hydroxypropyl group. ), so the occurrence of curling or cracking can be fully prevented. Moreover, when thickness is less than 15 micrometers, the hardness of a hard-coat layer may fall. On the other hand, when the thickness exceeds 25 μm, the hard coat layer itself may be cracked, and the hard coat film may curl up on the hard coat side due to curing shrinkage of the hard coat layer, which may cause practical problems.

The dilution solvent of the hard coat forming material is not particularly limited, and various substances can be used. Specifically, for example, dibutyl ether, dimethoxymethane, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1,3-dioxane Oleane, 1,3,5-trioxane, tetrahydrofuran, acetone, methyl ethyl ketone, diethyl ketone, diacetone, diisopropanone, cyclopentanone, cyclohexanone, methylcyclohexanone, formic acid Methyl ester, propyl formate, n-pentyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, n-pentyl acetate, acetylacetone, diacetone alcohol, methyl acetoacetate, ethyl acetoacetate Esters, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-methyl-2-butanol, cyclohexanone, isobutyl acetate, Methyl isobutyl ketone, 2-nonanone, 2-pentanone, 2-hexanone, 2-heptanone, 3-heptanone, etc. These can be used in combination of 1 type or 2 or more types. Ethyl acetate is preferably 20% by weight or more, more preferably 25% by weight or more, and particularly preferably 30% by weight to 70% by weight of the total diluting solvents. Thus, when triacetyl cellulose is used as the film base material 1, the hard coat layer 2 having particularly excellent adhesion can be formed. When the content of ethyl acetate exceeds 70% by weight relative to the total dilution solvent, the volatilization rate is fast, so uneven coating or uneven drying is prone to occur, and when it is less than 20% by weight, the adhesion to the substrate is reduced , which is sometimes not preferred.

With respect to the hard coat layer 2, for example, the surface of the film used in the formation of the above hard coat layer 2 is roughened in advance by suitable methods such as sand blasting, embossing rolls, chemical etching, etc., so that the surface of the film becomes fine. The concavo-convex structure, in combination with the method of forming the surface of the material itself for forming the hard coat layer 2 into a fine concavo-convex structure, etc., can make the concavo-convex state of the surface of the hard coat layer 2 non-uniform.

Various leveling agents can be added to the hard coat forming material. As the leveling agent, a fluorine-based or silicone-based leveling agent can be used suitably, and a silicone-based leveling agent is more preferably used. Examples of silicone-based leveling agents include reactive silicone, polydimethylsiloxane, polyether-modified polydimethylsiloxane, polymethylalkylsiloxane, and the like. Among these silicone-based leveling agents, reactive silicones are particularly preferred. By adding reactive silicone, lubricity is imparted to the surface and scratch resistance is maintained. Furthermore, when a layer containing a siloxane component is used as the low-refractive index layer, if a substance having a hydroxyl group is used as the reactive silicone, the adhesiveness is improved.

As a leveling agent of the said reactive silicone, what has a siloxane bond, an acrylate group, and a hydroxyl group can be illustrated, for example. More specifically, one can cite:

(1) (Dimethicone/methyl): (3-acryloyl-2-hydroxypropoxypropylsiloxane/methyl): (2-acryloyl-3-hydroxypropoxypropyl base siloxane)=0.8:0.16:0.04 molar ratio copolymer;

(2) Dimethicone: hydroxypropyl siloxane: 6-isocyanate hexyl isocyanuric acid: aliphatic polyester=6.3: 1.0: 2.2: 1.0 molar ratio copolymer;

(3) Dimethicone: methylpolyethylene glycol propyl ether siloxane with acrylate end: methylpolyethylene glycol propyl ether siloxane with hydroxyl end = 0.88: 0.07: 0.05 The molar ratio of the copolymer, etc.

The compounding quantity of a leveling agent is preferably 5 weight part or less with respect to 100 weight part of total resin components of a hard-coat forming material, More preferably, it is the range of 0.01-5 weight part.

When ultraviolet light is used in the curing mechanism of the hard coat forming material, if the above-mentioned leveling agent is blended into the hard coat forming material, the leveling agent will ooze out to the air interface during pre-drying and solvent drying, so that oxygen barriers can be prevented. Hard coating 2 having sufficient hardness even on the outermost surface can be obtained by curing the ultraviolet curable resin. In addition, since the silicone-based leveling agent imparts lubricity by oozing out to the surface of the hard coat layer 2, it is also possible to improve scratch resistance.

In the formation material of the above-mentioned hard coat layer 2, pigments, fillers, dispersants, plasticizers, ultraviolet absorbers, surfactants, antioxidants, thixotropic agents, etc. may be added as needed within the range that does not impair the formation. . These additives may be used alone or in combination of two or more.

A conventionally known photopolymerization initiator can be used for the hard coat forming material of the present embodiment. For example, 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'-diamino Benzophenone, 1-(4-isopropyl ether)-2-hydroxy-2-methylpropan-1-one, other thioxanthone-based compounds, etc.

In order to form the above-mentioned hard coat layer 2, a coating containing at least urethane acrylate (A), polyol (meth)acrylate (B) and an alkyl group containing two or more hydroxyl groups is applied on the film substrate 1. The hard coat forming material of the (meth)acrylic polymer (C) is subsequently allowed to cure. The hard coat forming material can be applied as a solution dissolved in a solvent at the time of application. When the hard coat forming material is applied as a solution, it is cured after drying.

As a method of coating the above-mentioned hard coat forming material on the film substrate 1, well-known coatings such as fountain coating, die coating, spin coating, spray coating, gravure coating, roll coating, and bar coating can be used. Applying method.

The curing mechanism of the above-mentioned hard coat forming material is not particularly limited, but ionizing radiation curing is preferred. Various active energies can be used in this mechanism, but ultraviolet light is suitable. As the energy line source, for example, a line 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. The irradiation amount of the energy ray source is preferably 50 to 5000 mJ/cm ² as the cumulative exposure amount at an ultraviolet wavelength of 365 nm. When the irradiation amount is less than 50 mJ/cm ² , hardening of the hard coat layer may decrease due to insufficient curing. Moreover, when exceeding 5000mJ/cm ^<2> , a hard-coat layer may color and transparency may fall.

As shown in FIG. 2 , an antireflection layer 5 may be provided on the hard coat layer 2 to form an antiglare antireflection hard coat film 6 . FIG. 2 is a schematic cross-sectional view showing the antiglare and antireflective hard coat film 6 of the present embodiment. When light hits an object, it repeats the phenomenon of reflection at the interface, absorption inside, and scattering, and passes through the back of the object. When a hard-coat film is mounted on an image display device, reflection of light at the interface between air and the hard-coat layer can be cited as one of the factors that lower the visibility of an image. The anti-reflection layer 5 is a layer that reduces the reflection of its surface. In addition, although not shown in FIG. 2 , hard coat layer 2 and antireflection layer 5 may be provided on both surfaces of film substrate 1 . In addition, in FIG. 2 , the case where one hard coat layer 2 and one antireflection layer 5 are provided is illustrated, but as long as the hard coat layer of the present invention is provided, the antireflection layer 5 may be two or more layers.

As the antireflection layer 5, a layer obtained by laminating an optical thin film (antireflection layer) whose thickness and refractive index are strictly controlled on the surface of the hard coat layer 2 can be mentioned. This is a method of exhibiting an anti-reflection function by mutually canceling the reversed phases of incident light and reflected light that have utilized the interference effect of light.

In designing the antireflection layer 5 based on the interference effect of light, there is a method of increasing the difference in refractive index between the antireflection layer 5 and the hard coat layer 2 as a mechanism for improving the interference effect. Generally, in the case of laminating 2 to 5 layers of optical films (films whose thickness and refractive index are strictly controlled) multilayer anti-reflection layer on the base material, by forming multiple layers of components with different refractive indices at a predetermined thickness, the The degree of freedom in the optical design of the anti-reflection layer 5 increases, the anti-reflection effect can be further improved, and it is also possible to flatten the spectroscopic reflection characteristics in the visible light region. Since the thickness accuracy of each layer of the optical thin film is required, the formation of each layer is generally performed by vacuum evaporation, sputtering, CVD, etc., which are dry methods.

Among the materials for forming the hard coat, titanium oxide, zirconium oxide, silicon oxide, magnesium fluoride, etc. can be used, but a laminate of a titanium oxide layer and a silicon oxide layer is preferably used in order to exhibit a greater antireflection function. The above laminate is preferably obtained by forming a titanium oxide layer with a high refractive index (refractive index: about 1.8) on the hard coat layer, and forming a silicon oxide layer with a low refractive index (refractive index: about 1.45) on the titanium oxide layer. A four-layer laminate formed by sequentially forming a titanium oxide layer and a silicon oxide layer on the two-layer laminate. By providing the antireflection layer of such a two-layer laminate or a four-layer laminate, it is possible to uniformly reduce reflection in the wavelength range (380 to 780 nm) of visible light.

In addition, by laminating a single-layer optical film on the film substrate 1, an antireflection effect can be exhibited. Even when the antireflection layer 5 is designed as a single layer, it is necessary to increase the difference in refractive index between the antireflection layer 5 and the hard coat layer 2 in order to maximize the antireflection function. When the film thickness of the above-mentioned antireflection layer 5 is d, the refractive index is n, and the wavelength of incident light is λ, the relationship between the film thickness of the antireflection layer 5 and its refractive index is nd=λ/ 4 relational formula. When the antireflection layer 5 is a low-refractive-index layer such that its refractive index is smaller than that of the film base material 1, the reflectance becomes the minimum under the condition that the above relation holds. For example, when the refractive index of the antireflection layer 5 is 1.45, the film thickness of the antireflection layer 5 at which the reflectance becomes the minimum with respect to incident light having a wavelength of 550 nm among visible rays is 95 nm.

The wavelength range of visible light exhibiting antireflection function is 380-780nm, especially the high-visibility wavelength range is 450-650nm, and the reflectance of 550nm, which is the central wavelength, is usually designed to be the minimum.

When the single-layer anti-reflection layer 5 is designed, its thickness accuracy is not as strict as that of the multi-layer anti-reflection layer, at least in the range of ±10% relative to the design thickness, that is, when the design wavelength is 95 nm, its thickness is 86 nm to 105 nm. within the range, it can be used without problems. Therefore, generally, when forming the antireflection layer 5 of a single layer, coating methods such as spray coating, die coating, spin coating, spray coating, gravure coating, roll coating, and bar coating, which are wet methods, can be used.

As a material for forming the antireflection layer 5 in a single layer, for example, resin-based materials such as ultraviolet curable acrylic resins, mixed-type materials in which inorganic fine particles such as colloidal silica are dispersed in the resin, tetraethoxysilane, Sol-gel materials of metal alkoxides such as tetraethoxytitanium, etc. In addition, each material may use a fluorine-containing compound in order to impart antifouling properties to the surface. From the viewpoint of scratch resistance, a low-refractive-index layer material having a large inorganic component content is excellent, and a sol-gel type material is particularly preferable. The sol-gel based material can be partially condensed and used.

Examples of the fluorine group-containing sol-gel material include perfluoroalkylalkoxysilanes. As the perfluoroalkyl alkoxysilane, for example, the general formula: CF ₃ (CF ₂ ) _n CH ₂ CH ₂ Si(OR) ₃ (wherein, R represents an alkane having 1 to 5 carbon atoms) group, and n represents an integer of 0 to 12). Specifically, for example, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecane Fluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, etc. Among them, compounds in which n is 2-6 are preferred.

As the low refractive index layer (antireflection layer), it is possible to preferably use a silicone oligomer containing a number average A material composed of a hard coat forming material of a fluorine compound having a styrene-equivalent number average molecular weight of 5,000 or more and having a fluoroalkyl structure and a polysiloxane structure.

An inorganic sol may be added to the low refractive index layer (antireflection layer) in order to improve film strength. The inorganic sol is not particularly limited, and examples thereof include silica, alumina, magnesium fluoride, etc., but silica sol is particularly preferable. The addition amount of the inorganic sol can be appropriately set within the range of 10 to 80 parts by weight relative to 100 parts by weight of the total solid content of the low-refractive index forming material. The particle size of the inorganic sol is preferably within a range of 2 to 50 nm, more preferably within a range of 5 to 30 nm.

Among the materials for forming the antireflection layer 5, hollow and spherical silicon oxide ultrafine particles are preferably contained. The hollow and spherical silicon oxide ultrafine particles preferably have an average particle diameter of about 5 to 300 nm. The ultrafine particles are hollow spheres formed by forming a cavity inside a shell with pores, and the solvent and the / or gas. It is preferable that the precursor substance for forming the above-mentioned voids remains in the voids. The thickness of the outer shell is preferably in the range of about 1 to 50 nm, and in the range of about 1/50 to 1/5 of the average particle diameter. The above-mentioned housing is preferably formed from a multilayer covering layer. Preferably, the pores are sealed, and the cavity is sealed by the housing. In the antireflection layer 5, maintaining porosity or voids can lower the refractive index of the antireflection layer 5, so it can be preferably used.

The hollow and spherical silicon oxide ultrafine particles have an average particle diameter of about 5 to 300 nm. This is because when the average particle diameter is less than 5 nm, the volume ratio of the shell in the spherical particles tends to increase and the volume ratio of the voids tends to decrease. On the other hand, when the average particle diameter exceeds 300 nm, it is difficult to obtain stable dispersion. liquid, and the transparency of the antireflection layer containing the ultrafine particles tends to decrease. The preferable average particle diameter of the hollow and spherical silicon oxide ultrafine particles is in the range of 10 to 200 nm. In addition, the said average particle diameter can be calculated|required by the dynamic light scattering method.

The method for producing hollow and spherical silicon oxide ultrafine particles includes, for example, the following steps (a) to (c). Hollow and spherical silicon oxide ultrafine particles are obtained as a dispersion liquid. As a method for producing such hollow and spherical silicon oxide ultrafine particles, for example, the method for producing silicon oxide-based fine particles disclosed in JP-A-2000-233611 can be suitably employed. Right now,

(a) A step of preparing a nuclear particle dispersion liquid simultaneously in an alkaline aqueous solution with a pH of 10 or higher, or in an alkaline aqueous solution with a pH of 10 or higher in which seed particles have been dispersed if necessary. Molar ratio (MO _X /SiO ₂ ) when silicate aqueous solution and/or acidic silicic acid solution, alkali-soluble inorganic compound aqueous solution is added, silicon oxide is represented by SiO ₂ , and inorganic compounds other than silicon oxide are represented by MO _X In the range of 0.3 to 1.0;

(b) a step of forming a first silicon oxide coating layer, that is, adding a silicon oxide source to the core particle dispersion to form a first silicon oxide coating layer on the core particles;

(c) A step of removing part or all of the elements constituting the core particles, that is, adding an acid to the dispersion liquid to remove part or all of the elements constituting the core particles.

The hollow and spherical silicon oxide ultrafine particles of the present invention have an average particle diameter in the range of 5 to 300 nm. This is because, when the average particle diameter is less than 5nm, the volume ratio of the shell in the spherical particles increases, and the volume ratio of the void decreases. On the other hand, when the average particle diameter exceeds 300nm, it is difficult to obtain a stable dispersion. In addition, , the transparency of the antireflection layer containing the ultrafine particles tends to decrease. The preferable average particle diameter of the hollow and spherical silicon oxide ultrafine particles is in the range of 10 to 200 nm. In addition, the said average particle diameter can be calculated|required by the dynamic light scattering method.

The above-mentioned hollow and spherical silicon oxide ultrafine particle dispersion liquid can be mixed with various matrix components to prepare a coating liquid for antireflection formation. Various matrix components refer to components that can form a film on the surface of the hard coat layer 2, and can be selected from resins suitable for conditions such as adhesion to the substrate, hardness, and coating properties. For example, Polyester resin, acrylic resin, urethane resin, vinyl chloride resin, epoxy resin, melamine resin, fluororesin, silicone resin, butyral resin, phenolic resin, vinyl acetate resin, UV curing Resins, electron beam curable resins, emulsion resins, water-soluble resins, hydrophilic resins, mixtures of these resins, and organic resins such as copolymers or modified products of these resins are also mentioned. In addition, as a material for forming the antireflection layer 5 in a single layer as described above, the exemplified hydrolyzable organosilicon compound or the like can be used as a matrix component.

When an organic resin is used as the matrix component, for example, using an appropriate organic solvent, an organic solvent dispersion obtained by substituting an organic solvent such as alcohol for water as a dispersion medium of the above-mentioned hollow and spherical silica ultrafine particles, An organic solvent dispersion dispersed in an organic solvent after being treated with a known coupling agent on the above-mentioned ultrafine particles and a substrate can be diluted as necessary to obtain a coating liquid for antireflection formation.

On the other hand, when a hydrolyzable organosilicon compound is used as a matrix component, for example, by adding water and an acid or base as a catalyst to a mixture of an alkoxysilane and an alcohol, a partial hydrolyzate of an alkoxysilane is obtained, The above-mentioned dispersion liquid is mixed therein, and diluted with an organic solvent as necessary to obtain a coating liquid.

The weight ratio of the silicon oxide ultrafine particles and the matrix component in the coating liquid is preferably in the range of silicon oxide ultrafine particles:matrix = 1:99 to 9:1. When the above-mentioned weight ratio exceeds 9:1, the strength of the antireflection layer 5 may be insufficient to be practical. On the other hand, when the above-mentioned weight ratio is less than 1:99, the effect of adding the above-mentioned silicon oxide ultrafine particles is difficult to appear.

The refractive index of the antireflection layer 5 formed on the surface of the hard coat layer 2 varies depending on the mixing ratio of silicon oxide ultrafine particles and matrix components and the refractive index of the matrix used, but is 1.2 to 1.42, which is a low refractive index. In addition, the refractive index of the silicon oxide ultrafine particle itself of the present invention is 1.2 to 1.38.

The anti-glare antireflection hard coat film 6 in which the antireflection layer 5 is provided on the hard coat layer 2 of the hard coat film is preferable in terms of pencil hardness. The surface of the hard coat layer 2 containing ultrafine particles forms minute unevenness, which affects the sliding of the pencil (the pencil is easy to catch and the force is easy to transmit). When the antireflection layer 5 is provided, unevenness becomes smooth, and generally, a layer having a pencil hardness of about 3H in the hard coat layer 2 can have a pencil hardness of 4H.

As a method for producing such hollow and spherical silicon oxide ultrafine particles, for example, the method for producing silicon oxide-based fine particles disclosed in JP-A-2000-233611 can be suitably employed.

The temperature for drying and curing when forming the antireflection layer (low refractive index layer) 5 is not particularly limited, and is usually 60°C to 150°C, preferably 70°C to 130°C, usually for 1 minute to 30 minutes, in consideration of productivity. In this case, it is more preferably about 1 minute to 10 minutes. In addition, after drying and curing, heat treatment is further performed to obtain a hard-coated anti-reflection film with higher hardness. The temperature of the heat treatment is not particularly limited, but it is usually 40°C to 130°C, preferably 50°C to 100°C for 1 minute to 100 hours, and more preferably for 10 hours or more to further improve scratch resistance. In addition, temperature and time are not limited to the above-mentioned ranges, and can be appropriately adjusted. For heating, a method of passing through a hot plate, an oven, a belt furnace, or the like can be appropriately employed.

Because the anti-reflection layer 5 is frequently installed on the outermost surface of the image display device, it is easily polluted from the external environment. In particular, pollutants such as fingerprints, hand dirt, sweat, and hairdressing materials are easy to adhere to around, and the surface reflectance changes due to the adhesion, or the attached matter becomes white and floats, and the display content appears to be unclear. The pollution is more obvious than in the case of In such a case, a fluorine-containing silane compound, a fluorine-containing organic compound, or the like may be laminated on the antireflection layer 5 in order to impart the functions related to the above-mentioned antiadhesion property and easy removal property.

By carrying out various surface treatments to the film substrate 1 or the hard coat layer 2 coated on the film substrate 1, the film substrate 1 and the hard coat layer 2, the film substrate 1 and the polarizer or the hard coat layer 2 can be improved. Adhesion of coating 2 and anti-reflection layer 5. As its surface treatment, low-pressure plasma treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, acid or alkali treatment can be used. In addition, the alkali saponification treatment preferably used as a surface treatment when triacetyl cellulose is used as a film substrate will be specifically described. Preferably, the surface of the cellulose ester film is dipped in an alkaline solution, and then washed with water and then dried in a cycle. Examples of the alkali solution include potassium hydroxide solution and sodium hydroxide solution, and the predetermined concentration of hydroxide ions is 0.1N to 3.0N, more preferably 0.5N to 2.0N. The temperature of the alkaline solution is in the range of 25°C to 90°C, more preferably 40°C to 70°C. Subsequently, water washing treatment and drying treatment are performed to obtain surface-treated triacetyl cellulose.

In addition, in order to prevent curling, the back surface of the film substrate 1 (the surface opposite to the surface on which the hard coat layer 2 is formed) may be subjected to solvent treatment as described below. The solvent treatment is carried out by applying a composition containing a solvent capable of dissolving or swelling the film substrate 1 by a conventionally known method. By applying such a solvent, the back side of the film substrate 1 is given the property of making it round, so that the film substrate 1 already provided with the hard coat layer 2 cancels the occurrence of curling on the side on which the hard coat layer 2 is formed. The force of the edge prevents the occurrence of curling.

As the above-mentioned solvent, in addition to the mixture of the solvent for dissolution and/or the solvent for swelling, a solvent for non-dissolution may be further contained. It performs using the composition which mixed the said solvent in an appropriate ratio according to the curling degree of the film base material 1, and the kind of resin, and the coating amount.

When further improving the anti-curling function, in terms of the solvent composition used, it is effective to increase the mixing ratio of the solvent that can dissolve it and/or the solvent that can make it swell, and decrease the ratio of the solvent that cannot dissolve it of. The mixing ratio is preferably used (solvent capable of dissolving and/or solvent capable of swelling): (solvent not capable of dissolving) = 10:0 to 1:9. Examples of the solvent that dissolves or swells the transparent resin film contained in such a mixed composition include benzene, toluene, xylene, dioxane, acetone, methyl ethyl ketone, N,N-dimethyl Methyl formamide, methyl acetate, ethyl acetate, trichloroethylene, methylene chloride, ethylene chloride, tetrachloromethane, trichloroethane, chloroform, etc. As a solvent which does not make it dissolve, methanol, ethanol, n-propanol, isopropanol, n-butanol etc. are mentioned, for example.

Using a gravure coater, a dip coater, a reverse coater, or an extrusion coater, etc., these solvent compositions are coated on the surface of the film substrate 1 so that the wet film thickness (film before drying) thickness) is 1 to 100 μm, more preferably 5 to 30 μm.

Each of the solvents applied in this way may scatter after drying or may remain in a small amount, but it is preferable that the solvent does not remain on the coated surface.

In addition, in order to prevent occurrence of curling, a transparent resin layer as described below may be provided on the back surface of the film substrate 1 (the surface opposite to the surface on which the hard coat layer 2 is formed). Examples of the above-mentioned transparent resin layer include layers mainly composed of thermoplastic resins, radiation curable resins, thermosetting resins, and other reactive resins. Among them, a layer containing a thermoplastic resin as a main component is particularly preferable.

Examples of the aforementioned thermoplastic resins include vinyl chloride-vinyl acetate copolymers, vinyl chloride resins, vinyl acetate resins, copolymers of vinyl acetate and vinyl alcohol, and partially hydrolyzed vinyl chloride-vinyl acetate copolymers. , vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer, ethylene-vinyl alcohol copolymer, chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, etc. cellulose derivatives such as nitrocellulose, cellulose acetate propionate, cellulose acetate butyrate resin, copolymers of maleic acid and/or acrylic acid, acrylate copolymers, acrylonitrile-styrene copolymers, Chlorinated polyethylene, acrylonitrile-chlorinated polyethylene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylic resin, polyvinyl acetal resin, polyvinyl butyral Resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, styrene-butylene Rubber-based resins such as vinyl resins and butadiene-acrylonitrile resins, silicone-based resins, fluorine-based resins, and the like. Among these thermoplastic resins, it is particularly preferable to use, for example, a cellulose-based resin layer such as diacetyl cellulose as the transparent resin layer.

In addition, the anti-glare hard-coat film 4 and the anti-glare anti-reflection hard-coat film 6 can usually be bonded on the film substrate 1 side to an optical member for LCD or ELD with an adhesive or an adhesive. The same surface treatment as above can be given to the film substrate 1 whenever bonding.

As an optical member, a polarizer or a polarizing plate is mentioned, for example. Polarizers generally use polarizers that have a transparent protective film on one or both sides of the polarizer. When a transparent protective film is provided on both sides of the polarizer, the inner and outer transparent protective films can be made of the same material or different materials. Polarizers are usually arranged on both sides of the liquid crystal cell. In addition, the polarizing plates were arranged so that the absorption axes of the two polarizing plates were substantially perpendicular to each other.

Next, a polarizing plate will be described as an example of an optical element on which the anti-glare hard-coat film 4 or the anti-glare anti-reflection hard-coat film 6 of the present invention is laminated. The hard-coated anti-glare film 4 or hard-coated anti-glare film 6 of the present invention can obtain a polarizer having the function of the present invention by laminating a polarizer or a polarizer using an adhesive or an adhesive.

There is no particular limitation on the above-mentioned polarizer, and various polarizers can be used. As a polarizer, for example, on hydrophilic polymer films such as polyvinyl alcohol-based films, partially formalized polyvinyl alcohol-based films, and ethylene-vinyl acetate copolymer-based partially saponified films, adsorption of iodine or Materials that are uniaxially stretched after dichroic substances such as dichroic dyes; polyene-based oriented films such as dehydration-treated products of polyvinyl alcohol or dehydrochloric acid-treated products of polyvinyl chloride, etc. Among them, a polarizer composed of a polyvinyl alcohol-based film and a dichroic substance such as iodine is particularly preferable because of its high polarization dichroism ratio. The thickness of these polarizers is not particularly limited, but is usually about 5 to 80 μm.

A polarizer obtained by uniaxially stretching a polyvinyl alcohol-based film dyed with iodine, for example, can be produced by dipping polyvinyl alcohol in an aqueous solution of iodine, dyeing it, and stretching it to 3 to 7 times its original length . If necessary, it may be immersed in an aqueous solution of potassium iodide or the like which may contain boric acid, zinc sulfate, zinc chloride, or the like. In addition, if necessary, the polyvinyl alcohol-based film may be immersed in water and washed with water before dyeing.

Washing the polyvinyl alcohol-based film with water not only removes dirt and anti-blocking agents on the surface of the polyvinyl alcohol-based film, but also prevents unevenness such as staining by swelling the polyvinyl alcohol-based film. Stretching may be performed after dyeing with iodine, stretching may be performed while dyeing, or dyeing with iodine may be performed after stretching. Stretching may also be performed in an aqueous solution of boric acid, potassium iodide, or the like, or in a water bath.

As the transparent protective film provided on one or both sides of the polarizer, a material having good properties in terms of transparency, mechanical strength, thermal stability, moisture shielding property, and stability of retardation value is preferable. Examples of materials for forming the transparent protective film include polyester-based resins such as polyethylene terephthalate and polyethylene naphthalate; and cellulose-based resins such as diacetyl cellulose and triacetyl cellulose. Acrylic resins such as polymethyl methacrylate; polystyrene or acrylonitrile-styrene copolymer, styrene resin, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, acrylonitrile-ethylene - Styrene-based resins such as styrene resins, styrene-maleic anhydride imide copolymers, and styrene-maleic anhydride copolymers; polycarbonate-based resins, etc. In addition, polyolefin-based resins such as cyclic olefin resins, norbornene-based resins, polyethylene, polypropylene, and ethylene-propylene copolymers; vinyl chloride-based resins; amide-based resins such as nylon or aromatic polyamides; aromatic polyamides Imide-based resins such as imides or polyimide-amides; sulfone-based resins; polyethersulfone-based resins; polyetheretherketone-based resins; polyphenylene sulfide-based resins; vinyl alcohol-based resins, vinylidene chloride Polyvinyl butyral resins; Acrylic resins; Polyoxymethylene resins; Epoxy resins; or a polymer film composed of a mixture of the resins, etc. is also used as the resin for forming the transparent protective film example given. In addition, the above-mentioned transparent protective film may be formed as a cured layer of a thermosetting or ultraviolet curable resin such as acrylic, urethane, acrylic urethane, epoxy, silicone, or the like.

In addition, polymer films described in Japanese Patent Laid-Open No. 2001-343529 (WO 01/37007), for example, comprising (A) a thermoplastic resin having a substituted and/or unsubstituted imino group in a side chain, and (B) ) A resin composition of a thermoplastic resin having substituted and/or unsubstituted phenyl and nitrile groups in the side chain. As a specific example, a film of a resin composition containing an alternating copolymer of isobutylene and N-methylmaleimide and an acrylonitrile-styrene copolymer can be mentioned. As the film, a film composed of a mixed extrusion product of a resin composition or the like can be used. These films have a small phase difference and a small photoelastic modulus, so when used as protective films such as polarizers, defects such as unevenness due to deformation can be eliminated. In addition, the moisture permeability is small, so the durability under humidification is excellent.

As the transparent protective film, cellulose-based resins such as triacetyl cellulose and norbornene-based resins are preferably used from the viewpoint of polarization characteristics, durability, and the like. Specifically, the product name "Fujitaku" manufactured by Fujifilm Co., Ltd., the product name "Zionoa" manufactured by Nippon Zeon Co., Ltd., the product name "Aiton" manufactured by JSR Co., Ltd., etc. are mentioned.

The thickness of the transparent protective film can be appropriately determined, but it is generally about 1 to 500 μm from the viewpoint of handling properties such as strength and handleability, and thin layer properties. More preferably, it is 5-200 micrometers. Particularly preferably, it is 10 to 150 μm. Within the above range, the polarizer can be mechanically protected, the polarizer does not shrink even when exposed to high temperature and high humidity, and stable optical characteristics are ensured.

In addition, it is best not to color the transparent protective film. Therefore, it is preferable to use the film thickness direction represented by Rth=(nx-nz) d (where nx is the refractive index in the direction of the slow axis in the film plane, nz is the refractive index in the film thickness direction, and d is the film thickness). The retardation value is a protective film of 90nm～+75nm. By using a protective film having a retardation value (Rth) in the thickness direction of −90 nm to +75 nm, it is possible to substantially eliminate coloring (optical coloring) of the polarizing plate caused by the protective film. The retardation value (Rth) in the thickness direction is more preferably -80 nm to +60 nm, particularly preferably -70 nm to +45 nm.

In the above-mentioned transparent protective film, the retardation value in the film plane and the retardation value in the thickness direction may affect the viewing angle characteristics of the liquid crystal display device, so it is preferable to use a transparent protective film with an optimized retardation value. Among them, the so-called transparent protective film that is expected to optimize the retardation value refers to the transparent protective film laminated on the surface of the polarizer near the liquid crystal cell, and the transparent protective film laminated on the surface of the polarizer far from the liquid crystal cell. Since the optical characteristics of the liquid crystal display device are not changed, it is not limited to this.

As the retardation value of the transparent protective film laminated on the surface of the polarizer near the liquid crystal cell, the retardation value (Re: (nx-ny)·d) in the film plane is preferably 0 to 5 nm. More preferably, it is 0 to 3 nm. More preferably, it is 0 to 1 nm. The retardation value (Rth) in the thickness direction is preferably 0 to 15 nm. More preferably, it is 0 to 12 nm. More preferably, it is 0 to 10 nm. Particularly preferably, it is 0 to 5 nm. Most preferably 0 to 3 nm.

Polarizers laminated with an anti-glare hard-coat film, etc., a transparent protective film, a polarizer, and a transparent protective film can be sequentially laminated on the hard-coat film, etc., and a polarizer can be sequentially laminated on an anti-glare hard-coat film, etc. , Transparent protective film.

In addition, the surface of the transparent protective film to which the polarizer is not bonded may be treated for the purpose of hard coating or anti-blocking. The purpose of the hard coat treatment is to prevent damage to the surface of the polarizer, for example, by adding an appropriate UV-curable resin such as acrylic or silicone to the surface of the transparent protective film, which has excellent hardness or sliding properties. Formation of a cured film, etc. In addition, anti-blocking treatment is performed to prevent sticking to adjacent layers. Wherein, besides being provided on the transparent protective film itself, the above-mentioned hard coat layer, anti-adhesion layer and the like may also be provided separately from the transparent protective film as other optical layers.

In addition, between the layers of the polarizing plate, for example, a hard coat layer, a primer layer, an adhesive layer, an adhesive layer, an antistatic layer, a conductive layer, a gas barrier layer, a water vapor barrier layer, a moisture barrier layer, etc. can be inserted. , or laminated to the surface of a polarizer. In addition, at the stage of forming each layer of the polarizing plate, for example, conductive particles, antistatic agents, various fine particles, plasticizers, etc. can be added, mixed, etc. to the forming materials of each layer. .

The lamination method of the above-mentioned transparent protective film and the polarizer is not particularly limited, for example, an adhesive made of an acrylic polymer or a vinyl alcohol polymer, or at least vinyl such as boric acid or borax, glutaraldehyde or melamine or oxalic acid can be used. Adhesives composed of water-soluble cross-linking agents of alcohol-based polymers, etc. Thereby, it is possible to obtain a transparent protective film that is difficult to peel off under the influence of humidity or heat and has excellent light transmittance or polarization. As the above-mentioned adhesive, it is preferable to use a polyvinyl alcohol-based adhesive from the viewpoint of excellent adhesiveness with polyvinyl alcohol which is a raw material of a polarizer.

When the polymer film containing the above norbornene-based resin is used as a transparent protective film and as an adhesive when laminating with a polarizer, it is preferable that it has excellent transparency, small birefringence, etc., and can sufficiently exhibit adhesion even if it is used as a thin layer. strong adhesive. As such an adhesive, for example, a dry lamination adhesive mixed with a polyurethane-based resin solution and a polyisocyanate resin solution, a styrene-butadiene rubber-based adhesive, or an epoxy-based two-component curable adhesive can be used. , such as an adhesive formed of two components of epoxy resin and polythiol, an adhesive formed of two components of epoxy resin and polyamide, etc., especially solvent-based adhesives and epoxy-based two-component curable adhesives, Transparent adhesives are preferred. Depending on the adhesive, there is an adhesive that can improve the adhesive force by using an appropriate primer for adhesion, and when such an adhesive is used, it is preferable to use a primer for adhesion.

As the above-mentioned bonding primer, there are no particular limitations as long as it is a layer that can improve the adhesiveness. A hydrolyzable alkoxysilyl silane-based coupling agent, a titanate-based coupling agent having a titanium-containing hydrolyzable hydrophilic group and an organic functional group in the same molecule, and a titanate-based coupling agent in the same molecule So-called coupling agents such as aluminate-based coupling agents with aluminum-containing hydrolyzable hydrophilic groups and organic functional groups; epoxy-based resins, isocyanate-based resins, urethane-based resins, ester carbamic acids Resins with organic reactive groups such as ester resins. Among them, a layer containing a silane-based coupling agent is preferable from the viewpoint of industrial ease of handling.

In order to facilitate lamination on a liquid crystal cell, an adhesive layer or an adhesive layer may be provided on both surfaces or one surface of the polarizing plate.

There is no particular limitation on the adhesive or adhesive used for the above-mentioned adhesive layer or adhesive layer. For example, acrylic polymers, silicone polymers, polyesters, polyurethanes, polyamides, polyvinyl ethers, vinyl acetate/vinyl chloride copolymers, modified polyolefins, cyclic Oxygen-based, fluorine-based, rubber-based polymers such as natural rubber and synthetic rubber are used as adhesives or binders of the base polymer. In particular, it is preferable to use an acrylic adhesive from the viewpoint of excellent optical transparency, adhesive properties showing moderate wettability, cohesiveness, and adhesiveness, and excellent weather resistance or heat resistance.

A crosslinking agent corresponding to the base polymer may be contained in the adhesive or adhesive. In addition, fillers or pigments, coloring agents or antioxidants, which are composed of natural or synthetic resins, glass fibers or glass beads, metal powder or other inorganic powders, etc. additives. In addition, an adhesive layer containing transparent fine particles and exhibiting light diffusing properties may also be formed.

Among the transparent particles, for example, silicon dioxide, calcium oxide, aluminum oxide, titanium oxide, zirconium oxide, tin oxide, indium oxide, cadmium oxide, antimony oxide, etc. having an average particle diameter of 0.5 to 20 μm can be used. One or more suitable particles such as conductive inorganic particles, or crosslinked or uncrosslinked organic particles composed of suitable polymers such as polymethyl methacrylate or polyurethane .

The adhesive or binder is generally used as an adhesive solution in which a base polymer or a composition thereof is dissolved or dispersed in a solvent and has a solid content concentration of about 10 to 50% by weight. As said solvent, organic solvents, such as toluene and ethyl acetate, and solvents corresponding to the type of adhesive, such as water, can be suitably selected and used.

The adhesive or adhesive may also be provided on one or both sides of the polarizing plate or the optical film as a laminate of layers of different compositions or kinds. The thickness of the above-mentioned adhesive or pressure-sensitive adhesive can be appropriately determined according to the purpose of use, adhesive force, etc., and is generally 1 to 500 μm, preferably 5 to 200 μm, and particularly preferably 10 to 100 μm.

The exposed surface of the adhesive layer or the adhesive layer may be temporarily covered with a release paper or a release film (also referred to as a release sheet) in order to prevent contamination and the like before use in practical use. In this way, it is possible to prevent contact with the adhesive layer or the adhesive layer under normal operating conditions. As the separator, for example, plastic films, rubber sheets, paper, cloth, non-woven fabrics, nets, hair The material obtained by coating a suitable thin sheet such as a foam sheet, a metal foil, or a laminate thereof is based on a conventional suitable separator.

As an optical element, an optical film obtained by laminating another optical member (optical layer) on the above-mentioned polarizing plate can be used in practical use. The optical layer is not particularly limited, but for example, reflective plates, semi-transmissive plates, phase difference plates (including 1/2 or 1/4 wave resistance plates), viewing angle compensation films, etc. can be used in the formation of liquid crystal display devices, etc. One or more optical layers are used. A particularly preferable polarizing plate is a reflective polarizing plate or a semi-transmitting polarizing plate in which a reflecting plate or a semi-transmitting reflecting plate is further laminated on the polarizing plate; polarizing plate; a wide viewing angle polarizing plate obtained by further laminating a viewing angle compensating film on the polarizing plate; or further laminating a brightness improving film (polarized light separation film having a polarization selective layer, such as D- BEF, etc.) and formed polarizers. In elliptically polarizing plates, polarizing plates with optical compensation, etc., a hard coat film is added to the polarizing plate side.

Furthermore, if necessary, it can also be used to impart scratch resistance, durability, weather resistance, heat and humidity resistance, heat resistance, moisture resistance, moisture permeability, antistatic properties, electrical conductivity, and interlayer adhesion. Improvement of various properties, performance, etc., such as improvement of mechanical strength, or insertion and lamination of functional layers.

A reflective polarizer is formed by providing a reflective layer on the polarizer, and can be used to form a type of liquid crystal display device that reflects incident light incident from the viewing side (display side) to display, and can omit the built-in light source such as a backlight. , thus having advantages such as easy thinning of the liquid crystal display device. When forming a reflective polarizer, it can be carried out by an appropriate method such as a method of providing a reflective layer made of metal or the like on one side of the polarizer through the above-mentioned transparent protective film or the like as necessary.

Specific examples of reflective polarizers include polarizers in which a reflective layer is formed by affixing a reflective metal foil such as aluminum or a vapor-deposited film on one side of a matte-treated transparent protective film as necessary.

Instead of attaching the reflecting plate directly to the transparent protective film of the above-mentioned polarizing plate, it is also possible to provide a reflecting layer on an appropriate film based on the transparent film to form a reflecting plate or the like, and then use it. Also, since the reflective layer is usually made of metal, it is preferable to use a transparent protective film or A form of use where the reflective surface is covered with a polarizer or the like.

In addition, in the above, the semi-transmissive polarizing plate can be obtained by forming a semi-transmissive reflective layer such as a half mirror that transmits light while reflecting light with the reflective layer. A transflective polarizing plate is usually provided on the back side of a liquid crystal cell, and can form a liquid crystal display device or the like of a type in which, when the liquid crystal display device or the like is used in a relatively bright environment, the reflection is from the viewing side (display side) to display images with incident light, and to display images in a relatively dark environment using a built-in light source such as a built-in backlight. That is, the transflective polarizing plate is very useful in the formation of liquid crystal display devices of the type that can save the energy of using a light source such as a backlight in a bright environment, and can also use a built-in light source in a relatively dark environment. .

An elliptically polarizing plate or a circular polarizing plate formed by further laminating a retardation film on a polarizing plate will be described. In the case of changing linearly polarized light into elliptically polarized light or circularly polarized light, changing elliptically polarized light or circularly polarized light into linearly polarized light, or changing the polarization direction of linearly polarized light, a retardation plate or the like can be used. In particular, a so-called 1/4 wave stop plate (also referred to as a λ/4 plate) can be used as a retardation plate that changes linearly polarized light into circularly polarized light and vice versa. 1/2 wave blocking plate (also known as λ/2 plate) is usually used in the case of changing the polarization direction of linearly polarized light.

The elliptical polarizing plate can be effectively used in the following situations, such as compensating (preventing) the coloring (blue or yellow) of the STN (Super Twisted Nematic) type liquid crystal display device due to the birefringence of the liquid crystal layer, thereby performing the above-mentioned coloring without coloring. The case of black and white display, etc. In addition, a polarizing plate that controls the three-dimensional refractive index can also compensate (prevent) coloring that occurs when viewing the screen of a liquid crystal display device from an oblique direction, and is therefore preferable. The circular polarizing plate is effectively used, for example, to adjust the color tone of an image of a reflective liquid crystal display device that displays an image in color, and also has a function of preventing reflection. Specific examples of the aforementioned retardation plate include p-polycarbonate, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polypropylene or other polyolefins, polyarylate, poly A birefringent film obtained by stretching a film composed of a suitable polymer such as amide, an oriented film of a liquid crystal polymer, a film supporting an oriented layer of a liquid crystal polymer, or the like. The retardation plate may be a material having an appropriate retardation according to the purpose of use, such as various wave resistance plates or materials for compensating coloring or viewing angle due to the birefringence of the liquid crystal layer, or two or more types may be laminated. Materials that control the optical properties such as phase difference of the retardation plate.

In addition, the above-mentioned elliptically polarizing plate or reflective elliptically polarizing plate is formed by appropriately combining and laminating a polarizing plate or reflective polarizing plate and a retardation plate. Such elliptically polarizing plates and the like can also be formed by sequentially stacking (reflective) polarizing plates and retardation plates in sequence during the manufacture of liquid crystal display devices to form a combination of (reflective) polarizing plates and retardation plates, and as above As mentioned above, members preliminarily formed as optical films such as elliptically polarizing plates are excellent in quality stability and lamination workability, and thus have the advantage of improving the production efficiency of liquid crystal display devices and the like.

The viewing angle compensation film is a film used to expand the viewing angle to make the image look clear even when the liquid crystal display screen is viewed from a slightly oblique direction that is not perpendicular to the screen. Such a viewing angle compensation retardation film is made of, for example, a retardation film, an alignment film such as a liquid crystal polymer, or a material in which an alignment layer such as a liquid crystal polymer is supported on a transparent substrate. A general retardation plate uses a birefringent polymer film that is uniaxially stretched in the plane direction. On the other hand, a retardation film that is used as a viewing angle compensation film can be birefringent in the plane direction. A stretched polymer film with birefringence, or a birefringent polymer with a controlled refractive index in the thickness direction that is uniaxially stretched in the plane direction and stretched in the thickness direction, or an obliquely oriented film Such biaxially stretched films and the like. As an oblique orientation film, for example, after bonding a heat-shrinkable film on a polymer film, under the action of the shrinkage force formed by heating, the polymer film is stretched or/and shrink-treated, and the liquid crystal is polymerized. materials with oblique orientation, etc. The base polymer of the phase difference plate can be the same polymer as the polymer described above for the phase difference plate, and it can be used to prevent coloring due to a change in the recognition angle of the phase difference caused by the liquid crystal cell, or to expand recognition. An appropriate material for the purpose such as a good angle of view.

In addition, from the viewpoint of realizing a wide viewing angle with good visibility, etc., an alignment layer composed of a liquid crystal polymer, especially an oblique alignment layer of a discotic liquid crystal polymer supported by a triacetyl cellulose film can be preferably used. An optical compensation phase difference plate made of an optically anisotropic layer.

A polarizing plate and a brightness improving film bonded together are usually used after being installed on the back side of a liquid crystal cell. The brightness improving film is a film that exhibits the property of reflecting linearly polarized light with a predetermined polarization axis or circularly polarized light with a predetermined direction when natural light enters due to the backlight of a liquid crystal display device or the like or reflection from the back side, etc. and allow other light to pass through. Therefore, the polarizing plate formed by laminating the brightness-improving film and the polarizing plate can allow the light from a light source such as a backlight to enter, and obtain transmitted light in a prescribed polarization state. At the same time, light other than the prescribed polarization state cannot be transmitted. be reflected. The light reflected on the surface of the brightness-improving film is reversed again by means of a reflective layer arranged on its back side, and it is incident on the brightness-improving film again, so that part or all of it is transmitted as light in a specified polarization state. By doing so, the light transmitted through the brightness improving film is increased, and at the same time, the polarized light that is difficult to absorb is supplied to the polarizer, thereby increasing the amount of light that can be used in displaying images, etc., thereby improving the brightness. That is, in the case where light is incident through the polarizer from the back side of the liquid crystal cell with a backlight or the like without using the brightness improving film, light having a polarization direction that does not coincide with the polarization axis of the polarizer is basically received by the polarizer. Absorbs and therefore cannot pass through polarizers. That is, although it varies depending on the characteristics of the polarizer used, about 50% of the light is absorbed by the polarizer. Therefore, the amount of light that can be used in liquid crystal image display, etc. decreases, resulting in dark images. Since the brightness improvement film repeatedly performs the following operations, that is, the light with a polarization direction that can be absorbed by the polarizer is not incident on the polarizer, but the light is reflected on the brightness improvement film, and then by means of the The reflective layer etc. on the side completes inversion, so that the light is incident on the brightness improving film again, so that the brightness improving film only changes the polarization direction of the light reflected and reversed between the two to pass through the polarizer. Since the polarized light in the polarization direction is transmitted and supplied to the polarizer, light such as a backlight can be effectively used for displaying images on the liquid crystal display device, thereby making the screen bright.

It is also possible to provide a diffusion plate between the brightness improving film and the reflective layer or the like. The light in the polarized state reflected by the brightness improving film is directed toward the reflective layer and the like, and the diffuser is provided to uniformly diffuse the passing light while canceling the polarized state into a non-polarized state. That is, the diffuser returns the polarized light to its original natural light state. Repeatedly, the light in the non-polarized state, that is, the natural light state, is irradiated to the reflective layer, etc., reflected by the reflective layer, and then passes through the diffusion plate again and is incident on the brightness improving film. By installing a diffuser between the brightness improving film and the above-mentioned reflective layer, etc., which restores the polarized light to its original natural light state, it is possible to maintain the brightness of the display screen while reducing the brightness unevenness of the display screen, thereby providing uniform and bright lighting. screen. By arranging such a diffuser plate, the number of repeated reflections of the initial incident light can be appropriately increased, and a uniform and bright display image can be provided by utilizing the diffusion function of the diffuser plate.

As the brightness improving film, for example, a dielectric multilayer film or a film multilayer laminate having different refractive index anisotropy, which exhibits the property of transmitting linearly polarized light with a predetermined polarization axis and reflecting other light, can be used. Films, oriented films of cholesteric liquid crystal polymers, or films that support the oriented liquid crystal layer on a film substrate, which reflect either left-handed or right-handed circularly polarized light and transmit other light Suitable films such as films with special properties.

Therefore, in the brightness improving film of the above-mentioned type that transmits linearly polarized light with a predetermined polarization axis, by making the transmitted light directly incident on the polarizer along the direction coincident with the polarization axis, it is possible to suppress damage caused by the polarizer. While absorbing the loss, the light can be transmitted efficiently. On the other hand, in a brightness-improving film of a type that transmits circularly polarized light, such as a cholesteric liquid crystal layer, although it is possible to directly make light incident on a polarizer, it is preferable to use a phase filter from the viewpoint of suppressing absorption loss. The circularly polarized light is linearly polarized by the difference plate, and then incident on the polarizer. Furthermore, by using a 1/4 wave blocking plate as the retardation plate, it is possible to convert circularly polarized light into linearly polarized light.

Regarding the phase difference plate that can function as a 1/4 wave blocking film in a wide wavelength range such as the visible light region, it can be obtained, for example, by using light-colored light with a wavelength of 550nm as a 1/4 wave blocking film. The manner in which the active retardation layer and the retardation layer exhibiting other retardation characteristics, such as a retardation layer that can function as a 1/2 wave-resistance plate, are overlapped. Therefore, the retardation plate disposed between the polarizing plate and the brightness improving film may be composed of one or more retardation layers.

In addition, for the cholesteric liquid crystal layer, it is also possible to combine materials with different reflection wavelengths to form an arrangement structure in which two or more layers overlap, thereby obtaining a member that reflects circularly polarized light in a wide wavelength range such as the visible light region. , so that transmitted circularly polarized light in a wider wavelength range can be obtained based on this.

In addition, the polarizing plate may be composed of a laminated polarizing plate and two or more optical layers, like the polarized light separation type polarizing plate. Therefore, a reflection type elliptically polarizing plate or a semi-transmitting type elliptically polarizing plate combined with the aforementioned reflective polarizing plate or semi-transmitting polarizing plate and a retardation plate may be used.

The lamination of the hard coat film to the above-mentioned optical elements, and the lamination of various optical layers to the polarizing plate can also be formed by sequentially and independently laminating in the manufacturing process of liquid crystal display devices, etc., and the member formed by laminating them in advance has It is excellent in terms of quality stability, assembly workability, etc., and has an advantage of improving the manufacturing process of liquid crystal display devices and the like. Appropriate bonding means such as adhesive layers can be used for lamination. When the above-mentioned polarizing plate or other optical films are bonded, their optical axes can be adjusted to an appropriate arrangement angle according to the intended retardation characteristics and the like.

On at least one side of the above-mentioned polarizing plate or an optical member such as an optical film such as a polarizing plate laminated with at least one layer, the above-mentioned hard coating film is provided, but on the surface where the hard coating film is not provided, it may also be provided for Adhesive layer for bonding with other components such as liquid crystal cells. The adhesive for forming the adhesive layer is not particularly limited, and for example, acrylic polymers, silicone polymers, polyesters, polyurethanes, polyamides, polyethers, fluorine-based or rubbers can be suitably selected and used. series of polymers such as base polymer adhesives. It is particularly preferable to use an adhesive that has excellent optical transparency like an acrylic adhesive, exhibits moderate wettability, cohesiveness, and adhesive properties, and is excellent in weather resistance, heat resistance, and the like.

Moreover, in addition to the above, from the prevention of foaming phenomenon or peeling phenomenon due to moisture absorption, the reduction of optical characteristics due to thermal expansion difference, or the warping of liquid crystal cells, and further from the high quality and excellent durability of liquid crystal display devices From the viewpoint of formability and the like, an adhesive layer with a low moisture absorption rate and excellent heat resistance is preferable.

A crosslinking agent corresponding to the base polymer may be contained in the above-mentioned adhesive or adhesive. In addition, the adhesive layer, etc. may contain, for example, natural or synthetic resins, especially tackifying resins, or fillers, pigments, colorants, antioxidants, etc. composed of glass fibers, glass beads, metal powder, and other inorganic powders. Additives that can be added to the adhesive layer. In addition, an adhesive layer or the like which contains fine particles and exhibits light diffusing properties may also be used.

The attachment of the pressure-sensitive adhesive layer to optical elements such as polarizing plates and optical films can be performed by an appropriate method. As an example, for example, the following method can be mentioned, that is, about 10 to 40 wt. % adhesive solution, and then directly attach it to the optical element through a suitable spreading method such as casting method or coating method; or transfer and stick it after forming an adhesive layer on the spacer based on the above way on optics etc. The adhesive layer can also be provided as an overlapping layer with layers different in composition, type, etc. of each layer. The thickness of the adhesive layer can be appropriately determined depending on the purpose of use, the adhesive force, etc., and is generally 1 to 500 μm, preferably 5 to 200 μm, and particularly preferably 10 to 100 μm.

The exposed surface of the adhesive layer may be temporarily covered with a spacer in order to prevent contamination or the like before use. This prevents contact with the adhesive layer in normal operating conditions. As the spacer, on the basis of satisfying the above-mentioned thickness conditions, for example, plastic films, rubber sheets, paper, cloth, Conventionally, suitable separators such as non-woven fabrics, nets, foamed sheets, metal foils, and laminates thereof, which have been coated with suitable sheets, are suitable.

Also, in the present invention, it is also possible to use, for example, salicylate-based compounds or benzophenol (benzophenol ) series compounds, benzotriazole-based compounds, cyanoacrylate-based compounds, nickel complex compounds and other ultraviolet absorbers, etc., to make them have ultraviolet absorbing ability and the like.

In addition, the antiglare hard coat film of the present invention can be used as a surface treatment film in a glass crack prevention laminate. The glass crack prevention laminate is formed by providing a surface treatment film on the glass crack prevention adhesive layer provided on one side of the optical film for liquid crystal display via a primer layer, and the glass crack prevention adhesive layer The dynamic storage elastic modulus G' at 20°C is 1×10 ⁷ Pa or less. Even if the anti-glare hard-coated film of the present invention is used for the anti-glass cracking laminated body of this structure, it can prevent the glass substrate of the liquid crystal panel from being cracked due to external impact, and it can prevent the glass substrate of the liquid crystal panel from being damaged by durability tests such as heating and humidification. Peeling or floating occurs on the optical film for liquid crystal.

The optical element provided with the hard-coat film of this invention can be suitably used for formation of various devices, such as a liquid crystal display device, etc. A liquid crystal display device can be formed by a conventional method. That is, in general, a liquid crystal display device can be formed by appropriately combining components such as a liquid crystal cell, an optical element, and an illumination system added as needed, and incorporating a driving circuit, etc. In the present invention, in addition to using the optical It is not particularly limited except for the element, and can be formed according to a conventional method. For the liquid crystal cell, for example, any type of liquid crystal cell such as TN type, STN type, or π type can be used.

Suitable liquid crystal display devices, such as a liquid crystal display device in which the above-mentioned optical element is arranged on one side or both sides of a liquid crystal cell, and a device using a backlight or a reflector in an illumination system, can be formed. At this time, the optical element of the present invention can be provided on one side or both sides of the liquid crystal cell. When the optical elements are arranged on both sides, they may be the same or different. In addition, when forming a liquid crystal display device, one or more layers such as a diffusion plate, an anti-glare layer, an anti-reflection film, a protective plate, a prism array, a lens array sheet, a light diffusion plate, a backlight, etc. Lights and other suitable components.

Next, an organic electroluminescent device (organic EL display device) will be described. Generally, in an organic EL display device, a transparent electrode, an organic light-emitting layer, and a metal electrode are sequentially stacked on a transparent substrate to form a luminous body (organic electroluminescent body). Here, the organic light-emitting layer is a laminate of various organic thin films. For example, a laminate of a hole injection layer made of a triphenylamine derivative or the like and a light-emitting layer made of a fluorescent organic solid such as anthracene is known, or A laminate of such a light-emitting layer and an electron injection layer made of a perylene derivative or the like, or a laminate of these hole injection layers, a light-emitting layer, and an electron injection layer can be combined in various ways.

The organic EL display device emits light according to the principle that holes and electrons are injected into the organic light-emitting layer by applying a voltage to the transparent electrode and the metal electrode, and the energy generated by the recombination of these holes and electrons excites the fluorescent substance , When the excited fluorescent substance returns to the ground state, it will emit light. The recombination mechanism in the middle is the same as that of a general diode, and it can be presumed from this that the current and luminous intensity show strong nonlinearity with rectification with respect to the applied voltage.

In an organic EL display device, at least one electrode must be transparent in order to extract light generated in the organic light-emitting layer, and a transparent electrode made of a transparent conductor such as indium tin oxide (ITO) is usually used as an anode. On the other hand, in order to facilitate electron injection and improve luminous efficiency, it is very important to use a substance with a small work function on the cathode, and metal electrodes such as Mg-Ag and Al-Li are usually used.

In the organic EL display device having such a configuration, the organic light-emitting layer is composed of an extremely thin film with a thickness of about 10 nm. Therefore, like the transparent electrode, the organic light-emitting layer transmits light almost completely. As a result, when the light is not emitted, the light incident from the surface of the transparent substrate and transmitted through the transparent electrode and the organic light-emitting layer and reflected on the metal electrode will be emitted to the surface side of the transparent substrate again. Therefore, when it is recognized from the outside, the organic EL The display surface of the device is like a mirror.

In an organic EL display device comprising an organic electroluminescent body as described below, a polarizing plate may be provided on the surface side of the transparent electrodes, and a phase difference plate may be provided between these transparent electrodes and the polarizing plate. It is formed by providing a transparent electrode on the front side of the organic light-emitting layer that emits light by applying a voltage, and providing a metal electrode on the back side of the organic light-emitting layer.

Since the retardation plate and the polarizing plate have the function of polarizing the light incident from the outside and reflected by the metal electrode, the mirror surface of the metal electrode cannot be recognized from the outside by the polarization function. In particular, when the 1/4 wave resistance plate is used to form the phase difference plate and the angle between the polarization directions of the polarizer and the phase difference plate is adjusted to π/4, the mirror surface of the metal electrode can be completely covered.

That is, of the external light incident on the organic EL display device, only the linearly polarized light component is transmitted due to the existence of the polarizing plate. The linearly polarized light is generally converted into elliptically polarized light by the phase difference plate, and when the phase difference plate is a 1/4 wave resistance plate and the angle between the polarization direction of the polarizer and the phase difference plate is π/4, it becomes circularly polarized Light.

The circularly polarized light passes through the transparent substrate, transparent electrode, and organic thin film, is reflected on the metal electrode, and then passes through the organic thin film, transparent electrode, and transparent substrate again, and is converted into linearly polarized light by the phase difference plate again. Then, since the linearly polarized light is perpendicular to the polarization direction of the polarizer, it cannot pass through the polarizer. As a result, the mirror surface of the metal electrode can be completely shaded.

Hereinafter, preferred embodiments of the present invention will be described in detail by way of illustration. However, the scope of the present invention is not limited thereto unless the materials, compounding amounts, and the like described in the examples are not particularly limited, and are merely examples. In addition, in each example, parts and % are based on weight unless otherwise indicated.

(Example 1)

100 parts of urethane acrylate composed of pentaerythritol-based acrylate and hydrogenated xylene diisocyanate are blended as urethane acrylate (hereinafter, component A), and polyol (meth)acrylate (hereinafter, B Components) of dipentaerythritol hexaacrylate (hereinafter, B1 component (monomer)) 49 parts, pentaerythritol triacrylate (hereinafter, B2 component (monomer)) 24 parts, and pentaerythritol tetraacrylate (hereinafter, B3 component (monomer) )) 41 parts, as a (meth)acrylic polymer (hereinafter, C component) having an alkyl group containing two or more hydroxyl groups (meth) having a 2-hydroxyethyl group and a 2,3-dihydroxypropyl group Acrylic polymer (manufactured by Dainippon Ink Chemical Industry Co., Ltd., trade name: PC1097) 59 parts. And then, by the mixed solvent that the mixing ratio of butyl acetate and ethyl acetate is 55:45 (relative to the ethyl acetate ratio of total solvent is 45%), dilute the PMMA particle ( Refractive index: 1.49) 30 parts, reactive leveling agent 0.5 part, polymerization initiator (Irgacure 184) 5 parts, and the solid content concentration was 55%, to prepare a hard coat forming material. In addition, the above-mentioned reactive leveling agent is produced in a molar ratio of dimethylsiloxane: hydroxypropylsiloxane: 6-isocyanate hexyl isocyanuric acid: aliphatic polyester = 6.3: 1.0: 2.2: 1.0 copolymerized copolymers.

Using a triacetyl cellulose film (refractive index: 1.48) with a thickness of 80 μm as a film substrate, the hard coat forming material was coated on the film using a bar coater, and the coating was dried by heating at 100° C. for 1 minute. Subsequently, a metal halide lamp was used to irradiate ultraviolet rays with a cumulative light intensity of 300 mJ/cm ² to perform curing treatment to form a hard coat layer with a thickness of 20 μm, thereby producing the antiglare hard coat film of this embodiment.

(Example 2)

In this example, except that the addition amount of PMMA particles was changed to 15 parts, the same method as in Example 1 was used to produce an anti-glare hard-coat film.

(Example 3)

In this embodiment, 30 parts of PMMA particles (refractive index: 1.49) with an average particle diameter of 15 μm are added, and the solid content concentration is changed to 35%. Glare hard coat film.

(Example 4)

In the present embodiment, 30 parts of PMMA particles (refractive index: 1.49) with an average particle diameter of 8 μm are added, and the film thickness of the hard coat layer is changed to 16 μm. In addition, the same method as in Example 1 is adopted, Production of anti-glare hard-coated films.

(Example 5)

In this example, an antiglare hard-coat film was produced in the same manner as in Example 1 except that the thickness of the hard coat layer was changed to 16 μm.

(Example 6)

In this example, except changing the thickness of the hard coat layer to 29 μm, an antiglare hard coat film was produced in the same manner as in Example 1.

(Example 7)

In the present embodiment, 30 parts of PMMA particles (refractive index: 1.49) with an average particle diameter of 15 μm are added, and the film thickness of the hard coat layer is changed to 23 μm. In addition, the same method as in Example 1 is adopted, Production of anti-glare hard-coated films.

(Embodiment 8)

In this example, an anti-glare hard-coat film was produced in the same manner as in Example 1 except that an antireflection layer was provided on the hard coat layer.

In addition, the antireflection formation employs the method shown below. That is, first, as a material for forming the antireflection layer, a siloxane oligomer (Collcoat N103 (manufactured by Colcoat Co., Ltd., solid content 2% by weight)), and measure its number average molecular weight. As a result, the number average molecular weight was 950. In addition, Opster-JTA105 (trade name, manufactured by JSR Co., Ltd., solid content 5% by weight) was prepared as a fluorine compound having a polystyrene-equivalent number average molecular weight of 5,000 or more and having a fluoroalkyl structure and a polysiloxane structure. Compound, when the number average molecular weight of this fluorine compound was measured, the number average molecular weight in terms of polystyrene was 8,000. In addition, as a curing agent, JTA105A (manufactured by JSR Corporation, 5% by weight of solid content) was used.

Next, 100 parts by weight of Opster JTA105, 1 part by weight of JTA105A, 590 parts by weight of Coulcoat N103, and 151.5 parts by weight of butyl acetate were mixed to prepare an antireflection layer forming material. This antireflection layer forming material is coated on the hard coat layer using a die coater, and the width is the same as that of the hard coat layer, and it is dried and cured by heating at 120° C. for 3 minutes to form an antireflection layer (low refraction layer). Index layer, thickness 0.1μm, refractive index 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 by the method shown below. That is, in a mixed solvent (IPA/MIBK/プチセロ/toluene (80/9/10.5/0.5)), disperse 100 parts of dipentaerythritol-based acrylate, silicone-based methacryloxypropyl and butyl groups 15 parts of polymer, 2.5 parts of hexanediol acrylate, 6 parts of lucerin type photopolymerization initiator, and hollow and spherical silicon oxide ultrafine particles with a diameter of 60 nm that have been surface-treated with a silane coupling agent having an acrylic group and have been hydrophobized , the solid content was adjusted to 3%, and the antireflection layer forming material was obtained. Using this antireflection layer forming material, an antireflection layer was formed on the hard coat layer in the same manner as in Example 7.

(Example 10)

First, in the same manner as in Example 1, the antiglare hard-coat film of this example was produced. Next, on the surface to be hard-coated (the surface opposite to the surface on which the hard-coat layer was formed) of the triacetyl cellulose film, the coating liquid described later was applied using a wire bar so that the wet thickness was 20 μm, and the The drying process was performed at 80° C. for 1 minute. In addition, as the coating liquid, a mixed solvent of acetone: ethyl acetate: IPA (isopropanol) = 37:58:5 was used.

(Example 11)

First, in the same manner as in Example 1, the antiglare hard-coat film of this example was produced. Next, on the surface to be hard-coated (the surface opposite to the surface on which the hard-coat layer was formed) of the triacetyl cellulose film, the coating liquid described later was applied using a wire bar so that the wet thickness was 20 μm, and the The drying process was performed at 80° C. for 1 minute. In addition, as the above coating liquid, a liquid in which diacetyl cellulose was blended in a mixed solvent of acetone: ethyl acetate: IPA (isopropanol) = 37: 58: 5 to have a solid content concentration of 0.5% was used.

(Example 12)

In this example, a solvent with a mixing ratio of butyl acetate and ethyl acetate of 79:21 (the ratio of ethyl acetate to the total solvent is 21%) was used as a mixed solvent, and this solvent was used to dilute and make it solid The component concentration was 63%, and a hard coat forming material was prepared, and the hard coat forming material was used to form a hard coat layer. A hard coat film was produced in the same manner as in Example 1 except that.

(Example 13)

In this example, a solvent having a mixing ratio of butyl acetate and MIBK (methyl isobutyl ketone) of 55:45 (the ratio of ethyl acetate to the total solvent was 45%) was used as a mixed solvent. , as in Example 10, an anti-glare anti-reflection hard-coated film was produced.

(Example 14)

In this example, a solvent whose mixing ratio of butyl acetate and butanol is 55:45 (the ratio of ethyl acetate to the total solvent is 45%) is used as a mixed solvent, except that it is the same as in Example 10. , Production of anti-glare anti-reflection hard-coated film.

(Example 15)

In this example, except that no reactive leveling agent was used, the same method as in Example 1 was used to prepare an anti-glare hard-coated film.

(comparative example 1)

Dilute 15 parts of polystyrene particles (refractive index: 1.59) with an average particle diameter of 3.5 μm, and a leveling agent (trade name: Megafat) with a mixed solvent of butyl acetate and toluene (butyl acetate: toluene = 13:87). F470N, 0.5 parts of Dainippon Ink Chemical Industry Co., Ltd.), 2.5 parts of synthetic montmorillonite, 5 parts of a polymerization initiator (trade name: Irgacure 907) so that the solid content concentration is 35%, and the formation of the hard coat layer is prepared Material.

Using a triacetyl cellulose film (refractive index: 1.48) with a thickness of 80 μm as a film substrate, the above-mentioned hard coat forming material is coated on the above-mentioned film using a bar coater to form a coating film, and the coating film is heated at 100°C 1 minute to allow it to dry. Subsequently, the coating film was irradiated with ultraviolet rays with a cumulative light intensity of 300 mJ/cm ² with a metal halide lamp, and cured to form a hard coat layer with a thickness of 5 μm, thereby producing an antiglare coating film of this comparative example.

(comparative example 2)

In this comparative example, the antiglare hard-coat film of this comparative example was obtained by the same method as Example 1 except having changed the addition amount of PMMA particle to 3 parts.

(comparative example 3)

In this comparative example, the antiglare hard-coat film of this comparative example was obtained by the same method as Example 1 except having changed the addition amount of PMMA particle to 70 parts.

(comparative example 4)

In this comparative example, PMMA particles (refractive index: 1.49) with an average particle diameter of 3 μm were used as fine particles, and the addition amount was changed to 30 parts. In addition, the same method as Comparative Example 1 was used to obtain this The anti-glare hard-coat film of a comparative example.

(thickness of hard coat)

The measurement was performed using a micrometer-type thickness gauge manufactured by Mitsutoyo Co., Ltd. The thickness of the hard-coat film provided with the hard-coat layer on the transparent film substrate was measured, and the film thickness of the hard-coat layer was calculated by subtracting the thickness of the substrate, and the result is shown in Table 1.

(thickness of anti-reflection layer)

It was calculated from the waveform of the interference spectrum using the instantaneous multi-side photosystem MCPD2000 (trade name) manufactured by Otsuka Electronics Co., Ltd.

In addition, the following evaluations were performed on the obtained hard-coated antiglare film (including hard-coated antiglare film). The results are shown in Table 1.

(turbidity)

Based on the turbidity (haze) of JIS-K7136 (1981 edition), it measured using the haze meter HR300 (manufactured by Murakami Color Technology Laboratory). The results are shown in Table 1.

(Gloss)

Regarding the glossiness, the measurement angle was set at 60°, and the measurement was performed using Suga Testing Instrument Co., Ltd. (digital variable angle gloss meter UGV-5DP) based on JIS K7105-1981.

(pencil hardness)

The surface of the anti-glare hard-coat film on which the hard-coat is not formed is placed on a glass plate, and the surface of the hard-coat (or anti-reflective layer) is implemented in accordance with the pencil hardness test described in JIS K-5400 (wherein, the load is 500g). test. The results are shown in Table 1.

(scratch resistance)

The value of the scratch resistance of the hard-coated anti-glare film or the hard-coated anti-reflection film was determined by the following test contents.

(1) Cut the sample into a size of at least 25 mm in width and 100 mm in length or more, and place it on a glass plate. The initial turbidity value is then determined.

(2) On the smooth section of a cylinder with a diameter of 25mm, evenly install it on steel wool #0000, reciprocate 30 times on the surface of the sample with a load of 1.5kg and a speed of about 100mm per second, and judge by visual evaluation of the following indicators .

○: No damage.

△: Slight scratches are present, but visibility is not affected.

×: There is obvious damage, and the visibility is impaired.

(Centerline average surface roughness Ra and average inclination angle θa)

A glass plate (thickness 1.3 mm) made by MATSUNAMI was bonded to the surface of the anti-glare hard-coat film on which the hard-coat layer was not formed using an adhesive. Measurement was performed using a high-precision micro-shape measuring instrument (trade name: Surfkoda ET4000, manufactured by Kosaka Laboratories Co., Ltd.), and the Ra value and 0a value described in JISB0601-1994 were obtained.

(adhesion)

Adhesion of the hard coat layer to the film substrate was evaluated by performing a square peel test described in JIS K5400. That is, the peeling test was performed 100 times, the number of peeling of the hard coat layer from the film base material was counted, and Table 1 is shown in the number of peeling/100.

(Reflectivity)

Measured for a film in which a black acrylic plate (thickness 2.0mm) manufactured by Mitsubishi Rayon (thickness 2.0mm) is bonded to the non-hard-coated surface of an anti-glare hard-coat film using an adhesive with a thickness of about 20 μm, and the reflection on the bonded back side is eliminated. The reflectivity of the surface of the anti-reflection layer. The reflectance uses the UV2400PC (with 8° inclined integrating sphere) spectrophotometer manufactured by Shimadzu Corporation to measure the spectroscopic reflectance (specular reflectance + diffuse reflectance), and obtain the C light source/2° viewing angle by calculation. The total reflectance (Y value) of the field. The results are shown in Table 1.

Claims (13)

1. a hard-coated antiglare film is characterized in that,

Be the hard-coated antiglare film that the hard conating that contains particulate is arranged at least one mask of transparent membrane base material,

The thickness of described hard conating is below the above 30 μ m of 15 μ m, and the mean grain size of described particulate is more than 30% below 75% of thickness of hard conating,

The θ a according to JIS B 0601 of the concaveconvex shape that forms by described particulate is more than 0.4 ° below 1.5 °,

The formation material of described hard conating comprise with respect to total resinous principle be 15-45 weight % urethane acrylate, be polyvalent alcohol (methyl) acrylate of 70-180 weight % and be (methyl) acrylate copolymer of having of the 25-110 weight % alkyl that contains two above hydroxyls with respect to described urethane acrylate with respect to described urethane acrylate.

2. hard-coated antiglare film according to claim 1 is characterized in that,

Described polyvalent alcohol (methyl) acrylate contains pentaerythritol triacrylate and pentaerythritol tetracrylate.

3. hard-coated antiglare film according to claim 1 and 2 is characterized in that,

On described hard conating, be provided with the anti-reflection layer of one deck at least.

4. hard-coated antiglare film according to claim 3 is characterized in that,

In described anti-reflection layer, contain hollow and spherical monox ultra micron.

5. hard-coated antiglare film according to claim 1 is characterized in that,

According to the glossiness of JIS K 7105 is more than 50 below 95.

6. the manufacture method of a hard-coated antiglare film is the manufacture method that forms the hard-coated antiglare film of hard conating at least one face of transparent membrane base material, it is characterized in that, comprising:

The operation of the formation material of modulation hard conating and in this formations material interpolation have the particulate of the mean grain size below 75% more than 30% of thickness of this hard conating and the operation of modulating;

At least one face at described film substrate applies described formation material, forms the operation of coated film; With

Make described coated film be solidified to form the operation of hard conating, the thickness of described hard conating is that the above 30 μ m of the 15 μ m θ a according to JIS B 0601 following and concaveconvex shape that form by described particulate is more than 0.4 ° below 1.5 °,

The formation material of described hard conating comprise the total resinous principle with respect to hard conating be 15-45 weight % urethane acrylate, be polyvalent alcohol (methyl) acrylate of 70-180 weight % and be (methyl) acrylate copolymer of having of the 25-110 weight % alkyl that contains two above hydroxyls with respect to described urethane acrylate with respect to described urethane acrylate.

7. the manufacture method of hard-coated antiglare film according to claim 6 is characterized in that,

Use contains the material of ethyl acetate as the diluting solvent of the formation material of described hard conating.

8. the manufacture method of hard-coated antiglare film according to claim 7 is characterized in that,

The content of described ethyl acetate is more than the 20 weight % with respect to total diluting solvent.

9. an optical element is characterized in that,

The described hard-coated antiglare film of claim 1 is arranged at least one face of optical component.

10. a polaroid is characterized in that,

Possesses any described hard-coated antiglare film in the claim 1～5.

11. a polaroid is characterized in that,

At polariscopic at least one face any described hard-coated antiglare film in the claim 1～5 is set.

12. an image display device is characterized in that,

Possesses any described hard-coated antiglare film in the claim 1～5.

13. an image display device is characterized in that,

Possess described optical element of claim 9 or claim 10 or 11 described polaroids.

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