CN1790060A - Hard-coated film and method of manufacturing the same - Google Patents

Abstract

The present invention provides a kind of hard coat film, be the hard coat film that is provided with hard coat on at least one face of transparent film base material, the forming material of described hard coat comprises polyurethane acrylate, polyalcohol (methyl) Acrylates and (meth)acrylic polymers having an alkyl group containing two or more hydroxyl groups. Thereby, a hard coat film having high hardness, suppressing curling due to curing shrinkage, and excellent flexibility can be provided, and a production method of a hard coat film that suppresses a decrease in production efficiency accompanying an increase in the number of manufacturing steps can be provided.

Description

Hard coat film and manufacturing method thereof

technical field

The present invention relates to a hard coat 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 layer thickness causes cracking or peeling of the hard coat layer, curling due to cure shrinkage of the hard coat layer, and as a result, it cannot be practically used. Therefore, in recent years, the disadvantages that have occurred are the result of the realization of high hardness of the hard-coated film, that is, cracking of the hard-coated film or curling caused by curing shrinkage. As a method for solving the above-mentioned problems, the following Proposals in JP-A-9-113728, JP-A-11-300873, JP-A-2000-52472, and JP-A-7-287102.

In Japanese Unexamined Patent Publication No. 9-113728, it is disclosed that a cured coating film layer composed of a composition containing an ultraviolet curable polyol (meth)acrylate resin is formed on at least one surface of a transparent resin film. Protective film. Furthermore, it also discloses that the above-mentioned ultraviolet curable polyol (meth)acrylate resin is dipentaerythritol acrylate. According to Japanese Unexamined Patent Publication No. 9-113728, when using a cured coating layer composed of a resin mainly composed of dipentaerythritol acrylate, the pencil hardness can be made 4H or more by making the thickness 10 μm or more. In addition, it is also described that curling due to curing shrinkage can be reduced by using an epoxy resin in combination, but it is difficult to sufficiently suppress curling in the invention described in JP-A-9-113728.

In Japanese Patent Application Laid-Open No. 11-300873, it is disclosed that at least one surface of the plastic film substrate film is provided with a buffer layer composed of one or more layers with a thickness of 3 to 50 μm, and then a layer with a thickness of 3 to 50 μm is formed on the buffer layer. A hard coat film made of a 15μm hard coat layer. According to this JP-A-11-300873, the pencil hardness of the hard coat film as a whole is 4H to 8H. However, because of the two-layer structure of the buffer layer and the hard coat layer, there are problems in that the number of steps increases and the production efficiency decreases.

JP-A-2000-52472 discloses a hard coat film provided with a cured resin film layer, wherein the cured resin film layer is formed by providing internally cross-linked ultrafine particles containing inorganic or organic matter on a substrate. The resin layer serves as the first hard coat layer, and thereafter, a thin film of a transparent cured resin that does not contain internally crosslinked ultrafine particles of inorganic matter or organic matter is provided. However, since the cured resin coating layer has a two-layer structure of a first hard coat layer and a second hard coat layer, as in the invention described in the above-mentioned Japanese Patent Application Laid-Open No. 11-300873, there are problems in that the number of steps increases and the production efficiency decreases. point.

In Japanese Patent Application Laid-Open No. 7-287102, an antireflection film having at least a hard coat layer and a low refractive index layer on at least one of the front and back surfaces of a transparent base film is disclosed as a material that can be used for a hard coat layer. , solvent-drying type resins can be mentioned. When containing a polymer that does not have a reactive group, there is an effect of suppressing curing shrinkage that occurs when ionizing radiation-curable resins, etc. are effective, and suppressing the occurrence of curling, but when such a polymer is added, there is a problem of not being able to obtain sufficient The problem of surface hardness.

Contents of the invention

The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a hard coat film having excellent flexibility while suppressing occurrence of curling due to cure shrinkage. Another object of the present invention is to provide a method for producing a hard coat film that suppresses a decrease in production efficiency due to an increase in the number of production steps. Furthermore, it aims at providing the polarizing plate and image display apparatus provided with the said hard-coat film.

In order to solve the above-mentioned conventional problems, the inventors of the present invention have intensively studied a hard coat film and a method for producing the same. As a result, they have found that the above-mentioned object can be achieved by adopting the following configurations, and have completed the present invention.

That is, in order to solve the above-mentioned problems, the present invention provides a hard-coated film, which is a hard-coated film with a hard coat on at least one surface of a transparent film substrate, wherein the hard coat is formed of a material comprising polyurethane Acrylates, polyol (meth)acrylates, and (meth)acrylic polymers having an alkyl group containing two or more hydroxyl groups.

According to the above configuration, by containing urethane acrylate as a forming material of the hard coat layer, 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. Further, by containing a (meth)acrylic polymer having two or more hydroxyl groups, it is possible to obtain a hard coat layer in which curing shrinkage is moderated and generation of curling is suppressed.

In the hard coat film described above, the polyol (meth)acrylate preferably contains 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 the above-mentioned hard coat film, it is preferable that the outer surface of the above-mentioned hard coat layer has a concavo-convex shape.

According to the above configuration, the concave-convex structure on the outer surface of the hard coat layer prevents reflection of light and scatters it only in a predetermined direction, so reflection can be prevented. Thereby, light antiglare property can be imparted.

In the hard coat film described above, it is preferable that an antireflection layer is formed on the outer surface of the 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 applying the hard-coat film of the said structure to an image display apparatus etc., for example, the fall of the visibility of the image of a display screen can be suppressed.

In the hard coat film described above, the antireflection layer preferably contains: a siloxane oligomer having a number average molecular weight of 500 to 10,000 in terms of ethylene glycol, and a polystyrene-equivalent number average molecular weight of 5,000 or more. A fluorine compound having a fluoroalkyl structure and a polysiloxane structure.

Like the above-mentioned constitution, when the antireflection layer is composed of a siloxane oligomer and a fluorine compound having a fluoroalkyl structure and a polysiloxane structure, the antireflection layer is formed by the siloxane oligomer and The polysiloxane structure of the fluorine compound reacts and cures, so the scratch resistance is improved. In addition, when the number average molecular weight of the siloxane oligomer is 500 or more, the coating and storage stability of the hard coat forming material is improved, and gelation of the coating liquid can be prevented. On the other hand, when the number average molecular weight is 10,000 or less, the antireflection layer can be a layer having good scratch resistance.

In the above-mentioned hard coat film, it is preferable that hollow and spherical silicon oxide ultrafine particles are contained in the above-mentioned antireflection layer.

Moreover, in the above-mentioned hard coat film, it is preferable that the forming material of the said hard coat layer contains a leveling agent.

In addition, the production method of the hard-coat film of the present invention is to solve the above-mentioned problem, the production method of the hard-coat film that forms hard-coat film on at least one surface of transparent film substrate, wherein, comprises: at least The step of preparing the forming material of the above-mentioned hard coat layer by adding urethane acrylate, polyol (meth)acrylate, and (meth)acrylic polymer having an alkyl group containing two or more hydroxyl groups; applying the above-mentioned forming material on A step of forming a coating film on at least one surface of the film substrate; a step of curing the coating film to form a hard coat layer.

According to the method described above, by using urethane acrylate as a hard coat forming material, a hard coat excellent in elasticity and flexibility can be formed. In addition, by using polyol (meth)acrylate, for example, without having a two-layer structure, a hard coat layer having sufficient hardness and scratch resistance can be formed. As a result, it is also possible to suppress an increase in the number of manufacturing steps and prevent a reduction in production efficiency. Furthermore, by including a (meth)acrylic polymer having an alkyl group containing two or more hydroxyl groups in the forming material, the curing shrinkage that occurs when the above-mentioned coating film is cured can be alleviated, and a hard coat layer that suppresses curling can be formed. .

In the manufacturing method of the said hard-coat film, it is preferable to use the solvent containing ethyl acetate as the said dilution solvent. Thereby, a hard coat layer excellent in adhesion to a film substrate can be formed.

In the method for producing the above-mentioned hard coat film, it is preferable that the content of the above-mentioned ethyl acetate is 20% by 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 hard coat film on at least one surface of the optical member.

In addition, the image display device of the present invention includes the aforementioned hard coat film or optical element in order to solve the above-mentioned problems.

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

That is, according to the present invention, urethane acrylate, polyol (meth)acrylate, and a (meth)acrylic polymer having an alkyl group containing two or more hydroxyl groups are contained in the forming material of the hard coat layer, so elasticity and A hard-coated film with excellent flexibility, less curling or cracking than before, and high surface hardness. In addition, there is no need to make the hard coat layer into a two-layer structure in order to increase the hardness like the conventional hard coat film, so the increase in the number of manufacturing steps can be suppressed and the decrease in production efficiency can be prevented.

Description of drawings

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

FIG. 2 is a schematic cross-sectional view showing the outline of an 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 a hard coat film according to this embodiment.

As shown in FIG. 1 , the hard coat film 3 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 hard coat film 3 of this embodiment is used as a protective film for a polarizing plate, as the film substrate 1, triacetyl cellulose, polycarbonate, acrylic polymer, polyamide having a cyclic or norbornene structure are preferable. Alkenes, 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 formed by using urethane acrylate (A), polyol (meth)acrylate (B) and (meth)acrylic polymer (C) having an alkyl group containing 2 or more hydroxyl groups as forming materials. constitute.

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 little, the flexibility and adhesiveness of the obtained hard-coat layer will fall, and if too much, the hardness of the hard-coated layer after hardening will fall. For this reason, urethane acrylate (A) is preferably 15% by weight to 55% by weight, more preferably 25% by weight to 45% by weight. When the addition amount of 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 not preferable. 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 particularly 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 polyol (meth)acrylate (B) is 70 weight% - 180 weight% of urethane acrylate (A) preferably, More preferably, it is 100 weight% - 150 weight%. When the ratio of polyol (meth)acrylate (B) to urethane acrylate (A) exceeds 180% by weight, curing shrinkage of the hard coat layer increases, and as a result, curling of the hard coat film increases. It is sometimes not preferable because it is large or the flexibility is reduced. 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 to urethane acrylate (A). 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.

Inorganic fine particles or organic fine particles may be blended in the hard coat layer 2 . 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.

The shape of the fine particles is not particularly limited, and may be spherical or bead-like, or may be indeterminate such as powder. One or more of these fine particles can be appropriately selected and used. The average particle diameter of the fine particles is 1 to 30 μm, preferably 2 to 20 μm. In addition, for the purpose of controlling the refractive index and imparting conductivity, ultrafine particles of metal oxides or the like may be dispersed and impregnated in the fine particles.

The blending amount of inorganic fine particles or organic fine particles is not particularly limited, and can be appropriately set. For example, when providing an anti-glare effect, it is preferable that it is 2-60 weight part with respect to 100 weight part of hard-coat formation materials. Moreover, when providing simple antiblocking property, 1-50 weight part is suitable with respect to 100 weight part of hard-coat forming materials.

The above-mentioned inorganic fine particles or organic fine particles preferably have a particle diameter of 100 nm or less. Ultrafine particles having a particle size of 100 nm or less have a function of adjusting the apparent refractive index of the hard coat layer 2 according to the blending amount. The refractive index of the film substrate 1 and the refractive index of the hard coat layer 2 are preferably close to each other. When the difference between the refractive index of the film base material 1 and the refractive index of the hard coat layer 2 is large, the reflected light of the external light incident on the hard coat film 3 occurs a phenomenon called interference fringes showing an iridescent hue, Sometimes degrades display quality. As a fluorescent lamp in an office under an environment where a display device having a hard-coated film 3 is used, three-wavelength fluorescent lamps with strong luminous intensity of a specific wavelength characterized by being able to see clearly have increased significantly. Interference fringes appear prominently.

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 25 μm, more preferably 18 to 23 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 an alkyl group containing two or more hydroxyl groups. ), 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.

With respect to the hard coat layer 2, the outer surface can be provided with a fine uneven structure to impart anti-glare properties. There is no particular limitation on the method of forming the fine uneven structure on the surface, and an appropriate method can be used. For example, a method of dispersing fine particles in the hard coat layer 2 to provide a fine uneven structure, etc. may be mentioned.

When the outer surface of the hard coat layer 2 is concavo-convex to provide anti-glare properties, the thickness thereof is preferably 15 to 35 μm, more preferably 20 to 30 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 35 μm, and when the hard coat layer 2 contains fine particles that do not undergo cure shrinkage, curling and cracking can be sufficiently prevented from occurring. In addition, when the thickness is less than 15 μm, the hardness of the hard coat layer 2 may decrease. On the other hand, when the thickness exceeds 35 μm, the hard coat layer itself cracks, and the hard coat film 2 curls on the hard coat side due to curing shrinkage of the hard coat layer 2, which may cause practical problems. In addition, the thickness of the hard-coat layer 2 when the outer surface has a concavo-convex shape means the maximum thickness including the portion up to the convex shape.

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.

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, the film substrate 1 is coated with at least urethane acrylate (A), polyol (meth)acrylate (B) and (methyl) having an alkyl group containing two or more hydroxyl groups. ) A hard coat forming material of the acrylic polymer (C), which is subsequently cured. 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 anti-reflection layer 4 may be provided on the above-mentioned hard coat layer 2 to form an anti-reflection hard coat film 5 . FIG. 2 is a schematic cross-sectional view showing the antireflection hard coat film 5 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 4 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 4 may be provided on both surfaces of film substrate 1 . In addition, in FIG. 2 , the case where each of the hard coat layer 2 and the antireflection layer 4 are provided is illustrated, but as long as the hard coat layer of the present invention is provided, the antireflection layer 4 may be two or more layers.

As the antireflection layer 4 , 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 is 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 4 based on the interference effect of light, there is a method of increasing the difference in refractive index between the antireflection layer 4 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 4 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 4 is designed as a single layer, it is necessary to increase the difference in refractive index between the antireflection layer 4 and the hard coat layer 2 in order to maximize the antireflection function. When the film thickness of the above-mentioned antireflection layer 4 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 4 and its refractive index is nd=λ/ 4 relational formula. When the antireflection layer 4 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 4 is 1.45, the film thickness of the antireflection layer 4 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 4 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 between 86 nm and 105 nm. within the range, it can be used without problems. Therefore, generally, when forming the single-layer antireflection layer 4 , 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 4 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 above-mentioned materials for forming the antireflection layer 4, 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 4, maintaining porosity or voids can lower the refractive index of the antireflection layer 4, 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, and can be selected from resins suitable for conditions such as adhesion to the substrate, hardness, and coatability. For example, Conventionally used polyester resins, acrylic resins, urethane resins, vinyl chloride resins, epoxy resins, melamine resins, fluororesins, silicone resins, butyral resins, phenolic resins, vinyl acetate resins, and UV-curable 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. In addition, as a material for forming the antireflection layer 4 in a single layer 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 weight ratio exceeds 9:1, the strength of the antireflection layer 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 4 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 antireflection hard coat film in which the antireflection layer 4 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 4 is provided, unevenness becomes smooth, and generally, a hard coat layer having a pencil hardness of about 3H 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 low refractive index layer is not particularly limited, and is usually 60 to 150° C., preferably 70 to 130° C., usually for 1 minute to 30 minutes, and in consideration of productivity, it is more preferably 1 minute. ~10 minutes or so. 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 is usually 40 to 130°C, preferably 50 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 4 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 4 in order to impart the above-mentioned functions related to the antiadhesive 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 4. 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 hard-coated film 3 and anti-reflection hard-coated film 5 can usually be bonded on the film base 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 hard coat film or antireflection hard coat film of the present invention is laminated. The hard coat film 3 or antireflection hard coat film 5 of the present invention can be laminated with a polarizer or a polarizer using an adhesive or an adhesive to obtain a polarizer having the function of the present invention.

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 "A-ton" 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). A protective film with a retardation value of -90nm to +75nm. By using a protective film having a retardation value (Rth) in the thickness direction of -90 nm to +75 nm, the coloring (optical coloring) of the polarizing plate caused by the protective film can be almost eliminated. 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.

In the polarizing plate laminated with a hard coat film or the like, a transparent protective film, a polarizer, and a transparent protective film may be sequentially laminated on a hard coat film or the like, or a polarizer and a transparent protective film may be sequentially laminated on a hard coat film or the like.

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 according to the purpose of use, the adhesive force, etc., and is generally 1 to 500 μm, preferably 5 to 200 μm, 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.

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 electroluminescence 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 take out the light generated in the organic light-emitting layer. Usually, a transparent electrode made of a transparent conductor such as indium tin oxide (ITO) is 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)

Dilute the following composition with a mixed solvent having a mixing ratio of butyl acetate and ethyl acetate of 46:54 (the ratio of ethyl acetate to the total solvent is 54%) so that the solid content concentration is 50%. Prepare a hard coat forming material, wherein the diluted substance includes: 100 parts of urethane acrylate composed of pentaerythritol-based acrylate and hydrogenated xylene diisocyanate as urethane acrylate (hereinafter, component A), and 100 parts of urethane acrylate as polyol 49 parts of dipentaerythritol hexaacrylate (hereinafter, B1 component (monomer)) of (meth)acrylate (hereinafter, B component), 41 parts of pentaerythritol tetraacrylate (hereinafter, B4 component (monomer)), and triacrylic acid 24 parts of pentaerythritol ester (hereinafter, B5 component (monomer)), as a (meth)acrylic polymer (hereinafter, C component) having an alkyl group containing two or more hydroxyl groups (hereinafter, C component) having 2-hydroxyethyl and 2,3 - 59 parts of dihydroxypropyl (meth)acrylic acid polymer (manufactured by Dainippon Inki Chemical Industry Co., Ltd., trade name: PC1070), 3 parts of polymerization initiator (Ingaquiure 184) relative to the total resin component, reactive leveling 0.5 parts of the agent. 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 hard coat film of this example.

(Example 2)

In this example, except changing the thickness of the hard-coat layer to 15 micrometers, the same method as Example 1 was carried out, and the hard-coat film was produced.

(Example 3)

In this example, except changing the thickness of the hard-coat layer to 25 micrometers, the same method as Example 1 was carried out, and the hard-coat film was produced.

(Example 4)

In this example, the same method as in Example 1 was adopted except that the compounding amount of the (meth)hard acrylic polymer having 2-hydroxyethyl and 2,3-dihydroxypropyl was changed to 96 parts , making a hard coat film.

(Example 5)

In this example, the same method as in Example 1 was adopted except that the compounding amount of the (meth)hard acrylic polymer having 2-hydroxyethyl and 2,3-dihydroxypropyl was changed to 36 parts , making a hard coat film.

(Example 6)

In this example, except that 30 parts of cross-linked acrylic particles (trade name: MX1000, manufactured by Soken Chemical Co., Ltd.) with an average particle diameter of 10 μm were added to the hard coat forming material, the same method as in Example 1 was adopted. , making a hard coat film.

(Example 7)

In this example, except that an antireflection layer was provided on the hard coat layer of the hard coat film obtained in Example 1, the same method as in Example 1 was used to produce an antireflection hard coat film.

In addition, the antireflection forming material was prepared by the method shown below. That is, first, as a material for forming the antireflection layer, Colcoat N103 (manufactured by Colcoat Co., Ltd., solid content 2% by weight) was prepared in advance as silicon with an average molecular weight of 500 to 10,000 in terms of ethylene glycol. Oxyalkylene oligomers, the number average molecular weight of which is measured. 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)

(Embodiment 8)

In this example, except that an antireflection layer (thickness: 95 nm) formed of an antireflection forming material as described below was provided, an antireflection hard coat film was produced in the same manner as in Example 7.

That is, in a mixed solvent of isopropanol/butyl acetate/methyl isobutyl ketone (54/14/32 (weight ratio)), disperse 54 parts of tetraalkoxysilane, and have fluoroalkyl structure and poly 23 parts of silane coupling agents with a siloxane structure, 23 parts of hollow and spherical silicon oxide ultrafine particles with a diameter of 60 nm that are surface-treated and hydrophobized by a silane coupling agent with an alkyl group, and the solid content is adjusted to 2.0%. reflective layer forming material.

Using this antireflection layer forming material, an antireflection layer was formed on the hard coat layer by the same method and conditions as in Example 7, thereby producing the antireflection hard coat film of this example.

(Example 9)

In this example, a 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 30 μm.

(Example 10)

In this example, a 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 10 μm.

(Example 11)

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 12)

First, the hard coat film of this example was produced in the same manner as in Example 1. 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 13)

In this example, a mixed solvent of acetone: ethyl acetate: IPA = 37:58:5 was used as the coating solution on the surface to be hard-coated of the triacetyl cellulose film. In the same manner as in Example 12, a hard coat film was produced.

(Example 14)

In this example, the hard coating film was prepared by the same method as in Example 1 except that reactive silicone as a reactive leveling agent was not added.

(Example 15)

In this example, a solvent with a mixing ratio of butyl acetate and MIBK (methyl isobutyl ketone) of 46:54 (MIBK ratio of 54% relative to the total solvent) was used as a mixed solvent, and the solid content was further mixed with this solvent. The concentration was diluted to 63% to prepare a hard coat forming material, and a hard coat film was produced in the same manner as in Example 1 except that the hard coat forming material was used to form a hard coat layer.

(Example 16)

In this example, a solvent with a mixing ratio of butyl acetate and butanol of 46:54 (the ratio of butanol to the total solvent is 54%) was used as a mixed solvent, and the solid content concentration was further diluted to 63% using this solvent. A hard coat film was prepared in the same manner as in Example 1 except that a hard coat forming material was prepared and a hard coat layer was formed using the hard coat forming material.

(Example 17)

In this example, 100 parts of urethane acrylate composed of pentaerythritol-based acrylate and isophorone diisocyanate (hereinafter, A1 component) as component A, 59 parts of B1 component and 37 parts of B4 component as B component were used. And 15 parts of B5 component, 26 parts of (meth)acrylic polymer having 2-hydroxyethyl group and 2,3-dihydroxypropyl group as C component, 2 parts of polymerization initiator (Irgacure 184) with respect to the total resin component , except that, the same method as in Example 1 was used to produce a hard coat film.

(Example 18)

In this example, 100 parts of the A1 component as the A component, 38 parts of the B1 component, 40 parts of the B4 component and 16 parts of the B5 component as the B component, and 2-hydroxyethyl and 2,3- 30 parts of dihydroxypropyl (meth)acrylic acid polymer, with respect to the total resin component polymerization initiator (with 2 parts of Irgacure 184 and 2,4,6-trimethylbenzoinphenylphosphine oxide 2.5 Parts) 3.5 parts, except that, the same method as in Example 1 was used to prepare a hard coat film.

(Example 19)

In this example, a hard coat film was produced in the same manner as in Example 6 except that the thickness of the hard coat layer was changed to 29 μm.

(comparative example 1)

In this comparative example, components A and C were not compounded, and 100 parts of dipentaerythritol hexaacrylate was compounded as component B, and 9 parts of butylene glycol acrylate (hereinafter, component B3) were compounded. The same method as in Example 1 was used to make a hard coat film.

(comparative example 2)

In this comparative example, 22 parts of the B4 component and 5 parts of the B5 component were used as the B component. Moreover, except having used 133 parts of polymethacrylate polymers instead of C component, the method similar to Example 1 was carried out, and the hard coat film was produced.

(comparative example 3)

In this comparative example, a mixture of 22 parts of the B4 component and 5 parts of the B5 component was used as the B component. Moreover, except having used 55 parts of polymethacrylate polymers instead of C component, the method similar to Example 1 was carried out, and the hard coat film was produced.

(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 coat film (including the antireflection hard coat film). The results are shown in Table 1.

(Reflectivity)

Measurement of the hard coat layer in which a black acrylic plate (thickness 2.0mm) manufactured by Mitsubishi Rayon (thickness 2.0 mm) is bonded to the surface of the hard coat film with an adhesive with a thickness of about 20 μm and the reflection on the bonded back side is eliminated. (or anti-reflection layer) surface reflectivity. 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.

(pencil hardness)

On the surface of the glass plate on which the hard coat film or anti-reflection hard coat film is not formed, the hard coat (or anti-reflection layer) surface shall be tested according to the pencil hardness test described in JIS K-5400 (wherein, the load 500g) to implement the test. The results are shown in Table 1.

(crimping)

Cut the hard-coated film into a 10cm square, place it on a glass plate with the hard-coated layer (or anti-reflection layer) facing upwards, measure the lifting length (mm) from the four corners of the glass plate, and use the average value as the curling evaluation indicators. In addition, the rounded thin film was set as "not measurable". Also, the results are shown in Table 1.

(flexibility)

The hard-coated film or hard-coated anti-reflective film was wound so that the film base was in direct contact with metal rolls of different diameters, and the presence or absence of cracks in the hard-coated layer (or anti-reflective layer) was visually judged. The diameter at which cracks did not appear was measured as a value of buckling property. The results are shown in Table 1.

(turbidity)

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

(scratch resistance)

The value of the scratch resistance of the hard-coated film or anti-reflection hard-coated 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 a smooth section of a cylinder with a diameter of 25mm, evenly install it on steel wool #0000, reciprocate 100 times on the surface of the sample with a load of 1.5kg and a speed of about 100mm per second, and then calculate the turbidity after the test .

(3) The value obtained by subtracting the initial haze value from the haze value after the test was used as an index of scratch resistance. In this evaluation, the larger the index value of scratch resistance, the higher the haze value after the test due to the scratches generated on the surface of the hard coat or antireflection layer in the steel wool test, which is compared with the initial stage. The value of the index of the poor scratch resistance of the haze value also increased.

(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.

Table 1 Refractive index of film substrate Hardcoat Refractive Index Film thickness (μm) Reflectivity(%) pencil hardness Curling(mm) Flexibility (mmΦ) Turbidity Adhesion Scratch resistance Example 1 1.48 1.51 20 4 4H twenty two 9.5 - 0/100 0.2 Example 2 1.48 1.51 15 4 4H 15 9.5 - 0/100 0.2 Example 3 1.48 1.51 25 4 4H 30 11 - 0/100 0.2 Example 4 1.48 1.51 20 4 4H 10 8 - 0/100 0.4 Example 5 1.48 1.51 20 4 5H 29 14 - 0/100 0.2 Example 6 1.48 1.51 20 4 4H 20 9.5 60 0/100 0.2 Example 7 1.48 1.51 20 2.5 4H 10 9.5 - 0/100 0.3 Example 8 1.48 1.51 20 1.6 4H 10 9.5 - 0/100 0.3 Example 9 1.48 1.51 30 4 5H 36 12.5 - 0/100 0.2 Example 10 1.48 1.51 10 4 3H 10 8 - 0/100 0.4 Example 11 1.48 1.51 20 4 4H twenty four 9.5 - 10/100 0.2 Example 12 1.48 1.51 20 4 4H 0 9.5 - 0/100 0.2 Example 13 1.48 1.51 20 4 4H 0 9.5 - 0/100 0.2 Example 14 1.48 1.51 20 4 4H twenty two 9.5 - 0/100 0.5 Example 15 1.48 1.51 20 4 4H twenty one 9.5 - 75/100 0.2 Example 16 1.48 1.51 20 4 4H twenty three 9.5 - 100/100 0.2 Example 17 1.48 1.53 20 4 4H 29 14 - 0/100 0 Example 18 1.48 1.53 20 4 4H 27 14 - 0/100 0 Example 19 1.48 1.51 29 4 5H 28 12.5 63 0/100 0.2 Comparative example 1 1.48 1.51 20 4 5H Above critical value 15.5 - 10/100 1.8 Comparative example 2 1.48 1.51 20 4 3H 0 11 - 0/100 1.4 Comparative example 3 1.48 1.51 20 4 3H 20 12.5 - 0/100 0.8

Table 2 A component (parts by weight) B component C component (weight part) Other added resins Compounding amount of microparticles (parts by weight) Compounding amount of polymerization initiator (parts by weight) Presence of anti-reflection layer Element Compounding amount (parts by weight) resin composition Compounding amount (parts by weight) Example 1 100 B1 ingredient/B4 ingredient/B5 ingredient 49/41/24 59 - - - 3 none Example 2 100 B1 ingredient/B2 ingredient 49/65 59 - - - 3 none Example 3 100 B1 ingredient/B2 ingredient 49/65 59 - - - 3 none Example 4 100 B1 ingredient/B2 ingredient 49/65 96 - - - 3 none Example 5 100 B1 ingredient/B2 ingredient 49/65 36 - - - 3 none Example 6 100 B1 ingredient/B2 ingredient 49/65 59 - - 30 3 none Example 7 100 B1 ingredient/B2 ingredient 49/65 59 - - - 3 have Example 8 100 B1 ingredient/B2 ingredient 49/65 59 - - - 3 have Example 9 100 B1 ingredient/B2 ingredient 49/65 59 - - - 3 none Example 10 100 B1 ingredient/B2 ingredient 49/65 59 - - - 3 none Example 11 100 B1 ingredient/B2 ingredient 49/65 59 - - - 3 none implement 100 B1 ingredient/B2 ingredient 49/65 59 - - - 3 none Example 12 Example 13 100 B1 ingredient/B2 ingredient 49/65 59 - - - 3 none Example 14 100 B1 ingredient/B2 ingredient 49/65 59 - - - 3 none Example 15 100 B1 ingredient/B2 ingredient 49/65 59 - - - 3 none Example 16 100 B1 ingredient/B2 ingredient 49/65 59 - - - 3 none Example 17 100 B1 ingredient/B4 ingredient/B5 ingredient 59/37/15 26 - - - 2 none Example 18 100 B1 ingredient/B4 ingredient/B5 ingredient 38/40/16 30 - - - 3.5 none Example 19 100 B1 ingredient/B2 ingredient 49/65 59 - - 30 3 none Comparative example 1 - B1 ingredient/B3 ingredient 100/9 - Butylene glycol acrylate 9 - 3 none Comparative example 2 100 B4 ingredient/B5 ingredient 22/5 - polymethacrylate methacrylate polymer 133 - 3 none Comparative example 3 100 B4 ingredient/B5 ingredient 22/5 - polymethacrylate methacrylate polymer 55 - 3 none

According to the above description, according to the present invention, a material containing urethane acrylate, polyol (meth)acrylate, and a (meth)acrylic polymer having an alkyl group containing two or more hydroxyl groups is used as a material for forming a hard coat layer. , so generally even in the case of forming a hard coat layer on a flexible film substrate, a hard coat film having high hardness and no curling or cracking and a method for producing the same can be provided. Furthermore, the hard-coated film of the present invention can be applied to optical elements such as polarizing films, and LCDs equipped with the polarizing film have sufficient hardness and scratch resistance even when used as household TV sets, so they are suitable use.

Claims (13)

1. a hard-coated film is the hard-coated film that is provided with hard conating at least one face of transparent membrane base material, it is characterized in that,

The formation material of described hard conating comprises urethane acrylate, polyvalent alcohol (methyl) acrylate and has (methyl) acrylate copolymer of the alkyl that contains two above hydroxyls.

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

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

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

The outside surface of described hard conating becomes concaveconvex shape.

4. according to any one described hard-coated film of claim 1～3, it is characterized in that,

On the outside surface of described hard conating, be formed with anti-reflection layer.

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

Described anti-reflection layer contains:

The number-average molecular weight that converts by ethylene glycol be 500～10000 siloxane oligomer and

Number-average molecular weight by polystyrene conversion is fluorine compounds more than 5000, that have fluoro-alkyl structure and polysiloxane structure.

6. according to claim 4 or 5 described hard-coated films, it is characterized in that,

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

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

The formation material of described hard conating contains levelling agent.

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

In diluting solvent, add urethane acrylate, polyvalent alcohol (methyl) acrylate at least and have (methyl) acrylate copolymer of the alkyl that contains two above hydroxyls, the operation of modulating the formation material of described hard conating;

The described formation material of coating at least one face of film substrate and form the operation of coated film; With

Make described coated film solidify and then form the operation of hard conating.

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

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

10. the manufacture method of hard-coated film according to claim 9 is characterized in that,

The content of described ethyl acetate is more than the 20 weight %.

11. an optical element is characterized in that,

Each described hard-coated film of claim 1～7 is arranged at least one face of optical component.

12. an image display device is characterized in that,

Possesses the described hard-coated film of claim 1.

13. an image display device is characterized in that,

Possesses the described optical element of claim 11.