KR20090004733A - Hard coat film and method of manufacturing the same - Google Patents

Abstract

A hard-coating film and a manufacturing method thereof are provided to obtain intended optical diffusion by forming phase-separated structure with hardening material and thermoplastic resin of active energy ray hardening compound. A hard-coating layer is formed on a base film. The hard-coating layer comprises hardening material and thermoplastic resin of active energy ray hardening compound. The mass rate between the hardening material and the thermoplastic resin of active energy ray hardening compound is the rate of 100:0.3 - 100:50. The hardening material and the thermoplastic resin of active energy ray hardening compound form phase-separated structure. The inside haze value of the hardening material and the thermoplastic resin of active energy ray hardening compound is 3~80%. The surface irregularity by the phase separation is formed in the hard-coating layer. The hard-coating layer comprises a transparency inorganic particle. A part of the transparency inorganic particle is exposed on the surface of the hard-coating layer.

Description

Hard coating film and manufacturing method thereof {HARD COAT FILM AND METHOD OF MANUFACTURING THE SAME}

The present invention relates to a hard coat film and a method of manufacturing the same. More specifically, the present invention provides a high-definition type image display device having a phase-separated structure, a hard coating layer having an internal haze value in a specific range, and having a color filter such as a liquid crystal display device. The present invention relates to a hard coat film which is very suitable as an anti-glare film.

In displays such as CRTs, LCDs, and PDPs, light may be incident on the screen from outside, and the light may be reflected to make the display image difficult to see. It is becoming an increasingly important task. As one of means for solving these problems, an anti-glare (AG) hard coating film is affixed on the display surface. For the method of imparting anti-glare property to the hard coating film, (1) hard coating layer (2) Method of incorporating filler into hard coating agent for hard coating layer formation, (3) Hard coating agent for hard coating layer formation. Two kinds of non-phase two components can be mixed and they can be broadly classified into three types of methods using phase separation. All of these suppress the regular reflection of external light by forming fine unevenness on the surface, and prevent the imaging of external light such as a fluorescent lamp. However, when the anti-glare film produced by the above method is used for a high-precision type LCD which has become mainstream in recent years, the image light is scattered in the place where the convex portion of the surface irregularities and the black matrix of the color filter overlap. The so-called glare phenomenon that the part shines dazzlingly is expressed. In order to solve this problem, in the high-precision LCD AG film, forming one layer which has internal light diffusivity for providing an anti-glare effect is examined. For example, Patent Document 1, Patent Document 2, and the like describe an antiglare film in which two layers of a light diffusion layer and an antiglare layer are formed on a base film. In Patent Document 3, an antiglare layer is provided on one side of the film. It forms and forms the light-diffusion layer in the other surface. These methods required two layers of light diffusing performance and antiglare layer to prevent glare. Moreover, in patent document 4, patent document 5, etc., the anti-glare film which has light diffusivity and anti-glare simultaneously is proposed by containing translucent microparticles | fine-particles with different refractive index in one layer. In any method, light diffusivity is achieved by using fine particles, and it is necessary to consider problems such as aggregation and sedimentation of fine particles in the coating agent.

[Patent Document 1]

Japanese Patent Application Laid-Open No. 2001-305314

[Patent Document 2]

JP 2003-302506 A

[Patent Document 3]

Japanese Patent Application Laid-Open No. 2004-271666

[Patent Document 4]

Japanese Patent No. 3507719

[Patent Document 5]

Japanese Patent No.3515401

Under the circumstances, the present invention achieves light diffusivity inside the hard coat layer by other means, rather than microparticles having problems of aggregation and sedimentation, which have been conventionally used, and particularly includes a color filter such as a liquid crystal display device. An object of the present invention is to provide a hard coating film having an antiglare function capable of effectively suppressing glare of a high-precision type image display device.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to achieve the said objective, the present inventors formed the hard-coating layer which contains the active energy ray hardening-type compound and a thermoplastic resin in a specific ratio, and contains the solvent mixture which has a specific property. By forming a coating film layer on a base film using a material, and irradiating and hardening an active energy ray to this, the hardened | cured material and thermoplastic resin of the said active energy ray hardening-type compound form a phase-separated structure, and It has been found that a hard coat layer having light diffusivity is formed and can achieve its purpose. This invention is completed based on this knowledge.

That is, the present invention,

[1] A hard coating layer containing a cured product of the (A) active energy ray-curable compound and (B) a thermoplastic resin in a mass ratio of 100: 0.3 to 100: 50 on the base film, wherein the hard coating layer , The (A) component and the (B) component forms a phase separation structure, and the hard coat film, characterized in that the internal haze value is 3 to 80%,

[2] the hard coat film according to the above [1], wherein the hard coat layer forms surface irregularities by phase separation;

[3] The hard coat film according to the above [1] or [2], wherein the hard coat layer further contains (E) transparent inorganic fine particles, and a part thereof is exposed to the surface to form irregularities.

[4] The hard coat film according to any one of the above [1] to [3], wherein the unevenness is physically formed on the surface of the hard coating layer by an external force;

[5] The hard coat film according to any one of the above [1] to [4], wherein the arithmetic mean roughness Ra measured according to JIS B O601-1994 on the surface of the hard coat layer is 0.015 to 0.3 μm,

[6] The hard coat film according to any one of the above [1] to [5], wherein an antiglare layer having surface irregularities is laminated on the surface of the hard coat layer;

[7] the hard coat film according to any one of [1] to [6], which is used in an image display device having a color filter, and

[8] A method of manufacturing a hard coat film by forming a coat layer using a hard coat layer forming material on a base film, then irradiating active energy rays to the coat layer to form a hard coat layer.

The hard coat layer forming material contains (A ') an active energy ray-curable compound and (B) a thermoplastic resin at a mass ratio of 100: 0.3 to 100: 50, and (C) the (A') component and ( [2] The above-mentioned [1], characterized by containing a positive solvent for component B) and (D) a poor solvent for component (B) in a mass ratio of 99: 1 to 10:90. It is to provide a method for producing a hard coat film described in.

According to the present invention, the cured product of the active energy ray-curable compound and the thermoplastic resin form a phase-separated structure, impart desired light diffusivity, and preferably have a hard coating layer having irregularities formed on the surface thereof, especially a liquid crystal display device or the like. It is possible to provide a hard coating film having an anti-glare function that can effectively suppress glare of a high-precision type image display device having a color filter.

In addition, according to the method of the present invention, it is possible to efficiently produce a hard coat film having an anti-glare function that can effectively suppress the glare.

The hard coat film of this invention has the hard coat layer which contained the hardened | cured material of (A) active energy ray hardening-type compound, and (B) thermoplastic resin in the ratio of mass ratio 100: 0.3-100: 50 on a base film, The said hard coat layer WHEREIN: The said (A) component and (B) component form the phase-separation structure, and internal haze value is 3 to 80%, It is characterized by the above-mentioned.

[Base film]

There is no restriction | limiting in particular about this base film, It can select suitably from a plastic film known as a base material of the conventional hard coating film for optics, and can use. Examples of such plastic films include polyester films such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, polyethylene films, polypropylene films, cellophane, diacetyl cellulose films, triacetyl cellulose films, and acetyl cellulose. Butylate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyether ether ketone film, Polyether sulfone film, polyetherimide film, polyimide film, fluororesin film, polyamide film, acrylic resin film, norbornene-based resin film, cycloolefin resin film and the like.

These base films may be either transparent or semitransparent, may be colored, or may be non-colored, and may be appropriately selected depending on the intended use. For example, when using it for the protection of a liquid crystal display body, a colorless and transparent film is very suitable.

Although the thickness of these base films does not have a restriction | limiting in particular, Although it selects suitably according to a situation, it is 15-250 micrometers normally, Preferably it is the range of 30-200 micrometers. Moreover, this base film can be surface-treated by the oxidation method, an uneven | corrugated method, etc. to one side or both sides as needed, for the purpose of improving adhesiveness with the layer formed in the surface. Examples of the oxidation method include corona discharge treatment, plasma treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone and ultraviolet irradiation treatment, and the like. A solvent treatment method and the like. Although these surface treatment methods are suitably selected according to the kind of base film, in general, the corona discharge treatment method is used preferably from a viewpoint of an effect, operability, etc.

In this invention, a barrier layer can be formed in the surface of the side in which the hard coat layer of this base film is formed as needed. This barrier layer is for protecting the base film from the solvent in the hard coat layer forming material when the hard coat layer is formed using the hard coat layer forming material on the base film.

[Hard Coating Layer]

In the hard coat film of the present invention, the hard coat layer contains a cured product of the (A) active energy ray curable compound and (B) a thermoplastic resin, and these are formed by forming a phase separation structure.

(Active energy ray curable compound)

The active energy ray-curable compound which is the (A ') component which forms the said (A) hardened | cured material is a thing which has an energy quantum in an electromagnetic wave or a charged particle beam, ie, superposition | polymerization which bridge | crosslinks and hardens | cures by irradiating an ultraviolet-ray or an electron beam etc. Means a sex compound.

As such an active energy ray hardening-type compound, a photopolymerizable prepolymer and / or a photopolymerizable monomer are mentioned, for example. Moreover, the silica fine particle which the polymerizable unsaturated group containing organic compound couple | bonded can also be used. The photopolymerizable prepolymer includes a radical polymerization type and a cationic polymerization type, and examples of the radical polymerization type photopolymerizable prepolymers include polyester acrylate type, epoxy acrylate type, urethane acrylate type, and polyol acrylate type. Etc. can be mentioned. Here, as a polyester acrylate type prepolymer, the hydroxyl group of the polyester oligomer which has a hydroxyl group in the sock end obtained by condensation of polyhydric carboxylic acid and a polyhydric alcohol, for example, is esterified by (meth) acrylic acid, or polyhydric carboxylic acid It can obtain by esterifying the hydroxyl group of the terminal part of the oligomer obtained by adding an alkylene oxide to (meth) acrylic acid.

An epoxy acrylate prepolymer can be obtained by, for example, reacting and esterifying (meth) acrylic acid to an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or a novolak type epoxy resin. A urethane acrylate prepolymer can be obtained by esterifying the polyurethane oligomer obtained by reaction of a polyether polyol, polyester polyol, and polyisocyanate, for example with (meth) acrylic acid. In addition, a polyol acrylate type prepolymer can be obtained by esterifying the hydroxyl group of a polyether polyol with (meth) acrylic acid. 1 type of these photopolymerizable prepolymers may be used, and may be used in combination of 2 or more type.

On the other hand, epoxy-type resin is normally used as a cationic polymerization type photopolymerizable prepolymer. Examples of the epoxy resins include compounds obtained by oxidizing polyhydric phenols such as bisphenol resins and novolak resins with epichlorohydrin, compounds obtained by oxidizing linear olefin compounds and cyclic olefin compounds with peroxides, and the like. Can be.

Moreover, as a photopolymerizable monomer, 1, 4- butanediol di (meth) acrylate, 1, 6- hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polystyrene glycol di, for example (Meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxy pivarin neopentyl glycol di (meth) acrylate, dicyclopentanyldi (meth) acrylate, caprolactone modified dicyclopente Nyldi (meth) acrylate, ethylene oxide modified phosphate di (meth) acrylate, allyl cyclohexyldi (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate , Dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolprop Tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa Polyfunctional acrylates, such as (meth) acrylate, are mentioned. 1 type of these photopolymerizable monomers may be used, may be used in combination of 2 or more type, and may be used together with the said photopolymerizable prepolymer.

In addition, the silica fine particles (hereinafter sometimes referred to as reactive silica fine particles) to which the polymerizable unsaturated group-containing organic compound is bound can react with the silanol groups on the silanol groups on the surface of the silica fine particles having an average particle diameter of about 0.005 to 1 μm. It can obtain by making the polymerizable unsaturated group containing organic compound which has a functional group react. As a polymerizable unsaturated group, a radically polymerizable acryloyl group, a methacryloyl group, etc. are mentioned, for example.

As a polymerizable unsaturated group containing organic compound which has a functional group which can react with the said silanol group, For example, General formula (I)

(Wherein R ¹ is a hydrogen atom or a methyl group, R ² is a halogen atom or

Term indicated by)

The compound etc. which are represented by are used preferably.

Examples of such a compound include acrylic acid, acrylic acid chloride, 2-isocyanate ethyl acrylate, glycidyl acrylate, 2,3-iminopropyl acrylate, 2-hydroxyethyl acrylate, acryloyloxypropyl trimethoxysilane, and the like. And methacrylic acid derivatives corresponding to these acrylic acid derivatives can be used. These acrylic acid derivatives and methacrylic acid derivatives may be used alone, or may be used in combination of two or more thereof.

The silica microparticles | fine-particles which the polymerizable unsaturated group containing organic compound obtained in this way couple | bonded are bridge | crosslinked and harden | cure by irradiation of an active energy ray as an active energy ray hardening component.

These reactive silica fine particles have the effect of improving the scratch resistance of the obtained hard coat film. It is preferable to select the compounding quantity of the said reactive silica microparticles to contain in the ratio of 10-90 mass% in the hard coat layer formed.

As an ultraviolet (UV) hardening type hard coating agent containing the compound which combines the organic compound which has a polymerizable unsaturated group with such silica microparticles | fine-particles, JSR Corporation product, brand names "Opstar Z7530", "Opstar Z7524" And "Opster TU4086" are commercially available.

These polymerizable compounds can use together a photoinitiator as needed. As this photoinitiator, about a radically polymerizable photopolymerizable prepolymer or a photopolymerizable monomer, For example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, Benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1 -Phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 4- (2- Hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2- Ethyl anthraquinone, 2-terrisi-butyl anthraquinone, 2-aminoanthraquinone, 2-methyl thioxanthone, 2-ethyl thioxanthone, 2-chloro thioxanthone, 2,4-dimethyl thioxanthone, 2 , 4-diethyl thioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethylamine benzoic acid ester, etc. are mentioned. Moreover, as a photoinitiator for a cation polymerization type photopolymerizable prepolymer, Onium, such as an aromatic sulfonium ion, an aromatic oxosulfonium ion, an aromatic iodonium ion, tetrafluorobolet, a hexaflourophosphate, The compound which consists of anions, such as hexafluoro antimonate and hexafluoro arsenate, is mentioned. These may be used 1 type or may be used in combination of 2 or more type, and the compounding quantity is normally selected in the range of 0.2-10 mass parts with respect to 100 mass parts of said photopolymerizable prepolymers and / or photopolymerizable monomers. .

In this invention, hardening of the said active energy ray hardening-type compound is explained in full detail in the manufacturing method of the hard coat film of this invention mentioned later.

((B) Thermoplastic Resin)

As a thermoplastic resin of (B) component which is a main component which comprises a hard coat layer with hardened | cured material of the active energy ray hardening-type compound which is the said (A) component, although various resin can be used without a restriction | limiting in particular, the said active energy ray hardening-type compound Polyester resins, polyester urethane resins, acrylic resins, and the like are very suitable in terms of phase separation properties and antiglare performance of the formed hard coat layer. These may be used individually by 1 type and may be used in combination of 2 or more type.

Here, as polyester-based resin, for example, ethylene glycol, propylene glycol, 1, 3- butanediol, 1, 4- butanediol, diethylene glycol, triethylene glycol, 1, 5- pentanediol, 1, 6- hexanediol , At least one selected from alcohol components such as neopentyl glycol, cyclohexane-1,4-dimethanol, hydrogenated bisphenol A, ethylene oxide and propylene oxide adduct of bisphenol A, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid And polymers obtained by condensation polymerization of at least one selected from carboxylic acid components such as cyclohexane-1,4-dicarboxylic acid, adipic acid, azelaic acid, maleic acid, fumaric acid, itaconic acid, and an acid anhydride, and the like. .

Moreover, as polyester urethane-type resin, the polymer etc. which were made by making various polyisocyanate compounds react with the polyester polyol which has a hydroxyl group in the terminal part obtained by carrying out the polycondensation of said alcohol component and carboxylic acid component are mentioned.

Moreover, as acrylic resin, the polymer of the at least 1 sort (s) of monomer chosen from the (meth) acrylic-acid alkylester of C1-C20 alkyl group, or the copolymer of said (meth) acrylic-acid alkylester and another copolymerizable monomer, etc. Can be mentioned.

Among them, polyester resins and / or polyester urethane resins are particularly preferable.

The content rate of the hardened | cured material of the active-energy-ray-curable compound of the said (A) component, and the thermoplastic resin of the said (B) component in the said hard-coating layer is selected in the range of 100: 0.3-100: 50 on a mass basis. . When content of (B) component is 0.3 mass part or more with respect to 100 mass parts of (A) component, desired light-diffusion property is provided in the inside of a hard-coat layer, and a fine uneven structure is easy to be formed in the surface, and 50 mass If it is below a part, the said hard coat layer will have favorable hardness (scratch resistance). The content ratio [(A) :( B)] is preferably 100: 0.5 to 100: 50, more preferably 100: 1 to 100: 45 on a mass basis.

(Phase Separation Structure)

In the said hard coat layer, the hardened | cured material of the active energy ray hardening-type compound which is above-mentioned (A) component, and the thermoplastic resin which is above-mentioned (B) component form the phase separation structure.

About this phase separation structure, the phase separation structure of the surface observed with a microscope is (1) uniform sponge / island structure, the size of this island is the range of 0.1 micrometer-20 micrometers in diameter, (2) the island of non-uniform size It is preferable that it is an excited sponge / island structure, and the largest diameter of this island is the range of 0.1 micrometer-50 micrometers, and (3) it forms a continuous (modulation) structure. In the case of the structure (1), when the diameter of the island is less than 0.1 μm, sufficient anti-glare property is not exhibited. On the contrary, when the diameter exceeds 20 μm, problems such as deterioration of sharpness and glare occur. In the case of the structure (2), when the diameter of the largest island is less than 0.1 µm, sufficient anti-glare property is not exhibited. On the contrary, when the diameter of the largest island exceeds 50 µm, problems such as deterioration of sharpness and glare occur. About the structure of (3), after apply | coating and drying the coating agent melt | dissolved in the solvent in formation of a hard coat layer, as long as the method of irradiating an active energy ray is employ | adopted, favorable optical physical property is shown.

As described above, in the hard coat layer, (A) component and (B) component form a phase separation structure, and the internal haze value is usually 3 to 80%, preferably 5 to 70%, more preferably It is preferable that it is 16 to 50%. Usually, since the internal haze value of an optical film base material is about 0%, the internal haze value of a hard coat film can be 3 to 80% by making the internal haze value of a hard coat layer into 3 to 80%. If the internal haze value is less than 3%, the effect of sufficiently preventing glare may not be obtained. If the internal haze value is more than 80%, the light transmittance may be adversely affected. In addition, in this invention, the internal haze value of a hard coat film is a film except the haze resulting from the scattering factor of the film surface on the opposite side to a base film among the light scattering factors which comprise the haze value of the said hard coat film. It means haze value by internal scattering factor only, and measure as follows. That is, prepare a transparent adhesive film having a known haze value, and attach the adhesive layer of the transparent adhesive film to the surface on the opposite side to the base film of the hard coating film to measure the internal haze value. And the haze value of the whole film with a transparent adhesive film is measured based on JISK7136. The value which subtracted the whole haze value of a transparent adhesive film from the obtained value is made into internal haze value. Moreover, as long as the haze value is transparent, what kind of adhesive film may be used for the transparent adhesive film to be used, but it is preferable that the value of a totally small haze value is small enough.

In this hard coat layer, it is preferable to have surface irregularities from a viewpoint of improving anti-glare performance. Although there is no restriction | limiting in particular in this surface uneven | corrugated shape formation method, (1) The method of forming unevenness | corrugation using phase separation of said (A) and (B) component, (2) A part of this is surface-surfaced using transparent fine particles A method of forming unevenness by exposing to unevenness; and (3) a method of physically forming unevenness by an external force, such as using a jig having an uneven shape. These methods may be used individually by 1 type, and may use 2 or more types together.

In the said hard coat layer, it is preferable that the arithmetic mean roughness Ra of the surface is between 0.015-0.3 micrometer from an anti-glare viewpoint. When surface roughness Ra is less than 0.015 micrometer, anti-glare property is hard to express, and when surface roughness Ra exceeds 0.3 micrometer, problems, such as glare and white generate | occur | produce that the permeability sharpness falls, arise.

In addition, the said arithmetic mean roughness Ra is a value measured based on JISB0601-1994. Here, for the purpose of preventing glare, anti-glare property is not essential. In this case, the surface roughness Ra may be less than 0.015 μm, for example, the clear hard coating layer may have a surface roughness Ra of 0.01 μm or less.

The thickness of the hard coat layer is preferably in the range of 0.5 to 20 µm. If the thickness is less than 0.5 μm, the scratch resistance of the hard coat film may not be sufficiently exhibited. If the thickness exceeds 20 μm, curling may occur in the hard coat film. From the standpoint of the balance between scratch resistance and 60 degree mirror glossiness, the more preferable thickness of this hard coat layer is in the range of 1 to 15 µm, and particularly preferably in the range of 2 to 10 µm.

In the hard coat layer, an antiglare layer having surface irregularities may be further laminated. It is preferable that an anti-glare layer consists of hardened | cured material of an active-energy-ray-curable material, and surface unevenness | corrugation can be formed similarly to the case of forming an uneven | corrugated shape in the said hard coat layer. The thickness of the antiglare layer is suitably about 1 to 20 μm, and the surface roughness Ra of the antiglare layer is preferably 0.015 to 0.3 μm.

Next, the manufacturing method of the hard coat film of this invention is demonstrated.

[Manufacturing method of hard coating film]

In the method for producing a hard coat film of the present invention, a coating film layer is formed on a base film using a hard coating layer forming material, and then a hard coating layer is formed by irradiating an active energy ray to the coating film to form a hard coating film. The hard coating layer forming material (hereinafter, may be simply referred to as a coating agent for a hard coating layer) comprises a (A ') active energy ray-curable compound and (B) a thermoplastic resin in a mass ratio of 100: 0.3 to 100. (C) a good solvent for the above (A ') component and (B) component and (D) the poor solvent for the above (B) component in a mass ratio of 99: 1 to 10:90. It is characterized by containing at a ratio of.

In the coating agent for a hard coating layer, when the content of the component (B) is 0.3 parts by mass or more with respect to 100 parts by mass of the component (A ′), desired light diffusibility is imparted to the interior of the formed hard coating layer, and the surface It is easy to form a fine concavo-convex structure, and if it is 50 mass parts or less, the said hard coat layer will have favorable hardness (scratch resistance). The content ratio [(A ') :( B)] is preferably from 100: 0.5 to 100: 50, more preferably from 100: 1 to 100: 45 on a mass basis.

(menstruum)

In the coating agent for a hard coating layer, the solvent consists of a good solvent for the above-mentioned (A ') component and (B) component, which is (C) component, and a poor solvent for the (B) component, which is (D) component. Solvent is used. Here, a good solvent and a poor solvent mean the solvent which has the solubility measured by the method shown below.

When the total amount of the solvent to be measured for solubility is added to 20 g and the mixture is mixed at a temperature of 25 ° C., a solution having uniform transparency can be obtained. It is assumed that it is a good solvent for the sample, and that it is turbid and that separation is confirmed is a poor solvent for the sample.

When the thermoplastic resin of the component (B) is, for example, a polyester resin or a polyester urethane resin, examples of the good solvent for the resin include cyclohexanone, acetone, ethyl acetate, tetrahydrofuran and methyl ethyl ketone. Can be illustrated. As the poor solvent, toluene, xylene, methyl isobutyl ketone, ethyl cellosolve, propylene glycol monomethyl ether, isobutanol, isopropanol, ethanol, methanol, hexane, purified water and the like can be exemplified.

Moreover, when the thermoplastic resin of (B) component is acrylic resin, as a good solvent, cyclohexanone, acetone, ethyl acetate, tetrahydrofuran, xylene, toluene, methyl ethyl ketone, methyl isobutyl ketone, ethyl cellosolve, Propylene glycol monomethyl ether, etc. can be illustrated. On the other hand, isobutanol, isopropanol, ethanol, methanol, hexane, purified water, etc. can be illustrated as a poor solvent.

In addition, all of the said good solvent and the poor solvent except purified water are good solvents with respect to the active energy ray hardening-type compound used normally.

In this invention, the solvent of the said (C) component may be used individually by 1 type, may be used in mixture of 2 or more types, and the solvent of the (D) component may be used individually by 1 type, and You may mix and use 2 or more types.

In the coating agent for the hard coating layer, the content ratio [(C) :( D)] of the solvent of the component (C) and the solvent of the component (D) is selected in the range of 99: 1 to 10:90 on a mass basis. do. When the content ratio is in the above range, good phase separation occurs at the time of forming the hard coat layer, the desired light diffusing property is imparted to the inside of the obtained hard coat layer, and fine concavo-convex structures are easily formed on the surface. The content ratio is preferably from 97: 3 to 15:85, more preferably from 95: 5 to 40:60 on a mass basis.

((E) Transparent Inorganic Particles)

In the coating agent for a hard coat layer, the hard component obtained by phase separation at the time of hard coat layer formation by containing the said (A '), (B), (C) and (D) component in said ratio, respectively. Desired light diffusivity is imparted to the inside of the coating layer, and fine concavo-convex structures are easily formed on the surface, and high precision anti-glare property is imparted. Thus, although it is not necessary to mix | blend the inorganic type microparticles | fine-particles or organic type microparticles | fine-particles for imparting anti-glare property to the coating agent for hard coat layers like before, a transparent inorganic weapon as (E) component as needed in the range which does not impair the effect of this invention. Microparticles | fine-particles can be mix | blended.

There is no restriction | limiting in particular in the said transparent inorganic fine particle, It can select from a variety of transparent inorganic fine particles conventionally used in order to provide anti-glare property to a hard coat layer, and can use suitably. As the transparent inorganic fine particles, colloidal silica fine particles having an average particle diameter of about 10 to 100 nm are particularly preferable.

In this invention, although the transparent inorganic fine particle of (E) component may be used individually by 1 type, and may be used in combination of 2 or more type, its content is much minimum compared with the prior art, and is usually the said ( It is about 0.1-10 mass parts with respect to 100 mass parts of total amounts of A ') component and (B) component. When content of the said microparticles | fine-particles exists in the said range, the hard coat layer formed will acquire stable optical characteristic, and will be provided more favorable anti-glare property. Preferable content of the said microparticles | fine-particles is 1-8 mass parts, More preferably, it is 1.5-5 mass parts.

In this invention, transparent organic fine particles can also be mix | blended suitably with the said transparent inorganic fine particle as needed.

(Formation of Hard Coating Layer)

Although there is no restriction | limiting in particular in content of a solvent in the coating agent for hard coat layers, Although what is necessary is just to select the said content suitably so that the coating agent of the viscosity suitable for application | coating may be carried out, 50-95 mass% is preferable.

In addition to the above-mentioned (A ')-(E) components, the said hard coat layer coating agent has various additives, for example, a photoinitiator, an antistatic agent, antioxidant, and an ultraviolet-ray, if desired in the range which does not impair the effect of this invention. An absorbent, a light stabilizer, a leveling agent, an antifoamer, etc. can be contained. In addition, a photoinitiator can use the thing similar to what was described in description of the hard-coat layer mentioned above.

In the present invention, a coating agent for a hard coat layer prepared as described above on a base film or on a barrier layer formed as desired on the surface thereof is a conventionally known method such as a bar coating method and a knife coating. Hard coating layer is formed by coating and forming a coating film by using a coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, and the like, and then drying and irradiating an active energy ray to the coating film. do.

In the present invention, when the coating agent for the hard coating layer on the barrier layer, the base film is not damaged by the solvent in the coating agent.

As an active energy ray, an ultraviolet-ray, an electron beam, etc. are mentioned, for example. The ultraviolet ray is obtained by a high pressure mercury lamp, a fusion H lamp, a xenon lamp, or the like, and the irradiation amount is usually 100-50OmJ / cm 2, while the electron beam is obtained by an electron beam accelerator or the like, and the irradiation amount is usually 150-350kV. . Among these active energy rays, ultraviolet rays are particularly suitable. In addition, when using an electron beam, a cured film can be obtained without adding a polymerization initiator.

(Formation of irregularities by external force)

As a method of physically forming the unevenness on the surface of the hard coat layer carried out as desired by an external force, for example, a method of transferring the unevenness is mentioned. Specifically, the coating film for hard coating layer is apply | coated to a base film, the uneven surface of the film (uneven film) which has an uneven surface is bonded to the coating film obtained by drying a solvent, and after irradiating an active energy ray in this state, The method of peeling off a film is mentioned. After removing the uneven film, the energy ray may be further irradiated. The irradiation conditions of the energy ray can be carried out under the same conditions as in the case of forming the hard coat layer described above. As the uneven film, it is preferable to transmit ultraviolet rays which are active energy rays. For example, a polyethylene terephthalate film having a layer cured by applying a mixture of energy ray-curable resins and fillers such as silica, and the surface by embossing or the like. The polyethylene film in which the unevenness | corrugation was formed is mentioned. The surface roughness Ra of the uneven surface is preferably 0.015 to 0.5 µm. When the surface roughness of the uneven film is in this range, the anti-glare property of the obtained hard coat film becomes good.

(Formation of antiglare layer)

As a method for forming an antiglare layer laminated on a hard coat layer as desired, for example, (1) A hard coat layer is formed of a coating agent for an antiglare layer containing an active energy ray-curable compound, a thermoplastic resin, and a solvent similarly to the hard coat film of the present invention. (2) A method for irradiating active energy rays to form unevenness by phase separation, irradiating active energy rays, and (2) applying an anti-glare layer coating agent comprising an inorganic fine particle or organic fine particles to an active energy ray-curable compound on a hard coating layer, and The method of irradiating an energy ray, (3) After apply | coating the anti-glare layer coating agent containing an active-energy-ray-curable compound to a hard-coat layer, the method of forming an unevenness | corrugation by external force, and irradiating an active energy ray etc. are mentioned. As the active energy ray-curable compound, the thermoplastic resin, the solvent, the inorganic fine particles and the organic fine particles, and the method of forming the unevenness by the external force, the same as those described in the description of the hard coat film of the present invention can be used. .

[Hard Coating Film]

The hard coat film of this invention formed in this way requires that an internal haze value is 3 to 80%. When the internal haze value is less than 3%, the performance of suppressing glare is insufficient, and when it exceeds 80%, visibility is reduced. Preferable internal haze value is 5 to 70%, and it is more preferable that it is 16 to 50%. Moreover, it is preferable to have favorable scratch resistance, and to have the optical characteristic shown below.

In the hard coat film of the present invention, the total haze value and the 60 degree mirror glossiness are indices of anti-glare properties, the total haze value is preferably 3% or more, and the 60 degree mirror glossiness is preferably 200 or less. If the total haze value is less than 3%, sufficient anti-glare property is hardly exhibited, and if the 60 degree mirror glossiness exceeds 200, the surface glossiness is large (large reflection of light), which may adversely affect the anti-glare property. . However, when the total haze value is too high, light transmittance deteriorates, which is not preferable. Moreover, 30 or more of the total value of normal sharpness is preferable. The total value of the image sharpness becomes an indicator of display quality, that is, visibility, and when this value is less than 30, sufficiently good display quality (visibility) cannot be obtained. Moreover, 88% or more of the total light transmittance is preferable, and when it is less than 88%, there exists a possibility that transparency may become inadequate. In addition, the internal haze value is as described above.

In terms of balance of anti-glare, display quality (visibility), light transmittance, transparency, the total haze value is preferably 10 to 80%, and the total value of the image sharpness is more preferably 35 or more, and the total light transmittance is More preferably, it is 90% or more.

In addition, in this invention, a total haze value means the total value of the haze value (internal haze value) resulting from the inside of a hard coat film, and the haze value resulting from the unevenness of a surface, and a haze meter for the said hard coat film Over, it measures based on JISK7136. In addition, 60 degree specular glossiness is measured with a gloss meter based on JISK7105.

The total value of the image sharpness is calculated according to JIS K 7105, and the image sharpness of five kinds of slits (slit width: 0.125 mm, 0.25 mm, 0.5 mm, 1 mm, and 2 mm) is obtained, and the total value of the five values obtained is obtained. It is defined as the sum of.

In addition, the measuring method of the said optical characteristic is demonstrated later.

In the hard coat film of the present invention, an antireflection layer, for example, a siloxane coating, a fluorine coating, or the like can be formed on the uppermost layer for the purpose of imparting antireflection to the uppermost layer. In this case, the thickness of the antireflection layer is preferably about 0.05 to 1 μm. By forming this antireflection layer, the reflected light of the screen generated from reflection by sunlight, fluorescent lamps, or the like is eliminated, and by suppressing the reflectance of the surface, the total light transmittance is increased and transparency is improved. Moreover, depending on the kind of antireflection layer, the antistatic property can be improved.

In the hard coat film of this invention, the adhesive layer for sticking to adherends, such as a liquid crystal display body, can be formed in the surface on the opposite side to the hard coat layer of a base film. As an adhesive which comprises this adhesive layer, acrylic adhesive, urethane adhesive, and silicone adhesive suitable for optical use are used preferably. The thickness of this adhesive layer is 5-100 micrometers normally, Preferably it is the range of 10-60 micrometers.

Moreover, a peeling film can be formed on this adhesive layer as needed. As this peeling film, what apply | coated peeling agents, such as a silicone resin, to various plastic films, such as polyethylene terephthalate and a polypropylene, etc. are mentioned, for example. Although there is no restriction | limiting in particular about the thickness of this peeling film, Usually, it is about 20-150 micrometers.

In the hard coat film of the present invention, the cured product of the active energy ray-curable compound and the thermoplastic resin form a phase-separated structure, are provided with a desired light diffusivity, and preferably have a hard coat layer having irregularities formed on the surface thereof. It can be used as a film, and is particularly suitable as an anti-glare hard coating film capable of effectively suppressing glare of a high-precision type image display device having color filters such as a liquid crystal display device.

<Example>

Next, although an Example demonstrates this invention in detail, this invention is not limited at all by these examples.

In addition, the performance of the hard coat film was evaluated according to the following method.

(1) Total light transmittance and total haze value

It measured according to JIS K 7136 using the Nippon Denshoku Kogyo Co., Ltd. haze meter "NDH2000".

(2) 60 degree mirror gloss

It measured based on JISK7105 using Nippon Denshoku Kogyo Co., Ltd. product gloss meter "VG2000".

(3) The total value of merchant sharpness

It measures based on JISK7105, using Sugashi Kenki Co., Ltd. product filamentometer "ICM-10P". The total value of five types of slits (slit width: 0.125 mm, 0.25 mm, 0.5 mm, 1 mm and 2 mm) was taken as the total value of the image sharpness.

(4) scratch resistance

The degree of damage when the surface of the coating layer was rubbed with steel wool (# O000) was visually observed. (Circle) shows that a scratch is not found.

(5) Arithmetic mean roughness Ra of the surface

Using the Mitsutoyo surface roughness measuring instrument "SV3000OS4", the outermost layer (hard coating layer, anti-glare layer, or anti-reflection layer) of the hard coat film was measured in accordance with JIS B O601-1994.

(6) internal haze value

2 mass parts of isocyanate crosslinking agents [Toyo Ink Co., Ltd. brand name "BHS-8515"] and 100 mass parts of toluene are added to 100 mass parts of acrylic adhesives [Nippon Carbide company make, brand name "PE-121"], and it is an adhesive solution Was produced. The adhesive solution was apply | coated to the 50-micrometer-thick polyethylene terephthalate (Toyo Boseki company make, brand name "A4300") film so that thickness after drying might be set to 20 micrometers, and it dried at 100 degreeC for 3 minutes, and produced the transparent adhesive film. The prepared transparent adhesive film was affixed on the hard coating layer, anti-glare layer, or anti-reflection layer of the hard coating film, and it was set as the sample for internal haze measurement. The haze value of the said transparent adhesive film and the sample for internal haze measurement was measured, and the value which subtracted the haze value of the transparent adhesive film measured separately from the haze value of the sample for internal haze measurement was made into the internal haze value of a hard coat film. In addition, when the internal haze value of the base film (triacetyl cellulose film) used by the Example and the comparative example was measured similarly, it was less than 0.01% and was a negligible value. In addition, the measurement of the haze value was measured based on JISK7136 using the Nippon Denshoku Kogyo Co., Ltd. haze meter "NDH2000".

(7) glare

The polarizing plate produced using the hard coat film obtained by the Example and the comparative example was installed in the surface which peeled the polarizing plate of the liquid crystal display "AQUOS LC-20AX5" by Sharp company, and observed the flicker of brightness visually. In addition, a polarizing plate has a hard coating film on one side of the polarizer which adsorbed iodine to stretched polyvinyl alcohol, and a triacetyl cellulose (hereinafter "TAC") film [product of Konica Minolta Opt Co., Ltd. product, brand name "KC8UX2M" ] Was bonded together and produced.

(8) Phase separation state

The phase separation state of the surface is easily confirmed by the digital microscope `` VHX-100 '' manufactured by Keyence Co., Ltd., the size of the island of the sea surface / island structure is measured using a scale, and the diameter of any ten islands in the center of the observation area is measured. Measured. Example 5 was measured about the clear hard coat layer before forming an anti-glare hard coat layer. In Example 6, since the antireflection layer was as thin as 0.1 μm, phase separation of the hard coating layer was observed.

[Preparation Example 1 Coating agent for anti-glare hard coating layer having both internal haze and surface irregularities]

Preparation of (A)

(A) 58 mass% of active energy ray hardening compounds containing an ultraviolet (UV) hardening-type hard coating agent [JSR Co., Ltd. product, brand name "Opstar TU4086", reactive silica microparticles, and polyfunctional acrylate as an active energy ray hardening type compound (A) , 2 mass% of antistatic agent, 35 mass% of methyl isobutyl ketone, 5 mass% of methyl ethyl ketone], polyester resin [Toyo Boseki Co., Ltd. product, brand name "Bylon 20SS", as a (B) thermoplastic resin, 30 mass% of polyester resin, 56 mass% of toluene, 14 mass% of methyl ethyl ketone] As a photoinitiator, 1-hydroxycyclohexyl phenyl ketone [Ciba Specialty Chemicals, Ltd. product, a brand name "Igacure 184 Solid content 100%] and 35 mass parts of ethyl cellosolve and 85 mass parts of cyclohexanone are uniformly mixed as 2.4 mass parts and a diluting solvent, and have both internal haze of 28 mass% of solid content, and both surface irregularities simultaneously. Anti-glare Hard Nose To prepare a coating layer (A). In addition, only ethyl cellosolve is the poor solvent (D) of (B) component in the said solvent, and the other is a good solvent (C) of (A) component and (B) component. The ratio of (C): (D) is 80.1: 19.9.

[Preparation Example 2 Preparation of Coating (B) for Hard Coating Layer Having Internal Haze but Less Surface Unevenness]

(A) 58 mass% of active energy ray hardening compounds containing an ultraviolet (UV) hardening-type hard coating agent [JSR Co., Ltd. product, brand name "Opstar TU4086", reactive silica microparticles, and polyfunctional acrylate as an active energy ray hardening type compound (A) , 2 mass% of antistatic agent, 35 mass% of methyl isobutyl ketone, 5 mass% of methyl ethyl ketone], polyester resin [Toyo Boseki Co., Ltd. product, brand name "Bylon 20SS", as a (B) thermoplastic resin, 30 mass% of polyester resin, 56 mass% of toluene, 14 mass% of methyl ethyl ketone] As a photoinitiator, 1-hydroxycyclohexyl phenyl ketone [Ciba Specialty Chemicals, Ltd. product, a brand name "Igacure 184 Solid content 100%] 2.4 parts by weight and 60 parts by weight of methyl ethyl ketone and 60 parts by weight of cyclohexanone as a diluting solvent are uniformly mixed, and the coating agent for a hard coating layer having an internal haze of 28% by weight of solid content but less surface irregularities (B) Was claim.

[Preparation Example 3 Preparation of coating agent (C) for anti-glare hard coating layer in which silica fine particles were added to coating agent of Preparation Example 2]

(A) 58 mass% of active energy ray hardening compounds containing an ultraviolet (UV) hardening-type hard coating agent [JSR Co., Ltd. product, brand name "Opstar TU4086", reactive silica microparticles, and polyfunctional acrylate as an active energy ray hardening type compound (A) , 2 mass% of antistatic agent, 35 mass% of methyl isobutyl ketone, 5 mass% of methyl ethyl ketone] As polyester resin (B) thermoplastic resin, the Toyo Boseki Co., Ltd. brand name "Bylon 20SS" , 30 mass% of polyester resin, 56 mass% of toluene, 14 mass% of methyl ethyl ketone] 1-hydroxycyclohexyl phenyl ketone [Ciba Specialty Chemicals Co., Ltd. product, a brand name] monocure as a photoinitiator 184 ", solid content 100%] As a 2.4 mass part, silica microparticles | fine-particles [Fuji Silysia Kagaku Co., Ltd. product, a brand name" Silopobic 702 ", solid content 100%] 1.0 mass part, and 60 mass parts of methyl ethyl ketones as a diluting solvent, 60 parts by mass of cyclohexanone The anti-glare hard coating layer coating agent (C) in which the silica fine particles are added to the coating agent of Preparation Example 2 having a solid content of 28% by mass, ie, both the internal haze and the surface uneven surface coating agent ( C) was prepared.

[Preparation Example 4 Preparation of coating agent (D) for antiglare layer having no surface haze but having surface irregularities]

As an active energy ray hardening-type compound, 95 mass% of active energy ray hardening-type compounds containing an ultraviolet (UV) hardening-type hard coating agent [product made by Daiichi Seika, brand name "Seikabeam EXF-01L (NS)", polyfunctional acrylate, photoinitiator 5 % By mass] 84 parts by mass, ultraviolet (UV) curable hard coating agent [manufactured by Dainichi Seika, trade name "Seikabeam EXF-01L (NE2)", 85% by mass of active energy ray-curable compound containing polyfunctional acrylate, average particle diameter 10 mass% of 7 μm silica filler, 5 mass% of photoinitiator] and 130 mass parts of ethyl cellosolve as a diluting solvent are mixed uniformly, and the coating agent for anti-glare layer (D) which does not have internal haze but has surface irregularities It prepared. In addition, the layer obtained by apply | coating and dry hardening this coating agent (D) has hard coatability.

[Preparation Example 5 Preparation of coating agent (E) for antireflection layer formation]

As an active energy ray-curable compound, 100 parts by mass of an ultraviolet (UV) curable hard coating agent [product of Arakawa Kagaku Co., Ltd., product name "Beamset 575CB", solid content 100%], and methyl isobutyl ketone (MIBK) dispersion of porous silica particles Total solid content after mixing 80 mass parts of a sieve [Shoukubaika Seiko Co., Ltd. product, brand name "ELCOM RT-1002SIV", solid content 21 mass%, porous silica particle: specific gravity 1.8, refractive index 1.30, average particle diameter 60nm] It diluted with MIBK so that a density | concentration might be 2 mass%, and the coating agent (E) for antireflection layer formation was prepared.

Example 1

The coating agent (A) obtained in the preparation example 1 was apply | coated so that the cured film thickness might be about 3.5 micrometers on the surface of the TAC film (Konica Minolta Opto Co., Ltd. product, brand name "KC8UX2M") of thickness 80micrometer. After drying for 1 minute in an oven at 70 ° C., a high-pressure mercury lamp was irradiated with ultraviolet light of 30mJ / cm 2 to form an anti-glare hard coating layer having both internal haze and surface irregularities, and a hard coating film was prepared.

Table 1 shows the performance of this hard coat film.

Example 2

The coating agent (B) obtained in the preparation example 2 was apply | coated immediately so that the cured film thickness might be set to about 3.5 micrometers on the surface of 80 micrometers TAC film (Konica Minolta Opto Co., Ltd. product, brand name "KC8UX2M"). After drying for 1 minute in an oven at 70 ° C., a hard coat layer (clear hard coat layer) was formed by irradiating ultraviolet light of 30mJ / cm 2 with a high pressure mercury lamp to prepare a hard coat film with internal haze.

Table 1 shows the performance of this hard coat film.

Example 3

The coating agent (C) obtained by the preparation example 3 was apply | coated immediately to the surface of the TAC film (Konica Minolta Opto Co., Ltd. product, brand name "KC8UX2M") of thickness 80micrometer so that a cured film thickness might be set to about 3.5 micrometers. After drying for 1 minute in an oven at 70 ° C., a high-pressure mercury lamp was used to irradiate 30 mJ / cm 2 of ultraviolet rays to form an anti-glare hard coating layer having both internal haze and surface irregularities, thereby obtaining a hard coating film.

Table 1 shows the performance of this hard coat film.

Example 4

The hard coat agent (A) obtained in the preparation example 1 was apply | coated to the clear hard coat layer which has the internal haze obtained in Example 2 so that a cured film thickness might be about 3.5 micrometers. After drying for 1 minute in an oven at 70 ° C., a high-pressure mercury lamp was used to irradiate 30 mJ / cm 2 of ultraviolet rays to form an anti-glare hard coating layer having both internal haze and surface irregularities, thereby obtaining a hard coating film.

Table 1 shows the performance of this hard coat film.

Example 5

The coating agent for anti-glare layer (D) obtained in the preparation example 4 was apply | coated so that the cured film thickness might be about 3.5 micrometers to the clear hard coat layer which has the internal haze obtained in Example 2. After drying for 1 minute in an oven at 70 ° C., a high-pressure mercury lamp was used to irradiate ultraviolet rays of 30,000 mJ / cm 2 to form an anti-glare hard coating layer having both internal haze and surface irregularities, and a hard coating film was prepared.

Table 1 shows the performance of this hard coat film.

Example 6

The anti-reflection layer forming coating agent (E) obtained in Preparation Example 5 was applied directly to the hard coat layer having both the internal haze and the surface irregularities obtained in Example 1 so that the cured film thickness was about 0.1 μm. After drying in an oven at 70 ° C. for 1 minute, 300 mJ / cm 2 of ultraviolet rays were irradiated with a high pressure mercury lamp to form an anti-glare hard coating layer having both internal haze and surface irregularities, thereby obtaining a hard coating film.

Table 1 shows the performance of this hard coat film.

Example 7

The coating agent (B) obtained in the preparation example 2 was apply | coated immediately so that the cured film thickness might be set to about 3.5 micrometers on the surface of 80 micrometers TAC film (Konica Minolta Opto Co., Ltd. product, brand name "KC8UX2M"). After drying in an oven at 70 ° C. for 1 minute, the uneven film having the surface roughness Ra = 0.3 μm is bonded thereto, and in this state is irradiated with 150 mJ / cm 2 ultraviolet rays by a high-pressure mercury lamp, and the uneven film is peeled off, and then 30000 mJ UV light of / cm 2 was irradiated to obtain a hard coat film having both internal haze and surface irregularities.

Table 1 shows the performance of this hard coat film.

In addition, the uneven film is a polyethylene terephthalate film having a thickness of 50 μm, a mixture of 100 parts by mass of ultraviolet curable resin `` SEIKA BEAM EXF-01L (NS) '' (product of Daiichi Seika) and 10 parts by mass of silica filler (average particle diameter 2 μm). What formed the hardened layer of 2 micrometers in thickness which used is used.

Comparative Example 1

The coating agent for anti-glare layer (D) obtained by the preparation example 4 was apply | coated so that the cured film thickness might be about 3.5 micrometers on the surface of the TAC film (Konica Minolta Opto Co., Ltd. product, brand name "KC8UX2M") of thickness 80micrometer. After drying for 1 minute in an oven at 70 ℃, a high pressure mercury lamp was irradiated with ultraviolet light of 30mJ / ㎠ to obtain a hard coating film having no internal haze but surface irregularities.

Table 1 shows the performance of this hard coat film.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Type of coating (A) (B) (C) (B) / (A) (B) / (D) (A) / (E) (B) (D) Total haze value (%) 38.13 24.71 40.39 50.91 24.16 51.85 66.56 1.90 Internal haze value (%) 30.76 22.81 24.50 43.68 22.68 30.62 46.54 0.01 Total light transmittance (%) 94.72 94.51 94.22 95.95 93.72 94.77 95.95 91.72 60 degree mirror gloss 68.1 111.4 37.5 77.7 150.9 20.1 18.6 112.4 Total value of merchant sharpness 399.7 481.5 350.1 230.4 199.0 239.4 39.4 244.8 Surface Roughness Ra (μm) 0.0473 0.0081 0.1033 0.1214 0.1241 0.0618 0.2126 0.1574 Glare none none none none none none none has exist Scratch resistance ○ ○ ○ ○ ○ ○ ○ ○  Phase separation Homogeneous sponge / island (4-6) Uniform sea level / island (0.5 to 1.0) Uniform sea level / island (0.5 to 1.0) Homogeneous sponge / island (1 to 15) Uniform sea level / island (0.5 to 1.0) Homogeneous sponge / island (4 to 5) Uniform sea level / island (0.5 to 1.0)  -

Numerical values in () in the phase separation state indicate the size of the island (unit μm).

[week]

Example 1: A hard coating film having an anti-glare hard coating layer having a phase separation structure having both internal haze and surface irregularities.

Example 2: A hard coating film having an internal haze but having a clear hard coating layer having a phase separation structure with less surface irregularities.

Example 3: A hard coat film having an anti-glare hard coat layer having a phase separation structure having an internal haze and surface irregularities in which a filler is added to the coating agent of Example 2.

Example 4: A hard coat film obtained by laminating an antiglare layer having a phase separation structure having an internal haze and surface irregularities on the clear hard coat layer of Example 2.

Example 5: The hard coat film which laminated | stacked the anti-glare layer which has surface uneven | corrugated shape by adding a filler on the clear hard coat layer of Example 2 although there is no internal haze.

Example 6: A hard coat film having an antireflection layer laminated on the anti-glare hard coat layer of Example 1.

Example 7: The hard coat film in which the surface asperity shape was formed in the clear hard coat layer of Example 2.

Comparative Example 1: A hard coat film having an antiglare hard coat layer containing a filler. There is almost no internal haze.

The hard coat film of the present invention is provided with a desired light diffusivity, preferably has a hard coat layer having irregularities formed on the surface thereof, and can be used as an anti-glare film, and is particularly provided with a high-precision color filter such as a liquid crystal display device. It is very suitable as an anti-glare film capable of effectively suppressing glare of a type image display apparatus.

Claims (9)

On a base film, it has a hard coat layer which contains the hardened | cured material of (A) active energy ray hardening-type compound, and (B) thermoplastic resin in the ratio of mass ratio 100: 0.3-100: 50, In the hard coating film, the component (A) and the component (B) form a phase separation structure, and the internal haze value is 3 to 80%. The method of claim 1, A hard coating film is formed by forming a surface unevenness by phase separation. The method of claim 1, The hard coat layer further contains (E) transparent inorganic fine particles, and a part of this is exposed to the surface to form irregularities. The method of claim 2, The hard coat layer further contains (E) transparent inorganic fine particles, and a part of this is exposed to the surface to form irregularities. The method according to any one of claims 1 to 4, A hard coating film formed by forming an unevenness on the surface of the hard coating layer by external force. The method according to any one of claims 1 to 4, Hard coating film, characterized in that the arithmetic mean roughness Ra measured in accordance with JIS B O601-1994 on the surface of the hard coating layer is 0.015 ~ 0.3μm. The method according to any one of claims 1 to 4, A hard coat film, characterized by laminating an antiglare layer having surface irregularities on the surface of the hard coat layer. The method according to any one of claims 1 to 4, A hard coating film used for an image display device having a color filter. As a method of manufacturing a hard coat film by forming a coating layer using a hard coating layer forming material on a base film, then irradiating active energy rays to the coating layer to form a hard coating layer. The hard coat layer forming material contains (A ') an active energy ray-curable compound and (B) a thermoplastic resin at a mass ratio of 100: 0.3 to 100: 50, and (C) the (A') component and ( A positive solvent for component B) and (D) a poor solvent for component (B) are contained at a mass ratio of 99: 1 to 10:90. The manufacturing method of the hard coat film of description.