JP2007108449A - Method for producing antiglare film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antiglare film excellent in adhesion after a light resistance test, having less white blur and excellent in film hardness such as abrasion resistance and pencil hardness. <P>SOLUTION: The antiglare film has an antiglare layer on a transparent triacetyl cellulose substrate, wherein the antiglare layer is formed by applying an ultraviolet-curing composition comprising an ultraviolet-curing resin compound (A) containing dipentaerythritol hexaacrylate, organic fine particles (B) having an average particle diameter of 3-10 μm, a photopolymerization initiator (C) and one or more organic solvents (D) which dissolve a transparent triacetyl cellulose base material on the transparent triacetyl cellulose substrate and curing the composition with ultraviolet radiation. An image display device using the antiglare film is excellent in reliability, antiglare property and image sharpness which are hard to be compatible so far. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to various displays such as liquid crystal displays, plasma displays, EL displays, rear projection displays, and CRT displays used as image display devices for televisions, computers, car navigation systems, in-vehicle instrument panels, mobile phones and the like. The present invention relates to an antiglare film provided on the surface for preventing reflection of an image and reflection of light.

Conventionally, for image display devices such as CRT, PDP, LCD, ELD, etc., especially for image display devices with flat surfaces such as PDP, LCD, ELD, etc., operation on the display screen by indoor lighting, sunlight incidence, etc. There was a problem that the reflection of the shadows of persons and the like significantly hindered the visibility of the image.
In order to suppress this reflection, Patent Document 1 discloses a technique of applying an antiglare effect to the surface by coating a resin containing a filler such as silica on the outermost surface of the display and forming irregularities on the surface. (See Patent Document 1: Japanese Patent Laid-Open No. 7-294740).
However, in order to obtain an antiglare effect using silica particles, a large amount of silica must be mixed in, so the surface is whitish and the contrast is low, resulting in a screen with low transparency (hereinafter referred to as white blur). End up. Furthermore, when a triacetyl cellulose film is used for the transparent substrate, if the coating film containing silica is subjected to saponification treatment by alkali dipping for the purpose of improving adhesion, the haze value of the obtained triacetyl cellulose film is large. It becomes a film with reduced contrast and transparency. As this cause, it is thought that the adhesiveness between the resin composition and the inorganic filler is low, and the interface is affected by alkali.

  Further, Patent Document 2 describes a method of imparting an antiglare effect to a surface by forming a hard coat layer in which organic polymer fine particles are mixed on the surface (Patent Document 2: JP-A-6-18706). Since the anti-glare property is expressed with a relatively small amount of use compared to the case where silica particles are used, there is an advantage that white blurring is small. Furthermore, the organic polymer fine particles have better adhesion between the resin composition and the organic polymer fine particles than inorganic fillers such as silica fine particles, and the interface is not easily affected by alkali even in the saponification treatment. However, the hard coat layer in which organic polymer fine particles are mixed on the surface is thick when the average particle size of the organic polymer fine particles is large, and the hard coat layer is likely to be thick. The film thickness of the layer becomes thin, and hard coat properties (particularly pencil hardness) are difficult to appear.

  In order to ensure hard coat properties even when the hard coat layer is thin, a resin composition obtained by curing an ionizing radiation curable resin having a large number of ethylenically unsaturated double bonds is often used. However, these ionizing radiation curable resins having a large number of ethylenically unsaturated double bonds tend to have large cure shrinkage and poor adhesion to the substrate. Further, as a reliability test of the antiglare film, there is a problem that the adhesiveness with the base material is further lowered after the light resistance test is performed. It is considered that this is because the hard coat layer was further cured by the ultraviolet rays irradiated in the light resistance test, the curing shrinkage was increased, and the adhesion was lowered.

Patent Documents 3 and 4 describe antiglare films formed from a coating solution using a solvent that dissolves a triacetylcellulose transparent base material for the purpose of improving the adhesion to a triacetylcellulose transparent substrate. (See Patent Document 3: JP-A-11-209717, Patent Document 4: JP-A 2002-169001)
However, merely using a solvent that dissolves the triacetylcellulose transparent substrate provides good adhesion after coating, but the adhesion after the light resistance test is not sufficient, which causes a problem.

JP 7-294740 A JP-A-6-18706 Japanese Patent Laid-Open No. 11-209717 JP 2002-169001 A

  An object of the present invention is to provide an antiglare film excellent in antiglare property, hard coat property, adhesion, particularly adhesion to a substrate after a light resistance test.

As a result of intensive studies in view of the above problems, the present inventors have found that an ultraviolet curable composition comprising a specific combination of an ultraviolet curable resin, organic fine particles, a photoinitiator, and a specific organic solvent on a triacetylcellulose transparent substrate. The present invention was completed by finding that an antiglare layer in which a fine uneven shape formed by curing a film can solve these drawbacks.
That is, the present invention is a method for producing an antiglare film having an antiglare layer on a triacetylcellulose transparent substrate,
Antiglare layer
An ultraviolet curable resin compound (A) comprising dipentaerythritol hexaacrylate (a) and other polyfunctional (meth) acrylate (a ′),
Organic fine particles (B) having an average particle diameter of 3 to 10 μm,
A photopolymerization initiator (C), and
One or more organic solvents that dissolve the triacetylcellulose transparent substrate (D)
An ultraviolet curable composition comprising a triacetyl cellulose substrate, and then cured with ultraviolet light,
When the ultraviolet curable resin compound (A) is dissolved in the organic solvent (D), the viscosity is 5 to 10 mPa when measured at a liquid temperature of 25 wt. -It is related with the manufacturing method of the glare-proof film which is s.

  Moreover, this invention relates to the said manufacturing method in which another polyfunctional (meth) acrylate (a ') contains hydroxypivalic acid neopentyl glycol diacrylate.

Further, in the present invention, the ultraviolet curable resin compound (A) contains 70 to 95% by weight of dipentaerythritol hexaacrylate,
5-30% by weight of at least one of hydroxypivalic acid neopentyl glycol diacrylate, tricyclodecane dimethylol diacrylate, and pentaerythritol triacrylate
It is related with the manufacturing method of the said anti-glare film characterized by including.

  Moreover, this invention relates to the anti-glare film manufactured with the manufacturing method of the said anti-glare film.

  Moreover, this invention relates to the said anti-glare film characterized by having an optical characteristic with a total light transmittance of 85% or more and a haze value of 3.0 to 35.0%.

In the present invention, the difference in refractive index between the ultraviolet curable resin compound (A) and the organic fine particles (B) is 0.02 or less, and
It is related with the said anti-glare film whose internal haze value by internal diffusion of an anti-glare layer is less than 1.

  The antiglare film of the present invention has excellent adhesion after a light resistance test, little white blur, and excellent coating film hardness such as scratch resistance and pencil hardness. An image display device using an antiglare film having excellent characteristics as described above is excellent in reliability, antiglare property, and image clarity, which has been difficult to achieve in the past.

Hereinafter, preferred embodiments of the present invention will be described.
The triacetyl cellulose transparent substrate in the present invention is cast by a single layer casting method or a multi-layer co-casting method, in which a triacetyl cellulose dope prepared by dissolving triacetyl cellulose in a solvent is cast. It is preferable to use a triacetylcellulose film prepared by this method. The thickness of the triacetyl cellulose transparent substrate can be appropriately determined, but is generally about 10 to 500 μm from the viewpoints of workability such as strength and handling, and thin layer properties. 20-300 micrometers is especially preferable, and 30-200 micrometers is more preferable.

  The antiglare film of the present invention is obtained by ultraviolet-curing an ultraviolet curable composition comprising (A) to (D) on a triacetylcellulose transparent substrate.

  The ultraviolet curable resin (A) in the present invention essentially contains dipentaerythritol hexaacrylate (a), contains other polyfunctional (meth) acrylate (a ′), and contains the ultraviolet curable resin compound (A). When the viscosity when dissolved in one or more organic solvents (D) that dissolve the triacetylcellulose transparent substrate was measured at a liquid temperature of 25 wt. 5 to 10 mPa · s. As the organic solvent (D) used for specifying the viscosity, the organic solvent (D) itself used when the ultraviolet curable composition containing (A) to (D) is obtained is used. Therefore, when the organic solvent (D) for making an ultraviolet curable composition is a mixed solvent, the viscosity is measured with the mixed solvent.

The UV curable resin compound (A) has a hard coat property represented by a scratch resistance (hereinafter referred to as scratch resistance) by a steel wool rubbing test, a hardness by a pencil scratch test (hereinafter referred to as pencil hardness), and a cross-cut cellophane tape peeling test. Antiglare such as adhesion to transparent triacetyl cellulose substrate (hereinafter referred to as adhesion), and adhesion to transparent triacetyl cellulose substrate after light resistance test (hereinafter referred to as adhesion after light resistance test) Used to satisfy the required physical properties of the film.
In particular, the adhesion after the light resistance test is such that the viscosity when the ultraviolet curable resin compound (A) is dissolved in one or more organic solvents (D) that dissolve the transparent triacetylcellulose substrate is an EL rotational viscometer. In the case of 5 to 10 mPa · s when measured at a liquid temperature of 25% at a non-volatile content of 60%, the ultraviolet curable resin compound (A) is stained with the organic solvent (D) on the transparent substrate of triacetyl cellulose. Since the adhesion to the transparent triacetyl cellulose substrate is improved, the adhesion after the light resistance test is also improved. When the viscosity is less than 5 mPa · s, penetration into the transparent triacetyl cellulose substrate increases, and the film thickness of the antiglare layer becomes too thin, so that sufficient hard coat properties cannot be obtained. Moreover, when it exceeds 10 mPa * s, there will be little penetration with respect to a triacetylcellulose transparent base material, and the adhesiveness after a light resistance test will become inadequate.

The other polyfunctional (meth) acrylate (a ′) has a viscosity when dissolved in one or more organic solvents (D) that dissolve the triacetylcellulose transparent base material when the ultraviolet curable resin compound (A) is used. It can be used in a range not departing from 5 to 10 mPa · s.
Other polyfunctional (meth) acrylates (a ′) include, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,4-dicyclohexane di (meth) acrylate, 1,6-hexanediol di (Meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 3-methylpentanediol di (meth) Acrylate, diethylene glycol bis β- (meth) acryloyloxypropionate, pentaerythritol tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri ( Acrylate), EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate, dipentaerythritol tetra (Meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified di Pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetra (meth) acrylate, polyurethane poly Relate, ester compounds of polyhydric alcohols and (meth) acrylic acid and polyester polyacrylate;
Polyurethane poly (meth) acrylate, polyester poly (meth) acrylate, polyether poly (meth) acrylate, polyacryl poly (meth) acrylate, polyalkyd poly (meth) acrylate, polyepoxy poly (meth) acrylate, polyspiroacetal poly (Meth) acrylate compounds of polyfunctional compounds such as (meth) acrylate, polybutadiene poly (meth) acrylate, polythiol polyene poly (meth) acrylate, polysilicon poly (meth) acrylate;
Vinylbenzene and its derivatives such as 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexane;
Vinyl sulfone compounds such as divinyl sulfone;
(Meth) acrylamide compounds such as methylbisacrylamide;
So-called high refractive index such as bis (4-methacryloylthiophenyl) sulfide, bisphenoxyethanol full orange acrylate, vinylnaphthalene, vinylphenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenylthioether, tetrabylomobisphenol A diepoxyacrylate, etc. And monomers.
The other polyfunctional (meth) acrylate (a ′) preferably contains at least one of hydroxypivalate neopentyl glycol diacrylate, tricyclodecane dimethylol diacrylate, and pentaerythritol triacrylate. The use of hydroxypivalic acid neopentyl glycol diacrylate is preferred.

Dipentaerythritol hexaacrylate (a), which is an essential component, is used to obtain hard coat properties, particularly hard coat properties even when the hard coat layer is thin. Other polyfunctional (meth) acrylates (a ′) are used for ensuring adhesion and adhesion after a light resistance test.
Hydroxypivalate neopentyl glycol diacrylate, tricyclodecane dimethylol diacrylate, and pentaerythritol triacrylate are one or more organic solvents (D) that dissolve the transparent triacetyl cellulose base material without relatively degrading the hard coat properties. It is used for lowering the viscosity when dissolved in the solution, further swelling the transparent substrate of triacetyl cellulose, and making the ultraviolet curable resin compound (A) easily soaked.

As the ultraviolet curable resin compound (A), dipentaerythritol hexaacrylate is 70 to 95% by weight, and hydroxypivalate neopentyl glycol diacrylate, tricyclodecane dimethylol diacrylate, and pentaerythritol triacrylate. It is preferable to contain 5 to 30% by weight of at least one of them.
If dipentaerythritol hexaacrylate is less than 70% by weight, the hard coat property of the antiglare layer becomes insufficient. If it exceeds 95% by weight, it dissolves in one or more organic solvents (D) that dissolve the transparent triacetyl cellulose substrate. Since the viscosity when it exceeds 10 mPa · s, the adhesion after the light resistance test becomes insufficient. Preferably it is 70-80 weight%. On the other hand, if the total of hydroxypivalate neopentyl glycol diacrylate, tricyclodecane dimethylol diacrylate, and pentaerythritol triacrylate exceeds 30% by weight, the hard coat property of the antiglare layer is lowered. Preferably it is 10-25 weight%.

  The ultraviolet curable resin compound (A) does not prevent the use of an appropriate amount of a known monofunctional monomer that is not a polyfunctional monomer within a range not departing from the technical idea of the present invention.

  These ultraviolet curable resin compounds (A) are preferably 5 to 95% by weight, more preferably 20 to 80% by weight based on the nonvolatile content in the ultraviolet curable composition. If it is less than 5% by weight, sufficient coating strength such as hard coat property cannot be obtained, and if it exceeds 95% by weight, the content of the organic fine particles (B) is decreased, and sufficient antiglare property cannot be obtained.

In the present invention, the organic fine particles (B) having an average particle diameter of 3 to 10 μm are provided with anti-glare properties by forming irregularities on the surface, for example, styrene beads, acrylic beads, styrene-acrylic beads, melamine beads. Benzoguanamine beads, polycarbonate beads, polyethylene beads, silicone beads, fluorine beads, vinylidene fluoride beads, polyvinyl chloride beads, epoxy beads, nylon beads, phenol beads, polyurethane beads, etc., but the refractive index of organic fine particles (B) From the viewpoint, acrylic beads and styrene-acrylic beads are preferable. The average particle size of these organic fine particles (B) is preferably 3 to 10 μm, and more preferably 3 to 6 μm. For the antiglare layer, it is preferable to use organic fine particles (B) in which particles having a particle size larger than one half of the film thickness occupy 40 to 100% of the entire particles. If the average particle size is less than 3 μm, the effect of scattering light is insufficient, so that the resulting anti-glare property is insufficient. If it exceeds 10 μm, the light scattering effect inside the anti-glare layer is reduced, resulting in glare in the image. It is easy to produce.
In addition, an average particle diameter can be measured by the electrical resistance method, for example.

  The organic fine particles (B) are preferably insoluble in water and organic solvents, and the shape may be indefinite or spherical. Moreover, these organic fine particles (B) may combine two or more types of particles in order to control surface irregularities. The addition amount of the organic fine particles (B) is preferably 3 to 30% by weight, and more preferably 5 to 20% by weight with respect to the nonvolatile content in the ultraviolet ray curable composition. If it is less than 3% by weight, sufficient antiglare property cannot be obtained. If it exceeds 30% by weight, antiglare property is good but white blurring tends to occur.

In addition, the difference in refractive index between the organic fine particles (B) having an average particle diameter of 3 to 10 μm and the ultraviolet curable resin compound (A) is 0.02 or less in terms of reducing the internal diffusion of the antiglare layer. And it is preferable that the internal haze value of the glare-proof layer formed by hardening these with ultraviolet rays is less than 1. If the difference in refractive index exceeds 0.02 and the internal haze value is 1 or more, the antiglare layer tends to be blurred, which is not preferable.
The internal haze value is obtained by removing the influence of surface irregularities from the haze value. Specifically, the internal haze value is obtained by applying a solution containing organic fine particles so as to eliminate the surface irregularities, and curing with ultraviolet rays. It can measure by the method of apply | coating the solution (resin is the same thing) which does not contain organic fine particles on the obtained coating film, and ultraviolet-curing and creating a coating film without surface unevenness, and measuring a haze.

  Examples of the photopolymerization initiator (C) in the present invention include acetophenones, benzoins, benzophenones, anthraquinones, phosphine oxides, ketals, anthraquinones, thioxanthones, and the like. Specifically, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, methylanthraquinone, 2-ethylanthraquinone, 2-aminoanthraquinone, 2,4,6-trimethylbenzoindiphenylphosphine oxide, Michler's ketone, isoamyl N, N-dimethylaminobenzoate, thioxan, 2-chlorothioxanthone 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, etc., and these photopolymerization initiators may be used in combination of two or more. It is also possible to. The usage-amount of these photoinitiators is 0.1-20 weight% with respect to an ultraviolet curable resin (A), Preferably it is 1-10 weight%.

Examples of the one or more organic solvents (D) that dissolve the triacetylcellulose transparent substrate in the present invention include dibutyl ether, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1,3-dioxolane, Ethers such as 1,3,5-trioxane, tetrahydrofuran, anisole, phenetole;
Ketones such as acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone;
Esters such as ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, γ-ptyrolactone;
Others, methyl 2-methoxyacetate, methyl 2-ethoxyacetate, ethyl 2-ethoxyacetate, ethyl 2-ethoxypropionate, 2-methoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 1,2-diacetoxyacetone, Examples include acetylacetone, diacetone alcohol, methyl acetoacetate, ethyl acetoacetate and the like. These can be used alone or in combination of two or more.

  The amount of the one or more organic solvent (D) that dissolves the triacetyl cellulose transparent substrate is preferably adjusted so that the nonvolatile content of the ultraviolet curable resin composition is 50 to 80% by weight. . More preferably, the nonvolatile content is 60 to 70% by weight. When the non-volatile content of the ultraviolet curable resin composition is less than 50% by weight, the amount of the one or more organic solvents (D) that dissolve the transparent triacetyl cellulose substrate used is too large. The viscosity becomes low, the film thickness of the antiglare layer formed on the triacetylcellulose transparent substrate is thin, and hard coat properties are difficult to appear. In addition, when the non-volatile content of the ultraviolet curable resin composition exceeds 80% by weight, the amount of one or more organic solvents (D) that dissolve the transparent triacetyl cellulose substrate used is reduced, and adhesion and light resistance are reduced. Adhesion after the property test becomes insufficient.

  Furthermore, in consideration of drying properties, leveling properties, etc. during coating, an organic solvent other than one or more organic solvents (D) that dissolves the triacetylcellulose transparent base material is adhered after adhesion and light resistance tests. It can be used in the range where the property does not deteriorate. Examples of the organic solvent include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, cyclohexyl alcohol, isobutyl acetate, methyl isobutyl ketone, 2-octanone, 2-pentanone, 2-hexanone, ethylene glycol ethyl ether, and ethylene glycol. Examples include isopropyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, ethyl carbitol, butyl carbitol, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, benzene, toluene, xylene, etc. A combination of more than one species can be used.

The ultraviolet curable composition used in the present invention may further contain a photosensitizer, a leveling agent, a thixotropic agent, etc. Examples of the photosensitizer include n-butylamine, triethylamine, triethanolamine, Examples thereof include poly-n-brylphosphine, and two or more of these photosensitizers can be used in combination as appropriate.

  The UV curable composition can be formed on a transparent substrate of triacetyl cellulose by bar coating, blade coating, spin coating, reverse coating, die coating, spray coating, roll coating, gravure coating, micro coating. After coating on a triacetylcellulose transparent substrate by coating methods such as gravure coating, lip coating, air knife coating, dipping method, etc., the solvent is dried if necessary, and further UV irradiation is applied to the coated UV light It is formed by crosslinking and curing a linear curable composition. As the ultraviolet rays, ultraviolet rays emitted from a light source such as a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, or a tungsten lamp can be used. The film thickness of the antiglare layer thus formed is not particularly limited as long as it has hard coat properties, and is appropriately determined depending on the particle diameter of the organic fine particles (B) to be used, but usually 1 to 10 μm, The thickness is preferably 2 to 5 μm.

  Further, a low refractive index layer having a refractive index lower than the refractive index of the antiglare layer is provided on the surface of the fine irregularities of the antiglare layer as a method for further improving the contrast and white blur of the screen display. You can also. As these low refractive index layers, for example, those having a polysiloxane structure are used, and preferably those having a fluorine-containing polysiloxane structure. Such a low refractive index layer can be formed by, for example, fluorine-containing alkoxysilane. The thickness of the low refractive index layer is preferably 0.05 to 0.15 μm. The low refractive index layer can be formed on the surface of the antiglare layer by an appropriate method. As a formation method, the same method as the formation of the antiglare layer can be used.

  Thus, the antiglare film of the present invention produced by forming an antiglare layer having fine irregularities on the surface of a triacetylcellulose transparent substrate has a total light transmittance of 85% or more and a haze. It preferably has optical properties of 3.0 to 35.0%, and has optical properties of 90% or higher total light transmittance and 4.0 to 20.0% haze value. Is more preferable. If the total light transmittance is less than 85%, an image with high contrast cannot be displayed. If the haze value is less than 3.0%, sufficient antiglare property cannot be obtained, and if it exceeds 35.0%, white blur tends to occur, which is not preferable.

  Moreover, an optical element can be adhered to the triacetyl cellulose transparent substrate of the antiglare film. Examples of the optical element include a polarizing plate, a retardation plate, an elliptical polarizing plate, a polarizing plate with optical compensation, and the like, and these can be used as a laminate. For adhesion of the optical element, an appropriate adhesive layer excellent in transparency, weather resistance, etc., such as an acrylic, rubber-based, or silicone-based pressure-sensitive adhesive or a hot-melt-based adhesive can be used.

As the polarizing plate, a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, an ethylene / vinyl acetate copolymer-based partially saponified film, or the like, which is stretched by adsorbing iodine, dye or the like, polyvinyl Examples include deflection films such as a dehydrated product of alcohol and a dehydrochlorinated product of polyvinyl chloride. Examples of the retardation plate include a uniaxial or biaxially stretched polymer film exemplified for the transparent substrate and a liquid crystal polymer film. The retardation plate may be formed from two or more stretched films. The elliptically polarizing plate and the polarizing plate with optical compensation can be formed by laminating a polarizing plate and a retardation plate. The elliptically polarizing plate and the polarizing plate with optical compensation have an antiglare layer formed on the surface on the polarizing plate side.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited only to these specific examples. In the examples, “parts” and “%” indicate “parts by weight” and “% by weight”, respectively.
[Formulation Example 1]
75 parts of dipentaerythritol hexaacrylate and 25 parts of neopentyl glycol diacrylate hydroxypivalate were dissolved in 73.5 parts of 1,3-dioxolane, and 5 parts of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Geigy) was added. . The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.524. To this solution, 5.2 parts of crosslinked polystyrene-methyl methacrylate particles (XX-12AE, manufactured by Sekisui Chemical Co., Ltd.) having an average particle size of 3.5 μm and a refractive index of 1.525 are added, and stirred at 4000 rpm for 15 minutes with a high-speed disper. An antiglare coating solution (1) was prepared. The internal haze value of the coating film obtained by applying this solution and curing with ultraviolet rays was 0.49%.
Further, 75 parts of dipentaerythritol hexaacrylate and 25 parts of neopentyl glycol diacrylate hydroxypivalate are dissolved in 66.7 parts of 1,3-dioxolane to prepare a solution having a nonvolatile content of 60%. The viscosity of was measured with an EL rotational viscometer and found to be 8 mPa · s.

The refractive index and internal haze were measured as follows.
(1) Refractive index: Measured by Appe refractometer (2) Internal haze: A solution containing no organic fine particles on a coating obtained by applying a solution containing organic fine particles and curing with ultraviolet rays (the same resin) ) Is applied, UV cured to form a coating film without surface irregularities, and haze is measured.

[Formulation Example 2]
Dissolve 75 parts of dipentaerythritol hexaacrylate, 20 parts of neopentyl glycol diacrylate hydroxypivalate, and 5 parts of tricyclodecane dimethylol diacrylate in 73.5 parts of 1,3-dioxolane to obtain a photopolymerization initiator (Irgacure 184). , Manufactured by Ciba Geigy). The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.524. To this solution, 5.2 parts of crosslinked polystyrene-methyl methacrylate particles (XX-12AE, manufactured by Sekisui Chemical Co., Ltd.) having an average particle size of 3.5 μm and a refractive index of 1.525 are added, and stirred at 4000 rpm for 15 minutes with a high-speed disper. An antiglare coating solution (2) was prepared. The internal haze value of the coating film obtained by applying this solution and curing with ultraviolet rays was 0.59%.
A solution having a nonvolatile content of 60% is obtained by dissolving 75 parts of dipentaerythritol hexaacrylate, 25 parts of neopentyl glycol diacrylate hydroxypivalate, and 5 parts of tricyclodecane dimethylol diacrylate in 66.7 parts of 1,3-dioxolane. Was measured, and the viscosity of the solution at a temperature of 25 ° C. was measured with an EL rotational viscometer. As a result, it was 7.5 mPa · s.

[Composition Example 3]
Dipentaerythritol hexaacrylate 75 parts, hydroxypivalate neopentyl glycol diacrylate 20 parts, pentaerythritol triacrylate 5 parts are dissolved in 1,3-dioxolane 73.5 parts, and a photopolymerization initiator (Irgacure 184, Ciba Geigy Corporation) is dissolved. 5 parts) was added. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.524. To this solution was added 11.1 parts of crosslinked polystyrene-methyl methacrylate particles (XX-12AE, manufactured by Sekisui Chemical Co., Ltd.) having an average particle size of 3.5 μm and a refractive index of 1.525, and the mixture was stirred with a high-speed disper at 4000 rpm for 15 minutes. An antiglare coating solution (3) was prepared. The internal haze value of the coating film obtained by applying this solution and curing with ultraviolet rays was 0.51%.
Further, 75 parts of dipentaerythritol hexaacrylate, 25 parts of neopentyl glycol diacrylate hydroxypivalate, and 5 parts of pentaerythritol triacrylate were dissolved in 66.7 parts of 1,3-dioxolane to prepare a solution having a nonvolatile content of 60%. When the viscosity of the solution at a temperature of 25 ° C. was measured with an EL type rotational viscometer, it was 7.0 mPa · s.

[Formulation Example 4]
80 parts of dipentaerythritol hexaacrylate and 20 parts of tricyclodecane dimethylol diacrylate were dissolved in 73.5 parts of 1,3-dioxolane, and 5 parts of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Geigy Corporation) was added. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.525. To this solution, 5.2 parts of crosslinked polystyrene-methyl methacrylate particles (XX-12AE, manufactured by Sekisui Chemical Co., Ltd.) having an average particle size of 3.5 μm and a refractive index of 1.525 are added, and stirred at 4000 rpm for 15 minutes with a high-speed disper. An antiglare coating solution (4) was prepared. The internal haze value of the coating film obtained by applying this solution and curing with ultraviolet rays was 0.69%.
Further, 80 parts of dipentaerythritol hexaacrylate and 20 parts of tricyclodecane dimethylol diacrylate were dissolved in 66.7 parts of 1,3-dioxolane to prepare a solution having a non-volatile content of 60%. It was 8.0 mPa * s when the viscosity was measured with the EL rotational viscometer.

[Formulation Example 5]
100 parts of dipentaerythritol hexaacrylate was dissolved in 73.5 parts of 1,3-dioxolane, and 5 parts of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Geigy Corporation) was added. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.525. To this solution, 5.2 parts of crosslinked polystyrene-methyl methacrylate particles (XX-12AE, manufactured by Sekisui Chemical Co., Ltd.) having an average particle size of 3.5 μm and a refractive index of 1.525 are added, and stirred at 4000 rpm for 15 minutes with a high-speed disper. An antiglare coating solution (5) was prepared. The internal haze value of the coating film obtained by applying this solution and curing with ultraviolet rays was 0.55%.
Further, 100 parts of dipentaerythritol hexaacrylate is dissolved in 66.7 parts of 1,3-dioxolane to prepare a solution having a nonvolatile content of 60%, and the viscosity of the solution at a temperature of 25 ° C. is measured with an EL type rotational viscometer. As a result, it was 12.0 mPa · s.

[Composition Example 6]
100 parts of hydroxypivalic acid neopentyl glycol diacrylate was dissolved in 73.5 parts of 1,3-dioxolane, and 5 parts of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Geigy Corporation) was added. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.520. To this solution, 5.2 parts of crosslinked polystyrene-methyl methacrylate particles (XX-12AE, manufactured by Sekisui Chemical Co., Ltd.) having an average particle size of 3.5 μm and a refractive index of 1.525 are added, and stirred at 4000 rpm for 15 minutes with a high-speed disper. An antiglare coating solution (6) was prepared. The internal haze value of the coating film obtained by applying this solution and curing with ultraviolet rays was 0.51%.
Further, 100 parts of hydroxypivalate neopentyl glycol diacrylate is dissolved in 66.7 parts of 1,3-dioxolane to prepare a solution having a nonvolatile content of 60%, and the viscosity of the solution at 25 ° C. is measured by an EL type rotational viscometer. It was 6.0 mPa * s when measured in (1).

[Composition Example 7]
75 parts of dipentaerythritol hexaacrylate and 25 parts of neopentyl glycol diacrylate hydroxypivalate were dissolved in 73.5 parts of 1,3-dioxolane, and 5 parts of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Geigy) was added. . The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.524. To this solution, 5.2 parts of crosslinked methyl methacrylate particles (Epter M1004, manufactured by Nippon Shokubai Co., Ltd.) having an average particle size of 4.0 μm and a refractive index of 1.490 are added, and stirred at 4000 rpm for 15 minutes with a high speed disper to apply anti-glare. A liquid (7) was prepared. The internal haze value of the coating film obtained by applying this solution and curing with ultraviolet rays was 6.50%.
Further, 75 parts of dipentaerythritol hexaacrylate and 25 parts of neopentyl glycol diacrylate hydroxypivalate are dissolved in 66.7 parts of 1,3-dioxolane to prepare a solution having a nonvolatile content of 60%. The viscosity of was measured with an EL rotational viscometer and found to be 8 mPa · s.

  Table 1 shows a summary of Formulation Examples 1-7.

[Example 1]
The antiglare coating liquid (1) of Formulation Example 1 was applied to a 80 μm thick triacetyl cellulose film (Fuji Photo Film Co., Ltd.) using a bar coater, and dried at 70 ° C. for 1 minute. Thereafter, the coating layer was cured by irradiating ultraviolet rays at a dose of 400 mJ / cm 2 using a high pressure mercury lamp in an oxygen concentration atmosphere of 0.3% or less by nitrogen purge to form an antiglare layer having a thickness of 4.5 μm. . The evaluation results of the obtained antiglare film are shown in Table 2.

1. Haze: A haze value was measured using a haze meter 300A (manufactured by Tokyo Denshoku).
2. Total light transmittance: The total light transmittance was measured using a haze meter 300A (manufactured by Tokyo Denshoku).
3. Pencil hardness: According to JIS K5400.
4). Adhesion test: JIS K5400 cross-cut tape method (interval of 1 mm).
5. Adhesion test after light resistance test: 63 ° C.-45% RH-65 mW / cm ² -24 hours with a super UV light resistance tester (Diepler Metal Weather Type KU-R5CI-A, light source: metal halide lamp) After conducting a light resistance test under the conditions, an adhesion test was conducted by the cross-cut tape method of JIS K5400 (interval of 1 mm).
6). Scratch resistance: using steel wool # 0000, 500 g / 10 reciprocal evaluation ◎: very good ○: good △: somewhat inferior ×: inferior Antiglare property: An exposed fluorescent lamp without louver was copied onto the prepared antiglare film, and the degree of blur of the reflected image was visually determined.
◎: The outline of the fluorescent lamp is not understood at all. ○: The outline of the fluorescent lamp is slightly understood. △: The fluorescent lamp is blurred but the outline can be identified. ×: The fluorescent lamp is hardly blurred (no anti-glare property)
8). White blur: An anti-glare film was bonded to the surface of the liquid crystal display using a transparent adhesive, and the blackness was visually determined by displaying black.
○: White blur is suppressed and there is black △: Some white blur is present ×: There is white blur and the screen is whitened

[Examples 2 to 4]
Thereafter, the antiglare coating solutions (2) to (4) were applied and cured in the same manner as in Example 1 to form an antiglare layer. The evaluation results of the obtained antiglare film are shown in Table 2.
[Comparative Examples 1 and 2 and Example 5]
In the same manner as in Example 1, the antiglare coating solutions (5) to (7) were applied and cured to form an antiglare layer. The evaluation results of the obtained antiglare film are shown in Table 2.

  From the results shown in Table 2, the following is clear. The antiglare films specified by the present invention in Examples 1 to 5 have good adhesion after the light resistance test, and simultaneously satisfy antiglare properties, pencil hardness, scratch resistance, and white blur (contrast).

On the other hand, the comparative example 1 does not contain hydroxypivalic acid neopentyl glycol diacrylate, tricyclodecane dimethylol diacrylate, pentaerythritol triacrylate in the ultraviolet curable resin compound (A), and a triacetyl cellulose transparent substrate is used. The viscosity when dissolved in one or more organic solvents (D) to be dissolved exceeds 10 mPa · s when measured at a liquid temperature of 25% at a non-volatile content of 60% with an EL rotational viscometer, The adhesion after the light resistance test is poor.
Comparative Example 2 contains hydroxypivalate neopentyl glycol diacrylate, and the viscosity when dissolved in one or more organic solvents (D) that dissolve the triacetyl cellulose transparent substrate is an EL type rotational viscometer. When measured at a liquid temperature of 60% and 25 ° C., it is 6 mPa · s, and the adhesion after the light resistance test is good, but it is an essential component, does not contain dipentaerythritol hexaacrylate, and is a pencil. Hardness and scratch resistance are poor.
In Example 5, the antiglare property, the hard coat property (pencil hardness), and the adhesion to the substrate after the light resistance test, which are the subjects of the present invention, are simultaneously satisfied. Furthermore, it can be used for applications that do not require a haze value or white blur. However, the difference in refractive index between the ultraviolet curable resin compound (A) and the organic fine particles (B) specified in the present invention exceeds 0.02, and the internal diffusion of the resin obtained by curing them with ionizing radiation. Since the internal haze value is 1 or more, white blur is poor.

The image display device comprising the antiglare film of the present invention is less likely to be scratched on the display surface, has little reflection of external light, has a good contrast, and is excellent in reliability in a light resistance test or the like.

Claims (6)

A method for producing an antiglare film having an antiglare layer on a triacetylcellulose transparent substrate,
Antiglare layer
An ultraviolet curable resin compound (A) comprising dipentaerythritol hexaacrylate (a) and other polyfunctional (meth) acrylate (a ′),
Organic fine particles (B) having an average particle diameter of 3 to 10 μm,
A photopolymerization initiator (C), and
One or more organic solvents that dissolve the triacetylcellulose transparent substrate (D)
An ultraviolet curable composition comprising a triacetyl cellulose transparent substrate, and then cured with ultraviolet light,
When the ultraviolet curable resin compound (A) is dissolved in the organic solvent (D), the viscosity is 5 to 10 mPa when measured at a liquid temperature of 25 wt. -The manufacturing method of the anti-glare film which is s. The production method according to claim 1, wherein the other polyfunctional (meth) acrylate (a ′) comprises hydroxypivalate neopentyl glycol diacrylate. The ultraviolet curable resin compound (A) contains 70 to 95% by weight of dipentaerythritol hexaacrylate,
5-30% by weight of at least one of hydroxypivalic acid neopentyl glycol diacrylate, tricyclodecane dimethylol diacrylate, and pentaerythritol triacrylate
The method for producing an antiglare film according to claim 1, wherein the antiglare film is contained. The anti-glare film manufactured with the manufacturing method of the anti-glare film in any one of Claims 1-3. 5. The antiglare film according to claim 4, which has optical properties of a total light transmittance of 85% or more and a haze value of 3.0 to 35.0%. The difference in refractive index between the ultraviolet curable resin compound (A) and the organic fine particles (B) is 0.02 or less, and
The antiglare film according to claim 4 or 5, wherein an internal haze value due to internal diffusion of the antiglare layer is less than 1.