JP2008081649A - Resin mixture composition curable by ionizing radiation and layered product using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which is excellent in coating solution stability, and corresponding to various optical controlling characteristics required in individual uses. <P>SOLUTION: The invention relates to the resin mixture composition which comprises (A) a group of resin compositions comprising 1-50% of a kind of translucent fine particles in a translucent resin, and (B) at least two kinds of resin compositions each selected from a group of resin compositions comprising 1-50% of different kind of translucent fine particles with refractive index different from the prescribed translucent fine particles in a translucent resin, and (C) a resin composition not including translucent fine particles, wherein the difference of the refractive indexes between the translucent fine particles and the translucent resin is less than 0.02 in the resin composition (A), and the difference of the refractive indexes between the translucent fine particles and the translucent resin is 0.03-0.10 in the resin composition (B). <P>COPYRIGHT: (C)2008,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 a resin mixture composition having good stability for providing an antiglare film provided on the surface for preventing reflection of images and reflection of light, and capable of adjusting to an arbitrary light control characteristic by mixing.

  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, it has been proposed to obtain an antiglare film by applying a translucent resin containing two or more translucent fine particles having different refractive indexes. (Patent No. 2990374) In order to obtain such an antiglare film, it is necessary to adjust the haze value by the effect of internal scattering and external scattering, and the mixing ratio of translucent fine particles and translucent resin, translucent fine particles and It is necessary to blend two or more kinds of translucent fine particles having different refractive index differences from the translucent resin and different particle sizes of the translucent fine particles. However, a paint containing two or more kinds of light-transmitting fine particles in the light-transmitting resin can provide only one type of anti-glare film having light control characteristics for a certain mixing ratio of light-transmitting fine particles. There is no problem. In addition, paints that contain two or more types of organic fine particles have the same settling speed due to the difference in specific gravity due to the difference in the material of the organic fine particles and the difference in weight due to the difference in particle size, and the uniformity of the paint is impaired. There is a problem that the nature is also bad. In addition, since organic and inorganic fine particles have different particle surface activities and treatments, they have different cohesiveness, making it difficult to obtain a uniform dispersion by the same method.

An object of the present invention is to provide a resin composition which is excellent in coating liquid stability and can cope with various optical control characteristics required for each application.
None.

  As a result of intensive studies in view of the above problems, the inventors of the present invention made a resin composition containing two or more kinds of translucent fine particles in the translucent resin, and these resin compositions were arbitrarily divided into two liquids. It has been found that these disadvantages can be eliminated by mixing the above, and the present invention has been completed.

That is, the present invention provides a resin composition (A) group containing 1 to 50% of one kind of light-transmitting fine particles in a light-transmitting resin, and a light-transmitting property having a refractive index different from that of the light-transmitting fine particles. Two or more resin compositions selected from the resin composition (B) group each containing 1 to 50% of each fine particle are blended, and further a resin composition (C) that does not contain translucent fine particles is blended. In the resin mixture composition, the difference in refractive index between the light-transmitting fine particles and the light-transmitting resin in the resin composition (A) is 0.02 or less, and in (B) The present invention relates to a resin mixture composition characterized in that the difference in refractive index between the light-transmitting fine particles and the light-transmitting resin is 0.03 to 0.10.
The present invention also relates to the above resin mixture composition, wherein the difference in refractive index between the translucent fine particles contained in each of the resin compositions (B) is 0.1 or more.
The present invention also relates to the above resin mixture composition, wherein the translucent resin is an ionizing radiation curable resin and has a refractive index of 1.49 to 1.53.
In the present invention, any one of the light-transmitting fine particles constituting the resin compositions (A) and (Bn) is an organic fine particle, and any one of the other resin compositions constituting (Bn) is contained. The translucent fine particles are inorganic fine particles, and the present invention relates to the above resin mixture composition.
Further, in the present invention, the organic fine particles have an average particle size of 0.1 to 10 μm, the inorganic fine particles are silicon dioxide particles, and the silicon dioxide particles have an average secondary particle size of 0.1 to 5 μm. It is related with the said resin mixing composition characterized by the above-mentioned.
Furthermore, this invention relates to the laminated body formed by apply | coating a resin mixed composition to a base film.
Furthermore, this invention relates to the said laminated body whose thickness of the said resin mixture composition layer is 1-20 micrometers.
In addition, this invention relates to the manufacturing method of the laminated body characterized by irradiating ionizing radiation after coating the said ionizing radiation curable resin mixed composition to a triacetyl cellulose transparent substrate.

  The present invention makes it possible to obtain a resin composition excellent in uniform dispersion of the coating liquid and having good coating liquid stability by dispersing only one type of translucent fine particles in the translucent resin. By blending two or more kinds of the resin composition, it is possible to arbitrarily adjust the haze light control characteristics required for various applications. Since the resin composition is applied onto a triacetylcellulose transparent substrate, the resin composition comprises a specific combination of ionizing radiation curable compound, organic fine particles, inorganic fine particles, a photoinitiator, and an organic solvent. Moreover, the laminate formed by curing the ionizing radiation curable resin composition on a triacetyl cellulose transparent substrate forms an antiglare layer in which a fine uneven shape is formed, and has excellent adhesion after a light resistance test, It can be used as an antiglare film having excellent coating film hardness such as scratch resistance and pencil hardness.

Hereinafter, preferred embodiments of the present invention will be described.
The reason why the difference in refractive index between the transparent fine particles contained in the resin composition (A) in the resin composition of the present invention and the light-transmitting resin is 0.02 or less is that the coating film is small because the refractive index of both is small. This is because it is possible to control the external cloud value due to the surface unevenness of the antiglare layer without affecting the transparency of the antiglare layer.

  The difference in refractive index between the translucent fine particles constituting the resin composition (B) and the translucent resin is set to 0.03 to 0.10, so that the internal cloud value of the antiglare layer can be controlled. Therefore, when the difference in refractive index is less than 0.03, the difference in refractive index between the two is too small, the internal cloud value cannot be obtained, and the light diffusion effect cannot be obtained. If the refractive index difference is larger than 0.1, the light diffusibility is too high and the entire film is whitened. Moreover, the difference in the refractive index of the light-transmitting fine particles contained in each of the resin compositions (B) is 0.1 or more when two or more types of resin compositions are mixed. The refractive index of the translucent fine particles can be regarded as the average value of the refractive index and the ratio of the translucent fine particles, and the fine refractive index can be set sufficiently depending on the mixing ratio of the translucent fine particles. Because you can. Further, since the difference in refractive index is 0.1 or more, the light diffusibility inside the coating film can be increased, and sufficient anti-glare property and at the same time obtaining an anti-glare film with good scintillation (glare). Because you can.

  Of the translucent fine particles, the average particle size of the organic fine particles is preferably 0.1 to 10 μm, and more preferably 2 to 6 μm. When the average particle size is less than 0.1 μm, the effect of scattering light is insufficient, and thus the obtained antiglare property is insufficient. When the average particle size exceeds 10 μm, the light diffusibility inside the antiglare layer decreases, so that scintillation ( ).

  Examples of organic fine particles include 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, phenols. Examples thereof include beads and polyurethane beads. The organic fine particles are preferably insoluble in water and organic solvents, and the shape may be indefinite or spherical. In particular, it is possible to synthesize fine particles with various refractive indexes (1.49-1.60) by arbitrarily adjusting the monomer ratio of styrene-acrylic beads, so the refractive index difference should be adjusted to the above numerical values. Is preferable because it is easy.

  Examples of the inorganic fine particles include silicon dioxide particles (refractive index: 1.46), titanium dioxide particles (refractive index: 2.3 to 2.7), zirconium oxide particles (refractive index: 2.05), and aluminum oxide particles. (Refractive index: 1.63) is increased. The inorganic fine particles usually have a refractive index of the translucent resin of 1.49 to 1.53, and the organic fine particles have a refractive index of usually 1.35 to 1.65, so that silicon dioxide particles (refractive index: 1.46) is preferable because it is easy to adjust the refractive index difference described in the claims.

  These inorganic fine particles preferably have an average secondary particle size of 0.1 to 5 μm from the viewpoint of maximizing the antiglare effect and improving transparency. When the thickness is 0.1 μm or less, the resulting antiglare film has a high surface gloss and an antiglare effect cannot be obtained. Furthermore, it is preferably 0.3 to 3 μm. The particle size was measured using a Coulter Multisizer (Beckman Coulter, Inc.) and an aperture size of 30 μm.

  Moreover, the addition amount of these translucent fine particles is preferably 1 to 50% by weight, and more preferably 5 to 30% by weight with respect to the total amount of the ionizing radiation curable resin composition. If it is less than 1% by weight, sufficient antiglare property cannot be obtained, and the light control characteristics of the haze value required for various applications cannot be adjusted. When it exceeds 50% by weight, it is possible to adjust the light control characteristics of the haze value required for various applications, but the fluidity of the resin composition is remarkably lowered and the workability is very high because the viscosity is increased. In addition, since the fine particles are easily aggregated, gelation occurs and the stability of the resin composition is impaired.

  The dispersion of the above-mentioned translucent fine particles is achieved by ordinary means until the composition becomes sufficiently uniform, and there are no particular restrictions on the disperser used for dispersion, for example, a kneader, roll mill, attritor, super mill. , Known dispersers such as a dissolver, a homomixer, and a sand mill.

  The ionizing radiation curable resin in the present invention functions as a binder for forming an antiglare layer by being polymerized and cured by ionizing radiation with a compound having an ethylenically unsaturated double bond, and is used for the surface of an image display device to be scratch resistant. And surface hardness are preferred, and those which impart hard coat properties to the antiglare layer are preferred. For example, hexanediol (meth) acrylate, 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, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO modified tri Methylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, potassium Lolactone-modified tris (acryloxyethyl) isocyanurate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, alkyl-modified di Pentaerythritol tri (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetra ( (Meth) acrylate, polyurethane polyacrylate, polyester polyacrylate and other polyhydric alcohols and (meth) acrylic acid Tellurium compounds: Polyurethane poly (meth) acrylate, polyester poly (meth) acrylate, polyether poly (meth) acrylate, polyacryl poly (meth) acrylate, polyalkyd poly (meth) acrylate, polyepoxy poly (meth) acrylate, police Polyfunctional (meth) acrylate compounds such as pyroacetal poly (meth) acrylate, polybutadiene poly (meth) acrylate, polythiol polyene poly (meth) acrylate, and polysilicon poly (meth) acrylate; 1,4-divinylbenzene, 4 -Vinylbenzoic acid-2-acryloylethyl ester, vinylbenzene such as 1,4-divinylcyclohexane and derivatives thereof; vinylsulfone compounds such as divinylsulfone; methylbisacrylamide, etc. (Meth) acrylamide compounds: bis (4-methacryloylthiophenyl) sulfide, bisphenoxyethanol full orange acrylate, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether, tetrabylomobisphenol A diepoxy Examples include so-called high refractive index monomers such as acrylate.

  Among these compounds having an ethylenically unsaturated double bond, from the viewpoint of coating strength and scratch resistance, poly (meth) acrylates such as polyurethane poly (meth) acrylates and polyepoxy poly (meth) acrylates having at least three functional groups (Meth) acrylates and polyfunctional acrylates having 3 or more acryloyl groups in the molecule can be preferably used. Polyepoxy poly (meth) acrylate is an epoxy resin whose ester group is esterified with (meth) acrylic acid and whose functional group is (meth) acryloyl group, and (meth) acrylic acid addition to bisphenol A type epoxy resin Products, (meth) acrylic acid addition products to novolac type epoxy resins, and the like.

  The polyurethane poly (meth) acrylate is obtained by reacting, for example, a diisocyanate and a (meth) acrylate having a hydroxyl group, or an isocyanate group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate under an excess of isocyanate groups. Some are obtained by reacting polymers with (meth) acrylates having a hydroxyl group. Alternatively, a hydroxyl group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate under hydroxyl-excess conditions can be obtained by reacting with a (meth) acrylate having an isocyanate group.

  Examples of polyols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentane glycol, neopentyl glycol, hexanetriol, trimellilol propane, polytetra Examples include methylene glycol and a condensation polymer of adipic acid and ethylene glycol.

  Examples of the polyisocyanate include tolylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate. Examples of (meth) acrylates having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and ditrimethylolpropane tetraacrylate. . Examples of (meth) acrylates having an isocyanate group include 2-methacryloyloxyethyl isocyanate and methacryloyl isocyanate.

  Specific examples of the polyfunctional group having three or more acryloyl groups in the molecule include the above-described polyhydric alcohol and acrylic acid ester compounds, and a single compound or a mixture of two or more compounds is preferable. As these compounds having an ethylenically unsaturated double bond, in particular, pentaerythritol tetraacrylate having 3 to 4 acryloyl groups in one molecule and very good wettability with a triacetyl cellulose film Pentaerythritol triacrylate and polyurethane poly (meth) acrylate having at least 5 functional groups are preferred.

  When the resin composition of the present invention is cured with radiation, a photopolymerization initiator is usually added. The type of the photopolymerization initiator is not particularly limited, and examples thereof include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, and thioxanthones. Specifically, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, diethoxyacetophenone, gendyl dimethyl ketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, benzophenone, 2 , 4,6-trimethylbenzoin diphenylphosphine oxide, Michler's ketone, isoamyl N, N-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, and the like. It can also be used together as appropriate. Examples of the photosensitizer include n-butylamine, triethylamine, triethanolamine, poly-n-brylphosphine, and the like. Two or more of these photosensitizers can be used in combination as appropriate.

Furthermore, an organic solvent may be included in order to adjust the viscosity of the resin composition and to improve the stability.
Examples of the organic solvent include aromatic solvents such as toluene and xylene; alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, and propylene glycol monomethyl ether. Solvent; ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol dimethyl ether , Glycol ethers such as ethylene glycol diethyl ether, diethylene glycol dimethyl ether, propylene glycol methyl ether; 2-methoxyethyl Glycol ether esters such as cetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, propylene glycol methyl ether acetate; chlorinated solvents such as chloroform, dichloromethane, trichloromethane, methylene chloride; tetrahydrofuran, diethyl ether, 1, Ether solvents such as 4-dioxane and 1,3-dioxolane; N-methylpyrrolidone, dimethylformamide, dimethylsulfoxide, dimethylacetamide and the like can be used alone or in combination. By mixing these solvents having different specific gravities, the specific gravity of the resin composition can be adjusted close to the specific gravity of the organic fine particles, and the precipitation and floating of the organic fine particles can be alleviated.

  When coating on the triacetylcellulose transparent substrate of the present invention, the adhesion of the coating film is a combination of an organic solvent that dissolves or swells the triacetylcellulose transparent substrate and a solvent that does not dissolve or swell the triacetylcellulose transparent substrate. In view of the above, it is advantageous to use a solvent having a large specific gravity difference in terms of adjusting the specific gravity of the resin composition. As the solvent, 1.3-dioxolane (specific gravity 1.06) that dissolves or expands the triacetylcellulose transparent base material and toluene (specific gravity 0.867) that does not dissolve or expand the triacetylcellulose transparent base material are applied. It is particularly preferable from the viewpoint of coating suitability such as evaporation rate.

  Furthermore, a dispersing agent may be included in order to disperse the translucent fine particles uniformly and stably in the resin composition. As the dispersant, a resin-type dispersant, a dispersant having an anionic polar group, or the like can be used. Examples of the resin-type pigment dispersant include Solsperse 24000 (manufactured by Zeneca Corporation), ASSY PB821 (Ajinomoto), Disperbyk-160, Disperbyk-161, Disperbyk-162, Disperbyk-163, Disperbyk-170 (manufactured by BYK Chemie), etc. Is mentioned. Specific examples of the dispersant having an anionic polar group include products supplied by Big Chemie Japan under the trade name of Dispersic, namely Disperbyk-111, Disperbyk-110, Disperbyk-116, Disperbyk-140. , Disperbyk -161, Disperbyk -162, Disperbyk -163, Disperbyk -164, Disperbyk -168, Disperbyk -170, Disperbyk -171, Disperbyk -174, Disperbyk -180, Disperbyk -182 etc. Although what is used can also be used, it is not specifically limited.

  The resin composition of the present invention can further contain a solvent-drying resin, a leveling agent, a thixotropic agent, and the like. Solvent-drying resins are mainly thermoplastic resins such as senol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea cocondensation resin, Silicon resin, polysiloxane resin or the like is used.

  When coating on the triacetylcellulose transparent substrate of the present invention, nitrocellulose, acetylcellulose, cellulose acetate propionate, and ethylhydroxyethylcellulose resin are advantageous in terms of adhesion and transparency of the coating film.

  As the base film in the present invention, a triacetyl cellulose film, a polyethylene terephthalate film, a diacetylene cellulose film, an acetate butyrate cellulose film, a polyether sulfone film, a polyacrylic resin film, a polyurethane resin film, a polyester film, and a polycarbonate film , Polysulfone film, polyether film, polymethylpentene film, polyether ketone film, (meth) acrylonitrile film, etc. can be used, but are not particularly limited to these films, and from among known transparent plastic films It can be selected and used as appropriate.

  A compound prepared by casting a triacetyl cellulose dope prepared by dissolving triacetyl cellulose in a solvent from the aspect of optical properties by either a single layer casting method or a multiple layer co-casting method. It is particularly desirable to use a triacetyl cellulose film having no refraction. 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 laminate of the present invention comprises two or more ionizing radiation curable resin compositions in which only one type of translucent fine particles is dispersed on a triacetyl cellulose transparent substrate and an ionizing radiation curable resin composition not containing translucent fine particles. After the application of the resin mixture composition blended with, ionizing radiation curing.

  In the present invention, the ionizing radiation curable mixed resin composition is coated on a triacetyl cellulose transparent substrate to form a laminate, and the ionizing radiation curable resin mixed composition is bar coated, blade coated, spin coated, and reverse coated. After coating on the base film substrate by coating methods such as diting, spray coating, roll coating, gravure coating, micro gravure coating, lip coating, air knife coating, dipping method, etc., the solvent is dried if necessary, Further, it is formed by crosslinking and curing the applied ionizing radiation curable resin mixed composition by irradiating with ionizing radiation. Examples of the ionizing radiation curing include ultraviolet ray curing, electron beam curing, visible light curing, X-ray curing, γ-ray curing, and active energy ray curing.

  For example, 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 size of the light-transmitting fine particles to be used, but is usually 1 to 20 μm, preferably Is 3-7 μm thick.

  As a method for further improving the contrast and white blur of the screen display on the surface of the fine unevenness of the antiglare layer obtained by curing the ionizing radiation curable resin mixed composition in the present invention on a transparent substrate such as triacetyl cellulose. A low refractive index layer having a lower refractive index than that of the antiglare layer can be provided. 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 and 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 an optical characteristic of 3.0 to 55.0%, and has an optical characteristic of a total light transmittance of 90% or more and a haze value of 4.0 to 45.0%. 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 55.0%, white blur tends to occur, such being undesirable.

  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 partially saponified film or the like, which is stretched by adsorbing iodine or a dye, etc., 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.

[Example]
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]
100 parts of pentaerythritol tetraacrylate (manufactured by Toagosei Co., Ltd.) are dissolved in 37.5 parts of toluene, 5 parts of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Geigy) is added, and the mixture is stirred at 2000 rpm with a high speed disper for 5 minutes. did.
Furthermore, a crosslinked polystyrene-methyl methacrylate bead (manufactured by Sekisui Chemical Co., Ltd.) having an average particle size of 3.5 μm and a refractive index of 1.53 was added to this solution, and the mixture was stirred at 2000 rpm for 15 minutes with a high-speed disper, with a nonvolatile content of 80%. An ionizing radiation curable resin composition (A) was prepared.

[Formulation Example 2]
100 parts of pentaerythritol tetraacrylate (manufactured by Toagosei Co., Ltd.) are dissolved in 25 parts of toluene and 75 parts of 1,3-dioxolane, and 5 parts of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Geigy Corporation) is added. For 5 minutes at 2000 rpm.
Further, crosslinked polystyrene beads having an average particle size of 3.5 μm and a refractive index of 1.59 (manufactured by Sekisui Chemical Co., Ltd.) were added to this solution, and the mixture was stirred with a high speed disper at 2000 rpm for 15 minutes, and ionizing radiation curable having a nonvolatile content of 60%. A resin composition (B1) was prepared.

[Composition Example 3]
100 parts of pentaerythritol tetraacrylate (manufactured by Toagosei Co., Ltd.) are dissolved in 25 parts of toluene and 75 parts of 1,3-dioxolane, and 5 parts of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Geigy Corporation) is added. For 5 minutes at 2000 rpm. Furthermore, 0.45 part of a dispersant (BYK111, manufactured by Big Chemie) was added to this solution, and 45 parts of silicon dioxide particles (average particle diameter 2.1 μm, refractive index 1.46 of secondary particles) were added. The mixture was stirred for 30 minutes at 4000 rpm with a high speed disper to prepare an ionizing radiation curable resin composition (B2) having a nonvolatile content of 60%.

[Formulation Example 4]
100 parts of pentaerythritol tetraacrylate (manufactured by Toagosei Co., Ltd.) are dissolved in 17.5 parts of toluene and 52.5 parts of 1,3-dioxolane, and further 5 parts of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Geigy). In addition, the mixture was stirred with a high speed disper at 2000 rpm for 5 minutes to prepare an ionizing radiation curable resin composition (C) having a nonvolatile content of 60%.
Table 1 shows a summary of Formulation Examples 1 to 4.

[Examples 1-2]
Ionizing radiation curable resin mixed compositions were prepared by the method shown in [Composition Examples 1 to 4]. None of the ionizing radiation curable resin compositions had precipitates of beads even after 7 days, and was excellent in coating solution stability. These ionizing radiation curable resin compositions were mixed in the blending amounts shown in Table 2 to prepare ionizing radiation curable resin mixed compositions (1) to (2) having a nonvolatile content of 50%. Ionizing radiation curable resin mixed compositions (1) to (2) were applied to an 80 μm thick triacetylcellulose film (Fuji Photo Film Co., Ltd.) with a bar coater and dried at 70 ° C. to 1 minute. Thereafter, the coating layer is 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% by weight or less by nitrogen purge to form an antiglare layer having a thickness of 5.5 μm. Formed. The obtained antiglare film was able to obtain antiglare films having various haze light control characteristics as shown in Table 2.

[Comparative Example 1]
37.62 parts of pentaerythritol tetraacrylate (manufactured by Toagosei Co., Ltd.) are dissolved in 35 parts of toluene and 15 parts of 1,3-dioxolane, and 1.88 parts of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Geigy). In addition, the mixture was stirred with a high speed disper at 2000 rpm for 5 minutes. Furthermore, 7.5 parts of a crosslinked polystyrene-methyl methacrylate bead (manufactured by Sekisui Chemical Co., Ltd.) having an average particle size of 3.5 μm and a refractive index of 1.53 and an average particle size of 3.5 μm and a refractive index of 1.59 were added to this solution. Three parts of cross-linked polystyrene beads (manufactured by Sekisui Chemical Co., Ltd.) were added, and the mixture was stirred with a high-speed disper at 2000 rpm for 15 minutes to prepare an ionizing radiation curable resin mixed composition (3) having a nonvolatile content of 50%.

[Comparative Example 2]
37.62 parts of pentaerythritol tetraacrylate (manufactured by Toagosei Co., Ltd.) are dissolved in 35 parts of toluene and 15 parts of 1,3-dioxolane, and 1.88 parts of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Geigy). In addition, the mixture was stirred with a high speed disper at 2000 rpm for 5 minutes. Furthermore, 0.45 part of a dispersant (BYK111, manufactured by Big Chemie) was added to this solution, and 4.5 parts of silicon dioxide particles (manufactured by Tosoh Silica) having an average secondary particle diameter of 2.1 μm and a refractive index of 1.46. The mixture was stirred for 30 minutes at 4000 rpm with a high-speed disper, and further 5 parts of crosslinked polystyrene beads having an average particle diameter of 3.5 μm and a refractive index of 1.59 (manufactured by Sekisui Chemical Co., Ltd.) were added. The mixture was stirred to prepare an ionizing radiation curable resin mixed composition (4) having a nonvolatile content of 50%.

  As in Examples 1 and 2, the ionizing radiation curable resin mixed compositions (3) to (4) were applied and cured to form an antiglare layer. The evaluation results of the obtained antiglare film are shown in Table 3. Although the same light control characteristics as those of Examples 1 and 2 were obtained, beads were precipitated in the coating solution after 1 day.

(1) Coating liquid stability: The resin composition was allowed to stand at 25 ° C., and the presence or absence of bead precipitation after 7 days was visually determined.
(2) Viscosity: Measured using an EL type viscometer. (At 25 ° C)
(3) Nonvolatile content: Nonvolatile content after drying in a hot air oven at 120 ° C. for 20 minutes is measured.
(4) Total light transmittance: The light transmittance was measured using a haze meter NDH-2000 (manufactured by Nippon Denshoku).
(5) Haze value: The haze value was measured using a haze meter NDH-2000 (manufactured by Nippon Denshoku).
(6) Internal haze value: Resin mixed composition solution containing no translucent fine particles on the antiglare layer (solution obtained by removing translucent fine particles from the resin mixed composition used when creating the antiglare layer) Was applied using a bar coater # 10 and dried in an electric oven at 100 ° C. for 1 minute. Thereafter, a nitrogen purge is performed to irradiate 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 to create a coating film without surface irregularities. The haze of the coating film was measured by the same method as (3).

(6) Antiglare property: An exposed fluorescent lamp without a 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)
(7) White blur: The antiglare film was bonded to the surface of the liquid crystal display using a transparent adhesive to display black, and the blackness was visually determined.

○: White blur is suppressed and there is black △: Some white blur is present ×: There is white blur and the screen is whitened

Claims (8)

  Each of the resin composition (A) group containing 1 to 50% of one kind of light-transmitting fine particles in the light-transmitting resin and each of the light-transmitting fine particles having a refractive index different from that of the light-transmitting fine particles described above. Two or more resin compositions selected from the resin composition (B) group containing 1 to 50% of each species are blended, and further a resin composition (C) that does not contain translucent fine particles is blended. In the resin mixture composition characterized in that the difference in refractive index between the translucent fine particles and the translucent resin in the resin composition (A) is 0.02 or less, and the translucent fine particles in (B) A resin mixed composition having a refractive index difference of 0.03 to 0.10 with respect to a light-transmitting resin.   The resin mixture composition according to claim 1, wherein a difference in refractive index between the translucent fine particles contained in each of the resin compositions (B) is 0.1 or more.   3. The resin mixture composition according to claim 1, wherein the translucent resin is an ionizing radiation curable resin and has a refractive index of 1.49 to 1.53.   Any of the translucent fine particles constituting the resin compositions (A) and (Bn) are organic fine particles, and the translucent fine particles contained in any one of the other resin compositions constituting (Bn) The resin mixture composition according to any one of claims 1 to 3, wherein the resin mixture composition is inorganic fine particles.   The organic fine particles have an average particle size of 0.1 to 10 μm, the inorganic fine particles are silicon dioxide particles, and the silicon dioxide particles have an average secondary particle size of 0.1 to 5 μm. The resin mixed composition according to any one of claims 1 to 4. The laminated body formed by apply | coating the resin mixed composition in any one of Claims 1-5 to a base film. The laminate according to claim 6, wherein the resin mixture composition layer has a thickness of 1 to 20 μm. The method for producing a laminate according to claim 6 or 7, wherein the ionizing radiation curable resin mixed composition according to any one of claims 1 to 7 is applied to a triacetyl cellulose transparent substrate and then irradiated with ionizing radiation.