JP2011186287A - Antiglare film and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antiglare film that has few discoloration phenomenon (white blurring) when an illumination lamp, such as a fluorescent lamp, is reflected on the surface of the side provided with an antiglare layer while having moderate antiglare properties without generating highly technological subject in quality and which has high scratch resistance. <P>SOLUTION: The antiglare film 1 is obtained by laminating the antiglare layer 12 including a binder matrix 121 and particles 12A on a transparent substrate 11, wherein a value (r<SB>A</SB>/H) obtained by dividing an average particle size (r<SB>A</SB>) of the particles by an average film thickness (H) of the antiglare layer is in the range of 0.20-0.90, and the binder matrix includes a resin curable by heat and ionizing radiation. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an antiglare film provided on the surface of a window or a display. In particular, the present invention relates to an antiglare film provided on the surface of a display such as a liquid crystal display (LCD), a CRT display, an organic electroluminescence display (ELD), a plasma display (PDP), a surface electric field display (SED), or a field emission display (FED). .

  In displays such as liquid crystal displays, CRT displays, EL displays, and plasma displays, an anti-glare film having a concavo-convex structure on the surface is displayed in order to prevent deterioration in visibility due to external light being reflected on the display surface during viewing. It is known to provide on the surface.

As the antiglare film, for example, the following techniques are known.
・ Technology to form an uneven structure on the surface of the anti-glare film by embossing method ・ Apply a coating liquid in which particles are mixed in the binder matrix forming material, and disperse the particles in the binder matrix. Technology for forming the concavo-convex structure In the antiglare film having the concavo-convex structure formed in this way on the surface, the external light entering the antiglare film is scattered by the surface concavo-convex structure, and the image of the external light becomes unclear, It becomes possible to prevent a decrease in visibility due to the transfer of external light to the display surface.

  Here, the anti-glare film in which unevenness is formed on the surface by embossing can completely control the unevenness on the surface. Therefore, reproducibility is good. However, if there is a defect or foreign matter adhesion on the embossing roll, there is a problem that a defect is generated at the roll pitch.

  On the other hand, the antiglare film using the binder matrix and particles has fewer steps than the antiglare film using the embossing. Therefore, it can be manufactured at low cost. Therefore, various modes of antiglare films in which particles are dispersed in a binder matrix are known (Patent Document 1).

Various techniques are disclosed for an antiglare film using a binder matrix and particles. For example, the following techniques are disclosed.
A technology that uses a binder matrix resin, spherical particles, and amorphous particles in combination (Patent Document 2).
A technique using a binder matrix resin and a plurality of particles having different particle diameters (Patent Document 3).
-A technology that has surface irregularities and defines the cross-sectional area of the recesses (Patent Document 4).

The following techniques are also disclosed.
-A technique that uses both internal scattering and surface scattering to make the antiglare layer have an internal haze (cloudiness) of 1 to 15% and a surface haze (cloudiness) of 7 to 30% (Patent Document 5).
A technique in which a binder resin and particles having a particle size of 0.5 to 5 μm are used, and the difference in refractive index between the resin and the particles is 0.02 to 0.2 (Patent Document 6).
A technique in which a binder resin and particles having a particle diameter of 1 to 5 μm are used, and the refractive index difference between the resin and the particles is 0.05 to 0.15 Furthermore, the technique which makes the solvent to be used, surface roughness, etc. into the predetermined range (patent document 7).
A technique that uses a binder resin and a plurality of particles and sets the difference in refractive index between the resin and the particles to 0.03 to 0.2 (Patent Document 8).
・ In addition, for the purpose of reducing contrast reduction and hue change when the viewing angle is changed, surface haze (cloudiness) is 3 or more, haze value in normal direction and haze value in ± 60 ° direction A technique in which the difference is 4 or less (Patent Document 9).

Thus, the anti-glare film of various structures is disclosed for various purposes. Recently, especially for TV applications, it is preferred that the anti-glare film is less likely to turn white when an illumination such as a fluorescent lamp is reflected on the surface with the anti-glare layer in a living room. Tend. The following technique is disclosed as such a solution.
A technique for preventing white blurring by a gentle uneven shape by agglomerating relatively small particles with respect to the film thickness into a Benard cell structure (Patent Document 10).

  Patent Document 10 has a problem that white blur can be significantly improved by gentle unevenness, but the antiglare property is insufficient due to the gentleness. In addition, it has been difficult to precisely control the aggregation of particles having a Benard cell structure, which has a high quality technical problem that uneven drying tends to occur.

JP-A-6-18706 JP 2003-260748 A JP 2004-004777 A JP 2003-004903 A Japanese Patent Laid-Open No. 11-305010 JP 11-326608 A JP 2000-338310 A JP 2000-180611 A JP-A-11-160505 Japanese Patent Application No. 2009-75621

  In the present invention, when an illumination such as a fluorescent lamp is reflected on the surface on the side provided with the anti-glare layer while having an appropriate anti-glare property without generating a high quality technical problem. It is an object of the present invention to provide an antiglare film that has less anti-glare film whitening phenomenon (white blur) and high scratch resistance.

  In order to solve the above problems, the invention according to claim 1 is an antiglare film in which an antiglare layer containing a binder matrix and particles is laminated on a transparent substrate, and the average particle diameter (r ) Divided by the average film thickness (H) of the antiglare layer (r / H) is in the range of 0.20 to 0.90, and the binder matrix is cured by heat and ionizing radiation. It is the anti-glare film characterized by including resin to do.

  The invention according to claim 2 is characterized in that the resin cured by the heat and ionizing radiation is a mixture of different thermosetting materials and ionizing radiation curable materials, respectively. It is a film.

  The invention according to claim 3 is characterized in that the resin curable by heat and ionizing radiation is a resin having a thermosetting part and a curable part by ionizing radiation. It is a film.

  According to a fourth aspect of the present invention, there is provided a method for producing the antiglare film, wherein the binder matrix is formed on one surface of the transparent substrate that is continuously conveyed, the resin being cured by heat and ionizing radiation. A step of applying a material, a coating liquid containing particles and a solvent on a transparent substrate, and drying and heating the coating liquid applied on the transparent substrate to cure the thermosetting material or the thermosetting part. A step of irradiating with ionizing radiation to cure the ionizing radiation curable material or a curable site by ionizing radiation. 4. The antiglare film according to claim 1, comprising: It is a manufacturing method.

  The invention according to claim 5 is the method for manufacturing the antiglare film, wherein the binder matrix is formed on one surface of the transparent substrate that is continuously transported and contains a resin that is cured by heat and ionizing radiation. A step of applying a material, a coating liquid containing particles and a solvent on a transparent substrate, and drying and heating the coating liquid applied on the transparent substrate to cure the thermosetting material or the thermosetting part. The method includes: a step of irradiating with ionizing radiation to cure the ionizing radiation curable material or a curable portion by ionizing radiation; and further, a step of promoting thermal curing by heating. 4. The method for producing an antiglare film according to any one of 3 above.

  Moreover, as invention which concerns on Claim 6, as for the glare-proof film in any one of Claims 1 thru | or 3, and a polarizing layer on the surface on the opposite side to the glare-proof layer formation surface of the transparent base material of the said glare-proof film, A polarizing plate comprising a transparent substrate.

  The invention according to claim 7 includes, in order from the observer side, the polarizing plate according to claim 6, the liquid crystal cell, the polarizing plate, and the backlight unit in this order, and the antiglare layer is the surface on the observer side. The liquid crystal display is characterized by the above.

  By setting it as the anti-glare film of the said structure, according to invention of Claim 1, it has an anti-glare layer, having favorable anti-glare property, without generating a quality advanced technical subject. When an illumination such as a fluorescent lamp is reflected on the surface on the side, it is possible to obtain an antiglare film with less anti-glare film (white blur).

  According to the invention described in claim 2, various combinations of thermosetting materials and ionizing radiation curable materials can be used when the effects of the invention described in claim 1 are manifested. Moreover, it becomes easy to give effects other than the effect of the invention of Claim 1 by this.

  Further, according to the invention described in claim 3, when the effect of the invention described in claim 1 is manifested, as compared with claim 2, local phase separation between the thermosetting material and the ionizing radiation curable material is achieved. The hardness of the antiglare film can be increased.

  Moreover, according to the invention of Claim 4, the anti-glare film which has the effect of the invention of any one of Claims 1 thru | or 3 can be manufactured in low cost and in large quantities.

  According to the invention described in claim 5, in addition to the invention described in claim 4, not only the initial mechanical strength of the antiglare film but also an antiglare film having weather resistance can be produced.

  In addition, according to the invention described in claim 6, the antiglare film turns white when illumination such as a fluorescent lamp is reflected on the surface on the side provided with the antiglare layer while having good antiglare property. A polarizing plate with less (white blur) can be obtained.

  In addition, according to the invention described in claim 7, the anti-glare film is whitened when illumination such as a fluorescent lamp is reflected on the surface having the anti-glare layer while having good anti-glare property. A liquid crystal display with less (white blur) can be obtained, and a liquid crystal display with high visibility can be obtained. Moreover, since it has sufficient surface hardness, the damage of the display surface in the manufacturing process of a liquid crystal display can be prevented, and the yield fall can be prevented.

It is a cross-sectional schematic diagram of the anti-glare film of one Example of this invention. It is a liquid crystal display using the anti-glare film of one Example of this invention. It is a schematic diagram of the manufacturing process of one Example of this invention.

  The antiglare film of the present invention will be described.

  The cross-sectional schematic diagram of the anti-glare film of this invention was shown in FIG. The antiglare film (1) of the present invention comprises an antiglare layer (12) on a transparent substrate (11). The antiglare layer (12) of the antiglare film (1) of the present invention comprises a binder matrix (120) and particles (121). Moreover, the manufacturing process of the anti-glare film of this invention was shown in FIG.

  In the present invention, the binder matrix forming material includes an ionizing radiation curable material and a thermosetting material, and / or a material having a thermosetting part and a curable part by ionizing radiation in one molecule. Features.

  A case where the binder matrix forming material does not include a thermosetting material and a material having a thermosetting site and a curing site by ionizing radiation in one molecule will be described. As the ionizing radiation curable material, an ultraviolet curable material is particularly used. When the ultraviolet curable material is cured with ultraviolet rays, the surface specifically proceeds while the oxygen concentration is low. That is, the surface cure shrinkage tends to proceed.

  In the production of an antiglare film containing a binder matrix and particles, when the surface shrinkage occurs, surface irregularities different from the surface irregularities formed by the intended particles are formed, and white blurring is formed. It becomes an anti-glare film with a lot of feeling. Possible methods for preventing surface cure shrinkage include (a) increasing the viscosity of the antiglare layer-forming material when irradiated with ultraviolet rays, or (b) inhibiting the progress of surface curing by irradiating ultraviolet rays under high-concentration oxygen. . However, in the method (a), the viscosity of the antiglare layer-forming material at the time of coating increases, the coating suitability deteriorates, and the manufacturing suitability of the antiglare film deteriorates. In the method (b), since surface hardening due to oxygen inhibition does not easily proceed, it is not possible to obtain sufficient surface hardness as an antiglare film.

  An antiglare layer at the time of application by containing an ionizing radiation curable material and a thermosetting material in the binder matrix forming material and / or containing a material having a thermosetting part and a curable part by ionizing radiation in one molecule. Without increasing the viscosity of the forming material, thermosetting of the antiglare layer forming material before irradiation with ultraviolet rays, a material having a thermosetting part in one molecule and a hardening part by ionizing radiation in one molecule Can do. At this time, unlike ultraviolet irradiation curing, specific curing of the surface is difficult to occur. Moreover, the hardening in this case should just increase the viscosity of a glare-proof layer forming material, and does not need to carry out the thermosetting reaction of all thermosetting materials and a thermosetting part.

  Along with the heat curing, the viscosity of the antiglare layer forming material can be increased upon irradiation with ultraviolet rays. Further, by irradiation with ultraviolet rays, an ionizing radiation curable material, a thermosetting portion in one molecule and a curable portion due to ionizing radiation. Can be cured. Thereby, formation of surface unevenness other than the surface unevenness intended for the design can be suppressed, and an antiglare film having a sufficient surface hardness and less white blur can be obtained. In addition, in consideration of surface curing by heat curing, ultraviolet irradiation may be performed under high concentration oxygen. Further, after the ultraviolet irradiation, heating may be further performed to promote thermosetting of the thermosetting material and the thermosetting portion. In addition, a molecule having a hydroxyl group may be required for thermosetting, and is not particularly limited, and includes an ionizing radiation curable material and a thermosetting material, and / or a thermosetting site in one molecule. A material having a curable site by ionizing radiation may have a hydroxyl group.

  In the antiglare film of the present invention, the binder matrix refers to a component excluding particles among the components contained in the antiglare layer. The antiglare film of the present invention is formed by applying a coating liquid for forming an antiglare layer on a transparent substrate. The binder matrix forming material of the present invention is a solid of the coating liquid for forming an antiglare layer. This refers to the minute minus the particles. Therefore, the binder matrix forming material includes an ionizing radiation curable material and a thermosetting material as required, and / or in addition to a material having a thermosetting part and a curable part by ionizing radiation in one molecule. Additives such as photopolymerization initiators and surface conditioners, thermoplastic resins and the like are included.

  In the antiglare film of the present invention, the value (r / H) obtained by dividing the average particle diameter (r) of the particles by the average film thickness (H) of the antiglare layer is 0.20 or more and 0.90. It is characterized by being within the following range.

  The antiglare film is provided with an uneven structure on the surface of the antiglare layer, thereby scattering external light incident on the surface of the antiglare film and blurring an image of the external light reflected on the surface of the antiglare film. When the antiglare layer comprises a binder matrix and particles, the unevenness on the surface of the antiglare layer, which is intended for the design, is formed by the presence of single particles or a plurality of aggregated particles in the binder matrix.

  However, if the degree of the uneven structure on the surface of the anti-glare film intended for design is made too small, the external light cannot be sufficiently scattered on the surface of the anti-glare film, that is, an appropriate anti-glare property cannot be obtained and is increased. If too much, external light will be excessively scattered on the surface of the anti-glare film, that is, when a light such as a fluorescent light is incident on the surface of the anti-glare film as external light, Become.

  In an anti-glare film, a moderate anti-glare property and no white blur are in a trade-off relationship, and both are compatible. With the binder matrix forming material of the present invention, excessive scattering on the surface of the antiglare film of external light can be suppressed by preventing formation of surface irregularities that are not intended for the design. However, when the value (r / H) obtained by dividing the average particle diameter (r) of the particles by the average film thickness (H) of the antiglare layer is larger than 0.9, the surface unevenness intended for the design becomes excessive, and the The glare is too strong and white blurring becomes large. Further, when the r / H is smaller than 0.2, the surface unevenness intended for the design cannot be formed. The value (r / H) obtained by dividing the average particle diameter (r) of the particles by the average film thickness (H) of the antiglare layer is more preferably 0.4 or more and 0.7 or less.

  Further, the average particle diameter (r) of the particles used in the present invention can be determined by a light scattering type particle size distribution measuring apparatus. Moreover, in this invention, the average film thickness (H) of a glare-proof layer is an average value of the film thickness of a glare-proof layer with surface unevenness | corrugation. The average film thickness can be determined by an electronic micrometer or a fully automatic fine shape measuring instrument.

  The antiglare film of the present invention is provided with a functional layer having antireflection performance, antistatic performance, antifouling performance, electromagnetic wave shielding performance, infrared absorption performance, ultraviolet absorption performance, color correction performance, and the like as necessary. Examples of these functional layers include an antireflection layer, an antistatic layer, an antifouling layer, an electromagnetic wave shielding layer, an infrared absorption layer, an ultraviolet absorption layer, and a color correction layer. These functional layers may be a single layer or a plurality of layers. The functional layer may have a plurality of functions as a single layer, such as an antireflection layer having antifouling performance. In addition, these functional layers may be provided between the transparent substrate and the antiglare layer, or may be provided on the antiglare layer. In the present invention, a primer layer, an adhesive layer, or the like may be provided between each layer in order to improve adhesion between various layers.

  FIG. 2 shows a liquid crystal display using the antiglare film of the present invention. The liquid crystal display of FIG. 2 includes an antiglare film (1), a polarizing plate (2), a liquid crystal cell (3), a polarizing plate (4), and a backlight unit (5) in this order. At this time, the antiglare film (1) side becomes the observation side, that is, the display surface.

  The backlight unit (5) includes a light source and a light diffusing plate. The liquid crystal cell has a structure in which an electrode is provided on one transparent substrate, an electrode and a color filter are provided on the other transparent substrate, and liquid crystal is sealed between both electrodes. The polarizing plate provided so as to sandwich the liquid crystal cell (3) has a structure in which the polarizing layer (23, 43) is sandwiched between the transparent base materials (21, 22, 41, 42).

  Moreover, in the liquid crystal display of this invention, you may provide another functional member. Other functional members include, for example, a diffusion film, a prism sheet, a brightness enhancement film for effectively using light emitted from a backlight, and a phase difference film for compensating for a phase difference between a liquid crystal cell and a polarizing plate. However, the transmissive liquid crystal display of the present invention is not limited to these.

  As the transparent substrate used in the present invention, glass, plastic film or the like can be used. The plastic film only needs to have appropriate transparency and mechanical strength. For example, polyethylene terephthalate (PET), triacetyl cellulose (TAC), diacetyl cellulose, acetyl cellulose butyrate, polyethylene naphthalate (PEN), cycloolefin polymer, polyimide, polyethersulfone (PES), polymethyl methacrylate (PMMA), A film such as polycarbonate (PC) can be used. Among them, a triacetyl cellulose film can be suitably used because it has little birefringence and good transparency. In particular, when the antiglare film of the present invention is provided on the surface of a liquid crystal display, as a transparent substrate. It is preferable to use triacetyl cellulose.

  Moreover, as shown in FIG. 2, it is also possible to provide a polarizing layer on the surface opposite to the surface on which the antiglare layer of the transparent substrate is provided. At this time, as a polarizing layer, what consists of extended polyvinyl alcohol (PVA) which added the iodine can be illustrated. At this time, the polarizing layer is held between transparent substrates.

  The antiglare layer-forming coating liquid for forming the antiglare layer includes a binder matrix forming material and particles.

  As the binder matrix forming material in the present invention, an ionizing radiation curable material, a thermosetting material, or a material having a thermosetting part and a curable part by ionizing radiation in one molecule can be used.

  At this time, an acrylic material is preferably used as the ionizing radiation curable material in the binder matrix forming material. Acrylic materials are synthesized from polyfunctional or polyfunctional (meth) acrylate compounds such as polyhydric alcohol acrylic acid or methacrylic acid ester, diisocyanate and polyhydric alcohol, and acrylic acid or methacrylic acid hydroxy ester. Such a polyfunctional urethane (meth) acrylate compound can be used. Besides these, as ionizing radiation type materials, polyether resins having an acrylate functional group, polyester resins, epoxy resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, and the like can be used. .

  In the present invention, “(meth) acrylate” refers to both “acrylate” and “methacrylate”. For example, “urethane (meth) acrylate” indicates both “urethane acrylate” and “urethane methacrylate”.

  Examples of the monofunctional (meth) acrylate compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( (Meth) acrylate, t-butyl (meth) acrylate, glycidyl (meth) acrylate, acryloylmorpholine, N-vinylpyrrolidone, tetrahydrofurfuryl acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) ) Acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, benzyl (Meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phosphoric acid (meth) acrylate, ethylene oxide modified phosphoric acid (meth) acrylate, phenoxy (meta) ) Acrylate, ethylene oxide modified phenoxy (meth) acrylate, propylene oxide modified phenoxy (meth) acrylate, nonylphenol (meth) acrylate, ethylene oxide modified nonylphenol (meth) acrylate, propylene oxide modified nonylphenol (meth) acrylate, methoxydiethylene glycol (meth) Acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxypropyl hydrogen Phthalate, 2- (meth) acryloyloxypropyl hexahydrohydrogen phthalate, 2- (meth) acryloyloxypropyl tetrahydrohydrogen phthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate , Hexafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, 2 -Adamantane derivatives mono (meth) acrylates such as adamantyl acrylate having a monovalent mono (meth) acrylate derived from adamantane and adamantanediol.

  Examples of the bifunctional (meth) acrylate compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, and nonanediol di (meth). ) Acrylate, ethoxylated hexanediol di (meth) acrylate, propoxylated hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (Meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, tripropylene glycol Ruji (meth) acrylate, di (meth) acrylate, such as hydroxypivalic acid neopentyl glycol di (meth) acrylate.

  Examples of the trifunctional or higher functional (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and tris 2-hydroxy. Ethyl isocyanurate tri (meth) acrylate, tri (meth) acrylate such as glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, etc. Trifunctional (meth) acrylate compounds, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol te Trifunctional or higher polyfunctionality such as la (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane hexa (meth) acrylate ( Examples thereof include a (meth) acrylate compound and a polyfunctional (meth) acrylate compound obtained by substituting a part of these (meth) acrylates with an alkyl group or ε-caprolactone.

  Moreover, as a urethane (meth) acrylate compound, the compound obtained by making a polyhydric alcohol, a polyvalent isocyanate, and a hydroxyl-containing acrylate react can be used, Specifically, Kyoeisha Chemical Co., Ltd. make, UA-306H. , UA-306T, UA-306I, etc., manufactured by Nippon Synthetic Chemical Co., Ltd., UV-1700B, UV-6300B, UV-7600B, UV-7605B, UV-7640B, UV-7650B, etc., Shin-Nakamura Chemical Co., Ltd., U-4HA U-6HA, UA-100H, U-6LPA, U-15HA, UA-32P, U-324A, etc., manufactured by Daicel UCB, Ebecryl-1290, Ebecryl-1290K, Ebecryl-5129, etc., manufactured by Negami Industrial Co., Ltd. UN-3220HA, UN-3220HB, UN-322 HC, it can be used UN-3220HS like.

  Thermosetting materials include epoxy resin, urea resin, phenol resin, diallyl phthalate resin, melanin resin, guanamine resin, unsaturated polyester resin, polyurethane resin, aminoalkyd resin, melamine-urea cocondensation resin, silicon resin, polysiloxane Examples thereof include resins.

  Examples of the material having a thermosetting part and a curable part by ionizing radiation in one molecule include acrylic materials having an acrylic group and an isocyanate group as functional groups in the molecule. For example, 2-isocyanato-ethyl methacrylate can be exemplified.

  In addition to the ionizing radiation curable material, the thermosetting material, and the material having a thermosetting part and a curable part by ionizing radiation in one molecule, a thermoplastic resin or the like may be added as the binder matrix forming material. it can. Examples of the thermoplastic resin include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, and methylcellulose, vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, vinylidene chloride and copolymers thereof, and the like. Acetal resins such as acrylic resins, polyvinyl formal, polyvinyl butyral, acrylic resins and copolymers thereof, acrylic resins such as methacrylic resins and copolymers thereof, polystyrene resins, polyamide resins, linear polyester resins, polycarbonate resins, etc. it can. By adding a thermoplastic resin, the adhesion between the transparent substrate and the antiglare layer can be improved. Moreover, the curling of the anti-glare film manufactured can be suppressed by adding a thermoplastic resin.

  Moreover, when using an ultraviolet-ray as ionizing radiation, a photoinitiator is added to the coating liquid for anti-glare layer formation. Although a well-known photoinitiator can be used for a photoinitiator, it is preferable to use what was suitable for the binder matrix formation material to be used. As the photopolymerization initiator, benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl methyl ketal, and alkyl ethers thereof are used. The usage-amount of a photoinitiator is 0.5 weight part-20 weight part with respect to binder matrix formation material. The amount is preferably 1 part by weight to 5 parts by weight.

  As particles used in the present invention, acrylic particles (refractive index 1.49 to 1.56), acrylic styrene particles (refractive index 1.49 to 1.59), polystyrene particles (refractive index 1.59), polycarbonate particles (Refractive index 1.58), melamine particles (refractive index 1.66), epoxy particles (refractive index 1.58), polyurethane particles (refractive index 1.55), nylon particles (refractive index 1.50), polyethylene particles (1.50 to 1.56), polypropylene particles (refractive index 1.49), silicone particles (refractive index 1.46), polytetrafluoroethylene particles (refractive index 1.35), polyvinylidene fluoride particles (refractive index) 1.42), polyvinyl chloride particles (refractive index 1.54), polyvinylidene chloride particles (refractive index 1.62), glass particles (refractive index 1.48), silica (refractive index 1. 3 to 1.47), or the like can be used. In the present invention, the particles may be a plurality of types of particles.

  A solvent is added to the coating solution for forming the antiglare layer as necessary. By adding a solvent, it is possible to uniformly disperse the particles and the binder matrix, and to adjust the viscosity of the coating liquid to an appropriate range when coating the antiglare layer forming coating liquid on the transparent substrate. Become.

  In the present invention, when triacetyl cellulose is used as a transparent substrate and an anti-glare layer is provided directly on the triacetyl cellulose film without any other functional layer, tri-cellulose is used as a solvent for the anti-glare layer forming coating solution. It is preferable to use a mixed solvent of a solvent that dissolves or swells the acetylcellulose film and a solvent that does not dissolve or swell the triacetylcellulose film. By using the mixed solvent, sufficient adhesion is obtained at the interface between the triacetylcellulose film and the antiglare layer. It can be set as the anti-glare film which has.

  At this time, as a solvent for dissolving or swelling the triacetyl cellulose film, ethers such as dibutyl ether, dimethoxymethane, dimethoxyethane, diethoxyethane, propylene oxide, dioxane, dioxolane, trioxane, tetrahydrofuran, anisole and phenetole, and acetone are used. , Methyl ketones such as methyl ethyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, and ethylcyclohexanone, as well as ethyl formate, propyl formate, n-pentyl formate, methyl acetate, ethyl acetate Some esters such as methyl propionate, ethyl propionate, n-pentyl acetate, and γ-ptyrolactone, Bed, cellosolve, butyl cellosolve, cellosolve such as cellosolve acetate. These can be used alone or in combination of two or more.

  Solvents that do not dissolve or swell the triacetyl cellulose film include aromatic hydrocarbons such as toluene, xylene, cyclohexane and cyclohexylbenzene, hydrocarbons such as n-hexane, methyl isobutyl ketone, methyl butyl ketone and the like. Some esters such as ketones, butyl acetate, and isobutyl acetate are included. These can be used alone or in combination of two or more.

  In the present invention, an additive called a surface conditioner may be added in order to prevent the occurrence of coating film defects such as repellency and unevenness in the antiglare layer (coating film) to be applied and formed. Surface modifiers are also called leveling agents, antifoaming agents, interfacial tension modifiers, and surface tension modifiers, depending on their function, all of which reduce the surface tension of the coating film (antiglare layer) that is formed. Is provided.

  Examples of additives that are usually used as surface conditioners include silicone additives, fluorine additives, acrylic additives, and the like. As the silicone-based additive, a derivative having polydimethylsiloxane as a basic structure and having a modified side chain of the polydimethylsiloxane structure is used. For example, polyether-modified dimethylsiloxane is used as a silicone additive. Further, as the fluorine-based additive, a compound having a perfluoroalkyl group is used. As the acrylic additive, an additive having a basic structure in which an acrylic monomer, a methacrylic monomer, or a styrene monomer is polymerized is used. In addition, in the case of acrylic additives, the basic structure is a structure obtained by polymerizing acrylic monomers, methacrylic monomers, and styrene monomers, and substituents such as alkyl groups, polyether groups, polyester groups, hydroxyl groups, and epoxy groups in the side chain. May be contained.

  Moreover, in the coating liquid for anti-glare layer formation of this invention, you may add another additive other than the surface regulator mentioned above in the coating liquid. However, it is preferable that these additives do not affect the transparency and light diffusibility of the antiglare layer to be formed. As functional additives, antistatic agents, ultraviolet absorbers, infrared absorbers, antifouling agents, water repellents, refractive index modifiers, adhesion improvers, curing agents, and the like can be used, thereby forming The antiglare layer can have functions other than the antiglare function such as an antistatic function, an ultraviolet absorption function, an infrared absorption function, an antifouling function, and a water repellent function.

  The antiglare layer-forming coating solution is applied onto a transparent substrate to form a coating film. As a coating method at that time, a coating method using a roll coater, a reverse roll coater, a gravure coater, a knife coater, a bar coater, or a die coater can be used. Among them, it is preferable to use a die coater that can be applied at a high speed by a roll-to-roll method. The solid content concentration of the coating liquid varies depending on the coating method. Solid content concentration should just be about 30 to 70 weight% by weight ratio.

  An antiglare layer is formed by irradiating the coating film obtained by applying the coating liquid on the transparent substrate with ionizing radiation. As the ionizing radiation, ultraviolet rays and electron beams can be used. In the case of ultraviolet curing, a light source such as a high pressure mercury lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc, or a xenon arc can be used. In the case of electron beam curing, electron beams emitted from various electron beam accelerators such as cockloftwald type, bandegraph type, resonant transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type can be used. . The electron beam preferably has an energy of 50 to 1000 KeV. An electron beam having an energy of 100 to 300 KeV is more preferable.

  In addition, you may provide a drying process in the hardening process of a thermosetting site | part before the process of ionizing radiation hardening. In particular, when the coating liquid contains a binder matrix material, particles, and a solvent, it is necessary to provide a drying step before irradiation with ionizing radiation in order to remove the solvent of the formed coating film. Examples of the drying means include heating, air blowing, and hot air.

  As described above, the antiglare film of the present invention is produced.

The outline of the formation process of an anti-glare layer is shown below (refer FIG. 3). The antiglare film of the present invention is continuously formed by a roll-to-roll method. The web-shaped transparent substrate being wound is continuously run from the unwinding portion (31) to the winding portion (36). At this time, the transparent substrate (11) is applied to the coating unit (coating step) (32), The antiglare layer (12) is continuously formed on the transparent substrate (11) by passing through a drying / heating furnace (drying step / thermosetting step) (33) and an ionizing radiation irradiation device (curing step) (34). It is formed and an anti-glare film (1) can be manufactured.
Further, when passing through the winding unit (36) from the drying / heating furnace (33), a heating furnace (39) for further promoting thermosetting after passing through the ionizing radiation irradiation unit (hardening step) (34) is provided. It is also possible to use it.

  Examples are shown below.

Example 1
A triacetyl cellulose film (TD-80U manufactured by Fuji Photo Film) was used as a transparent substrate. As the coating solution, a coating solution for forming an antiglare layer obtained by adding a solvent to the binder matrix and particles described in (Table 1) was used. The solvent was 25 parts by weight of methyl ethyl ketone and 25 parts by weight of toluene with respect to 100 parts by weight of the solid content (binder matrix and particles) in the coating solution for forming the antiglare layer. And the anti-glare layer coating liquid was apply | coated on the triacetyl cellulose, and the coating film was obtained. The obtained coating film is dried and heated at 100 ° C. for 2 minutes to remove the solvent contained in the coating film and polymerize the thermosetting site, and then the oxygen concentration is 0.03% or less using a high-pressure mercury lamp. The coating film was cured by irradiating with an ultraviolet ray of 250 mJ / cm ² under an atmosphere to produce an antiglare film having an antiglare layer on a transparent substrate. The average film thickness (H) of the obtained antiglare layer was 6.8 μm.

  At this time, the average film thickness (H) of the antiglare layer of the antiglare film was measured with a scanning electron microscope. The average particle size (R) of the particles was measured using a light scattering particle size distribution measuring device (SALD-7000, manufactured by Shimadzu Corporation). The average film thickness (H) of the obtained antiglare layer was 6.8 μm.

(Example 2)
As the coating solution, a coating solution for forming an antiglare layer obtained by adding a solvent to the binder matrix and particles described in (Table 1) was used. The solvent was 50 parts by weight of isopropyl alcohol with respect to 100 parts by weight of the solid content (binder matrix and particles) in the coating solution for forming the antiglare layer. Thereafter, an antiglare film was produced in the same manner as in Example 1.

  Further, in (Example 3) to (Example 7) and (Comparative Example 1) to (Comparative Example 7), as shown in (Table 1), the average particle diameter (r) of the particles, the antiglare layer The antiglare films of (Example 3) to (Example 6) and (Comparative Example 1) to (Comparative Example 7) were produced by changing the average film thickness (H), the binder matrix, and the curing conditions. In (Example 3) to (Example 7) and (Comparative Example 1) to (Comparative Example 7), an antiglare film was produced in the same manner as in (Example 1) with respect to the amount of solvent and ultraviolet rays.

  About the anti-glare film obtained by said (Example 1)-(Example 7) and (Comparative Example 1)-(Comparative Example 7), it is (1) anti-glare property and (2) white blur by the following methods. (3) The scratch resistance was evaluated.

(1) “Anti-glare”
With the antiglare films obtained in the above Examples and Comparative Examples attached to a black plastic plate via an adhesive, the clarity of the image in which a fluorescent lamp or the like was reflected was visually evaluated.

  As a result of the visual evaluation, the case where the fluorescent lamp image was not noticed was marked as “◯”, and the case where the fluorescent lamp image was clear and worrisome was marked as “X”.

(2) “White blur”
In a state where the antiglare film obtained in the examples and comparative examples was attached to a black plastic plate via an adhesive, a fluorescent lamp was reflected, and the light diffusion degree of the antiglare film was visually evaluated. .

  The case where the degree of light diffusion was small and the anti-glare film did not feel whitish was designated as “◯”, and the case where whitish was felt and unacceptable was designated as “X”.

(3) “Abrasion resistance”
The antiglare film obtained in the above Examples and Comparative Examples was subjected to a load of 500 g / cm ^{2 on} the antiglare film using a Gakushin type friction fastness tester (AB-301 manufactured by Tester Sangyo Co., Ltd.). Using steel wool (Japan Steel Wool Bonster # 0000), rubbing 10 times, rubbing the surface on which the antiglare layer is not laminated with sandpaper, and then applying a matte black paint. Changes were assessed visually.

  At this time, the case where no change in appearance was confirmed was indicated by “◯”, and the case where the change in appearance was conspicuous was indicated by “X”.

  Table 2 shows the evaluation results of “antiglare”, “white blur” and “scratch resistance” of the antiglare films obtained in the Examples and Comparative Examples.

  In (Example 1) to (Example 7), compared with the anti-glare films of (Comparative Example 1) to (Comparative Example 7), it has moderate anti-glare property, less white blur, and high. An antiglare film having scratch resistance could be obtained.

  The antiglare film of the present invention relates to an antiglare film provided on the surface of a window or a display. In particular, the present invention relates to an antiglare film provided on the surface of a display such as a liquid crystal display (LCD), a CRT display, an organic electroluminescence display (ELD), a plasma display (PDP), a surface electric field display (SED), or a field emission display (FED). Phenomenon that does not cause high-quality technical problems and has a good anti-glare property, but turns brown when lighting such as a fluorescent lamp is reflected on the surface with the anti-glare layer It is suitably used as an antiglare film with little (white blur).

DESCRIPTION OF SYMBOLS 1 Anti-glare film 11 Transparent base material 12 Anti-glare layer 120 Binder matrix 121 Particles 2 Polarizing plate 21 Transparent base material 22 Transparent base material 23 Polarizing layer 3 Liquid crystal cell 41 Transparent base material 42 Transparent base material 43 Polarizing layer 5 Backlight unit 31 Unwinding roll 32 Coating unit 33 Drying / heating furnace 34 Ionizing radiation irradiation device 35 Roll 36 Winding roll 37 Guide roll 38 Backup roll 39 Heating furnace

Claims (7)

An antiglare film in which an antiglare layer containing a binder matrix and particles is laminated on a transparent substrate,
The value (r _A / H) obtained by dividing the average particle diameter (r _A ) of the particles by the average film thickness (H) of the antiglare layer is in the range of 0.20 to 0.90,
And the said binder matrix contains resin hardened | cured by a heat | fever and ionizing radiation, The anti-glare film characterized by the above-mentioned.   The antiglare film according to claim 1, wherein the resin cured by the heat and ionizing radiation is a mixture of different thermosetting materials and ionizing radiation curable materials.   2. The antiglare film according to claim 1, wherein the resin cured by heat and ionizing radiation is a resin having a thermosetting site and a curing site by ionizing radiation in one molecule. A method for producing the antiglare film,
A step of applying a binder matrix-forming material containing a resin that is cured by heat and ionizing radiation, and a coating liquid containing particles and a solvent on one surface of a transparent substrate that is continuously conveyed on the transparent substrate;
Drying and heating the coating liquid applied on the transparent substrate to cure the thermosetting material or thermosetting part;
Irradiating with ionizing radiation to cure the ionizing radiation curable material or the curable site by ionizing radiation; and
The method for producing an antiglare film according to any one of claims 1 to 3, further comprising: A method for producing the antiglare film,
A step of applying a binder matrix-forming material containing a resin that is cured by heat and ionizing radiation, and a coating liquid containing particles and a solvent on one surface of a transparent substrate that is continuously conveyed on the transparent substrate;
Drying and heating the coating liquid applied on the transparent substrate to cure the thermosetting material or thermosetting part;
Irradiating with ionizing radiation to cure the ionizing radiation curable material or the curable site by ionizing radiation; and
Furthermore, the process of promoting thermosetting by heating,
The method for producing an antiglare film according to any one of claims 1 to 3, further comprising:   An anti-glare film according to any one of claims 1 to 3, and a polarizing layer and a transparent substrate on a surface opposite to the anti-glare layer forming surface of the transparent substrate of the anti-glare film. Polarizer.   A liquid crystal display comprising the polarizing plate according to claim 6, a liquid crystal cell, a polarizing plate, and a backlight unit in this order from the viewer side, and an antiglare layer on the surface on the viewer side.

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