JP2006273901A - Antiglare hard coating agent and antiglare hard coat film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an antiglare hard coating agent containing a silica particle component showing high dispersibility and capable of easily developing desired characteristics as an additive to impart antiglare properties and high hardness to a hard coating agent, and to obtain an antiglare hard coat film capable of developing the characteristics of a hard coat layer for a long period of time by applying the antiglare hard coating agent to form the hard coat layer. <P>SOLUTION: The antiglare hard coating agent comprises a silica-containing composite, in which silica particles having an average particle size of 1-10 μm is combined with an isocyanate compound having a polymerizable unsaturated group through a urethane bond, dispersed in a solution containing a polymerizable compound having a polymerizable unsaturated group. The antiglare hard coating agent is applied to a film to form a hard coat layer thereon. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an antiglare hard coat agent and an antiglare hard coat film having the antiglare hard coat agent as a hard coat layer.

  In displays used in flat panel displays such as plasma displays and liquid crystal displays, touch panels, personal computers, etc., when light such as sunlight or fluorescent light is reflected on the display screen, the reflection of this light makes it difficult to see the screen. . Therefore, an antiglare film for suppressing this reflection phenomenon is provided. By sticking this antiglare film on the display screen of the display, this phenomenon is suppressed.

  This anti-glare film is coated with a hard coat agent containing silica particles in a silicone or acrylic resin binder and dried on the surface of the film. Is obtained by curing the resin component. For example, Patent Document 1 and Patent Document 2 propose a hard coat agent containing silica particles having a predetermined refractive index and an average particle diameter, and an antiglare film coated with the hard coat agent. .

  According to the said invention, as FIG. 1 of patent document 1 shows, with drying of a hard-coat agent, a silica particle appears in the surface layer of a hard-coat agent, and an unevenness | corrugation is formed. Antireflection glare is imparted to the film by the irregular reflection of reflected light by the unevenness.

JP-A-9-230103 JP-A-9-211202

  The hard coat agent is a mixture of silica particles in a resin binder. However, since the dispersibility of the silica particles in the resin binder is not considered, the silica particles are likely to settle. Therefore, when this hard coat agent is applied to a film, it must be carried out while stirring the hard coat agent, resulting in a problem of poor workability.

  In addition, this hard coat agent requires steps of drying and curing after being applied to a film. At this time, since the silica particles are aggregated, there is a problem that glare occurs in the image when the obtained antiglare film is attached to a display.

  Furthermore, the adhesion between the silica particles and the resin binder is not considered. Therefore, when this antiglare film is used over a long period of time, the surface silica particles are peeled off. Then, there is a problem that the roughness of the surface layer of the hard coat layer is increased or the antiglare property and the hardness property are lost.

  The problem to be solved by the present invention is that, as an additive for imparting antiglare property and high hardness to a hard coat agent, it exhibits high dispersibility and easily develops desired properties. Anti-glare hard coat agent containing silica particles and an anti-glare hard coat capable of expressing the characteristics of the hard coat layer over a long period of time by using this anti-glare hard coat agent as a hard coat layer To get a film.

  The invention according to claim 1 for solving the above-mentioned problem is a silica-containing composite comprising silica particles having an average particle diameter of 1 to 10 μm and an isocyanate compound having a polymerizable unsaturated group bonded via a urethane bond. Is an anti-glare hard coat agent characterized by being dispersed in a solution.

  In the invention described in claim 2, the silica-containing composite in which silica particles having an average particle diameter of 1 to 10 μm and an isocyanate compound having a polymerizable unsaturated group are bonded via a urethane bond is polymerizable unsaturated. An antiglare hard coat agent which is dispersed in a solution containing a polymerizable compound having a group.

  The invention according to claim 3 is a single amount having silica particles having an average particle diameter of 1 to 10 μm and a plurality of isocyanate groups, and having a polymerizable unsaturated group in at least one isocyanate group among the isocyanate groups. An antiglare hard coat agent characterized in that a silica-containing composite formed by bonding an isocyanate compound into which a body is introduced via a urethane bond is dispersed in a solution.

  The invention according to claim 4 has silica particles having an average particle size of 1 to 10 μm and a plurality of isocyanate groups, and among these isocyanate groups, at least one isocyanate group has a polymerizable unsaturated group. Antiglare property, characterized in that a silica-containing composite formed by bonding an isocyanate compound into which a body is introduced via a urethane bond is dispersed in a solution containing a polymerizable compound having a polymerizable unsaturated group It is a hard coat agent.

  The invention according to claim 5 is the antiglare hard coat according to any one of claims 1 to 4, wherein the silica-containing composite contains 0.1 to 20% by weight of silica particles. It is an agent.

  The invention according to claim 6 is an antiglare hard coat film, wherein the antiglare hard coat agent according to any one of claims 1 to 5 is applied on a film.

  In general, when the particle size is small, the particles tend to aggregate and difficult to uniformly disperse. According to the invention described in claim 1, the hard coat agent is imparted with antiglare property and high hardness. Although silica particles having an average particle diameter of 1 to 10 μm are employed as an additive, silica particles exist as a complex with an isocyanate compound and have a polymerizable unsaturated group. Silica-containing composite that exhibits high dispersibility as an additive for imparting antiglare and high hardness properties to hard coat agents by agglomeration between polymerizable unsaturated groups without aggregation of particles An antiglare hard coat agent containing a body can be obtained.

  In the invention according to claim 2, silica particles having an average particle diameter of 1 to 10 μm are used as an additive for imparting antiglare and high hardness to the hard coat agent. Exists as a complex with an isocyanate compound and has a polymerizable unsaturated group, so that the silica particles are not aggregated, and the polymerizable unsaturated group bonded to the silica particles and the polymerizable unsaturated group in the solution are not. Antiglare hard coating agent containing silica-containing composite having high dispersibility as an additive for imparting antiglare property and high hardness to hard coating agent by polymerization between saturated groups Can be obtained. Moreover, the polymerizable unsaturated group in the solution also has an effect of improving the adhesion between the hard coat layer and the base film.

  In the invention described in claim 3, a monomer having a polymerizable unsaturated group is introduced into at least one of the isocyanate groups of the isocyanate compound having a plurality of isocyanate groups, and the monomers are bonded to the silica particles via urethane bonds. Therefore, the synthesized silica-containing composite is composed of a composite of silica particles, an isocyanate component, and a monomer having a polymerizable unsaturated group. In addition, it also has the properties of a monomer having this polymerizable unsaturated group. According to the invention described in claim 3, by appropriately selecting a monomer for introducing a polymerizable unsaturated group into the isocyanate compound, the property of the monomer can be imparted to the silica-containing composite. Therefore, in addition to the effect of the invention described in claim 1, an antiglare hard coat agent capable of increasing the range of molecular design choices in expressing desired properties can be obtained.

  In the invention described in claim 4, a monomer having a polymerizable unsaturated group is introduced into at least one of the isocyanate groups of the isocyanate compound having a plurality of isocyanate groups, and the monomer is bonded to the silica particles via a urethane bond. Therefore, the synthesized silica-containing composite is composed of a composite of silica particles, an isocyanate component, and a monomer having a polymerizable unsaturated group. In addition, it also has the properties of a monomer having this polymerizable unsaturated group. According to the invention described in claim 4, by appropriately selecting a monomer for introducing a polymerizable unsaturated group into the isocyanate compound, the property of the monomer can be imparted to the silica-containing composite. Therefore, in addition to the effect of the invention described in claim 2, an antiglare hard coat agent capable of increasing the range of molecular design choices in expressing desired characteristics can be obtained.

  According to the invention described in claim 5, the antiglare hard coat agent described in claims 1 to 4 is characterized in that the silica-containing composite contains 0.1 to 20% by weight of silica particles. Since the dispersibility of the contained silica-containing composite is high, the silica-containing composite does not aggregate or settle, and when the hard coat agent of the present invention is used as a hard coat film, image glare and An anti-glare hard coat film having no hardness unevenness can be obtained.

  According to the invention described in claim 6, since the antiglare hard coat agent described in claims 1 to 4 has a high dispersibility of the silica-containing composite and contains a polymerizable component, Since the solution containing the composite is applied in a uniformly dispersed state on the film and dried, the silica particles do not peel off, have excellent adhesion to the film, and prevent glare and hardness unevenness in the image. Hard coat film is obtained.

  Further, since both the silica-containing composite and the polymerizable compound have a polymerizable unsaturated group, when the antiglare hard coat agent is cured, the silica-containing composites or the silica-containing composite And the polymerizable compound are firmly bonded by a polymerization reaction. Therefore, the anti-glare hard coat film using the hard-coat layer as the anti-glare hard coat agent maintains the dispersibility of the silica-containing composite and the hard coat without peeling off the silica-containing composite from the hard coat layer. The properties of the layer can be developed over a long period of time.

  Embodiments of the present invention will be described below. As the silica particles used in the present invention, those having an average particle diameter of 1 to 10 μm are used, more preferably those having an average particle diameter of 2 to 5 μm. When the particle diameter of the silica particles is small, sufficient antiglare property cannot be obtained. Moreover, when the particle diameter is large, it causes glare on the screen, and further, the silica particles are liable to settle and the dispersion stability is lowered. The particle shape of the silica particles is preferably an indeterminate shape that easily causes light scattering, and further, silica particles having a hydroxyl group on the surface are desirable.

  As the isocyanate compound having a polymerizable unsaturated group used in the present invention, a compound containing a (meth) acryloyl group and an isocyanate group, such as acryloyl isocyanate, methacryloyl isocyanate, 2-isocyanate ethyl acrylate, 2-isocyanate ethyl methacrylate, and the like. Can be used.

  Examples of the isocyanate compound having a plurality of isocyanate groups include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5. -Naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane triisocyanate, 3,3 ' -Dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis (4-cyclohexyl isocyanate) 2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanatoethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, tolidine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate , Tetramethylxylylene diisocyanate, 2,5 (or 6) -bis (isocyanatemethyl) -bicyclo [2.2.1] heptane, trimethylolpropane adduct of triethylene diisocyanate, isocyanurate of triethylene diisocyanate, diphenylmethane -4,4'-diisocyanate oligomers, hexamethylene diisocyanate biuret, hexamethylene diisocyanate isocyanate Rate bodies, uretdione of hexamethylene diisocyanate, can be used isocyanurate and the like of isophorone diisocyanate. Moreover, you may use these isocyanate compounds individually or in combination of 2 or more types.

  In the isocyanate compound having a plurality of isocyanate groups, a polymerizable unsaturated group is introduced into at least one of the isocyanate groups. As a compound for introducing a polymerizable unsaturated group, a hydroxyl group-containing acrylate monomer, for example, a monofunctional acrylate or a polyfunctional acrylate can be used. Of these, polyfunctional acrylates are preferably used. As the monofunctional acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, polyethylene glycol acrylate, or the like can be used. Examples of the polyfunctional acrylate include trimethylolpropane diacrylate, ethoxylated trimethylolpropane diacrylate, propoxylated trimethylolpropane diacrylate, and hydroxyl group-containing acrylate monomers such as pentaerythritol tri (meth) acrylate. By using this polyfunctional acrylate, the acrylate density can be increased, and the hardness characteristics can be further extracted by increasing the degree of crosslinking of the organic substance.

  Examples of the compound having a polymerizable unsaturated group that reacts with an isocyanate group include (meth) acrylic acid, itaconic acid, cinnamic acid, maleic acid, fumaric acid, 2- (meth) acryloxypropylhexahydrogenphthalate , Unsaturated aliphatic carboxylic acids such as 2- (meth) acryloxyethyl hexahydrogen phthalate, 2- (meth) acryloxypropyl phthalate, 2- (meth) acryloxypropyl ethyl phthalate -Unsaturated aromatic carboxylic acids having a carboxyl group such as thio, and amino groups such as vinyloxyethylamine, vinyl oxide decylamine, allyloxypropylamine, 2-methylallyloxyhexylamine, vinyloxy- (2-hydroxy) butylamine Containing monomers and the like can be used. These may be used alone or in combination of two or more.

  In order to promote the reaction for introducing a polymerizable unsaturated group into the isocyanate group of the isocyanate compound and the reaction between the silica particles and the isocyanate group, a catalyst may be added. For example, copper naphthenate, cobalt naphthenate, zinc naphthenate, di-n-butyltin laurate, triethylamine, 1,4-diazabicyclo [2.2.2] octane, 2,6,7-trimethyl-1,4-diazabicyclo [2.2.2] A urethane catalyst such as octane may be used in an amount of 0.01 to 1 part by weight with respect to 100 parts by weight of the total amount of reactants.

  The reaction for introducing the polymerizable unsaturated group into the polyisocyanate is carried out in the presence of a urethane catalyst in an inert solvent for the isocyanate group, for example, an aromatic hydrocarbon solvent such as toluene or xylene, acetic acid Ester solvents such as ethyl and butyl acetate, ketone solvents such as methyl ethyl ketone and cyclohexanone, glycol ether ester solvents such as ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate and ethyl-3-ethoxypropionate, tetrahydrofuran and dioxane It is carried out using one or more polar solvents such as ether solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and furfural. Examples of the reactive solvent include acrylic monomers such as methyl methacrylate.

  Silica particles can be obtained by mixing the above silica particles and an isocyanate compound having a polymerizable unsaturated group introduced into an organic solvent or a reactive solvent, and further mixing them in the presence of a catalyst as necessary. The hydroxyl group of and the isocyanate group of an isocyanate compound couple | bond together by a urethane bond, and a silica containing composite_body | complex is obtained.

  Content of the silica particle contained in a silica containing composite is 0.1 to 20 weight%. If it exceeds 20% by weight, the silica particles aggregate during the urethane reaction between the silica particles and the isocyanate group, causing glare when the antiglare hard coat film is formed. Moreover, the compound which has a polymerizable unsaturated group can be arbitrarily mixed according to the target optical performance.

  When an isocyanate compound having a plurality of isocyanate groups and a hydroxyl group-containing acrylate monomer are mixed in an organic solvent or a reactive solvent and mixed in the presence of a catalyst as necessary, a hydroxyl group-containing acrylate monomer is added to the isocyanate group of the isocyanate compound. Are bonded by a urethane bond, and a polymerizable unsaturated group of acrylate is introduced into the isocyanate compound. After this step, the silica-containing composite is obtained by mixing the isocyanate compound having the polymerizable unsaturated group introduced therein and silica particles in an organic solvent or a reactive solvent, if necessary, in the presence of a catalyst. It is done. This reaction method will be referred to as an individual method.

  Said individual system passes the process of couple | bonding a silica particle after the process of introduce | transducing a polymerizable unsaturated group into an isocyanate compound. These reactions can be carried out simultaneously in a lump. In this method, silica particles, an isocyanate compound having a plurality of isocyanate groups, and a hydroxyl group-containing acrylate monomer are all mixed in an organic solvent or a reactive solvent, and these are mixed in the presence of a catalyst as necessary. This is the reaction method. According to this system, a silica-containing composite is obtained after simultaneously performing a urethane bond between silica particles and an isocyanate compound and a urethane bond between a hydroxyl group-containing acrylate monomer and an isocyanate compound. This reaction method is referred to as a batch method.

  In order to obtain the silica-containing composite, any of the above-described individual method or batch method may be used. The selection of these reaction methods depends on the production efficiency of the silica-containing composite, the characteristics required for the silica-containing composite, Take into account the appropriate selection. On that basis, it is preferable to select an individual system in order to secure these sufficient bonds in the urethane bond between the hydroxyl group-containing acrylate monomer and the isocyanate compound and the urethane bond between the silica particles and the isocyanate compound.

  In the reaction, IR or amine titration is performed over time, and the concentration of the remaining isocyanate groups is measured. Then, the end point of the reaction between the isocyanate group and the silica particles is defined as the point at which the change in concentration disappears. If unreacted isocyanate groups remain, the storage stability is lowered. Therefore, unreacted isocyanate groups may be blocked with a blocking agent. As the blocking agent, alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol, or compounds that react with the isocyanate group can be used.

  The polymerizable compound having a polymerizable unsaturated group to be mixed and polymerized with the silica-containing composite includes alkyl ester of acrylic acid or methacrylic acid, unsaturated nitrile monomer, unsaturated carboxylic acid, amide group-containing monomer, methylol group-containing A polymerizable compound having a polymerizable unsaturated group in the molecular chain such as a monomer, an alkoxymethyl group-containing monomer, an epoxy group-containing monomer, a polyfunctional monomer, or a vinyl ester can also be used.

  Examples of alkyl esters of acrylic acid or methacrylic acid include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl Examples include methacrylate, isopropyl acrylate, butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, and lauryl methacrylate. Examples of unsaturated nitrile monomers include acrylonitrile and methacrylonitrile. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, monoalkyl itaconate and the like. As the amide group-containing monomer, acrylamide, methacrylamide, N, N-methylenebisacrylamide, diacetone acrylamide, maleic acid amide, maleimide and the like can be used. As the methylol group-containing monomer, N-methylol acrylamide, N-methylol methacrylamide, dimethylol acrylamide, dimethylol methacrylamide and the like can be used. As the alkoxymethyl group-containing monomer, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-butoxymethylacrylamide, N-butoxymethylmethacrylamide and the like can be used. As the epoxy group-containing monomer, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, methyl glycidyl acrylate, or methyl glycidyl methacrylate can be used. As polyfunctional monomers, divinylbenzene, polyoxyethylene diacrylate, polyoxyethylene dimethacrylate, polyoxypropylene diacrylate, polyoxypropylene dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate, Trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate and the like can be used. Examples of vinyl esters that can be used include vinyl acetate, vinyl propionate, olefins such as butadiene, isoprene, and chlorine-containing vinyl monomers such as vinyl chloride, vinylidene chloride, chloroprene, and other styrene. These compounds having a polymerizable unsaturated group may be used alone or in combination of two or more. By using a polyfunctional monomer among these monomers, the crosslink density of the organic component can be improved and the curing characteristics can be further extracted.

  After applying this anti-glare hard coat agent to various substrates and volatilizing the solvent by applying heat to the extent that it does not affect the properties of the various substrates, by methods such as heating, light irradiation, electron beam irradiation, etc. The polymer is cured by polymerizing a dry film containing the silica-containing composite.

  When curing by heating, an initiator is added to the antiglare hard coat agent. As the initiator, a peroxide, an azobis compound, or the like can be used. Examples of the peroxide include dibutyl peroxide, benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, and the like. Examples of the azobis compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis- 2-Methylbutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 2,2′-azobis (2-methylpropionamidine) dihydrochloride and the like can be used.

  When curing by light, a photoinitiator is added to the antiglare hard coat agent. As photoinitiators, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4 , 4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthate 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl)- 2,4,4-trimethylpentylphosphine oxide or the like can be used. Moreover, as commercially available photoinitiators, Irgacure 184, 369, 651, 500, 907, CGI 1700, CGI 1750, CGI 1850, CG 24-61 (trade name) manufactured by Ciba Geigy, Lucirin LR8728 (trade name) manufactured by BASF, Merck's Darocur 1116 and 1173 (above, trade names), UCBacryl P36 (trade name), and the like can be used.

  When curing with an electron beam, no special initiator is required.

  In order to ensure adhesion to various substrates as an antiglare hard coat agent, a tackifier resin may be appropriately blended. As the tackifier resin, phenol resins such as modified rosin, polymerized rosin, phenol resin, and alkylphenol resin, and aromatic petroleum resins such as coumarone indene, aliphatic hydrocarbon, and terpene resin can be used. Furthermore, those obtained by carboxyl modification or hydroxyl modification may be used.

  Moreover, you may mix | blend metal oxides, such as a zinc oxide, a calcium oxide, magnesium oxide, with this glare-proof hard coat agent in order to prevent aging.

  Further, an antistatic function can be imparted to the antiglare hard coat agent by adding an antistatic agent, a conductive polymer, a metal oxide or the like. Antistatic agents include polyoxyethylene alkyl ether, polyoxyethylene alkylphenol, polyoxyethylene alkylamine, polyoxyethylene alkylamide, fatty acid polyethylene glycol ester, fatty acid sorbitan ester, polyoxyethylene fatty acid sorbitan ester, fatty acid glycerin ester, alkyl Polyethyleneimine, an alkylamine salt, an alkyl quaternary ammonium salt, an alkylimidazoline derivative, an acrylate compound having ethylene oxide as a skeleton, or the like can be used as a cationic system. In addition, an ion conduction type antistatic agent in which metal ions such as lithium ions are mixed can also be used. As the conductive polymer, polyaniline, polypyrrole, polythiophene, poly3,4-ethylenedioxythiophene, and derivatives thereof can be used. As the metal oxide, antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), aluminum-doped zinc oxide, antimony suboxide, or the like can be used.

  The antiglare hard coat film is obtained by applying the antiglare hard coat agent obtained as described above to a film, and drying and curing it.

  Films that serve as the base material for this antiglare hard coat film include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, polyvinyl chloride, poly Made of vinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetheretherketone, polyethersulfone, polyetherimide, polyimide, fluorine resin, nylon, acrylic resin, etc. A film can be used. For the purpose of improving the adhesion between these base film and anti-glare hard coat agent, surface roughening treatment such as sandblasting or solvent treatment, or easy adhesion, corona discharge treatment, chromic acid treatment, flame treatment, Surface treatment such as hot air treatment, ozone / ultraviolet irradiation treatment, surface oxidation treatment such as electron beam irradiation treatment, etc. can be performed.

  Application of the antiglare hard coat agent to the film can be performed by a conventionally known method such as a gravure coating method, a bar coating method, a knife coating method, a roll coating method, a blade coating method, or a die coating method. In the present invention, the coating thickness of the antiglare hard coat agent is 1 to 10 μm, more preferably 2 to 5 μm. This is because when the coating thickness is thin, sufficient scratch resistance and scratch resistance cannot be obtained, and when the coating thickness is thick, silica particles are not exposed on the surface, resulting in poor antiglare performance and large warpage of the film. .

Next, examples of the present invention will be described. This example shows a specific example of the present invention, and the embodiment of the present invention is not limited to the following.

  The antiglare hard coat agent according to the present invention was prepared as follows.

Example 1
100 parts by weight of toluene as a solvent, 10 parts by weight of silica particles having an average particle size of 2.5 μm (trade name X-80, manufactured by Tokuyama Corporation), and 2-methacryloyloxyethyl isocyanate (MOI) having a molecular weight of 155 as an isocyanate compound ( A mixture of 90 parts by weight of Showa Denko KK and 0.1 part by weight of di-n-butyltin dilaurate (DBTDL) as a catalyst was stirred at room temperature for 24 hours. The concentration of isocyanate groups was measured by IR to confirm that there were no remaining isocyanate groups, and a solution containing a silica compound-containing monomer was obtained. Next, 2 parts by weight of Irgacure 907 (manufactured by Ciba Geigy, trade name, the same below) was added as a polymerization initiator to 100 parts by weight of the silica compound-containing monomer to obtain the antiglare hard coat agent of Example 1. .

(Example 2)
20 parts by weight of silica particles (Nippon Silica Industry Co., Ltd., trade name E-150J) having an average particle size of 4.7 μm and 100 parts by weight of toluene as a solvent, and 2-methacryloyloxyethyl isocyanate (MOI) having a molecular weight of 155 as an isocyanate compound ) (Made by Showa Denko KK) and a mixed solution obtained by adding 80 parts by weight of di-n-butyltin dilaurate (DBTDL) as a catalyst was stirred at room temperature for 24 hours. It was confirmed by IR that there was no remaining isocyanate group, and a silica compound-containing monomer was obtained. Next, 16.7 parts by weight of pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name A-TMMT) and 16.7 parts by weight of toluene are mixed with 100 parts by weight of the silica compound-containing monomer. The antiglare hard coat agent of Example 2 was obtained by adding 2 parts by weight of Irgacure 907 as a polymerization initiator.

(Example 3)
79.5 parts by weight of toluene as a solvent, 29 parts by weight of 2-hydroxyethyl methacrylate (HEMA) as a hydroxyl group-containing acrylate monomer, 50 parts by weight of isophorone diisocyanate (IPDI) as an isocyanate compound, and dilauric acid diacid as a catalyst -N-butyltin (DBTDL) 0.1 weight part was added, and the HEMA-IPDI monomer was obtained. Next, this monomer was added to 0.4 parts by weight of silica particles having an average particle size of 8.0 μm (Fuji Silysia Co., Ltd., trade name: Silysia 450), and stirred at room temperature for 24 hours, and then isopropanol was added. Subsequently, it was confirmed by IR that there were no remaining isocyanate groups, and a silica compound-containing monomer was obtained. 2 parts by weight of Irgacure 907 as a polymerization initiator was added to 100 parts by weight of the silica compound-containing monomer to obtain an antiglare hard coat agent of Example 3.

Example 4
105 parts by weight of toluene as a solvent, 60 parts by weight of pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name A-TMM-3LM-N) as a hydroxyl group-containing acrylate monomer, and 24 parts by weight of isophorone diisocyanate (IPDI) And 0.1 part by weight of di-n-butyltin dilaurate (DBTDL) was added as a catalyst to obtain a pentaerythritol triacrylate-IPDI monomer. Next, this pentaerythritol triacrylate-IPDI monomer was added to 21 parts by weight of silica particles having an average particle size of 2.5 μm (trade name X-80, manufactured by Tokuyama Corporation), and stirred at room temperature for 24 hours, and then isopropanol was added. It was. It was confirmed by IR that there were no remaining isocyanate groups, and a silica compound-containing monomer was obtained. Furthermore, 16.7 parts by weight of toluene and 16.7 parts by weight of pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name A-TMMT) were mixed with 100 parts by weight of the silica compound-containing monomer. The solution was added, and 3 parts by weight of Irgacure 907 was added as a polymerization initiator to obtain an antiglare hard coat agent of Example 4.

(Example 5)
83 parts by weight of methyl ethyl ketone as a solvent, 29 parts by weight of 2-hydroxyethyl methacrylate (HEMA) as a hydroxyl group-containing acrylate monomer, 50 parts by weight of equimolar isophorone diisocyanate (IPDI) as an isocyanate compound, and di-n dilaurate as a catalyst -0.1 part by weight of butyltin (DBTDL) was added to obtain a HEMA-IPDI monomer. Next, this monomer was added to 4 parts by weight of silica particles having an average particle size of 8.0 μm (Fuji Silysia Co., Ltd., trade name: Cylicia 450), stirred at room temperature for 24 hours, and then isopropanol was added. Subsequently, it was confirmed by IR that there were no remaining isocyanate groups, and a silica compound-containing monomer was obtained. 2 parts by weight of Irgacure 907 as a polymerization initiator was added to 100 parts by weight of the silica compound-containing monomer to obtain an antiglare hard coat agent of Example 5.

(Example 6)
100 parts by weight of toluene as a solvent, 10 parts by weight of silica particles having an average particle size of 3.1 μm (trade name UF-310, manufactured by Tokuyama Corporation), and 2-methacryloyloxyethyl isocyanate having a molecular weight of 155 as an isocyanate compound (Showa Denko Co., Ltd.) A mixture of 90 parts by weight (made by company) and 0.1 parts by weight of di-n-butyltin dilaurate (DBTDL) as a catalyst was stirred at room temperature for 24 hours. And the density | concentration of the isocyanate group was measured by IR, it confirmed that there was no remaining isocyanate group, and the solution containing a silica compound containing monomer was obtained. Next, 5 parts by weight of Irgacure 907 (manufactured by Ciba Geigy, trade name, the same applies hereinafter) was added as a polymerization initiator to the silica compound-containing monomer to obtain the antiglare hard coat agent of Example 1.

The antiglare hard coat agent of Examples 1 to 6 above was applied to a PET film (polyethylene terephthalate film, manufactured by Toray Industries, Inc., trade name Lumirror) having a thickness of 188 μm so that the film thickness after curing was 5 μm. . Subsequently, 300 mJ / cm < ² > of ultraviolet rays were radiated to the coated surface with a high-pressure mercury lamp of 80 W / cm to cure the coated surface, and the antiglare hard coat films of Examples 1 to 6 were obtained, respectively.

In order to compare the properties of the antiglare hard agent of Examples 1 to 6 and the antiglare hard coat film, the coating agents of Comparative Examples 1 to 5 and Comparative Examples 1 to 5 in which these coating agents are applied. A coated film was prepared as follows. These comparative examples are intended to perform characteristic comparison from the viewpoints described below.
Comparative Example 1: Silica particles and isocyanate compound are not urethane-bonded.
Comparative Example 2: Silica particles simply mixed with a curing agent.
Comparative Example 3: The average particle diameter of the silica particles is larger than 10 μm.
Comparative Example 4: The average particle diameter of the silica particles is smaller than 1 μm.
Comparative Example 5: Silica particles are not included.

(Comparative Example 1)
100 parts by weight of toluene as a solvent, 100 parts by weight of 2-methacryloyloxyethyl isocyanate (MOI, Showa Denko KK) having a molecular weight of 155 as an isocyanate compound, equimolar or more of isopropanol, and dilauric acid di- The isocyanate group was inactivated by adding 0.04 part by weight of n-butyltin (DBTDL). To this mixed solution, 10 parts by weight of silica particles having an average particle size of 2.5 μm (trade name X-80, manufactured by Tokuyama Corporation) was mixed and stirred at room temperature for 24 hours. Next, 2 parts by weight of Irgacure 907 as a polymerization initiator was added to 100 parts by weight of the silica compound-containing monomer to obtain a coating agent of Comparative Example 1.

(Comparative Example 2)
Silica particles having an average particle size of 4.7 μm (Nippon Silica Industry Co., Ltd.) were added to a solution prepared by mixing 100 parts by weight of toluene as a solvent with 100 parts by weight of pentaerythritol tetraacrylate (trade name A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd. Co., Ltd., trade name E-150J) 20 parts by weight was mixed and stirred at room temperature for 24 hours, and then 3 parts by weight of Irgacure 907 was added as a polymerization initiator to obtain a coating agent of Comparative Example 2.

(Comparative Example 3)
In the antiglare hard coat agent of Example 1, instead of silica particles having an average particle size of 2.5 μm, silica particles having an average particle size of 11.3 μm (manufactured by Fuji Silysia Chemical Co., Ltd., trade name 780) are used. The coating agent of Comparative Example 3 having the same composition, composition ratio, and preparation method was obtained.

(Comparative Example 4)
In the antiglare hard coat agent of Example 1, instead of silica particles having an average particle size of 2.5 μm, silica particles having an average particle size of 0.2 μm (trade name SH-03, manufactured by Tokuyama Corporation) are used. The coating agent of Comparative Example 4 having the same composition, the blending ratio of the composition, and the preparation method was obtained.

(Comparative Example 5)
In the antiglare hard coat agent of Example 1, the silica particles were not mixed, and the other composition, the blending ratio of the composition, and the preparation method of Comparative Example 5 having the same preparation method were obtained.

  The coating agents of Comparative Examples 1 to 5 were applied to a PET film in the same manner as in Example and cured to obtain coated films of Comparative Examples 1 to 5.

  The silica precipitation of the antiglare hard coating agents of Examples 1 to 6 and the coating agents of Comparative Examples 1 to 4 obtained as described above was measured. In addition, since the silica particle is not contained in the coating agent of the comparative example 5, this measurement is not performed. Further, glare of the antiglare hard coat film of Examples 1 to 6 and the coat film of Comparative Examples 1 to 5, pen sliding durability, total light transmittance, haze degree, mapping definition, adhesion, pencil Hardness, scratch resistance, wipeability, and contact angle were measured. The measurement methods for the above measurement items and the evaluation criteria for the measurement results are as follows.

(Silica particle sedimentation)
10 g of the antiglare hard coating agent of the example or the coating agent of the comparative example is placed in a test tube (nominal dimension 18 × 165) having an inner diameter of 16φ and allowed to stand, and the time for the layer thickness of the supernatant liquid to reach 2 mm is set. It was measured.
Evaluation criteria Pass ○: longer than 6 hours. Fail x: 0 to 6 hours.

(Glitter evaluation)
The antiglare hard coat film of the example or the coat film of the comparative example is placed on the surface of the liquid crystal display in which green is displayed on the entire surface, and visually observed from a distance of 30 cm. At this time, the presence or absence of “unnatural shine” in which the luminance of a specific portion was increased was confirmed.
Evaluation criteria Pass ○: “Unnatural brightness” is not recognized. Fail x: “Unnatural shine” is recognized.

(Pen sliding durability)
A 300 g vertical load is applied to the pen tip of a polyacetal pen (R0.8), and a 25 mm reciprocating sliding is performed 50,000 times. After the test, the state of scratches on the antiglare hard coat film was visually confirmed.
Evaluation criteria Pass ○: No scratches are observed. Fail x: Scratches are recognized.

(Total light transmittance)
Measurement was performed with a haze meter (manufactured by Suga Test Instruments Co., Ltd.) based on the provisions of JIS K 7361-1 (2000 edition) 3.2.
Evaluation criteria Pass ○: 90% or more. Fail x: Less than 90%.

(Haze degree)
It measured with the haze meter (made by Suga Test Instruments) based on the prescription | regulation of JISK7136 (2000 version).
Evaluation criteria Pass ○: 2 to 15%. Fail x: Less than 2% or more than 15%.

(Map clarity)
Measurement was performed with a TM-type image clarity measuring instrument (manufactured by Suga Test Instruments) based on the provisions of JIS K 7105 (2000 edition).
Evaluation criteria When haze is less than 10; Pass ○: 80% or more. Fail x: Less than 80%.
When haze is 10 or more; Pass ○: 70% or more. Fail x: Less than 70%.

(Adhesion)
According to a cross-cut test based on JIS K 5600-5-6 (1999 edition). A 10 × 10 square is formed on the coated surface with a cutter knife, and cellophane tape is applied on the square. Next, the cellophane tape is pulled upward at an angle of 45 °, and the squares that have not been peeled off are counted.
Evaluation criteria Pass ○: Number of remaining squares 100. Fail x: The number of remaining squares is less than 100.

(Pencil hardness)
In accordance with JIS K 5600, a scratch test was performed by applying a load from directly above the pencil fixed at 45 degrees, and the pencil hardness without scratches was displayed.
Evaluation criteria Pass ○: Pencil hardness 2H or more. Fail x: Pencil hardness is less than 2H.

(Abrasion)
With steel wool # 0000 (manufactured by Nippon Steel Wool Co., Ltd.), after 10 reciprocating frictions with a load of 2 kg, the presence or absence of scratches is visually confirmed.
Evaluation criteria Pass ○: No scratch. Fail x: There is a scratch.

The evaluation results are shown in Table 1. Moreover, as comprehensive evaluation, the number of passes / the number of all evaluation items (= 9) was shown.

  As can be seen from the above overall evaluation, the coating agent and the coating film of the comparative example had no overall evaluation of 9/9, and a coating agent and a coating film satisfying all desired properties were not obtained.

  On the other hand, the overall evaluation of the antiglare hard coat agent and the antiglare hard coat film of Examples 1 to 6 is 9/9. That is, according to the present invention, an antiglare hard coat agent and an antiglare hard coat film satisfying all desired properties could be obtained.

Claims (6)

Antiglare, characterized in that a silica-containing composite in which silica particles having an average particle diameter of 1 to 10 μm and an isocyanate compound having a polymerizable unsaturated group are bonded via a urethane bond is dispersed in a solution. Hard coat agent. A silica-containing composite in which silica particles having an average particle diameter of 1 to 10 μm and an isocyanate compound having a polymerizable unsaturated group are bonded via a urethane bond includes a polymerizable compound having a polymerizable unsaturated group. An anti-glare hard coat agent characterized by being dispersed in a solution. Silica particles having an average particle diameter of 1 to 10 μm, and an isocyanate compound having a plurality of isocyanate groups, in which a monomer having a polymerizable unsaturated group is introduced into at least one isocyanate group. An anti-glare hard coat agent, wherein a silica-containing composite bonded through a urethane bond is dispersed in a solution. Silica particles having an average particle diameter of 1 to 10 μm, and an isocyanate compound having a plurality of isocyanate groups, in which a monomer having a polymerizable unsaturated group is introduced into at least one isocyanate group. An anti-glare hard coat agent, wherein a silica-containing composite bonded through a urethane bond is dispersed in a solution containing a polymerizable compound having a polymerizable unsaturated group. The antiglare hard coat agent according to any one of claims 1 to 4, wherein the silica-containing composite contains 0.1 to 20% by weight of silica particles. An anti-glare hard coat film, comprising the anti-glare hard coat agent according to any one of claims 1 to 5 coated on a film.