JP2006265271A - Antistatic hard coating agent and hard coat film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic hard coating agent and a hard coat film each having high light transmittance, not causing irregular reflection and excellent in surface hardness and scratch resistance, a wiping property and a re-coating property. <P>SOLUTION: The antistatic hard coating agent is obtained by formulating at least one of lithium salts represented by formulas (1), (2) and (3) (formula (1): Li<SP>+</SP>CF<SB>3</SB>SO<SB>3</SB><SP>-</SP>; formula (2): Li<SP>+</SP>(CF<SB>3</SB>SO<SB>2</SB>)<SB>2</SB>N<SP>-</SP>; formula (3): Li<SP>+</SP>ClO<SB>4</SB><SP>-</SP>) with a monomer having an ethylenic unsaturated double bond. A colloidal silica-containing monomer, in which urethane bond of a hydroxy group of the colloidal silica dispersed in an organic solvent with an isocyanate group is formed by reacting the colloidal silica with an isocyanate compound having the isocyanate group and a polymerizable unsaturated group, is used as the monomer having the ethylenic unsaturated double bond. The lithium salt is formulated in an amount of 5-30 pts.wt. based on 100 pts.wt. resin solid content of the monomer having the ethylenic unsaturated double bond. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an antistatic hard coat agent and a hard coat film.

Plastic film is used in various industries such as the automobile industry and home appliance industry because it is lightweight and inexpensive in addition to its workability and transparency, but it is softer than glass and scratches on the surface. It has drawbacks such as easy attachment. In order to remedy this drawback, it is a common means to apply a hard coat agent such as a silicon-based paint, an acrylic paint, or a melamine paint on the surface. In addition, a coating agent having an antistatic function has been developed for the purpose of preventing dust adhesion and preventing dust from being mixed when handling a plastic film.
JP 2001-214092 A Japanese Patent No. 3198494 Patent No. 3207926 Japanese Patent No. 3454492 JP 2000-7944 JP 2001-113649 A JP 2002-67238 A JP 2000-347001

  Conventionally, as coating agents for the purpose of preventing static charge, surfactants, metal fillers, carbon, etc. are added, or conjugated conductive polymers are mixed or reacted to impart a conductive function. It has been.

  For example, Japanese Patent Application Laid-Open No. 2001-214092 discloses a technique of mixing a metal oxide with a polyfunctional acrylate or the like.

  Japanese Patent No. 3198494 is a coating agent containing conductive oxide particles. However, since metal oxide particles are mixed, there is a drawback that the transparency of the coating agent and the coating film is impaired. .

  Japanese Patent No. 3207926 is a photocurable resin composition comprising a combination of an alkali metal, alkaline earth metal salt and ammonium salt and an imidazoline type surfactant. Japanese Patent No. 3454492 discloses an antistatic plasticizer containing a reactive anionic / nonionic surfactant or a quaternary ammonium salt, a quaternary ammonium salt having a phenyl ketone skeleton, and at least one unsaturated in the molecule. As a compound having a group, a resin composition comprising (meth) acrylic acid ester and a photoinitiator is disclosed. These two patents are curing with a surfactant, and are not suitable for applications that are susceptible to humidity and require moisture resistance.

  In addition, some conjugated conductive polymers such as polypyrrole, polythiophene, and polyacetylene are inferior in transparency and have a problem in that the conductivity decreases due to ultraviolet degradation of the conjugated portion.

  On the other hand, the hard coat agent is generally a mixed system with an organic material although there is a hard coat resin using an inorganic material. These are not a combination of an organic material such as an acrylic resin and an inorganic material such as colloidal silica at the molecular level. In addition, although there is a possibility of chemical bonding between a coupling agent such as silane added as an additive and an inorganic material, the reactivity with the introduced vinyl group is not sufficient, scratch resistance, scratch resistance, etc. Satisfactory physical properties have not been obtained.

  In JP-A-2000-7944, JP-A-2001-113649, and JP-A-2002-67238, a cured film of a resin composition having good adhesion to plastic, abrasion resistance, solvent resistance, and good sliding with an untreated film. For the purpose of obtaining a film having a molecular weight, comprising a radiation curable polyfunctional acrylate having at least two (meth) acryloyl groups in the molecule and colloidal silica having a primary particle size of 1 to 200 nanometers. Although the problem is solved by the resin composition or the polyfunctional urethane acrylate, the compound having a tetrahydrofurfuryl group and a (meth) acryloyl group, the inorganic substance and the polymerizable compound are not particularly chemically bonded. However, there is a problem in durability and adhesion.

  Japanese Patent Application Laid-Open No. 2000-347001 discloses a technique relating to a photopolymerizable composition and a hard coat agent that have extremely small curing shrinkage, excellent adhesion, and excellent transparency, abrasion resistance, and solvent resistance. . However, the means to solve depends on the cationic ring-opening polymerization of the epoxy resin and the reactivity between the epoxy group and the silica by the organic solvent-dispersed colloidal silica having an average particle size of 5 to 200 nm, and the curing speed and freedom of compounding There are problems that cannot be widely applied.

  JP-A-2004-143201 is a cured film having excellent adhesion to a plastic substrate and an antireflection film with tetrahydrofuran ring-containing (meth) acrylate that imparts adhesion to a plastic substrate and active energy ray-curable silica. Obtaining techniques are disclosed. However, active energy ray-curable silica is not polyfunctional, and the bond between tetrahydrofuran ring-containing (meth) acrylate and silica is not specified.

  The present invention has been studied in view of such background art, and has an antistatic hard coat agent and a hard coat film that have high light transmittance and do not cause irregular reflection, and are excellent in surface hardness, scratch resistance, wiping properties, and recoatability. Is intended to provide.

  That is, the invention described in claim 1 comprises at least one lithium salt represented by the following formulas (1), (2), and (3) and a monomer having an ethylenically unsaturated double bond, The antistatic hard coat agent, wherein the lithium salt is 5 to 30 parts by weight based on 100 solids of the monomer.

Equation _{^{(1) Li + CF 3 SO}} 3 -
Formula (2) Li ⁺ (CF ₃ SO ₂ ) ₂ N ⁻
Formula (3) Li ⁺ ClO ₄ ⁻
The invention according to claim 2 is a method in which the monomer having an ethylenically unsaturated double bond reacts with colloidal silica dispersed in an organic solvent and an isocyanate compound having an isocyanate group and a polymerizable unsaturated group. 2. The antistatic hard coat agent according to claim 1, which is a colloidal silica-containing monomer in which the hydroxyl group of the colloidal silica and the isocyanate group are urethane-bonded, and is polymerized with the colloidal silica and the isocyanate group. By reacting with an isocyanate compound having a polymerizable unsaturated group, the cured product has excellent surface hardness and scratch resistance, and colloidal silica is not a dispersion system, so it has excellent light transmittance, and antistatic hard The gist is that it is suitable as a coating agent.

  Moreover, the wiping property is excellent due to the hydrophilic / hydrophobic balance of colloidal silica. Furthermore, since the lubricant is not used, it has characteristics such as excellent recoatability.

  In the invention according to claim 3, the monomer having an ethylenically unsaturated double bond has colloidal silica dispersed in an organic solvent, and two or more isocyanate groups in the molecule, and at least one of them. Colloidal silica-containing monomer in which an isocyanate group having a polymerizable unsaturated group introduced into an isocyanate group is reacted with an isocyanate compound having a polymerizable unsaturated group, and the hydroxyl group of the colloidal silica and the isocyanate group are urethane-bonded The antistatic hard coat agent according to claim 1, wherein the polymerizable unsaturated group is reacted with at least one of two or more isocyanate groups, and the remaining isocyanate groups are reacted with colloidal silica. This makes it possible to introduce a polyfunctional group, thereby diversifying and facilitating molecular design.

  The invention according to claim 4 is a curable resin composition obtained by mixing and polymerizing the colloidal silica-containing monomer and a polymerizable compound, the monomer having an ethylenically unsaturated double bond. The antistatic hard coat agent according to claim 1, wherein the adhesiveness to various film substrates and the like can be further improved by mixing and polymerizing a polymerizable compound.

The invention according to claim 5 is a hard coat film in which the antistatic hard coat agent is applied and cured to form a hard coat layer, and the total light transmittance is 90% or more. A hard coat film having a surface resistance value of 10 ¹³ Ω / □ or less and a pencil hardness of 2H or more,
The invention according to claim 6 is the hard coat film according to claim 5, wherein the content of silica contained in the hard coat layer is 20 to 70% by weight in solid content ratio.

  The hard coat film according to claim 5 and 6, wherein the isocyanate group and colloidal silica are reacted as described above, the polymerizable unsaturated group as a polymerization component is polymerized, or the isocyanate group and colloidal silica are reacted. Since it has a hard coat layer in which a colloidal silica-containing monomer and a polymerizable compound are mixed and polymerized and includes a hard coat layer containing at least 20% by weight or more in terms of solid content as the amount of silica, as described later It has a surface hardness of 2H or more in terms of pencil hardness and is excellent in light transmittance and antistatic property while being excellent in scratch resistance.

  In the antistatic hard coat agent and hard coat film of the present invention, the colloidal silica is not simply dispersed in the hard coat layer, but the isocyanate group in the resin component having a polymerizable unsaturated group and the hydroxyl group of the colloidal silica By reacting, the resin component and the silica are excellent in adhesion, and the introduction of polymerizable unsaturated groups can be made multifunctional, so that it can be cured for a short time without using electron beam curing. Can do. Moreover, despite having a high silica content, high transparency, scratch resistance, and scratch resistance can be obtained, and it can be suitably used for polarizing plates in liquid crystal displays or for protecting various displays. it can.

  In addition, various functional materials are added to the hard coat film of the present invention for the purpose of imparting functions such as antireflection, electromagnetic shielding, electrical conductivity, adhesive processing, and polarization function, coating, vapor deposition, sputtering, film laminating. Etc. are also possible.

  Hereinafter, the present invention will be described in detail.

  The lithium salt used in the present invention is represented by the following formula (1) and / or (2).

Equation _{^{(1) Li + CF 3 SO}} 3 -
Formula (2) Li ⁺ (CF ₃ SO ₂ ) ₂ N ⁻
Formula (3) Li ⁺ ClO ₄ ⁻
The anions shown in the formulas (1) and (2) have several types of resonance structures, and delocalization of negative charges occurs, so that they are very stable as negative ions. Furthermore, there is also an effect of strong electron withdrawing property of the fluorinated alkyl group, and lithium ions are very easily separated. For this reason, these lithium salts express high lithium ion conductivity in an organic solvent or resin.

  The anion represented by the formula (3) is very easy to dissociate lithium ions and exhibits high lithium ion conductivity in an organic solvent or resin.

  The lithium salt has the following characteristics as compared with the surfactant-type antistatic agent. First, since it does not scatter from the surface of the coating film or fall off due to wiping like a surfactant, it has excellent antistatic performance. Secondly, since there is no bleeding on the coating film surface, recoatability is excellent. Thirdly, since lithium ions contained in the coating film, rather than moisture adsorbed on the surface, serve as an ion-conducting medium, the conductivity is dependent on humidity like a surfactant and is conductive at low humidity. Will not drop.

  Further, the lithium salt has the following characteristics as compared with the hydrophilic polymer type antistatic agent. First, in the hydrophilic polymer type antistatic agent, the water adsorbed on the hydrophilic group located on the surface serves as an ion-conducting medium, so a considerable amount of hydrophilic polymer is added to obtain sufficient hydrophilic group on the surface. Although it is necessary and has a great influence on the physical properties of the coating film such as the surface hardness, since the lithium salt obtains conductivity by movement of lithium ions, the addition amount can be suppressed to a small amount as described later. Secondly, since lithium ions contained in the coating film, rather than moisture adsorbed on the surface, serve as an ion-conducting medium, the conductivity is dependent on humidity like a hydrophilic polymer and is conductive at low humidity. Will not drop.

  Further, the lithium salt has the following characteristics as compared with the conductive metal oxide type antistatic agent. First, there is no coloring like a metal oxide and it has very high transparency. Second, in order to obtain conductivity by contacting fine particles of several hundred nanometers or less in the coating film with metal oxide, an addition amount close to the same amount as the base resin is required. Since the salt obtains conductivity by the movement of lithium ions, the addition amount can be suppressed to a small amount as described later. Third, when added to the hard coating agent, a special dispersing device such as a bead mill is not required unlike the metal oxide fine particles, and it is simple.

  Furthermore, the lithium salt has the following characteristics as compared with conductive polymer type antistatic agents such as polypyrrole, polythiophene, and polyaniline. First, there is no coloring like a conductive polymer, and it has extremely high transparency. Secondly, in order to dissolve the conductive polymer, a halogen-containing solvent or a special solvent having toxicity and toxicity is generally required. However, the lithium salt can be dissolved in a general organic solvent, and the coating agent The design range is wide and the environmental load can be further suppressed.

  By using these lithium salts as an antistatic agent for a hard coating agent containing a colloidal silica-containing monomer having an ethylenically unsaturated double bond, the characteristics as a hard coating agent are not lost. It is an antistatic hard coat agent which is colored and has high light transmittance and does not cause irregular reflection, and has excellent surface hardness, scratch resistance, wiping property and recoatability. .

  The addition amount of these lithium salts is preferably 5 to 30 parts by weight with respect to the resin solid content 100 of the monomer having an ethylenically unsaturated double bond. If it exceeds, transparency tends to be inferior.

  The monomer having an ethylenically unsaturated double bond is obtained by reacting a colloidal silica dispersed in an organic solvent with an isocyanate compound having an isocyanate group and a polymerizable unsaturated group, and the hydroxyl group of the colloidal silica and the isocyanate group. And a colloidal silica-containing monomer having a urethane bond, or colloidal silica dispersed in an organic solvent, and two or more isocyanate groups in the molecule, and at least one isocyanate group having a polymerizable unsaturated group And a colloidal silica-containing monomer obtained by reacting an isocyanate group having introduced thereinto with an isocyanate compound having a polymerizable unsaturated group and urethane-bonding the hydroxyl group of the colloidal silica and the isocyanate group.

  The silica according to the present invention is not particularly limited, and various commercial products having an average particle diameter of 100 nm or less and an organic solvent as a dispersion medium can be used. When silica having a larger particle diameter is used, not only the storage stability is deteriorated, but also the desired elasticity, hardness and heat resistance aimed at in the present invention cannot be expressed at the same time. There are problems such as cloudiness. Those having an average particle diameter of 5 to 50 nm are more preferred. Silica may be a compound having a silicate, but it is preferable to use colloidal silica having a hydrophobic group dispersible in an organic solvent in which a part of the hydroxyl group present on the silica surface is chemically modified. More preferably, a hydrophobic organic material having a water solubility of 0.1 to 12% by weight, wherein a part of hydroxyl groups on the surface of colloidal silica is modified with a silylating agent such as a disiloxane compound and / or a monoalkoxysilane compound. It is desirable that it is colloidally dispersed in a solvent.

  Examples of the organic solvent as a dispersion medium for colloidal silica include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, n-butyl acetate, diisopropyl ether, and dibutyl ether. Examples of the reactive solvent include acrylic monomers such as methyl methacrylate.

  A compound containing a polymerizable unsaturated group and an isocyanate group to be reacted with colloidal silica dispersed in an organic solvent is a compound having a polymerizable unsaturated group and an isocyanate group in the same molecule, specifically, acryloyl isocyanate, methacryloyl. Examples include isocyanate, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, and the like.

  Alternatively, it is a compound having two or more isocyanate groups in the molecule and having an isocyanate group and a polymerizable unsaturated group by introducing a polymerizable unsaturated group into at least one isocyanate group. Examples of the group include a vinyl group, an allyl group, and a (meth) acryloyl group. In the present specification, “(meth) acryloyl” means “acryloyl or methacryloyl”.

  Examples of the compound containing two or more 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, methylene bis (4-cyclohexyl isocyanate), 2,2,4- Limethylhexamethylene diisocyanate, bis (2-isocyanatoethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, tolidine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diene Isocyanate, 2,5 (or 6) -bis (isocyanate methyl) -bicyclo [2.2.1] heptane, trimethylolpropane adduct of triethylene diisocyanate, isocyanurate of triethylene diisocyanate, diphenylmethane-4,4 ′ -Diisocyanate oligomer, hexamethylene diisocyanate biuret, hexamethylene diisocyanate isocyanurate, Uretdione Sa diisocyanate, isocyanurate and the like of isophorone diisocyanate.

  Moreover, these polyisocyanates can be used individually or in combination of 2 or more types.

  Examples of the compound having a polymerizable unsaturated group introduced into at least one isocyanate group of the polyisocyanate include a hydroxyl group-containing monomer.

  Examples of monofunctional acrylates include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and polyethylene glycol acrylate.

  Examples of polyfunctional acrylates include hydroxyl group-containing monomers such as trimethylolpropane diacrylate, ethoxylated trimethylolpropane diacrylate, propoxylated trimethylolpropane diacrylate, and pentaerythritol tri (meth) acrylate.

  Of these, polyfunctional acrylates are preferred. This is because the hardness characteristics of silica can be further extracted by increasing the acrylate density and increasing the degree of crosslinking of the organic matter. The number of functional groups is preferably from 3 to 6, and if it exceeds 6 functionalities, curing with a low-power lamp is possible, but unsaturated groups remain after coating and curing, resulting in lack of light resistance such as discoloration. A high-power lamp is required, leading to a reduction in crosslink density, making it difficult to extract the hardness characteristics of silica.

  Examples of the compound having a polymerizable unsaturated group that reacts with an isocyanate group other than a hydroxyl group include (meth) acrylic acid, itaconic acid, cinnamic acid, maleic acid, fumaric acid, 2- (meth) acryloxypropylhexahydrogen. Unsaturated aliphatic carboxylic acids such as phthalate, 2- (meth) acryloxyethyl hexahydrogen phthalate, 2- (meth) acryloxypropyl phthalate, 2- (meth) acryloxypropyl Unsaturated aromatic carboxylic acid having a carboxyl group such as ethyl phthalate, vinyloxyethylamine, vinyl oxide decylamine, allyloxypropylamine, 2-methylallyloxyhexylamine, vinyloxy- (2-hydroxy) butylamine, etc. An amino group-containing monomer can also be used.

  These compounds having a polymerizable unsaturated group can be used alone or in combination of two or more.

  In order to promote the reaction for introducing a polymerizable unsaturated group into the polyisocyanate and the reaction between the colloidal silica 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] It is preferable to use 0.01 to 1 part by weight of a urethanization catalyst such as octane with respect to 100 parts by weight of the total amount of reactants.

  The reaction for introducing a 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. , Ester solvents such as ethyl acetate 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 one or more polar solvents such as ether solvents such as dioxane, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and furfural.

  In the course of the reaction between the isocyanate group and colloidal silica, IR or amine titration is performed, and the concentration of the remaining isocyanate group is measured over time. If there are residual isocyanate groups, alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol and compounds capable of reacting with the isocyanate groups may be added to block excess isocyanate groups. Presence of residual isocyanate groups leads to a decrease in storage stability.

  Further, as described in claim 4, for the purpose of further improving the adhesion to various film substrates and the like, a polymerizable compound may be mixed and copolymerized with a colloidal silica-containing monomer. Examples of the functional compound include alkyl esters of acrylic acid or methacrylic acid, unsaturated nitrile monomers, unsaturated carboxylic acids, amide group-containing monomers, methylol group-containing monomers, alkoxymethyl group-containing monomers, epoxy group-containing monomers, multifunctional monomers, Examples thereof include radical polymerization compounds having a reactive double bond in the molecular chain such as vinyl ester and olefin.

  Examples of alkyl esters of acrylic 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, Examples include propyl 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.

  Radical polymerizable compounds other than those described above may be combined as necessary. For example, amide group-containing monomers, specifically acrylamide, methacrylamide, N, N-methylenebisacrylamide, diacetone acrylamide, maleic acid amide, maleimide, methylol group-containing monomers, specifically N-methylol acrylamide, N- Methylol methacrylamide, dimethylol acrylamide, dimethylol methacrylamide, alkoxymethyl group-containing monomer, specifically N-methoxymethyl acrylamide, N-methoxymethyl methacrylamide, N-butoxymethyl acrylamide, N-butoxymethyl methacrylamide, epoxy Group-containing monomers, specifically glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, methyl glycidyl acrylate, methyl glycidyl meta Relate, multifunctional monomers, specifically divinylbenzene, polyoxyethylene diacrylate, polyoxyethylene dimethacrylate, polyoxypropylene diacrylate, polyoxypropylene dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, trimethylol Propane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, mono- or diesters of α, β-ethylenically unsaturated dicarboxylic acids such as mono- or dibutyl maleate, mono- or dioctyl fumarate, vinyl esters , Specifically vinyl acetate, vinyl propionate, olefins such as butadiene, isoprene, chlorine containing vinyl Nomar may include, for example, vinyl chloride, vinylidene chloride, chloroprene, etc. Other styrene.

  These compounds having a reactive double bond may be used alone or in combination of two or more.

  Examples of the polymerization initiator used for copolymerization include peroxides and azobis compounds. Examples of peroxides include dibutyl peroxide, benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, and the like. Examples of the 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.

  Moreover, radiation polymerization is also possible, and it is also possible to use a radiation polymerization initiator. For example, 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-chlorothioxanthone, 2-methyl Ru-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4 , 4-trimethylpentylphosphine oxide and the like, and as commercially available products Irgacure 184, 369, 651, 500, 907, CGI 1700, CGI 1750, CGI 1850, CG 24-61 (above, manufactured by Ciba Geigy); Lucirin LR8728 (manufactured by BASF); 1173 (manufactured by Merck); Ubekrill P36 (manufactured by UCB) and the like.

  Content of colloidal silica is 20 weight% or more by the solid content ratio in the resin hardened | cured material used as a hard-coat layer, Preferably it is 20 to 70 weight%. If it is less than 20% by weight, the hardness is inferior, and if it exceeds 70% by weight, the transparency is inferior. If it exceeds the appropriate range, the total light transmittance is 90% or more, and the cured resin has a pencil hardness of 2H or more. Is not obtained, and the scratch resistance and scratch resistance are poor.

  In addition, in order to ensure the adhesiveness with respect to various base materials etc. as an antistatic hard-coat agent, tackifying resin (henceforth TF) is mix | blended suitably. For TF, resins such as modified rosin, polymerized rosin, phenolic resins such as phenolic resins and alkylphenolic resins, aromatic petroleum based resins such as coumarone indene, aliphatic hydrocarbons and terpene resins can be used. Those modified with carboxyl or hydroxyl can also be used.

  In addition, metal oxides such as zinc oxide, calcium oxide, and magnesium oxide are blended as blending materials for the purpose of improving aging prevention.

  The plastic film as the base material of the hard coat film of the present invention is, for example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film , Polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyether ether ketone film, polyether sulfone film, poly Etherimide film, polyimide film, fluorine resin film, Nylon film, can be used an acrylic resin film, any known. The substrate may be in the form of a sheet or plate depending on the application.

  The colloidal silica-containing monomer or the colloidal silica-containing monomer and a polymerizable compound are mixed to improve adhesion with the polymerized curable resin composition. Surface roughening treatment by a method or the like, or surface treatment such as corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, electron beam irradiation treatment, etc. may be applied.

  There are no particular restrictions on the coating method and coating thickness of the antistatic coating agent of the present invention, and known methods such as gravure coating, bar coating, knife coating, roll coating, blade coating, and die coating It can apply | coat etc. so that the thickness of a coating film may be set to 1-50 micrometers after drying. If it is less than 1 μm, sufficient scratch resistance and scratch resistance cannot be obtained, and if it exceeds 50 μm, there is a problem in handling such as warping of the obtained film. Preferably, it is 5-30 micrometers.

EXAMPLES Hereinafter, although an Example and a comparative example are given and demonstrated in detail about this invention, a specific example is shown and it does not specifically limit to these.
Example 1
Production of Colloidal Silica-Containing Monomer (A) Ethyl acetate solvent-dispersed colloidal silica (SiO ₂ component 30%, average particle size 20 nm / manufactured by Nissan Chemical Co., Ltd.) 130 parts by weight, 2-methacryloyloxyethyl isocyanate (MOI) (Molecular weight 155 / manufactured by Showa Denko KK) 30 parts by weight and 0.1 part by weight of di-n-butyltin dilaurate (DBTDL) as a catalyst were added and stirred for 24 hours. The reaction of the isocyanate group was confirmed by IR, and the solvent was removed with an evaporator to obtain a colloidal silica-containing monomer (A).
Production of Antistatic Hard Coating Agent (A) To 100 parts by weight of the colloidal silica-containing monomer (A) synthesized above (non-volatile content 36%), a MEK solution of Li ⁺ CF ₃ SO ₃ ⁻ (non-volatile content 50%) / Sanko Chemical Co., Ltd.) 5 parts by weight were mixed and stirred. As an initiator, 1 part by weight of Irgacure 907 was added to obtain an antistatic hard coat agent (A).
Production of Hard Coat Film (A) Next, the antistatic hard coat agent (A) was applied to a 188 μm PET (polyethylene terephthalate: Lumirror (trade name) manufactured by Toray Industries, Inc.) film so that the film thickness after curing would be 10 μm. The hard coat film (C) was obtained by applying an ultraviolet treatment of 300 mJ with an 80 W / cm mercury lamp.
Example 2
Production of colloidal silica-containing monomer (B) 2.84 parts by weight of 2-hydroxyethyl methacrylate (HEMA) 4.85 parts by weight of isophorone diisocyanate (IPDI) and 0.01 part by weight of DBTDL as a catalyst , HEMA-IPDI monomer was obtained. This monomer was added to 40 parts by weight of MIBK-dispersed colloidal silica (SiO ₂ component 30%, average particle diameter 20 nm / manufactured by Nissan Chemical Co., Ltd.) and stirred for 24 hours at room temperature, and then isopropanol was added. The reaction of the isocyanate group was confirmed by IR, and unreacted isopropanol was removed with an evaporator to obtain a colloidal silica-containing monomer (B).
Production of antistatic hard coat agent (B) MEK solution of Li ⁺ CF ₃ SO ₃ ⁻ (nonvolatile content 50%) to 100 parts by weight of colloidal silica-containing monomer (B) synthesized above (nonvolatile content 36%) / Sanko Chemical Co., Ltd.) 5 parts by weight were mixed and stirred. As an initiator, 1 part by weight of Irgacure 907 was added to obtain an antistatic hard coat agent (B).
Manufacture of Hard Coat Film (B) Next, the antistatic hard coat agent (B) is coated on a 188 μm PET (polyethylene terephthalate: Lumirror (trade name) manufactured by Toray Industries, Inc.) film so that the film thickness after curing is 10 μm. The hard coat film (B) was obtained by applying an ultraviolet treatment of 300 mJ with an 80 W / cm mercury lamp.
Example 3
Production of colloidal silica-containing monomer (C) 2.85 parts by weight of 2-hydroxyethyl methacrylate (HEMA) 4.85 parts by weight of isophorone diisocyanate (IPDI) and 0.01 part by weight of DBTDL as a catalyst were added. , HEMA-IPDI monomer was obtained. This monomer was added to 20 parts by weight of MIBK-dispersed colloidal silica (SiO ₂ component 30%, average particle size 20 nm / manufactured by Nissan Chemical Co., Ltd.) and stirred for 24 hours at room temperature, and then isopropanol was added. The reaction of the isocyanate group was confirmed by IR, and unreacted isopropanol was removed with an evaporator to obtain a colloidal silica-containing monomer. 20 parts by weight of MMA was mixed with 80 parts by weight of the obtained colloidal silica-containing monomer to obtain a colloidal silica-containing monomer (C).
Manufacture of antistatic hard coat agent (C) MEK solution of Li ⁺ CF ₃ SO ₃ ⁻ (nonvolatile content 50%) to 100 parts by weight of colloidal silica-containing monomer (C) synthesized above (nonvolatile content 36%) / Sanko Chemical Co., Ltd.) 5 parts by weight were mixed and stirred. As an initiator, 1 part by weight of Irgacure 907 was added to obtain an antistatic hard coat agent (A).
Manufacture of Hard Coat Film (C) Next, the antistatic hard coat agent (C) is coated on a 188 μm PET (polyethylene terephthalate: Lumirror (trade name) manufactured by Toray Industries, Inc.) film so that the film thickness after curing is 10 μm. The hard coat film (C) was obtained by applying an ultraviolet treatment of 300 mJ with an 80 W / cm mercury lamp.
Example 4
In Example 3, the same procedure was followed except that the amount of Li ⁺ CF ₃ SO ₃ ⁻ MEK solution (non-volatile content 50% / manufactured by Sanko Chemical Industry Co., Ltd.) was 10 parts by weight. D) was obtained.
Example 5
In Example ^{_{3, Li + CF 3 SO 3}} - except that a solution in MEK amount of 13 parts by weight of (non-volatile content of 50% / Sanko Kogyo Co., Ltd.) was carried out as a hard coat film ( E) was obtained.
Example 6
A hard coat film was obtained under the same conditions as in Example 1 except that the addition amount of a MEK solution of Li ⁺ CF ₃ SO ₃ ^— (non-volatile content: 50% / manufactured by Sanko Chemical Industry Co., Ltd.) was 17 parts by weight. .
Comparative Example 1
In Example ^3, Li + _CF three SO ₃ ^- except that a solution in MEK amount of 3 parts by weight of (non-volatile content of 50% / Sanko Kogyo Co., Ltd.) was carried out as a hard coat film ( a) was obtained.
Comparative Example 2
In Example 3, it was carried out in the same manner except that the amount of Li ⁺ CF ₃ SO ₃ ⁻ MEK solution (non-volatile content 50% / manufactured by Sanko Chemical Co., Ltd.) was changed to 29 parts by weight. b) was obtained.
Comparative Example 3
100 parts by weight of the colloidal silica-containing monomer (C) synthesized in Example 3 (non-volatile content: 36%) and 2 weight of surfactant type antistatic agent electrostripper EA (non-volatile content: 100% / manufactured by Kao Corporation) The parts were mixed and stirred. Next, a mixed solution containing 1 part by weight of Irgacure 907 as an initiator was applied to a 188 μm PET (polyethylene terephthalate: Lumirror (trade name) manufactured by Toray Industries, Inc.) film so that the film thickness after curing was 10 μm. An ultraviolet treatment of 300 mJ was performed with an 80 W / cm mercury lamp to obtain a hard coat film (c).
Comparative Example 4
100 parts by weight of the colloidal silica-containing monomer (C) synthesized in Example 3 (non-volatile content 36%) was mixed with 30 parts by weight of solvent-soluble polypyrrole SSPY (non-volatile content 1% / Mitani Sangyo Co., Ltd.). And stirred. Next, a mixed solution obtained by adding 1 part by weight of Irgacure 907 as an initiator was applied to a 188 μm PET (polyethylene terephthalate: Lumirror (trade name) manufactured by Toray Industries, Inc.) film so that the film thickness after curing would be 10 μm. A hard coat film (d) was obtained by performing UV treatment at 300 mJ with a mercury lamp of / cm.
Comparative Example 5
100 parts by weight of colloidal silica-containing monomer (C) synthesized in Example 3 (non-volatile content: 36%) and 100 parts by weight of ATO fine particle MEK dispersion SNS-10M (non-volatile content: 30% / Ishihara Sangyo Co., Ltd.) Were mixed and stirred. Next, a mixed solution containing 1 part by weight of Irgacure 907 as an initiator was applied to a 188 μm PET (polyethylene terephthalate: Lumirror (trade name) manufactured by Toray Industries, Inc.) film so that the film thickness after curing was 10 μm. An ultraviolet treatment of 300 mJ was performed with an 80 W / cm mercury lamp to obtain a hard coat film (e).

The evaluation results are shown in Table 1.

The evaluation method was as follows.
1) Total light transmittance: Measured with a haze meter (manufactured by Suga Test Instruments) based on the provisions of JIS K 7361-1 (2000 edition) 3.2.
2) Degree of haze: Measured with a haze meter (manufactured by Suga Test Instruments Co., Ltd.) according to JIS K 7136 (2000 edition).
3) Adhesiveness: Based on a cross-cut test based on JIS K 5600-5-6 (1999 edition), 10 × 10 squares are made on the coated surface, cellophane tape is applied, and the tensile peeling state is confirmed upward. . The squares that were not peeled off were counted. “Number of remaining eyes / Total number of eyes (100)”
4) Pencil hardness: According to JIS K 5600, a scratch test was performed by applying a load from right above the pencil fixed at an angle of 45 degrees, and the pencil hardness without scratches was displayed.
5) Scratch resistance: Evaluated based on whether or not scratches are caused by rubbing 10 times with a load of 2 kg using steel wool # 0000 (manufactured by Nippon Steel Wool Co., Ltd.). It was divided into 5 stages according to scratches and evaluated as follows.

    Evaluation 5: There is no scratch at all.

    Evaluation 4: 1 to 3 scratches are included.

    Evaluation 3: Scratches equivalent to 4 to 7 are entered.

    Evaluation 2: Scratches equivalent to 8 to 15 are entered.

Evaluation 1: There are numerous scratches.
6) Surface resistivity: Measured using a digital ultrahigh resistance / microammeter R8340A (Advantest Co., Ltd.) based on JIS K 6911-5-13 (1995 edition).
7) Recoatability: A 100 nm silicon oxide / tin oxide thin film was formed on the hard coat film by vapor deposition. Based on a cross-cut test based on JIS K 5600-5-6 (1999 edition) for adhesion to the deposited film, create a 10 × 10 grid on the coated surface, apply cellophane tape, and pull upward to check the peel-off status. Check. The squares that were not peeled off were counted. “Number of remaining eyes / Total number of eyes (100)”
8) Wettability: According to the wettability test method JISK6768 (1999 edition). The wettability standard reagent (Wako Pure Chemical Industries) was soaked in a cotton swab, and when it was applied to the surface of a subject, the minimum value of the reagent number that wets completely was taken as the wetting index.
9) Wipeability: Hand dirt was adhered on the surface and the wipeability was evaluated with a 140 denier nylon cloth.

○: Can be wiped within 3 reciprocations △: Can be wiped within 10 reciprocations ×: Not completely removable

Claims (6)

It comprises at least one lithium salt represented by the following formulas (1), (2) and (3) and a monomer having an ethylenically unsaturated double bond, and the lithium salt is a resin of the monomer. An antistatic hard coat agent characterized by being 5 to 30 parts by weight with respect to a solid content of 100.
Equation _{^{(1) Li + CF 3 SO}} 3 -
Formula (2) Li ⁺ (CF ₃ SO ₂ ) ₂ N ⁻
Formula (3) Li ⁺ ClO ₄ ⁻ The monomer having an ethylenically unsaturated double bond is reacted with colloidal silica dispersed in an organic solvent and an isocyanate compound having an isocyanate group and a polymerizable unsaturated group, and the hydroxyl group of the colloidal silica and the isocyanate are reacted. 2. The antistatic hard coat agent according to claim 1, which is a colloidal silica-containing monomer having a urethane group bonded thereto. The monomer having an ethylenically unsaturated double bond has colloidal silica dispersed in an organic solvent, two or more isocyanate groups in the molecule, and a polymerizable unsaturated group in at least one isocyanate group It is a colloidal silica-containing monomer obtained by reacting an isocyanate group having a polymerizable unsaturated group introduced therein with an isocyanate compound having a polymerizable unsaturated group and urethane-bonding the hydroxyl group of the colloidal silica and the isocyanate group. Item 2. An antistatic hard coat agent according to Item 1. The monomer having an ethylenically unsaturated double bond is a curable resin composition obtained by mixing and polymerizing the colloidal silica-containing monomer and a polymerizable compound. 1. An antistatic hard coat agent according to 1. A hard coat film in which the antistatic hard coat agent is applied and cured to form a hard coat layer, the total light transmittance is 90% or more, and the surface resistance value of the hard coat layer is 10 ¹³ Ω / □ A hard coat film having a pencil hardness of 2H or more. 6. The hard coat film according to claim 5, wherein the content of silica contained in the hard coat layer is 20 to 70% by weight in solid content ratio.