TW201504365A - Coating material and coating composition - Google Patents

Abstract

The present invention provides a coating material which is sought to improve antifouling property and ensure excellent wipe and sliding properties as well as a coating composition. The coating material is obtained by reacting acrylic polymer, diisocyanate, polyether polyol, which at least have hydroxyl group at the side chain, with photopolymerizable compound that has both hydroxyl group and photopolymerizable group. Further, the coating composition is made to contain the coating material and the photopolymerizable initiator. With reference to the coating material and coating composition, it can improve antifouling property of the coating surface and ensure excellent wipe and sliding properties.

Description

Coating material and coating composition

The present invention relates to a coating material and a coating composition, and more particularly to a coating material and a coating composition for coating the surface of a member used in various industrial fields.

In the past, it is easy to adhere to stains such as fingerprint marks on various optical members such as a touch panel, a display, a lens, and a glass, and if the stain is adhered, the visibility is lowered, so that it is required to suppress the adhesion of stains (to impart antifouling properties), Make fingerprint smudges and the like less conspicuous, or improve the ease of wiping of the adhered stains (wiping off). Further, in recent years, it has been demanded that the optical member used in a touch panel or the like is easily slid (providing "slidability") to improve operability.

As a method of satisfying such a requirement, for example, a method of coating the surface of an optical member with an antifouling coating material is known, and as such a coating material, Patent Document 1 discloses the following fingerprint-resistant photocurable composition. And comprising: a polyether skeleton-containing (meth)acrylic acid having at least one (meth) acrylate group at both ends and having a water tolerance of 6.0 ml or less and a solubility parameter of 12 or less. A urethane (A), a photopolymerizable polyfunctional compound (B), and a photopolymerization initiator (C).

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-95707

However, when the fingerprint-resistant photocurable composition described in Patent Document 1 is used, there is a problem that the obtained coating surface is insufficient in wiping property or slidability.

An object of the present invention is to provide a coating material and a coating composition which are capable of improving the antifouling property and ensuring excellent wiping property and slidability.

In order to achieve the above object, the coating material of the present invention is obtained by reacting at least an acrylic polymer having a hydroxyl group in a side chain, a diisocyanate, a polyether polyol, and a photopolymerizable compound having a hydroxyl group and a photopolymerizable group. obtain.

Moreover, it is preferable that the coating material of the present invention has a glass transition temperature of 30 ° C or more as determined by the Fox equation of the acrylic polymer.

Further, in the coating material of the present invention, the acrylic polymer preferably has a content ratio of a hydroxyl group-containing vinyl monomer, methyl (meth) acrylate, and methyl (meth) acrylate. 50% by mass or more of the monomer composition is obtained by polymerization.

Further, the coating material of the present invention preferably has a hydroxyl value of from 10 to 50 mgKOH/g as determined by the B method of JIS K 1557-1 (2007).

Further, the coating material of the present invention is preferably obtained by reacting the above-mentioned diisocyanate, the above polyether polyol, and the photopolymerizable compound, and having an isocyanate group and a photopolymerizable group at the molecular terminal. The isocyanate group of the prepolymer reacts with the hydroxyl group of the above acrylic polymer on the side chain.

Moreover, the coating material of the present invention is preferably obtained by making 100 parts by mass of the total amount of the acrylic polymer, the diisocyanate, the polyether polyol, and the photopolymerizable compound. The acrylic polymer is used in an amount of 5 to 80 parts by mass, the diisocyanate is 5 to 30 parts by mass, and the polyether polyol is used in an amount of 5 to 40 parts by mass. The photopolymerizable compound is obtained by reacting at a ratio of 10 to 50 parts by mass.

Moreover, the coating composition of the present invention is characterized by comprising the above-mentioned coating material and a photopolymerization initiator.

According to the coating material of the present invention and the coating composition containing the coating material, the antifouling property of the coated surface can be improved, and excellent wiping property and slidability can be ensured.

<coated material>

The coating material of the present invention can be obtained by reacting at least an acrylic polymer having a hydroxyl group in a side chain, a diisocyanate, a polyether polyol, and a photopolymerizable compound having both a hydroxyl group and a photopolymerizable group.

. Acrylic polymer having hydroxyl groups in the side chain

The acrylic polymer having a hydroxyl group in the side chain (hereinafter sometimes referred to simply as an acrylic polymer) is, for example, comprising an alkyl (meth)acrylate as a main component and further comprising an alkyl group (meth)acrylate. The monomer composition of the ester-copolymerized hydroxyl group-containing vinyl monomer is obtained by polymerization.

Alkyl (meth)acrylate

The alkyl (meth)acrylate is an alkyl methacrylate and/or an alkyl acrylate, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate. , butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl ester, decyl (meth) acrylate, decyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentadienyl (meth) acrylate (meth)acrylate) and so on.

The (meth)acrylic acid alkyl ester is preferably methyl (meth)acrylate or butyl (meth)acrylate, more preferably methyl (meth)acrylate, and particularly preferably methacrylic acid. Ester (MMA).

These alkyl (meth)acrylates may be used alone or in combination of two or more.

The blending ratio of the alkyl (meth)acrylate is, for example, 40% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and usually less than 100% based on the total amount of the monomer composition. quality%.

Further, the blending ratio of methyl (meth) acrylate is preferably 50% by mass or more, more preferably 60% by mass or more, and usually less than 100% by mass based on the total amount of the monomer composition.

When the blending ratio of the methyl (meth) acrylate is in the above range, the glass transition temperature of the acrylic polymer can be set high, and excellent slidability can be ensured on the coated surface obtained by using the coating material.

Hydroxy-containing vinyl monomer

The hydroxyl group-containing vinyl monomer is a hydroxyl group-containing (meth)acrylic acid alkyl ester, and specific examples thereof include 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, (meth)acrylic acid 8 -hydroxyoctyl ester, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, 4-hydroxymethylcyclohexyl (meth)acrylate, N-hydroxyl (meth)acrylate Base amine and the like.

The hydroxyl group-containing vinyl monomer is preferably 2-hydroxyethyl (meth)acrylate, and more preferably 2-hydroxyethyl acrylate (2-HEA).

These hydroxyl group-containing vinyl monomers may be used singly or in combination of two or more.

The blending ratio of the hydroxyl group-containing vinyl monomer is, for example, 50% by mass or less, preferably 40% by mass or less, and usually 5% by mass or more based on the total amount of the monomer composition.

Copolymerizable vinyl monomer

Further, the monomer composition may further contain a copolymerizable vinyl monomer copolymerizable with the alkyl (meth)acrylate and/or the hydroxyl group-containing vinyl monomer.

Examples of the copolymerizable vinyl monomer include an epoxy group-containing vinyl monomer, a mercapto group-containing vinyl monomer, a cyano group-containing vinyl monomer, and a quinone imine group-containing vinyl monomer. a functional group-containing vinyl monomer such as a carboxyl group-containing vinyl monomer or an alkoxy polyalkylene glycol-based vinyl monomer (except for a hydroxyl group-containing vinyl monomer) a copolymerized ethylene containing at least one functional group selected from the group consisting of an epoxy group, a decylamino group, a cyano group, a quinone imine group, a carboxyl group, an alkoxy-terminated alkyl diol group, and the like, and having no hydroxyl group Base monomer.

Examples of the epoxy group-containing vinyl monomer include glycidyl (meth)acrylate and methyl glycidyl (meth)acrylate.

Examples of the mercapto group-containing vinyl monomer include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, and N,N-diethyl(meth)propene. Indoleamine, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-hydroxymethyl (A Acrylamide, N-methylolpropane (meth) acrylamide, N-vinylcarboxylic acid amide, dimethylaminopropyl acrylamide, diacetone acrylamide , N-methylol acrylamide and the like. Among them, N,N-dialkyl(meth)acrylamide, such as N,N-dimethyl(meth)acrylamide, is preferable, and N,N-dimethyl decylamine is more preferable. (DMAA).

Examples of the cyano group-containing vinyl monomer include acrylonitrile and methacrylonitrile.

Examples of the vinyl monomer containing a quinone imine group include, for example, N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N- a maleic imine monomer such as phenyl maleimide; for example, N-methyl itaconimine, N-ethyl itaconimine, N-butyl itaconide, N - octyl ketimine, N-2-ethylhexyl ketimine, N-cyclohexyl ketimine, N-Lauryl ketimine, etc. (itaconimide) Monomer For example, N-(methyl)propenyloxymethylene succinimide, N-(methyl)propenyl-6-oxyhexamethylene succinimide, N-(methyl) propylene An amber quinone imine monomer such as decyl-8-oxyoctamethylene succinimide.

Examples of the carboxyl group-containing vinyl monomer include unsaturated carboxylic acids such as (meth)acrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, and cinnamic acid; for example, fumaric anhydride, An unsaturated dicarboxylic anhydride such as maleic anhydride or itaconic anhydride; for example, monomethyl itaconate, monobutyl itaconate, 2-acryloyloxyethyl phthalate An unsaturated monocarboxylic acid monoester; for example, an unsaturated tricarboxylic acid such as 2-methylpropenyloxyethyl trimellitate or 2-methylpropenyloxyethyl pyromellitic acid ester An ester; for example, a carboxyalkyl acrylate such as carboxyethyl acrylate or carboxypentyl acrylate.

Examples of the vinyl monomer having an alkoxy-terminated alkylene glycol group include methoxypolyethylene glycol (meth)acrylate.

Further, examples of the copolymerizable vinyl monomer include polyfunctional monomers having a plurality of radically polymerizable functional groups.

Examples of the polyfunctional monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene glycol. (meth)acrylate or the like (mono or poly) ethylene glycol di(meth)acrylate, or propylene glycol di(meth)acrylate or the like (mono or poly)alkylene glycol di(meth)acrylate Further, examples thereof include neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, and trimethylolpropane. Tris(meth)acrylate, pentaerythritol tri(meth)acrylate, tetramethylolmethanetri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, divinylbenzene, etc. .

In addition, examples of the copolymerizable vinyl monomer include vinyl esters such as vinyl acetate and vinyl propionate, and examples thereof include ethylene, propylene, isoprene, and butyl. An olefin-based monomer such as a diene or an isobutylene; for example, an aryl (meth)acrylate such as phenyl (meth)acrylate; for example, an aromatic vinyl such as styrene or vinyl toluene; for example, (meth)acrylic acid An alkoxy group-containing monomer such as methoxyethyl ester or ethoxyethyl (meth)acrylate; for example, a vinyl ether monomer such as vinyl ether; for example, a halogen atom-containing monomer such as vinyl chloride; for example, N-vinylpyrrolidone, N-(1-methylvinyl)pyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperidone N-vinylpyrene , N-vinylpyrrole, N-vinylimidazole, N-vinyl Oxazole, N-vinyl Porphyrin, tetrahydrofurfuryl (meth)acrylate, (meth)acrylonitrile A vinyl group-containing heterocyclic compound such as a phenyl group; for example, an acrylate monomer containing a halogen atom such as a fluorine atom.

The copolymerizable vinyl monomer is preferably a functional group-containing vinyl monomer, and more preferably a mercapto group-containing vinyl monomer.

These copolymerizable vinyl monomers may be used singly or in combination.

In the case of using a copolymerizable vinyl monomer, the compounding ratio is, for example, 10 to 50% by mass, preferably 20 to 40% by mass based on the total amount of the monomer composition.

. Method for preparing acrylic polymer having hydroxyl group in side chain

Further, by polymerizing the above monomer composition, an acrylic polymer having a hydroxyl group in a side chain can be obtained.

Examples of the polymerization method include emulsion polymerization (including suspension polymerization), solution polymerization, and block polymerization, and examples thereof include emulsion polymerization and solution polymerization.

Emulsion polymerization

In the emulsion polymerization, for example, a polymerization initiator, an emulsifier, an optional chain transfer agent, and the like are mixed with water in the above monomer composition to carry out polymerization. More specifically, for example, a known emulsion polymerization method such as a one-time addition method (primary polymerization method) or a batch addition method (multistage polymerization method) may be employed. Further, the reaction conditions and the like are appropriately selected.

The polymerization initiator is not particularly limited, and a polymerization initiator generally used in emulsion polymerization is used. For example, benzammonium peroxide, lauric acid peroxide, hexyl peroxide, third hexyl peroxy neodecanoate, tert-butyl peroxytrimethylacetate (tert-butyl) Organic peroxides such as peroxidepivalate; for example, 2,2-azobis-isobutyronitrile, 2,2-azobis-2,4-dimethylvaleronitrile, 2,2-azobis-4- An azo compound such as methoxy-2,4-dimethylvaleronitrile or azobis-2-methylbutyronitrile (ABN-E, manufactured by Nippon Hydrazine Industries).

These polymerization initiators may be used alone or in combination of two or more. Among these polymerization initiators, preferred are azo compounds.

The blending ratio of the polymerization initiator can be appropriately selected, and is, for example, 0.01 to 5 parts by mass based on 100 parts by mass of the monomer composition.

The emulsifier is not particularly limited, and a known emulsifier (for example, an anionic emulsifier or a nonionic emulsifier) which is usually used in emulsion polymerization is used.

Further, the blending ratio of the emulsifier is, for example, 0.1 to 5 parts by mass based on 100 parts by mass of the monomer composition.

The chain transfer agent is adjusted as needed to adjust the molecular weight of the acrylic polymer, and examples thereof include mercaptans such as 1-dodecanethiol.

These chain transfer agents may be used singly or in combination, and the compounding ratio thereof is, for example, 0.1 to 1 part by mass based on 100 parts by mass of the monomer composition.

Further, the acrylic polymer obtained by such emulsion polymerization is prepared into an emulsion (water dispersion type), that is, an aqueous dispersion of an acrylic polymer.

The solid content (nonvolatile content) concentration in the aqueous dispersion of the acrylic polymer is, for example, 5 to 50% by mass.

Solution polymerization

In the solution polymerization, the polymerization initiator, the optional chain transfer agent, and the like are mixed with the monomer composition in an organic solvent to carry out polymerization.

The organic solvent may be one which dissolves the above monomer composition, and examples thereof include a ketone organic solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone; methyl acetate, ethyl acetate, and butyl acetate; Ester-based organic solvent; polar solvent such as dimethylformamide, dimethylhydrazine, N-methyl-2-pyrrolidone; alcoholic organic solvent such as methanol, ethanol, isopropanol; toluene, xylene An aromatic hydrocarbon-based organic solvent such as "Solvesso 100" (manufactured by Exxon Mobil Chemical Co., Ltd.); n-hexane, cyclohexane, methylcyclohexane, "Laws" (manufactured by Shell Chemicals), and "Mineral Spirit EC" (Shell) An aliphatic hydrocarbon/alicyclic hydrocarbon-based organic solvent such as Chemicals; an organic solvent such as methyl sirlox, ethyl sirlox, butyl siroli, etc.; tetrahydrofuran, An ether-based organic solvent such as an alkane; a carbitol-based organic solvent such as n-butyl carbitol or iso-amyl carbitol.

These organic solvents may be used singly or in combination of two or more. Further, the blending ratio of the organic solvent is appropriately set depending on the purpose and use.

In the solution polymerization, the above monomer composition is polymerized in an organic solvent for 3 to 12 hours in the presence of a polymerization initiator, for example, at 30 to 150 °C.

The acrylic polymer obtained by such solution polymerization is prepared as an organic solvent solution (solution type), that is, an organic solvent solution of an acrylic polymer.

The solid content concentration in the organic solvent solution of the acrylic polymer is, for example, 5 to 50% by mass, preferably 10 to 40% by mass.

. Physical quantity and physical properties of an acrylic polymer having a hydroxyl group in a side chain

Average molecular weight

The weight average molecular weight of the acrylic polymer having a hydroxyl group in the side chain is, for example, 5,000 to 150,000, preferably 10,000 to 120,000. Further, the number average molecular weight of the obtained acrylic polymer is, for example, from 1,000 to 50,000, preferably from 5,000 to 50,000.

Further, the weight average molecular weight and the number average molecular weight can be determined, for example, by a gel permeation chromatography (GPC) equipped with a differential refractive index detector (RID) to determine the molecular weight distribution of the acrylic polymer, and according to the obtained chromatogram. (chart), calculated using standard polystyrene as a calibration curve (the same applies hereinafter).

Glass transition temperature

The glass transition temperature of the acrylic polymer obtained by the Fox equation is, for example, 23 ° C or higher, preferably 30 ° C or higher, more preferably 45 ° C or higher, and usually 120 ° C or lower.

When the glass transition temperature of the acrylic polymer is at least the above lower limit, excellent slidability can be ensured on the coated surface obtained by using the coating material.

Viscosity

When the acrylic polymer is prepared into a solution, the viscosity (25 ° C) is, for example, 2 to 200 mPa. s, preferably 5~150mPa. s.

Further, the viscosity can be measured using a cone and plate viscometer (according to JIS K 5600-2-3: 1999, "General Test Methods for Coatings - Part 2: Properties of Coatings, Stability - Section 3: Viscosity (cone-plate viscometer method) )") The measurement was performed (the same applies hereinafter).

Hydroxyl value

Further, the hydroxyl value of the acrylic polymer (according to JIS K 1557-1:2007 (ISO14900:2001), "Plastics-Polyurethane Raw Material Polyol Test Method - Part 1: Method of Calculating Hydroxyl Value" 4.2 The B method is, for example, 5 to 70 mgKOH/g, preferably 10 to 50 mgKOH/g, more preferably 10 to 45 mgKOH/g.

When the hydroxyl value of the acrylic polymer is in the above range, excellent hardness can be secured on the coated surface obtained by using the coating material, and slidability can be improved.

. Diisocyanate

The diisocyanate is not particularly limited, and examples thereof include an aromatic diisocyanate (for example, toluene diisocyanate (2,4- or 2,6-toluene diisocyanate or a mixture thereof), phenyl diisocyanate (m-, p-phenylene) Isocyanate or a mixture thereof, 1,5-naphthalene diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or a mixture thereof), 4 , 4'-toluidine diisocyanate, etc.), an aromatic aliphatic diisocyanate (for example, xylene diisocyanate (1,3- or 1,4-dimethylphenyl diisocyanate or a mixture thereof), tetramethyl xylene diisocyanate ( 1,3- or 1,4-tetramethylxylene diisocyanate or a mixture thereof), an aliphatic diisocyanate (for example, 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, etc., alicyclic diisocyanate (for example, cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), methylene bis(cyclohexyl isocyanate), norbornane Diisocyanate, bis(isocyanatemethyl)cyclohexane, etc.).

These diisocyanates may be used alone or in combination of two or more.

The diisocyanate is preferably an aliphatic diisocyanate or an alicyclic diisocyanate from the viewpoints of light resistance and yellowing resistance.

. Polyether polyol

The polyether polyol is obtained, for example, by a low molecular weight polyol (for example, ethylene glycol, propylene glycol, glycerin, etc.) or an aromatic/aliphatic polyamine (for example, ethylenediamine, toluenediamine, etc.). The initiator is obtained by subjecting an alkylene oxide such as ethylene oxide and/or propylene oxide to an addition reaction. For example, a polyethylene polyol, a polypropylene polyol, a polyethylene polypropylene polyol (random or block copolymer), etc. are mentioned.

Further, examples of the polyether polyol include polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran.

These polyether polyols may be used alone or in combination of two or more.

The hydroxyl value of the polyether polyol (B method according to JIS K 1557-1 (2007)) is, for example, 3 to 600 mgKOH/g, preferably 5 to 300 mgKOH/g.

Further, the polyether polyol has an average functional group number of, for example, 1 to 8, preferably 2 to 6. Further, the average functional group number of the polyether polyol can be determined from the type of the initiator and the blending ratio.

The number average molecular weight of the polyether polyol is, for example, from 300 to 30,000, preferably from 700 to 20,000. Further, the number average molecular weight of the polyether polyol can also be determined from the above hydroxyl value and the average number of functional groups.

. Photopolymerizable compound having hydroxyl group and photopolymerizable group

In the photopolymerizable compound having a hydroxyl group and a photopolymerizable group (hereinafter referred to as a hydroxyl group-containing photopolymerizable compound), the photopolymerizable group is a photopolymerizable functional group, and specific examples thereof include: Methyl) propylene fluorenyl, alkenyl, cinnamyl, cinnamylidene acetyl group, benzylidene acetophenone, styrylpyridyl, α-phenylmaleimido Phenyl azide, sulfonyl azide, carbonyl azide, diazonium, o-quinonediazide, furyl propylene sulfhydryl, coumarinyl, pyrone group, hydrazine Base, benzophenone, sulfhydryl, dithiocarbamate, xanthate group, 1,2,3-thiadiazolyl, cyclopropenyl, azadioxabicyclo Azadioxabicyclo and the like. The photopolymerizable group is preferably a (meth) acrylonitrile group.

In the hydroxyl group-containing photopolymerizable compound, the number of the hydroxyl group and the photopolymerizable group is not particularly limited, and may be one (single) or two or more (plural). In the case where the hydroxyl group-containing photopolymerizable compound has a plurality of photopolymerizable groups, the photopolymerizable groups may be the same or different from each other.

The hydroxyl group-containing photopolymerizable compound may, for example, be a photopolymerizable compound having one hydroxyl group and one photopolymerizable group in one molecule; for example, pentaerythritol III; (meth) acrylate, dipentaerythritol penta (meth) acrylate is equivalent to a photopolymerizable compound having one hydroxyl group and two or more photopolymerizable groups in one molecule; for example, pentaerythritol di(a) Photopolymerization of acrylate, dipentaerythritol tri(meth)acrylate, and dipentaerythritol tetra(meth)acrylate equal to two or more hydroxyl groups and two or more photopolymerizable groups in one molecule The compound: 2,2-dihydroxyethyl acrylate is equal to a photopolymerizable compound having two or more hydroxyl groups and one photopolymerizable group in one molecule.

These hydroxyl group-containing photopolymerizable compounds may be used alone or in combination of two or more.

Hydroxyl-free photopolymerizable compound

Further, a photopolymerizable compound containing a hydroxyl group-photopolymerizable compound and a photopolymerizable group having no hydroxyl group (hereinafter referred to as a hydroxyl group-free photopolymerizable compound) may be used in combination.

Examples of the hydroxyl group-free photopolymerizable compound include an alkylene group such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate. Diol di(meth)acrylate; for example, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di( a polyalkylene glycol di(meth)acrylate such as methyl acrylate; for example, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylic acid Ester, 1,9-nonanediol di(meth)acrylate, dicyclopentadienyl di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate, hydroxypivalic acid new Pentandiol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate; for example, bisphenol A EO addition diacrylate, caprolactone modified dicyclopentene di(meth) acrylate, ethylene oxide modified di(meth) acrylate, allylated di(methyl) Cyclohexyl acrylate, Cyanurate di(meth)acrylate or such alkylene oxide modification, divinylbenzene, butanediol-1,4-divinyl ether, cyclohexane dimethanol divinyl ether, diethylene glycol Divinyl ether, dipropylene glycol divinyl ether, hexanediol divinyl ether, triethylene glycol divinyl ether, phenyl glycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer (AH-600 , phenyl glycidyl ether acrylate toluene diisocyanate urethane prepolymer (AT-600, manufactured by Kyoeisha Chemical Co., Ltd.) is equal to two photopolymerizable groups in one molecule. a photopolymerizable polyfunctional compound; for example, trimethylolpropane tri(meth)acrylate, tris(acryloxy)ethyl isocyanurate, or an alkylene oxide modification or isomeric cyanide The tris(meth)acrylate of the acid alkylene oxide modified product is equivalent to a photopolymerizable polyfunctional compound having three photopolymerizable groups in one molecule; for example, ditrimethylolpropane tetra(meth)acrylate, new Pentaerythritol tetra(meth) acrylate or the alkylene oxide modifier is equivalent to having 4 photopolymerizable groups in one molecule Polymeric polyfunctional compound; for example, dipentaerythritol hexa(meth) acrylate, neopentyl alcohol triacrylate hexamethylene diisocyanate urethane prepolymer (UA-306H, Kyoeisha a photopolymerizable polyfunctional compound having 6 photopolymerizable groups in one molecule, manufactured by a chemical company, caprolactone modified dipentaerythritol hexa(meth) acrylate, or the like. Wait.

These hydroxyl group-free photopolymerizable compounds may be used alone or in combination of two or more.

Combination of hydroxyl-containing photopolymerizable compound and hydroxyl-free photopolymerizable compound

Further, when a hydroxyl group-containing photopolymerizable compound is used in combination with a hydroxyl group-free photopolymerizable compound, the compounding ratio is relative to a hydroxyl group-containing photopolymerizable compound and a hydroxyl group-free photopolymerizable compound. The total amount of the hydroxyl group-containing photopolymerizable compound is, for example, 10 to 90 parts by mass, preferably 50 to 70 parts by mass, and the hydroxyl group-free photopolymerizable compound is, for example, 10 to 90 parts by mass, preferably 30. ~50 parts by mass.

. Composition of coating material

Further, in the production of the coating material, the blending ratio of each of the above raw material components (i.e., acrylic polymer, diisocyanate, polyether polyol, and hydroxyl group-photopolymerizable compound) is 100 masses with respect to the total amount of the materials. The acrylic polymer is, for example, 5 to 90 parts by mass, preferably 10 to 80 parts by mass, the diisocyanate is, for example, 1 to 40 parts by mass, preferably 5 to 30 parts by mass, and the polyether polyol is, for example, 1 to 1 part. 60 parts by mass, preferably 5 to 40 parts by mass, and the photopolymerizable compound is, for example, 5 to 70 parts by mass, preferably 10 to 50 parts by mass.

When the blending ratio of each raw material component is in the above range, it is possible to improve the antifouling property of the coated surface obtained by using the coating material, and to secure excellent stain wiping property.

On the other hand, when the blending ratio of the acrylic polymer is less than the above lower limit, there is a case where the slidability of the coated surface obtained by using the coating material is inferior and the smear is not sufficiently ensured.

In addition, when the blending ratio of the acrylic polymer exceeds the above upper limit, the antifouling property of the coated surface obtained by using the coating material cannot be sufficiently ensured, and for example, a fingerprint or the like may easily adhere.

In addition, when the blending ratio of the diisocyanate is less than the above lower limit, the antifouling property of the coated surface obtained by using the coating material cannot be sufficiently ensured, and for example, a fingerprint or the like may easily adhere.

In addition, when the blending ratio of the diisocyanate exceeds the above upper limit, the antifouling property of the coated surface obtained by using the coating material cannot be sufficiently ensured, and for example, a fingerprint or the like may easily adhere.

In addition, when the blending ratio of the polyether polyol is less than the above lower limit, the antifouling property of the coated surface obtained by using the coating material cannot be sufficiently ensured, and for example, a fingerprint or the like may easily adhere.

In addition, when the blending ratio of the polyether polyol exceeds the above upper limit, there is a case where the slidability of the coated surface obtained by using the coating material is inferior and the smear is easily removed.

In addition, when the composition of the photopolymerizable compound does not reach the above lower limit, there is a case where the slidability of the coated surface obtained by using the coating material is inferior and the smear is not sufficiently ensured.

In addition, when the composition of the photopolymerizable compound exceeds the above upper limit, there is a case where the slidability of the coated surface obtained by using the coating material is inferior and the smear is not sufficiently ensured.

. Preparation method of coating material

Further, the reaction of each of the above components is carried out by a known method such as a one-shot method or a prepolymer method, and a prepolymer method is preferably used.

In the prepolymer method, first, a diisocyanate, a polyether polyol, and a photopolymerizable compound are reacted to synthesize a prepolymer having an isocyanate group and a photopolymerizable group at the molecular terminal, and thereafter, the obtained pre-polymer is obtained. The isocyanate group of the polymer reacts with the hydroxyl group of the acrylic polymer on the side chain.

Specifically, the diisocyanate, the polyether polyol, and the photopolymerizable compound are first formulated (mixed) in such a manner that the isocyanate group in the diisocyanate is equivalent to the hydroxyl group in the polyether polyol and the photopolymerizable compound. The ratio (NCO/hydroxyl) exceeds 1, for example, 1.1 to 10, preferably 1.5 to 4.5, and the urethane is subjected to, for example, 0.5 to 24 hours in a reaction vessel at, for example, room temperature to 150 ° C. Reaction.

Further, in the urethanation reaction, an organic solvent may be optionally adjusted.

The organic solvent is exemplified as the organic solvent. These organic solvents may be used singly or in combination of two or more. Further, the blending ratio of the organic solvent is appropriately set depending on the purpose and use.

Further, in the above urethanation reaction, a urethane-based catalyst may be added as needed.

Examples of the urethane-based catalyst include dimethyl dilaurate, dibutyl dilaurate, dioctyltin laurate, dioctyltin dilaurate, bismuth-based catalyst, and the like. .

These urethane-based catalysts may be used alone or in combination of two or more.

Further, in the above urethanation reaction, a polymerization inhibitor may be further adjusted as needed.

The polymerization inhibitor may, for example, be an anthracene such as p-benzoquinone, hydroquinone monomethyl ether, naphthoquinone, phenanthrenequinone, formazan or 2,5-diphenyl-p-benzoquinone; for example, hydroquinone , p-tert-butylcatechol, 2,5-di-t-butyl hydroquinone, mono-t-butyl hydroquinone, 2,5-di-third amyl hydroquinone The like is hydroquinone; for example, phenol such as p-methoxyphenol or di-tert-butyl-p-cresol hydroquinone monomethyl ether.

These polymerization inhibitors may be used alone or in combination of two or more. Further, among these, phenols are preferable, and p-methoxyphenol is more preferable.

Further, if necessary, the unreacted diisocyanate may be removed from the obtained prepolymer by a known removal method such as distillation or extraction.

Further, in the prepolymer, the average functional group number of the isocyanate group is, for example, 1 to 3.0, preferably 1 to 2.5.

Further, the weight average molecular weight of the obtained prepolymer is, for example, 4,000 to 40,000, preferably 8,000 to 25,000.

Further, the number average molecular weight of the obtained prepolymer is, for example, 1000~ 15000, preferably 2000~10000.

Further, the prepolymer may be prepared as a solution of the above organic solvent. In this case, the solid content concentration is, for example, 10 to 90% by mass, preferably 20 to 80% by mass.

When the prepolymer is prepared into a solution, the viscosity (25 ° C) is, for example, 2 to 20 mPa. s, preferably 5~10mPa. s.

Then, in the method, the obtained prepolymer and the acrylic polymer are, for example, an equivalent ratio of the isocyanate group in the prepolymer of the above organic solvent to the hydroxyl group in the acrylic polymer (NCO/hydroxyl group) For example, the formulation (mixing) is formulated in a manner of 0.7 to 1.3, preferably 0.9 to 1.1, and the urethanization reaction is carried out in a reaction vessel at, for example, room temperature to 150 ° C for, for example, 0.5 to 24 hours.

In the urethanization reaction, as described above, the above urethane-based catalyst and polymerization inhibitor may be added as needed.

According to the coating material obtained by such a prepolymer method, the antifouling property of the coated surface can be improved, and excellent stain repellency can be ensured.

Further, in the coating material, a known additive such as an ultraviolet absorber, an antioxidant, a light stabilizer, a heat stabilizer, an antistatic agent, an antifoaming agent or the like may be added as needed.

Such an additive may be added to at least one of the above-mentioned raw material components (that is, an acrylic polymer, a diisocyanate, a polyether polyol, and a hydroxyl group-containing photopolymerizable compound) and/or the above prepolymer, and When the reaction of the prepolymer and the acrylic polymer is carried out, it may be additionally added, or may be directly added to the coating material obtained by the reaction of the prepolymer and the acrylic polymer. Further, the blending ratio of the additives is appropriately set depending on the purpose and use.

. Physical quantity and physical properties of coated materials

Further, the weight average molecular weight of the coating material obtained in this manner is, for example, 5,000 to 100,000, preferably 10,000 to 80,000.

Further, the number average molecular weight of the obtained coating material is, for example, 1000~ 50000, preferably 4000~40000.

Further, the coating material may be prepared as a solution of the above organic solvent. In this case, the solid content concentration is, for example, 10 to 90% by mass, preferably 20 to 80% by mass.

When the coating material is prepared into a solution, the viscosity (25 ° C) is, for example, 1 to 100 mPa. s, preferably 5~80mPa. s.

Moreover, according to the coating material, the antifouling property of the coated surface can be improved, and excellent wiping property and slidability can be ensured.

<Coating composition>

Specifically, such a coating material is prepared into a coating composition by, for example, adding a photopolymerization initiator and mixing and stirring. That is, the coating composition contains the above-mentioned coating material and a photopolymerization initiator.

. Photopolymerization initiator

Examples of the photopolymerization initiator include a benzoin ether photopolymerization initiator, a benzophenone photopolymerization initiator, and 9-oxosulfuric acid. Photopolymerization initiator, alkylphenone photopolymerization initiator, mercapto phosphine oxide photopolymerization initiator, titanocene photopolymerization initiator, oxime ester photopolymerization initiator, diazo An aniline photopolymerization initiator, a naphthoquinone diazo sulfonic acid photopolymerization initiator, a dimethylaminobenzoic acid photopolymerization initiator, and the like.

Examples of the benzoin ether photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone-based photopolymerization initiator include benzophenone, methyl phthalic acid benzoate, 4-phenylbenzophenone, and 4-benzoguanidin-4'-methyl group. - Diphenyl sulfide and 2,4,6-trimethylbenzophenone.

9-oxosulfur A photopolymerization initiator, for example, 2-isopropyl-9-oxosulfur 2,4-diethyl-9-oxosulfur 2,4-dichloro-9-oxosulfur And 1-chloro-4-propoxy-9-oxosulfur Wait.

Examples of the alkylphenone-based photopolymerization initiator include 2-hydroxy-2-methyl-1-phenyl-propane-1 ketone and 2,2-dimethoxy-1,2-diphenyl. Ethyl-1-one, 1-hydroxy-cyclohexyl-phenyl-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane 1-ketone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-methyl-1-(4-methylthienyl)-2- Lolinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Polinyl)phenyl]-1-butanone and the like.

Examples of the fluorenylphosphine oxide-based photopolymerization initiator include 2,4,6-trimethylbenzimidium-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzhydrazide). )-phenylphosphine oxide and the like.

Examples of the titanocene-based photopolymerization initiator include bis(η 5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole- 1-yl)-phenyl) titanium or the like.

Examples of the oxime ester photopolymerization initiator include 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzamide)] (1,2- Octanedion, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydrazide)-9H-carbazole- 3-yl]-, 1-(0-ethenylhydrazine), oxy-phenyl-acetic acid 2-[2-o-oxy-2-phenylethenyloxyethoxy]ethyl ester, oxy -Phenyl-acetic acid 2-(2-hydroxyethoxy)ethyl ester or the like.

These photopolymerization initiators may be used alone or in combination of two or more.

The blending ratio of the photopolymerization initiator is, for example, 1 to 30 parts by mass, preferably 5 to 20 parts by mass, per 100 parts by mass of the coating material (solid content).

. Other blending ingredients

Further, the coating composition may further contain a photopolymerizable compound, a curing agent, or the like as needed.

Photopolymerizable compound

The photopolymerizable compound may, for example, be the above-mentioned hydroxyl group-containing photopolymerizable compound or, for example, the above-mentioned hydroxyl group-free photopolymerizable compound.

These photopolymerizable compounds may be used alone or in combination of two or more.

In the case of blending a photopolymerizable compound, the blending ratio is, for example, 10 to 500 parts by mass, preferably 100 to 300, per 100 parts by mass of the coating material (solid content). Parts by mass.

hardener

Examples of the curing agent include polyisocyanates such as the above diisocyanates or polyisocyanate derivatives.

Examples of the polyisocyanate derivative include, for example, a polymer (for example, a 2-mer or a trimer) of the above-mentioned diisocyanate, and a urea-form modified product (for example, a polyisocyanate and a low molecular weight polyol (for example, three). a urea-form modified product produced by the reaction of methylolpropane or the like), a modified polyol (for example, a polyol modified product obtained by reacting a polyisocyanate with the above-mentioned low molecular weight polyol), or a biuret modification a chemical (for example, a biuret modified product formed by the reaction of the above polyisocyanate with water or an amine, etc.), a urea modified product (for example, a urea modified product formed by the reaction of the above polyisocyanate with the above polyamine) Wait), two An oxadiazine trione modification (for example, formed by the reaction of the above polyisocyanate with carbon dioxide gas) two a triketone modified product, etc., a carbodiimide modified product (a carbodiimide modified product formed by a decarboxylation condensation reaction of the above polyisocyanate), a uretdione modified product, a uretonimine modified product, or the like .

Further, examples of the curing agent include an unsaturated compound (isocyanate group-containing (meth) acrylate) having an isocyanate group and a (meth) acrylonitrile group.

Examples of the isocyanate group-containing (meth) acrylate include 2-propenyloxyethyl isocyanate (trade name: Karenz MOI, manufactured by Showa Denko Co., Ltd.), 2-methylpropenyloxyethyl isocyanate, and the like ( The (meth) acrylonitrile group is a (meth) propylene decyl isocyanate in which an alkylene group is bonded to an isocyanate group having 2 to 6 carbon atoms, or the like.

Examples of the derivative include a (meth) acrylate having an isocyanate group which is blocked by a blocking agent, and specific examples thereof include methacrylic acid 2-(ortho[1' -Methyl propyleneamino]carboxyamino)ethyl ester (trade name: Karenz MOI-BM, manufactured by Showa Denko Co., Ltd.).

These hardeners may be used alone or in combination of two or more.

In the case of blending the curing agent, the blending ratio is, for example, 0.1 to 10 parts by mass, preferably 1 to 5 parts by mass, per 100 parts by mass of the coating material (solid content).

Further, the coating composition may be prepared as a solution of the above organic solvent. In this case, the solid content concentration is, for example, 10 to 90% by mass, preferably 20 to 80% by mass.

Further, according to the coating composition, the antifouling property of the coated surface can be improved, and excellent wiping property and slidability can be ensured.

. Method of using the coating composition and physical properties of the coating film

Further, such a coating composition is formed by coating a surface of a substrate and irradiating it with light such as ultraviolet rays to form a coating film (coating layer).

The material of the substrate is not particularly limited, and examples thereof include a resin substrate such as a polycarbonate resin, a polyacryl resin, or a styrene resin; for example, an inorganic substrate such as glass; for example, stainless steel or steel; A metal substrate such as aluminum.

Examples of the coating method include coating by a dip coating method, a spray coating method, a roll coating method, a doctor blade method, a screen printing method, or the like, or casting using a bar coater or an applicator.

The film thickness of the coating film is not particularly limited and is, for example, 2 to 90 μm, preferably 5 to 50 μm.

Further, the coating film obtained from the above coating composition is excellent in transparency, and specifically, the haze value of the coating film is, for example, 1.0% or less, preferably 0.8% or less, and usually more than 0%.

Further, the haze value was measured by a fog meter in accordance with JIS K 7136 (2000).

Further, the coating film obtained from the coating composition is excellent in hardness, and specifically, the hardness of the surface (coated surface) of the coating film is, for example, HB or more in terms of pencil hardness, preferably H or more, and usually F. the following.

Further, the pencil hardness was measured by a pencil hardness test in accordance with JIS K 5600-5-4 (1999).

Further, the coating film obtained from the coating composition is excellent in antifouling property (fingerprint resistance), and specifically, the water contact angle measured by a contact angle meter is, for example, 50 to 75 degrees, preferably 52 to 72. The oleic acid contact angle is, for example, 5 to 25 degrees, preferably 10 to 20 degrees.

Further, the coating film obtained from the above coating composition is also excellent in easy-to-sweepability, specifically, the dynamic friction coefficient in a dry state (23 ° C - 50% RH) (measurement condition: 10 mm) The stainless steel ball, load 200 g, speed 5 mm/s) is, for example, 0.35 or less, preferably 0.25 or less, and usually 0.05 or more.

Further, the coating film obtained from the coating composition is excellent in adhesion to the substrate, and further, the coating film is excellent in smear wiping property, so that the coating film can be favorably removed with a small number of wiping times. Attached stains (fingerprints, etc.).

Further, the coating film (coated surface) obtained in this manner is excellent in antifouling property and excellent in easy smear erasability, and is formed on, for example, a touch panel or a display. a surface of the image display panel of the outermost layer of the device, or a surface protective film surface adhered to the surface of the image display panel, for example, a lens surface such as glasses or goggles, and a window material for construction, The surface of window materials for vehicles, window materials for measuring instruments, etc., to improve antifouling properties and wiping properties.

[Examples]

Hereinafter, the present invention will be described based on Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited by the following examples.

In addition, the measuring method of the physical property used by a synthesis example, an Example, a comparative example, etc. is shown below.

<Measurement of Weighted Average Molecular Weight and Number Average Molecular Weight by Gel Permeation Chromatograph>

A sample of about 0.2 mg was taken, dissolved in 10 mL of tetrahydrofuran, and measured by a gel permeation chromatography (GPC) equipped with a differential refractive index detector (RID) to obtain a molecular weight distribution of the sample.

Thereafter, the weight average molecular weight of the sample was calculated from the obtained chromatogram using standard polystyrene as a calibration curve. The measurement device and measurement conditions are shown below.

Data processing device: article number HLC-8220GPC (manufactured by Tosoh Corporation)

Differential refractive index detector: RI detector built into the product number HLC-8220GPC

Column: Item No. TSK gel GMH _XL (manufactured by Tosoh) 3

Mobile phase: tetrahydrofuran

Column flow: 0.5mL/min

Injection volume: 20μL

Measuring temperature: 40 ° C

Standard polystyrene molecular weight: 1250, 3250, 9200, 28500, 68000, 165000, 475000, 950,000, 1900000

<viscosity>

The viscosity of the sample at 25 ° C was measured using a cone and plate viscometer in accordance with JIS K 5600-2-3:1999.

<hydroxy value>

The hydroxyl value of the sample was measured in accordance with the B method (phthalic acid method) of JIS K 1557-1 (2007).

[Synthesis of acrylic polymer]

Synthesis Example A-1

233 parts by mass of methyl ethyl ketone (hereinafter referred to as MEK) as a solvent was added to the reaction container, and the temperature was raised to 85 °C.

On the other hand, in a monomer composition composed of 90 parts by mass of methyl methacrylate and 10 parts by mass of 2-hydroxyethyl acrylate, azobis-2-methylbutyronitrile as a polymerization catalyst is stirred and mixed. (ABN-E, manufactured by Nippon Hydrazine Industries Co., Ltd.) 4 parts by mass, thereby preparing a monomer mixture.

Then, the monomer mixture was added dropwise to the above solvent at 85 ° C for 2 hours, and after the completion of the dropwise addition, it was aged for 4 hours, thereby obtaining an acrylic polymerization having a hydroxyl group in the side chain. A solution of the substance (nonvolatile content: 30% by mass).

The weight average molecular weight, the number average molecular weight, the glass transition temperature, the viscosity, and the hydroxyl value of the obtained acrylic polymer are shown in Table 1.

Further, the weight average molecular weight, the number average molecular weight, the viscosity, and the hydroxyl value were determined by the above method. Further, the glass transition temperature was calculated from the Fox equation.

Synthesis Example A-2~A-9

A solution of an acrylic polymer having a hydroxyl group in a side chain was obtained in the same manner as in Synthesis Example A-1 except that a monomer composition, a polymerization catalyst, and a solvent were blended in the composition shown in Table 1. Volatile component 30% by mass). Further, in Synthesis Example A-7, the reaction temperature was set to 70 °C.

The weight average molecular weight, the number average molecular weight, the glass transition temperature, the viscosity, and the hydroxyl value of the obtained acrylic polymer are shown in Table 1.

Furthermore, the details of the abbreviations in the table are listed below.

. MMA: Methyl methacrylate

. DMAA: N,N-dimethyl methacrylate

. BA: butyl acrylate

. 2-HEA: 2-hydroxyethyl acrylate

. ABN-E: azobis-2-methylbutyronitrile, manufactured by Nippon Hydrazine Industries

[Synthesis of Prepolymer]

Synthesis Example B-1

233 parts by mass of MEK as a solvent was added to the reaction vessel, and the temperature was raised to 80 °C.

Then, 15 parts by mass of hexamethylene diisocyanate, Epan U-105 (polyoxyethylene polyoxypropylene diol (quantitative average molecular weight: 6400), manufactured by First Industrial Pharmaceutical Co., Ltd.), 30 parts by mass, and Aronix were added to the reaction vessel. M-403 (photopolymerizable compound, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate mixture (nepentaerythritol pentaacrylate content: 50 to 60% by mass, manufactured by Toagosei Co., Ltd.) 55 In parts by mass (NCO/OH equivalent ratio: 2.9), 0.1 parts by mass of tin dimethyl dilaurate as a catalyst and 0.05 parts by mass of p-methoxyphenol as a polymerization inhibitor were added, and mixed at 80 ° C. hour.

Thereby, a solution (non-volatile content: 30% by mass) of a prepolymer having an isocyanate group and a photopolymerizable group at the molecular end was obtained.

The weight average molecular weight, the number average molecular weight and viscosity of the obtained prepolymer, and the NCO/OH equivalent ratio in the reaction are shown in Table 2.

Synthesis Example B-2~B-10

The molecular terminal was obtained in the same manner as in Synthesis Example B-1 except that a diisocyanate, a polyether polyol, a photopolymerizable compound, a catalyst, a polymerization inhibitor, and a solvent were prepared in the composition formula shown in Table 2. A solution of a prepolymer having an isocyanate group and a photopolymerizable group (nonvolatile content: 30% by mass).

The weight average molecular weight, the number average molecular weight and viscosity of the obtained prepolymer, and the NCO/OH equivalent ratio in the reaction are shown in Table 2.

Furthermore, the details of the abbreviations in the table are listed below.

. HDI: hexamethylene diisocyanate

. Epan U105: polyoxyethylene polyoxypropylene diol (quantitative average molecular weight 6400), manufactured by the first industrial pharmaceutical company

. Sannix PP-1000: Polyoxypropylene diol (quantitative average molecular weight of 1000), manufactured by Sanyo Chemical Industry Co., Ltd.

. Aronix M-403: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (nepentaerythritol pentaacrylate content is 50 to 60% by mass, manufactured by Toagosei Co., Ltd.)

[Preparation of coated material]

Example C-1

40 parts by mass of the solution of the acrylic polymer obtained in Synthesis Example A-1 and 60 parts by mass of the solution of the prepolymer obtained in Synthesis Example B-1 were added to the reaction container, and then as a catalyst. 0.1 parts by mass of methyl dilaurate and 0.05 parts by mass of p-methoxyphenol as a polymerization inhibitor were mixed at 80 ° C for 3 hours to obtain a solution of a coating material (nonvolatile content: 30% by mass).

The weight average molecular weight, the number average molecular weight, and the viscosity of the obtained coating material are shown in Table 3.

Examples C-1 to C-23 and Comparative Example D-1

A solution of the coating material (nonvolatile content) was obtained in the same manner as in Example C-1 except that the acrylic polymer, the prepolymer, the catalyst, and the polymerization inhibitor were blended in the composition shown in Table 3. 30% by mass).

The weight average molecular weight, the number average molecular weight, and the viscosity of the obtained coating material are shown in Table 3.

[Preparation of coating composition]

Use case 1

10 parts by mass of a solution of the coating material obtained in Example C-1, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (photopolymerization initiator, DAROCUR 1173, Ciba Japan) Manufactured by the company, 0.8 parts by mass, neopentyl alcohol triacrylate hexamethylene diisocyanate urethane prepolymer (urethane urethane, UA-306H, manufactured by Kyoeisha Chemical Co., Ltd.) 27 parts by mass And 63 parts by mass of MEK were stirred and mixed, thereby preparing a coating composition.

The composition of the coating composition is shown in Table 4.

Use example 2~28

Using the coating materials obtained in Examples C-1 to C-23 and Comparative Example D-1, the coating materials, photopolymerization initiators, and amide groups were prepared in the formulations shown in Tables 4 and 5. A coating composition was prepared in the same manner as in Application Example 1, except that the acid ester, the isocyanate group-containing (meth) acrylate, the polyisocyanate, and the solvent were used.

Further, in Use Example 27, the prepolymer synthesized in Synthesis Example B-9 was used instead of the coating material.

[Evaluation]

The coating composition obtained in each of the use examples was applied onto a polyethylene terephthalate (PET) film so as to have a dry film thickness of about 5 μm using a bar coater No. 10. Then, after removing the solvent by heating at 80 ° C for 3 minutes, ultraviolet light was exposed at 400 mJ/cm ² using a high pressure mercury lamp (120 W/cm) to cure the coating composition, thereby obtaining a coating film.

The PET film on which the coating film was formed was used as a test plate, and the coating film was evaluated in accordance with the following evaluation method.

<Fog value>

The measurement was carried out in accordance with JIS K 7136 (2000) using a fog meter NDH5000 (manufactured by Nippon Denshoku Industries Co., Ltd.).

Further, the smaller the haze value, the more excellent the transparency.

<pencil hardness>

A pencil hardness test was carried out in accordance with JIS K 5600-5-4:1999.

Further, in the pencil hardness test, the hardness was arranged from the low to the high in the order of B, HB, F, and H.

Furthermore, in the pencil hardness, the larger the number before the "H", the higher the hardness, and the larger the number before the "B", the lower the hardness.

<adhesion>

The adhesion was tested in accordance with JIS K 5600-5-6:1999.

Specifically, the film coated on the test plate was cut in the longitudinal and lateral directions by a cutting blade to form 100 cross-cuts (cut pieces) like a substrate. Then, tape (Nichiban Tape No. 1, manufactured by Nichiban Co., Ltd.) was attached to the cross-cut. Then, after peeling off the attached transparent tape, the number of cross-cuts remaining without peeling was counted, and the number of cross-cuts/number of cross-cuts was evaluated.

Further, the more the number of residual cross-cuts is formed with respect to the number of cross-cuts formed, the more excellent the adhesion is.

<Oil detachment>

0.1 g of n-hexadecane was dropped on the surface of the test plate. Then, a cellulose non-woven fabric (Bemcot M-3, manufactured by Asahi Kasei Co., Ltd.) was applied to wipe the n-hexadecane attached to the surface of the test plate 10 times with a load of 300 g.

Thereafter, the haze (turbidity) of the surface of the test plate before and after the test was measured using a fog meter NDH5000 (manufactured by Nippon Denshoku Industries Co., Ltd.). Then, the difference ΔE in haze before and after the test was calculated.

Further, the smaller the value of ΔE, the better the wiping off of the fingerprint trace due to sebum, that is, the better the antifouling property.

<Dynamic friction coefficient>

In a dry state (23 ° C - 50% RH), a surface measuring machine TriboStation TYPE: 32 (manufactured by HEIDON) was used for measuring conditions of 10 mm. The dynamic friction coefficient of the test plate was measured under a stainless steel ball, a load of 200 g, and a speed of 5 mm/s.

Furthermore, the smaller the dynamic friction coefficient, the better the slidability.

<water contact angle>

0.4 μL of water droplets were dropped on the surface of the test plate, and the contact angle was measured using a contact angle meter (Drop Master 500, manufactured by Kyowa Interface Science Co., Ltd.).

Furthermore, the lower the water contact angle, the more the fingerprint or the like can be prevented from adhering.

<Oleic acid contact angle>

0.4 μL of oleic acid was dropped on the surface of the test plate, and the contact angle was measured using a contact angle meter (Drop Master 500, manufactured by Kyowa Interface Science Co., Ltd.).

Further, the lower the contact angle of oleic acid, the more the fingerprint or the like can be prevented from adhering.

Furthermore, the details of the abbreviations in the table are listed below.

. DAROCUR 1173: 2-Hydroxy-2-methyl-1-phenyl-propan-1-one, photopolymerization initiator, manufactured by Ciba Japan

. UA-306H: Pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer (urethane acrylate), manufactured by Kyoeisha Chemical Co., Ltd.

. Karenz MOI: 2-propenyloxyethyl isocyanate, manufactured by Showa Denko

. D-165N: Biuret modification of hexamethylene diisocyanate, manufactured by Mitsui Chemicals Co., Ltd.

[Industrial availability]

According to the coating material and the coating composition of the present invention, a coating film excellent in antifouling property, wiping property, and slidability can be formed. Therefore, the coating material and the coating composition of the present invention can be used to improve the antifouling property, the wiping property, and the slidability of the surfaces of various optical members such as a touch panel, a display, a lens, and a glass.

Claims (7)

A coating material obtained by reacting at least an acrylic polymer having a hydroxyl group in a side chain, a diisocyanate, a polyether polyol, and a photopolymerizable compound having both a hydroxyl group and a photopolymerizable group. The coating material according to the first aspect of the invention, wherein the glass transition temperature of the acrylic polymer obtained by the Fox equation is 30 ° C or higher. The coating material according to claim 1 or 2, wherein the acrylic polymer is obtained by using a hydroxyl group-containing vinyl monomer and methyl (meth)acrylate and methyl (meth)acrylate The monomer composition having a content ratio of 50% by mass or more is obtained by polymerization. The coating material according to any one of claims 1 to 3, wherein the hydroxy value of the acrylic polymer determined according to the method B of JIS K 1557-1 (2007) is 10 to 50 mgKOH/g. . The coating material according to any one of claims 1 to 4, which is obtained by reacting the above-mentioned diisocyanate, the above polyether polyol, and the photopolymerizable compound, and has an isocyanate group at the molecular terminal and The isocyanate group of the photopolymerizable group prepolymer is obtained by reacting with the hydroxyl group of the acrylic polymer in the side chain. The coating material according to any one of claims 1 to 5, wherein the coating material is 100 mass based on the total amount of the acrylic polymer, the diisocyanate, the polyether polyol, and the photopolymerizable compound. The acrylic polymer is used in an amount of 10 to 80 parts by mass, and the diisocyanate is used in an amount of 5 to 30 parts by mass. The polyether polyol is obtained by reacting the photopolymerizable compound in a ratio of 10 to 50 parts by mass in an amount of 5 to 40 parts by mass. A coating composition comprising the coating material according to any one of claims 1 to 6 and a photopolymerization initiator.