WO2015011804A1 - Coating material and coating composition - Google Patents

Abstract

The present invention provides a coating material and a coating composition, both of which enable the improvement in stain-proof properties and can assure excellent wipe-off properties and sliding properties. The coating material is produced by reacting at least an acrylic polymer having a hydroxy group in a side chain, a diisocyanate, a polyether polyol and a photopolymerizable compound having both a hydroxy group and a photopolymerizable group with one another. The coating composition comprises the coating material and a photopolymerization initiator. According to the coating material and the coating composition, it becomes possible to improve the stain-proof properties of a coated surface and to assure excellent wipe-off properties and sliding properties of the coated surface.

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.

Conventionally, various optical members such as touch panels, displays, lenses, and glass are likely to be contaminated with fingerprint marks and the like, and since the visibility decreases when the dirt adheres, the adhesion of dirt is suppressed (antifouling property) It is required to make the fingerprint dirt and the like less noticeable and to improve the ease of wiping off the adhered dirt (wiping property). Furthermore, in recent years, optical members used for touch panels and the like have also been required to improve operability by making their surfaces easy to slip (providing “slidability”).

As a method for meeting such a requirement, for example, it is known that the surface of an optical member is coated with an antifouling coating material. A polyether skeleton-containing urethane (meth) acrylate (A) having at least one (meth) acrylate group, a water tolerance of 6.0 ml or less, and a solubility parameter of 12 or less, a photopolymerizable polyfunctional compound ( A fingerprint-resistant photocurable composition comprising B) and a photopolymerization initiator (C) is disclosed.

JP 2010-95707 A

However, when the fingerprint-resistant photocurable composition described in Patent Document 1 is used, there is a problem that wiping property and slipperiness on the obtained coating surface are not sufficient.

An object of the present invention is to provide a coating material and a coating composition capable of improving antifouling properties and ensuring excellent wiping properties and slipping properties.

In order to achieve the above object, the coating material of the present invention comprises 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. It is characterized by being obtained by reaction.

In the coating material of the present invention, it is preferable that the glass transition temperature obtained by the Fox formula of the acrylic polymer is 30 ° C. or higher.

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

In the coating material of the present invention, it is preferable that the hydroxyl value of the acrylic polymer determined in accordance with JIS K 1557-1 (2007) B method is 10 to 50 mgKOH / g.

The coating material of the present invention is obtained by reacting the diisocyanate, the polyether polyol, and the photopolymerizable compound, and has a prepolymer isocyanate group having both an isocyanate group and a photopolymerizable group at a molecular end; It is preferable that the acrylic polymer is obtained by reacting with a hydroxyl group in the side chain.

Further, the coating material of the present invention comprises 10 to 80 parts by mass of the acrylic polymer with respect to 100 parts by mass in total of the acrylic polymer, the diisocyanate, the polyether polyol, and the photopolymerizable compound. The diisocyanate is preferably obtained by reacting 5 to 30 parts by mass of the polyether polyol, 5 to 40 parts by mass of the polyether polyol, and 10 to 50 parts by mass of the photopolymerizable compound.

The coating composition of the present invention is characterized by containing 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 coating surface can be improved, and excellent wiping properties and slipperiness can be ensured.

<Coating 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 a hydroxyl group in the side chain An acrylic polymer having a hydroxyl group in the side chain (hereinafter sometimes simply referred to as an acrylic polymer) contains, for example, a (meth) acrylic acid alkyl ester as a main component, ) It is obtained by polymerizing a monomer composition containing a hydroxyl group-containing vinyl monomer copolymerizable with an acrylic acid alkyl ester.

(Meth) acrylic acid alkyl ester Examples of (meth) acrylic acid alkyl ester include methacrylic acid alkyl ester and / or alkyl acrylate alkyl ester, such as methyl (meth) acrylate, ethyl (meth) acrylate, (meth ) Propyl acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethyl (meth) acrylate Xyl, nonyl (meth) acrylate, decyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, and the like.

The alkyl (meth) acrylate is preferably methyl (meth) acrylate and butyl (meth) acrylate, more preferably methyl (meth) acrylate, and particularly preferably methyl methacrylate. (MMA).

These (meth) acrylic acid alkyl esters can be used alone or in combination of two or more.

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

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

If the mixing ratio of methyl (meth) acrylate is within the above range, the glass transition temperature of the acrylic polymer can be set high, and excellent slipperiness can be ensured on the coating surface obtained using the coating material. it can.

Hydroxyl Group-Containing Vinyl Monomer A hydroxyl group-containing vinyl monomer is a (meth) acrylic acid alkyl ester containing a hydroxyl group, specifically, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxy (meth) acrylate. Propyl, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxy (meth) acrylate Examples include octyl, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, 4-hydroxymethylcyclohexyl (meth) acrylate, and N-hydroxymethylamide (meth) acrylate.

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

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

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

Copolymerizable vinyl monomer The monomer composition may further contain a copolymerizable vinyl monomer copolymerizable with a (meth) acrylic acid alkyl ester and / or a hydroxyl group-containing vinyl monomer.

Examples of the copolymerizable vinyl monomer include an epoxy group-containing vinyl monomer, an amide group-containing vinyl monomer, a cyano group-containing vinyl monomer, an imide group-containing vinyl monomer, a carboxyl group-containing vinyl monomer, and an alkoxypolyalkylene glycol group-containing vinyl monomer. A functional group-containing vinyl monomer (excluding a hydroxyl group-containing vinyl monomer), that is, containing at least one functional group selected from an epoxy group, an amide group, a cyano group, an imide group, a carboxyl group, an alkoxypolyalkylene glycol group, and the like. And a copolymerizable vinyl monomer containing no hydroxyl group.

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

Examples of the amide group-containing vinyl monomer include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N-butyl (meth) acrylamide. N-methoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, N-vinylcarboxylic acid amide, dimethylaminopropyl acrylamide, diacetone acrylamide, N-methylol acrylamide, etc. It is done. Among them, N, N-dialkyl (meth) acrylamide such as N, N-dimethyl (meth) acrylamide is preferable, and N, N-dimethylacrylamide (DMAA) is more preferable.

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

Examples of the imide group-containing vinyl monomer include maleimide monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, and N-phenylmaleimide, such as N-methylitaconimide, N-ethylitaconimide, N -Itacimide monomers such as butyl itaconimide, N-octyl itaconimide, N-2-ethylhexyl itaconimide, N-cyclohexyl leuconacimide, N-lauryl itaconimide, for example, N- (meth) acryloyloxymethylene succinimide, N- Examples thereof include succinimide monomers such as (meth) acryloyl-6-oxyhexamethylene succinimide and N- (meth) acryloyl-8-oxyoctamethylene succinimide.

Examples of the carboxy group-containing vinyl monomer include (meth) acrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, cinnamic acid and other unsaturated carboxylic acids such as fumaric anhydride, maleic anhydride, itaconic anhydride. Unsaturated dicarboxylic anhydrides such as acids, for example, monomethyl itaconate, monobutyl itaconate, 2-acryloyloxyethylphthalic acid and the like, for example, 2-methacryloyloxyethyl trimellitic acid, 2-methacryloyl Examples thereof include unsaturated tricarboxylic acid monoesters such as oxyethyl pyromellitic acid, for example, carboxyalkyl acrylates such as carboxyethyl acrylate and carboxypentyl acrylate.

Examples of the alkoxypolyalkylene glycol group-containing vinyl monomer include methoxypolyethylene glycol (meth) acrylate.

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

Examples of the polyfunctional monomer include (mono or poly) ethylene glycol di (meth) acrylate such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate. (Meth) acrylate and (mono or poly) alkylene glycol di (meth) acrylate such as propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate , Pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tetramethylol methanetri (meth) acrylate And dipentaerythritol hexa (meth) acrylate, divinylbenzene and the like.

As the copolymerizable vinyl monomer, in addition to the above copolymerizable vinyl monomer, for example, vinyl esters such as vinyl acetate and vinyl propionate, for example, olefinic monomers such as ethylene, propylene, isoprene, butadiene, and isobutylene. For example, (meth) acrylic acid aryl esters such as phenyl (meth) acrylate, for example, aromatic vinyls such as styrene and vinyl toluene, for example, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, etc. Alkoxy group-containing monomers such as vinyl ether monomers such as vinyl ether, halogen atom-containing monomers such as vinyl chloride, such as N-vinylpyrrolidone, N- (1-methylvinyl) pyrrolidone, N-vinylpyridine, N- Bi Lupiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-vinylmorpholine, tetrahydrofurfuryl (meth) acrylate, (meth) acryloyl Examples thereof include vinyl group-containing heterocyclic compounds such as morpholine, for example, acrylate monomers containing halogen atoms such as fluorine atoms.

As the copolymerizable vinyl monomer, a functional group-containing vinyl monomer is preferable, and an amide group-containing vinyl monomer is more preferable.

These copolymerizable vinyl monomers can be used alone or in combination.

When a copolymerizable vinyl monomer is used, the blending ratio is, for example, 10 to 50% by mass, preferably 20 to 40% by mass, based on the total amount of the monomer composition.

-Preparation method of acrylic polymer having hydroxyl group in side chain Then, an acrylic polymer having a hydroxyl group in the side chain can be obtained by polymerizing the monomer composition described above.

Examples of the polymerization method include emulsion polymerization (including suspension polymerization), solution polymerization, bulk polymerization, and the like, and preferably emulsion polymerization and solution polymerization.

Emulsion polymerization In emulsion polymerization, for example, a polymerization initiator, an emulsifier, and, if necessary, a chain transfer agent are blended and polymerized in water together with the monomer composition described above. More specifically, for example, known emulsion polymerization methods such as a batch charging method (batch polymerization method) and a split charging method (multistage polymerization method) can be employed. In addition, reaction conditions etc. are selected suitably.

The polymerization initiator is not particularly limited, and a polymerization initiator usually used for emulsion polymerization is used. For example, organic peroxides such as benzoyl peroxide, lauroyl peroxide, caproyl peroxide, t-hexyl peroxyneodecanate, t-butyl peroxybivalate, such as 2,2-azobis-iso-butyronitrile, 2,2-azobis-2,4-dimethylvaleronitrile, 2,2-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobis-2-methylbutyronitrile (ABN-E, manufactured by Nippon Hydrazine Kogyo Co., Ltd.) ) And the like.

These polymerization initiators can be used alone or in combination of two or more. Of these polymerization initiators, an azo compound is preferable.

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

The emulsifier is not particularly limited, and known emulsifiers commonly used in emulsion polymerization (for example, anionic emulsifiers, nonionic emulsifiers, etc.) are used.

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

The chain transfer agent is blended as necessary, and adjusts the molecular weight of the acrylic polymer. Examples thereof include mercaptans such as 1-dodecanethiol.

These chain transfer agents can be used alone or in combination, and the blending ratio thereof is, for example, 0.1 to 1 part by mass with respect to 100 parts by mass of the monomer composition.

The acrylic polymer obtained by such emulsion polymerization is prepared as an emulsion (water dispersion type), that is, an acrylic polymer aqueous dispersion.

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

Solution Polymerization In the solution polymerization, the above-described monomer composition and the above-described polymerization initiator and, if necessary, a chain transfer agent are blended and polymerized in an organic solvent.

The organic solvent only needs to dissolve the monomer composition described above. Examples thereof include ketone organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ester organic solvents such as methyl acetate, ethyl acetate, and butyl acetate, dimethylformamide. , Polar solvents such as dimethyl sulfoxide, N-methyl-2-pyrrolidone, alcoholic organic solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, aromatics such as toluene, xylene, “Solvesso 100” (manufactured by ExxonMobil Chemical) Hydrocarbon organic solvents, n-hexane, cyclohexane, methylcyclohexane, “Loose” (manufactured by Shell Chemicals), “Mineral Spirit EC” (manufactured by Shell Chemicals), and other aliphatic hydrocarbon / alicyclic hydrocarbons Organic solvent Methyl cellosolve, ethyl cellosolve, cellosolve organic solvents such as butyl cellosolve, tetrahydrofuran, ether organic solvents such as dioxane, n- butyl carbitol, etc. carbitol organic solvents such as iso- amyl carbitol.

These organic solvents can be used alone or in combination of two or more. The mixing ratio of the organic solvent is appropriately set depending on the purpose and application.

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

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

Physical amount and physical properties of acrylic polymer having a hydroxyl group in the side chain Average molecular weight of the acrylic polymer having a hydroxyl group in the side chain is, for example, 5000 to 150,000, and preferably 10,000 to 120,000. The number average molecular weight of the obtained acrylic polymer is, for example, 1000 to 50000, preferably 5000 to 50000.

In addition, the weight average molecular weight and the number average molecular weight are obtained by measuring the molecular weight distribution of the acrylic polymer by a gel permeation chromatograph (GPC) equipped with a differential refractive index detector (RID), for example. Chart) can be calculated using standard polystyrene as a calibration curve (the same applies hereinafter).

Glass transition temperature The glass transition temperature calculated | required by the Fox formula of an acrylic polymer is 23 degreeC or more, for example, Preferably, it is 30 degreeC or more, More preferably, it is 45 degreeC or more, Usually, 120 degreeC or less.

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

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

Viscosity was measured using a cone and plate viscometer (JIS K 5600-2-3: 1999), “Paint General Test Methods-Part 2: Paint Properties and Stability-Section 3: Viscosity (Cone and Plate Viscometer Method) ”(hereinafter the same shall apply).

The hydroxyl value of acrylic polymer (JIS K 1557-1: 2007 (ISO 14900: 2001), “Plastics—Polyurethane raw material polyol test method—Part 1: Determination of hydroxyl value”) (Compliance) 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 coating surface obtained using the coating material, and the slipperiness can be improved.

Diisocyanate Diisocyanate is not particularly limited, and for example, aromatic diisocyanate (for example, tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof), phenylene diisocyanate (m-, p-phenylene diisocyanate) 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 ), Araliphatic diisocyanates (eg, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or mixtures thereof), tetramethyl xylylene diisocyanate (1,3- or , 4-tetramethylxylylene diisocyanate or mixtures thereof), aliphatic diisocyanates (eg, 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexa Methylene diisocyanate, etc.), alicyclic diisocyanates (eg, cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorodiisocyanate), methylene bis (cyclohexyl isocyanate), norbornane diisocyanate, bis (isocyanatomethyl) ) Cyclohexane and the like.

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

Preferred examples of the diisocyanate include aliphatic diisocyanates and alicyclic diisocyanates from the viewpoints of light resistance and yellowing resistance.

-Polyether polyol Polyether polyol is, for example, low molecular weight polyol (for example, ethylene glycol, propylene glycol, glycerin, etc.) or aromatic / aliphatic polyamine (for example, ethylenediamine, tolylenediamine, etc.) as an initiator, ethylene oxide. And / or an addition reaction of alkylene oxide such as propylene oxide. For example, polyethylene polyol, polypropylene polyol, polyethylene polypropylene polyol (random or block copolymer) and the like can be mentioned.

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

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

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

Further, the average number of functional groups of the polyether polyol is, for example, 1 to 8, preferably 2 to 6. In addition, the average functional group number of polyether polyol can be calculated | required from the kind and mixture ratio of an initiator.

The number average molecular weight of the polyether polyol is, for example, 300 to 30000, preferably 700 to 20000. The number average molecular weight of the polyether polyol can also be determined from the hydroxyl value and the average number of functional groups.

Photopolymerizable compound having both a hydroxyl group and a photopolymerizable group In a photopolymerizable compound having both a hydroxyl group and a photopolymerizable group (hereinafter referred to as a hydroxyl group-containing photopolymerizable compound), the photopolymerizable group is a photopolymerizable group. Specific examples of polymerizable functional groups include (meth) acryloyl group, alkenyl group, cinnamoyl group, cinnamylideneacetyl group, benzalacetophenone group, styrylpyridine group, α-phenylmaleimide group, phenyl Azide group, sulfonyl azide group, carbonyl azide group, diazo group, o-quinonediazide group, furylacryloyl group, coumarin group, pyrone group, anthracene group, benzophenone group, stilbene group, dithiocarbamate group, xanthate group, 1,2,3 -Thiadiazole group, cyclopropene group, azadioxabicyclo group, etc. That. The photopolymerizable group is preferably a (meth) acryloyl group.

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

Examples of the hydroxyl group-containing photopolymerizable compound include a photopolymerizable compound having one hydroxyl group and one photopolymerizable group in one molecule, such as the above-described hydroxyl group-containing vinyl monomer, such as pentaerythritol tri (meta ) Acrylate, dipentaerythritol penta (meth) acrylate, etc., photopolymerizable compounds having one hydroxyl group and two or more photopolymerizable groups in one molecule, such as pentaerythritol di (meth) acrylate, dipentaerythritol Photopolymerizable compounds having two or more hydroxyl groups and two or more photopolymerizable groups in one molecule, such as tri (meth) acrylate and dipentaerythritol tetra (meth) acrylate, 2,2-dihydroxyethyl acrylate Photopolymerization having two or more hydroxyl groups and one photopolymerizable group in one molecule Such compounds.

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

Hydroxyl-free-photopolymerizable compound In addition, if necessary, a hydroxyl-containing-photopolymerizable compound and a photopolymerizable compound having no hydroxyl group and having a photopolymerizable group (hereinafter referred to as hydroxyl-free-photopolymerizable). A compound).

Examples of the hydroxyl group-free photopolymerizable compound include alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and neopentyl glycol di (meth) acrylate, such as diethylene glycol. Poly (alkylene glycol) di (meth) acrylates such as di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, such as 1,4-butane Diol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, dicyclopentadiene di (meth) acrylate, Opentyl glycol adipate di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, for example, bisphenol AEO addition diacrylate , Caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate, allylated cyclohexyldi (meth) acrylate, isocyanurate di (meth) acrylate or their alkylene oxide-modified products, divinylbenzene, butanediol -1,4-divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, dipropylene glycol divinyl ether Terdipropylene glycol divinyl ether, hexanediol divinyl ether, triethylene glycol divinyl ether, phenylglycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer (AH-600, manufactured by Kyoeisha Chemical Co., Ltd.), phenylglycidyl ether acrylate toluene diisocyanate urethane prepolymer (AT -600, manufactured by Kyoeisha Chemical Co., Ltd.) and other photopolymerizable polyfunctional compounds having two photopolymerizable groups in one molecule, such as trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, or A photomultiplier having three photopolymerizable groups in one molecule, such as a modified alkylene oxide or a tri (meth) acrylate of an isocyanuric acid alkylene oxide. Photopolymerizable polyfunctional compounds having four photopolymerizable groups in one molecule, such as ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate or their modified alkylene oxides Compound, for example, dipentaerythritol hexa (meth) acrylate, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer (UA-306H, manufactured by Kyoeisha Chemical Co., Ltd.), caprolactone-modified dipentaerythritol hexa (meth) acrylate, or alkylene oxide thereof Examples include a photopolymerizable polyfunctional compound having six photopolymerizable groups in one molecule such as a modified product.

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

Use of a hydroxyl group-containing photopolymerizable compound and a hydroxyl group-free-photopolymerizable compound When a hydroxyl group-containing photopolymerizable compound and a hydroxyl group-free-photopolymerizable compound are used in combination, For example, 10 to 90 parts by mass, preferably 50 to 70 parts by mass of the hydroxyl group-containing photopolymerizable compound with respect to 100 parts by mass of the total amount of the contained-photopolymerizable compound and the hydroxyl group-free-photopolymerizable compound. The hydroxyl group-free-photopolymerizable compound is, for example, 10 to 90 parts by mass, preferably 30 to 50% by mass.

-Composition of coating material In the production of the coating material, the blending ratio of each of the above-mentioned raw material components (that is, acrylic polymer, diisocyanate, polyether polyol and hydroxyl group-containing photopolymerizable compound) is 100 parts by mass in total. On the other hand, the acrylic polymer is, for example, 5 to 90 parts by mass, preferably 10 to 80 parts by mass, and the diisocyanate is, for example, 1 to 40 parts by mass, preferably 5 to 30 parts by mass. The polyol is, for example, 1 to 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.

If the blending ratio of each raw material component is within the above range, it is possible to improve the antifouling property of the coating surface obtained using the coating material, and to ensure excellent wiping off of dirt.

On the other hand, if the blending ratio of the acrylic polymer is less than the lower limit, the coating surface obtained by using the coating material is inferior in slipperiness, and the ease of wiping off the dirt may not be sufficiently secured.

Further, when the blending ratio of the acrylic polymer exceeds the above upper limit, the antifouling property of the coating surface obtained using the coating material cannot be sufficiently secured, and for example, fingerprints may be easily attached.

Further, if the blending ratio of diisocyanate is less than the above lower limit, the antifouling property of the coating surface obtained using the coating material cannot be sufficiently ensured, and for example, fingerprints may be easily attached.

In addition, even when the blending ratio of diisocyanate exceeds the above upper limit, it is not possible to sufficiently ensure the antifouling property of the coating surface obtained by using the coating material, for example, fingerprints are likely to adhere. is there.

Moreover, if the blending ratio of the polyether polyol is less than the above lower limit, the antifouling property of the coating surface obtained using the coating material cannot be sufficiently ensured, for example, fingerprints may be easily attached. is there.

In addition, when the blending ratio of the polyether polyol exceeds the above upper limit, the slipperiness of the coating surface obtained using the coating material is inferior, and the ease of wiping off the dirt may not be ensured sufficiently.

Also, if the blending prescription of the photopolymerizable compound is less than the above lower limit, the slipperiness of the coating surface obtained using the coating material is inferior, and the ease of wiping off dirt may not be ensured sufficiently.

In addition, when the blending prescription of the photopolymerizable compound exceeds the above upper limit, the coating surface obtained using the coating material is inferior in slipperiness, and it may not be possible to ensure sufficient wiping of dirt.

-Preparation method of coating material Moreover, in reaction of each above-mentioned component, well-known methods, such as a one shot method and a prepolymer method, are employ | adopted, for example, Preferably, the prepolymer method is employ | adopted.

In the prepolymer method, first, a diisocyanate, a polyether polyol and a photopolymerizable compound are reacted to synthesize a prepolymer having both an isocyanate group and a photopolymerizable group at the molecular end, and then the isocyanate group of the obtained prepolymer. And the hydroxyl group of the acrylic polymer in the side chain is reacted.

Specifically, first, the diisocyanate, the polyether polyol and the photopolymerizable compound, and the equivalent ratio of the isocyanate group in the diisocyanate to the hydroxyl group in the polyether polyol and the photopolymerizable compound (NCO / hydroxyl group) is 1. It is formulated (mixed) so as to exceed, for example, 1.1 to 10, preferably 1.5 to 4.5, and in the reaction vessel, for example, at room temperature to 150 ° C., for example, 0.5 to Let urethanation reaction for 24 hours.

In the urethanization reaction, an organic solvent can be blended as necessary.

Examples of the organic solvent include the organic solvents described above. These organic solvents can be used alone or in combination of two or more. The mixing ratio of the organic solvent is appropriately set depending on the purpose and application.

In the urethanization reaction, a urethanization catalyst can be added as necessary.

Examples of the urethanization catalyst include dimethyltin dilaurate, dibutyltin dilaurate, dioctyltin laurate, dioctyltin dilaurate, and bismuth catalyst.

These urethanization catalysts can be used alone or in combination of two or more.

In the above urethanization reaction, a polymerization inhibitor can be further blended as necessary.

Examples of the polymerization inhibitor include quinones such as p-benzoquinone, p-methoquinone, naphthoquinone, phenanthraquinone, toluquinone, and 2,5-diphenyl-p-benzoquinone, such as hydroquinone, pt-butylcatechol, Hydroquinones such as 2,5-di-t-butylhydroquinone, mono-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, such as p-methoxyphenol, di-t-butylparacresol hydroquinone monomethyl And phenols such as ether.

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

Furthermore, if necessary, unreacted diisocyanate may be removed from the resulting prepolymer by known removal means such as distillation or extraction.

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

The weight average molecular weight of the obtained prepolymer is, for example, 4000 to 40000, preferably 8000 to 25000.

Further, the number average molecular weight of the obtained prepolymer is, for example, 1000 to 15000, preferably 2000 to 10,000.

The prepolymer can also be prepared as a solution of the above-mentioned organic solvent, in which case the solid content concentration is, for example, 10 to 90% by mass, preferably 20 to 80% by mass.

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

Next, in this method, the prepolymer and the acrylic polymer obtained are, for example, in the above-described organic solvent, the equivalent ratio of the isocyanate group in the prepolymer to the hydroxyl group in the acrylic polymer (NCO / hydroxyl group) is, for example, Formulated (mixed) to 0.7 to 1.3, preferably 0.9 to 1.1, and in a reaction vessel, for example, at room temperature to 150 ° C., for example, 0.5 to 24 hours Urethanation reaction.

In the urethanization reaction, as described above, the above-described urethanization catalyst and further a polymerization inhibitor can be added as necessary.

According to the coating material obtained by such a prepolymer method, it is possible to improve the antifouling property of the coating surface and to ensure excellent wiping of dirt.

In addition, a well-known additive, for example, a ultraviolet absorber, antioxidant, a light stabilizer, a heat stabilizer, an antistatic agent, an antifoamer etc., can be added to a coating material as needed.

Such an additive is added in advance to at least one of the above-described raw material components (that is, acrylic polymer, diisocyanate, polyether polyol, and hydroxyl group-containing photopolymerizable compound) and / or the above-described prepolymer. It can also be added separately during the reaction of the prepolymer and the acrylic polymer, and can also be added directly to the coating material obtained by the reaction of the prepolymer and the acrylic polymer. In addition, the mixture ratio of an additive is suitably set according to the objective and use.

-Physical quantity and physical properties of coating material The weight average molecular weight of the coating material thus obtained is, for example, 5000 to 100,000, preferably 10,000 to 80,000.

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

The coating material can also be prepared as a solution of the above-mentioned organic solvent. In that 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 as a solution, the viscosity (25 ° C.) is, for example, 1 to 100 mPa · s, preferably 5 to 80 mPa · s.

Further, according to this coating material, it is possible to improve the antifouling property of the coating surface and to ensure excellent wiping property and slipperiness.

<Coating composition>
Specifically, such a coating material is prepared as a coating composition by adding, for example, a photopolymerization initiator and mixing and stirring. That is, a coating composition contains said coating material and a photoinitiator.

-Photopolymerization initiator Examples of the photopolymerization initiator include benzoin ether photopolymerization initiators, benzophenone photopolymerization initiators, thioxanthone photopolymerization initiators, alkylphenone photopolymerization initiators, and acylphosphine oxide light. Polymerization initiator, titanocene photopolymerization initiator, oxime ester photopolymerization initiator, diazophenylamine photopolymerization initiator, naphthoquinone diazosulfonic acid photopolymerization initiator, dimethylaminobenzoic acid photopolymerization initiator, etc. It is done.

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 photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, and 2,4,6-trimethylbenzophenone.

Examples of the thioxanthone photopolymerization initiator include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

Examples of the alkylphenone photopolymerization initiator include 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, and 1-hydroxy. -Cyclohexyl-phenyl-ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) Chill] -1- [4- (4-morpholinyl) phenyl] -1-butanone and the like.

Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like.

Examples of titanocene photopolymerization initiators include bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium. Etc.

Examples of the oxime ester photopolymerization initiator include 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), oxy-phenyl-acetic acid 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester, oxy -Phenyl-acetic acid 2- (2-hydroxyethoxy) ethyl ester and the like.

These photopolymerization initiators can 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 with respect to 100 parts by mass of the coating material (solid content).

-Other compounding components Moreover, the coating composition can contain a photopolymerizable compound, a hardening | curing agent, etc. further as needed.

Photopolymerizable Compound Examples of the photopolymerizable compound include the hydroxyl group-containing / photopolymerizable compound described above, and the hydroxyl group-free / photopolymerizable compound described above, for example.

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

When the photopolymerizable compound is blended, the blending ratio is, for example, 10 to 500 parts by mass, preferably 100 to 300 parts by mass with respect to 100 parts by mass of the coating material (solid content).

Curing agent Examples of the curing agent include polyisocyanates such as the above-described diisocyanates and polyisocyanate derivatives.

Examples of the polyisocyanate derivative include the above-mentioned diisocyanate, for example, the above-mentioned polyisocyanate multimer (for example, dimer, trimer, etc.), allophanate-modified product (for example, the above-mentioned polyisocyanate and low molecular weight polyol). (E.g., allophanate-modified product produced by reaction with trimethylolpropane, etc.), polyol-modified product (e.g., polyol-modified product produced by reaction of polyisocyanate and low molecular weight polyol described above), biuret-modified product ( For example, a biuret modified product produced by reaction of the above polyisocyanate with water or amines), a urea modified product (for example, a urea modified product produced by reaction of the above polyisocyanate with the above polyamine, etc.), Oxadiazine ON-modified products (for example, oxadiazine trione produced by the reaction of polyisocyanate and carbon dioxide), carbodiimide modified products (carbodiimide-modified product produced by decarboxylation condensation reaction of polyisocyanate), uretdione modification Body, modified uretonimine and the like.

Moreover, examples of the curing agent further include unsaturated compounds (isocyanate group-containing (meth) acrylate) having both an isocyanate group and a (meth) acryloyl group.

Examples of the isocyanate group-containing (meth) acrylate include 2-acryloyloxyethyl isocyanate (trade name Karenz MOI, manufactured by Showa Denko KK), 2-methacryloyloxyethyl isocyanate, (meth) acryloyl groups having 2 to 6 carbon atoms. And (meth) acryloyl isocyanate or a derivative thereof bonded to an isocyanate group via an alkylene group.

Examples of the derivative include (meth) acrylate having an isocyanate group in which an isocyanate group is masked with a blocking agent, and specific examples include 2- (0- [1′-methylpropylideneamino] carboxyamino methacrylate. ) Ethyl (trade name Karenz MOI-BM, manufactured by Showa Denko KK).

These curing agents can be used alone or in combination of two or more.

When the curing agent is blended, the blending ratio is, for example, 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight with respect to 100 parts by weight of the coating material (solid content).

The coating composition can also be prepared as a solution of the above-mentioned organic solvent. In that case, the solid content concentration is, for example, 10 to 90% by mass, preferably 20 to 80% by mass.

And according to this coating composition, while improving the antifouling property of a coating surface, it can ensure the outstanding wiping property and slipperiness.

-How to use the coating composition and physical properties of the coating film And, such a coating composition is applied to the surface of the base material and irradiated with light such as ultraviolet rays to be photocured, whereby the coating film (coating layer) ).

The material of the base material is not particularly limited. For example, a resin base material such as a polycarbonate resin, a polyacrylic resin, or a styrene resin, for example, an inorganic base material such as glass, for example, stainless steel, steel, aluminum, or the like. A metal base material etc. are mentioned.

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, and casting using a bar coater or an applicator.

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

And the coating film obtained from said coating composition is excellent in transparency, and specifically, the haze value of a coating film is 1.0% or less, for example, Preferably, it is 0.8% or less, Usually over 0%.

The haze value is measured with a haze meter in accordance with JIS K 7136 (2000).

The coating film obtained from the above coating composition is excellent in hardness. Specifically, the hardness of the coating film surface (coating surface) is, for example, HB or more, preferably H or more, as pencil hardness. , F or less.

The pencil hardness is measured by a pencil hardness test in accordance with JIS K 5600-5-4 (1999).

Further, the coating film obtained from the above 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 Is 52 to 72 degrees, and the oleic acid contact angle is, for example, 5 to 25 degrees, preferably 10 to 20 degrees.

In addition, the coating film obtained from the above coating composition is excellent in wiping ease. Specifically, the coefficient of dynamic friction in a dry state (23 ° C.-50% RH) (measurement condition: 10 mm φ 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.

In addition, the coating film obtained from the above coating composition has excellent adhesion to the substrate, and since such a coating film also has excellent dirt wiping property, it is possible to wipe less adhered dirt (such as fingerprints). It can be removed satisfactorily by the number of removals.

And the coating film (coating surface) obtained in this way is excellent in antifouling property, and also excellent in the ease of wiping off dirt. For example, it is disposed in the outermost layer of an image display device such as a touch panel or a display. The surface of the image display panel to be applied, for example, the surface of a surface protective film that is bonded to the surface of the image display panel to protect the image display panel, for example, the surface of a lens such as glasses or goggles, and the window material for construction It is formed in order to improve antifouling properties and wiping properties on the surfaces of vehicle window materials, instrument window materials and the like.

Next, the present invention will be described based on synthesis examples, examples and comparative examples, but the present invention is not limited to the following examples.

In addition, the measuring method of the physical property used in a synthesis example, an Example, a comparative example, etc. is shown below.
<Measurement of weight average molecular weight and number average molecular weight by gel permeation chromatography>
About 0.2 mg of a sample was collected, dissolved in 10 mL of tetrahydrofuran, and measured by a gel permeation chromatograph (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 (chart) using standard polystyrene as a calibration curve. The measurement apparatus and measurement conditions are shown below.
Data processor: Part number HLC-8220GPC (manufactured by Tosoh Corporation)
Differential refractive index detector: RI detector column built in part number HLC-8220GPC: Part number TSKgel GMH _XL (manufactured by Tosoh Corp.) 3 mobile phases: tetrahydrofuran column Flow rate: 0.5 mL / min
Injection volume: 20 μL
Measurement 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 according to JIS K 5600-2-3: 1999 using a cone plate viscometer.
<Hydroxyl value>
The hydroxyl value of the sample was measured according to method B (phthalation method) of JIS K 1557-1 (2007).

[Synthesis of acrylic polymer]
Synthesis Example A-1
In a reaction vessel, 233 parts by mass of methyl ethyl ketone (hereinafter, MEK) was charged as a solvent, and the temperature was raised to 85 ° C.

On the other hand, a monomer composition consisting of 90 parts by weight of methyl methacrylate and 10 parts by weight of 2-hydroxyethyl acrylate was mixed with azobis-2-methylbutyronitrile (ABN-E, manufactured by Nippon Hydrazine Kogyo) 4 as a polymerization catalyst. A monomer mixed solution was prepared by stirring and mixing parts by mass.

Next, the monomer mixture was dropped into the solvent at 85 ° C. over 2 hours, and after completion of the dropwise addition, the mixture was aged for 4 hours to obtain an acrylic polymer solution having a hydroxyl group in the side chain (nonvolatile content 30% by mass). .

Table 1 shows the weight average molecular weight, number average molecular weight, glass transition temperature, viscosity, and hydroxyl value of the resulting acrylic polymer.

The weight average molecular weight, number average molecular weight, viscosity and hydroxyl value were determined by the above methods. The glass transition temperature was calculated by Fox's equation.

Synthesis Examples A-2 to A-9
A solution of an acrylic polymer having a hydroxyl group in the side chain (non-volatile content: 30% by mass) in the same manner as in Synthesis Example A-1, except that the monomer composition, the polymerization catalyst, and the solvent were blended according to the formulation shown in Table 1. Got. In Synthesis Example A-7, the reaction temperature was 70 ° C.

Table 1 shows the weight average molecular weight, number average molecular weight, glass transition temperature, viscosity, and hydroxyl value of the resulting acrylic polymer.

The details of the abbreviations in the table are as follows.
MMA: methyl methacrylate DMAA: N, N-dimethylacrylamide BA: butyl acrylate 2-HEA: 2-hydroxyethyl acrylate ABN-E: azobis-2-methylbutyronitrile, Nippon Hydrazine Kogyo Co., Ltd. Made

[Prepolymer synthesis]
Synthesis example B-1
In a reaction vessel, 233 parts by mass of MEK was charged as a solvent, and the temperature was raised to 80 ° C.

Next, in a reaction vessel, 15 parts by mass of hexamethylene diisocyanate, 30 parts by mass of Epan U-105 (polyoxyethylene polyoxypropylene glycol (number average molecular weight 6400), manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and Aronix M-403 (Photopolymerizable compound, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate mixture (pentaerythritol pentaacrylate content 50 to 60% by mass, manufactured by Toagosei Co., Ltd.) 55 parts by mass (NCO / OH equivalent ratio 2.9) Further, 0.1 part by mass of dimethyltin dilaurate as a catalyst and 0.05 part by mass of p-methoxyphenol as a polymerization inhibitor were added and mixed at 80 ° C. for 3 hours.

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

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

Synthesis Examples B-2 to B-10
Except for blending diisocyanate, polyether polyol, photopolymerizable compound, catalyst, polymerization inhibitor and solvent in the formulation shown in Table 2, the isocyanate group and photopolymerizable at the molecular end were the same as in Synthesis Example B-1. A prepolymer solution having both groups (non-volatile content: 30% by mass) was obtained.

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

The details of the abbreviations in the table are as follows.
・ HDI: hexamethylene diisocyanate ・ Epan U105: polyoxyethylene polyoxypropylene glycol (number average molecular weight 6400), manufactured by Daiichi Kogyo Seiyaku Co., Ltd. ・ Sanix PP-1000: polyoxypropylene glycol (number average molecular weight 1000), Sanyo Chemical Alonix M-403 manufactured by Kogyo Co., Ltd .: Dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate mixture (pentaerythritol pentaacrylate content: 50-60 mass%, manufactured by Toagosei Co., Ltd.

[Preparation of coating material]
Example C-1
In a reaction vessel, 40 parts by mass of the acrylic polymer solution obtained in Synthesis Example A-1 and 60 parts by mass of the prepolymer solution obtained in Synthesis Example B-1 were charged. Further, dimethyltin was used as a catalyst. Add 0.1 part by weight of dilaurate and 0.05 part by weight of p-methoxyphenol as a polymerization inhibitor and mix at 80 ° C. for 3 hours to obtain a coating material solution (non-volatile content 30% by weight). It was.

Table 3 shows the weight average molecular weight, number average molecular weight, and viscosity of the obtained coating material.

Examples C-1 to C-23 and Comparative Example D-1
A coating material solution (non-volatile content: 30% by mass) was obtained in the same manner as in Example C-1, except that an acrylic polymer, a prepolymer, a catalyst, and a polymerization inhibitor were blended according to the formulation shown in Table 3.

Table 3 shows the weight average molecular weight, number average molecular weight, and viscosity of the obtained coating material.

[Preparation of coating composition]
Example 1
10 parts by mass of the coating material solution obtained in Example C-1 and 2-hydroxy-2-methyl-1-phenyl-propan-1-one (photopolymerization initiator, DAROCUR 1173, manufactured by Ciba Japan) A coating composition was prepared by stirring and mixing 0.8 parts by mass, 27 parts by mass of pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer (urethane acrylate, UA-306H, manufactured by Kyoeisha Chemical Co., Ltd.), and 63 parts by mass of MEK. Prepared.

Table 4 shows the formulation of the coating composition.

Usage examples 2 to 28
Using the coating materials obtained in Examples C-1 to C-23 and Comparative Example D-1, and containing the coating materials, photopolymerization initiators, urethane acrylates and isocyanate groups in the formulations shown in Tables 4 and 5 ( A coating composition was prepared in the same manner as in Use Example 1, except that meth) acrylate, polyisocyanate and solvent were blended.

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 use example was subjected to bar coater no. 10 was applied onto a polyethylene terephthalate (PET) film. And after heating at 80 degreeC for 3 minutes and removing a solvent, ultraviolet light was exposed at 400 mJ / cm < ² > using the high pressure mercury lamp (120 W / cm), the coating composition was hardened, and the coating film was obtained.

Using the PET film on which the coating film was formed as a test plate, the coating film was evaluated according to the following evaluation method.
<Haze value>
Based on JIS K7136 (2000), it measured using haze meter NDH5000 (made by Nippon Denshoku Industries Co., Ltd.).

In addition, it shows that it is excellent in transparency, so that haze value is small.

<Pencil hardness>
A pencil hardness test was performed in accordance with JIS K 5600-5-4: 1999.

In the pencil hardness test, B, HB, F, and H are arranged in order from the lower hardness to the higher hardness.

The pencil hardness indicates that the greater the number before “H”, the higher the hardness, and the greater the number before “B”, the lower the hardness.

<Adhesion>
The adhesion was tested according to JIS K 5600-5-6: 1999.

Specifically, 100 crosscuts (cut pieces) were formed by cutting the coating applied to the test plate in the vertical and horizontal directions with a cutter knife and reaching the substrate. Then, an adhesive tape (Nichiban Tape No. 1, manufactured by Nichiban Co., Ltd.) was attached on the crosscut. Then, after peeling the adhered cellophane adhesive tape, the number of crosscuts remaining without peeling was counted and evaluated as the number of remaining crosscuts / number of formed crosscuts.

In addition, it shows that it is excellent in adhesiveness, so that there are many remaining crosscut numbers with respect to the formation crosscut number.

<Oil wiping off>
0.1 g of normal hexadecane was dropped on the surface of the test plate. Then, normal hexadecane adhering to the test plate surface was wiped 10 times with a cellulose nonwoven fabric (Bencot M-3, manufactured by Asahi Kasei Co., Ltd.) under a load of 300 g.

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

It should be noted that the smaller the value of ΔE, the better the wiping property of fingerprint traces caused by sebum, that is, the better the antifouling property.

<Dynamic friction coefficient>
Under a dry condition (23 ° C.-50% RH), the surface friction measuring device Tribo Station TYPE: 32 (manufactured by HEIDON) under the measurement conditions of 10 mmφ stainless steel ball, load 200 g, speed 5 mm / s, dynamic friction coefficient of the test plate Was measured.

In addition, it shows that sliding property is so favorable that a dynamic friction coefficient is small.

<Water contact angle>
A 0.4 μL water droplet was dropped on the surface of the test plate, and the contact angle was measured with a contact angle meter (Drop Master 500, manufactured by Kyowa Interface Science Co., Ltd.).

In addition, it shows that adhesion of fingerprints etc. can be prevented, so that water contact angle is low.

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

In addition, it shows that adhesion of fingerprints etc. can be prevented, so that an oleic acid contact angle is low.

The details of the abbreviations in the table are as follows.
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) , Kyoeisha Chemical Co., Ltd., Karenz MOI: 2-acryloyloxyethyl isocyanate, Showa Denko Co., Ltd., D-165N: a biuret modified product of hexamethylene diisocyanate, manufactured by Mitsui Chemicals, Inc.

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

Claims (7)

at least,
An acrylic polymer having a hydroxyl group in the side chain;
Diisocyanate,
Polyether polyol,
A coating material obtained by reacting a photopolymerizable compound having both a hydroxyl group and a photopolymerizable group. The coating material according to claim 1, wherein a glass transition temperature obtained by the Fox formula of the acrylic polymer is 30 ° C or higher. The acrylic polymer is
It is obtained by polymerizing a monomer composition containing a hydroxyl group-containing vinyl monomer and methyl (meth) acrylate, and the content ratio of methyl (meth) acrylate is 50% by mass or more. The coating material according to claim 1 or 2. The hydroxyl value determined in accordance with JIS K 1557-1 (2007) method B of the acrylic polymer is 10 to 50 mgKOH / g, according to any one of claims 1 to 3. Coating material. An isocyanate group of a prepolymer obtained by reacting the diisocyanate, the polyether polyol and the photopolymerizable compound, and having both an isocyanate group and a photopolymerizable group at the molecular end;
The coating material according to any one of claims 1 to 4, which is obtained by reacting the acrylic polymer with a hydroxyl group in a side chain. For a total amount of 100 parts by mass of the acrylic polymer, the diisocyanate, the polyether polyol, and the photopolymerizable compound,
10 to 80 parts by mass of the acrylic polymer,
5 to 30 parts by mass of the diisocyanate,
5 to 40 parts by mass of the polyether polyol,
The coating material according to any one of claims 1 to 5, which is obtained by reacting the photopolymerizable compound at a ratio of 10 to 50 parts by mass. A coating material according to any one of claims 1 to 6;
A coating composition comprising a photopolymerization initiator.