KR101726201B1

KR101726201B1 - Two-pack type curable coating agent

Info

Publication number: KR101726201B1
Application number: KR1020157000470A
Authority: KR
Inventors: 마사오 키구치; 료이치 나카이
Original assignee: 하리마 카세이 가부시키가이샤
Priority date: 2012-08-10
Filing date: 2013-07-24
Publication date: 2017-04-12
Also published as: TW201418380A; JP5921986B2; CN104540908B; KR20150023683A; JP2014037454A; TWI519613B; CN104540908A; WO2014024686A1

Abstract

The present invention provides a two-part curing type coating material capable of forming a coating layer excellent in transparency, hardness, scratch resistance, oil wipe resistance and tensile elongation. The two-liquid curing type coating material of the present invention comprises 100 parts by weight of an acryl-based polymer having a photopolymerizable group and a hydroxyl group on the side chain and having a hydroxyl value of 30 to 350 mgKOH / g and a weight average molecular weight (Mw) of 5000 to 200000, 0.3 to 35 parts by weight of a polyether polyol, 3 to 70 parts by weight of a polylactone polyol and 6 to 500 parts by weight of a photopolymerizable polyfunctional compound having at least two photopolymerizable groups in one molecule, 3 to 100 parts by weight of a curing agent.

Description

TWO-PACK TYPE CURABLE COATING AGENT}

The present invention relates to a two-part curing type coating agent for forming a coating layer covering the surface of a two-component curing type coating agent, in particular, a member used in various industrial fields.

Various optical members such as a touch panel, a display, a lens, and a glass have been conventionally used. In particular, the touch panel is used as an input device to an information terminal. Information necessary for the information terminal can be input by touching the fingertip on the surface panel of the touch panel.

When the fingertip touches the optical member, oil fractions such as aliphatic hydrocarbons present on the surface of the fingertip are likely to be fingerprints and adhere to the optical member. (1) the attached oil can be easily wiped off and removed, (2) the amount of oil remaining on the optical member after wiping And that the oil does not hinder the visibility of the optical member. Hereinafter, the characteristics of the above (1) and (2) are also referred to as " oil polishing property ".

In addition, when the surface of the optical member is scratched or the surface of the optical member is deformed by the chemical, visibility of the optical member is impaired, and therefore it is required to impart the scratch resistance and chemical resistance to the surface of the optical member.

In order to solve the above-mentioned demand, coating layer is formed by applying coating agent to the surface of the optical member. The coating layer is required to have transparency in order to ensure visibility, and the optical member in which the coating layer is formed may be molded into a desired shape, and it is also required that the coating layer is free from cracks or the like, do.

(B) an acrylic polymer having active hydrogen and a weight average molecular weight (Mw) of 5,000 to 200,000, (C) a silane coupling agent, and , (D) a polylactone polyol, (F) a surfactant having an active hydrogen, and (E) a curing agent at a predetermined ratio.

However, the coating layer formed of the hydrophilic coating agent is inferior in scratch resistance and chemical resistance, and the hydrophilic coating requires time for curing, so that the productivity is low.

Patent Document 2 discloses a method for producing a polyurethane foam comprising the steps of (1-A) preparing an acrylic polyol having a predetermined hydrophilic group, (1-B) an acrylic polyol having a Mw of 50000 or less, (1-C) , And (1-D) polyisocyanate and an amino resin as at least a constituent component.

However, the coating layer formed of the oil-cleansing resin composition is inferior in scratch resistance and tensile elongation, and the hydrophilic coating requires time for curing, so that the productivity is low.

Patent Document 3 discloses a photopolymerizable composition comprising (A) 3 to 40% by weight of a predetermined acrylic resin, (B) 0.1 to 5% by weight of a polyoxyethylene-polyoxypropylene block copolymer, and (C) Discloses a photocurable hydrophilic coating agent comprising 55 to 95% by weight of a synthetic polyfunctional compound.

However, the coating layer formed of the photocurable hydrophilic coating agent falls in tensile elongation, and the coating layer formed of the coating agent has a problem that cracks are easily caused by deformation.

Patent Document 4 discloses that a reaction product of a hydroxyl group equivalent of the component (a1) / an alkoxyl group (b) of the component (b) as the reaction product of the alcohols of the compound (a1) having a hydroxyl group and a (meth) acryloyl group and the alkoxysilane partial condensate Discloses a curable composition having a thermosetting property and an active energy ray curability containing a reaction product (A) having an equivalent (equivalent ratio) of 0.1 to 0.4 as a curing component. However, the coating layer formed of the curable composition has a problem that the oil scarability is poor.

Patent Document 5 discloses a compound obtained by reacting an acrylic resin, an isocyanate group-containing silane coupling agent having a predetermined structure, and a hydroxyl group-containing polyfunctional acrylate having a hydroxyl group and at least three acryloyl groups in the molecule, Discloses an active energy ray curable abrasion-resistant coating composition containing a polyfunctional acrylate having a diaryl group, a urethane acrylate having two or more acryloyl groups in a molecule, a silica sol containing an organic solvent as a dispersion medium, and an organic solvent.

However, the coating layer formed of the above-mentioned active energy ray-curable abrasion-resistant coating composition has a problem that the oil scarability is poor.

WO2009 / 144999 Japanese Patent Application Laid-Open No. 2010-53286 WO2011 / 13497 Japanese Patent Application Laid-Open No. 2002-212248 Japanese Patent Application Laid-Open No. 6-287470

The present invention provides a two-part curing type coating material capable of forming a coating layer excellent in transparency, hardness, scratch resistance, oil wipe resistance and tensile elongation.

The two-liquid curing type coating material of the present invention comprises 100 parts by weight of an acrylic polymer having a photopolymerizable group and a hydroxyl group on the side chain and having a hydroxyl value of 30 to 350 mgKOH / g and a weight average molecular weight of 5000 to 200000, 0.3 to 35 parts by weight of a silane coupling agent, 0.3 to 35 parts by weight of a polyether polyol, 3 to 70 parts by weight of a polylactone polyol, and 6 to 500 parts by weight of a photopolymerizable polyfunctional compound having at least two photopolymerizable groups in one molecule and a curing agent 3 containing a polyisocyanate To 100 parts by weight.

In the above two-liquid curing type coating, the main subject is a photosensitive resin composition comprising 100 parts by weight of an acrylic polymer having a photopolymerizable group and a hydroxyl group in side chains and having a hydroxyl value of 30 to 350 mg KOH / g and a weight average molecular weight of 5,000 to 200,000, 0.3 to 35 parts by weight of a polyether polyol, 3 to 70 parts by weight of a polylactone polyol and 6 to 500 parts by weight of a photopolymerizable polyfunctional compound having at least two photopolymerizable groups in one molecule .

The acrylic polymer constituting the two-liquid curing type coating agent of the present invention is preferably an acrylic polymer having a photopolymerizable group and a hydroxyl group in a side chain and having at least two photopolymerizable groups and a hydroxyl group in a side chain. Examples of the photopolymerizable group include an acryloyl group, a methacryloyl group, a styryl group, a vinyl group and an allyl group, as long as they have a photopolymerizable group of a photopolymerizable polyfunctional compound described later and a radically polymerizable ethylenically unsaturated double bond , An acryloyl group, and a methacryloyl group are preferable.

The acrylic polymer is subjected to radical polymerization with the photopolymerizable group of the photopolymerizable polyfunctional compound in the photopolymerizable group to form a crosslinked structure, and the hardness of the coating layer formed by the two-liquid curable coating agent (hereinafter, may be simply referred to as " It is possible to improve the scratch resistance. In addition, the acrylic polymer imparts chemical resistance, such as alkali resistance and solvent resistance, and hydrophilicity to the coating layer.

The acrylic polymer having a photopolymerizable group and a hydroxyl group in the side chain (hereinafter, may be simply referred to as " acrylic polymer ") is obtained by radical polymerization of a monomer composition containing a radically polymerizable monomer containing, for example, a hydroxyl group or a glycidyl group To prepare a polymer, and adding a compound having an isocyanate group and a photopolymerizable group to a part of the hydroxyl groups of the obtained polymer. Further, in the case of using a radically polymerizable monomer containing a glycidyl group, it is necessary to generate a hydroxyl group by ring-opening a glycidyl group with an acid. Examples of the acid include maleic acid, maleic anhydride, fumaric acid, acrylic acid, methacrylic acid, omega -carboxy-polycaprolactone monoacrylate, and phthalic acid monohydroxyethyl acrylate. Examples of the acid include acrylic acid, methacrylic acid desirable. The acid may be used singly or in combination of two or more kinds. By using an acid having an ethylenically unsaturated double bond in the molecule such as acrylic acid and methacrylic acid as the acid for ring opening the glycidyl group, the glycidyl group can be converted and the photopolymerizable group can be simultaneously introduced.

The amount of the acid used when ring opening the glycidyl group is preferably 0.3 to 1.5 equivalents, more preferably 0.5 to 1.2 equivalents per equivalent of glycidyl group. When the amount of the acid is too small, the photopolymerizable group of the side chain is decreased, so that the hardness or the chemical resistance of the coating layer obtained from the two-liquid curing type coating agent may be lowered. If the amount of the acid is large, unreacted acid remains in the subject, so that the alkali resistance or water resistance of the coating layer obtained from the two-liquid curing type coating agent may be lowered.

As the polymerization method of the monomer composition, a general method is used, and examples thereof include emulsion polymerization (including suspension polymerization), solution polymerization, bulk polymerization and the like, and emulsion polymerization and solution polymerization are preferred.

For example, the acrylic polymer may be prepared by polymerizing a monomer composition comprising a radically polymerizable monomer containing an alkyl (meth) acrylate and a hydroxyl group or glycidyl group copolymerizable with alkyl (meth) To prepare an acrylic polyol, and adding a compound having an isocyanate group and a photopolymerizable group to a part of the hydroxyl groups of the obtained acrylic polyol. In addition, when a radically polymerizable monomer containing a glycidyl group is used, it is necessary to generate a hydroxyl group by ring-opening a glycidyl group as described above. In the present invention, (meth) acrylate means acrylate or methacrylate.

An example of a more specific method for producing an acrylic polymer will be described. A monomer composition comprising a radically polymerizable monomer containing an alkyl (meth) acrylate and a hydroxyl group or glycidyl group copolymerizable with an alkyl (meth) acrylate is subjected to radical polymerization in the presence of a radical polymerization initiator to produce an acrylic polyol do. Subsequently, a solution of the obtained acrylic polyol is fed into a reaction vessel, and a compound having an isocyanate group and a photopolymerizable group, and a metal catalyst are added to the reaction vessel. If necessary, polymerization inhibitors such as p-methoxyphenol and hydroquinone (HQ) may be added to the reaction vessel. Thereafter, a compound having an isocyanate group and a photopolymerizable group in a part of the hydroxyl groups of the acrylic polyol is obtained by allowing the reaction mixture to react for 6 to 12 hours while controlling the reaction liquid to be at 30 to 1500 占 폚 while blowing oxygen into the reaction vessel An acrylic polymer having a photopolymerizable group and a hydroxyl group in the side chain can be prepared. In addition, when a radically polymerizable monomer containing a glycidyl group is used, it is necessary to generate a hydroxyl group by ring-opening a glycidyl group as described above.

As the radical polymerization initiator, those generally used in radical polymerization are used, and examples thereof include organic peroxides such as benzoyl peroxide, lauroyl peroxide, caproyl peroxide, t-hexyl peroxyneodecanate and t-butyl peroxy pivalate, Azobis-isobutyronitrile, 2,2-azobis-2,4-dimethylvaleronitrile, 2,2-azobis-4-methoxy-2,4-dimethylvalero (Azobis-2-methylbutylonitrile (trade name " ABN-E ", manufactured by Nihon Hydrazine cement Co., Ltd.), and azo compounds are preferable. The radical polymerization initiator may be used singly or in combination of two or more. The blending amount of the radical polymerization initiator is appropriately selected, but is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the monomer composition.

Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (Meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl Pentadienyl (meth) acrylate, and the like. The alkyl (meth) acrylate may be used alone or in combination of two or more.

As the alkyl (meth) acrylate, methyl (meth) acrylate and butyl (meth) acrylate are preferable, methyl (meth) acrylate is more preferable, and methyl methacrylate is particularly preferable.

The content of the alkyl (meth) acrylate in the monomer composition is preferably 10% by weight or more, more preferably 20% by weight or more, because the water resistance of the coating layer may be lowered.

The content of the alkyl (meth) acrylate in the monomer composition is preferably 90% by weight or less, more preferably 80% by weight or less, because the content of the alkyl (meth) acrylate is preferably such that the hydrophilicity of the coating layer is lowered and the wiping resistance of the coating layer is lowered.

Examples of the radically polymerizable monomer containing a hydroxyl group include alkyl (meth) acrylates containing a hydroxyl group, acrylic acid N-hydroxymethylamide, methacrylic acid N-hydroxymethylamide, 4-hydroxymethylcyclohexyl , And alkyl (meth) acrylates containing a hydroxyl group are preferable, and alkyl (meth) acrylates having a hydroxyl group in the alkyl group are more preferable. Examples of the alkyl (meth) acrylate containing a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) Hydroxybutyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, Acrylate, and 12-hydroxylauryl (meth) acrylate. The alkyl (meth) acrylate containing a hydroxyl group may be used singly or in combination of two or more.

As the radically polymerizable monomer containing a hydroxyl group, 2-hydroxyethyl (meth) acrylate is preferable, and 2-hydroxyethyl acrylate (2-HEA) is more preferable.

As the radically polymerizable monomer containing a glycidyl group, an alkyl (meth) acrylate containing a glycidyl group is preferable. Examples of the alkyl (meth) acrylate containing a glycidyl group include glycidyl (meth) acrylate, and glycidyl methacrylate is preferable. The alkyl (meth) acrylate containing a glycidyl group may be used singly or in combination of two or more.

The content of the radically polymerizable monomer containing a hydroxyl group in the monomer composition is preferably 60% by weight or less, more preferably 40% by weight or less, particularly preferably 30% by weight or less, Do. The content of the radically polymerizable monomer containing a hydroxyl group in the monomer composition is preferably 5% by weight or more because the hydrophilicity of the coating layer is lowered and the wiping performance of the coating layer is lowered.

The content of the radically polymerizable monomer containing a glycidyl group in the monomer composition is preferably 90% by weight or less, more preferably 80% by weight or less, because the water resistance of the coating layer may be lowered. The content of the radically polymerizable monomers containing a glycidyl group in the monomer composition is preferably 10% by weight or more, more preferably 20% by weight or more, because the content of the radically polymerizable monomer containing the glycidyl group may be lowered to lower the hydrophilicity of the coating layer, , And particularly preferably at least 50 wt%.

Examples of the compound having an isocyanate group and a photopolymerizable group include 2-acryloyloxymethyl isocyanate (trade name: "CALENSE MOI", manufactured by Showa Denko K.K.), 2-methacryloylethoxyethyl isocyanate (Meth) acryloyl isocyanate bonded to an isocyanate group through an alkylene group having 2 to 6 carbon atoms or a derivative thereof.

As the derivative, for example, (meth) acrylate having an isocyanate group masked with a block group can be given. Specific examples include methacrylic acid 2- (O- [1'-methylpropylideneamino] carboxyamino) ethyl (trade name: "CALENS MOI-BM" available from Showa Denko K.K.). The derivatives may be used singly or in combination of two or more.

Examples of the metal catalyst include dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin dilaurate, triphenylphosphine, and bismuth-based catalysts.

In the addition of a compound having an isocyanate group and a photopolymerizable group to an acryl polyol, the ratio of the number of moles of isocyanate group (-NCO) to the number of moles of hydroxyl group (-OH) in the radically polymerizable monomer containing a hydroxyl group used for preparing the acrylic polyol (-NCO / -OH) is preferably 0.05 to 0.9, more preferably 0.1 to 0.9.

The acrylic polymer can be prepared in such a ratio that the hydroxyl groups are left without consuming all of the hydroxyl groups in the reaction with the isocyanate group and the compound having the photopolymerizable group. By thus leaving a hydroxyl group in the acrylic polymer, hydrophilicity can be imparted to the coating layer formed of the two-liquid curing type coating agent, and the coating layer can be wiped with oil and excellent in smell resistance.

When the content of the alkyl (meth) acrylate component is small in the acrylic polymer having a radically polymerizable monomer component containing an alkyl (meth) acrylate component and a hydroxyl group or a glycidyl group, the water resistance of the coating layer may be lowered, By weight or more, more preferably 20% by weight or more.

In the acrylic polymer having an alkyl (meth) acrylate component and a radically polymerizable monomer component containing a hydroxyl group or a glycidyl group, if the content of the alkyl (meth) acrylate component is large, the hydrophilic property of the coating layer is lowered, Is preferably 90% by weight or less, more preferably 80% by weight or less.

If the content of the radically polymerizable monomer component containing a hydroxyl group in the acrylic polymer having an alkyl (meth) acrylate component and a radically polymerizable monomer component containing a hydroxyl group is too large, the water resistance of the coating layer may decrease, By weight, more preferably 40% by weight or less, and particularly preferably 30% by weight or less.

When the content of the radically polymerizable monomer component containing a hydroxyl group in the acrylic polymer having an alkyl (meth) acrylate component and a radically polymerizable monomer component containing a hydroxyl group is low, the hydrophilicity of the coating layer is lowered, May be lowered, and it is preferably not less than 5% by weight.

When the content of the radically polymerizable monomer component containing a glycidyl group in an acrylic polymer having a radically polymerizable monomer component containing an alkyl (meth) acrylate component and a glycidyl group is high, the water resistance of the coating layer is lowered , It is preferably 90% by weight or less, and more preferably 80% by weight or less.

When the content of the radically polymerizable monomer component containing a glycidyl group is small in the acrylic polymer having a radically polymerizable monomer component containing an alkyl (meth) acrylate component and a glycidyl group, the hydrophilicity of the coating layer is lowered, The oil wipe-off property of the oil may deteriorate. Therefore, it is preferably 10% by weight or more, more preferably 20% by weight or more, and particularly preferably 50% by weight or more.

If the hydroxyl value of the acryl-based polymer is low, the part to be thermally cured in the two-liquid curing type coating is reduced and the tensile elongation of the coating layer is lowered. If it is high, the chemical resistance of the coating layer is lowered, , It is limited to 30 to 350 mgKOH / g, preferably 50 to 320 mgKOH / g, and more preferably 60 to 270 mgKOH / g. The hydroxyl value of the polymer in the present invention means the hydroxyl value of the solid content.

The hydroxyl value of the acryl-based polymer was measured in accordance with JIS K 1557-1: 2007 (ISO 14900: 2001) "Method of Testing Plastics-Polyurethane Raw Polyols - Part 1: Determination of Hydroxyl Value" Value.

When the weight average molecular weight (Mw) of the acrylic polymer is low, the scratch resistance and chemical resistance of the coating layer are deteriorated. When the acrylic polymer is high, the tensile elongation of the coating layer is lowered and the appearance of the coating layer is lowered. Preferably from 6,000 to 150,000, and more preferably from 10,000 to 100,000.

The weight average molecular weight (Mw) of the acrylic polymer can be determined by measuring the molecular weight distribution of the acrylic polymer by gel permeation chromatography (GPC) equipped with, for example, a differential refractive index detector (RID) The standard polystyrene can be calculated as a calibration curve.

The subject of the two-liquid curing type coating agent of the present invention contains a silane coupling agent. The silane coupling agent is an organic silicon compound represented by the following formula (1), and is a compound having a hydroxyl group-reactive functional group X having a hydroxyl group of an acryl-based polymer, a hydroxyl group of a polyether polyol or a hydroxyl group of a polylactone polyol, Silicon compound.

X _n -Si-Y _(4-n) ... Equation (1)

X is a hydroxyl group-reactive functional group having reactivity with a hydroxyl group of a polyether polyol or a hydroxyl group of a polylactone polyol, Y is a hydrolyzable group, and n is an integer of 1 to 3. When n is 2 or 3, plural Xs may be the same or different. When n is 1 or 2, plural Ys may be the same or different.

The silane coupling agent forms a crosslinked structure with an acryl-based polymer, a polyether polyol or a polylactone polyol in a hydroxyl-reactive functional group, and a hydrolyzable group is hydrolyzed and polycondensed to form a polysiloxane to form a crosslinked structure in a network And imparts tensile elongation and chemical resistance to the coating layer.

The hydroxyl-reactive functional group of the silane coupling agent is not particularly limited as long as it is a functional group capable of forming a chemical bond by reacting with a hydroxyl group, and examples thereof include glycidoxyalkyl groups (such as glycidoxypropyl groups) (Such as an amide group), a mercaptoalkyl group (e.g., a mercaptopropyl group), a ureido alkyl group (e.g., a ureidopropyl group), an isocyanate alkyl group And an aminoalkyl group, an isocyanate alkyl group are preferable.

The hydrolyzable group of the silane coupling agent is not particularly limited as long as it is capable of forming a polysiloxane by hydrolysis and polycondensation, and examples thereof include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, An amide group, an amide group, an amide group, an amide group, an amide group, an amide group, an amide group, an amide group, an amide group, an amide group, Examples of the alkoxy group include a methoxy group, an ethoxy group, a butoxy group and a propoxy group, and a methoxy group and an ethoxy group are preferable.

Specific examples of the silane coupling agent include glycidoxypropyltrimethoxysilane (trade name: KBM403, manufactured by Shinetsu Kagaku Kogyo K.K., trade name Sara Puren S-510, manufactured by Thixoso K.K.) An epoxy group-containing silane coupling agent such as propyl triethoxysilane (trade name "KBE403" available from Shinetsu Kagaku Kogyo Co., Ltd., trade name "Z-6041" available from Toray Dow Corning Co., Ltd.); Aminopropyltrimethoxysilane (trade name: KBM903 manufactured by Shin-Etsu Chemical Co., Ltd., trade name: Z-6610 manufactured by Toray Dow Corning Co., Ltd.), N-2- (Trade name "KBE603" manufactured by Shin-Etsu Chemical Co., Ltd.), aminopropyltriethoxysilane (trade name "KBE903" manufactured by Shinetsu Kagaku Kogyo K.K., trade name "Saraforylene S330" Silane coupling agents such as amino group-containing silane coupling agents; Mercapto group-containing silane coupling agents such as mercaptopropyltrimethoxysilane (trade name "KBM803" available from Shinetsu Kagaku Kogyo Co., Ltd., trade name "Z-6062" available from Toray Dow Corning Co., Ltd.); Urethane group-containing silane coupling agents such as ureidopropyltriethoxysilane (trade name "KBE585" available from Shinetsu Kagaku Kogyo Co., Ltd., "Z-6676" available from Toray Dow Corning Co., Ltd.); And isocyanate group-containing silane coupling agents such as isocyanate propyltriethoxysilane (trade name: " KBE9007 ", manufactured by Shin-Etsu Chemical Co., Ltd.). As the silane coupling agent, since the two-part curing type coating agent is excellent in stability and reactivity, it is preferable to use glycidoxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, isocyanate propyltriethoxy Silane is preferable, and? -Aminopropyltriethoxysilane and N-2- (aminoethyl) -3-aminopropyltriethoxysilane are more preferable.

When the content of the silane coupling agent in the two-liquid curing type coating agent is small, the tensile elongation or chemical resistance of the coating layer is lowered. If the content of the silane coupling agent is less than 100 parts by weight, Preferably 1 to 30 parts by weight, more preferably 1.5 to 20 parts by weight, and particularly preferably 1.3 to 10 parts by weight.

Polyether polyol is contained in the subject of two-liquid curing type coating. The polyether polyol is imparted with hydrophilicity to the coating layer formed of the two-liquid curing type coating agent, thereby improving the wiping resistance of the coating layer.

The polyether polyol can be produced, for example, by reacting ethylene oxide and / or an aliphatic polyol with an initiator in the presence of a low molecular weight polyol (e.g., ethylene glycol, propylene glycol, glycerin, etc.) or aromatic polyamine / aliphatic polyamine (e.g. ethylenediamine, tolylenediamine) Or an alkylene oxide such as propylene oxide. The polyether polyol preferably includes an alkylene oxide because it can improve the hydrophilicity of the coating layer formed by the two-liquid curing type coating agent to improve the oil wiping property of the coating layer. Examples of the polyether polyol include polyoxyethylene polyoxypropylene glycol ether, polyethylene polyol, polypropylene polyol, polyethylene polypropylene polyol (random or block copolymer), and polyoxyethylene polyoxypropylene glycol ether desirable.

Examples of the polyether polyol include polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran and the like.

These polyether polyols may be used singly or in combination of two or more. The hydroxyl value of the polyether polyol is preferably from 3 to 600 mgKOH / g, more preferably from 5 to 300 mgKOH / g. The hydroxyl value of the polyether polyol refers to a value measured in accordance with Method B of JIS K1557-1 (2007).

The average number of functional groups of the polyether polyol is preferably from 1 to 8, more preferably from 2 to 6. The average number of functional groups of the polyether polyol can be determined from the kind of the initiator and the compounding ratio.

The weight average molecular weight of the polyether polyol is preferably from 300 to 30000, more preferably from 700 to 20,000. The weight average molecular weight of the polyether polyol can be determined by measuring the molecular weight distribution of the polyether polyol by gel permeation chromatography (GPC) equipped with, for example, a differential refractive index detector (RID) The standard polystyrene can be calculated using the calibration curve.

When the content of the polyether polyol contained in the subject of the two-liquid curing type coating agent is small, the degree of wiping off of the coating layer formed of the two-liquid curing type coating agent is lowered, And is preferably 0.3 to 35 parts by weight, more preferably 1 to 30 parts by weight, further preferably 1.3 to 20 parts by weight, and particularly preferably 1.3 to 10 parts by weight, based on 100 parts by weight of the acrylic polymer.

A polylactone polyol is contained in the subject of the two-liquid curing type coating. The polylactone polyol imparts excellent tensile elongation to the coating layer formed of the two-liquid curing type coating agent.

The polylactone polyol is obtained, for example, by ring-opening polymerization of a lactone monomer with polyhydric alcohols as an initiator.

Specific examples of polyhydric alcohols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, Butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2,2,4- Methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol, glycerin, trimethylolpropane, trimethylol Octane, pentaerythritol, and the like.

Examples of the lactone monomer include? -Caprolactone,? -Methyl-? -Caprolactone,? -Methyl-? -Caprolactone,? -Methyl-? -Caprolactone,?,? - dimethyl-? - caprolactone, Caprolactones such as 5-trimethyl-epsilon -caprolactone; polyvalerolactones such as? -valerolactone and? -methyl-? -valerolactone; Propiolactones; Butyrolactones; Enanthoracontone; Dodecanolactone, and the like. A derivative of a lactone monomer may be used.

As an example of the polylactone polyol, polycaprolactone diol is represented by the following general formula (2).

H [O (CH ₂ ) ₅ (C = O)] mO-R-O [(C = O) (CH ₂ ) ₅ O] n-H ... Equation (2)

In the formula (2), R is alkylene having 2 to 18 carbon atoms such as -C ₂ H ₄ -, -C ₂ H ₄ OC ₂ H ₄ -, -C (CH ₃ ) ₂ C ₂ H ₄ - , m and n are each a positive integer, and m + n is an integer of 4 to 35.

As an example of the polylactone polyol, polycaprolactone triol is obtained by bonding three polyester chains having a terminal hydroxyl group to a trivalent hydrocarbon group R ¹ , as shown by the formula (3).

R ^One - (O [(C-O) - (CH ₂ ) ₅ O] pH) ₃ ... Equation (3)

In the formula (3), R < ¹ &

And p is an integer of 1 to 30,

Specific examples of the polylactone polyol include commercially available products such as polycaprolactone triol (e.g., "Fraxel 303", "Fraxel 305", "Fraxel 308" and "Fraxel 312", trade names, manufactured by Daicel Chemical Industries, , And polycaprolactone diol ("Fraxel 205", "Fraxel 208", "Fraxel 210" and "Fraxel 212" available from Daicel Chemical Industries Ltd.). The polylactone polyol is preferably a polycaprolactone polyol. Since the number of carbon atoms connecting the polyester bonds is relatively large, excellent tensile elongation can be imparted to the coating layer formed of the two-liquid curing type coating agent.

When the content of the polylactone polyol in the subject of the two-liquid curing type coating material is small, the tensile elongation of the coating layer formed of the two-liquid curing type coating material is lowered. When the content of the polylactone polyol is small, the hardness, The amount is limited to 3 to 70 parts by weight, preferably 5 to 50 parts by weight, more preferably 10 to 35 parts by weight, and particularly preferably 15 to 35 parts by weight, based on 100 parts by weight of the acrylic polymer.

Among themes of the two-liquid curing type coating agent, a photopolymerizable polyfunctional compound having two or more photopolymerizable groups in one molecule (hereinafter sometimes simply referred to as " photopolymerizable polyfunctional compound ") is contained. The photopolymerizable polyfunctional compound forms a crosslinked structure by radical polymerization with the photopolymerizable group of the acrylic polymer, and the coating layer formed of the two-liquid curable coating agent has excellent hardness, scratch resistance and chemical resistance.

The photopolymerizable group contained in the photopolymerizable polyfunctional compound is not particularly limited as long as it has a photopolymerizable group of an acryl-based polymer and a radically polymerizable ethylenically unsaturated double bond and may be an acryloyl group, a methacryloyl group, a styryl group, a vinyl group, And an acryloyl group or a methacryloyl group is preferable.

Examples of the photopolymerizable polyfunctional compound having two photopolymerizable groups in one molecule include alkylene (meth) acrylates such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate and neopentyl glycol di Glycol di (meth) acrylate; (Meth) acrylates such as diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate and tripropylene glycol di Rate; Acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, dicyclopentadienedi (meth) (Meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, dicyclopentanyl di (meth) acrylate; Caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified di (meth) acrylate, allyl cyclohexyl di (meth) acrylate, bisphenol A EO added diacrylate, caprolactone modified dicyclopentenyl di Acrylate, isocyanurate di (meth) acrylate or an alkylene oxide-modified product thereof, divinylbenzene, butanediol-1,4-divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether , Dipropylene glycol divinyl ether, hexanediol divinyl ether, triethylene glycol divinyl ether, phenylglycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer (trade name: AH-600 manufactured by Kyoeisha Chemical Co., Ltd.) ), Phenylglycidyl ether acrylate toluene diisocyanate urethane prepolymer (trade name "AT-6" manufactured by Kyoeisha Chemical Co., Ltd.) 00 "). The photopolymerizable polyfunctional compound may be used singly or in combination of two or more.

Examples of the photopolymerizable polyfunctional compound having three photopolymerizable groups in one molecule include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, tris Acryloxyethyl) isocyanurate, and tri (meth) acrylates of an alkylene oxide modified product thereof and an isocyanuric acid alkylene oxide modified product.

Examples of the photopolymerizable polyfunctional compound having four photopolymerizable groups in one molecule include dimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and alkylene oxide-modified compounds thereof .

Examples of photopolymerizable polyfunctional compounds having five photopolymerizable groups in one molecule include dipentaerythritol penta (meth) acrylate or alkylene oxide-modified compounds thereof.

Examples of the photopolymerizable polyfunctional compound having six photopolymerizable groups in one molecule include dipentaerythritol hexa (meth) acrylate, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer (manufactured by Kyoeisha Chemical Co., Ltd. Quot; UA-306H "), caprolactone-modified dipentaerythritol hexa (meth) acrylate, and alkylene oxide-modified products thereof.

When the number of the photopolymerizable groups contained in the photopolymerizable polyfunctional compound increases, the crosslinking of the coating layer formed of the two-liquid curable coating agent becomes more dense and the hardness of the coating layer becomes higher, so that the number of the photopolymerizable groups is preferably 3 or more, more preferably 4 or more , And five or more are particularly preferable. The number of photopolymerizable groups contained in the photopolymerizable polyfunctional compound is preferably 20 or less, more preferably 15 or less.

If the content of the photopolymerizable polyfunctional compound in the subject of the two-liquid curing type coating material is small, the coating layer formed of the two-liquid curing type coating material lowers in hardness, scratch resistance and chemical resistance, Is preferably from 6 to 500 parts by weight, more preferably from 3 to 100 parts by weight, still more preferably from 30 to 100 parts by weight, still more preferably from 30 to 85 parts by weight, based on 100 parts by weight of the acrylic polymer.

In the subject of the two-liquid curing type coating, a photopolymerizable monofunctional compound having one photopolymerizable group in one molecule may be contained, if necessary. The photopolymerizable monofunctional compound is used to improve the dryness of the two-liquid curing type coating agent by adjusting the viscosity of the two-liquid curing type coating agent and increasing the solid content concentration.

Specific examples of the photopolymerizable monofunctional compound include aliphatic (meth) acrylates, alicyclic (meth) acrylates, aromatic (meth) acrylates, ether (meth) acrylates, vinyl monomers, (meth) Drew and the like. In the present invention, (meth) acrylamide means acrylamide or methacrylamide.

Examples of the photopolymerizable monofunctional compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, lauryl (meth) Acrylate, isobutyl (meth) acrylate, isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, isooctyl (Meth) acrylate, 2-ethylhexyl-carbitol (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, nonylphenoxypolyethylene glycol (Meth) acrylate, phenoxyethyl (meth) acrylate, para-cumylphenol ethylene oxide-modified (meth) acrylate, vinylpyrrolidone, vinylcaprolactam and acryloylmorpholine.

If the content of the photopolymerizable monofunctional compound in the subject of the two-liquid curing type coating agent is too large, the reactivity of the two-liquid curing type coating agent is lowered and the hardness and chemical resistance of the resulting coating layer may be lowered. It is preferably 150 parts by weight or less, more preferably 90 parts by weight or less, particularly preferably 60 parts by weight or less.

In the above description, the case where the compound contained in the subject of the two-liquid curing type coating is not reacted has been described. However, some of the compounds contained in the subject of the two-liquid curing type coating may be reacted. When a part of the compound contained in the subject of the two-liquid curing type coating is reacting, the above-mentioned content of the compound means the content of the compound before the compounds react with each other.

The curing agent of the two-liquid curing type coating agent contains a polyisocyanate. The isocyanate group of the polyisocyanate reacts with the hydroxyl group of the acrylic polymer, the hydroxyl group of the polyether polyol or the hydroxyl group of the polylactone polyol to form a urethane bond, whereby a crosslinked structure is introduced into the coating layer and the coating layer formed of the two- do.

The polyisocyanate is not particularly limited as long as it is an isocyanate having two or more isocyanate groups in one molecule. Examples of the polyisocyanate include diisocyanates, diisocyanates (for example, dimers and trimer), diisocyanates And the resulting coated layer is excellent in hardness and chemical resistance. Therefore, a modified product of a diisocyanate is preferable, and a modified product of a biuret of a diisocyanate is more preferable.

The diisocyanate is not particularly limited and examples thereof include aromatic diisocyanates such as tolylene diisocyanate (2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate or a mixture thereof), phenylene diisocyanate (m -Phenylene diisocyanate, p-phenylenediisocyanate or a mixture thereof), 1,5-naphthalene diisocyanate, diphenylmethane diisocyanate (4,4'-diphenylmethane diisocyanate, 2,4'- Isocyanate, 2,2'-diphenylmethane diisocyanate or mixtures thereof), 4,4'-toluidine diisocyanate, etc.), aromatic aliphatic diisocyanates (e.g., xylylene diisocyanate (1,3- Isocyanate, 1,4-xylylene diisocyanate or a mixture thereof), tetramethyl xylylene diisocyanate (1,3-tetramethylxy 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,5-tetramethylene diisocyanate, etc.), aliphatic diisocyanates (e.g., Hexamethylene diisocyanate), an alicyclic diisocyanate (e.g., cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (such as isopentane diisocyanate, Borane diisocyanate), methylene bis (cyclohexyl isocyanate), norbornadiisocyanate, bis (isocyanatomethyl) cyclohexane, and the like. The diisocyanate may be used singly or in combination of two or more.

Examples of the modified product of the diisocyanate include allophanate-modified products (for example, allophanate-modified products produced from the reaction of a diisocyanate with a low molecular weight polyol (such as trimethylolpropane) and the like) (For example, a biuret modified product produced by reaction of diisocyanate with water or an amine), a nouring modified product (e.g., a modified nourishing product produced by a trimerization reaction between isocyanates) , A polyol modified product (for example, a polyol product resulting from the reaction of a diisocyanate with the above-described low molecular weight polyol, etc.), a urea modified product (e.g., a diisocyanate and a polyamine (e.g., ethylene diamine, tolylenediamine Etc.), oxadiazatrione-modified compounds (for example, those obtained by reacting diisocyanate with carbonic acid gas (For example, a carbodiamide-modified product produced by a decarbonic acid condensation reaction of a diisocyanate), a uretdione modifier, a uretonimine-modified product , And a biuret modified product is preferable.

As a commercially available product of the modified product of diisocyanate, for example, trade name " Takenate D-165N " (trade name, manufactured by Mitsui Takeda Chemical), trade name " Takenate D-170N " D-178N " (allophanate type).

When the content of the curing agent in the two-liquid curing type coating agent is small, the tensile elongation of the coating layer formed of the two-liquid curing type coating agent lowers, and when it is large, the coating layer formed of the two- Is preferably 3 to 100 parts by weight, more preferably 5 to 70 parts by weight, and even more preferably 6 to 35 parts by weight, based on 100 parts by weight.

The main agent and curing agent of the two-liquid curing type coating agent may contain an additive agent if necessary within a range not to impair the physical properties of the two-liquid curing type coating agent. Examples of the additive include photopolymerization initiators, antioxidants, light stabilizers, heat stabilizers, antistatic agents, antifoaming agents and the like.

Examples of the photopolymerization initiator include benzoin ether photopolymerization initiators, benzophenone photopolymerization initiators, thioxanthone photopolymerization initiators, alkylphenon photopolymerization initiators, acylphosphine oxide photopolymerization initiators, titanocene photopolymerization initiators, oximeester photopolymerization initiators , A diazophenylamine photopolymerization initiator, a naphthoquinone diazosulfonic acid photopolymerization initiator, and a dimethylaminobenzoic acid photopolymerization initiator. The photopolymerization initiator may be used singly or in combination of two or more.

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 o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, 2,4,6- .

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

Examples of the alkylphenon-based photopolymerization initiator include 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane- Hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- Methyl-l- (4-methylthiophenyl) - < / RTI > 2-dimethylamino-1- (4-morpholinophenyl) -butanone-l, 2- (dimethylamino) -2 - [(4-methylphenyl) ) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone.

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

Examples of the titanocene photopolymerization initiator include bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H- Titanium, and the like.

Examples of the oxime ester photopolymerization initiator include 1,2-octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime)], ethanone, 1- [ 2-phenyl-acetic acid 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester, oxy- Phenyl-acetic acid 2- (2-hydroxyethoxy) ethyl ester and the like.

When the content of the photopolymerization initiator is less than the content of the two-part curing type coating agent, the photopolymerization of the two-part curing type coating agent may not proceed sufficiently, and if it is large, the hardness of the coating layer may be lowered due to decomposition products of the photopolymerization initiator , Preferably 0.3 to 60 parts by weight, and more preferably 1 to 35 parts by weight, based on 100 parts by weight of the acrylic polymer.

If the content of the photopolymerization initiator in the curing agent of the two-liquid curing type coating agent is too small, the photocuring of the two-liquid curing type coating agent may not proceed sufficiently, and if it is large, the hardness of the coating layer may decrease due to decomposition products of the photopolymerization initiator , Preferably 0.3 to 60 parts by weight, more preferably 1 to 35 parts by weight, based on 100 parts by weight of the acrylic polymer in the subject to be used together with the curing agent.

The subject of the two-liquid curing type coating agent of the present invention is prepared by mixing an acrylic polymer, a silane coupling agent, a polyether polyol, a polylactone polyol, a photopolymerizable polyfunctional compound, and an additive agent, .

The subject of the two-liquid curing type coating may be prepared as a solution of an organic solvent. In this case, the solid content concentration of the subject matter is preferably from 10 to 90% by weight, more preferably from 20 to 80% by weight.

Specifically, a preliminary mixed solution is prepared by preliminarily mixing a silane coupling agent, a polyether polyol, a polylactone polyol, a photopolymerizable polyfunctional compound, and an additive agent added as required, and then gradually adding an acrylic polymer to the preliminary mixed solution To prepare a two-part curing type coating.

More specifically, a preliminary mixed solution is prepared by preliminarily mixing a silane coupling agent, a polyether polyol, a polylactone polyol, a photopolymerizable polyfunctional compound, and an additive agent added as required, at 10 to 40 ° C, The acrylic polymer is gradually added dropwise over 30 to 60 minutes. After the dropping of the acrylic polymer into the preliminary mixed liquid is completed, the preliminary mixed liquid is stirred at 10 to 40 DEG C for 30 to 60 minutes to prepare a subject.

The curing agent of the two-liquid curing type coating agent includes a polyisocyanate, and when an additive is contained in addition to the polyisocyanate, the additive is added to the polyisocyanate and mixed.

As a method of using the two-liquid curing type coating agent, a curing agent is first mixed with the subject of the two-liquid curing type coating agent and the two-liquid curing type coating agent is applied to the substrate. It is preferable to mix the curing agent on the subject of the two-liquid curing type coating agent immediately before applying the two-liquid curing type coating agent to the substrate.

The material of the substrate is not particularly limited, and examples thereof include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, synthetic resins such as polycarbonate resin, polyacrylic resin, styrene resin and ABS resin, , Metals such as stainless steel, steel and aluminum, and the like.

Examples of the method of applying the two-liquid curing type coating agent to a substrate include a coating method using a dip coating method, a spray coating method, a roll coating method, a doctor blade method, a screen printing method, a casting method using a bar coater, .

The film thickness of the coating film of the two-liquid curing type coating agent applied on the substrate is not particularly limited, but is preferably 2 to 90 m, more preferably 5 to 50 m.

Then, the coating film of the two-liquid curing type coating agent applied on the substrate is heated and thermally cured. The temperature of the thermosetting of the two-liquid curing type coating agent is preferably 60 to 180 占 폚, more preferably 80 to 150 占 폚. The time for thermal curing of the two-liquid curing type coating agent is preferably 1 to 30 minutes, more preferably 1 to 10 minutes.

Next, by irradiating the thermally cured coating film with light such as ultraviolet rays, the coating film is further cured to form a coating layer. The coating layer thus obtained is excellent in transparency, hardness, scratch resistance, oil wipe resistance and tensile elongation. Further, the coating film of the two-liquid curing type coating agent may be formed by photo-curing and then thermosetting.

The coating layer is excellent in transparency. Specifically, the haze of the coating layer is preferably 1.0% or less, more preferably 0.8% or less. The haze of the coating layer is a value measured by a haze meter in accordance with JIS K 7136 (2000).

The coating layer is excellent in hardness. Specifically, the hardness of the coating layer is preferably not less than H, and more preferably not less than 2H. The pencil hardness refers to a value measured by a pencil hardness test according to JIS K 5600-5-4 (1999).

The coating layer is excellent in oil wiping property. Specifically, the water contact angle measured by the contact angle meter is preferably 50 to 75 °, more preferably 52 to 72 °. The contact angle of oleic acid is preferably 5 to 25 DEG, more preferably 10 to 20 DEG.

The coating layer is excellent in adhesion to a substrate. In addition, since the coating layer is also excellent in oil wiping ability, the oil (fingerprint, etc.) adhering to the surface of the coating layer can be satisfactorily removed with a small number of wiping operations.

The coating layer may be formed on the surface of an optical member (for example, a surface of an image display panel provided on an outermost layer of an image display device such as a touch panel or a display, A surface of a surface protective film to be adhered to a surface, a lens surface such as a spectacle, a goggle, and the like, a window surface for a building, a vehicle, a meter, etc.). The coating layer is also excellent in transparency after wiping off the oil, and the visibility of the optical member can be secured. Further, since the coating layer is excellent in hardness, scratch resistance and chemical resistance, excellent transparency can be maintained over a long period of time, and the visibility of the optical member can be securely secured.

(Effects of the Invention)

According to the two-liquid curing type coating agent of the present invention, a coating layer having excellent transparency, hardness, scratch resistance, oil polishing property and tensile elongation can be formed.

Therefore, the two-liquid curing type coating agent of the present invention can be preferably used to form a coating layer for protecting the surface of the substrate requiring visibility.

Further, the coating layer formed of the two-liquid curing type coating agent has appropriate hydrophilicity by the hydroxyl group or the ether moiety. Accordingly, even when oil is adhered to the surface of the coating layer, water can be smoothly penetrated between the surface of the coating layer and the oil, so that the oil can be floated from the surface of the coating layer to easily remove the oil.

The coating layer has suitable hydrophilicity, but also has a proper lipophilicity due to the carbon chain moiety. Therefore, even when oil adhered on the coating layer is not completely removed and remains on the coating layer, the oil on the coating layer is not raised in a water droplet form on the coating layer, and can not be recognized visually So that it is in a state in which it is spread in a thin film shape. Therefore, the oil does not cause irregular reflection of light, and the coating layer maintains excellent transparency.

Further, since the coating layer has excellent tensile elongation, even when the base material with the coating layer formed thereon is deformed to form a desired shape, cracks or the like do not occur in the coating layer smoothly following the deformation of the base material. Therefore, a substrate having a surface protected by a coating layer and having a desired shape can be easily obtained.

Further, since the coating layer has excellent hardness, scratch resistance and chemical resistance, the coating layer can maintain excellent transparency and appearance over a long period of time.

The two-liquid curing type coating material of the present invention does not need to contain colloidal silica, so that the obtained coating layer has excellent hardness and does not cause lowering of tensile elongation caused by containing colloidal silica. Therefore, the coating layer formed of the two-liquid curing type coating agent has excellent hardness and tensile elongation.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Synthesis of acrylic polymers A1 to 13)

233 parts by weight of methyl isobutyl ketone (MIBK) was supplied as a solvent into the reaction vessel, and the mixture was heated to 88 占 폚 and maintained.

(MMA), glycidyl methacrylate (GMA), butyl acrylate (BA), N, N-dimethylacrylamide (DMAA), and 2-hydroxy A monomer composition comprising ethyl acrylate (2-HEA) was fed into methyl isobutyl ketone in a reaction vessel and mixed.

Subsequently, azobis-2-methylbutylonitrile (ABN-E) was gradually added dropwise to the monomer composition over a period of 2 hours, followed by allowing to stand for 1 hour. Further, azobis-2-methylbutyronitrile was gradually added dropwise to the monomer composition over 2 hours, and then the monomer composition was maintained at 88 占 폚 over 3 hours. The total amount of azobis-2-methylbutyronitrile added into the monomer composition is shown in Tables 1 to 3.

Thereafter, the monomer composition was heated to 110 DEG C and subjected to radical polymerization for 2 hours to prepare an acrylic polymer.

The weight average molecular weight (Mw), the number average molecular weight (Mn), the glass transition temperature (Tg), the viscosity and the hydroxyl value of the obtained acrylic polymers A1 to A13 were measured in the following manner and the results are shown in Tables 1 to 3 . The glass transition temperature (Tg) of the acrylic polymer was calculated by the Fox's formula and is shown in Tables 1 to 3. The hydroxyl value of the acrylic polymers A1 to 13 means the hydroxyl value of the solid component.

(Measurement of weight average molecular weight and number average molecular weight by gel permeation chromatography)

About 0.2 mg of the obtained acrylic polymer was taken as a sample, dissolved in 10 milliliters of tetrahydrofuran and measured by gel permeation chromatography (GPC) equipped with a differential refractive index detector (RID), and the molecular weight distribution of the sample was measured .

The weight average molecular weight and the number average molecular weight of the sample were calculated from the obtained chromatogram (chart) using standard polystyrene as a calibration curve. The measurement apparatus and measurement conditions are shown below.

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

Differential Refractive Index Detector: RI detector built in part number HLC-8220GPC

Column: Part number TSKgel GMH _XL (made by Tosoh) 3 pieces

Mobile phase: tetrahydrofuran

Column flow rate: 0.5 mL / min

Injection volume: 20 μL

Measuring temperature: 40 ° C

Standard polystyrene molecular weight: 1250, 3250, 9200, 28500, 68000, 165000, 475000, 950000, 1900000

(Viscosity)

The viscosity of the obtained acrylic polymer at 25 캜 was measured using a cone plate viscometer according to JIS K 5600-2-3: 1999.

(Hydroxyl group)

The hydroxyl value of the obtained acrylic polymer was measured according to 4.2 B method of JIS K 1557-1: 2007 (ISO 14900: 2001) "Testing method of plastic-polyurethane raw material polyol - Part 1: Determination of hydroxyl value".

(Synthesis of acrylic polymers B1 to B15)

Methyl isobutyl ketone (MIBK) shown in Tables 4 to 6 as a solvent was supplied into the reaction vessel and heated to 80 캜 and maintained.

(Trade name "Carlen AOI", manufactured by Showa Denko K.K.), acrylic acid, dibutyl tin dilaurate, dibutyl tin dilaurate, dibutyl tin dilaurate, Triphenylphosphine, and p-methoxyphenol were fed into a reaction vessel and mixed to prepare a mixed solution.

The mixed solution was reacted at the reaction temperatures shown in Tables 4 to 6 for the reaction times shown in Tables 4 to 6 to prepare an acryl-based polymer solution containing an acryl-based polymer B1-15 having an ethylenically unsaturated double bond and a hydroxyl group in the side chain.

The weight average molecular weights (Mw), number average molecular weights (Mn), viscosity and hydroxyl value of the obtained acrylic polymers B1 to B15 were measured in the above manner, and the results are shown in Tables 4 to 6. The ratios of the number of moles of the isocyanate group (-NCO) to the number of moles of the hydroxyl group (-OH) in the 2-hydroxyethyl acrylate used in the production of the acrylic polymers A1 to 6 and 10 to 13 are shown in Tables 4 to 6 . The hydroxyl value of the acrylic polymers B1 to B5 is the hydroxyl value of the solid content.

(Examples 1 to 30 and Comparative Examples 1 to 17)

(Trade name "KBE-9007" manufactured by Shin-Etsu Chemical Co., Ltd.), N-2- (aminoethyl) -3-aminopropyltriethoxysilane (Trade name: KBE-603 manufactured by Shin-Etsu Chemical Co., Ltd.), glycidoxytrimethoxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.), polyoxyethylene poly (Trade name: " Epan U105 ", a hydroxyl value of 19 mgKOH / g, an average number of functional groups: 2, a weight average molecular weight: 6400), polyoxypropylene glycol ether (manufactured by Sanyo Chemical Industries, (Trade name: Sunnix PP-1000, hydroxyl value: 112 mgKOH / g, average number of functional groups: 2, weight average molecular weight: 1000), polycaprolactone triol Fraxel 303 "), polycaprolactone diol (trade name " Fraxel ", trade name, manufactured by Daicel Chemical Industries, (Trade name "UA-306H" available from Kyoeisha Chemical Co., Ltd.), phenylglycidyl ether acrylate hexamethylene diisocyanate prepolymer (manufactured by Kyoeisha Chemical Co., Ltd.) AH-600 "manufactured by Kaku Co., Ltd.), colloidal silica (trade name" MIBK-ST "manufactured by Nissan Chemical Industries, Ltd.) and methyl isobutyl ketone were uniformly mixed to prepare a premix solution. The acrylic polymer solution containing the acrylic polymer B1 to 15 was slowly added dropwise to the premix mixture solution over 10 minutes so that the acrylic polymer B1 to 15 had an amount (solid content) shown in Tables 7 to 11 over 10 minutes. After the dropping of the acrylic polymer solution into the preliminary mixed solution was completed, the preliminary mixed solution was stirred at 30 캜 for 30 to 60 minutes to prepare a two-part curing type coating agent. Then, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (product name "DAROCUR 1173" manufactured by BASF) shown in Tables 7 to 11 was added to the subject of two- . The solids concentration of the subject of the two-liquid curing type coating was 30% by weight.

A predetermined amount of a buret-modified product of hexamethylene diisocyanate (trade name "Takenate D-165N" available from Mitsui Takeda Chemical Co., Ltd.) shown in Tables 7 to 11 was used as a curing agent for two-

On the subject of the two-liquid curing type coating, a predetermined amount of a modified buret of hexamethylene diisocyanate shown in Tables 7 to 11 was added as a curing agent. Immediately after the addition, a two-liquid curing type coating agent was applied on a polyethylene terephthalate (PET) film using a bar coater No. 10 so that the dry film thickness became about 5 mu m.

Thereafter, the two-liquid curing type coating agent was heated at 80 DEG C for 3 minutes to remove the solvent, and the two-liquid curing type coating agent was thermally cured. Then, the obtained thermosetting coating was irradiated with a high- Ultraviolet rays were irradiated at 500 mJ / cm < 2 > to further cure the thermosetting coating to form a coating layer. In Comparative Example 12, the two-part curing type coating agent was heated at 80 DEG C for 20 minutes to remove the solvent, and the two-part curing type coating agent was thermally cured

The haze, pencil hardness, adhesion, oil removability, scratch resistance, alkali resistance, solvent resistance, tensile elongation, water contact angle and oleic acid contact angle of the obtained coating layer were measured by the following methods, and the results are shown in Tables 7 to 11 .

(Hayes)

The haze of the coating layer was measured using a haze meter (trade name "NDH5000" manufactured by Nihon Denshoku Kogyo Co., Ltd.) in accordance with the test method of "Determination of haze of plastic / transparent material" of JIS K7136. Further, the smaller the haze value, the better the transparency.

(Pencil hardness)

The pencil hardness of the coating layer was measured by a pencil hardness test according to JIS K 5600-5-4: 1999. In the pencil hardness test, B, HB, F, and H are arranged in the order from the low hardness side to the high hardness side. The pencil hardness means that the larger the number in front of "H", the higher the hardness, and the larger the number in front of "B", the lower the hardness.

(Adhesion)

The adhesion of the coating layer was measured in accordance with JIS K 5600-5-6: 1999. Specifically, incisions were formed in a lattice shape to reach the polyethylene terephthalate film on the coating layer. The coating layer was divided into 100 divided pieces by lattice-like incision. The divided pieces had a flat square shape with one side of 1.0 mm. An adhesive tape (Nichiban Tape No. 1, trade name, Nichia Reflective Agent) was attached to the entirety of the divided pieces. The adhesive tape thus adhered was peeled from the polyethylene terephthalate film, and the number of the split pieces remaining on the polyethylene terephthalate film was counted. The adhesion was evaluated as (the number of the split pieces remaining on the polyethylene terephthalate film / the number of split pieces formed on the polyethylene terephthalate film). In addition, the larger the number of the split pieces remaining on the polyethylene terephthalate film, the better the adhesion.

(Oil removability)

0.1 g of normal hexadecane was passed over the surface of the coating layer. Then, normal hexadecane adhered to the surface of the coating layer was wiped 10 times by applying a load of 300 g with a nonwoven fabric made of cellulose (trade name "Bencoat M-3" available from Asahi Kasei Corporation).

Then, the haze (turbidity) of the surface of the coating layer was measured before and after wiping using a haze meter (trade name "NDH5000" manufactured by Nihon Denshoku Kogyo Co., Ltd.). Then, the haze difference (? E) of the coating layer before and after wiping was calculated. In addition, the smaller the value of? E, the better the wipe-off property of fingerprint marks caused by sebum.

(Scratch resistance)

A steel wool (product number # 0000, manufactured by BONSTAR CO., LTD.) Was subjected to 50 reciprocations along the surface of the coating layer while applying a load of 300 g per 1 cm 2 on the surface of the coating layer. The haze (turbidity) of the surface of the coating layer before and after the test was measured using a haze meter (trade name "NDH5000" manufactured by Nihon Denshoku Kogyo Co., Ltd.). Then, the difference (? E) between the haze of the coating layer before and after the test was calculated. The smaller the value of? E, the better the scratch resistance.

(Alkali resistance)

The polyethylene terephthalate film on which the coating layer was formed was immersed in a 5 wt% sodium hydroxide aqueous solution at 40 ° C ± 2 ° C for 3 days. The haze (turbidity) of the surface of the coating layer before and after immersion was measured using a haze meter (trade name " NDH5000 ", manufactured by Nihon Denshoku Kogyo K.K.). Then, the haze difference? E of the coating layer before and after immersion was calculated. The smaller the value of? E, the better the alkali resistance.

(Solvent resistance)

After acetone was dropped onto the surface of the coating layer, a load of 100 g was added to perform a rubbing test 100 times. The haze (turbidity) of the surface of the coating layer before and after the test was measured using a haze meter (trade name "NDH5000" manufactured by Nihon Denshoku Kogyo Co., Ltd.). Then, the difference (? E) between the haze of the coating layer before and after the test was calculated. The smaller the value of? E, the better the solvent resistance.

(Tensile elongation)

After adding a curing agent to the subject of the two-liquid curing type coating agent, a two-liquid curing type coating agent was immediately coated on a polyethylene terephthalate (PET) film having a thickness of 188 탆 using a bar coater No. 10 Respectively.

Thereafter, the two-liquid curing type coating agent was heated at 80 DEG C for 3 minutes to remove the solvent, and the two-liquid curing type coating agent was thermally cured. Then, the obtained thermosetting coating was irradiated with a high- Ultraviolet rays were irradiated at 500 mJ / cm < 2 > to further cure the thermosetting coating to form a coating layer.

The tensile elongation of the obtained coating layer was measured in accordance with a test method for plastic-tensile properties (JIS K7127). The test specimens were stretched under the conditions of a thickness of 30 μm, a width of 25 mm and a length of 115 mm under the conditions of a tensile speed of 100 mm / min, a chuck distance of 80 mm, The length (L) of the test piece at the point of the fracture was measured, and the tensile elongation was calculated based on the following formula.

Tensile elongation (%) = 100 x (L-115)

(Water contact angle)

A drop of 0.4 microliters of water was flowed on the surface of the coating layer and the contact angle was measured with a contact angle meter (trade name "Drop Master 500", manufactured by Kyowa Hakko Kagaku Co., Ltd.). Further, the lower the water contact angle, the better the oil wiping resistance.

(Contact angle of oleic acid)

0.4 microliters of oleic acid was flowed on the surface of the coating layer and the contact angle was measured by a contact angle meter (trade name "Drop Master 500", manufactured by Kyowa Kikai Kagaku Co., Ltd.). Further, the lower the contact angle of oleic acid is, the better the oil wiping resistance is.

(Industrial availability)

The two-liquid curing type coating agent of the present invention can form a coating layer excellent in transparency, hardness, scratch resistance, oil-wipe resistance and tensile elongation, so that visibility of various optical members (touch panel, display, lens, May be used to form a coating layer for protecting the surface of the required substrate.

Claims

100 parts by weight of an acryl-based polymer having a photopolymerizable group and a hydroxyl group in side chains and having a hydroxyl value of 30 to 350 mgKOH / g and a weight-average molecular weight of 5,000 to 200,000, 0.3 to 35 parts by weight of a silane coupling agent, 0.3 to 35 parts by weight of a polyether polyol, 3 to 70 parts by weight of a polylactone polyol, and 6 to 500 parts by weight of a photopolymerizable polyfunctional compound (excluding the acrylic polymer) having 2 to 20 photopolymerizable groups in a molecule, and a curing agent 3 containing a polyisocyanate To 100 parts by weight of a two-component curing type coating material.

The method according to claim 1,
The subject matter includes 100 parts by weight of an acryl-based polymer having a photopolymerizable group and a hydroxyl group at side chains and having a hydroxyl value of 30 to 350 mgKOH / g and a weight average molecular weight of 5,000 to 200,000, 0.3 to 35 parts by weight of a silane coupling agent, 0.3 to 35 parts by weight of a polyether polyol , 3 to 70 parts by weight of a polylactone polyol, and 6 to 500 parts by weight of a photopolymerizable polyfunctional compound having 2 to 20 photopolymerizable groups in one molecule (excluding the acrylic polymer) 2-curing type clay.

3. The method according to claim 1 or 2,
Wherein the curing agent comprises a polyisocyanate derivative.