CN104540908B

CN104540908B - Two-pack type curable coating agent

Info

Publication number: CN104540908B
Application number: CN201380042565.XA
Authority: CN
Inventors: 木口雅雄; 中井亮; 中井亮一
Original assignee: Harima Chemical Inc
Current assignee: Harima Chemical Inc
Priority date: 2012-08-10
Filing date: 2013-07-24
Publication date: 2017-01-25
Anticipated expiration: 2033-07-24
Also published as: JP5921986B2; CN104540908A; KR101726201B1; JP2014037454A; KR20150023683A; TWI519613B; WO2014024686A1; TW201418380A

Abstract

The present invention provides a two-pack type curable coating agent which is capable of forming a coating layer that has excellent transparency, hardness, scratch resistance, oil wiping-off properties and tensile elongation. A two-pack type curable coating agent of the present invention is characterized by containing: a base material which contains 100 parts by weight of an acrylic polymer that comprises a photopolymerizable group and a hydroxyl group in side chains and has a hydroxyl number of 30-350 mgKOH/g and a weight average molecular weight (Mw) of 5,000-200,000, 0.3-35 parts by weight of a silane coupling agent, 0.3-35 parts by weight of a polyether polyol, 3-70 parts by weight of a polylactone polyol and 6-500 parts by weight of a photopolymerizable polyfunctional compound that comprises two or more photopolymerizable groups in each molecule; and 3-100 parts by weight of a curing agent which contains a polyisocyanate.

Description

Bi-component curing type coating agent

Technical field

The present invention relates to bi-component curing type coating agent, specifically relate to be formed make in various industrial fields With the surface of component carry out the bi-component curing type coating agent of coating coating layer.

Background technology

All the time, the various optical component such as touch-screen, display, lens, glass is used.Especially touch-screen is used as Input unit to information terminal.By making the surface panel of finger tip contacts touch-screen and can input required in information terminal Information.

During finger tip contacts optical component, the oil such as aliphatic hydrocarbon existing for the surface of finger tip easily form fingerprint trace and Attachment.Because the visuality that oil is attached to optical component during optical component can reduce, therefore when being attached with oil, to simultaneously Ask: (1) is easily wiped away, removed accompanying oil, and (2), after wiping away, the oil residuing in optical component is without compromising on optics The visuality of component.Hereinafter the characteristic of above-mentioned (1) and (2) is generically and collectively referred to as " the oil property wiped away ".

Additionally, the surface of optical component is scratched or when go bad because of chemicals in the surface of optical component, can damage The visuality of optical component, therefore it is required that give the surface of optical component with resistance to marring and chemical proofing.

In order to solve above-mentioned requirements, form the side of coating layer using by the surface coating agent in optical component Method.Coating layer requires the transparency in order to ensure visuality, and then, it is formed with the optical component institute to be configured to sometimes of coating layer Need shape, also require coating layer during this shaping will not produce cracking etc., that is, require that there is excellent tensile elongation.

As this coating agent, For example, Patent Document 1 discloses a kind of hydrophilic coating agent, it is to specify ratio bag Containing following component: host, its contain (a) colloidal silica sol, (b) active hydrogen weight average molecular weight (mw) 5,000～ 200000 acrylic polymer, the surface-active of (c) silane coupler, (d) poly-lactone polyol and (f) active hydrogen Agent；And (e) curing agent.

However, there are following problems: the resistance to marring of the coating layer being formed by above-mentioned hydrophilic coating agent and chemically-resistant in it Medicine is poor, and then, above-mentioned hydrophilic coating agent solidification is time-consuming, and therefore productivity ratio is low.

Patent Document 2 discloses a kind of oil uncomplicated laundering resin combination, it at least contains (1-a) as constituent Impart the acrylic polyol of regulation hydrophilic radical, the acrylic polyol of (1-b) below mw50000, (1-c) is selected from has At least one in machine metallic compound, alkaline organic silane compound and (1-d) are in polyisocyanates, amino resins At least one curing agent.

However, there are following problems: the resistance to marring of the coating layer being formed by above-mentioned oil uncomplicated laundering resin combination in it Poor with tensile elongation, and then, above-mentioned hydrophilic coating agent solidification is time-consuming, and therefore productivity ratio is low.

Patent Document 3 discloses a kind of light-cured type hydrophilic coating agent, it contains the acrylic resin that (a) specifies In 3～40 weight %, (b) polyox-yethylene-polyoxypropylene block copolymer 0.1～5 weight % and (c) molecule, there are 2 Optical polymerism polyfunctional compound 55～95 weight % of above polymerism group.

However, there are following problems: the tensile elongation of the coating layer being formed by above-mentioned light-cured type hydrophilic coating agent in it Rate is poor, and the coating layer being formed by coating agent easily produces cracking because of deformation.

Patent Document 4 discloses a kind of solidification compound with Thermocurable and active energy ray-curable, It is to have hydroxyl and the compound (a1) of (methyl) acryloyl group to be condensed instead with the dealcoholysis of alkoxysilane moiety condensation product (b) Answer thing, the equivalent (equivalent proportion) of the alkoxyl of hydroxyl equivalent/(b) composition containing aforementioned (a1) composition is 0.1～0.4 reaction Product (a) is as curability composition.However, asking of the oil property wiped away difference is had by the coating layer that above-mentioned solidification compound is formed Topic.

Patent Document 5 discloses the active energy ray-curable coating composition of resistance to abrasion, it contains acrylic compounds Resin, there is the coupling agent containing isocyanato silanes of regulation structure and intramolecular has hydroxyl and more than 3 acryloyl groups Compound, intramolecular obtained by the reaction of hydroxyl polyfunctional acrylic ester has the multifunctional acrylic acid of more than 3 acryloyl groups Ester, intramolecular have the urethane acrylate of more than 2 acryloyl groups, using organic solvent as the dioxy of decentralized medium SiClx colloidal sol and organic solvent.

However, oil is had by the coating layer that the above-mentioned active energy ray-curable coating composition of resistance to abrasion is formed wiping The problem of going property difference.

Patent document 1:wo2009/144999

Patent document 2: Japanese Unexamined Patent Publication 2010-53286 publication

Patent document 3:wo2011/13497

Patent document 4: Japanese Unexamined Patent Publication 2002-212248 publication

Patent document 5: Japanese Unexamined Patent Publication 6-287470 publication

Content of the invention

Problems to be solved by the invention

The present invention provides a kind of bi-component curing type coating agent, and it can form the transparency, hardness, resistance to marring, oil The property wiped away and the excellent coating layer of tensile elongation.

For solution to problem

The bi-component curing type coating agent of the present invention is characterised by, it comprises host and curing agent, and described host contains Side chain there is polymerism group and hydroxyl and hydroxyl value be 30～350mgkoh/g, weight average molecular weight be 5000～200000 third Alkene acids polymers 100 weight portion, silane coupler 0.3～35 weight portion, PPG 0.3～35 weight portion, polylactone Polyalcohol 3～70 weight portion, and there is in a molecule optical polymerism polyfunctional compound 6 of more than 2 polymerism groups ～500 weight portions；Described curing agent contains polyisocyanates, and described curing agent is 3～100 weight portions.

Further characterized in that, in above-mentioned bi-component curing type coating agent, in host in following components one Part of compounds there occurs reaction, described group be divided into side chain have polymerism group and hydroxyl and hydroxyl value be 30～ 350mgkoh/g, weight average molecular weight be 5000～200000 acrylic polymer 100 weight portion, silane coupler 0.3～ 35 weight portions, PPG 0.3～35 weight portion, poly-lactone polyol 3～70 weight portion and, there are 2 in a molecule Optical polymerism polyfunctional compound 6～500 weight portion of above polymerism group.

The acrylic polymer constituting the bi-component curing type coating agent of the present invention has polymerism group in side chain And hydroxyl, preferably it is respectively provided with the polymerism group of more than 2 and the acrylic polymer of hydroxyl in side chain.Gather as light Conjunction property group, as long as have can carry out radical polymerization with the polymerism group of optical polymerism polyfunctional compound described later Ethylenical unsaturated double bonds, can include acryloyl group, methylacryloyl, styryl, vinyl, pi-allyl etc., excellent Select acryloyl group, methylacryloyl.

Acrylic polymer polymerism group with optical polymerism polyfunctional compound at its polymerism group Carry out radical polymerization and form cross-linked structure, it is possible to increase (had below by the coating layer that bi-component curing type coating agent is formed When be referred to as " coating layer ") hardness, improve resistance to marring.And then, acrylic polymer give coating layer with alkali resistance and The chemical proofings such as solvent resistance and hydrophily.

There are the acrylic polymer (hereinafter sometimes referred to simply as " acrylic compounds of polymerism group and hydroxyl in side chain Polymer ") for example can manufacture as follows: by making the monomer of the free radical polymerization monomer comprising hydroxyl or glycidyl Composition carries out radical polymerization to manufacture polymer, a part of hydroxyl addition of resulting polymers is had NCO and The compound of polymerism group, thus manufactures.Wherein, when using the free radical polymerization monomer containing glycidyl, Need to make glycidyl open loop generate hydroxyl by acid.As acid, for example, can include maleic acid, maleic anhydride, rich horse Acid, acrylic acid, methacrylic acid, ω-carboxyl-polycaprolactone single-acrylate, phthalic acid list hydroxyl ethyl ester acrylate etc., Preferably acrylic acid, methacrylic acid.In addition, acid can be used alone can also be applied in combination two or more.By using acrylic acid This intramolecular has the acid of ethylenical unsaturated double bonds as the acid for making glycidyl open loop with methacrylic acid, can Carry out the open loop of glycidyl and the importing of polymerism group simultaneously.

For the consumption of the acid making during glycidyl open loop, with respect to 1 equivalent glycidyl, preferably 0.3～1.5 Equivalent, more preferably 0.5～1.2 equivalent.When the amount of acid is very few, the polymerism group of side chain reduces, therefore sometimes by double groups The hardness of coating layer that point curing type coating agent obtains or chemical proofing can reduce.When the amount of acid is many, can remain in host Unreacted acid, the alkali resistance of the coating layer therefore sometimes being obtained by bi-component curing type coating agent or resistance to water can reduce.

As the polymerization of monomer composition, using conventional method, for example, can include emulsion polymerization and (include suspending Polymerization), polymerisation in solution, polymerisation in bulk etc., preferred emulsion polymerization, polymerisation in solution.

For example, acrylic polymer for example can obtain as follows: by making containing (methyl) alkyl acrylate and containing Have that have can be with the monomer group of the hydroxyl of (methyl) alkyl acrylate copolymer or the free radical polymerization monomer of glycidyl Compound carries out radical polymerization to manufacture acrylic polyol, a part of hydroxyl addition of gained acrylic polyol is had different Cyanic acid ester group and the compound of polymerism group, thus obtain.Wherein, using the radical polymerization containing glycidyl During property monomer, as described above, needing to make glycidyl open loop generate hydroxyl.It should be noted that in the present invention, (first Base) acrylate refers to acrylate or methacrylate.

One example of the more specifically manufacture method of acrylic polymer is illustrated.By in radical polymerization Make in the presence of initiator containing (methyl) alkyl acrylate and can be with (methyl) alkyl acrylate copolymer containing having The monomer composition of the free radical polymerization monomer of hydroxyl or glycidyl carries out radical polymerization to manufacture acrylic acid multielement Alcohol.Then, the solution of gained acrylic polyol is supplied in reaction vessel, further in reaction vessel add have different The compound of cyanic acid ester group and polymerism group and metallic catalyst.Wherein it is possible to as desired in reaction vessel Add the polymerization inhibitors such as p methoxy phenol, quinhydrones (hq).Then, it is blown into oxygen in reaction vessel, on one side for example will be anti- The hydraulic control system of answering is reacted at 30～1500 DEG C and through 6～12 hours, thus a part of hydroxyl addition to acrylic polyol There is the compound of NCO and polymerism group, can manufacture and have the third of polymerism group and hydroxyl in side chain Alkene acids polymers.In addition, when using the free radical polymerization monomer containing glycidyl, as described above, needing to make contracting Water glyceryl open loop is generating hydroxyl.

As radical polymerization initiator, using conventional material in radical polymerization, can include: such as peroxidating Organic mistakes such as the tertiary own ester of benzoyl, lauroyl peroxide, peroxidating hexanoyl, peroxidating neodecanoic acid, tert-Butyl peroxypivalate Oxide, such as 2,2- azodiisobutyronitrile, 2,2- azo two -2,4- methyl pentane nitrile, 2,2- azo two -4- methoxyl group -2, 4- methyl pentane nitrile, azo two -2- methylbutyronitrile (trade name " abn-e " that japan hydrazine co., inc. manufacture) etc. Azo-compound, preferably azo-compound.Wherein, radical polymerization initiator can be used alone and can also be applied in combination 2 kinds More than.The compounding amount of radical polymerization initiator can suitably select, with respect to monomer composition 100 weight portion, preferably 0.01 ～5 weight portions.

As (methyl) alkyl acrylate, for example, can include: (methyl) methyl acrylate, (methyl) acrylic acid second Ester, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) Heptylacrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) acrylic acid nonyl ester, (methyl) third Olefin(e) acid last of the ten Heavenly stems ester, (methyl) benzyl acrylate, (methyl) acrylic acid DCPA etc..Wherein, (methyl) alkyl acrylate Can be used alone and can also be applied in combination two or more.

As (methyl) alkyl acrylate, preferably (methyl) methyl acrylate, (methyl) butyl acrylate, more preferably (methyl) methyl acrylate, particularly preferred methyl methacrylate.

In monomer composition, when the content of (methyl) alkyl acrylate is few, the resistance to water of coating layer can reduce sometimes, Therefore it is preferably more than 10 weight %, more than more preferably 20 weight %.

In monomer composition, when the content of (methyl) alkyl acrylate is many, the hydrophily of coating layer reduces, and sometimes applies The oil property wiped away of layer of cloth can reduce, below therefore preferably 90 weight %, below more preferably 80 weight %.

As the free radical polymerization monomer containing hydroxyl, can include (methyl) alkyl acrylate containing hydroxyl, Acrylic acid-n- hydroxymethyl acid amides, methacrylic acid-n- hydroxymethyl acid amides, 4- Hydroxymethyl-cyclo-hexyl (methyl) acrylic acid Ester etc., (methyl) alkyl acrylate preferably containing hydroxyl, (methyl) acrylic acid of hydroxyl is more preferably had on alkyl Arrcostab.As (methyl) alkyl acrylate containing hydroxyl, for example, can include: (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid -3- hydroxy propyl ester, (methyl) acrylic acid -2- hydroxybutyl, (first Base) acrylic acid -4- hydroxybutyl, the own ester of (methyl) acrylic acid -6- hydroxyl, (methyl) acrylic acid -8- hydroxyl monooctyl ester, (methyl) third Olefin(e) acid -10- hydroxyl last of the ten Heavenly stems ester, (methyl) acrylic acid -12- hydroxylauric ester etc..Wherein, (methyl) acrylic acid alkyl containing hydroxyl Ester can be used alone and can also be applied in combination two or more.

As the free radical polymerization monomer containing hydroxyl, preferably (methyl) 2-Hydroxy ethyl acrylate, more preferably propylene Acid -2- hydroxy methacrylate (2-hea).

As the free radical polymerization monomer containing glycidyl, preferably comprise (methyl) acrylic acid of glycidyl Arrcostab.As (methyl) alkyl acrylate containing glycidyl, (methyl) glycidyl acrylate can be included Deng preferably GMA.Wherein, (methyl) alkyl acrylate containing glycidyl can individually make With can also be applied in combination two or more.

In monomer composition, when the content of the free radical polymerization monomer containing hydroxyl is many, coating layer is water-fast sometimes Property can reduce, below therefore preferably 60 weight %, below more preferably 40 weight %, below particularly preferably 30 weight %. In monomer composition, when the content of the free radical polymerization monomer containing hydroxyl is few, the hydrophily of coating layer reduces, and sometimes applies The oil property wiped away of layer of cloth can reduce, more than therefore preferably 5 weight %.

In monomer composition, when the content of the free radical polymerization monomer containing glycidyl is many, coating layer sometimes Resistance to water can reduce, below therefore preferably 90 weight %, below more preferably 80 weight %.In monomer composition, contain When having the content of the free radical polymerization monomer of glycidyl few, the hydrophily of coating layer reduces, the oil of coating layer sometimes The property wiped away can reduce, more than therefore preferably 10 weight %, more than more preferably 20 weight %, particularly preferably 50 weight % with On.

As the compound with NCO and polymerism group, for example, can include 2- acryloyl-oxyethyl Isocyanates (trade name " karenz moi " that Showa Denko K. K manufactures), 2- methacryloxyethyl isocyanic acid (methyl) acryloyl group isocyanic acid that ester etc. (methyl) acryloyl group is bonded with NCO by the alkylidene of carbon number 2～6 Ester or their derivative etc..

As derivative, for example, can include (methyl) acrylate with the NCO sheltered with end-capping reagent Deng.As specific example, methacrylic acid -2- (o- [1 '-methyl propylidene base amino] carboxyamino) ethyl (Showa can be included The trade name " karenz moi-bm " that electrician Co., Ltd. manufactures) etc..Wherein, derivative can be used alone and can also combine Using two or more.

As above-mentioned metallic catalyst, for example, can include: dibutyl tin laurate, dioctyltin laurate, February Cinnamic acid dioctyl tin, triphenylphosphine, bismuth series catalysts etc..

When adding the compound with NCO and polymerism group in acrylic polyol, isocyanates The molal quantity of base (- nco) is with respect to the free radical polymerization monomer containing hydroxyl used in the manufacture of acrylic polyol In the molal quantity of hydroxyl (- oh) ratio (- nco/-oh) be preferably 0.05～0.9, more preferably 0.1～0.9.

By being compounded by above-mentioned ratio, acrylic polymer can be manufactured in the state of remaining hydroxyl, and Will not with the reaction of the compound with NCO and polymerism group in consume whole hydroxyls.So, by making Residual hydroxyl in acrylic polymer, can give the coating layer being formed by bi-component curing type coating agent with hydrophily, energy Enough make the oil property wiped away of coating layer excellent.

There is (methyl) alkyl acrylate composition and the free-radical polymerised list containing hydroxyl or glycidyl In the acrylic polymer of body composition, when the content of (methyl) alkyl acrylate composition is few, the resistance to water of coating layer sometimes Can reduce, more than therefore preferably 10 weight %, more than more preferably 20 weight %.

There is (methyl) alkyl acrylate composition and the free-radical polymerised list containing hydroxyl or glycidyl In the acrylic polymer of body composition, when the content of (methyl) alkyl acrylate composition is many, the hydrophily of coating layer reduces, Sometimes the oil property wiped away of coating layer can reduce, below therefore preferably 90 weight %, below more preferably 80 weight %.

In the propylene with (methyl) alkyl acrylate composition and the free radical polymerization monomer composition containing hydroxyl In acids polymers, when the content of the free radical polymerization monomer composition containing hydroxyl is many, the resistance to water of coating layer can drop sometimes Low, below therefore preferably 60 weight %, below more preferably 40 weight %, below particularly preferably 30 weight %.

In the propylene with (methyl) alkyl acrylate composition and the free radical polymerization monomer composition containing hydroxyl In acids polymers, when the content of the free radical polymerization monomer composition containing hydroxyl is few, the hydrophily of coating layer reduces, sometimes The oil property wiped away of coating layer can reduce, more than therefore preferably 5 weight %.

There is (methyl) alkyl acrylate composition and the free radical polymerization monomer composition containing glycidyl Acrylic polymer in, when the content of the free radical polymerization monomer composition containing glycidyl is many, coating layer sometimes Resistance to water can reduce, below therefore preferably 90 weight %, below more preferably 80 weight %.

There is (methyl) alkyl acrylate composition and the free radical polymerization monomer composition containing glycidyl Acrylic polymer in, when the content of the free radical polymerization monomer composition containing glycidyl is few, the parent of coating layer Aqueous reduction, sometimes the oil property wiped away of coating layer can reduce, more than therefore preferably 10 weight %, more preferably 20 weight % More than, more than particularly preferably 50 weight %.

When the hydroxyl value of acrylic polymer is low, the part carrying out heat cure in bi-component curing type coating agent reduces, The tensile elongation of coating layer reduces；When the hydroxyl value of acrylic polymer is high, the chemical proofing of coating layer reduce and The degraded appearance of coating layer, the transparency reduce, and are therefore defined to 30～350mgkoh/g, preferably 50～320mgkoh/g, more It is preferably 60～270mgkoh/g.In the present invention, the hydroxyl value of polymer refers to the hydroxyl value of solid constituent.

It should be noted that the hydroxyl value of acrylic polymer refer to according to jis k 1557-1:2007 (iso14900: 2001) value that the 4.2b method of " plastics-urethane raw polyalcohol test method-the 1: hydroxyl value seek method " records.

When weight average molecular weight mw of acrylic polymer is low, the resistance to marring of coating layer and chemical proofing reduce； When above-mentioned weight average molecular weight mw is high, the tensile elongation of coating layer reduces and the degraded appearance of coating layer, the transparency reduce, because This is defined to 5000～200000, preferably 6000～150000, more preferably 10000～100000.

It should be noted that weight average molecular weight mw of acrylic polymer for example can calculate as follows: by being equipped with The gel permeation chromatograph (gpc) of differential refraction rate detector (rid) measures the molecular weight distribution of acrylic polymer, according to Gained chromatogram (spectrogram) is calculated using polystyrene standard as calibration curve.

Silane coupler is contained in the host of bi-component curing type coating agent of the present invention.Silane coupler is following formula (1) organo-silicon compound shown in, are containing many with the hydroxyl of acrylic polymer, the hydroxyl of PPG or polylactone The hydroxyl of first alcohol has the organo-silicon compound of the hydroxyl reactive functional group x and hydrolization group y of reactivity.

x_n-si-y_(4-n)... formula (1)

Wherein, x is the hydroxyl tool with the hydroxyl of acrylic polymer, the hydroxyl of PPG or poly-lactone polyol There is the hydroxyl reactive functional group of reactivity, y is hydrolization group, and n is 1～3 integer.When n is 2 or 3, multiple x can phase Together can also be different.When n is 1 or 2, multiple y can be the same or different.

Silane coupler is polynary with acrylic polymer, PPG or polylactone at hydroxyl reactive functional group Form cross-linked structure between alcohol, and polysiloxanes is formed thus becoming crosslinked with net-shaped by hydrolization group hydrolysis, polycondensation Structure, gives coating layer with tensile elongation and chemical proofing.

As the hydroxyl reactive functional group of silane coupler, as long as the functional group of chemical bond can be formed just with hydroxyl It is not particularly limited, for example, can include glycidoxyalkyl (such as glycidoxypropyl group etc.), aminoalkyl (such as ammonia Base propyl group etc.), mercaptoalkyl (such as mercaptopropyi etc.), ureidoalkyl (such as ureido-propyl etc.), isocyanate-yl alkyl (example As NCO propyl group etc.) etc., preferably aminoalkyl, isocyanate-yl alkyl.

As the hydrolization group of silane coupler, as long as polysiloxanes can be formed and just do not have by hydrolysis, polycondensation It is particularly limited to, for example, can include: hydrogen atom, halogen atom, alkoxyl, acyloxy, ketoxime base, amino, amide groups, sour acid amides Base, aminooxy group, sulfydryl, alkenyloxy etc., in terms of the resistance to water of gained coating layer and chemical proofing from the point of view of preferred alcoxyl Base.As alkoxyl, for example, can include methoxyl group, ethyoxyl, butoxy, propoxyl group etc., preferably methoxyl group, ethyoxyl.

As the specific example of silane coupler, for example, can include: glycidoxypropyltrime,hoxysilane (SHIN-ETSU HANTOTAI Trade name " the silaplane that the trade name " kbm403 " of chemical industry Co., Ltd. manufacture, chisso corporation manufacture S-510 " etc.), glycidoxypropyl group triethoxysilane (Shin-Etsu Chemial Co., Ltd manufacture trade name Trade name " z-6041 " etc. that " kbe403 ", Dong Li Dow Corning Corporation manufacture) etc. contain epoxy silane coupling；Aminopropyl three Methoxy silane (the commodity that the trade name " kbm903 " of Shin-Etsu Chemial Co., Ltd's manufacture, Dong Li Dow Corning Corporation manufacture Name " z-6610 " etc.), (Shin-Etsu Chemial Co., Ltd manufactures n-2- (amino-ethyl)-APTES Trade name " kbe603 "), aminopropyltriethoxywerene werene (Shin-Etsu Chemial Co., Ltd manufacture trade name Trade name " silaplane s330 " etc. that " kbe903 ", chisso corporation manufacture) etc. contain amino silicane coupling agent； Mercaptopropyi trimethoxy silane (trade name " kbm803 " of Shin-Etsu Chemial Co., Ltd's manufacture, Dong Li Dow Corning Corporation The trade name " z-6062 " etc. manufacturing) etc. contain mercaptosilane coupling agents；Ureidopropyltriethoxysilane (SHIN-ETSU HANTOTAI's chemical industry strain Trade name " z-6676 " etc. that trade name " kbe585 " that formula commercial firm manufactures, Dong Li Dow Corning Corporation manufacture) etc. contain carbamic acid Ester group silane coupler；NCO propyl-triethoxysilicane (the trade name that Shin-Etsu Chemial Co., Ltd manufactures " kbe9007 " etc.) etc. coupling agent containing isocyanato silanes etc..As silane coupler, due to bi-component curing type coating agent Stability and reactivity is excellent and preferred glycidoxypropyltrime,hoxysilane, n-2- (amino-ethyl) -3- aminopropan Ethyl triethoxy silicane alkane, NCO propyl-triethoxysilicane, more preferably γ aminopropyltriethoxy silane, n-2- (amino-ethyl)-APTES.

When the content of the silane coupler in bi-component curing type coating agent is few, the tensile elongation of coating layer or chemically-resistant Medicine reduces；When the content of silane coupler is many, the oil property wiped away of coating layer reduces, therefore with respect to acrylic Thing 100 weight portion, is defined to 0.3～35 weight portion, preferably 1～30 weight portion, more preferably 1.5～20 weight portions, especially It is preferably 1.3～10 weight portions.

PPG is contained in the host of bi-component curing type coating agent.PPG gives by bi-component curing type The coating layer that coating agent is formed, with hydrophily, improves the oil property wiped away and the anti-finger printing of coating layer.

PPG for example obtains as follows: with low molecular weight polyols (such as ethylene glycol, propane diols, glycerine etc.) or virtue Fragrant race polyamines/aliphatic polyamine (for example, ethylenediamine, toluenediamine etc.) as initiator, to oxirane and/or expoxy propane Carry out addition reaction Deng epoxyalkane, thus obtain.PPG can improve and be formed by bi-component curing type coating agent The hydrophily of coating layer, the oil property wiped away of raising coating layer, therefore preferably comprise epoxyalkane.As PPG, example As polyoxyethylene polyoxypropylene glycol ether, polyethylene polyols, polypropylene polyalcohol, polyethylene polypropylene polyalcohol can be included (random or block copolymer) etc., preferably polyoxyethylene polyoxypropylene glycol ether.

Additionally, as PPG, also can enumerate by polytetramethylene obtained from the ring-opening polymerisation of oxolane Ether glycol etc..

These PPGs can be used alone and can also be applied in combination two or more.The hydroxyl value of PPG is preferred For 3～600mgkoh/g, more preferably 5～300mgkoh/g.It should be noted that the hydroxyl value of PPG refers to foundation The value that the b method of jis k1557-1 (2007) records.

The average functional group number of PPG is preferably 1～8, more preferably 2～6.Wherein, PPG is average Functional group number can be obtained according to the species of initiator and compounding ratio.

The weight average molecular weight of PPG is preferably 300～30000, more preferably 700～20000.Need explanation It is that the weight average molecular weight of PPG for example can calculate as follows: by being equipped with the solidifying of differential refraction rate detector (rid) Glue penetration chromatograph (gpc) measures the molecular weight distribution of PPG, according to gained chromatogram (spectrogram) with standard polyphenyl second Alkene calculates as calibration curve.

When the content of the PPG containing in the host of bi-component curing type coating agent is few, by bi-component curing type quilt The oil property wiped away covering the coating layer of dosage form one-tenth reduces；When the content of PPG is many, dosage form is coated to by bi-component curing type The hardness of coating layer, resistance to marring and the chemical proofing that become reduce, therefore with respect to acrylic polymer 100 weight Part, it is defined to 0.3～35 weight portion, preferably 1～30 weight portion, more preferably 1.3～20 weight portions, particularly preferably 1.3 ～10 weight portions.

Poly-lactone polyol is contained in the host of bi-component curing type coating agent.Given by double groups by poly-lactone polyol Divide the coating layer that curing type coating agent is formed with excellent tensile elongation.

Poly-lactone polyol for example carries out ring-opening polymerisation as initiator to internal ester monomer using polyalcohols and obtains.

As the specific example of polyalcohol, for example, can include: ethylene glycol, 1,2-PD, 1,3-PD, 1,2- fourth Glycol, 1,3 butylene glycol, 2- methyl-1,3-propanediol, 1,4- butanediol, neopentyl glycol, 1,5- pentanediol, 3- methyl isophthalic acid, 5- Pentanediol, 1,6-HD, 2,2,4- trimethyl -1,3- pentanediol, 2- ethyl -1,3- hexylene glycol, 2- methyl isophthalic acid, 8- pungent two Alcohol, 1,9- nonanediol, 1,10- decanediol, 1,12- octacosanol, glycerine, trimethylolpropane, trihydroxy methyl octane, season penta Tetrol etc..

As internal ester monomer, can include: 6-caprolactone, Alpha-Methyl -6-caprolactone, Beta-methyl -6-caprolactone, γ-first Base -6-caprolactone, β, the caprolactone class such as δ-dimethyl-E-caprolactone, 3,3,5- trimethyl -6-caprolactone；δ-valerolactone, β-first The poly- valerolactone class such as base-δ-valerolactone；Propiolactone class；Butyrolactone；Heptalactone；Dodecalactone etc..It can also be internal ester monomer Derivative.

As an example of poly-lactone polyol, shown in for example following formula (2) of polycaprolactone glycol.

h[o(ch₂)₅(c=o)] mo-r-o [(c=o) (ch₂)₅O] n-h ... formula (2)

Wherein, in formula (2), r is-c₂h₄-、-c₂h₄oc₂h₄-、-c(ch₃)₂c₂h₄- wait the alkylidene of carbon number 2～18, m and n It is positive integer respectively, m+n is 4～35 integer.

Additionally, as an example of poly-lactone polyol, shown in polycaprolactone trihydroxylic alcohol such as formula (3), in the alkyl of trivalent r¹On be bonded 3 polyester chains with terminal hydroxyl.

r¹- (o [(c=o)-(ch₂)₅o]ph)₃... formula (3)

Wherein, in formula (3), r¹It is

In the trivalent alkyl of carbon number 2～18, p is 1～30 integer.

As the specific example of poly-lactone polyol, as commercially available product, can include: polycaprolactone trihydroxylic alcohol is (for example Daicel chemical industries, ltd. manufacture trade name " placcel 303 ", " placcel 305 ", " placcel 308 ", " placcel 312 "), polycaprolactone glycol (daicel chemical industries, ltd. manufacture " placcel 205 ", " placcel 208 ", " placcel 210 ", " placcel 212 ") etc..Polynary as polylactone Alcohol, preferably polycaprolactone polyol.Its reason is that the carbon number due to polyester key being connected to each other is more, therefore, it is possible to give by The coating layer that bi-component curing type coating agent is formed is with excellent tensile elongation.

When the content of the poly-lactone polyol in the host of bi-component curing type coating agent is few, it is coated to by bi-component curing type The tensile elongation of the coating layer that dosage form becomes reduces；When the content of poly-lactone polyol is many, due to being coated to by bi-component curing type The hardness of coating layer, resistance to marring and chemical proofing that dosage form becomes reduce, therefore with respect to acrylic polymer 100 weight Amount part, is defined to 3～70 weight portions, preferably 5～50 weight portions, more preferably 10～35 weight portions, particularly preferably 15～ 35 weight portions.

Containing the photopolymerization in a molecule with more than 2 polymerism groups in the host of bi-component curing type coating agent Property polyfunctional compound (hereinafter sometimes referred to simply as " optical polymerism polyfunctional compound ").Optical polymerism polyfunctional compound pass through Carry out radical polymerization and form cross-linked structure with the polymerism group of acrylic polymer, be coated to by bi-component curing type The coating layer that dosage form becomes has excellent hardness, resistance to marring and chemical proofing.

As the polymerism group containing in optical polymerism polyfunctional compound, as long as having energy and acrylic The polymerism group of thing carries out the ethylenical unsaturated double bonds of radical polymerization, can include acryloyl group, metering system Acyl group, styryl, vinyl, pi-allyl etc., preferably acryloyl group, methylacryloyl.

As the optical polymerism polyfunctional compound in a molecule with 2 polymerism groups, for example, can include: second The alkylidenes such as glycol two (methyl) acrylate, propane diols two (methyl) acrylate, neopentyl glycol two (methyl) acrylate Glycol two (methyl) acrylate；Diethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, dipropyl two PAG two (methyl) acrylate such as alcohol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate；1, 4- butanediol two (methyl) acrylate, 1,6-HD two (methyl) acrylate, 1,9- nonanediol two (methyl) acrylic acid Ester, bicyclopentadiene two (methyl) acrylate, NPGA neopentyl glycol adipate two (methyl) acrylate, hydroxy new pentane acid new penta Glycol two (methyl) acrylate, Tricyclodecane Dimethanol two (methyl) acrylate, two (methyl) acrylic acid two ring pentyl ester；Season Penta tetrol two (methyl) acrylate, bis-phenol aeo addition diacrylate, caprolactone modification two (methyl) acrylic acid dicyclopentenyl Ester, ethylene-oxide-modified di(2-ethylhexyl)phosphate (methyl) acrylate, allylation cyclohexyl two (methyl) acrylate, isocyanuric acid ester Two (methyl) acrylate or their epoxyalkane modified body, divinylbenzene, butanediol -1,4- divinyl ether, hexamethylene Alkane dimethanol divinyl ether, diethylene glycol divinyl ether, DPG divinyl ether, hexylene glycol divinyl ether, three Ethylene glycol divinyl ether, phenyl glycidyl ether acrylate hexamethylene diisocyanate carbamate prepolymer are (altogether Rong She KCC manufacture trade name " ah-600 "), phenyl glycidyl ether acrylate toluene di-isocyanate(TDI) ammonia Carbamate prepolymer (trade name " at-600 " that Kyoeisha Chemical Co., Ltd. manufactures) etc..Wherein, optical polymerism is multifunctional Compound can be used alone and can also be applied in combination two or more.

As the optical polymerism polyfunctional compound in a molecule with 3 polymerism groups, for example, can include: three Hydroxymethyl-propane three (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol three (methyl) acrylic acid Ester, three (acryloyl-oxyethyl) isocyanuric acid esters or their epoxyalkane modified body, isocyanuric acid epoxyalkane modified body Three (methyl) acrylate etc..

As the optical polymerism polyfunctional compound in a molecule with 4 polymerism groups, for example, can include: double Trimethylolpropane four (methyl) acrylate, pentaerythrite four (methyl) acrylate or their epoxyalkane modified body Deng.

As the optical polymerism polyfunctional compound in a molecule with 5 polymerism groups, for example, can include: two Pentaerythrite five (methyl) acrylate or their epoxyalkane modified body etc..

As the optical polymerism polyfunctional compound in a molecule with 6 polymerism groups, for example, can include: two Pentaerythrite six (methyl) acrylate, pentaerythritol triacrylate hexamethylene diisocyanate carbamate prepolymer (trade name " ua-306h " that Kyoeisha Chemical Co., Ltd. manufactures), caprolactone modification dipentaerythritol six (methyl) acrylic acid Ester or their epoxyalkane modified body etc..

During the increasing number of the polymerism group containing in optical polymerism polyfunctional compound, by bi-component curing type quilt The crosslinking covering the coating layer of dosage form one-tenth is finer and close, and the hardness of coating layer increases, therefore preferably more than 3, more preferably 4 More than, particularly preferably more than 5.The quantity of the polymerism group containing in optical polymerism polyfunctional compound is preferably 20 Individual following, more preferably less than 15.

When the content of the optical polymerism polyfunctional compound in the host of bi-component curing type coating agent is few, solid by bi-component The hardness of coating layer, resistance to marring and chemical proofing that change type coating agent is formed reduce；Optical polymerism polyfunctional compound Content many when, the tensile elongation of the coating layer being formed by bi-component curing type coating agent reduces, therefore with respect to acrylic acid Birds of the same feather flock together compound 100 weight portion, be defined to 6～500 weight portions, preferably 3～100 weight portions, more preferably 30～100 weight Part, particularly preferably 30～85 weight portions.

Can contain as desired in a molecule in the host of bi-component curing type coating agent and there is 1 optical polymerism base The optical polymerism monofunctional compound of group.Optical polymerism monofunctional compound is used for adjusting the viscous of bi-component curing type coating agent Degree, and improve the drying property of bi-component curing type coating agent by improving solid component concentration.

As the specific example of optical polymerism monofunctional compound, can include: aliphatic category (methyl) acrylate, fat Ring type class (methyl) acrylate, the fragrant same clan's (methyl) acrylate, ethers (methyl) acrylate, vinyl monomer, (methyl) acrylic amide etc..It should be noted that in the present invention, (methyl) acrylamide refers to acrylamide or methyl-prop Acrylamide.

As optical polymerism monofunctional compound, for example, can include: (methyl) 2-Hydroxy ethyl acrylate, 2- hydroxyl- 3- acryloxypropyl (methyl) acrylate, (methyl) dodecylacrylate, (methyl) octadecyl acrylate, (methyl) cyclohexyl acrylate, (methyl) Isooctyl acrylate monomer, the different tetradecane base ester of (methyl) acrylic acid, (methyl) acrylic acid are different Stearyl, (methyl) isobornyl acrylate, ethyoxyl-diethylene glycol (methyl) acrylate, 2- ethylhexyl-Ka Bi Alcohol (methyl) acrylate, neopentyl glycol benzoic ether (methyl) acrylate, Nonylphenoxy polyethylene glycol (methyl) propylene Acid esters, ech modification phenoxy group (methyl) acrylate, Phenoxyethyl (methyl) acrylate, p -cumylphenol oxirane Modified (methyl) acrylate, vinyl pyrrolidone, caprolactam, acryloyl morpholine etc..

When the content of the optical polymerism monofunctional compound in the host of bi-component curing type coating agent is many, bi-component solidifies The reactivity reduction of type coating agent, the hardness of gained coating layer and chemical proofing reduce, therefore with respect to acrylic acid sometimes Birds of the same feather flock together compound 100 weight portion, below preferably 150 weight portions, below more preferably 90 weight portions, particularly preferably 60 weight portions Below.

In above-mentioned, the situation that the compound that contains in the host to bi-component curing type coating agent does not react is carried out Illustrate, and the compound containing in the host of bi-component curing type coating agent can also some react.In bi-component When a part of compound containing in the host of curing type coating agent there occurs reaction, the above-mentioned content of compound refers to compound Between reacted before content.

Polyisocyanates is contained in the curing agent of bi-component curing type coating agent.The NCO of polyisocyanates passes through Form carbamate with the hydroxyl reaction of the hydroxyl of acrylic polymer, the hydroxyl of PPG or poly-lactone polyol Key and import cross-linked structure in coating layer, the tensile elongation of the coating layer being formed by bi-component curing type coating agent is excellent.

As polyisocyanates, as long as the isocyanates in a molecule with more than 2 NCOs does not just have spy Do not limit, for example, can include diisocyanate, the polyploid (such as dimer, trimer etc.) of diisocyanate, two isocyanides Modified body of acid esters etc., because the hardness of gained coating layer and chemical proofing are excellent, the preferably modified body of diisocyanate, The biuret modified body of more preferably diisocyanate.

As diisocyanate, it is not particularly limited, for example, can include: aromatic diisocyanate (such as toluene two Isocyanates (2,4 toluene diisocyanate, 2,6- toluene di-isocyanate(TDI) or their mixture), phenylene diisocyanate ( Phenylene diisocyanate, PPDI or their mixture), 1,5- naphthalene diisocyanate, diphenyl methane two isocyanide (4,4 '-methyl diphenylene diisocyanate, 2,4 '-methyl diphenylene diisocyanate, 2,2 '-diphenyl methane two are different for acid esters Cyanate or their mixture), 4,4 '-toluidine diisocyanate etc.), araliphatic diisocyanate (such as benzene two Methyl diisocyanate (1,3- xylylene diisocyanate, 1,4- xylylene diisocyanate or their mixture), (1,3- tetramethyl xylylene diisocyanate, 1,4- durol dimethyl two are different for tetramethyl xylylene diisocyanate Cyanate or their mixture) etc.), (for example 1,3- trimethylene diisocyanate, 1,4- tetra- are sub- for aliphatic diisocyanate Methyl diisocyanate, 1,5- pentamethylene diisocyanate, 1,6- hexamethylene diisocyanate etc.), alicyclic two isocyanides Acid esters (such as cyclohexane diisocyanate, 3- isocyanatomethyl -3,5,5- trimethylcyclohexylisocyanate (different Fo Er Ketone diisocyanate), di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), norbornene alkyl diisocyanate, double (isocyanatomethyl) Hexamethylene) etc..Wherein, diisocyanate can be used alone and can also be applied in combination two or more.

As the modified body of diisocyanate, for example, can include: allophanate-modified body (for example passes through two isocyanic acids Allophanate-modified body that ester reacts and generates with low molecular weight polyols (such as trimethylolpropane etc.) etc.), biuret Modified body (biuret modified body for example reacting and generating with water or amine by diisocyanate etc.), urea acid esters modified body (urea acid esters modified body for example reacted by the trimerizing between isocyanates and generate etc.), polyalcohol modified body are (for example logical Cross polyalcohol modified body that diisocyanate reacts and generates with above-mentioned low molecular weight polyols etc.), urea-modified body (for example logical Cross urea-modified body that diisocyanate reacts and generates with polyamines (such as ethylenediamine, toluenediamine etc.) etc.), diazine triketone Modified body (diazine triketone for example being generated by diisocyanate and carbonic acid solid/liquid/gas reactions etc.), carbon imidodicarbonic diamide modified body (carbon imidodicarbonic diamide modified body for example being generated by the decarburization acid condensation reaction of diisocyanate etc.), urea diketone modified body, Uretonimine-modified body etc., preferably biuret modified body.

As the commercially available product of the modified body of diisocyanate, for example, can include Mitsui Takeda Chemical Co., Ltd's manufacture Trade name " takenate d-165n " (biuret form), trade name " takenate d-170n " (urea acid esters type), trade name " takenate d-178n " (allophanic acid ester type) etc..

When the content of the curing agent in bi-component curing type coating agent is few, the coating being formed by bi-component curing type coating agent The tensile elongation of layer reduces；When the content of curing agent is many, the oil of the coating layer being formed by bi-component curing type coating agent is wiped Going property reduces, and therefore with respect to acrylic polymer 100 weight portion of host, is defined to 3～100 weight portions, preferably 5～ 70 weight portions, more preferably 6～35 weight portions.

In the host and curing agent of bi-component curing type coating agent, bi-component curing type coating agent can not damaged It is added as needed on additive in the range of physical property.As additive, for example can include Photoepolymerizationinitiater initiater, antioxidant, Light stabilizer, heat-resisting stabilizing agent, antistatic additive, defoamer etc..

As Photoepolymerizationinitiater initiater, for example, can include: benzoin ethers Photoepolymerizationinitiater initiater, benzophenone photopolymerization Initiator, thioxanthene ketone class Photoepolymerizationinitiater initiater, alkylbenzene ketone Photoepolymerizationinitiater initiater, acylphosphine oxide class Photoepolymerizationinitiater initiater, Titanocenes class Photoepolymerizationinitiater initiater, oxime esters Photoepolymerizationinitiater initiater, benzene diazonium amine Photoepolymerizationinitiater initiater, naphthoquinones diazosulfonic acid Class Photoepolymerizationinitiater initiater, dimethylaminobenzoic acid class Photoepolymerizationinitiater initiater etc..Wherein, Photoepolymerizationinitiater initiater can be used alone Can be applied in combination two or more.

As benzoin ethers Photoepolymerizationinitiater initiater, for example, can include: benzoin, benzoin methylether, benzoin ethyl ether, Benzoin iso-propylether, benzoin isobutyl ether etc..

As benzophenone Photoepolymerizationinitiater initiater, for example, can include: benzophenone, methyl o-benzoylbenzoate, 4- phenyl benzophenone, 4- benzoyl -4'- methyl-diphenylsulfide, 2,4,6- tri-methyl benzophenone etc..

As thioxanthene ketone class Photoepolymerizationinitiater initiater, for example, can include: ITX, 2,4- diethyl thioxanthene Ketone, 2,4- bis- clopenthixal ketone, 1- chloro- 4- propoxythioxanthone etc..

As alkylbenzene ketone Photoepolymerizationinitiater initiater, for example, can include: 2- hydroxy-2-methyl -1- phenyl -propyl- 1- ketone, 2,2- dimethoxy -1,2- diphenyl second -1- ketone, 1- hydroxy-cyclohexyl-phenyl -one, 1- [4- (2- hydroxyl-oxethyl)-benzene Base] -2- hydroxy-2-methyl -1- propyl- 1- ketone, 2- hydroxyl -1- { 4- [4- (2- hydroxy-2-methyl-propiono)-benzyl] phenyl } - 2- methyl -propyl- 1- ketone, 2- methyl isophthalic acid-(4- methyl mercapto phenyl) -2- morpholino propyl- 1- ketone, 2- benzyl -2- dimethylamino -1- (4- morphlinophenyl)-butanone -1,2- (dimethylamino) -2- [(4- aminomethyl phenyl) methyl] -1- [4- (4- morpholinyl) phenyl] - 1- butanone etc..

As acylphosphine oxide class Photoepolymerizationinitiater initiater, for example, can include: 2,4,6- trimethylbenzoyls-hexichol Base-phosphine oxide, double (2,4,6- trimethylbenzoyl)-phenyl phosphine oxide etc..

As titanocenes class Photoepolymerizationinitiater initiater, for example, can include: double (η 5-2,4- cyclopentadiene -1- bases)-bis- (2, The fluoro- 3- of 6- bis- (1h- pyrroles's -1- base)-phenyl) titanium etc..

As oxime esters Photoepolymerizationinitiater initiater, for example, can include: 1- [4- (thiophenyl) phenyl] -1,2- octanedione 2- (o- benzoyl oxime), 1- [9- ethyl -6- (2- toluyl) -9h- carbazole -3- base] -1- (o- acetyl group oxime) ethyl ketone, oxygen benzene Guanidine-acetic acid 2- [2- oxo -2- phenylacetyl epoxide ethyoxyl] ethyl ester, oxygen phenylacetic acid 2- (2- hydroxyl-oxethyl) ethyl ester etc..

In the host of bi-component curing type coating agent, when the content of Photoepolymerizationinitiater initiater is few, bi-component curing type sometimes The photocuring of coating agent carries out insufficient；When the content of Photoepolymerizationinitiater initiater is many, the hardness of coating layer can be drawn because of photopolymerization sometimes Send out the analyte of agent and reduce, therefore with respect to acrylic polymer 100 weight portion, preferably 0.3～60 weight portion, more excellent Elect 1～35 weight portion as.

In the curing agent of bi-component curing type coating agent, when the content of Photoepolymerizationinitiater initiater is few, bi-component solidification sometimes The photocuring of type coating agent carries out insufficient；When the content of Photoepolymerizationinitiater initiater is many, the hardness of coating layer can be because of photopolymerization sometimes The analyte of initiator and reduce, therefore with respect to acrylic polymer 100 weight in the host being applied in combination with curing agent Amount part, preferably 0.3～60 weight portion, more preferably 1～35 weight portion.

The host of the bi-component curing type coating agent of the present invention is by mixing propylene with by way of reaching above-mentioned content ratio Acids polymers, silane coupler, PPG, poly-lactone polyol, optical polymerism polyfunctional compound and as needed And the additive adding is preparing.

The host of bi-component curing type coating agent can also be prepared into the solution of organic solvent.Should in the case of, the consolidating of host Body constituent concentration is preferably 10～90 weight %, more preferably 20～80 weight %.

Specifically, by silane coupler, PPG, poly-lactone polyol, optical polymerism polyfunctional compound and After the additive premixing added as desired is obtained premix, while being slowly added acrylic compounds in this premix Polymer side is mixed, and thus makes the host of bi-component curing type coating agent.

And then, specifically, by silane coupler, PPG, poly-lactone polyol, the multifunctional chemical combination of optical polymerism Thing and the additive adding as desired are pre-mixed after premix is obtained, with 30～60 minutes to this at 10～40 DEG C It is slowly added dropwise acrylic polymer in premix.Acrylic polymer, will after the completion of dropwise addition in premix Premix stirs 30～60 minutes at 10～40 DEG C, thus makes host.

Additionally, the curing agent of bi-component curing type coating agent includes polyisocyanates, going back in addition to polyisocyanates During containing additive, to be made by adding additive mixing in polyisocyanates.

As the Operation Key of bi-component curing type coating agent, first, mixed in the host of bi-component curing type coating agent Close curing agent, bi-component curing type coating agent is coated base material.Just bi-component curing type coating agent preferably in sight is coated Before base material in the host of bi-component curing type coating agent mixed curing agent.

As the material of base material, be not particularly limited, for example, can include: polyethylene terephthalate, poly- to benzene The polyester resins such as dioctyl phthalate butanediol ester, polycarbonate resin, polyacrylics, styrene resin, abs resin On synthetic resin, the inorganic material such as glass, metal such as stainless steel, steel, aluminium etc..

Method as bi-component curing type coating agent is coated base material, for example, can include: based on dip coating, spraying The coating process of method, rolling method, doctor blade method, silk screen print method etc., using the casting etc. of rod coater, point gum machine etc..

The thickness of the film of the bi-component curing type coating agent being coated on base material is not particularly limited, preferably 2～ 90 μm, more preferably 5～50 μm.

Then, the film of the bi-component curing type coating agent being coated on base material is heated and heat cure.Bi-component solidifies The temperature of the heat cure of type coating agent is preferably 60～180 DEG C, more preferably 80～150 DEG C.Bi-component curing type coating agent Preferably 1～30 minute time of heat cure, more preferably 1～10 minute.

Then, by light such as the film irradiation ultraviolet radiations to heat cure, the further photocuring of film is made to form coating layer. The transparency of so obtained coating layer, hardness, resistance to marring, the oil property wiped away and tensile elongation are excellent.In addition, bi-component The film of curing type coating agent can also form coating layer by carrying out heat cure after carrying out photocuring.

The transparency of coating layer is excellent, and specifically, the mist degree of coating layer is preferably less than 1.0%, more preferably 0.8% Below.It should be noted that the mist degree of coating layer is the value being recorded by mist degree instrument according to jis k 7136 (2000).

The hardness of coating layer is excellent, and specifically, the hardness of coating layer is pressed pencil hardometer and is preferably more than h, more preferably For more than 2h.It should be noted that pencil hardness refers to survey by pencil hardness test according to jis k 5600-5-4 (1999) The value obtaining.

The oil property wiped away of coating layer is excellent, and specifically, the water contact angle that recorded by contact angle instrument is preferably 50～ 75 °, more preferably 52～72 °.Oleic acid contact angle is preferably 5～25 °, more preferably 10～20 °.

Coating layer is with respect to the excellent adhesion of base material.And then, the oil property wiped away of coating layer is also excellent, therefore, it is possible to Less wipes the oil (fingerprint etc.) that number of times removes the surface being attached to coating layer well.

Coating layer in order to improve optical component surface (for example be easily stained with because being touched by people fingerprint touch-screen, The surface of the graphical representation panel that the outermost layer of the graphical representation device such as display arranges, in order to protect graphical representation panel And the surface of the surface protection film in the laminating of its surface, the lens surface of glasses, goggles etc., build use, vehicle is used, measuring instrument Window material surface of table etc.) the oil property wiped away and formed.Coating layer is also excellent in the transparency after wiping oil away, can Guarantee the visuality of optical component.Additionally, coating layer due to hardness, resistance to marring and chemical proofing excellent and can be long-term Maintain the excellent transparency, positively guarantee the visuality of optical component.

The effect of invention

According to the bi-component curing type coating agent of the present invention, the transparency can be formed, hardness, resistance to marring, oil are wiped away Property and the excellent coating layer of tensile elongation.

Therefore, the bi-component curing type coating agent of the present invention can be used for formation well and is used for protecting requirement to have visually The coating layer of the substrate surface of property.

And then, the coating layer being formed by bi-component curing type coating agent has the hydrophilic of appropriateness by hydroxyl, ether moiety Property.Therefore, even if it is also possible to make water successfully be impregnated with to the table of coating layer in the case that the surface attachment of coating layer has oil Between face and oil, so that oil is floated from the surface of coating layer, be readily removable oil.

Coating layer has the hydrophily of appropriateness, on the other hand, because carbon chain moiety also has the lipophile of appropriateness.Therefore, Even if the oil in the case that the oil on being attached to coating layer does not remove completely and slightly remains on coating layer, on coating layer Point also will not be formed on coating layer and be in the raised state of drops and the journey cannot be recognized with naked eyes can be formed on coating layer Degree thinly extends the state of film-like.Therefore, oil will not produce the diffusing reflection of light, and coating layer can remain excellent transparent Property.

Additionally, coating layer has excellent tensile elongation, even if therefore in order to become the base material being formed with coating layer In the case that shape makes it deform for desired shape, also can successfully followed base material deformation, coating layer will not produce tortoise Split.Protected by coating layer and there is the base material of desired shape therefore, it is possible to the surface that obtains easily.

And then, coating layer has excellent hardness, resistance to marring and chemical proofing, and therefore coating layer can be tieed up for a long time Hold the excellent transparency and outward appearance.

Then, the bi-component curing type coating agent of the present invention need not contain colloidal silica, and gained coating layer has excellent Different hardness, and then also will not occur to reduce because of the tensile elongation producing containing colloidal silica.Therefore, by bi-component The coating layer that curing type coating agent is formed has excellent hardness and tensile elongation.

Specific embodiment

Hereinafter enumerate embodiment that the present invention is described in further detail, but be not limited to the present embodiment completely.

(synthesis of acrylic polymer a1～13)

Supply methyl iso-butyl ketone (MIBK) (mibk) 233 weight portion as solvent in reaction vessel, be heated to 88 DEG C and tie up Hold.

By the methyl methacrylate containing the ormal weight shown in table 1～3 (mma), GMA (gma), butyl acrylate (ba), n, the list of n- DMAA (dmaa) and acrylate -2- hydroxyethyl (2-hea) Body composition is supplied in the methyl iso-butyl ketone (MIBK) in reaction vessel and mixes.

Then, mixed it with 2 hours when being slowly added dropwise azo two -2- methylbutyronitrile (abn-e) in monomer composition Afterwards, place 1 hour.And then, after being slowly added dropwise azo two -2- methylbutyronitrile in monomer composition with 2 hours, by monomer group Compound maintains 3 hours in 88 DEG C.The total amount of the azo two -2- methylbutyronitrile being added drop-wise in monomer composition is shown in table 1～3.

Then, monomer composition is heated to 110 DEG C to carry out radical polymerization in 2 hours and acrylic polymer is obtained.

By weight average molecular weight mw of following main points mensure gained acrylic polymer a1～13, number-average molecular weight mn, glass Glass transition temperature tg, viscosity and hydroxyl value, the results are shown in table 1～3.The glass transition temperature tg root of acrylic polymer Calculate according to Fox's formula, be shown in table 1～3.In addition, the hydroxyl value of acrylic polymer a1～13 refers to the hydroxyl of solid constituent Value.

(weight average molecular weight based on gel permeation chromatography and the mensure of number-average molecular weight)

Take about 0.2mg as sample from gained acrylic polymer, be dissolved in 10 milliliters of oxolane, by dress The gel permeation chromatograph (gpc) having differential refraction rate detector (rid) is measured, and obtains the molecular weight distribution of sample.

Then, according to gained chromatogram (spectrogram), using polystyrene standard as calibration curve, the weight average calculating sample divides Son amount and number-average molecular weight.Measure device and condition determination be shown in following.

Data processing equipment: production number hlc-8220gpc (TOSOH Co., Ltd's manufacture)

Differential refraction rate detector: be built-in with the ri detector of production number hlc-8220gpc

Chromatographic column: production number tskgel gmh_xl(TOSOH Co., Ltd's manufacture) 3

Mobile phase: oxolane

Column flow: 0.5ml/ minute

Injection rate: 20 μ l

Temperature of the measurement: 40 DEG C

Polystyrene standard molecular weight: 1250,3250,9200,28500,68000,165000,475000,950000, 1900000

(viscosity)

Measure gained acrylic polymer using cone and plate viscometer according to jis k 5600-2-3:1999 at 25 DEG C Viscosity.

(hydroxyl value)

Foundation jis k 1557-1:2007 (iso 14900:2001) " plastics-urethane raw polyalcohol test method- 1st: hydroxyl value seek method " 4.2b method measure gained acrylic polymer hydroxyl value.

[table 1]

[table 2]

[table 3]

(synthesis of acrylic polymer b1～15)

Supply in reaction vessel as the methyl iso-butyl ketone (MIBK) (mibk) shown in the table 4～6 of solvent, be heated to 80 DEG C simultaneously Maintain.

By acrylic polymer a1～13 containing the ormal weight shown in table 4～6,2- acryloyl-oxyethyl isocyanic acid Ester (trade name " karenz aoi " that Showa Denko K. K manufactures), acrylic acid, dibutyl tin laurate, triphenylphosphine It is supplied in reaction vessel with p methoxy phenol and mix, prepared mixed liquor.

Make be reacted the reaction time as shown in table 4～6 under reaction temperature shown in table 4～6 for the mixed liquor, be obtained and contain Have side chain have ethylenical unsaturated double bonds and hydroxyl acrylic polymer b1～15 acrylic polymer solution.

By weight average molecular weight mw of above-mentioned main points mensure gained acrylic polymer b1～15, number-average molecular weight mn, glue Degree and hydroxyl value, the results are shown in table 4～6.Additionally, will be different used in acrylic polymer a1～6,10～13 manufacture The ratio of the molal quantity with respect to the hydroxyl (- oh) in 2-Hydroxy ethyl acrylate for the molal quantity of cyanic acid ester group (- nco) is illustrated in Table 4～6.It should be noted that the hydroxyl value of acrylic polymer b1～15 refers to the hydroxyl value of solid constituent.

[table 4]

[table 5]

[table 6]

(embodiment 1～30, comparative example 1～17)

Uniformly γ-NCO propyl-triethoxysilicane (SHIN-ETSU HANTOTAI's chemistry work of the ormal weight shown in mixture table 7～11 Industry Co., Ltd. manufacture trade name " kbe-9007 "), n-2- (amino-ethyl)-APTES (SHIN-ETSU HANTOTAI Chemical industry Co., Ltd. manufacture trade name " kbe-603 "), (the SHIN-ETSU HANTOTAI's chemical industry strain of glycidoxy trimethoxy silane Formula commercial firm manufacture trade name " kbm-403 "), the polyoxyethylene polyoxypropylene glycol ether (commodity of Di-ichi Kogyo Seiyaku Co., Ltd. Name " epan u105 ", hydroxyl value: 19mgkoh/g, average functional group number: 2, weight average molecular weight: 6400), polyoxypropylene glycol ether (three Foreignize into Industrial Co., Ltd manufacture trade name " sannix pp-1000 ", hydroxyl value: 112mgkoh/g, average functional group number: 2nd, weight average molecular weight: 1000), polycaprolactone trihydroxylic alcohol (daicel chemical industries, the trade name of ltd. " placcel 303 "), the polycaprolactone glycol (trade name " placcel of daicel chemical industries, ltd. 205 "), pentaerythritol triacrylate hexamethylene diisocyanate carbamate prepolymer (Kyoeisha Chemical Co., Ltd. Trade name " ua-306h "), phenyl glycidyl ether acrylate hexamethylene diisocyanate prepolymer (common prosperity society chemistry The trade name " ah-600 " of Co., Ltd.), colloidal silica (trade name " mibk-st " of Nissan Chemical Ind Ltd) And methyl iso-butyl ketone (MIBK), prepared premix.It was slowly added dropwise containing acrylic polymer b1 in premix with 10 minutes So that acrylic polymer b1～15 reach the amount shown in table 7～11, (solid becomes～15 acrylic polymer solution Point).After terminating the dropping acrylic polymer solution in premix, premix is stirred 30～60 points at 30 DEG C Clock is obtained the host of bi-component curing type coating agent.Then, add table 7～11 institute in the host of bi-component curing type coating agent 2- hydroxy-2-methyl -1- phenyl -propyl- 1- the ketone (ProductName " darocur 1173 " of basf company) of the ormal weight showing.Double groups The solid component concentration dividing the host of curing type coating agent is 30 weight %.

Biuret modified body (three well force field chemistry by the hexamethylene diisocyanate of the ormal weight shown in table 7～11 The trade name " takenate d-165n " of Co., Ltd.) as bi-component curing type coating agent curing agent.

Add hexa-methylene two isocyanic acid of the ormal weight shown in table 7～11 in the host of bi-component curing type coating agent The biuret modified body of ester is as curing agent.Using rod coater no.10, bi-component curing type coating agent is applied immediately after interpolation Cloth is on polyethylene terephthalate (pet) film so that dry film thickness is about 5 μm.

Then, bi-component curing type coating agent is heated 3 minutes at 80 DEG C and remove solvent and so that bi-component is solidified After type coating agent carries out heat cure, gained heat cure overlay film is used with high-pressure sodium lamp (120w/cm) with 500mj/cm²Irradiate purple Outside line makes the further photocuring of heat cure overlay film form coating layer.In addition, in comparative example 12, bi-component curing type is coated to Agent is heated 20 minutes at 80 DEG C and is removed solvent and make bi-component curing type coating agent heat cure.

Measure the mist degree of gained coating layer, pencil hardness, adaptation, oil removal, resistance to marring, resistance to by following main points Alkalescence, solvent resistance, tensile elongation, water contact angle and oleic acid contact angle, the results are shown in table 7～11.

(mist degree)

Use mist degree instrument (Japan's electricity according to the test method(s) of " the seeking method of the mist degree of plastic transparent material " of jis k 7136 The trade name " ndh5000 " of color Industrial Co., Ltd) measure coating layer mist degree.It should be noted that the value of mist degree is less, thoroughly Bright property is more excellent.

(pencil hardness)

Implement pencil hardness test to measure the pencil hardness of coating layer according to jis k 5600-5-4:1999.Wherein, exist In pencil hardness test, hardness is ordered as b, hb, f, h from low to high successively.For pencil hardness, before " h ", carried numeral is bigger Represent that hardness is higher, before " b ", carried numeral is bigger represents that hardness is lower.

(adaptation)

Measure the adaptation of coating layer according to jis k 5600-5-6:1999.Specifically, with latticed on coating layer Form the otch reaching pet film.Coating layer is divided into 100 cutting plates by latticed otch. Cutting plate is the plane square shape of one side 1.0mm.Attach adhesive tape (nichiban co., ltd. system in the entirety of cutting plate Make trade name " nichiban tape 1 ").Then, by the adhesive tape being attached from pet film Peel off, count the quantity of the cutting plate remaining on pet film.(to remain in poly terephthalic acid The quantity of the cutting plate that the quantity of the cutting plate on glycol ester film/on pet film is formed) To evaluate adaptation.It should be noted that the quantity remaining in the cutting plate on pet film is more, Represent that adaptation is more excellent.

(oil removal)

Drip 0.1g hexadecane on the surface of coating layer.Then, with cellulose non-woven fabrics (Asahi Kasei Corporation Trade name " bemcot m-3 ") and apply 300g load the hexadecane on the surface being attached to coating layer has been carried out 10 times wiping Wipe.

Then, measured before wiping using mist degree instrument (trade name " ndh5000 " that electricity Se Industrial Co., Ltd of Japan system is made) Mist degree (turbidity) with the painting layer surface after wiping.Then, the poor δ of the mist degree of coating layer before calculating wiping and after wiping e.It should be noted that the value of δ e is less, the oil property wiped away of fingerprint trace being caused by sebum etc. is better.

(resistance to marring)

On the surface of coating layer, while applying to steel wool (the production number #0000 that bonstar sales co., ltd. manufacture) Plus 300g/cm²Load side make its along coating layer surface come and go 50 times.Using mist degree instrument (Nippon Denshoku Industries Co., Ltd. The trade name " ndh5000 " manufacturing) painting layer surface before determination test and after test mist degree (turbidity).Then, calculate examination The poor δ e of the mist degree of coating layer before testing and after test.It should be noted that the value of δ e is less, resistance to marring is better.

(alkali resistance)

The pet film of the coating layer 5 weight % NaOH at 40 DEG C ± 2 DEG C will be formed with Impregnate 3 days in the aqueous solution.Measure dipping using mist degree instrument (trade name " ndh5000 " that electricity Se Industrial Co., Ltd of Japan system is made) Front and dipping after painting layer surface mist degree (turbidity).Then, the difference of the mist degree of coating layer before calculating dipping and after dipping δe.It should be noted that the value of δ e is little, alkali resistance is better.

(solvent resistance)

After the surface of coating layer dropping acetone, apply 100g load and carry out 100 friction tests.Using mist degree instrument The mist of the painting layer surface before (trade name " ndh5000 " that electricity Se Industrial Co., Ltd of Japan system is made) determination test and after test Degree (turbidity).Then, the poor δ e of the mist degree of coating layer before calculating test and after test.It should be noted that the value of δ e is got over Little, solvent resistance is better.

(tensile elongation)

After adding curing agent in the host of bi-component curing type coating agent, immediately using rod coater no.10 in thickness Coating bi-component curing type coating agent on 188 μm of polyethylene terephthalate (pet) film is so that dry film thickness is 30 μm.

Then, bi-component curing type coating agent being heated 3 minutes at 80 DEG C removes solvent and makes bi-component solid After change type coating agent carries out heat cure, gained heat cure overlay film is used with high-pressure sodium lamp (120w/cm) with 500mj/cm²Irradiate Ultraviolet makes the further photocuring of heat cure overlay film form coating layer.

Test method (jis k7127) according to plastics-tensile properties measures the tensile elongation of gained coating layer.Measure Condition is as follows: using thick 30 μm, wide 25mm, long 115mm test film, draw speed 100mm/ minute, chuck spacing 80mm, Tension test sheet under conditions of distance between bench marks 25mm, 23 DEG C of temperature, length l of the test film during fracture of determination test piece, it is based on Following formula calculates tensile elongation.

Tensile elongation (%)=100 × (l-115)

(water contact angle)

Drip 0.4 microlitre of water droplet in painting layer surface, and by contact angle instrument, (consonance interface science Co., Ltd. manufactures Trade name " drop master500 ") measure contact angle.It should be noted that water contact angle is lower, represent that the oil property wiped away is got over Excellent.

(oleic acid contact angle)

Drip 0.4 microlitre of oleic acid in painting layer surface, and by contact angle instrument, (consonance interface science Co., Ltd. manufactures Trade name " drop master500 ") measure contact angle.It should be noted that oleic acid contact angle is lower, represent the oil property wiped away More excellent.

[table 7]

[table 8]

[table 9]

[table 10]

[table 11]

Industrial applicability

The bi-component curing type coating agent of the present invention can form the transparency, hardness, resistance to marring, the oil property wiped away and draw Stretch the excellent coating layer of percentage elongation, can be consequently used for forming protection various optical components (touch-screen, display, lens, glass Deng) etc. require have visuality base material surface coating layer.

Claims

1. it is characterised in that comprising host and curing agent, wherein, described host contains side to a kind of bi-component curing type coating agent Chain there is polymerism group and hydroxyl and hydroxyl value be 30～350mgkoh/g, weight average molecular weight be 5000～200000 propylene Acids polymers 100 weight portion, silane coupler 0.3～35 weight portion shown in following formula (1), PPG 0.3～35 Weight portion, poly-lactone polyol 3～70 weight portion, and there is in a molecule optical polymerism of more than 2 polymerism groups Polyfunctional compound 6～500 weight portion；Described curing agent contains polyisocyanates, and described curing agent is 3～100 weight portions,

x_n-si-y_(4-n)... formula (1)

Wherein, x is that have instead with the hydroxyl of the hydroxyl of acrylic polymer, the hydroxyl of PPG or poly-lactone polyol The hydroxyl reactive functional group of answering property, y is hydrolization group, and n is 1～3 integer, n be 2 or 3 when, multiple x be identical or Different, when n is 1 or 2, multiple y are identical or different.

2. bi-component curing type coating agent according to claim 1 is it is characterised in that chemical combination in the following compositions of host A part for thing there occurs reaction, described composition for side chain have polymerism group and hydroxyl and hydroxyl value be 30～ 350mgkoh/g, weight average molecular weight be 5000～200000 acrylic polymer 100 weight portion, silane coupler 0.3～ Have in 35 weight portions, PPG 0.3～35 weight portion, poly-lactone polyol 3～70 weight portion and a molecule 2 with Optical polymerism polyfunctional compound 6～500 weight portion of upper polymerism group.

3. bi-component curing type coating agent according to claim 1 and 2 is it is characterised in that curing agent contains polyisocyanic acid Ester derivant.