CN104540908A - Two-pack type curable coating agent - Google Patents

Two-pack type curable coating agent Download PDF

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Publication number
CN104540908A
CN104540908A CN201380042565.XA CN201380042565A CN104540908A CN 104540908 A CN104540908 A CN 104540908A CN 201380042565 A CN201380042565 A CN 201380042565A CN 104540908 A CN104540908 A CN 104540908A
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weight
methyl
coating layer
coating agent
hydroxyl
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CN104540908B (en
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木口雅雄
中井亮一
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Harima Chemical Inc
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Harima Chemical Inc
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
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    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
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    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
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    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
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    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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    • C08G18/718—Monoisocyanates or monoisothiocyanates containing silicon
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
    • C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
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    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
    • C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
    • C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
    • C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
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    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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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

Two-pack curing coating agent
Technical field
The present invention relates to two-pack curing coating agent, specifically relate to the two-pack curing coating agent for the formation of the coating layer be coated to the surface of the component used in various industrial field.
Background technology
All the time, the various optical component such as touch-screen, indicating meter, lens, glass is used.Especially touch-screen is used as the input unit to intelligent terminal.Required information can be inputted in intelligent terminal by making the surface panel of finger tip contacts touch-screen.
During finger tip contacts optical component, the oil contents such as the aliphatic hydrocarbon existing for the surface of finger tip easily form fingerprint trace and adhere to.Because when oil content is attached to optical component, the visuality of optical component can reduce, therefore when being attached with oil content, require: (1) is easily wiped away, remove accompanying oil content simultaneously, (2) after wiping away, the oil content residuing in optical component can not damage the visuality of optical component.Below the characteristic of above-mentioned (1) and (2) is generically and collectively referred to as " the oil content property wiped away ".
In addition, when the surface of optical component is scratched or go bad because of pharmaceutical chemicals in the surface of optical component, the visuality of optical component can be damaged, therefore require that the surface of giving optical component is with resistance to marring and chemical proofing.
In order to solve above-mentioned requirements, adopt the method being formed coating layer by the surface coated coating agent at optical component.Coating layer is in order to ensure visual and require the transparency, and then the optical component being formed with coating layer will be configured as desired shape sometimes, and when also requiring this shaping, coating layer can not produce be full of cracks etc., namely requires to have excellent tensile elongation.
As this coating agent, such as, Patent Document 1 discloses a kind of hydrophilic coating agent, it comprises following composition with regulation ratio: host, the tensio-active agent that colloidal silica sol that it contains (A), (B) have the acrylic polymers of the weight-average molecular weight (Mw) 5,000 ~ 200,000 of active hydrogen, (C) silane coupling agent, (D) poly-lactone polyol and (F) have active hydrogen; And (E) solidifying agent.
But it exists following problems: resistance to marring and the chemical proofing of the coating layer formed by above-mentioned hydrophilic coating agent are poor, and then above-mentioned hydrophilic coating agent solidification is consuming time, and therefore productivity is low.
Patent Document 2 discloses a kind of oil easily detergency resin combination, it at least imparts the acrylic polyol of regulation hydrophilic radical containing (1-A) as constituent, the acrylic polyol of (1-B) below Mw50000, (1-C) are selected from least one in organometallic compound, alkaline organic silane compound and (1-D) is selected from least one solidifying agent in polyisocyanates, aminoresin.
But it exists following problems: the resistance to marring of the coating layer formed by the easy detergency resin combination of above-mentioned oil and tensile elongation rate variance, and then above-mentioned hydrophilic coating agent solidification is consuming time, and therefore productivity is low.
Patent Document 3 discloses a kind of light-cured type hydrophilic coating agent, there is in the acrylic resin 3 ~ 40 % by weight that it contains (A) specifies, (B) polyox-yethylene-polyoxypropylene block copolymer 0.1 ~ 5 % by weight and (C) a part the optical polymerism polyfunctional compound 55 ~ 95 % by weight of more than 2 optical polymerism groups.
But there is following problems in it: the tensile elongation rate variance of the coating layer formed by above-mentioned light-cured type hydrophilic coating agent, the coating layer formed by coating agent easily produces be full of cracks because of distortion.
Patent Document 4 discloses a kind of solidification compound with Thermocurable and active energy ray-curable; it is for having hydroxyl and the compound (a1) of (methyl) acryl and the dealcoholization condensation reaction thing of alkoxysilane moiety condenses (b), and the equivalent (equivalence ratio) of the alkoxyl group of hydroxyl equivalent/(b) composition containing aforementioned (a1) composition is that the reaction product (A) of 0.1 ~ 0.4 is as solidified nature composition.But the coating layer formed by above-mentioned solidification compound has the problem of the oil content property wiped away difference.
Patent Document 5 discloses the active energy ray-curable coating composition of resistance to abrasion, it contain acrylic resin, have the polyfunctional acrylic ester in the compound obtained containing the hydroxyl polyfunctional acrylic ester in isocyanato silanes coupling agent and molecule with hydroxyl and more than 3 acryls reacts of regulation structure, molecule with more than 3 acryls, the urethane acrylate in molecule with more than 2 acryls, using organic solvent as the silicon dioxide gel of dispersion medium and organic solvent.
But the coating layer formed by the above-mentioned active energy ray-curable coating composition of resistance to abrasion has the problem of the oil content property wiped away difference.
Patent documentation 1:WO2009/144999
Patent documentation 2: Japanese Unexamined Patent Publication 2010-53286 publication
Patent documentation 3:WO2011/13497
Patent documentation 4: Japanese Unexamined Patent Publication 2002-212248 publication
Patent documentation 5: Japanese Unexamined Patent Publication 6-287470 publication
Summary of the invention
the problem that invention will solve
The invention provides a kind of two-pack curing coating agent, it can form the coating layer of the transparency, hardness, resistance to marring, the oil content property wiped away and tensile elongation excellence.
for the scheme of dealing with problems
The feature of two-pack curing coating agent of the present invention is, it comprises host and solidifying agent, described host contain side chain there is optical polymerism group and hydroxyl and hydroxyl value be 30 ~ 350mgKOH/g, weight-average molecular weight be 5000 ~ 200000 acrylic polymers 100 weight part, silane coupling agent 0.3 ~ 35 weight part, polyether glycol 0.3 ~ 35 weight part, poly-lactone polyol 3 ~ 70 weight part, and optical polymerism polyfunctional compound 6 ~ 500 weight part in a part with more than 2 optical polymerism groups; Described solidifying agent contains polyisocyanates, and described solidifying agent is 3 ~ 100 weight parts.
It is further characterized in that, in above-mentioned two-pack curing coating agent, a part of compound in following component in host there occurs reaction, described component is that side chain has optical polymerism group and hydroxyl and hydroxyl value is 30 ~ 350mgKOH/g, weight-average molecular weight is acrylic polymers 100 weight part of 5000 ~ 200000, silane coupling agent 0.3 ~ 35 weight part, polyether glycol 0.3 ~ 35 weight part, poly-lactone polyol 3 ~ 70 weight part, and, there is in a part optical polymerism polyfunctional compound 6 ~ 500 weight part of more than 2 optical polymerism groups.
The acrylic polymers forming two-pack curing coating agent of the present invention has optical polymerism group and hydroxyl at side chain, preferably has the optical polymerism group of more than 2 and the acrylic polymers of hydroxyl respectively at side chain.As optical polymerism group; the ethylenical unsaturated double bonds of radical polymerization can be carried out with the optical polymerism group of optical polymerism polyfunctional compound described later as long as have; acryl, methacryloyl, styryl, vinyl, allyl group etc. can be listed, preferred acryl, methacryloyl.
Acrylic polymers carries out radical polymerization at the optical polymerism group of its optical polymerism group place and optical polymerism polyfunctional compound and forms crosslinking structure, can improve the hardness of the coating layer (below sometimes referred to as " coating layer ") formed by two-pack curing coating agent, improve resistance to marring.And then acrylic polymers gives coating layer with the chemical proofing such as alkali resistance and solvent resistance and wetting ability.
The acrylic polymers (below sometimes referred to as " acrylic polymers ") at side chain with optical polymerism group and hydroxyl such as can manufacture as follows: carry out the incompatible manufacture polymkeric substance of radical polymerization by making the monomer composition of the free radical polymerization monomer comprising hydroxyl or glycidyl, a part of hydroxyl addition of resulting polymers is had to the compound of isocyanate group and optical polymerism group, manufacture thus.Wherein, when using the free radical polymerization monomer containing glycidyl, need to make glycidyl open loop generate hydroxyl by acid.As acid, include, for example out toxilic acid, maleic anhydride, fumaric acid, vinylformic acid, methacrylic acid, ω-carboxyl-polycaprolactone single-acrylate, phthalic acid list hydroxyl urethane acrylate etc., preferred vinylformic acid, methacrylic acid.In addition, acid can be used alone and also can combinationally use two or more.There is the acid of ethylenical unsaturated double bonds as the acid for making glycidyl open loop by using in vinylformic acid and this molecule of methacrylic acid, the open loop of glycidyl and the importing of optical polymerism group can be carried out simultaneously.
For the consumption of acid when making glycidyl open loop, relative to 1 equivalent glycidyl, be preferably 0.3 ~ 1.5 equivalent, be more preferably 0.5 ~ 1.2 equivalent.When the amount of acid is very few, the optical polymerism group of side chain reduces, and hardness or the chemical proofing of the coating layer therefore sometimes obtained by two-pack curing coating agent can reduce.When the amount of acid is many, the acid of meeting remained unreacted in host, alkali resistance or the water tolerance of the coating layer therefore sometimes obtained by two-pack curing coating agent can reduce.
As the polymerization process of monomer composition, use conventional method, include, for example out letex polymerization (comprising suspension polymerization), solution polymerization, mass polymerization etc., preferred emulsion polymerization, solution polymerization.
Such as, acrylic polymers such as can obtain as follows: by making containing (methyl) alkyl acrylate and can carrying out the incompatible manufacture acrylic polyol of radical polymerization with the monomer composition of the free radical polymerization monomer of the hydroxyl of (methyl) alkyl acrylate copolymer or glycidyl containing having, a part of hydroxyl addition of gained acrylic polyol is had to the compound of isocyanate group and optical polymerism group, obtain thus.Wherein, when using the free radical polymerization monomer containing glycidyl, as mentioned above, need to make glycidyl open loop to generate hydroxyl.It should be noted that, in the present invention, (methyl) acrylate refers to acrylate or methacrylic ester.
An example of the manufacture method more specifically of acrylic polymers is described.By making under the existence of radical polymerization initiator containing (methyl) alkyl acrylate and the incompatible manufacture acrylic polyol of radical polymerization can being carried out with the monomer composition of the free radical polymerization monomer of the hydroxyl of (methyl) alkyl acrylate copolymer or glycidyl containing having.Then, the solution of gained acrylic polyol is supplied in reaction vessel, in reaction vessel, adds compound and the metal catalyst with isocyanate group and optical polymerism group further.Wherein, the stopper such as p methoxy phenol, quinhydrones (HQ) can be added as required in reaction vessel.Then, while be blown into oxygen in reaction vessel, such as reaction solution controlled at 30 ~ 1500 DEG C and reacted through 6 ~ 12 hours on one side, thus a part of hydroxyl addition of acrylic polyol is had to the compound of isocyanate group and optical polymerism group, the acrylic polymers that side chain has optical polymerism group and hydroxyl can be manufactured on.In addition, when using the free radical polymerization monomer containing glycidyl, as mentioned above, need to make glycidyl open loop to generate hydroxyl.
As radical polymerization initiator, be used in material conventional in radical polymerization, can list: the organo-peroxides such as such as benzoyl peroxide, lauroyl peroxide, peroxidation hexanoyl, the tertiary own ester of peroxidation neodecanoic acid, tert-Butyl peroxypivalate, such as 2,2-Diisopropyl azodicarboxylate, 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 (JAPAN HYDRAZINE CO., INC. the trade(brand)name " ABN-E " manufactured) etc. azo-compound, preferred azo-compound.Wherein, radical polymerization initiator can be used alone and also can combinationally use two or more.The compounding amount of radical polymerization initiator can suitably be selected, and relative to monomer composition 100 weight part, is preferably 0.01 ~ 5 weight part.
As (methyl) alkyl acrylate, include, for example out: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) amyl acrylate, (methyl) Ethyl acrylate, (methyl) heptylacrylate, (methyl) Octyl acrylate, (methyl) ethyl acrylate, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) benzyl acrylate, (methyl) vinylformic acid DCPA etc.Wherein, (methyl) alkyl acrylate can be used alone and also can combinationally use two or more.
As (methyl) alkyl acrylate, preferably (methyl) methyl acrylate, (methyl) butyl acrylate, more preferably (methyl) methyl acrylate, particularly preferably methyl methacrylate.
In monomer composition, when the content of (methyl) alkyl acrylate is few, the water tolerance of coating layer can reduce sometimes, is therefore preferably more than 10 % by weight, is more preferably more than 20 % by weight.
In monomer composition, when the content of (methyl) alkyl acrylate is many, the wetting ability of coating layer reduces, and the oil content property wiped away of coating layer can reduce sometimes, is therefore preferably less than 90 % by weight, is more preferably less than 80 % by weight.
As the free radical polymerization monomer containing hydroxyl, (methyl) alkyl acrylate containing hydroxyl, vinylformic acid-N-hydroxymethyl acid amides, methacrylic acid-N-hydroxymethyl acid amides, 4-Hydroxymethyl-cyclo-hexyl (methyl) acrylate etc. can be listed, be preferably (methyl) alkyl acrylate containing hydroxyl, be more preferably (methyl) alkyl acrylate alkyl with hydroxyl.As (methyl) alkyl acrylate containing hydroxyl, include, for example out: (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-3-hydroxy propyl ester, (methyl) vinylformic acid-2-hydroxybutyl, (methyl) vinylformic acid-4-hydroxybutyl, the own ester of (methyl) vinylformic acid-6-hydroxyl, (methyl) vinylformic acid-8-hydroxyl monooctyl ester, (methyl) vinylformic acid-10-hydroxyl ester in the last of the ten Heavenly stems, (methyl) vinylformic acid-12-hydroxylauric ester etc.Wherein, (methyl) alkyl acrylate containing hydroxyl can be used alone and also can combinationally use two or more.
As the free radical polymerization monomer containing hydroxyl, preferably (methyl) 2-Hydroxy ethyl acrylate, more preferably 2-Hydroxy ethyl acrylate (2-HEA).
As the free radical polymerization monomer containing glycidyl, (methyl) alkyl acrylate preferably containing glycidyl.As (methyl) alkyl acrylate containing glycidyl, (methyl) glycidyl acrylate etc. can be listed, preferable methyl glycidyl acrylate.Wherein, (methyl) alkyl acrylate containing glycidyl can be used alone and also can combinationally use two or more.
In monomer composition, when the content of the free radical polymerization monomer containing hydroxyl is many, the water tolerance of coating layer can reduce sometimes, is therefore preferably less than 60 % by weight, is more preferably less than 40 % by weight, is particularly preferably less than 30 % by weight.In monomer composition, when the content of the free radical polymerization monomer containing hydroxyl is few, the wetting ability of coating layer reduces, and the oil content property wiped away of coating layer can reduce sometimes, is therefore preferably more than 5 % by weight.
In monomer composition, when the content of the free radical polymerization monomer containing glycidyl is many, the water tolerance of coating layer can reduce sometimes, is therefore preferably less than 90 % by weight, is more preferably less than 80 % by weight.In monomer composition, when the content of the free radical polymerization monomer containing glycidyl is few, the wetting ability of coating layer reduces, sometimes the oil content property wiped away of coating layer can reduce, therefore be preferably more than 10 % by weight, be more preferably more than 20 % by weight, be particularly preferably more than 50 % by weight.
As the compound with isocyanate group and optical polymerism group, include, for example out (methyl) acryls such as 2-acryloyloxyethyl isocyanate (Showa Denko K. K manufacture trade(brand)name " Karenz MOI "), 2-methacryloxyethyl isocyanic ester by the alkylidene group of carbon number 2 ~ 6 and (methyl) propenoyl isocyanate of isocyanate group bonding or their derivative etc.
As derivative, include, for example (methyl) acrylate etc. providing the isocyanate group that useful end-capping reagent has been sheltered.As object lesson, methacrylic acid-2-(O-[1 '-methyl propylidene base is amino] carboxyamino) ethyl (trade(brand)name " Karenz MOI-BM " that Showa Denko K. K manufactures) etc. can be listed.Wherein, derivative can be used alone and also can combinationally use two or more.
As above-mentioned metal catalyst, include, for example out: dibutyl tin laurate, dioctyltin laurate, tin dilaurate dioctyl tin, triphenylphosphine, bismuth series catalysts etc.
When in acrylic polyol, interpolation has the compound of isocyanate group and optical polymerism group, the mole number of isocyanate group (-NCO) is preferably 0.05 ~ 0.9 relative to the ratio (-NCO/-OH) of the mole number containing the hydroxyl (-OH) in the free radical polymerization monomer of hydroxyl used in the manufacture of acrylic polyol, is more preferably 0.1 ~ 0.9.
By being undertaken compounding by above-mentioned ratio, acrylic polymers can be manufactured under the state remaining hydroxyl, and can not with have isocyanate group and optical polymerism group compound reaction in consume whole hydroxyl.So, by making residual hydroxyl in acrylic polymers, the coating layer that formed by two-pack curing coating agent can be given with wetting ability, the oil content property wiped away the excellence of coating layer can be made.
There is (methyl) alkyl acrylate composition and containing in the acrylic polymers of free radical polymerization monomer composition of hydroxyl or glycidyl, when the content of (methyl) alkyl acrylate composition is few, sometimes the water tolerance of coating layer can reduce, therefore be preferably more than 10 % by weight, be more preferably more than 20 % by weight.
There is (methyl) alkyl acrylate composition and containing in the acrylic polymers of free radical polymerization monomer composition of hydroxyl or glycidyl, when the content of (methyl) alkyl acrylate composition is many, the wetting ability of coating layer reduces, sometimes the oil content property wiped away of coating layer can reduce, therefore be preferably less than 90 % by weight, be more preferably less than 80 % by weight.
In the acrylic polymers with (methyl) alkyl acrylate composition and the free radical polymerization monomer composition containing hydroxyl, when the content of the free radical polymerization monomer composition containing hydroxyl is many, sometimes the water tolerance of coating layer can reduce, therefore less than 60 % by weight are preferably, be more preferably less than 40 % by weight, be particularly preferably less than 30 % by weight.
In the acrylic polymers with (methyl) alkyl acrylate composition and the free radical polymerization monomer composition containing hydroxyl, when the content of the free radical polymerization monomer composition containing hydroxyl is few, the wetting ability of coating layer reduces, sometimes the oil content property wiped away of coating layer can reduce, and is therefore preferably more than 5 % by weight.
In the acrylic polymers with (methyl) alkyl acrylate composition and the free radical polymerization monomer composition containing glycidyl, when the content of the free radical polymerization monomer composition containing glycidyl is many, sometimes the water tolerance of coating layer can reduce, therefore be preferably less than 90 % by weight, be more preferably less than 80 % by weight.
In the acrylic polymers with (methyl) alkyl acrylate composition and the free radical polymerization monomer composition containing glycidyl, when the content of the free radical polymerization monomer composition containing glycidyl is few, the wetting ability of coating layer reduces, sometimes the oil content property wiped away of coating layer can reduce, therefore more than 10 % by weight are preferably, be more preferably more than 20 % by weight, be particularly preferably more than 50 % by weight.
When the hydroxyl value of acrylic polymers is low, the part of carrying out thermofixation in two-pack curing coating agent reduces, and the tensile elongation of coating layer reduces; During the hydroxyl value height of acrylic polymers, the chemical proofing of coating layer reduces and the degraded appearance of coating layer, the transparency reduce, and is therefore defined as 30 ~ 350mgKOH/g, is preferably 50 ~ 320mgKOH/g, is more preferably 60 ~ 270mgKOH/g.In the present invention, the hydroxyl value of polymkeric substance refers to the hydroxyl value of solids component.
It should be noted that, the hydroxyl value of acrylic polymers refers to the value that the 4.2B method according to JIS K 1557-1:2007 (ISO14900:2001) " plastics-urethane raw polyvalent alcohol test method-1: hydroxyl value ask method " records.
When the weight-average molecular weight Mw of acrylic polymers is low, the resistance to marring of coating layer and chemical proofing reduce; During above-mentioned weight-average molecular weight Mw height, the tensile elongation of coating layer reduces and the degraded appearance of coating layer, the transparency reduce, and is therefore defined as 5000 ~ 200000, is preferably 6000 ~ 150000, is more preferably 10000 ~ 100000.
It should be noted that, the weight-average molecular weight Mw of acrylic polymers such as can calculate as follows: the molecular weight distribution being measured acrylic polymers by the gel permeation chromatograph (GPC) being equipped with differential refraction rate detector (RID), is calculated as typical curve using polystyrene standard according to gained color atlas (spectrogram).
Containing silane coupling agent in the host of two-pack curing coating agent of the present invention.Silane coupling agent is the silicoorganic compound shown in following formula (1), is to contain the silicoorganic compound with the hydroxyl of the hydroxyl of acrylic polymers, the hydroxyl of polyether glycol or poly-lactone polyol with reactive hydroxyl reactive functional group X and hydrolization group Y.
X n-Si-Y (4-n)formula (1)
Wherein, X has reactive hydroxyl reactive functional group with the hydroxyl of the hydroxyl of acrylic polymers, the hydroxyl of polyether glycol or poly-lactone polyol, and Y is hydrolization group, and n is the integer of 1 ~ 3.When n is 2 or 3, multiple X can be the same or different.When n is 1 or 2, multiple Y can be the same or different.
Silane coupling agent forms crosslinking structure at place of hydroxyl reactive functional group and between acrylic polymers, polyether glycol or poly-lactone polyol, and form polysiloxane by hydrolization group hydrolysis, polycondensation thus become crosslinking structure with net-shaped, giving coating layer with tensile elongation and chemical proofing.
As the hydroxyl reactive functional group of silane coupling agent, as long as the functional group that can form chemical bond with hydroxyl is just not particularly limited, include, for example out glycidoxyalkyl (such as glycidoxypropyl group etc.), aminoalkyl group (such as aminopropyl etc.), mercaptoalkyl (such as mercaptopropyi etc.), ureidoalkyl (such as ureido-propyl etc.), isocyanate-yl alkyl (such as isocyanate group propyl group etc.) etc., preferred aminoalkyl group, isocyanate-yl alkyl.
As the hydrolization group of silane coupling agent, as long as can by hydrolysis, polycondensation and form polysiloxane and be just not particularly limited, include, for example out: hydrogen atom, halogen atom, alkoxyl group, acyloxy, ketoxime base, amino, amide group, sour amide group, aminooxy, sulfydryl, alkenyloxy etc., from the viewpoint of water tolerance and the preferred alkoxyl group of chemical proofing of gained coating layer.As alkoxyl group, include, for example out methoxyl group, oxyethyl group, butoxy, propoxy-etc., preferred methoxyl group, oxyethyl group.
As the object lesson of silane coupling agent, include, for example out: glycidoxypropyltrime,hoxysilane (trade(brand)name " SILAPLANE S-510 " etc. that the trade(brand)name " KBM403 " that Shin-Etsu Chemial Co., Ltd manufactures, CHISSOCORPORATION manufacture), glycidoxypropyl group triethoxyl silane (trade(brand)name " Z-6041 " etc. that the trade(brand)name " KBE403 " that Shin-Etsu Chemial Co., Ltd manufactures, Dong Li Dow Corning Corporation manufacture) etc. are containing epoxy silane coupling, TSL 8330 (the trade(brand)name " KBM903 " that Shin-Etsu Chemial Co., Ltd manufactures, the trade(brand)name " Z-6610 " etc. that Dong Li Dow Corning Corporation manufactures), N-2-(amino-ethyl)-APTES (trade(brand)name " KBE603 " that Shin-Etsu Chemial Co., Ltd manufactures), aminopropyltriethoxywerene werene (the trade(brand)name " KBE903 " that Shin-Etsu Chemial Co., Ltd manufactures, the trade(brand)name " SILAPLANE S330 " etc. that CHISSO CORPORATION manufactures) etc. containing amino silicane coupling agent, mercaptopropyi Trimethoxy silanes (trade(brand)name " Z-6062 " etc. that the trade(brand)name " KBM803 " that Shin-Etsu Chemial Co., Ltd manufactures, Dong Li Dow Corning Corporation manufacture) etc. are containing mercaptosilane coupling agents, the amido-containing acid ester base silane coupling agents such as ureidopropyltriethoxysilane (trade(brand)name " Z-6676 " etc. that the trade(brand)name " KBE585 " that Shin-Etsu Chemial Co., Ltd manufactures, Dong Li Dow Corning Corporation manufacture), isocyanate group propyl-triethoxysilicanes (trade(brand)name " KBE9007 " etc. that Shin-Etsu Chemial Co., Ltd manufactures) etc. are containing isocyanato silanes coupling agent etc.As silane coupling agent, due to the stability of two-pack curing coating agent and reactivity excellent and preferably glycidoxypropyltrime,hoxysilane, N-2-(amino-ethyl)-APTES, isocyanate group propyl-triethoxysilicane, more preferably γ aminopropyltriethoxy silane, N-2-(amino-ethyl)-APTES.
When the content of the silane coupling agent in two-pack curing coating agent is few, the tensile elongation of coating layer or chemical proofing reduce; When the content of silane coupling agent is many, the oil content property wiped away of coating layer reduces, therefore relative to acrylic polymers 100 weight part, be defined as 0.3 ~ 35 weight part, be preferably 1 ~ 30 weight part, be more preferably 1.5 ~ 20 weight parts, be particularly preferably 1.3 ~ 10 weight parts.
Containing polyether glycol in the host of two-pack curing coating agent.Polyether glycol gives the coating layer that formed by two-pack curing coating agent with wetting ability, improves the oil content property wiped away and the anti-finger printing of coating layer.
Polyether glycol such as obtains as follows: with low molecular weight polyols (such as ethylene glycol, propylene glycol, glycerine etc.) or aromatic polyamine/aliphatic polyamine (such as, quadrol, tolylene diamine etc.) as initiator, addition reaction is carried out to the epoxy alkane such as oxyethane and/or propylene oxide, obtains thus.Polyether glycol can improve the wetting ability of the coating layer formed by two-pack curing coating agent, improve the oil content property wiped away of coating layer, therefore preferably containing epoxy alkane.As polyether glycol, include, for example out polyoxyethylene polyoxypropylene glycol ether, polyethylene polyols, polypropylene polyvalent alcohol, polyethylene polypropylene polyvalent alcohol (random or segmented copolymer) etc., preferred polyoxyethylene polyoxypropylene glycol ether.
In addition, as polyether glycol, the polytetramethylene ether diol etc. obtained by the ring-opening polymerization of tetrahydrofuran (THF) can also be enumerated.
These polyether glycols can be used alone and also can combinationally use two or more.The hydroxyl value of polyether glycol is preferably 3 ~ 600mgKOH/g, is more preferably 5 ~ 300mgKOH/g.It should be noted that, the hydroxyl value of polyether glycol refers to the value that the B method of foundation JIS K1557-1 (2007) records.
The average functional group number of polyether glycol is preferably 1 ~ 8, is more preferably 2 ~ 6.Wherein, the average functional group number of polyether glycol can be obtained according to the kind of initiator and compounding ratio.
The weight-average molecular weight of polyether glycol is preferably 300 ~ 30000, is more preferably 700 ~ 20000.It should be noted that, the weight-average molecular weight of polyether glycol such as can calculate as follows: the molecular weight distribution being measured polyether glycol by the gel permeation chromatograph (GPC) being equipped with differential refraction rate detector (RID), is calculated as typical curve using polystyrene standard according to gained color atlas (spectrogram).
When the content of the polyether glycol contained in the host of two-pack curing coating agent is few, the oil content property wiped away of the coating layer formed by two-pack curing coating agent reduces; When the content of polyether glycol is many, the hardness of the coating layer formed by two-pack curing coating agent, resistance to marring and chemical proofing reduce, therefore relative to acrylic polymers 100 weight part, be defined as 0.3 ~ 35 weight part, be preferably 1 ~ 30 weight part, be more preferably 1.3 ~ 20 weight parts, be particularly preferably 1.3 ~ 10 weight parts.
Containing poly-lactone polyol in the host of two-pack curing coating agent.The coating layer that formed by two-pack curing coating agent is given with the tensile elongation of excellence by poly-lactone polyol.
Poly-lactone polyol such as carries out ring-opening polymerization using polyalcohols as initiator to internal ester monomer and obtains.
As the object lesson of polyvalent alcohol, include, for example out: ethylene glycol, 1,2-propylene glycol, 1,3-PD, 1,2-butyleneglycol, 1,3-butyleneglycol, 2-methyl isophthalic acid, ammediol, BDO, neopentyl glycol, 1,5-PD, 3-methyl isophthalic acid, 5-pentanediol, 1,6-hexylene glycol, 2,2,4-trimethylammoniums-1,3-pentanediol, 2-ethyl-1,3-hexylene glycol, 2-methyl isophthalic acid, 8-ethohexadiol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecandiol, glycerine, TriMethylolPropane(TMP), trishydroxymethyl octane, tetramethylolmethane etc.
As internal ester monomer, can list: the caprolactone classes such as 6-caprolactone, Alpha-Methyl-6-caprolactone, Beta-methyl-6-caprolactone, γ-methyl-epsilon-caprolactone, β, δ-dimethyl-E-caprolactone, 3,3,5-trimethylammoniums-6-caprolactone; The poly-valerolactone classes such as δ-valerolactone, Beta-methyl-δ-valerolactone; Propiolactone class; Butyrolactone; Oenantholacton; Dodecalactone etc.Also can be the derivative of internal ester monomer.
As an example of poly-lactone polyol, polycaprolactone glycol is as shown in following general formula (2).
H [O (CH 2) 5(C=O)] mO-R-O [(C=O) (CH 2) 5o] n-H ... formula (2)
Wherein, in formula (2), R is-C 2h 4-,-C 2h 4oC 2h 4-,-C (CH 3) 2c 2h 4-waiting the alkylidene group of carbon number 2 ~ 18, m and n is positive integer respectively, and m+n is the integer of 4 ~ 35.
In addition, as an example of poly-lactone polyol, polycaprolactone trivalent alcohol such as formula shown in (3), at the alkyl R of 3 valencys 1upper bonding 3 has the polyester chain of terminal hydroxyl.
R 1-(O [(C=O)-(CH 2) 5o] pH) 3formula (3)
Wherein, in formula (3), R 1be
In 3 valency alkyl of carbon number 2 ~ 18, p is the integer of 1 ~ 30.
As the object lesson of poly-lactone polyol, as commercially available product, can list: polycaprolactone trivalent alcohol (such as Daicel Chemical Industries, Ltd. the trade(brand)name " PLACCEL 303 " manufactured, " PLACCEL 305 ", " PLACCEL 308 ", " PLACCEL 312 "), polycaprolactone glycol (DaicelChemical Industries, Ltd. manufacture " PLACCEL 205 ", " PLACCEL 208 ", " PLACCEL 210 ", " PLACCEL 212 ") etc.As poly-lactone polyol, preferred polycaprolactone polyol.Its reason is, because the carbon number be connected to each other by polyester key is more, therefore, it is possible to the coating layer that imparting is formed by two-pack curing coating agent is with the tensile elongation of excellence.
When the content of the poly-lactone polyol in the host of two-pack curing coating agent is few, the tensile elongation of the coating layer formed by two-pack curing coating agent reduces; When the content of poly-lactone polyol is many, because the hardness of the coating layer that formed by two-pack curing coating agent, resistance to marring and chemical proofing reduce, therefore relative to acrylic polymers 100 weight part, be defined as 3 ~ 70 weight parts, be preferably 5 ~ 50 weight parts, be more preferably 10 ~ 35 weight parts, be particularly preferably 15 ~ 35 weight parts.
Containing the optical polymerism polyfunctional compound (below sometimes referred to as " optical polymerism polyfunctional compound ") in a part with more than 2 optical polymerism groups in the host of two-pack curing coating agent.Optical polymerism polyfunctional compound forms crosslinking structure by carrying out radical polymerization with the optical polymerism group of acrylic polymers, and the coating layer formed by two-pack curing coating agent has excellent hardness, resistance to marring and chemical proofing.
As the optical polymerism group contained in optical polymerism polyfunctional compound; the ethylenical unsaturated double bonds of radical polymerization can be carried out with the optical polymerism group of acrylic polymers as long as have; acryl, methacryloyl, styryl, vinyl, allyl group etc. can be listed, preferred acryl, methacryloyl.
As the optical polymerism polyfunctional compound in a part with 2 optical polymerism groups, include, for example out: aklylene glycol two (methyl) acrylate such as ethylene glycol bisthioglycolate (methyl) acrylate, propylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, polyalkylene glycol two (methyl) acrylate such as Diethylene Glycol two (methyl) acrylate, TEG two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, 1,4-butyleneglycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, Dicyclopentadiene (DCPD) two (methyl) acrylate, NPGA neopentyl glycol adipate two (methyl) acrylate, hydroxy new pentane acid neopentyl glycol two (methyl) acrylate, Tricyclodecane Dimethanol two (methyl) acrylate, two (methyl) vinylformic acid two ring pentyl ester, tetramethylolmethane two (methyl) acrylate, dihydroxyphenyl propane EO addition diacrylate, caprolactone modification two (methyl) vinylformic 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 epoxy alkane modification body, Vinylstyrene, butyleneglycol-1, 4-divinyl ether, cyclohexanedimethanol divinyl base ether, diethylene glycol divinyl ether, dipropylene glycol divinyl ether, hexylene glycol divinyl ether, triethyleneglycol divinylether, phenyl glycidyl ether acrylate hexamethylene diisocyanate carbamate prepolymer (trade(brand)name " AH-600 " that Kyoeisha Chemical Co., Ltd. manufactures), phenyl glycidyl ether acrylate tolylene diisocyanate carbamate prepolymer (trade(brand)name " AT-600 " that Kyoeisha Chemical Co., Ltd. manufactures) etc.Wherein, optical polymerism polyfunctional compound can be used alone and also can combinationally use two or more.
As the optical polymerism polyfunctional compound in a part with 3 optical polymerism groups, include, for example out: three (methyl) acrylate etc. of trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol three (methyl) acrylate, three (acryloyl-oxyethyl) isocyanuric acid esters or their epoxy alkane modification body, isocyanuric acid epoxy alkane modification body.
As the optical polymerism polyfunctional compound in a part with 4 optical polymerism groups, include, for example out: ditrimethylolpropane four (methyl) acrylate, tetramethylolmethane four (methyl) acrylate or their epoxy alkane modification body etc.
As the optical polymerism polyfunctional compound in a part with 5 optical polymerism groups, include, for example out: Dipentaerythritol five (methyl) acrylate or their epoxy alkane modification body etc.
As the optical polymerism polyfunctional compound in a part with 6 optical polymerism groups, include, for example out: Dipentaerythritol six (methyl) acrylate, pentaerythritol triacrylate hexamethylene diisocyanate carbamate prepolymer (trade(brand)name " UA-306H " that Kyoeisha Chemical Co., Ltd. manufactures), caprolactone modification Dipentaerythritol six (methyl) acrylate or their epoxy alkane modification body etc.
During the increasing number of the optical polymerism group contained in optical polymerism polyfunctional compound, being cross-linked of the coating layer formed by two-pack curing coating agent is finer and close, and the hardness of coating layer increases, and is therefore preferably more than 3, be more preferably more than 4, be particularly preferably more than 5.The quantity of the optical polymerism group contained in optical polymerism polyfunctional compound is preferably less than 20, is more preferably less than 15.
When the content of the optical polymerism polyfunctional compound in the host of two-pack curing coating agent is few, the hardness of the coating layer formed by two-pack curing coating agent, resistance to marring and chemical proofing reduction; When the content of optical polymerism polyfunctional compound is many, the tensile elongation of the coating layer formed by two-pack curing coating agent reduces, therefore relative to acrylic polymers 100 weight part, be defined as 6 ~ 500 weight parts, be preferably 3 ~ 100 weight parts, be more preferably 30 ~ 100 weight parts, be particularly preferably 30 ~ 85 weight parts.
The optical polymerism monofunctional compound in a part with 1 optical polymerism group can be contained as required in the host of two-pack curing coating agent.Optical polymerism monofunctional compound for adjusting the viscosity of two-pack curing coating agent, and improves the drying property of two-pack curing coating agent by improving solid component concentration.
As the object lesson of optical polymerism monofunctional compound, can list: aliphatic category (methyl) acrylate, ester ring type class (methyl) acrylate, the fragrant same clan (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 Methacrylamide.
As optical polymerism monofunctional compound, include, for example out: (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 tetradecyl ester of (methyl) vinylformic acid, (methyl) vinylformic acid isooctadecane base ester, (methyl) isobornyl acrylate, oxyethyl group-Diethylene Glycol (methyl) acrylate, 2-ethylhexyl-Trivalin SF (methyl) acrylate, neopentyl glycol benzoic ether (methyl) acrylate, Nonylphenoxy polyoxyethylene glycol (methyl) acrylate, ECH modification phenoxy group (methyl) acrylate, Phenoxyethyl (methyl) acrylate, p-cumylphenol ethylene-oxide-modified (methyl) acrylate, vinyl pyrrolidone, caprolactam, acryloyl morpholine etc.
When the content of the optical polymerism monofunctional compound in the host of two-pack curing coating agent is many, the reactivity of two-pack curing coating agent reduces, sometimes the hardness of gained coating layer and chemical proofing reduce, therefore relative to acrylic polymers 100 weight part, be preferably below 150 weight parts, be more preferably below 90 weight parts, be particularly preferably below 60 weight parts.
In above-mentioned, the situation that the compound contained in the host to two-pack curing coating agent does not react is illustrated, and the compound contained in the host of two-pack curing coating agent also can some react.When a part of compound contained in the host of two-pack curing coating agent there occurs reaction, the above-mentioned content of compound refers to the content before reacting between compound.
Containing polyisocyanates in the solidifying agent of two-pack curing coating agent.The isocyanate group of polyisocyanates imports crosslinking structure by forming amino-formate bond with the hydroxyl reaction of the hydroxyl of acrylic polymers, the hydroxyl of polyether glycol or poly-lactone polyol in coating layer, and the tensile elongation of the coating layer formed by two-pack curing coating agent is excellent.
As polyisocyanates, as long as the isocyanic ester in a part with more than 2 isocyanate group is just not particularly limited, include, for example out vulcabond, the polyploid (such as dipolymer, trimer etc.) of vulcabond, the modification body etc. of vulcabond, due to hardness and the chemical proofing excellence of gained coating layer, the modification body of preferred vulcabond, the more preferably biuret modified body of vulcabond.
As vulcabond, be not particularly limited, include, for example out: aromatic diisocyanate (such as tolylene diisocyanate (2,4 toluene diisocyanate, 2,6-tolylene diisocyanate or their mixture), phenylene diisocyanate (m-benzene diisocyanate, PPDI or their mixture), 1,5-naphthalene diisocyanate, diphenylmethanediisocyanate (4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate, 2,2 '-diphenylmethanediisocyanate or their mixture), 4,4 '-toluidine diisocyanate etc.), araliphatic diisocyanate (such as xylylene diisocyanate (1,3-xylylene diisocyanate, Isosorbide-5-Nitrae-xylylene diisocyanate or their mixture), tetramethyl-xylylene diisocyanate (1,3-tetramethyl-xylylene diisocyanate, Isosorbide-5-Nitrae-tetramethyl-xylylene diisocyanate or their mixture) etc.), aliphatic diisocyanate (such as 1,3-trimethylene diisocyanate, Isosorbide-5-Nitrae-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate etc.), alicyclic diisocyanate (such as cyclohexyl diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (isophorone diisocyanate), methylene-bis (cyclohexyl isocyanate), norbornene alkyl diisocyanate, two (isocyanatomethyl) hexanaphthene) etc.Wherein, vulcabond can be used alone and also can combinationally use two or more.
As the modification body of vulcabond, include, for example out: allophanate-modified body (such as by allophanate-modified body etc. that vulcabond and low molecular weight polyols (such as TriMethylolPropane(TMP) etc.) are reacted and generated), biuret modified body (such as by biuret modified body etc. that vulcabond and water or amine react and generate), urea acid esters modification body (the urea acid esters modification body etc. such as generated by the trimerizing reaction between isocyanic ester), polyalcohol modified body (such as by polyalcohol modified body etc. that vulcabond and above-mentioned low molecular weight polyols are reacted and generated), urea-modified body is (such as by vulcabond and polyamines (such as quadrol, tolylene diamine etc.) react and the urea-modified body etc. of generation) oxadiazine triketone modification body (such as reacted by vulcabond and carbonic anhydride and generate oxadiazine triketone etc.), carbon imide modification body (the carbon imide modification body etc. such as generated by the decarbonate condensation reaction of vulcabond), urea diketone modification body, uretonimine-modified body etc., preferred biuret modified body.
As the commercially available product of the modification body of vulcabond, include, for example out trade(brand)name " TAKENATE D-165N " (biuret form), trade(brand)name " TAKENATED-170N " (urea acid esters type), trade(brand)name " TAKENATE D-178N " (allophanic acid ester type) etc. that Mitsui Takeda Chemical Co., Ltd manufactures.
When the content of the solidifying agent in two-pack curing coating agent is few, the tensile elongation of the coating layer formed by two-pack curing coating agent reduces; When the content of solidifying agent is many, the oil content property wiped away of the coating layer formed by two-pack curing coating agent reduces, and therefore relative to acrylic polymers 100 weight part of host, is defined as 3 ~ 100 weight parts, be preferably 5 ~ 70 weight parts, be more preferably 6 ~ 35 weight parts.
In the host and solidifying agent of two-pack curing coating agent, in the scope of physical property not damaging two-pack curing coating agent, additive can be added as required.As additive, include, for example out Photoepolymerizationinitiater initiater, antioxidant, photostabilizer, heat-resisting stabilizing agent, static inhibitor, defoamer etc.
As Photoepolymerizationinitiater initiater, include, for example out: benzoin ethers Photoepolymerizationinitiater initiater, benzophenone Photoepolymerizationinitiater initiater, thioxanthene ketone Photoepolymerizationinitiater initiater, alkylbenzene ketone Photoepolymerizationinitiater initiater, acylphosphine oxide class Photoepolymerizationinitiater initiater, two luxuriant titanium class Photoepolymerizationinitiater initiaters, oxime ester class 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 and also can combinationally use two or more.
As benzoin ethers Photoepolymerizationinitiater initiater, include, for example out: bitter almond oil camphor, benzoin methylether, ethoxybenzoin, benzoin iso-propylether, benzoin isobutyl ether etc.
As benzophenone Photoepolymerizationinitiater initiater, include, for example out: benzophenone, methyl o-benzoylbenzoate, 4-phenyl benzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, 2,4,6-tri-methyl benzophenones etc.
As thioxanthene ketone Photoepolymerizationinitiater initiater, include, for example out: ITX, 2,4-diethyl thioxanthones, 2,4-bis-clopenthixal ketones, the chloro-4-propoxythioxanthone of 1-etc.
As alkylbenzene ketone Photoepolymerizationinitiater initiater, include, for example out: 2-hydroxy-2-methyl-1-phenyl-propyl-1-ketone, 2, 2-dimethoxy-1, 2-phenylbenzene second-1-ketone, 1-hydroxy-cyclohexyl-phenyl-one, 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-third-1-ketone, 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl] phenyl }-2-methyl-propyl-1-ketone, 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholino third-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, include, for example out: 2,4,6-trimethylbenzoy-dipheny-phosphine oxide, two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide etc.
As two luxuriant titanium class Photoepolymerizationinitiater initiaters, include, for example out: two (η 5-2,4-cyclopentadiene-1-base)-bis-(the fluoro-3-of 2,6-bis-(1H-pyrroles-1-base)-phenyl) titanium etc.
As oxime ester class Photoepolymerizationinitiater initiater; include, for example out: 1-[4-(thiophenyl) phenyl]-1,2-octanedione 2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-toluyl)-9H-carbazole-3-base]-1-(O-ethanoyl oxime) ethyl ketone, oxygen phenylacetic acid 2-[2-oxo-2-phenylacetyl oxygen base oxethyl] ethyl ester, oxygen phenylacetic acid 2-(2-hydroxyl-oxethyl) ethyl ester etc.
In the host of two-pack curing coating agent, when the content of Photoepolymerizationinitiater initiater is few, the photocuring of two-pack curing coating agent carries out insufficient sometimes; When the content of Photoepolymerizationinitiater initiater is many, the hardness of coating layer can reduce because of the resolvent of Photoepolymerizationinitiater initiater sometimes, therefore relative to acrylic polymers 100 weight part, is preferably 0.3 ~ 60 weight part, is more preferably 1 ~ 35 weight part.
In the solidifying agent of two-pack curing coating agent, when the content of Photoepolymerizationinitiater initiater is few, the photocuring of two-pack curing coating agent carries out insufficient sometimes; When the content of Photoepolymerizationinitiater initiater is many, sometimes the hardness of coating layer can reduce because of the resolvent of Photoepolymerizationinitiater initiater, therefore relative to acrylic polymers 100 weight part in the host combinationally used with solidifying agent, be preferably 0.3 ~ 60 weight part, be more preferably 1 ~ 35 weight part.
The host of two-pack curing coating agent of the present invention is by mixing acrylic polymers, silane coupling agent, polyether glycol, poly-lactone polyol, optical polymerism polyfunctional compound and as required and prepared by the additive added to reach above-mentioned containing proportional mode.
The host of two-pack curing coating agent also can be prepared into the solution of organic solvent.In this situation, the solid component concentration of host is preferably 10 ~ 90 % by weight, is more preferably 20 ~ 80 % by weight.
Specifically, by silane coupling agent, polyether glycol, poly-lactone polyol, optical polymerism polyfunctional compound and as required and add additive pre-mixing obtain premix after, mix while slowly add acrylic polymers limit in this premix, make the host of two-pack curing coating agent thus.
And then, specifically, by silane coupling agent, polyether glycol, poly-lactone polyol, optical polymerism polyfunctional compound and the additive added after pre-mixing obtains premix at 10 ~ 40 DEG C as required, slowly drip acrylic polymers with in 30 ~ 60 points of these premixs of clockwise.After the dropping of acrylic polymers in premix terminates, premix is stirred 30 ~ 60 minutes at 10 ~ 40 DEG C, makes host thus.
In addition, the solidifying agent of two-pack curing coating agent comprises polyisocyanates, when also containing additive except polyisocyanates, makes by adding additive and mix in polyisocyanates.
As the Operation Key of two-pack curing coating agent, first, mixed curing agent in the host of two-pack curing coating agent, coats base material by two-pack curing coating agent.Preferably just two-pack curing coating agent in sight coat base material before in the host of two-pack curing coating agent mixed curing agent.
As the material of base material, be not particularly limited, include, for example out: the polyester resin such as polyethylene terephthalate, polybutylene terephthalate, the synthetic resins such as polycarbonate resin, polyacrylics, styrene resin, ABS resin, the inorganic materials such as glass, the metals etc. such as stainless steel, steel, aluminium.
As method two-pack curing coating agent being coated base material, include, for example out: based on dip coating, spraying method, rolling method, scrape the coating process of the skill in using a kitchen knife in cookery, silk screen print method etc., use the casting etc. of excellent coating machine, point gum machine etc.
The thickness of the film of the two-pack curing coating agent be coated on base material is not particularly limited, is preferably 2 ~ 90 μm, is more preferably 5 ~ 50 μm.
Then, film thermofixation by heating of the two-pack curing coating agent on base material is coated on.The temperature of the thermofixation of two-pack curing coating agent is preferably 60 ~ 180 DEG C, is more preferably 80 ~ 150 DEG C.The time of the thermofixation of two-pack curing coating agent is preferably 1 ~ 30 minute, is more preferably 1 ~ 10 minute.
Then, by light such as the film irradiation ultraviolet radiations to thermofixation, make the further photocuring of film and form coating layer.The transparency of the coating layer so obtained, hardness, resistance to marring, the oil content property wiped away and tensile elongation are excellent.In addition, the film of two-pack curing coating agent also can by carrying out thermofixation after carrying out photocuring and forming coating layer.
The transparency of coating layer is excellent, and specifically, the mist degree of coating layer is preferably less than 1.0%, is more preferably less than 0.8%.It should be noted that, the mist degree of coating layer is the value 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 preferably more than H by pencil hardometer, is more preferably more than 2H.It should be noted that, pencil hardness refers to the value recorded by pencil hardness test according to JIS K 5600-5-4 (1999).
The oil content property wiped away the excellence of coating layer, specifically, the water contact angle recorded by contact angle instrument is preferably 50 ~ 75 °, is more preferably 52 ~ 72 °.Oleic acid contact angle is preferably 5 ~ 25 °, is more preferably 10 ~ 20 °.
Coating layer is relative to the excellent adhesion of base material.And then the oil content property wiped away of coating layer is also excellent, therefore, it is possible to remove the oil content (fingerprint etc.) on the surface being attached to coating layer well with less wiping number of times.
Coating layer is in order to improve the surface of optical component (such as on the easy surface being stained with the graphical representation panel of the outermost layer arranging of the graphical representation device such as touch-screen, indicating meter of fingerprint because being touched by people; the surface of the surface protection film of fitting on its surface to protect graphical representation panel; the window material surface etc. of, vehicle, metrical instrument such as the lens surface ， Jian Building of glasses, eye-protection glasses etc.) the oil content property wiped away and formed.Also excellent in the transparency of coating layer after wiping oil content away, the visuality of optical component can be guaranteed.In addition, coating layer due to hardness, resistance to marring and chemical proofing excellent and can long term maintenance excellence the transparency, positively guarantee the visuality of optical component.
the effect of invention
According to two-pack curing coating agent of the present invention, the coating layer of the transparency, hardness, resistance to marring, the oil content property wiped away and tensile elongation excellence can be formed.
Therefore, two-pack curing coating agent of the present invention can well for the formation of for the protection of the coating layer requiring to have visual substrate surface.
And then, the coating layer formed by two-pack curing coating agent by hydroxyl, ether moiety and have appropriateness wetting ability.Therefore, even if when the surface attachment of coating layer has oil content, water also can be made successfully to soak between the surface and oil content of coating layer, oil content is floated from the surface of coating layer, easily removes oil content.
Coating layer has the wetting ability of appropriateness, on the other hand, because carbon chain moiety also has the lipophilicity of appropriateness.Therefore, even if when slightly remaining on coating layer when being attached to the oil content on coating layer and not removing completely, the oil content on coating layer also can not be formed in the state in drops projection on coating layer and can be formed on coating layer and the degree of identification cannot be extended to membranaceous state thinly with naked eyes.Therefore, oil content can not produce the diffuse-reflectance of light, and coating layer can maintain the excellent transparency.
In addition, coating layer has excellent tensile elongation, even if therefore when making it be out of shape in order to the base material being formed with coating layer is configured as desired shape, also successfully can follow the distortion of base material, coating layer can not produce be full of cracks etc.Therefore, it is possible to the surface that obtains easily is protected by coating layer and has the base material of desired shape.
And then coating layer has excellent hardness, resistance to marring and chemical proofing, therefore coating layer can the transparency of long term maintenance excellence and outward appearance.
Then, two-pack curing coating agent of the present invention is without the need to containing colloidal silica, and gained coating layer has excellent hardness, and then the tensile elongation reduction because producing containing colloidal silica also can not occur.Therefore, the coating layer formed by two-pack curing coating agent has excellent hardness and tensile elongation.
Embodiment
Below enumerate embodiment to be described in further detail the present invention, but be not limited to the present embodiment completely.
(synthesis of acrylic polymers A1 ~ 13)
In reaction vessel, supply methyl iso-butyl ketone (MIBK) (MIBK) 233 weight part as solvent, be heated to 88 DEG C and maintain.
The monomer composition of the methyl methacrylate (MMA) containing the specified amount shown in table 1 ~ 3, glycidyl methacrylate (GMA), butyl acrylate (BA), N,N-DMAA (DMAA) and acrylate-2-hydroxyethyl (2-HEA) to be supplied in the methyl iso-butyl ketone (MIBK) in reaction vessel and to mix.
Then, after slowly dripping the mixing of azo two-2-methylbutyronitrile (ABN-E) limit with 2 hours limits in monomer composition, place 1 hour.And then, after slowly dripping azo two-2-methylbutyronitrile with 2 hours in monomer composition, monomer composition is maintained 3 hours in 88 DEG C.The total amount being added drop-wise to the azo two-2-methylbutyronitrile in monomer composition is shown in table 1 ~ 3.
Then, monomer composition is heated to 110 DEG C carry out radical polymerization in 2 hours and obtain acrylic polymers.
Measure weight-average molecular weight Mw, the number-average molecular weight Mn of gained acrylic polymers A1 ~ 13, glass transition temperature Tg, viscosity and hydroxyl value by following main points, the results are shown in table 1 ~ 3.The glass transition temperature Tg of acrylic polymers calculates according to Fox's formula, is shown in table 1 ~ 3.In addition, the hydroxyl value of acrylic polymers A1 ~ 13 refers to the hydroxyl value of solids component.
(based on the weight-average molecular weight of gel permeation chromatography and the mensuration of number-average molecular weight)
About 0.2mg is got as sample from gained acrylic polymers, be dissolved in tetrahydrofuran (THF) 10 milliliters, measured by the gel permeation chromatograph (GPC) being equipped with differential refraction rate detector (RID), obtain the molecular weight distribution of sample.
Then, according to gained color atlas (spectrogram), using polystyrene standard as typical curve, weight-average molecular weight and the number-average molecular weight of sample is calculated.Determinator and condition determination are shown in following.
Data processing equipment: production number HLC-8220GPC (TOSOH Co., Ltd's manufacture)
Differential refraction rate detector: the RI detector being built-in with production number HLC-8220GPC
Chromatographic column: production number TSKgel GMH xL(TOSOH Co., Ltd's manufacture) 3
Mobile phase: tetrahydrofuran (THF)
Post flow: 0.5mL/ minute
Injection rate: 20 μ L
Measure temperature: 40 DEG C
Polystyrene standard molecular weight: 1250,3250,9200,28500,68000,165000,475000,950000,1900000
(viscosity)
Cone-and-plate viscometer is used to measure the viscosity of gained acrylic polymers at 25 DEG C according to JIS K 5600-2-3:1999.
(hydroxyl value)
4.2B method according to JIS K 1557-1:2007 (ISO 14900:2001) " plastics-urethane raw polyvalent alcohol test method-1: hydroxyl value ask method " measures the hydroxyl value of gained acrylic polymers.
[table 1]
[table 2]
[table 3]
(synthesis of acrylic polymers B1 ~ 15)
Supply in reaction vessel as the methyl iso-butyl ketone (MIBK) (MIBK) shown in table 4 ~ 6 of solvent, be heated to 80 DEG C and maintain.
Acrylic polymers A1 ~ 13 containing the specified amount shown in table 4 ~ 6,2-acryloyloxyethyl isocyanate (Showa Denko K. K manufacture trade(brand)name " Karenz AOI "), vinylformic acid, dibutyl tin laurate, triphenylphosphine and p methoxy phenol to be supplied in reaction vessel and to mix, obtained mixed solution.
Mixed solution is reacted under the temperature of reaction shown in table 4 ~ 6, the obtained acrylic polymer solution containing having acrylic polymers B1 ~ 15 of ethylenical unsaturated double bonds and hydroxyl at side chain by the reaction times shown in table 4 ~ 6.
Measure weight-average molecular weight Mw, the number-average molecular weight Mn of gained acrylic polymers B1 ~ 15, viscosity and hydroxyl value by above-mentioned main points, the results are shown in table 4 ~ 6.In addition, by acrylic polymers A1 ~ 6,10 ~ 13 manufacture in the mole number of isocyanate group (-NCO) that uses be illustrated in table 4 ~ 6 relative to the ratio of the mole number of the hydroxyl (-OH) in 2-Hydroxy ethyl acrylate.It should be noted that, the hydroxyl value of acrylic polymers B1 ~ 15 refers to the hydroxyl value of solids component.
[table 4]
[table 5]
[table 6]
(embodiment 1 ~ 30, comparative example 1 ~ 17)
γ-isocyanate group the propyl-triethoxysilicane (trade(brand)name " KBE-9007 " that Shin-Etsu Chemial Co., Ltd manufactures) of the specified amount shown in Homogeneous phase mixing table 7 ~ 11, N-2-(amino-ethyl)-APTES (trade(brand)name " KBE-603 " that Shin-Etsu Chemial Co., Ltd manufactures), glycidoxy Trimethoxy silane (trade(brand)name " KBM-403 " that Shin-Etsu Chemial Co., Ltd manufactures), the polyoxyethylene polyoxypropylene glycol ether (trade(brand)name " EPAN U105 " of Di-ichi Kogyo Seiyaku Co., Ltd., hydroxyl value: 19mgKOH/g, average functional group number: 2, weight-average molecular weight: 6400), polyoxypropylene glycol ether (the trade(brand)name " SANNIX PP-1000 " that Sanyo Chemical Industries, Ltd. manufactures, hydroxyl value: 112mgKOH/g, average functional group number: 2, weight-average molecular weight: 1000), polycaprolactone trivalent alcohol (Daicel ChemicalIndustries, Ltd. trade(brand)name " PLACCEL 303 "), polycaprolactone glycol (Daicel ChemicalIndustries, Ltd. trade(brand)name " PLACCEL 205 "), pentaerythritol triacrylate hexamethylene diisocyanate carbamate prepolymer (trade(brand)name " UA-306H " of Kyoeisha Chemical Co., Ltd.), phenyl glycidyl ether acrylate hexamethylene diisocyanate prepolymer (trade(brand)name " AH-600 " of Kyoeisha Chemical Co., Ltd.), colloidal silica (trade(brand)name " MIBK-ST " of Nissan Chemical Ind Ltd) and methyl iso-butyl ketone (MIBK), obtained premix.With the acrylic polymer solution slowly dripped in 10 points of clockwise premixs containing acrylic polymers B1 ~ 15, acrylic polymers B1 ~ 15 are made to reach the amount (solids component) shown in table 7 ~ 11.After terminating to drip acrylic polymer solution in premix, premix is stirred at 30 DEG C the host of 30 ~ 60 minutes obtained two-pack curing coating agents.Then, in the host of two-pack curing coating agent, add the 2-hydroxy-2-methyl-1-phenyl-propyl-1-ketone (ProductName " DAROCUR 1173 " of BASF AG) of the specified amount shown in table 7 ~ 11.The solid component concentration of the host of two-pack curing coating agent is 30 % by weight.
Using the solidifying agent of the biuret modified body (trade(brand)name " TAKENATE D-165N " of Mitsui Takeda Chemical Co., Ltd) of the hexamethylene diisocyanate of the specified amount shown in table 7 ~ 11 as two-pack curing coating agent.
The biuret modified body of the hexamethylene diisocyanate of the specified amount shown in table 7 ~ 11 is added as solidifying agent in the host of two-pack curing coating agent.Use excellent coating machine No.10 to be coated on polyethylene terephthalate (PET) film by two-pack curing coating agent after interpolation immediately, make dry film thickness be about 5 μm.
Then, two-pack curing coating agent is heated 3 minutes at 80 DEG C and removes solvent and make after two-pack curing coating agent carries out thermofixation, to use high voltage mercury lamp (120W/cm) with 500mJ/cm to gained thermofixation overlay film 2irradiation ultraviolet radiation makes the further photocuring of thermofixation overlay film and forms coating layer.In addition, in comparative example 12, two-pack curing coating agent is heated 20 minutes at 80 DEG C and removes solvent and make the thermofixation of two-pack curing coating agent.
Measure the mist degree of gained coating layer by following main points, pencil hardness, adaptation, oil content remove property, resistance to marring, alkali resistance, solvent resistance, tensile elongation, water contact angle and oleic acid contact angle, the results are shown in table 7 ~ 11.
(mist degree)
Test method(s) according to the mist degree of the plastic transparent material " ask method " of JIS K 7136 uses mist degree instrument (trade(brand)name " NDH5000 " of Japanese electricity Se Industrial Co., Ltd) to measure the mist degree of coating layer.It should be noted that, the value of mist degree is less, and the transparency is more excellent.
(pencil hardness)
The pencil hardness that pencil hardness test measures coating layer is implemented according to JIS K 5600-5-4:1999.Wherein, in pencil hardness test, hardness sorts from low to high successively as B, HB, F, H.For pencil hardness, " H " front be with numeral larger expression hardness is higher, and " B " front be with numeral larger expression hardness is lower.
(adaptation)
The adaptation of coating layer is measured according to JIS K 5600-5-6:1999.Specifically, coating layer forms with latticed the otch arriving pet film.Coating layer is divided into 100 cutting plates by latticed otch.Cutting plate is the plane square shape of 1.0mm on one side.Self adhesive tape (manufacturers of the Nichiban Co., Ltd. name of an article " No. 1, Nichiban Tape ") is attached in the entirety of cutting plate.Then, attached self adhesive tape is peeled off from pet film, count the quantity of the cutting plate remained on pet film.Adaptation is evaluated with (remaining in the quantity of the cutting plate of the quantity of the cutting plate on pet film/formed on pet film).It should be noted that, the quantity remaining in the cutting plate on pet film is more, represents that adaptation is more excellent.
(oil content removal)
Drip on the surface of coating layer 0.1g n-hexadecane.Then, with Mierocrystalline cellulose non-woven fabrics (trade(brand)name " BEMCOT M-3 " of Asahi Kasei Corporation) and the n-hexadecane of load to the surface being attached to coating layer applying 300g has carried out 10 wipings.
Then, the mist degree (turbidity) of the painting layer surface before using mist degree instrument (trade(brand)name " NDH5000 " that Japanese electricity Se Industrial Co., Ltd manufactures) to measure wiping and after wiping.Then, the poor Δ E of the mist degree of the coating layer before calculating wiping and after wiping.It should be noted that, the value of Δ E is less, and the oil content property wiped away of the fingerprint trace caused by sebum etc. is better.
(resistance to marring)
On the surface of coating layer, while apply 300g/cm to steel wool (the production number #0000 that Bonstar Sales Co., Ltd. manufactures) 2load limit make its surface along coating layer come and go 50 times.The mist degree (turbidity) of the painting layer surface before using mist degree instrument (trade(brand)name " NDH5000 " that Japanese electricity Se Industrial Co., Ltd manufactures) determination test and after test.Then, the poor Δ E of the mist degree of the coating layer before test and after test is calculated.It should be noted that, the value of Δ E is less, and resistance to marring is better.
(alkali resistance)
The pet film being formed with coating layer is flooded 3 days in 5 % by weight aqueous sodium hydroxide solutions of 40 DEG C ± 2 DEG C.The mist degree (turbidity) of the painting layer surface before using mist degree instrument (trade(brand)name " NDH5000 " that Japanese electricity Se Industrial Co., Ltd manufactures) to measure dipping and after dipping.Then, the poor Δ E of the mist degree of the coating layer before dipping and after dipping is calculated.It should be noted that, the value of Δ E is little, and alkali resistance is better.
(solvent resistance)
After the surface of coating layer drips acetone, apply 100g load and carry out 100 rub(bing)tests.The mist degree (turbidity) of the painting layer surface before using mist degree instrument (trade(brand)name " NDH5000 " that Japanese electricity Se Industrial Co., Ltd manufactures) determination test and after test.Then, the poor Δ E of the mist degree of the coating layer before test and after test is calculated.It should be noted that, the value of Δ E is less, and solvent resistance is better.
(tensile elongation)
Add solidifying agent in the host of two-pack curing coating agent after, use excellent coating machine No.10 to be coated with two-pack curing coating agent immediately on polyethylene terephthalate (PET) film of thickness 188 μm, make dry film thickness be 30 μm.
Then, two-pack curing coating agent is heated at 80 DEG C and removal of solvents was made after two-pack curing coating agent carries out thermofixation, to use high voltage mercury lamp (120W/cm) with 500mJ/cm to gained thermofixation overlay film in 3 minutes 2irradiation ultraviolet radiation makes the further photocuring of thermofixation overlay film and forms coating layer.
The tensile elongation of gained coating layer is measured according to the test method (JIS K7127) of plastics-tensile properties.Condition determination is as follows: use thick 30 μm, wide 25mm, long 115mm test film, draw speed 100mm/ minute, chuck spacing 80mm, distance between bench marks 25mm, temperature 23 DEG C condition under to stretch test film, the length L of the test film during fracture of determination test sheet, calculates tensile elongation based on following formula.
Tensile elongation (%)=100 × (L-115)
(water contact angle)
Drip at painting layer surface the water droplet of 0.4 microlitre, measures contact angle by contact angle instrument (trade(brand)name " Drop Master500 " that consonance interface science Co., Ltd. manufactures).It should be noted that, water contact angle is lower, represents that the oil content property wiped away is more excellent.
(oleic acid contact angle)
Drip at painting layer surface the oleic acid of 0.4 microlitre, measures contact angle by contact angle instrument (trade(brand)name " Drop Master500 " that consonance interface science Co., Ltd. manufactures).It should be noted that, oleic acid contact angle is lower, represents that the oil content property wiped away is more excellent.
[table 7]
[table 8]
[table 9]
[table 10]
[table 11]
utilizability in industry
Two-pack curing coating agent of the present invention can form the coating layer of the transparency, hardness, resistance to marring, the oil content property wiped away and tensile elongation excellence, therefore, it is possible to require the coating layer on the surface with visual base material for the formation of the various optical component of protection (touch-screen, indicating meter, lens, glass etc.) etc.

Claims (3)

1. a two-pack curing coating agent, it is characterized in that, comprise host and solidifying agent, wherein, described host contain side chain there is optical polymerism group and hydroxyl and hydroxyl value be 30 ~ 350mgKOH/g, weight-average molecular weight be 5000 ~ 200000 acrylic polymers 100 weight part, silane coupling agent 0.3 ~ 35 weight part, polyether glycol 0.3 ~ 35 weight part, poly-lactone polyol 3 ~ 70 weight part, and optical polymerism polyfunctional compound 6 ~ 500 weight part in a part with more than 2 optical polymerism groups; Described solidifying agent contains polyisocyanates, and described solidifying agent is 3 ~ 100 weight parts.
2. two-pack curing coating agent according to claim 1, it is characterized in that, a part for compound in the following compositions of host there occurs reaction, described composition is that side chain has optical polymerism group and hydroxyl and hydroxyl value is 30 ~ 350mgKOH/g, weight-average molecular weight is acrylic polymers 100 weight part of 5000 ~ 200000, silane coupling agent 0.3 ~ 35 weight part, polyether glycol 0.3 ~ 35 weight part, there is in poly-lactone polyol 3 ~ 70 weight part and a part optical polymerism polyfunctional compound 6 ~ 500 weight part of more than 2 optical polymerism groups.
3. two-pack curing coating agent according to claim 1 and 2, it is characterized in that, solidifying agent contains polyisocyanate derivative.
CN201380042565.XA 2012-08-10 2013-07-24 Two-pack type curable coating agent Active CN104540908B (en)

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