CN101294046B - Ultraviolet light solidified polyurethane water-based paint and preparation method thereof - Google Patents
Ultraviolet light solidified polyurethane water-based paint and preparation method thereof Download PDFInfo
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- CN101294046B CN101294046B CN2008100391993A CN200810039199A CN101294046B CN 101294046 B CN101294046 B CN 101294046B CN 2008100391993 A CN2008100391993 A CN 2008100391993A CN 200810039199 A CN200810039199 A CN 200810039199A CN 101294046 B CN101294046 B CN 101294046B
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Abstract
The invention belongs to the field of chemical engineering technology, in particular to an ultraviolet-curing water polyurethane coating and the preparation method thereof. The preparation method comprises the following steps: introducing polythiol and alkene respectively serving as end groups into a polyurethane pre-polymer terminated by polyester polyol or isocyanate by chemical bonding; preparing the water polyurethane dispersion coating containing polythiol and polyalkene by the self-emulsification method; and preparing the ultraviolet-curing water polyurethane coating with a solid content of 15 to 55% on the basis of the two polyurethane water dispersion coatings. The coating of the invention has the advantages of excellent storage stability at room temperature, high ultraviolet curing speed, uniform curing degree, high conversion rate of functional group (almost up to 100%), and no oxygen block effect, and can be used in the fields of environmental protection, building, household appliances, automobiles, optical disks, optical fibers, etc. The inventive method has the advantages of simple and environment-friendly process, high coating quality, high input-output ratio, low cost and wide application prospect.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of functional group transformation efficiency height and no oxygen and hinder ultraviolet light solidified polyurethane water-based paint of property and preparation method thereof.
Background technology
Along with science and technology development, the aqueous polyurethane coating of uV curable is because of advantages such as it has that good energy consumption is low, pollution-free, curing speed is fast, high-performance and high environmental protection, obtained development rapidly in recent years, it has obtained using widely in material fields such as environmental protection, building, household electrical appliance, upholster, floor, automobile, CD and optical fiber.The UV curable aqueous polyurethane coating overwhelming majority still still is urethane acrylate class (CN 1869139A at present, CN1616514A, CN 1796478A, CN 101034258A, CN 1696226A), though they can the fast setting film forming under conditions such as light trigger and ultraviolet lighting, such ultraviolet-curing paint also exists following big defectives.Increasing photo-curing mechanism with the free radical chain of polyurethane acrylate paint is example, cause solidifying inhomogeneous easily owing to the incipient gel phenomenon, degree of crosslinking is not high, and then having influence on physics and the chemical property that this photocuring is filmed, cured film generally has shortcomings such as mechanics transition range broad and easy stress cracking.In addition, this also is a problem that often faces of traditional radical photopolymerization reaction, then is that oxygen can play a kind of stopping effect to the ultraviolet light polymerization process, causes the final transformation efficiency not high (50%～80%) of functional group such as unsaturated double-bond.Therefore, the aqueous polyurethane coating of developing and develop the novel uV curable of functional group's transformation efficiency higher (＞90%) such as a class is solidified evenly, unsaturated double-bond and mechanical property excellence has important scientific meaning and huge economic.
Based on the ultraviolet light polymerization system of mercaptan-alkene (Thiol-ene) system, be a kind of free radical addition and chain transfer double growth process, finally form the uniform cross-linked network structure of a kind of height.So it had both had that energy consumption of acrylate-polyurethanes coating is low, curing speed is fast and advantage such as high environmental protection, again with the no oxygen stopping effect, the all even mechanics transition range of cured film is narrower, also have and be close to 100% advantage [C.E.Hoyle such as high functional group transformation efficiency, T.Y.Lee, T.Roper, Thiol-Enes:Chemistry of the Past with Promise for the Future, J.Polym.Sci.Part A:PolymChem.2004,42:5301-5338].[N.B.CRAMER according to the literature, C.N.BOWMAN, Kinetics ofThiol-Ene and Thiol-Acrylate Photopolymerizations with Real-Time Fourier Transform Infrared, Journal ofPolymer Science:Part A:Polymer Chemistry, 2001,39:3311-3319], air and in the nitrogen different atmosphere laser curing velocity of some mercaptan-alkene system about the same fast, even oxygen also participates in the polymerization process, oxygen is also very faint to final film mechanics/physicals effect.Therefore the Thiol-ene system of uV curable has caused the sizable research interest of domestic and international researchist, but seldom has report that the Thiol-ene system is incorporated into the aqueous polyurethane coating field up to now.Domesticly also belong to blank in the research aspect the novel ultraviolet light solidfication water polyurethane coating of mercaptan-alkene system, and external research report is also few, at present, only there are seminars such as the W.A.Douglas of University of Southern Mississippi's macromolecular of the U.S. and M.W.Urban that some close bibliographical informations [D.B.Otts is arranged in the world, E.Heidenreich, M.W.Urban, Novel waterborne UV-crosslinkable thiol-ene polyurethanedispersions:Synthesis and film formation, Polymer, 2005,46:8162-8168], but these work only concentrate on the aqueous polyurethane dispersion of unsaturated double-bond and the research of multi-thiol small molecule monomer system, and its stable storing performance is lower.Remove this, have only German BASF AG relevant for the further patent report of the polyurethane aqueous dispersions of crosslinking reaction [M.U.Licht, L.N.Kokel, S.K.
Et al., Aqueous Polyurethane Dispersions HavingLatent Crosslinking Properties, 1998, US 5840823], mentioning component A in this patent is the low molecular weight polycaprolactone ammonia ester dispersion that contains unsaturated double-bond, B component is the low molecular weight polycaprolactone ammonia ester dispersion that contains mercaptan, primary amine or secondary amine functional groups, A and B two components form the mixing polyurethane dispersions that " single component " (1K) can further crosslinked ability, and the bibliographical information of seminars such as this point and W.A.Douglas and M.W.Urban is similar.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, UV curable aqueous polyurethane coating of a kind of high functional group transformation efficiency, no oxygen obstruction and strong mechanical performance and preparation method thereof is provided.
The present invention earlier is respectively the method for end group by chemical bonding with multi-thiol (Thiol) and alkene (Ene) and is incorporated in polyester polyol or the isocyanate-terminated base polyurethane prepolymer for use as, prepares the water-borne PU dispersion coatings that contains multi-thiol and polynary alkene by self-emulsification again.Serve as the UV curable aqueous polyurethane coating of basis a kind of high functional group of preparation transformation efficiency, no oxygen obstruction and strong mechanical performance then with above-mentioned two kinds of polyurethane aqueous dispersions coating.Because groups such as mercaptan and alkene are dispersed in respectively in the different polyurethane aqueous dispersions, do not stablize because of not contacting each other during room temperature storage, when even both mix, also because the negative-negative Coulomb repulsion effect of aqueous polyurethane particle and stable existence, in system moisture evaporation fully both each other fully contact and under action of ultraviolet light curing reaction.Compare with low mechanical property with the stable storing performance extreme difference of lipophilicity Thiol-ene material system and the medium functional group transformation efficiency of hydrophilic urethane acrylate system, this polyurethane water-based paint had both had the excellent storage stability of polyurethane water-based paint system, advantages such as the quick laser curing velocity, state of cure that has the Thiol-ene material system again evenly, functional group's transformation efficiency is close to 100%, no oxygen stopping effect, cured film physics and mechanical property excellence.Advantage such as that preparation method of the present invention has is simple and convenient, pollution-free, environmental friendliness, film quality height, input-output ratio height, with low cost and application prospect are extensive, the product that utilizes the present invention to prepare has advantages such as high functional group transformation efficiency, no oxygen obstruction and strong mechanical performance, be new generation of green environment-friendly and high-performance Chemicals, can be applicable to fields such as environmental protection, building, household electrical appliance, upholster, floor, automobile, CD and optical fiber.
The preparation method of the UV curable aqueous polyurethane coating that the present invention proposes, concrete steps are as follows:
(1) with vulcabond, polyester polyol, 2,2 '-dimethylol propionic acid, catalyzer and organic solvent are even with the mixed of 100: 300～400: 10～50: 0.05～5: 300～500 (weight), the temperature reaction certain hour, make reaction be tending towards finishing, promptly be able to isocyanate-terminated polyurethane prepolymer.
(2) with above-mentioned isocyanate-terminated polyurethane prepolymer, multi-thiol compound, catalyzer and organic solvent, mix in ratio with 100: 1～50: 0.5～2: 50～200 (weight), temperature is controlled at 58～65 ℃, reaction continues 4～12 hours, temperature is reduced to 45～55 ℃, add 0.5～5g triethylamine again, reacted 15～60 minutes.Measure 200～500ml deionized water, slowly be added dropwise in the said mixture, keeping the whole dropping time is 30～60 minutes, and temperature is 45～50 ℃.After dropwising, temperature is 30～38 ℃, continues reaction 15～45 minutes again, after vacuum filtration is removed organic solvent, obtains containing the water-borne PU dispersion coatings of multi-thiol, and the content of sulfydryl is 1.05 * 10 in this coating
-4～1.26 * 10
-3Mol/g coating, its solid content is 15～65%.
(3) with above-mentioned isocyanate-terminated polyurethane prepolymer, the hydroxy functional acrylate that is added with stopper, catalyzer and organic solvent, ratio in 100: 1～50: 0.5～2: 50～200 (weight) mixes, temperature is controlled at 58～65 ℃, reaction continues 4～12 hours, temperature is reduced to 45～55 ℃, add 0.5～5g triethylamine again, reacted 15～60 minutes.Measure 200～500ml deionized water, slowly be added dropwise in the said mixture, keeping the whole dropping time is 30～60 minutes, and temperature is 45～50 ℃.After dropwising, temperature is 30～38 ℃, continues reaction 15～45 minutes again, after vacuum filtration is removed organic solvent, obtains containing the aqueous polyurethane acrylate coating of unsaturated double-bond, and the content of unsaturated double-bond is 1.0 * 10 in this coating
-4～1.05 * 10
-3Mol/g coating, its solid content is 15～65%.
(4) with the above-mentioned aqueous polyurethane coating that contains multi-thiol and double bond containing aqueous polyurethane acrylate coating with sulfydryl: two keys=0.2～1.0: 1 (mol ratio) mixed, the light trigger that adds coating quality 1～10% then, at ambient temperature, high-speed stirring 30～60 minutes, the additive that adds coating quality 1～10% then, continue high-speed stirring 15～60 minutes, promptly make the ultraviolet light solidfication water polyurethane coating of a kind of high functional group transformation efficiency, no oxygen obstruction and strong mechanical performance, its solid content is 15～55%.
Among the present invention, said vulcabond, it can be aromatic diisocyanate, as Toluene-2,4-diisocyanate, the 4-vulcabond, Toluene-2,4-diisocyanate, the 6-vulcabond, 4,4 '-diphenylmethanediisocyanate, 1, the 5-naphthalene diisocyanate, the ethylbenzene vulcabond, 4, the 6-Xylene Diisocyanate, 3,3 '-dimethyl diphenyl-4,4 '-vulcabond or 3,3 '-dimethyl-4,4 '-diphenylmethanediisocyanate, perhaps aliphatic diisocyanate is as hexamethylene diisocyanate, hexamethylene diisocyanate, cyclohexyl diisocyanate, 4,4 '-dicyclohexyl methane diisocyanate or different Buddhist ketone vulcabond etc.Said polyester polyol can be adipate polyester polyvalent alcohol, benzoic anhydride polyester polyol, polycaprolactone polyol, high-molecular-weight poly ester polyol, the extraordinary polyester polyol of being with side group or PCDL etc.; Said catalyzer can be dibutyltin dilaurate, stannous octoate, N-methylmorpholine or triethylenediamine, and consumption is a 0.1%-2% weight; Said organic solvent can be acetone, butanone, toluene, dimethylbenzene, ethyl acetate, N-Methyl pyrrolidone, N, dinethylformamide and N,N-dimethylacetamide etc.; Said light trigger; can be benzophenone, benzoin methyl ether, Alpha-hydroxy Benzoin ethyl ether, Alpha-hydroxy isopropyl benzene ketone, 4 '-(2-hydroxy ethoxy)-2-hydroxy-2-methyl Propiophenone, Alpha-hydroxy phenylcyclohexane ketone, isopropyl thioxanthone, 2-(4-methylthio phenyl formyl radical)-2-morpholinyl propane or oligomeric-hydroxyketone, or any several mixture in them.
Among the present invention, described multi-thiol compound selects 2,2 for use '-dimercaptoethane, 2,2 '-dimercapto ethyl-sulfide, 1,2,3-tri-thiol propane, Ji Wusi mercaptan or 2,3-two (2,2 '-the mercapto ethyl) propylmercaptan, or any several mixtures among them.Among the present invention, described hydroxy functional acrylate can be (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) vinylformic acid-2-hydroxypropyl acrylate, trimethylolpropane diacrylate or pentaerythritol triacrylate, perhaps any several composition in them.
Among the present invention, described additive can be a solubility promoter, wetting agent, thickening material, membrane-forming agent etc.
The UV curable aqueous polyurethane coating of the high functional group transformation efficiency of the present invention's preparation, no oxygen obstruction and strong mechanical performance has good room temperature storage stability, its stability (room temperature, no light trigger and no ultraviolet source)＞100 days; Film forming properties is good, and its sticking power can reach 1 grade; Functional group's transformation efficiency that photocuring is filmed is higher, the transformation efficiency of mercaptan＞95%, the transformation efficiency of two keys＞95%; No oxygen hinders behavior; The mechanics satisfactory mechanical property that photocuring is filmed, the hardness of cured coating film＞10.5 Kg/mm
2, film apparent glossiness and water tolerance etc. all can reach the practical application standard.This invention, the introducing of multi-thiol-alkene system can make aqueous polyurethane have higher functional group's transformation efficiency, mechanics mechanical property and no oxygen obstruction property.
Advantage of the present invention is: 1. the present invention has prepared a kind of high functional group transformation efficiency, no oxygen hinders and the UV curable aqueous polyurethane coating of strong mechanical performance, the package stability of this coating＞100 day, sticking power can reach 1 grade, the transformation efficiency of mercaptan＞95%, the transformation efficiency of two keys＞95%, no oxygen hinders behavior, the hardness＞10.5Kg/mm of photocuring cured coating film
2, film apparent glossiness and water tolerance etc. all can reach the practical application standard; Advantage such as preparation method 2. of the present invention has that technology is simple and convenient, pollution-free, environmental friendliness, film quality height, input-output ratio height, with low cost and application prospect are extensive, be new generation of green environment-friendly and high-performance Chemicals, can be applicable to fields such as environmental protection, building, household electrical appliance, upholster, floor, automobile, CD and optical fiber.
Embodiment
The present invention will be further described below in conjunction with embodiment:
Embodiment 1
With different Buddhist ketone vulcabond, adipate polyester polyvalent alcohol, 2,2 '-dimethylol propionic acid, dibutyltin dilaurate and acetone were with 100: 360: 40: the mixed of 2: 400 (weight) is even, be warmed up to 60 ℃ of reactions 8 hours, make reaction be tending towards finishing, promptly be able to isocyanate-terminated polyurethane prepolymer; Again will be with isocyanate-terminated polyurethane prepolymer, 1,2,3-tri-thiol propane, dibutyltin dilaurate and acetone, with 100: 12: 1: the ratio of 100 (weight), stir, temperature is controlled at about 60 ℃, reaction continues 5 hours, add the 4g triethylamine again, temperature is reduced to 45 ℃, reacts 35 minutes.Measure the 125ml deionized water, slowly be added dropwise in the said mixture, keeping the whole dropping time is 45 minutes.After dropwising, continue reaction 30 minutes again.After removing acetone under 35 ℃ of vacuum, obtain containing the water-borne PU dispersion coatings of multi-thiol, its solid content 35%, to survey the content of sulfydryl in this aqueous polyurethane coating be 3.38 * 10 with returning argentometry
-4Mol/g coating; Again with above-mentioned with isocyanate-terminated polyurethane prepolymer, 2-hydroxyethyl methacrylate, dibutyltin dilaurate and acetone, with 100: 12: 1: the ratio of 100 (weight), stir, temperature is controlled at about 60 ℃, reaction continues 5 hours, add the 4g triethylamine again, temperature is reduced to 45 ℃, reacts 35 minutes.Measure the 125ml deionized water, slowly be added dropwise in the said mixture, keeping the whole dropping time is 45 minutes.After dropwising, continue reaction 30 minutes again.After removing acetone under 35 ℃ of vacuum, obtain containing the aqueous polyurethane acrylate coating of unsaturated double-bond, solid content 35%, the content of two keys is 4.55 * 10 in this aqueous polyurethane coating
-4Mol/g coating.
At last with the above-mentioned water-borne PU dispersion coatings that contains multi-thiol and the aqueous polyurethane acrylate coating that contains unsaturated double-bond with sulfydryl: after two keys=0.8: 1 (mol ratio) mix, add 4 '-(2-the hydroxy ethoxy)-2-hydroxy-2-methyl Propiophenone of coating quality 3% and the Polyacrylic Acid Thickener of coating quality 2.0%, high-speed stirring is 30 minutes at ambient temperature, make the ultraviolet light solidfication water polyurethane coating of a kind of high functional group transformation efficiency, no oxygen obstruction and strong mechanical performance, its solid content is 29%.
This coating resin fundamental property excellence, its outward appearance is little yellow transparent, and solid content is about 35%, and period of storage is more than 3 months; Film adhesive can reach 1 grade; The about 45m/min of laser curing velocity (UV light source: 4.5KW * 3, light source and coating light are solid apart from 20cm); The transformation efficiency of mercaptan is 99%, and the transformation efficiency of two keys is 96%; No oxygen hinders behavior; The hardness that photocuring is filmed is 10.8Kg/mm
2
Embodiment 2
Identical with embodiment 1, but with isocyanate-terminated polyurethane prepolymer, 1,2, the ratio of 3-tri-thiol propane, dibutyltin dilaurate and acetone 100: 12: 1: 100 become 100: 20: 1: 100.
Embodiment 3
Identical with embodiment 1, but with isocyanate-terminated polyurethane prepolymer, 1,2, the ratio of 3-tri-thiol propane, dibutyltin dilaurate and acetone 100: 12: 1: 100 become 100: 5: 1: 100.
Embodiment 4
But with the ratio of isocyanate-terminated polyurethane prepolymer, 2-hydroxyethyl methacrylate, dibutyltin dilaurate and acetone 100: 12: 1: 100 become 100: 20: 1: 100.
Embodiment 5
But with the ratio of isocyanate-terminated polyurethane prepolymer, 2-hydroxyethyl methacrylate, dibutyltin dilaurate and acetone 100: 12: 1: 100 become 100: 5: 1: 100.
Embodiment 6
Identical with embodiment 1, but contain the water-borne PU dispersion coatings of multi-thiol and contain the sulfydryl of the aqueous polyurethane acrylate coating of unsaturated double-bond: and two key ratios become 0.6: 1 (mol ratio) by 0.8: 1 (mol ratio).
Embodiment 7
Identical with embodiment 1, but contain the water-borne PU dispersion coatings of multi-thiol and contain the sulfydryl of the aqueous polyurethane acrylate coating of unsaturated double-bond: and two key ratios become 0.4: 1 (mol ratio) by 0.8: 1 (mol ratio).
Embodiment 8
Identical with embodiment 1, but contain the water-borne PU dispersion coatings of multi-thiol and contain the sulfydryl of the aqueous polyurethane acrylate coating of unsaturated double-bond: and two key ratios become 1.0: 1 (mol ratio) by 0.8: 1 (mol ratio).
Embodiment 9
Identical with embodiment 1, but the consumption of 4 '-(2-hydroxy ethoxy)-2-hydroxy-2-methyl Propiophenone becomes 1.0% by coating quality 3%.
Embodiment 10
Identical with embodiment 1, but 4 '-(2-hydroxy ethoxy)-2-hydroxy-2-methyl Propiophenone becomes 1-hydroxyl-1-phenylcyclohexane acetone, and its consumption is constant.
Embodiment 11
Identical with embodiment 1, but 1,2,3-tri-thiol propane becomes Ji Wusi mercaptan, and its consumption is constant.
Embodiment 12
Identical with embodiment 1, but 2-hydroxyethyl methacrylate becomes trimethylolpropane diacrylate, and its consumption is constant.
The high functional group transformation efficiency that obtains among the embodiment 2-12, no oxygen obstruction and the ultraviolet light solidfication water polyurethane coating of strong mechanical performance and the coating of embodiment 1 have similar performance.
Claims (6)
1. the preparation method of a ultraviolet light solidfication water polyurethane coating is characterized in that concrete steps are:
(1) with vulcabond, polyester polyol, 2,2 '-dimethylol propionic acid, catalyzer and organic solvent mix with 100: 300～400: 10～50: 0.05～5: 300～500 part by weight, the temperature reaction certain hour, make reaction be tending towards finishing, promptly be able to isocyanate-terminated polyurethane prepolymer;
(2) with above-mentioned isocyanate-terminated polyurethane prepolymer, multi-thiol compound, catalyzer and organic solvent, mix by part by weight with 100: 1～50: 0.5～2: 50～200, temperature is controlled at 58～65 ℃, reaction continues 4～12 hours, temperature is reduced to 45～55 ℃, add 0.5～5g triethylamine again, reacted 15～60 minutes; Measure 200～500ml deionized water, slowly be added dropwise in the said mixture, keeping the whole dropping time is 30～60 minutes, and temperature is 45～50 ℃; After dropwising, temperature is 30～38 ℃, continues reaction 15～45 minutes again, after vacuum filtration is removed organic solvent, obtains containing the water-borne PU dispersion coatings of multi-thiol, and the content of sulfydryl is 1.05 * 10 in this coating
-4～1.26 * 10
-3Mol/g coating, its solid content is 15～65%;
(3) with above-mentioned isocyanate-terminated polyurethane prepolymer, the hydroxy functional acrylate that is added with stopper, catalyzer and organic solvent, part by weight by 100: 1～50: 0.5～2: 50～200 mixes, temperature is controlled at 58～65 ℃, reaction continues 4～12 hours, temperature is reduced to 45～55 ℃, add 0.5～5g triethylamine again, reacted 15～60 minutes; Measure 200～500ml deionized water, slowly be added dropwise in the said mixture, keeping the whole dropping time is 30～60 minutes, and temperature is 45～50 ℃; After dropwising, temperature is 30～38 ℃, continues reaction 15～45 minutes again, after vacuum filtration is removed organic solvent, obtains containing the aqueous polyurethane acrylate coating of unsaturated double-bond, and the content of unsaturated double-bond is 1.0 * 10 in this coating
-4～1.05 * 10
-3Mol/g coating, its solid content is 15～65%;
(4) with the above-mentioned aqueous polyurethane coating that contains multi-thiol and double bond containing aqueous polyurethane acrylate coating with sulfydryl: two keys=0.2～1.0: 1 is mixed in molar ratio, the light trigger that adds coating quality 1～10% then, high-speed stirring is 30～60 minutes at ambient temperature, the additive that adds coating quality 1～10% then, continue to stir 15～60 minutes, promptly make ultraviolet light solidfication water polyurethane coating.
2. preparation method according to claim 1, it is characterized in that described vulcabond, it is Toluene-2,4-diisocyanate, the 4-vulcabond, Toluene-2,4-diisocyanate, the 6-vulcabond, 4,4 '-diphenylmethanediisocyanate, 1, the 5-naphthalene diisocyanate, the ethylbenzene vulcabond, 4, the 6-Xylene Diisocyanate, 3,3 '-dimethyl diphenyl-4,4 '-vulcabond or 3,3 '-dimethyl-4,4 '-diphenylmethanediisocyanate, or hexamethylene diisocyanate, cyclohexyl diisocyanate, 4,4 '-dicyclohexyl methane diisocyanate or different Buddhist ketone vulcabond; Said polyester polyol is adipate polyester polyvalent alcohol, benzoic anhydride polyester polyol, polycaprolactone polyol or PCDL; Said catalyzer is dibutyltin dilaurate, stannous octoate, N-methylmorpholine or triethylenediamine; Said organic solvent is acetone, butanone, toluene, dimethylbenzene, ethyl acetate, N-Methyl pyrrolidone, N, dinethylformamide or N,N-dimethylacetamide.
3. preparation method according to claim 1; it is characterized in that said light trigger is benzophenone, benzoin methyl ether, Alpha-hydroxy Benzoin ethyl ether, Alpha-hydroxy isopropyl benzene ketone, 4 '-(2-hydroxy ethoxy)-2-hydroxy-2-methyl Propiophenone, Alpha-hydroxy phenylcyclohexane ketone, isopropyl thioxanthone or 2-(4-methylthio phenyl formyl radical)-2-morpholinyl propane, or any several mixture among them.
4. preparation method according to claim 1, it is characterized in that said multi-thiol compound selects 2 for use, 2 '-dimercaptoethane, 2,2 '-dimercapto ethyl-sulfide, 1,2,3-tri-thiol propane, Ji Wusi mercaptan or 2,3-two (2,2 '-the mercapto ethyl) propylmercaptan, or any several mixture among them.
5. preparation method according to claim 1, it is characterized in that said hydroxy functional acrylate is (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) vinylformic acid-2-hydroxypropyl acrylate, trimethylolpropane diacrylate or pentaerythritol triacrylate, or their central several composition.
6. ultraviolet light solidfication water polyurethane coating for preparing as the described preparation method of one of claim 1～5.
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| KR101764954B1 (en) * | 2011-06-17 | 2017-08-03 | 디아이씨 가부시끼가이샤 | Fluorine-containing curable resin, active energy beam-curable composition, and cured product thereof |
| CN103333285B (en) * | 2013-06-09 | 2015-11-18 | 广东工业大学 | A kind of UV-curable lateral chain fluorine-containing waterborne polyurethane coating and preparation method thereof |
| CN103897579A (en) * | 2014-02-25 | 2014-07-02 | 君子兰化工（上海）有限公司 | Improved waterborne polyurethane UV light-cured woodware coating |
| CN105669938B (en) * | 2016-03-24 | 2018-07-10 | 万华化学集团股份有限公司 | Aqueous radiation curable urethane acrylate composition and preparation method and coating |
| CN106479333A (en) * | 2016-10-09 | 2017-03-08 | 华南理工大学 | A kind of ultraviolet light polymerization hybrid super-hydrophilic coating and preparation method thereof |
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| CN114960227B (en) * | 2022-07-05 | 2023-07-21 | 常熟新常泰汽车内饰科技有限公司 | High-strength automobile cover plate and processing technology thereof |
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