CN105505196A - Water-based UV (ultraviolet) photocuring paint and preparation method thereof - Google Patents
Water-based UV (ultraviolet) photocuring paint and preparation method thereof Download PDFInfo
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- CN105505196A CN105505196A CN201511024838.5A CN201511024838A CN105505196A CN 105505196 A CN105505196 A CN 105505196A CN 201511024838 A CN201511024838 A CN 201511024838A CN 105505196 A CN105505196 A CN 105505196A
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- water
- urethane acrylate
- mass ratio
- curable coating
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003973 paint Substances 0.000 title abstract description 15
- 238000000016 photochemical curing Methods 0.000 title abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 36
- 239000004814 polyurethane Substances 0.000 claims abstract description 36
- 229920002635 polyurethane Polymers 0.000 claims abstract description 36
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 77
- 238000000576 coating method Methods 0.000 claims description 61
- 239000011248 coating agent Substances 0.000 claims description 60
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 34
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 30
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 30
- 229920000642 polymer Polymers 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 239000004970 Chain extender Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 150000001336 alkenes Chemical class 0.000 claims description 16
- -1 amine salt Chemical class 0.000 claims description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims description 16
- 239000013530 defoamer Substances 0.000 claims description 16
- 239000003995 emulsifying agent Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000004744 fabric Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical group COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 4
- 150000002334 glycols Chemical class 0.000 claims description 4
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 4
- 229920001610 polycaprolactone Polymers 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 claims description 3
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 3
- 238000001723 curing Methods 0.000 abstract description 10
- 239000006185 dispersion Substances 0.000 abstract description 8
- 239000002518 antifoaming agent Substances 0.000 abstract 1
- 238000007711 solidification Methods 0.000 description 7
- 230000008023 solidification Effects 0.000 description 7
- 238000004383 yellowing Methods 0.000 description 5
- 230000003993 interaction Effects 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
Abstract
The invention provides a water-based UV (ultraviolet) photocuring paint which comprises the following components in parts by weight: 80-95 parts of polyurethane acrylate dispersion, 0.1-2 parts of leveling agent, 0.1-2 parts of defoaming agent and 2-8 parts of photoinitiator. The polyurethane acrylate dispersion is a first polyurethane acrylate dispersion or second polyurethane acrylate dispersion. The first polyurethane acrylate dispersion is Bayer AG polyurethane acrylate 2869-1. The water-based UV photocuring paint has higher double bond curing rate and conversion rate; and after the water-based UV photocuring paint is stood for 6 months, the paint film basically does not become yellow. Besides, the invention also provides a preparation method of the water-based UV photocuring paint.
Description
Technical field
The present invention relates to paint field, particularly relate to a kind of water-based ultraviolet (UV) curable coating and preparation method thereof.
Background technology
Photo-cured coating is also known as photoactive coating, and it utilizes UV initiation to have chemically active liquid material rapid polymerization to be cross-linked, instantaneous solidification film forming.The advantage of the traditional oiliness photo-cured coating technology of waterborne radiation curable coating inherit and development and water-borne coatings, ink technology, because its environmental protection, wide application, safety, construction be relatively simple etc., superior performance advantage becomes rapidly study hotspot, water-soluble photoinitiator, as the important component part of waterborne radiation curable coating, is also paid attention to day by day.Although waterborne UV coating is popular, easy xanthochromia after existing waterborne UV coating solidification.
Summary of the invention
Given this, water-based ultraviolet (UV) curable coating being difficult to xanthochromia and preparation method thereof after a kind of solidification is necessary to provide.
A kind of water-based ultraviolet (UV) curable coating, meter comprises following component by weight:
Urethane acrylate dispersoid 80 ~ 95 parts;
Flow agent 0.1 ~ 2 part;
Defoamer 0.1 ~ 2 part;
Light trigger 2 ~ 8 parts;
Wherein, described urethane acrylate dispersoid is the first urethane acrylate dispersoid or the second urethane acrylate dispersoid;
Described first urethane acrylate dispersoid is the urethane acrylate 2869-1 of Bayer A.G;
Described second urethane acrylate dispersoid is prepared by the following method:
Under nitrogen protection, by isophorone diisocyanate at 70 ~ 80 DEG C of preheating 10 ~ 20min, then drip dibasic alcohol stirring reaction 2 ~ 3h, wherein, the mass ratio of described dibasic alcohol and isophorone diisocyanate is 20 ~ 68:18 ~ 35;
Then, be cooled to 55 ~ 65 DEG C after adding hydrophilic chain extender reaction 1 ~ 1.5h, wherein, the mass ratio of described hydrophilic chain extender and isophorone diisocyanate is 2 ~ 7:18 ~ 35;
Then, add alkene class end-capping reagent, stopper and catalyzer simultaneously, be cooled to 40 ~ 45 DEG C after insulation reaction 4 ~ 5h, wherein, the mass ratio of described alkene class end-capping reagent, described stopper, described catalyzer and isophorone diisocyanate is 3 ~ 15:0.003 ~ 0.08:0.1 ~ 1:18 ~ 35;
Then, add amine salt forming agent, regulate pH to be 7 ~ 8, obtain water white aqueous polyurethane acrylate performed polymer, wherein, the mass ratio of described amine salt forming agent and isophorone diisocyanate is 2 ~ 5:18 ~ 35;
Emulsifying agent is added in described aqueous polyurethane acrylate performed polymer, stir, then add deionized water in batches, described first urethane acrylate dispersoid is obtained after being uniformly dispersed, wherein, the mass ratio of described emulsifying agent and aqueous polyurethane acrylate performed polymer is 0.1 ~ 1:99 ~ 100, and the mass ratio of described aqueous polyurethane acrylate performed polymer and deionized water is 35 ~ 50:45 ~ 60.
Wherein in an embodiment, described dibasic alcohol is one or more the mixture in PCDL, polycaprolactone diols, polyether Glycols.
Wherein in an embodiment, described hydrophilic chain extender is one or more mixtures in dimethylol propionic acid, dimethylolpropionic acid.
Wherein in an embodiment, described alkene class end-capping reagent is one or more mixtures in hydroxyethyl methylacrylate, Hydroxyethyl acrylate, pentaerythritol triacrylate, Rocryl 410, Propylene glycol monoacrylate, described stopper is methoxyphenol, and described catalyzer is dibutyl tin laurate.
Wherein in an embodiment, described amine salt forming agent is triethylamine.
Wherein in an embodiment, described emulsifying agent is TX-10.
Wherein in an embodiment, described flow agent is BYK333 and BYK349 mixture, and wherein, the mass ratio of BYK333 and BYK349 is 1:2.
Wherein in an embodiment, described defoamer is BYK028.
Wherein in an embodiment, described light trigger is 2-hydroxy-2-methyl-phenyl-acetone-1,2-hydroxy-2-methyl-to hydroxyethyl ether phenyl-acetone-1 or 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl-1-acetone.
A preparation method for water-based ultraviolet (UV) curable coating, comprises the following steps:
In urethane acrylate dispersoid, add flow agent, defoamer and light trigger successively, dispersed with stirring is even, then adopts 200 ~ 400 order filter-cloth filterings, obtains described water-based ultraviolet (UV) curable coating;
Wherein, described urethane acrylate dispersoid is the first urethane acrylate dispersoid or the second urethane acrylate dispersoid;
Described first urethane acrylate dispersoid is the urethane acrylate 2869-1 of Bayer A.G;
Described second urethane acrylate dispersoid is prepared by the following method:
Under nitrogen protection, by isophorone diisocyanate at 70 ~ 80 DEG C of preheating 10 ~ 20min, then drip dibasic alcohol stirring reaction 2 ~ 3h, wherein, the mass ratio of described dibasic alcohol and isophorone diisocyanate is 20 ~ 68:18 ~ 35;
Then, be cooled to 55 ~ 65 DEG C after adding hydrophilic chain extender reaction 1 ~ 1.5h, wherein, the mass ratio of described hydrophilic chain extender and isophorone diisocyanate is 2 ~ 7:18 ~ 35;
Then, add alkene class end-capping reagent, stopper and catalyzer simultaneously, be cooled to 40 ~ 45 DEG C after insulation reaction 4 ~ 5h, wherein, the mass ratio of described alkene class end-capping reagent, described stopper, described catalyzer and isophorone diisocyanate is 3 ~ 15:0.003 ~ 0.08:0.1 ~ 1:18 ~ 35;
Then, add amine salt forming agent, regulate pH to be 7 ~ 8, obtain water white aqueous polyurethane acrylate performed polymer, wherein, the mass ratio of described amine salt forming agent and isophorone diisocyanate is 2 ~ 5:18 ~ 35;
Emulsifying agent is added in described aqueous polyurethane acrylate performed polymer, stir, then add deionized water in batches, described second urethane acrylate dispersoid is obtained after being uniformly dispersed, wherein, the mass ratio of described emulsifying agent and aqueous polyurethane acrylate performed polymer is 0.1 ~ 1:99 ~ 100, and the mass ratio of described aqueous polyurethane acrylate performed polymer and deionized water is 35 ~ 50:45 ~ 60.
Above-mentioned water-based ultraviolet (UV) curable coating, adopt suitable urethane acrylate dispersoid, flow agent, defoamer, light trigger, urethane acrylate dispersoid is many containing double bond, easy solidification, and not containing reactive amines in selected light trigger structure, after the double bond crosslinking curing in urethane acrylate dispersoid, not easily oxidation by air, inhibited from yellowing.Above-mentioned water-based ultraviolet (UV) curable coating, by the interaction between urethane acrylate dispersoid, flow agent, defoamer, light trigger, the film curing speed that the water-based ultraviolet (UV) curable coating obtained is formed is fast, and is not easy to turn yellow, in placement after 6 months, there is not xanthochromia in paint film substantially.
Accompanying drawing explanation
Fig. 1 is preparation method's schema of the second urethane acrylate dispersoid of an embodiment.
Embodiment
In order to make object of the present invention, technical scheme and advantage more clear, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The water-based ultraviolet (UV) curable coating of one embodiment, meter comprises following component by weight:
Urethane acrylate dispersoid 80 ~ 95 parts;
Flow agent 0.1 ~ 2 part;
Defoamer 0.1 ~ 2 part;
Light trigger 2 ~ 8 parts.
Wherein, urethane acrylate dispersoid is the first urethane acrylate dispersoid or the second urethane acrylate dispersoid.First urethane acrylate dispersoid is the urethane acrylate 2869-1 of Bayer A.G.
Flow agent can be BYK333 and BYK349 mixture, and wherein, the ratio of BYK333 and BYK349 is 1:2.
Defoamer can be BYK028.
Light trigger can be 2-hydroxy-2-methyl-phenyl-acetone-1 (1173), 2-hydroxy-2-methyl-to hydroxyethyl ether phenyl-acetone-1 (2959) or 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl-1-acetone (907).Preferably, light trigger is 1173.
Refer to Fig. 1, the second urethane acrylate dispersoid is prepared by the following method:
S10, under nitrogen protection; by isophorone diisocyanate (IPDI) at 70 ~ 80 DEG C of preheating 10 ~ 20min; then drip dibasic alcohol stirring reaction 2 ~ 3h, wherein, the mass ratio of dibasic alcohol and isophorone diisocyanate is 20 ~ 68:18 ~ 35.
Dibasic alcohol can be one or more the mixture in PCDL, polycaprolactone diols, polyether Glycols.
S20, then, be cooled to 55 ~ 65 DEG C after adding hydrophilic chain extender reaction 1 ~ 1.5h, wherein, the mass ratio of hydrophilic chain extender and isophorone diisocyanate is 2 ~ 7:18 ~ 35.
Hydrophilic chain extender can be one or more mixtures in dimethylol propionic acid, dimethylolpropionic acid.
S30, then, add alkene class end-capping reagent, stopper and catalyzer simultaneously, be cooled to 40 ~ 45 DEG C after insulation reaction 4 ~ 5h, wherein, the mass ratio of alkene class end-capping reagent, stopper, catalyzer and isophorone diisocyanate is 3 ~ 15:0.003 ~ 0.08:0.1 ~ 1:18 ~ 35.
Alkene class end-capping reagent can be one or more mixtures in hydroxyethyl methylacrylate, Hydroxyethyl acrylate, pentaerythritol triacrylate, Rocryl 410, Propylene glycol monoacrylate.
Stopper can be methoxyphenol.
Catalyzer can be dibutyl tin laurate.
S40, then, add amine salt forming agent, regulate pH to be 7 ~ 8, obtain water white aqueous polyurethane acrylate performed polymer, wherein, the mass ratio of amine salt forming agent and isophorone diisocyanate is 2 ~ 5:18 ~ 35.
Amine salt forming agent can be triethylamine.
S50, in aqueous polyurethane acrylate performed polymer, add emulsifying agent, stir, then add deionized water to be uniformly dispersed in batches, obtain the second urethane acrylate dispersoid, wherein, the mass ratio of emulsifying agent and aqueous polyurethane acrylate performed polymer is 0.1 ~ 1:99 ~ 100, and the mass ratio of aqueous polyurethane acrylate performed polymer and deionized water is 35 ~ 50:45 ~ 60.
Emulsifying agent can be TX-10.
In above-mentioned second urethane acrylate dispersoid, selected isocyanic ester is isophorone diisocyanate, and the urethane acrylate of synthesis has excellent yellowing resistance, and hardness is good, and introduce polyfunctionality monomer, curing speed is fast.And the preparation method of the second urethane acrylate dispersoid is simple, easily operates.
Above-mentioned water-based ultraviolet (UV) curable coating, adopt suitable urethane acrylate dispersoid, flow agent, defoamer, light trigger, urethane acrylate dispersoid is many containing double bond, easy solidification, and not containing reactive amines in selected light trigger structure, after the double bond crosslinking curing in urethane acrylate dispersoid, not easily oxidation by air, inhibited from yellowing.Above-mentioned water-based ultraviolet (UV) curable coating, by the interaction between urethane acrylate dispersoid, flow agent, defoamer, light trigger, the film curing speed that the water-based ultraviolet (UV) curable coating obtained is formed is fast, and is not easy to turn yellow, in placement after 6 months, there is not xanthochromia in paint film substantially.
In addition, a kind of preparation method of above-mentioned water-based ultraviolet (UV) curable coating is also provided, comprises the following steps:
In urethane acrylate dispersoid, add flow agent, defoamer and light trigger successively, dispersed with stirring is even, then adopts 200 ~ 400 order filter-cloth filterings, obtains water-based ultraviolet (UV) curable coating.
Wherein, urethane acrylate dispersoid is the first urethane acrylate dispersoid or the second urethane acrylate dispersoid.
First urethane acrylate dispersoid is the urethane acrylate 2869-1 of Bayer A.G.
Second urethane acrylate dispersoid is prepared by the following method:
S10, under nitrogen protection, by isophorone diisocyanate at 70 ~ 80 DEG C of preheating 10 ~ 20min, then drip dibasic alcohol stirring reaction 2 ~ 3h, wherein, the mass ratio of dibasic alcohol and isophorone diisocyanate is 20 ~ 68:18 ~ 35.
S20, then, be cooled to 55 ~ 65 DEG C after adding hydrophilic chain extender reaction 1 ~ 1.5h, wherein, the mass ratio of hydrophilic chain extender and isophorone diisocyanate is 3 ~ 15:18 ~ 35.
S30, then, add alkene class end-capping reagent, stopper and catalyzer simultaneously, be cooled to 40 ~ 45 DEG C after insulation reaction 4 ~ 5h, wherein, the mass ratio of alkene class end-capping reagent, stopper, catalyzer and isophorone diisocyanate is 3 ~ 15:0.003 ~ 0.08:0.1 ~ 1:18 ~ 35.
S40, then, add amine salt forming agent, regulate pH to be 7 ~ 8, obtain water white aqueous polyurethane acrylate performed polymer, wherein, the mass ratio of amine salt forming agent and isophorone diisocyanate is 2 ~ 5:18 ~ 35.
S50, in aqueous polyurethane acrylate performed polymer, add emulsifying agent, stir, then add deionized water in batches, the second urethane acrylate dispersoid is obtained after being uniformly dispersed, wherein, the mass ratio of emulsifying agent and aqueous polyurethane acrylate performed polymer is 0.1 ~ 1:99 ~ 100, and the mass ratio of aqueous polyurethane acrylate performed polymer and deionized water is 35 ~ 50:45 ~ 60.
The kind of dibasic alcohol, hydrophilic chain extender, alkene class end-capping reagent, stopper, catalyzer, amine salt forming agent and emulsifying agent as described above, does not repeat them here.
The preparation method of above-mentioned water-based ultraviolet (UV) curable coating is simple, easily operates.Above-mentioned water-based ultraviolet (UV) curable coating, adopt suitable urethane acrylate dispersoid, flow agent, defoamer, light trigger, urethane acrylate dispersoid is many containing double bond, easy solidification, and not containing reactive amines in selected light trigger structure, after the double bond crosslinking curing in urethane acrylate dispersoid, not easily oxidation by air, inhibited from yellowing.Above-mentioned water-based ultraviolet (UV) curable coating, by the interaction between urethane acrylate dispersoid, flow agent, defoamer, light trigger, the film curing speed that the water-based ultraviolet (UV) curable coating obtained is formed is fast, and is not easy to turn yellow, in placement after 6 months, there is not xanthochromia in paint film substantially.
Be specific embodiment part below.
Embodiment 1
The isophorone diisocyanate (IPDI) of 180g is added, 70 DEG C of preheating 10min in the there-necked flask of logical nitrogen protection.Drip 200g polycaprolactone diols (M=500g/mol) PCDL subsequently in reaction flask, stirring reaction 3h, after add 20g dimethylol propionic acid reaction 1h, be cooled to 55 DEG C.Then, add 30g hydroxyethyl methylacrylate, 0.03g methoxyphenol and 1g dibutyl tin laurate, insulation reaction 5h simultaneously, be cooled to 40 DEG C.Then, add 15g triethylamine, modulation pH7, discharging, obtains water white aqueous polyurethane acrylate performed polymer.Getting 41.5g aqueous polyurethane acrylate performed polymer adds in dispersion cylinder, adds 0.1gTX-10, stirs, and adds 58.3g deionized water in batches and is uniformly dispersed, obtain the second urethane acrylate dispersoid.
Get the second urethane acrylate dispersoid 47.8g, the mass ratio adding 0.3g is successively the mixture of BYK333 and BYK349 of 1:2, the BYK028 of 0.15g, and the 1-hydroxy-cyciohexyl-benzophenone (184) of 1.75g, dispersed with stirring is even, adopt 300 order filter-cloth filterings, obtain the water-based ultraviolet (UV) curable coating being numbered A1.
According to same collocation method, preparation is numbered the water-based ultraviolet (UV) curable coating of A2-A6.The component of the water-based ultraviolet (UV) curable coating of A2-A6 is substantially identical with the component of A1 water-based ultraviolet (UV) curable coating; its difference is; the light trigger being numbered the water-based ultraviolet (UV) curable coating of A2-A6 adopts 2 successively; 4,6-trimethylbenzoy-dipheny phosphine oxide (TPO), 1173,2959,907 and 2-isopropyl thioxanthone (ITX).The component of the water-based ultraviolet (UV) curable coating of A1-A6 is as shown in table 1.
Table 1
Embodiment 2
The isophorone diisocyanate (IPDI) of 175g is added, 80 DEG C of preheating 10min in the there-necked flask of logical nitrogen protection.Drip 340g PCDL subsequently in reaction flask, stirring reaction 2h, after add 35g dimethylolpropionic acid reaction 1.5h, be cooled to 65 DEG C.Then, add 55g Hydroxyethyl acrylate, 0.4g methoxyphenol and 5g dibutyl tin laurate, insulation reaction 4h simultaneously, be cooled to 45 DEG C.Then, add 25g triethylamine, modulation pH8, discharging, obtains water white aqueous polyurethane acrylate performed polymer.Getting 41.5g aqueous polyurethane acrylate performed polymer adds in dispersion cylinder, adds 0.04gTX-10, stirs, and adds 41.5g deionized water in batches and is uniformly dispersed, obtain the second urethane acrylate dispersoid.
Get the second urethane acrylate dispersoid 47.5g, the mass ratio adding 1g is successively the mixture of BYK333 and BYK349 of 1:2, the light trigger 1173 of BYK028 and 4g of 1g, and dispersed with stirring is even, adopt 200 order filter-cloth filterings, obtain the water-based ultraviolet (UV) curable coating being numbered A7.
Embodiment 3
The isophorone diisocyanate (IPDI) of 200g is added, 75 DEG C of preheating 10min in the there-necked flask of logical nitrogen protection.Drip 400g polyether Glycols subsequently in reaction flask, stirring reaction 2.5h, after add the mixture reaction 1.2h of 40g dimethylol propionic acid and dimethylolpropionic acid, be cooled to 58 DEG C.Then, add 40g Propylene glycol monoacrylate, 0.1g methoxyphenol and 5g dibutyl tin laurate, insulation reaction 4.5h simultaneously, be cooled to 42 DEG C.Then, add 30g triethylamine, modulation pH7.6, discharging, obtains water white aqueous polyurethane acrylate performed polymer.Getting 41.5g aqueous polyurethane acrylate performed polymer adds in dispersion cylinder, adds 0.4gTX-10, stirs, and adds 77g deionized water in batches and is uniformly dispersed, obtain the second urethane acrylate dispersoid.
Get the second urethane acrylate dispersoid 50g, the mass ratio adding 1g is successively the mixture of BYK333 and BYK349 of 1:2, the light trigger 1173 of BYK028 and 4g of 1g, and dispersed with stirring is even, adopt 400 order filter-cloth filterings, obtain the water-based ultraviolet (UV) curable coating being numbered A8.
Embodiment 4
According to the collocation method of embodiment 1, preparation is numbered the water-based ultraviolet (UV) curable coating of B1-B6.The component of the water-based ultraviolet (UV) curable coating of B1-B6 respectively with the component one_to_one corresponding of the water-based ultraviolet (UV) curable coating of A1-A6, substantially identical, its difference is, the urethane acrylate dispersoid in the water-based ultraviolet (UV) curable coating of B1-B6 adopts the first urethane acrylate dispersoid.The component of the water-based ultraviolet (UV) curable coating of B1-B6 is as shown in table 2.
Table 2
Embodiment 5
The second urethane acrylate dispersoid is prepared according to the method for embodiment 1.Get the second urethane acrylate dispersoid, the mass ratio added successively is the mixture of BYK333 and BYK349 of 1:2, BYK028 and light trigger 1173, dispersed with stirring is even, adopt 300 order filter-cloth filterings, preparation is numbered the water-based ultraviolet (UV) curable coating of A11-A17.Adopt the water-based ultraviolet (UV) curable coating of the preparation B11-B17 that uses the same method, unlike, change the second urethane acrylate dispersoid into first urethane acrylate dispersoid.The component of the water-based ultraviolet (UV) curable coating of A11-A17 is as shown in table 3.The component of the water-based ultraviolet (UV) curable coating of B11-B17 is as shown in table 4.
Table 3
Table 4
Experiment shows, under identical photo curing condition, find that the double bond curing degree transformation efficiency of A3, A4, A5 water-based ultraviolet (UV) curable coating and B3, B4, B5 water-based ultraviolet (UV) curable coating is higher, and after placing 6 months, paint film yellowing degree is low.After placing 6 months, there is not xanthochromia in this paint film of two groups of A3 and B3, xanthochromia degree minimum substantially.1173 is preferably light trigger.A1, A2, A6, B1, B2 and B6 group xanthochromia is serious.Illustrate thus, light trigger 1173,2959 and 907 and have good interaction between urethane acrylate dispersoid, flow agent and defoamer, the paint film photo-curing rate of preparation is high, and paint film is placed the long period and also can not be turned yellow.
A7, A8 water-based ultraviolet (UV) curable coating double bond curing degree transformation efficiency is higher, and after placing 6 months, this paint film of two groups substantially xanthochromia does not occur.
Under identical photo curing condition, in A11-A17 water-based ultraviolet (UV) curable coating and B11-B17 water-based ultraviolet (UV) curable coating, the double bond conversion rate of water-based ultraviolet (UV) curable coating increases along with the increase of photoinitiator levels, after being increased to certain value, double bond turnover ratio engenders downtrending, and wherein A13, A14 and B14 group solidification rate is the fastest, double bond conversion rate is the highest, illustrates thus, when light trigger addition is 4 ~ 4.5%, effect is best.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a water-based ultraviolet (UV) curable coating, is characterized in that, meter comprises following component by weight:
Urethane acrylate dispersoid 80 ~ 95 parts;
Flow agent 0.1 ~ 2 part;
Defoamer 0.1 ~ 2 part;
Light trigger 2 ~ 8 parts;
Wherein, described urethane acrylate dispersoid is the first urethane acrylate dispersoid or the second urethane acrylate dispersoid;
Described first urethane acrylate dispersoid is the urethane acrylate 2869-1 of Bayer A.G;
Described second urethane acrylate dispersoid is prepared by the following method:
Under nitrogen protection, by isophorone diisocyanate at 70 ~ 80 DEG C of preheating 10 ~ 20min, then drip dibasic alcohol stirring reaction 2 ~ 3h, wherein, the mass ratio of described dibasic alcohol and isophorone diisocyanate is 20 ~ 68:18 ~ 35;
Then, be cooled to 55 ~ 65 DEG C after adding hydrophilic chain extender reaction 1 ~ 1.5h, wherein, the mass ratio of described hydrophilic chain extender and isophorone diisocyanate is 2 ~ 7:18 ~ 35;
Then, add alkene class end-capping reagent, stopper and catalyzer simultaneously, be cooled to 40 ~ 45 DEG C after insulation reaction 4 ~ 5h, wherein, the mass ratio of described alkene class end-capping reagent, described stopper, described catalyzer and isophorone diisocyanate is 3 ~ 15:0.003 ~ 0.08:0.1 ~ 1:18 ~ 35;
Then, add amine salt forming agent, regulate pH to be 7 ~ 8, obtain water white aqueous polyurethane acrylate performed polymer, wherein, the mass ratio of described amine salt forming agent and isophorone diisocyanate is 2 ~ 5:18 ~ 35;
Emulsifying agent is added in described aqueous polyurethane acrylate performed polymer, stir, then add deionized water in batches, described second urethane acrylate dispersoid is obtained after being uniformly dispersed, wherein, the mass ratio of described emulsifying agent and aqueous polyurethane acrylate performed polymer is 0.1 ~ 1:99 ~ 100, and the mass ratio of described aqueous polyurethane acrylate performed polymer and deionized water is 35 ~ 50:45 ~ 60.
2. water-based ultraviolet (UV) curable coating as claimed in claim 1, it is characterized in that, described dibasic alcohol is one or more the mixture in PCDL, polycaprolactone diols, polyether Glycols.
3. water-based ultraviolet (UV) curable coating as claimed in claim 1, it is characterized in that, described hydrophilic chain extender is one or more mixtures in dimethylol propionic acid, dimethylolpropionic acid.
4. water-based ultraviolet (UV) curable coating as claimed in claim 1, it is characterized in that, described alkene class end-capping reagent is one or more mixtures in hydroxyethyl methylacrylate, Hydroxyethyl acrylate, pentaerythritol triacrylate, Rocryl 410, Propylene glycol monoacrylate, described stopper is methoxyphenol, and described catalyzer is dibutyl tin laurate.
5. water-based ultraviolet (UV) curable coating as claimed in claim 1, it is characterized in that, described amine salt forming agent is triethylamine.
6. water-based ultraviolet (UV) curable coating as claimed in claim 1, it is characterized in that, described emulsifying agent is TX-10.
7. water-based ultraviolet (UV) curable coating as claimed in claim 1, it is characterized in that, described flow agent is BYK333 and BYK349 mixture, and wherein, the mass ratio of BYK333 and BYK349 is 1:2.
8. water-based ultraviolet (UV) curable coating as claimed in claim 1, it is characterized in that, described defoamer is BYK028.
9. water-based ultraviolet (UV) curable coating as claimed in claim 1, it is characterized in that, described light trigger is 2-hydroxy-2-methyl-phenyl-acetone-1,2-hydroxy-2-methyl-to hydroxyethyl ether phenyl-acetone-1 or 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl-1-acetone.
10. a preparation method for water-based ultraviolet (UV) curable coating, is characterized in that, comprises the following steps:
In urethane acrylate dispersoid, add flow agent, defoamer and light trigger successively, dispersed with stirring is even, then adopts 200 ~ 400 order filter-cloth filterings, obtains described water-based ultraviolet (UV) curable coating;
Wherein, described urethane acrylate dispersoid is the first urethane acrylate dispersoid or the second urethane acrylate dispersoid;
Described first urethane acrylate dispersoid is the urethane acrylate 2869-1 of Bayer A.G;
Described second urethane acrylate dispersoid is prepared by the following method:
Under nitrogen protection, by isophorone diisocyanate at 70 ~ 80 DEG C of preheating 10 ~ 20min, then drip dibasic alcohol stirring reaction 2 ~ 3h, wherein, the mass ratio of described dibasic alcohol and isophorone diisocyanate is 20 ~ 68:18 ~ 35;
Then, be cooled to 55 ~ 65 DEG C after adding hydrophilic chain extender reaction 1 ~ 1.5h, wherein, the mass ratio of described hydrophilic chain extender and isophorone diisocyanate is 2 ~ 7:18 ~ 35;
Then, add alkene class end-capping reagent, stopper and catalyzer simultaneously, be cooled to 40 ~ 45 DEG C after insulation reaction 4 ~ 5h, wherein, the mass ratio of described alkene class end-capping reagent, described stopper, described catalyzer and isophorone diisocyanate is 3 ~ 15:0.003 ~ 0.08:0.1 ~ 1:18 ~ 35;
Then, add amine salt forming agent, regulate pH to be 7 ~ 8, obtain water white aqueous polyurethane acrylate performed polymer, wherein, the mass ratio of described amine salt forming agent and isophorone diisocyanate is 2 ~ 5:18 ~ 35;
Emulsifying agent is added in described aqueous polyurethane acrylate performed polymer, stir, then add deionized water in batches, described second urethane acrylate dispersoid is obtained after being uniformly dispersed, wherein, the mass ratio of described emulsifying agent and aqueous polyurethane acrylate performed polymer is 0.1 ~ 1:99 ~ 100, and the mass ratio of described aqueous polyurethane acrylate performed polymer and deionized water is 35 ~ 50:45 ~ 60.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106752866A (en) * | 2016-12-09 | 2017-05-31 | 中物功能材料研究院有限公司 | Aqueous UV tinplates coating and preparation method thereof |
| CN106752868A (en) * | 2016-12-09 | 2017-05-31 | 中物功能材料研究院有限公司 | Aqueous UV tinplates coating and preparation method thereof |
| CN106752867A (en) * | 2016-12-09 | 2017-05-31 | 中物功能材料研究院有限公司 | Aqueous UV tinplates coating and preparation method thereof |
| CN112358806A (en) * | 2021-01-12 | 2021-02-12 | 广东大自然家居科技研究有限公司 | Modified coating for ceramic tile-like wood floor and preparation method thereof |
| CN113121987A (en) * | 2021-04-21 | 2021-07-16 | 李立 | Water-based 3D printing material and preparation method and application thereof |
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| CN1844182A (en) * | 2006-03-22 | 2006-10-11 | 中国科学技术大学 | Process for preparing ultraviolet curable aqueous polyurethane resin |
| CN101423677A (en) * | 2008-12-18 | 2009-05-06 | 江南大学 | Method for preparing transparent and heat insulating water ultraviolet curing coating |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1844182A (en) * | 2006-03-22 | 2006-10-11 | 中国科学技术大学 | Process for preparing ultraviolet curable aqueous polyurethane resin |
| CN101423677A (en) * | 2008-12-18 | 2009-05-06 | 江南大学 | Method for preparing transparent and heat insulating water ultraviolet curing coating |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106752866A (en) * | 2016-12-09 | 2017-05-31 | 中物功能材料研究院有限公司 | Aqueous UV tinplates coating and preparation method thereof |
| CN106752868A (en) * | 2016-12-09 | 2017-05-31 | 中物功能材料研究院有限公司 | Aqueous UV tinplates coating and preparation method thereof |
| CN106752867A (en) * | 2016-12-09 | 2017-05-31 | 中物功能材料研究院有限公司 | Aqueous UV tinplates coating and preparation method thereof |
| CN112358806A (en) * | 2021-01-12 | 2021-02-12 | 广东大自然家居科技研究有限公司 | Modified coating for ceramic tile-like wood floor and preparation method thereof |
| CN113121987A (en) * | 2021-04-21 | 2021-07-16 | 李立 | Water-based 3D printing material and preparation method and application thereof |
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