CN102807814B - Nano silica-modified recoatable ultraviolet (UV) varnish used on plastic and preparation method for varnish - Google Patents
Nano silica-modified recoatable ultraviolet (UV) varnish used on plastic and preparation method for varnish Download PDFInfo
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- CN102807814B CN102807814B CN201210261376.9A CN201210261376A CN102807814B CN 102807814 B CN102807814 B CN 102807814B CN 201210261376 A CN201210261376 A CN 201210261376A CN 102807814 B CN102807814 B CN 102807814B
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- 229920003023 plastic Polymers 0.000 title claims abstract description 13
- 239000004033 plastic Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002966 varnish Substances 0.000 title abstract 6
- 239000011347 resin Substances 0.000 claims abstract description 49
- 229920005989 resin Polymers 0.000 claims abstract description 49
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000178 monomer Substances 0.000 claims abstract description 32
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229920002635 polyurethane Polymers 0.000 claims abstract description 26
- 239000004814 polyurethane Substances 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 13
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 13
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 13
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 19
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000654 additive Substances 0.000 claims description 16
- 230000000996 additive effect Effects 0.000 claims description 16
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 claims description 16
- 150000002148 esters Chemical class 0.000 claims description 14
- 239000003921 oil Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 239000005543 nano-size silicon particle Substances 0.000 claims description 13
- 239000004568 cement Substances 0.000 claims description 11
- 125000000524 functional group Chemical group 0.000 claims description 7
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical group C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 3
- 238000003556 assay Methods 0.000 claims description 3
- 238000009288 screen filtration Methods 0.000 claims description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JZMPIUODFXBXSC-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.CCOC(N)=O JZMPIUODFXBXSC-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 239000006223 plastic coating Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Cosmetics (AREA)
Abstract
The invention provides nano silica-modified recoatable ultraviolet (UV) varnish used on plastic and a preparation method for the varnish. The varnish comprises the following components in percentage by weight: 5 to 10 percent of hexa-functional acrylic polyurethane UV resin, 10 to 15 percent of trifunctional acrylic polyurethane UV resin, 15 to 20 percent of difunctional acrylic polyurethane UV resin, 10 to 15 percent of trifunctional monomer, 15 to 20 percent of difunctional monomer, 10 to 15 percent of thermoplastic acrylic resin, 2 to 2.5 percent of fluorine-modified acrylate leveling agent, 3 to 3.5 percent of photoinitiator, 0.5 to 1 percent of nano silica aid and 5 to 6 percent of methyl ethyl ketone. The varnish can be directly reworked without being primed in the using process.
Description
Technical field
The present invention relates to gloss oil technical field, particularly can recoat UV (ultraviolet) gloss oil and preparation method with nano-silicon dioxide modified on a kind of plastic cement.
Background technology
UV coating is environment-friendly type high performance coating popular after 2005, because product specification is high, generally do not do over again, through in a few years applying, popularize use in an all-round way, use range expands, cost also declines, many clients start to raise an objection to can not doing over again of UV, common plastic coating before just can do over again after having defective products directly to polish to respray, UV coating due to technical development initial stage direction be high-end, do not consider to do over again, more existing technical side and production firm reach by spraying one deck water of doing over again the performance that can do over again, but still do not reach the requirement of directly doing over again, due to the recoat difficulty of UV coating, qualification rate is not high, puzzlement is brought to production, waste a large amount of manpower and materials.
Summary of the invention
The invention provides on a kind of plastic cement with nano-silicon dioxide modified can recoat UV gloss oil and preparation method, directly do over again, without bottoming.
To achieve these goals, the invention provides following technical scheme:
On plastic cement with nano-silicon dioxide modified can a recoat UV gloss oil, it comprises:
Six functional acrylic urethane UV resins 5 ~ 10%; Trifunctional acroleic acid polyurethane UV resin 10 ~ 15%; Two functional group acroleic acid polyurethane UV resins 15 ~ 20%; Trifunctional monomer 10 ~ 15%; Two monomers 15 ~ 20%; Thermoplastic acrylic resin 10 ~ 15%; Fluorin modified crylic acid ester flow agent 2 ~ 2.5%; Light trigger 3 ~ 3.5%; Nanometer titanium dioxide silicon additive 0.5 ~ 1%; Methylethylketone 5 ~ 6%.
The present invention also provide on a kind of above-mentioned plastic cement with nano-silicon dioxide modified can recoat UV gloss oil preparation method, it is characterized in that, comprise step:
First by six functional acrylic urethane UV resins and trifunctional acroleic acid polyurethane UV resin and two functional acrylic urethane UV resins, drop in stirrer, drop into the pre-dispersed work in-process of nanometer titanium dioxide silicon additive again, stir 10 ~ 15 minutes under the speed of 1200 ~ 1500 revs/min, to stirring, drop into trifunctional monomer and two monomers again, then stir 10 ~ 15 minutes under the speed of 1200 ~ 1500 revs/min, to stirring, reduce rotating speed to 800 rev/min again, add thermoplastic acrylic resin, fluorin modified crylic acid ester flow agent, stir 5 minutes to even, finally add in advance with the light trigger that methylethylketone dissolves, 5 minutes are stirred to even by the speed of 800 revs/min.Stop stirring, pack by 500 order filter screen filtration after the assay was approved.
By implementing above technical scheme, there is following technique effect: on plastic cement provided by the invention with nano-silicon dioxide modified can recoat UV gloss oil, six official's resin contents can be reduced, make full use of the lower shrinkage of trifunctional acroleic acid polyurethane UV resin and two functional acrylic urethane UV resins, high adhesive force, snappiness, low cross-linking characteristic, improve the adherence of interlayer recoat, cancel the silicone based flow agents such as conventional BYK333, use fluorin modified crylic acid ester flow agent instead, eliminate the impact that recoat that silicone based flow agent brings is bad, utilize the high transparent of nano silicon, high surface, high voidage, high fillibility, high-wearing feature, reduce film shrinkability, improve hardness of film and resistance to marring, and provide crosslinked group for recoat, utilize the low viscosity of trifunctional monomer and two monomers, rapid reaction characteristic, improve film fullness ratio, setting rate, utilize the not bridging property of thermoplastic acrylic resin, recoat is provided to adhere to, and select low viscosity, low-molecular-weight UV bottom paint resin, low viscosity lower molecular weight provides levelling gloss, fullness ratio, UV bottom paint resin character provides the sticking power of UV recoat.When not reducing hardness, need not spray conventional water of doing over again, spraying of can directly doing over again, decreases production process, improves the yield of finished product.
Embodiment
Technical scheme for a better understanding of the present invention, is described below in detail embodiment provided by the invention.
The embodiment of the present invention provide on a kind of plastic cement with nano-silicon dioxide modified can recoat UV gloss oil, it is characterized in that, comprising:
Six functional acrylic urethane UV resins 5 ~ 10%; Trifunctional acroleic acid polyurethane UV resin 10 ~ 15%; Two functional group acroleic acid polyurethane UV resins 15 ~ 20%; Trifunctional monomer 10 ~ 15%; Two monomers 15 ~ 20%; Thermoplastic acrylic resin 10 ~ 15%, fluorin modified crylic acid ester flow agent 2 ~ 2.5%; Light trigger 3 ~ 3.5%; Nanometer titanium dioxide silicon additive 0.5 ~ 1%; Methylethylketone 5 ~ 6%.This six functional acrylics urethane UV resin is aliphatic polyurethane six acrylate, trifunctional acroleic acid polyurethane UV resin is aliphatic polyurethane triacrylate, two functional group's acroleic acid polyurethane UV resins are aliphatic urethane diacrylate, and this trifunctional monomer is: TMPTA (Viscoat 295); This two monomer is: HDDA (1,6 hexanediol diacrylate); Light trigger is 1-hydroxy-cyciohexyl benzophenone; Nanometer titanium dioxide silicon additive is: aerosil, and thermoplastic acrylic resin is the low viscous UV bottom paint resin of small-molecular-weight; Fluorin modified crylic acid ester flow agent is: fluorine richness polyacrylic ester.
Embodiment 1: six functional acrylic urethane UV resin 5%; Trifunctional acroleic acid polyurethane UV resin 15%; Two functional group acroleic acid polyurethane UV resins 20%; Trifunctional monomer 15%; Two monomers 20%; Thermoplastic acrylic resin 13.5% fluorin modified crylic acid ester flow agent 2%; Light trigger 3%; Nanometer titanium dioxide silicon additive 0.5%; Methylethylketone 6%.
Embodiment 2: six functional acrylic urethane UV resin 7.5%; Trifunctional acroleic acid polyurethane UV resin 15%; Two functional group acroleic acid polyurethane UV resins 20%; Trifunctional monomer 15%; Two monomers 20%; Thermoplastic acrylic resin 10%; Fluorin modified crylic acid ester flow agent 2.5%; Light trigger 3.5%; Nanometer titanium dioxide silicon additive 0.5%; Methylethylketone 6%.
Embodiment 3: six functional acrylic urethane UV resin 10%; Trifunctional acroleic acid polyurethane UV resin 10%; Two functional group acroleic acid polyurethane UV resins 20%; Trifunctional monomer 15%; Two monomers 19%; Thermoplastic acrylic resin 15%; Fluorin modified crylic acid ester flow agent 2%; Light trigger 3%; Nanometer titanium dioxide silicon additive 1%; Methylethylketone 5%.
Above three formulas all have good recoatability.
On this plastic cement with nano-silicon dioxide modified can recoat UV gloss oil preparation method:
First by six functional acrylic urethane UV resins and trifunctional acroleic acid polyurethane UV resin and two functional acrylic urethane UV resins, drop in stirrer, drop into the pre-dispersed work in-process of nanometer titanium dioxide silicon additive again, stir 10 ~ 15 minutes under the speed of 1200 ~ 1500 revs/min, to stirring, drop into trifunctional monomer and two monomers again, then stir 10 ~ 15 minutes under the speed of 1200 ~ 1500 revs/min, to stirring, reduce rotating speed to 800 rev/min again, add thermoplastic acrylic resin, fluorin modified crylic acid ester flow agent, stir 5 minutes to even, finally add in advance with the light trigger that methylethylketone dissolves, 5 minutes are stirred to even by the speed of 800 revs/min, stop stirring, pack by 500 order filter screen filtration after the assay was approved.In the present embodiment, after adding light trigger, palpus lucifuge, prevents from seeing that light local produces slight curing cross-linked, causes quality problems.
In the above-described embodiments, nanometer titanium dioxide silicon additive is carried out pre-dispersed, due to nanometer titanium dioxide silicon additive high surface, high voidage, can not play a role by General Decentralized method, we adopt two monomers 15% and nanometer titanium dioxide silicon additive 1% in formula to stir 20 ~ 30 minutes under the condition of high speed 3000 revs/min, , find through experiment, when rotating speed is below 3000 revs/min, nanometer titanium dioxide silicon additive can not well disperse, more than 3000 revs/min, the two just can must be made to mix completely, abundant dispersion, then grind 3 ~ 4 times on three-roller, reach below 10um to fineness just can use, nanometer titanium dioxide silicon additive is made to reach nano-scale dispersion state, give full play to the special-effect of nanometer titanium dioxide silicon additive under nano level: high transparent, high surface, high voidage, high fillibility, high-wearing feature.
In the above-described embodiments, because general UV gloss oil all adopts organosilicon flow agent, as BYK333 etc., effective, dosage is few, generally adds 0.5% and just can reach good levelling effect, but exist can not the shortcoming of recoat.And with the flow agent of common non-organic silicon class, can not reach and be satisfied with levelling effect, screen by experiment, levelling problem can be solved with a kind of special fluorin modified crylic acid ester flow agent, dosage needs more than 2%, and cost comparatively organosilicon flow agent is slightly high, but on recoat without impact.
In the above-described embodiments, six official's resins and trifunctional acroleic acid polyurethane UV resin and two functional acrylic urethane UV resins, three official's monomers, the rational proportion of two official's monomers, six official's resin ratio are too high, during solidification, cross-linking density is too high, hardness is too high, and recoat effect is bad, and six official's resin ratio are too low, during solidification, cross-linking density is too low, and hardness is inadequate; Trifunctional acroleic acid polyurethane UV resin and two functional acrylic urethane UV resins have low viscosity, lower shrinkage, and snappiness is good, high adhesive force, high fullness ratio, intermediate density crosslinking feature, can improve the adherence of interlayer recoat, three officials, two official's monomers reduce system viscosity, improve rate of crosslinking, hardness of film, at the bottom of UV, thermoplastic acrylic resin provides recoatability, through test of many times, when aforementioned proportion, there is rational over-all properties, and do not affect recoatability.
To sum up, 5 ~ 10% are down to by conventional 20 ~ 25% by reducing by six official's resin contents, make full use of the lower shrinkage of trifunctional acroleic acid polyurethane UV resin and two functional acrylic urethane UV resins, high adhesive force, snappiness, low cross-linking characteristic, improve the adherence of interlayer recoat, cancel the silicone based flow agents such as conventional BYK333, select fluorin modified crylic acid ester flow agent, eliminate the impact that recoat that silicone based flow agent brings is bad, utilize the high transparent of nano silicon, high surface, high voidage, high fillibility, high-wearing feature, reduce film shrinkability, improve hardness of film and resistance to marring, and provide crosslinked group for recoat, utilize trifunctional monomer and two monomer's rapid reaction characteristics, improve film setting rate, thermoplastic acrylic resin at the bottom of UV is utilized to provide recoatability, reach the UV gloss oil that recoat is effective.
A kind of the plastic cement above embodiment of the present invention provided can recoat UV gloss oil and preparation method be described in detail with nano-silicon dioxide modified, for one of ordinary skill in the art, according to the thought of the embodiment of the present invention, all will change in specific embodiments and applications, in sum, this description should not be construed as limitation of the present invention.
Claims (1)
1. on plastic cement with nano-silicon dioxide modified can a recoat UV gloss oil, it is characterized in that, comprising:
Six functional acrylic urethane UV resins 5 ~ 10%; Trifunctional acroleic acid polyurethane UV resin 10 ~ 15%; Two functional group acroleic acid polyurethane UV resins 15 ~ 20%; Trifunctional monomer 10 ~ 15%; Two monomers 15 ~ 20%; Thermoplastic acrylic resin 10 ~ 15%; Fluorin modified crylic acid ester flow agent 2 ~ 2.5%; Light trigger 3 ~ 3.5%; Nanometer titanium dioxide silicon additive 0.5 ~ 1%; Methylethylketone 5 ~ 6%, wherein, described trifunctional monomer is Viscoat 295, two monomers are 1,6 hexanediol diacrylate.
2. as claimed in claim 1 on plastic cement with nano-silicon dioxide modified can a recoat UV gloss oil preparation method, it is characterized in that, comprise step:
First by six functional acrylic urethane UV resins and trifunctional acroleic acid polyurethane UV resin and two functional acrylic urethane UV resins, drop in stirrer, drop into the pre-dispersed work in-process of nanometer titanium dioxide silicon additive again, stir 10 ~ 15 minutes under the speed of 1200 ~ 1500 revs/min, to stirring, drop into trifunctional monomer and two monomers again, then stir 10 ~ 15 minutes under the speed of 1200 ~ 1500 revs/min, to stirring, reduce rotating speed to 800 rev/min again, add fluorin modified crylic acid ester flow agent, stir 5 minutes to even, finally add in advance with the light trigger that methylethylketone dissolves, 5 minutes are stirred to even by the speed of 800 revs/min, stop stirring, pack by 500 order filter screen filtration after the assay was approved.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210261376.9A CN102807814B (en) | 2012-07-26 | 2012-07-26 | Nano silica-modified recoatable ultraviolet (UV) varnish used on plastic and preparation method for varnish |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210261376.9A CN102807814B (en) | 2012-07-26 | 2012-07-26 | Nano silica-modified recoatable ultraviolet (UV) varnish used on plastic and preparation method for varnish |
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| Publication Number | Publication Date |
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| CN102807814A CN102807814A (en) | 2012-12-05 |
| CN102807814B true CN102807814B (en) | 2015-04-08 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788860B (en) * | 2014-01-15 | 2016-03-30 | 中山永辉化工有限公司 | One can recoat plastic cement UV radiation curable coating and production method and using method |
| CN106957597B (en) * | 2017-04-17 | 2020-03-24 | 深圳市美丽华油墨涂料有限公司 | UV curing coating and preparation method and application thereof |
| CN107151527B (en) * | 2017-05-19 | 2020-03-24 | 上海绘兰材料科技有限公司 | Acrylate resin composition for optical film back coating, optical film back coating and preparation method thereof |
| CN113683911B (en) * | 2021-08-23 | 2022-09-27 | 昆山大世界油墨涂料有限公司 | Ultraviolet light hardening type matte gloss oil capable of being subjected to plastic absorption and preparation method and application thereof |
| CN115895424B (en) * | 2022-12-05 | 2023-10-24 | 澳达树熊涂料(惠州)有限公司 | Solvent-free UV-LED cured transparent adhesive coating and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1557882A (en) * | 2004-01-14 | 2004-12-29 | 惠州市华阳化工有限公司 | Ultraviolet cured paint |
| WO2005066287A1 (en) * | 2003-12-23 | 2005-07-21 | General Electric Company | Uv curable coating compositions and uses thereof |
| CN101760110A (en) * | 2010-02-11 | 2010-06-30 | 南京海泰纳米材料有限公司 | Ultraviolet curing nano transparent heat-insulation composite coating |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005066287A1 (en) * | 2003-12-23 | 2005-07-21 | General Electric Company | Uv curable coating compositions and uses thereof |
| CN1898341A (en) * | 2003-12-23 | 2007-01-17 | 通用电气公司 | Uv curable coating compositions and uses thereof |
| CN1557882A (en) * | 2004-01-14 | 2004-12-29 | 惠州市华阳化工有限公司 | Ultraviolet cured paint |
| CN101760110A (en) * | 2010-02-11 | 2010-06-30 | 南京海泰纳米材料有限公司 | Ultraviolet curing nano transparent heat-insulation composite coating |
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