CN102643599A - UV (Ultraviolet)-thermoplastic resin composite laser aluminum-plated coating composition - Google Patents
UV (Ultraviolet)-thermoplastic resin composite laser aluminum-plated coating composition Download PDFInfo
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Abstract
The invention discloses a UV (Ultraviolet)-thermoplastic resin composite laser aluminum-plated coating composition. The coating composition comprises the following components in parts by weight: 20-80 parts of light-cured resin, 0-50 parts of thermoplastic resin, 1-30 parts of light initiator, 20-200 parts of diluting agent and 0-10 parts of auxiliary agent. Compared with the prior art, the UV-thermoplastic resin composite laser aluminum-plated coating composition can realize a groove with a mould pressing depth so that the formed laser pattern stereoscopic impression is strong; furthermore, the UV-thermoplastic resin composite laser aluminum-plated coating composition adopts light-cured cross-linking to form a film and the heat resistance of the coating is good; and a laser pattern is not easy to deform by heating in a use process so that the timeliness of a laser aluminum-plated film is long.
Description
Technical field
The present invention relates to a kind of composite citicall limited aluminium paint, relate in particular to a kind of UV-thermoplastic resin composite citicall limited aluminium paint compsn.
Background technology
PET citicall limited aluminium film relies on its functions peculiar property and the sense of outward appearance intensive metal, dazzling laser effect to occupy a tiny space at packaging field always, is widely used in novel housing material fields such as tobacco and wine, food, makeup, tealeaves, gift.The basic property of composite citicall limited aluminium paint is its tack and mold pressing effect, and tack comprises two portions: coating is to the sticking power of basement membrane (being generally the PET film), and aluminium coated is to adhesive force of coatings; The mold pressing effect is meant through mould pressing process and on coating, demonstrates the holographic laser effect.
Existing composite citicall limited aluminium paint is a solvent-based system, and in a large number with an organic solvent, volatile organic matter (VOCs) content height causes severe contamination to producing with environment for use on the one hand, also exists the problem that solvent cost is limited by the international oil price fluctuation on the other hand.In addition, because of containing solvent in the coating, need baking oven that solvent is dried during use, make the coating film forming, this process consumes mass energy; And UV coating has the environmental protection that is superior to solvent based coating and energy-conservation advantage has become extensive common recognition.
The solvent-borne type citicall limited aluminium paint is when making the holographic laser effect through mould pressing process; Coating is film forming; Adopt hot pressed technology to extrude laser effect at film forming coating patrix; On film forming coating, extrude very dark groove and be difficult to, so generally form the groove all more shallow (degree of depth is all at nano level) on the laser pattern coating.And now Along with people's to packing require increasingly highly, the very laser pattern of deep trench (degree of depth is a micron order) has appearred, the existing compound radium-shine coating of solvent-borne type can not satisfy production requirement.The existing PE of employing expects the alternative dark groove of conventional solvent type coating process mold pressing of pouring membrane process, but the laser pattern that adopts the making of PE material pouring membrane process is out of shape the effect that the back influences laser pattern because of thermo-labile yielding.
Summary of the invention
The objective of the invention is to overcome the deficiency of above-mentioned conventional solvent type composite citicall limited aluminium paint and the existence of PE material, a kind of UV-thermoplastic resin composite citicall limited aluminium paint compsn is provided.This UV-thermoplastic resin composite citicall limited aluminium paint compsn is because of adopting the mode film forming of photocuring; So mould pressing process can adopt mold pressing and film-forming to carry out simultaneously; Like this when mold pressing because of coating or liquid, the dark groove of mold pressing just can realize that the laser pattern stereoscopic sensation of formation is strong; In addition; This UV-thermoplastic resin composite citicall limited aluminium paint compsn adopts photocured cross-linked film forming; Coating heat resistance can be good, and in use laser pattern is difficult for temperature distortion, so UV-thermoplastic resin composite citicall limited aluminium paint is done the ageing length of citicall limited aluminium film.
The objective of the invention is to realize through following technical scheme:
The present invention relates to a kind of UV-thermoplastic resin composite citicall limited aluminium paint compsn, comprise following component and parts by weight:
Light-cured resin 20～80,
Thermoplastic resin 0～50,
Light trigger 1～30,
Thinner 20～200,
Auxiliary agent 0～10.
Preferably, comprise following component and parts by weight:
Light-cured resin 30～70,
Thermoplastic resin 0～30,
Light trigger 1～15,
Thinner 30～120,
Auxiliary agent 0～5.
Preferably, said light-cured resin is the light-cured resin that contains plural ethylene type unsaturated link(age) in the molecule.
Preferably, said thermoplastic resin is one or more in urethane resin, vinyl resin, cellulose ester resin, nitro-cotton resin, vinyl chloride-vinyl acetate resin, chlorinated polypropylene, petroleum resin, the Vinylite.
The light trigger of selecting for use in the UV-thermoplastic resin composite citicall limited aluminium paint of the present invention does not have special restriction.Preferably; Said light trigger is benzoin, benzoin alkyl oxide, acetophenones light trigger, anthraquinone photoinitiator, thioxanthone photoinitiator, ketal photoinitiator, organo-peroxide, mercaptan compound, Organohalogen compounds, Benzophenones light trigger, 2; 4; 6-trimethylbenzoyl diphenylphosphine oxide compound, two [2,6-two fluoro-3-(1H-pyrryl-1) phenyl] titanium luxuriant (Irgacure784), two (pentafluorophenyl group) titanium are luxuriant, in the anthraquinone/tertiary amine light initiation system, camphorquinone (claiming camphane spinach ketone CQ again)/tertiary amine light initiation system, 3-ketone group tonka bean camphor/tertiary amine light initiation system, 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholinyl acetone-1,2-benzyl-2-dimethyl amido-1-(4-morpholinyl phenyl)-butane-1-ketone one or more.
Further preferably, said benzoin alkyl oxide is one or more in benzoin methyl ether, benzoin ethyl ether, the benzoin isopropyl ether; Said acetophenones light trigger is a methyl phenyl ketone, 2,2-dimethoxy-2-phenyl methyl phenyl ketone, 2,2-diethoxy-2-phenyl methyl phenyl ketone, 1,1-dichloroacetophenone, N, one or more in the N-dimethyl amine benzoylformaldoxime; Said anthraquinone photoinitiator is one or more in 2-methylanthraquinone, 2-ethyl-anthraquinone, 2-tertiary butyl anthraquinone, the 1-chloroanthraquinone; Said thioxanthone photoinitiator is 2,4-dimethyl-thioxanthone, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2, one or more in the 4-di-isopropyl thioxanthone; Said ketal photoinitiator is one or both in methyl phenyl ketone dimethyl ketal, the benzyl dimethyl ketal; Said organo-peroxide is one or both in Lucidol, the dicumyl peroxide base; Said mercaptan compound is 2,4, one or more in 5-three aromatic base imidazoles diploids, hibon, 2-sulfenyl benzoglyoxaline, 2-sulfenyl benzoxazole, the 2-sulfurio benzo thiazole; Said Organohalogen compounds are 2,4, one or more in 6-three-s-triazine, tribromo-ethanol, the trisbromomethyl phenyl ketone; Said Benzophenones light trigger is a benzophenone, 4, one or both in 4 '-two diethylammonium amido UVNUL MS-40.
Preferably, said thinner is photopolymerization monomer or organic solvent.
Further preferably, said photopolymerization monomer is one or more in (methyl) propenoate of containing hydroxyl, simple function (methyl) propenoate, difunctionality (methyl) propenoate, multifunctional (methyl) propenoate, ethoxylation polyfunctional acrylic ester, the propoxylation polyfunctional acrylic ester.
Further preferably, said (methyl) propenoate that contains hydroxyl is one or more in (methyl) Hydroxyethyl acrylate, tetramethylolmethane three (methyl) propenoate, Dipentaerythritol five (methyl) propenoate; Said simple function (methyl) propenoate is one or more in (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) Bing Xisuandingzhi, (methyl) lauryl acrylate; Said difunctionality (methyl) propenoate is 1, two (methyl) propenoate, two of 6-pinakon contract/two (methyl) propenoate, two of tripropylene glycol contract/and in two (methyl) propenoate of triethylene Glycol, two (methyl) propenoate of ethoxyquin dihydroxyphenyl propane, two (methyl) propenoate of NSC 6366 diethoxy/propoxy-one or more; Said multifunctional (methyl) propenoate is one or more in trimethylolpropane tris (methyl) propenoate, tetramethylolmethane four (methyl) propenoate, Dipentaerythritol six (methyl) propenoate.
Further preferably, said organic solvent is one or more in ether solvent, esters solvent, ketones solvent, aromatic solvent, the oil series solvent.
Further preferably, said ether solvent is one or more in ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol list ether, the dipropylene glycol monobutyl ether; Said esters solvent is one or more in vinyl acetic monomer, N-BUTYL ACETATE, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetic ester, diethylene glycol ether acetate alone, diethylene glycol monobutyl ether acetic ester, propylene glycol monomethyl ether acetate, dihydroxypropane single-ether acetic ester, propylene glycol monobutyl ether acetic ester, dipropylene glycol monomethyl ether acetate, dipropylene glycol list ethyl ether acetate ester, the dipropylene glycol monobutyl ether acetate ester; Said ketones solvent is one or more in butanone, pimelinketone, the isophorone; Said aromatic solvent is one or more in toluene, YLENE, the durene; Said oil series solvent is one or more in petroleum naphtha, oxidation petroleum naphtha, the solvent naphtha.
Preferably, said auxiliary agent comprises one or more the mixing in flow agent, skimmer, stopper, the light-initiated auxiliary agent.
Further preferably, said light-initiated auxiliary agent is N, N-dimethyl amido TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M. ethyl ester, N, N-dimethyl amido TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M. isopentyl ester, amyl group-4-dimethyl amido benzoic ether, triethylamine or trolamine.
Compared with prior art, the present invention has following beneficial effect:
1, because of adopting the UV prescription, with it before traditional solvent-borne formulation compare, so the UV prescription can adopt less solvent or not contain solvent, can reduce solvent evaporates compare traditional solvent-borne formulation, the minimizing atmospheric pollution;
2, adopt UV to solidify, save the energy and quick, enhance productivity;
Temperature was low when 3, UV solidified, and the influence of base material heated distortion reduces;
4, UV-thermoplastic resin composite citicall limited aluminium paint is compared with solvent-borne type laser pattern that citicall limited aluminium paint is done, and gloss is high, stereoscopic sensation is strong, and not yielding, and yield rate is high;
5, compare before the solvent-borne type citicall limited aluminium paint can only mold pressing nano level depth groove laser pattern, UV-thermoplastic resin composite citicall limited aluminium paint can be done darker laser pattern groove, reaches the groove of the micron order degree of depth.
Embodiment
Below in conjunction with specific embodiment the present invention is elaborated.Following examples will help those skilled in the art further to understand the present invention, but not limit the present invention in any form.Should be pointed out that to those skilled in the art, under the prerequisite that does not break away from the present invention's design, can also make some distortion and improvement.These all belong to protection scope of the present invention.
Comparative Examples 1
This Comparative Examples provides a kind of solvent-borne type composite citicall limited aluminium paint compsn, and its preparation method comprises the steps:
(a) get the raw materials ready according to component shown in the table 1 and parts by weight;
(b) said feed composition is mixed, middling speed was disperseed 2 hours, filtered, and promptly got the solvent-borne type composite citicall limited aluminium paint.
Comparative Examples 2
This Comparative Examples is a PE material, and in order to as a comparison, its parts by weight are as shown in table 1.
Embodiment 1～5
Embodiment 1～5 provides UV-thermoplastic resin composite citicall limited aluminium paint compsn respectively, and feed composition and parts by weight that each compsn is corresponding are as shown in table 1;
Respectively that each embodiment is corresponding feed composition mixes by its parts by weight, and middling speed was disperseed 2 hours, filters, and promptly gets corresponding UV-thermoplastic resin composite citicall limited aluminium paint combination.
Table 1 feed composition and parts by weight
Embodiment 6, Performance Detection
The coating composition that respectively embodiment 1～5 and Comparative Examples 1 is made carries out Performance Detection, measures planeness, sticking power, the fastness of aluminizing, specimen page outward appearance, the heat resistance parameter of coating.
The method of concrete performance test item and correspondence is following:
One, planeness
Coating is coated on the good PET film of pre-treatment the coating planeness of visual specimen page with spread coating.
Testing method: visual observation test specimen page outward appearance.
Appraisal procedure: the specimen page smooth surface is smooth to be excellent, and air spots is sent out wrinkle for poor.
Two, sticking power
With spread coating coating is coated on the good PET film of pre-treatment, is compressed on coating to the pattern of mold pressing version during curing.Adopt the adhesive tape method that specimen page sticking power is tested.
Appraisal procedure: do not come off for excellent fully, have to come off on a small quantity, come off in a large number for poor for very.
Three, the fastness of aluminizing
With spread coating coating is coated on the good PET film of pre-treatment, is compressed on coating to the pattern of mold pressing version during curing, adopt vapour deposition method that aluminium lamination is plated on the coating.Adopt the adhesive tape method that specimen page sticking power is tested.
Appraisal procedure: aluminium coated does not come off for excellent fully, has to come off on a small quantity for very, comes off in a large number for poor.
Four, specimen page outward appearance
With spread coating coating is coated on the good PET film of pre-treatment, is compressed on coating to the pattern of mold pressing version during curing, adopt vapour deposition method that aluminium lamination is plated on the coating.
Testing method: visual observation test specimen page outward appearance.
Appraisal procedure: the specimen page picture on surface is complete full, and aluminium coated brightness is high, aberration is little.
Five, heatproof
With spread coating coating is coated on the good PET film of pre-treatment, is compressed on coating to the pattern of mold pressing version during curing.Specimen page is put under the mold pressing version rising moulded board temperature.
Appraisal procedure: the specimen page picture on surface is under moulded board, and the pattern how many coatings are temperature reach disappears.
Performance test results is as shown in table 2:
Table 2 Performance Detection situation
Can know by table 2; The UV-thermoplastic resin composite citicall limited aluminium paint compsn that embodiment 1～5 makes is compared with the solvent-borne type composite citicall limited aluminium paint compsn of Comparative Examples 1: the compsn planeness and the specimen page outward appearance of embodiment preparation all have improvement, and heat resistance has greatly improved; Compare with the PE material of Comparative Examples 2: planeness, sticking power, the fastness of aluminizing and specimen page outward appearance all have improvement, and heat resistance also has greatly improved.
Embodiment 7～11
Embodiment 7～11 provides UV-thermoplastic resin composite citicall limited aluminium paint compsn respectively, and corresponding feed composition and parts by weight are as shown in table 3; Respectively that each embodiment is corresponding feed composition mixes by its parts by weight, and middling speed was disperseed 2 hours, filters, and promptly gets corresponding UV-thermoplastic resin composite citicall limited aluminium paint compsn.
The coating composition that embodiment 7～11 makes all has good planeness, sticking power, the fastness of aluminizing, specimen page outward appearance and heat resistance.And, because of adopting the mode film forming of photocuring, so mould pressing process can adopt mold pressing and film-forming to carry out simultaneously, like this when mold pressing because of coating or liquid, the dark groove of mold pressing just can realize that the laser pattern stereoscopic sensation of formation is strong; In addition, this coating adopts photocured cross-linked film forming, and coating heat resistance can be good, and in use laser pattern is difficult for temperature distortion, so this coating is done the ageing length of citicall limited aluminium film.
Table 3 feed composition and parts by weight
Claims (13)
1. a UV-thermoplastic resin composite citicall limited aluminium paint compsn is characterized in that, comprises following component and parts by weight:
Light-cured resin 20～80,
Thermoplastic resin 0～50,
Light trigger 1～30,
Thinner 20～200,
Auxiliary agent 0～10.
2. UV-thermoplastic resin composite citicall limited aluminium paint compsn according to claim 1 is characterized in that, comprises following component and parts by weight:
Light-cured resin 30～70,
Thermoplastic resin 0～30,
Light trigger 1～15,
Thinner 30～120,
Auxiliary agent 0～5.
3. UV-thermoplastic resin composite citicall limited aluminium paint compsn according to claim 1 and 2 is characterized in that said light-cured resin is the light-cured resin that contains plural ethylene type unsaturated link(age) in the molecule.
4. UV-thermoplastic resin composite citicall limited aluminium paint compsn according to claim 1 and 2; It is characterized in that said thermoplastic resin is one or more the mixing in urethane resin, vinyl resin, cellulose ester resin, nitro-cotton resin, vinyl chloride-vinyl acetate resin, chlorinated polypropylene, petroleum resin, the Vinylite.
5. UV-thermoplastic resin composite citicall limited aluminium paint compsn according to claim 1 and 2; It is characterized in that; Said light trigger is benzoin, benzoin alkyl oxide, acetophenones light trigger, anthraquinone photoinitiator, thioxanthone photoinitiator, ketal photoinitiator, organo-peroxide, mercaptan compound, Organohalogen compounds, Benzophenones light trigger, 2; 4; 6-trimethylbenzoyl diphenylphosphine oxide compound, two [2,6-two fluoro-3-(1H-pyrryl-1) phenyl] titanium luxuriant, two (pentafluorophenyl group) titanium is luxuriant, one or more the mixing in the anthraquinone/tertiary amine light initiation system, camphorquinone/tertiary amine light initiation system, 3-ketone group tonka bean camphor/tertiary amine light initiation system, 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholinyl acetone-1,2-benzyl-2-dimethyl amido-1-(4-morpholinyl phenyl)-butane-1-ketone.
6. UV-thermoplastic resin composite citicall limited aluminium paint compsn according to claim 5 is characterized in that,
Said benzoin alkyl oxide is one or more the mixing in benzoin methyl ether, benzoin ethyl ether, the benzoin isopropyl ether;
Said acetophenones light trigger is a methyl phenyl ketone, 2,2-dimethoxy-2-phenyl methyl phenyl ketone, 2,2-diethoxy-2-phenyl methyl phenyl ketone, 1,1-dichloroacetophenone, N, the mixing of one or more in the N-dimethyl amine benzoylformaldoxime;
Said anthraquinone photoinitiator is one or more the mixing in 2-methylanthraquinone, 2-ethyl-anthraquinone, 2-tertiary butyl anthraquinone, the 1-chloroanthraquinone;
Said thioxanthone photoinitiator is 2,4-dimethyl-thioxanthone, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2, the mixing of one or more in the 4-di-isopropyl thioxanthone;
Said ketal photoinitiator is one or both the mixing in methyl phenyl ketone dimethyl ketal, the benzyl dimethyl ketal;
Said organo-peroxide is one or both the mixing in Lucidol, the dicumyl peroxide base;
Said mercaptan compound is 2,4, the mixing of one or more in 5-three aromatic base imidazoles diploids, hibon, 2-sulfenyl benzoglyoxaline, 2-sulfenyl benzoxazole, the 2-sulfurio benzo thiazole;
Said Organohalogen compounds are 2,4, the mixing of one or more in 6-three-s-triazine, tribromo-ethanol, the trisbromomethyl phenyl ketone;
Said Benzophenones light trigger is a benzophenone, 4, the mixing of one or both in 4 '-two diethylammonium amido UVNUL MS-40.
7. UV-thermoplastic resin composite citicall limited aluminium paint compsn according to claim 1 and 2 is characterized in that said thinner is photopolymerization monomer or organic solvent.
8. UV-thermoplastic resin composite citicall limited aluminium paint compsn according to claim 7; It is characterized in that said photopolymerization monomer is one or more the mixing in (methyl) propenoate of containing hydroxyl, simple function (methyl) propenoate, difunctionality (methyl) propenoate, multifunctional (methyl) propenoate, ethoxylation polyfunctional acrylic ester, the propoxylation polyfunctional acrylic ester.
9. UV-thermoplastic resin composite citicall limited aluminium paint compsn according to claim 8 is characterized in that,
Said (methyl) propenoate that contains hydroxyl is one or more in (methyl) Hydroxyethyl acrylate, tetramethylolmethane three (methyl) propenoate, Dipentaerythritol five (methyl) propenoate;
Said simple function (methyl) propenoate is one or more in (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) Bing Xisuandingzhi, (methyl) lauryl acrylate;
Said difunctionality (methyl) propenoate is 1, two (methyl) propenoate, two of 6-pinakon contract/two (methyl) propenoate, two of tripropylene glycol contract/and in two (methyl) propenoate of triethylene Glycol, two (methyl) propenoate of ethoxyquin dihydroxyphenyl propane, two (methyl) propenoate of NSC 6366 diethoxy/propoxy-one or more;
Said multifunctional (methyl) propenoate is one or more in trimethylolpropane tris (methyl) propenoate, tetramethylolmethane four (methyl) propenoate, Dipentaerythritol six (methyl) propenoate.
10. UV-thermoplastic resin composite citicall limited aluminium paint compsn according to claim 7 is characterized in that, said organic solvent is one or more the mixing in ether solvent, esters solvent, ketones solvent, aromatic solvent, the oil series solvent.
11. UV-thermoplastic resin composite citicall limited aluminium paint compsn according to claim 10 is characterized in that,
Said ether solvent is one or more in ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol list ether, the dipropylene glycol monobutyl ether;
Said esters solvent is one or more in vinyl acetic monomer, N-BUTYL ACETATE, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetic ester, diethylene glycol ether acetate alone, diethylene glycol monobutyl ether acetic ester, propylene glycol monomethyl ether acetate, dihydroxypropane single-ether acetic ester, propylene glycol monobutyl ether acetic ester, dipropylene glycol monomethyl ether acetate, dipropylene glycol list ethyl ether acetate ester, the dipropylene glycol monobutyl ether acetate ester;
Said ketones solvent is one or more in butanone, pimelinketone, the isophorone;
Said aromatic solvent is one or more in toluene, YLENE, the durene;
Said oil series solvent is one or more in petroleum naphtha, oxidation petroleum naphtha, the solvent naphtha.
12. UV-thermoplastic resin composite citicall limited aluminium paint compsn according to claim 1 and 2 is characterized in that said auxiliary agent is one or more in flow agent, skimmer, stopper, the light-initiated auxiliary agent.
13. UV-thermoplastic resin composite citicall limited aluminium paint compsn according to claim 12; It is characterized in that; Said light-initiated auxiliary agent is N; N-dimethyl amido TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M. ethyl ester, N, N-dimethyl amido TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M. isopentyl ester, amyl group-4-dimethyl amido benzoic ether, triethylamine or trolamine.
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| CN102167948A (en) * | 2011-02-25 | 2011-08-31 | 上海长润发涂料有限公司 | UV (ultraviolet) photo-cured acrylic resin composition |
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| CN105949966A (en) * | 2016-06-22 | 2016-09-21 | 常州瑞杰新材料科技股份有限公司 | Special UV paint for PP (polypropylene) substrates |
| CN111601795A (en) * | 2017-12-14 | 2020-08-28 | 意大利艾坚蒙树脂有限公司 | Water-soluble 3-coumarin ketones |
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| CN113321990A (en) * | 2021-06-22 | 2021-08-31 | 广东鑫皇冠新材料有限公司 | Ultraviolet curing coating and preparation method thereof |
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