CN101864204B - Dedicated high-performance primer of ultraviolet-curing vacuum coating for reflector of automobile lamps - Google Patents
Dedicated high-performance primer of ultraviolet-curing vacuum coating for reflector of automobile lamps Download PDFInfo
- Publication number
- CN101864204B CN101864204B CN201010195657XA CN201010195657A CN101864204B CN 101864204 B CN101864204 B CN 101864204B CN 201010195657X A CN201010195657X A CN 201010195657XA CN 201010195657 A CN201010195657 A CN 201010195657A CN 101864204 B CN101864204 B CN 101864204B
- Authority
- CN
- China
- Prior art keywords
- acrylate
- resin
- priming paint
- paint according
- ultraviolet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000001771 vacuum deposition Methods 0.000 title claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 39
- 229920005989 resin Polymers 0.000 claims abstract description 39
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 229920001577 copolymer Polymers 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 19
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 17
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- -1 alkoxide acrylate Chemical class 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- 239000003973 paint Substances 0.000 claims description 14
- 230000037452 priming Effects 0.000 claims description 14
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 13
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 13
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000011159 matrix material Substances 0.000 claims description 11
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 10
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 6
- 239000012965 benzophenone Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 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 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 6
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 5
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 5
- SSOONFBDIYMPEU-UHFFFAOYSA-N [3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COCC(CO)(CO)COC(=O)C=C SSOONFBDIYMPEU-UHFFFAOYSA-N 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 4
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 3
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 3
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229940043232 butyl acetate Drugs 0.000 claims description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 2
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 claims description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 claims description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 2
- VFZKVQVQOMDJEG-UHFFFAOYSA-N 2-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(=O)C=C VFZKVQVQOMDJEG-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 229940022682 acetone Drugs 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical group C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 2
- ZOJPTQRKWVDKTP-UHFFFAOYSA-N decane methanol prop-2-enoic acid Chemical compound C(C=C)(=O)O.C(C=C)(=O)O.CO.CO.CCCCCCCCCC ZOJPTQRKWVDKTP-UHFFFAOYSA-N 0.000 claims description 2
- 238000009396 hybridization Methods 0.000 claims description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 2
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229940093499 ethyl acetate Drugs 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 12
- 238000000576 coating method Methods 0.000 abstract description 12
- 238000001723 curing Methods 0.000 abstract description 11
- 238000005187 foaming Methods 0.000 abstract description 3
- 238000000016 photochemical curing Methods 0.000 abstract description 3
- 238000002203 pretreatment Methods 0.000 abstract description 3
- 239000004412 Bulk moulding compound Substances 0.000 abstract 2
- 239000003085 diluting agent Substances 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 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 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- SORGEQQSQGNZFI-UHFFFAOYSA-N [azido(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(N=[N+]=[N-])OC1=CC=CC=C1 SORGEQQSQGNZFI-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000206 moulding compound Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention discloses dedicated high-performance primer of an ultraviolet-curing vacuum coating for a reflector of automobile lamps. The primer comprises the following components by percentage: 40% to 80% of base resin, 8% to 50% of auxiliary resin, 10% to 40% of active diluents, 0.5% to 10% of photoinitiator, 0.05% to 8% of promoter and 0% to 50% of solvent. The invention further discloses a novel photo-curing copolymer serving as the base resin for the UV (ultraviolet) primer before the automobile lamp is coated with film. The UV coating prepared from the base resin can be directly sprayed and photo-cured needing no pre-treatment of BMC (bulk molding compound) substrates and the coated film has the advantages of good adhesion and high resistance to high temperature, thus preventing a reflector surface formed by vacuum aluminization from emitting chromatic light and foaming after being baked at 240 DEG C for 2 hours.
Description
Technical field
The invention belongs to the coating field of new, be specifically related to the special-purpose primer of ultraviolet-curing vacuum coating of a kind of reflector of automobile lamps.
Background technology
The automobile front speculum adopts glass fiber reinforcement unsaturated polyester moulding compound (BMC) injection moulding mostly, for obtaining good specular reflection effect, carry out vacuum aluminum-coated before, need spraying one deck varnish on the BMC base material earlier, the confining surface pore obtains smooth, flat surface.Before 2006, this class varnish of domestic use all is solvent-borne type high-temperature baking baking vanish, but this baking vanish is longer set time, and production efficiency is low, energy consumption is high, and equipment drops into higher.Ultraviolet light polymerization (UV) coating is because of film performance excellence, production efficiency height, energy-saving and environmental protection, economic dispatch advantage, and America and Europe, Japan etc. are incorporated into it in the automobile speculum manufacture craft.At present, domestic many car light manufacturing concern has begun to attempt this technology, but this class import UV coating price costliness.Therefore, car light manufacturing concern presses for domestic enterprise and produces similar UV coating.And this kind UV coating key point be select BMC had adhere to, can resistant to elevated temperatures resin, do not see the report that associated resin is arranged in the documents and materials at present.
Summary of the invention
The purpose of this invention is to provide the special-purpose primer of ultraviolet-curing vacuum coating of a kind of high-performing car lamp reflector, this UV coating does not need the BMC base material is carried out pre-treatment, directly sprays posterior photocuring, gained film adhesive excellence, resistance to elevated temperatures is good, toasts phenomenons such as can not occurring sending out color foaming in 2 hours down in 240 ℃ behind the vacuum aluminum-coated formation mirror surface.
Another object of the present invention provides a kind of novel photocureable polymer, its as vehicle lamp coating before with the matrix resin of UV priming paint, can make UV coating have the performance of above-mentioned excellence.
Purpose of the present invention can reach by following measure:
The special-purpose primer of ultraviolet-curing vacuum coating of a kind of high-performing car lamp reflector, the composition of this priming paint and quality proportioning are as follows:
Matrix resin 40～80%, preferred 50～60%,
Assisted resin 8～50%, preferred 8～20%,
Reactive thinner 10～40%, preferred 10～25%,
Light trigger 0.5～10%, preferred 1～5%,
Auxiliary agent 0.05～8%, preferred 0.05～1%,
Solvent 0～50%, preferred 1～15%
Above-mentioned each component sum is 100%.
Wherein said matrix resin is for being monomer polymerization and by the acrylic acid-grafted polymkeric substance that forms with isobornyl methacrylate, butyl acrylate, Hydroxyethyl acrylate and glycidyl methacrylate.
The preparation method of matrix resin is: with isobornyl methacrylate, butyl acrylate, Hydroxyethyl acrylate and glycidyl methacrylate is monomer, with the Diisopropyl azodicarboxylate is initiator, synthetic segmented copolymer under solution polymerization, and then with acrylic acid-grafted on it.Wherein solution polymerization temperature is 75～95 ℃, and solution polymerization solvent is a toluene; The graft reaction temperature is 90～100 ℃, also adds catalyzer tetramethyl ammonium chloride and MEHQ during graft reaction.
The mol ratio of each monomer isobornyl methacrylate, butyl acrylate, Hydroxyethyl acrylate and glycidyl methacrylate is 13～8: 5～8 in the matrix resin: 1～5: 1, and the mol ratio of vinylformic acid and glycidyl methacrylate is 0.8～1.2: 1; The weight-average molecular weight of matrix resin is 10000～100000, and is preferred 10000～50000, more preferably 10000～40000.
At least a in the urethane acrylate of the optional urethane acrylate of described assisted resin, epoxy acrylate, acrylic acid oligomer ester, silicon modification, the fluorine-silicon modified acrylic ester oligomer.
Described reactive thinner is Hydroxyethyl acrylate (HEA), hydroxyethyl methylacrylate (HEMA), isobornyl acrylate (IBOA), propylene glycol diacrylate (DPGDA), 1,6 hexanediol diacrylate (HDDA), tricyclic decane dimethanol diacrylate (DCPDA), tripropylene glycol diacrylate (TPGDA), Viscoat 295 (TMPTA), three (2-hydroxyethyl) tricarbimide triacrylates (THEICTA), tetramethylol methane tetraacrylate (PETA), Dipentaerythritol five acrylate (DPPA), dipentaerythritol acrylate (DPHA), the alkoxide acrylate, at least a in the inorganic-organic hybridization material.
Described light trigger is 1-hydroxyl-cyclohexyl-phenyl ketone (Irgacure 184), 2-hydroxy-2-methyl-1-phenyl-1-acetone (Darocur 1173), 2-methyl isophthalic acid-(4-(methylthio group) phenyl)-2-morpholinyl-1-acetone (Irgacure 907), 2; 4, at least a in 6-trimethylbenzoyl-diphenyl phosphine oxide (TPO), benzophenone (BP), isopropyl thioxanthone (ITX), benzophenone (BP), the reactive amines.
Described auxiliary agent is a flow agent, can be selected from: at least a in polydimethylsiloxane, fluorine modified polyorganosiloxane, polyether-modified polysiloxane copolymer, polyester-modified polysiloxanes multipolymer, (methyl) acrylic polymer, the fluorin modified crylic acid ester.
At least a in the optional ethyl acetate of described solvent, propyl acetate, butylacetate, acetone, butanone, methyl iso-butyl ketone (MIBK), pimelinketone, diisobutyl ketone, toluene, dimethylbenzene, methyl alcohol, ethanol, propyl alcohol, isopropylcarbinol, ethylene glycol ethyl ether, butyl glycol ether, ethyl cellosolve acetate, propylene glycol monomethyl ether, the methylcarbonate.
A key of the present invention is to synthesize a kind of novel block photocureable polymer (to be called for short IBHG, synthetic route is seen formula 1), as the main resin of speculum with priming paint, it is the special-purpose primer of ultraviolet-curing vacuum coating resin of high-performing car lamp reflector, this resin is with isobornyl methacrylate, butyl acrylate, Hydroxyethyl acrylate and glycidyl methacrylate are monomer polymerization and by the acrylic acid-grafted polymkeric substance that forms, each monomer isobornyl methacrylate wherein, butyl acrylate, the mol ratio of Hydroxyethyl acrylate and glycidyl methacrylate is 13～8: 5～8: 1～5: 1, and the mol ratio of vinylformic acid and glycidyl methacrylate is 0.8～1.2: 1; The weight-average molecular weight of this resin is 10000～100000.
This resin polarity is very low, can be well attached on the BMC material, and resistance to elevated temperatures is fabulous, and its heat decomposition temperature is more than 300 ℃.This block polymer gets by the radical polymerization of several function monomers, and wherein, isobornyl methacrylate (IBOMA) gives resin low polarity, by having ring-type thereon, can improve the hardness and the high thermal resistance of resin again; Butyl acrylate (BA) is the snappiness that is used for regulating resin; Hydroxyethyl acrylate (HEA) polarity is higher, strengthens adhering to of resin and vacuum-coating; Glycidyl methacrylate (GMA) provide active site, makes vinylformic acid (AA) grafting on it, the function of giving resin ultraviolet light curable.Behind each monomer polymerization and resin on the basis of having given full play to each advantage, further make by the UV coating that with IBHG is matrix resin to have more excellent performance.
The synthetic method of IBHG resin is as follows: resin synthesizes in the reaction vessel that agitator, reflux exchanger, constant pressure funnel and thermometer are housed and carries out, and feeds nitrogen simultaneously, avoids the oxygen resistance.Reaction vessel is placed water bath with thermostatic control, add toluene, be heated to the required temperature of polyreaction as solvent.Then IBOMA, BA, HEA, GMA monomer and AIBN initiator are mixed to join in the constant pressure funnel slow being added in the reaction vessel.React for some time again after adding, make the monomer primitive reaction complete.Get the AA of or close mole number identical again, add tetramethyl ammonium chloride, MEHQ, then mixed solution is joined in the good multipolymer of above-mentioned reaction, at a certain temperature reaction respectively as catalyzer and stopper with GMA.
Adopt IBHG resin UV coating prepared of the present invention, adhere to have well on the base material BMC in difficulty and adhere to, do not need the BMC base material is carried out pre-treatment, directly sprays posterior photocuring, gained film adhesive excellence, resistance to elevated temperatures is good, toasts phenomenons such as can not occurring sending out color foaming in 2 hours down in 240 ℃ behind the vacuum aluminum-coated formation mirror surface.
Embodiment
With specific examples the present invention is further elaborated below, only is used for explanation, do not limit scope of invention.
1, the IBHG resin is synthetic
Get 222.3gIBOMA, 88.4gBA, 34.8gHEA and 14.2gGMA respectively, add the 5.4g Diisopropyl azodicarboxylate, transfer in the constant pressure funnel after mixing as initiator.Take by weighing 144g toluene and join in the four-hole boiling flask, be placed in 85 ℃ of water-baths, assembling condensation, whipping appts, logical nitrogen is heated to 85 ℃, under agitation drips of solution in the constant pressure funnel is added in the four-hole boiling flask, treat drips of solution add after insulation reaction 3h again.Get 3.6g vinylformic acid, 0.036g tetramethyl ammonium chloride, the mixing of 0.018g MEHQ again, use the 15g acetic acid ethyl dissolution, join in the four-hole boiling flask, react 2.5h down at 95 ℃.Final product IBHG-I detects its performance after filtering, and acid number is 7.4mgKOH/g, and weight-average molecular weight is 24510.
Get 212.5gIBOMA, 85.3gBA, 36.8gHEA and 14.2gGMA respectively, add the 5.4g Diisopropyl azodicarboxylate, transfer in the constant pressure funnel after mixing as initiator.Take by weighing 144g toluene and join in the four-hole boiling flask, be placed in 87 ℃ of water-baths, assembling condensation, whipping appts, logical nitrogen is heated to 87 ℃, under agitation drips of solution in the constant pressure funnel is added in the four-hole boiling flask, treat drips of solution add after insulation reaction 3h again.Get 3.9g vinylformic acid, 0.036g tetramethyl ammonium chloride, the mixing of 0.018g MEHQ again, use the 15g acetic acid ethyl dissolution, join in the four-hole boiling flask, react 2.5h down at 96 ℃.Final product IBHG-II detects its performance after filtering, and acid number is 7.5mgKOH/g, and weight-average molecular weight is 26620.
2, primer base
Embodiment 1
The mass percent prescription of the special-purpose primer of ultraviolet-curing vacuum coating of a kind of reflector of automobile lamps: IBHG-I 60%, phenolic aldehyde epoxy acrylate 10%, and TMPTA 20%, DPHA 5%, Irgacure 1842%, flow agent polydimethylsiloxane 0.1%, methyl iso-butyl ketone (MIBK) 2.9%.
Promptly get priming paint after above-mentioned each component mixed.
Embodiment 2
The mass percent prescription of the special-purpose primer of ultraviolet-curing vacuum coating of a kind of reflector of automobile lamps: IBHG-I 65%, urethane acrylate 10%, and TMPTA 10%, THEICTA 10%, Darocur1173 2%, flow agent fluorine modified polyorganosiloxane 0.1%, methyl iso-butyl ketone (MIBK) 2.9%.
Embodiment 3
The mass percent prescription of the special-purpose primer of ultraviolet-curing vacuum coating of a kind of reflector of automobile lamps: IBHG-II 65%, fluorine-silicon modified acrylic ester oligomer 10%, PETA 15%, Darocur 1,173 2%, the polyether-modified polysiloxane copolymer 0.1% of flow agent, methyl iso-butyl ketone (MIBK) 7.9%.
Embodiment 4
The mass percent prescription of the special-purpose primer of ultraviolet-curing vacuum coating of a kind of reflector of automobile lamps: IBHG-II 50%, epoxy acrylate 8%, PETA 7%, DPHA 5%, Darocur 1,173 2%, flow agent polyester-modified polysiloxanes multipolymer 0.1%, butylacetate 20%, ethyl acetate 11.9%.
Phenolic aldehyde epoxy acrylate, epoxy acrylate are respectively the 625C-45,6233 of Changxing, Taiwan company in the above-mentioned prescription, and urethane acrylate is the CN965 of Sartomer company, and the fluorine-silicon modified acrylic ester oligomer is the 347-1 of the two key chemical industry in Taiwan.
3, performance test
The MC material is after oil removing, dedusting, and with the spraying of the priming paint of above-mentioned prescription thereon, the control thickness is at 12-16um, and infrared again levelling 5 minutes is 900-1000mj/cm at the UV energy
2Following curing is carried out vacuum aluminum-coatedly then, detects its performance.
Existing UV coating is high temperature resistant to be 200 ℃, solidifies energy greater than burnt every square centimeter of 3000 millis; And all anti-240 ℃ of high temperature of this product solidify energy all less than burnt every square centimeter of 2300 millis.
Claims (10)
1. the special-purpose primer of ultraviolet-curing vacuum coating of a high-performing car lamp reflector is characterized in that the composition of this priming paint and quality proportioning are as follows:
Matrix resin 40～80%
Assisted resin 8～50%
Reactive thinner 10～40%
Light trigger 0.5～10%
Auxiliary agent 0.05～8%
Solvent 0～50%
Wherein said matrix resin is for being monomer polymerization and by the acrylic acid-grafted polymkeric substance that forms with isobornyl methacrylate, butyl acrylate, Hydroxyethyl acrylate and glycidyl methacrylate; The mol ratio of each monomer isobornyl methacrylate, butyl acrylate, Hydroxyethyl acrylate and glycidyl methacrylate is 13～8: 5～8: 1～5: 1, and the mol ratio of vinylformic acid and glycidyl methacrylate is 0.8～1.2: 1.
2. priming paint according to claim 1, the preparation method who it is characterized in that described matrix resin is: with isobornyl methacrylate, butyl acrylate, Hydroxyethyl acrylate and glycidyl methacrylate is monomer, with the Diisopropyl azodicarboxylate is initiator, synthetic segmented copolymer under solution polymerization, and then with acrylic acid-grafted on it.
3. priming paint according to claim 2 is characterized in that the solution polymerization temperature is 75～95 ℃, and solution polymerization solvent is a toluene; The graft reaction temperature is 90～100 ℃, also adds catalyzer tetramethyl ammonium chloride and stopper MEHQ during graft reaction.
4. priming paint according to claim 1 and 2, the weight-average molecular weight that it is characterized in that described matrix resin is 10000～100000.
5. priming paint according to claim 1 is characterized in that described assisted resin is selected from least a in the origoester acrylate of the urethane acrylate of urethane acrylate, epoxy acrylate, acrylic acid oligomer ester, silicon modification, silicon modification.
6. priming paint according to claim 1, it is characterized in that described reactive thinner is selected from Hydroxyethyl acrylate, hydroxyethyl methylacrylate, isobornyl acrylate, propylene glycol diacrylate, 1,6 hexanediol diacrylate, tricyclic decane dimethanol diacrylate, tripropylene glycol diacrylate, Viscoat 295, three (2-hydroxyethyl) tricarbimide triacrylate, tetramethylol methane tetraacrylate, Dipentaerythritol five acrylate, dipentaerythritol acrylate, the alkoxide acrylate, at least a in the inorganic-organic hybridization material.
7. priming paint according to claim 1; it is characterized in that described light trigger is selected from 1-hydroxyl-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2-methyl isophthalic acid-(4-(methylthio group) phenyl)-2-morpholinyl-1-acetone, 2; 4, at least a in 6-trimethylbenzoyl-diphenyl phosphine oxide, benzophenone, isopropyl thioxanthone, benzophenone, the reactive amines.
8. priming paint according to claim 1, it is characterized in that described auxiliary agent is a flow agent, be selected from least a in polydimethylsiloxane, fluorine modified polyorganosiloxane, polyether-modified polysiloxane copolymer, polyester-modified polysiloxanes multipolymer, (methyl) acrylic polymer, the fluorin modified crylic acid ester.
9. priming paint according to claim 1 is characterized in that described solvent is selected from least a in ethyl acetate, propyl acetate, butylacetate, acetone, butanone, methyl iso-butyl ketone (MIBK), pimelinketone, diisobutyl ketone, toluene, dimethylbenzene, methyl alcohol, ethanol, propyl alcohol, isopropylcarbinol, ethylene glycol ethyl ether, butyl glycol ether, ethyl cellosolve acetate, propylene glycol monomethyl ether, the methylcarbonate.
10. the special-purpose primer of ultraviolet-curing vacuum coating resin of a high-performing car lamp reflector, it is characterized in that this resin is for being monomer polymerization and by the acrylic acid-grafted polymkeric substance that forms with isobornyl methacrylate, butyl acrylate, Hydroxyethyl acrylate and glycidyl methacrylate, wherein the mol ratio of each monomer isobornyl methacrylate, butyl acrylate, Hydroxyethyl acrylate and glycidyl methacrylate is 13～8: 5～8: 1～5: 1, and the mol ratio of vinylformic acid and glycidyl methacrylate is 0.8～1.2: 1; The weight-average molecular weight of this resin is 10000～100000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010195657XA CN101864204B (en) | 2010-06-09 | 2010-06-09 | Dedicated high-performance primer of ultraviolet-curing vacuum coating for reflector of automobile lamps |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010195657XA CN101864204B (en) | 2010-06-09 | 2010-06-09 | Dedicated high-performance primer of ultraviolet-curing vacuum coating for reflector of automobile lamps |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101864204A CN101864204A (en) | 2010-10-20 |
| CN101864204B true CN101864204B (en) | 2011-07-06 |
Family
ID=42956142
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010195657XA Expired - Fee Related CN101864204B (en) | 2010-06-09 | 2010-06-09 | Dedicated high-performance primer of ultraviolet-curing vacuum coating for reflector of automobile lamps |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101864204B (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206463B (en) * | 2010-03-31 | 2015-01-07 | 东莞市佩琦涂料有限公司 | Vacuum plating UV cured primer |
| CN102070979B (en) * | 2010-12-17 | 2012-09-05 | 惠州市长润发涂料有限公司 | Vacuum ultraviolet curing coating for reflective lamp shade of automobile |
| CN102649884A (en) * | 2011-02-24 | 2012-08-29 | 深圳市长辉新材料科技有限公司 | Oil-resistant agent and preparation method thereof |
| CN102134437B (en) * | 2011-02-28 | 2012-08-22 | 上虞市佑谦特种材料有限公司 | UV (ultraviolet)-curing glass coating paint |
| CN103289457A (en) * | 2012-03-02 | 2013-09-11 | 上海富臣化工有限公司 | UV curtain coating flexible topcoat gloss paint |
| CN102675528A (en) * | 2012-05-24 | 2012-09-19 | 上海中新裕祥化工有限公司 | UV-curing water-based alicyclic epoxy acrylate emulsion |
| WO2015044137A1 (en) * | 2013-09-27 | 2015-04-02 | Bayer Materialscience Ag | Formable hard coated pc/pmma coextruded films |
| CN104387947A (en) * | 2014-11-27 | 2015-03-04 | 上海协承昌化工有限公司 | UV coating with mirror surface effect |
| CN105585927B (en) * | 2016-03-24 | 2017-10-10 | 浙江新迪在龙涂料科技有限公司 | A kind of LED solidifications spary coating type vacuum metallizing coating and preparation method thereof |
| CN105907219B (en) * | 2016-04-22 | 2018-07-06 | 河北智生环保科技有限公司 | A kind of reproducible radium-shine ultraviolet light cross-linking glass coating and preparation method |
| CN106118556B (en) * | 2016-07-21 | 2018-06-26 | 浙江欧丽数码喷绘材料有限公司 | A kind of preparation method of the anti-scratch crystal film of surface advertisement |
| CN106531285B (en) * | 2016-11-03 | 2018-07-06 | 广州市尤特新材料有限公司 | A kind of ultraviolet light curing conductive silver paste, preparation method and application |
| CN108485481A (en) * | 2016-12-13 | 2018-09-04 | 君子兰化工（上海）有限公司 | UV ordor removings spray based white primer |
| CN108047854B (en) * | 2017-12-27 | 2020-04-21 | 江苏宏泰高分子材料有限公司 | Water-based ultraviolet-curing BMC high-temperature-resistant coating |
| CN109233664A (en) * | 2018-06-12 | 2019-01-18 | 哈尔滨工业大学无锡新材料研究院 | A kind of UV curing type adhesive, preparation method and application |
| CN110003679A (en) * | 2019-02-28 | 2019-07-12 | 苏州卡利肯新光讯科技有限公司 | A kind of bulk film reflecting mirror and preparation method thereof |
| CN110760260A (en) * | 2019-11-24 | 2020-02-07 | 邵美忠 | Dual-curing vacuum coating primer and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070197727A1 (en) * | 2006-02-16 | 2007-08-23 | Laura Ann Lewin | Multi component coating composition |
| CN100427520C (en) * | 2006-06-16 | 2008-10-22 | 浙江大学 | Preparation method of fluorin modified crylic acid resin for helicopter skining paint |
| CN101481437B (en) * | 2009-01-23 | 2011-04-27 | 华南理工大学 | Preparation of high closeness polyacrylacid ester dispersion |
| CN101659727B (en) * | 2009-09-22 | 2013-01-16 | 江苏柏鹤涂料有限公司 | Acrylic hyperbranched resin and application thereof in mirror back paint |
-
2010
- 2010-06-09 CN CN201010195657XA patent/CN101864204B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101864204A (en) | 2010-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101864204B (en) | Dedicated high-performance primer of ultraviolet-curing vacuum coating for reflector of automobile lamps | |
| CN101747594B (en) | Epoxy acrylate prepolymer resin and preparation method thereof and application in photocurable coating | |
| CN102093782B (en) | Ultraviolet-cured digital painting ink and preparation method thereof | |
| CN103210008B (en) | Curable resin composition | |
| CN101541845B (en) | (meth) acrylate copolymer for syrup and resin composition thereof | |
| CN102925052B (en) | Double-curing vacuum plating UV (Ultraviolet) coating finish | |
| CN109825200A (en) | Side vinyl type copolymerized acrylate UV visbreaking adhesive and preparation method thereof | |
| CN102604035B (en) | Ultraviolet cured two-degree-of-functionality polyurethane acrylic ester base coating resin for vacuum coating | |
| CN103409058B (en) | Non-yellowing ultraviolet light curing abrasion resistant paint and preparation method thereof | |
| CN102167951B (en) | Environment-friendly dual-curing vacuum coating primer special for automobile wheel hub | |
| CN104204109A (en) | Acetoacetyl thermosetting resin for zero VOC gel coating | |
| CN104231148A (en) | Hydroxyl acrylic resin and preparation method thereof | |
| CN102504623A (en) | Peeling layer composition and its preparation method and application | |
| CN102443349A (en) | Vacuum coating ultraviolet curing coating with excellent weather resistance and hydrolysis resistance | |
| CN103517946A (en) | Acrylic resin composition, acrylic resin sheet, acrylic resin laminate, and manufacturing method for same | |
| CN101619116B (en) | Thermoplastic fluorine-containing acrylic resin and preparation method thereof | |
| CN101585766B (en) | Epoxy acrylate containing alicyclic structure and preparation method thereof | |
| CN101967211A (en) | Preparation method of low molecular weight polyacrylic ester acrylic ester for photo-curing | |
| CN104312420A (en) | Ultraviolet light-heat dual-curing primer for vacuum coating of vehicle headlight and application method | |
| CN105400251A (en) | Hard coating composition, polarizing film using same and display | |
| CN105542098A (en) | Modified aldehyde-ketone resin as well as preparation method and application thereof | |
| CN102206297B (en) | Low polymer for ultraviolet light cured coating and printing ink, and preparation method thereof | |
| CN102535245A (en) | UV-cured alcohol-water type nano hybrid paper glazing coating and preparation method thereof | |
| CN102838486A (en) | Ultraviolet light curing polyester acrylate and preparation method thereof | |
| CN104910758A (en) | High-strength antibacterial ultraviolet-curable coating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: HIPRO POLYMER MATERIALS (JIANGSU) CO., LTD. Free format text: FORMER NAME: YIXING HIPRO CHEMICAL CO., LTD. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: 214217 Industrial North Zone, Wan Stone Town, Jiangsu, Yixing Patentee after: HIPRO POLYMER MATERIALS (JIANGSU) Co.,Ltd. Address before: 214217 Industrial North Zone, Wan Stone Town, Jiangsu, Yixing Patentee before: YIXING HONGTAI CHEMICAL Co.,Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110706 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |