CN109650739A - 玻璃构件及其制备方法 - Google Patents
玻璃构件及其制备方法 Download PDFInfo
- Publication number
- CN109650739A CN109650739A CN201811605708.4A CN201811605708A CN109650739A CN 109650739 A CN109650739 A CN 109650739A CN 201811605708 A CN201811605708 A CN 201811605708A CN 109650739 A CN109650739 A CN 109650739A
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- Prior art keywords
- glass
- component
- coating
- installation elements
- resin composition
- Prior art date
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- 239000011521 glass Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title description 6
- 238000009434 installation Methods 0.000 claims abstract description 28
- 239000011248 coating agent Substances 0.000 claims abstract description 26
- 238000000576 coating method Methods 0.000 claims abstract description 26
- 229920001971 elastomer Polymers 0.000 claims abstract description 8
- 239000000806 elastomer Substances 0.000 claims abstract description 8
- 239000004033 plastic Substances 0.000 claims abstract description 5
- 229920003023 plastic Polymers 0.000 claims abstract description 5
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 33
- 239000010703 silicon Substances 0.000 claims description 32
- 229910052710 silicon Inorganic materials 0.000 claims description 32
- 239000011342 resin composition Substances 0.000 claims description 28
- 239000007858 starting material Substances 0.000 claims description 13
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 238000004040 coloring Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000000049 pigment Substances 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 2
- 230000035515 penetration Effects 0.000 claims description 2
- 238000007761 roller coating Methods 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 16
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 14
- 229910000077 silane Inorganic materials 0.000 description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000000945 filler Substances 0.000 description 9
- -1 Hydroxyl Chemical group 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
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- 125000003545 alkoxy group Chemical group 0.000 description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
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- 238000007789 sealing Methods 0.000 description 4
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- 125000002723 alicyclic group Chemical group 0.000 description 3
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- 150000001875 compounds Chemical class 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
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- 229920005573 silicon-containing polymer Polymers 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 239000002318 adhesion promoter Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- UOBRDZDWGZDBST-UHFFFAOYSA-N dibutyltin;oxalic acid Chemical compound OC(=O)C(O)=O.CCCC[Sn]CCCC UOBRDZDWGZDBST-UHFFFAOYSA-N 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 238000011900 installation process Methods 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- WMGSQTMJHBYJMQ-UHFFFAOYSA-N aluminum;magnesium;silicate Chemical compound [Mg+2].[Al+3].[O-][Si]([O-])([O-])[O-] WMGSQTMJHBYJMQ-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
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- 239000010428 baryte Substances 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical class [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- HORSPSPNXPFOMT-UHFFFAOYSA-N butoxy(silyloxy)silane Chemical compound C(CCC)O[SiH2]O[SiH3] HORSPSPNXPFOMT-UHFFFAOYSA-N 0.000 description 1
- SOJMRVMQZIYFFJ-UHFFFAOYSA-N butoxy(silyloxysilyloxy)silane Chemical class C(CCC)O[SiH2]O[SiH2]O[SiH3] SOJMRVMQZIYFFJ-UHFFFAOYSA-N 0.000 description 1
- ZZHNUBIHHLQNHX-UHFFFAOYSA-N butoxysilane Chemical class CCCCO[SiH3] ZZHNUBIHHLQNHX-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
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- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- FPOSCXQHGOVVPD-UHFFFAOYSA-N chloromethyl(trimethoxy)silane Chemical compound CO[Si](CCl)(OC)OC FPOSCXQHGOVVPD-UHFFFAOYSA-N 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
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- 238000002788 crimping Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- WCRDXYSYPCEIAK-UHFFFAOYSA-N dibutylstannane Chemical compound CCCC[SnH2]CCCC WCRDXYSYPCEIAK-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
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- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
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- 239000010439 graphite Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
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- 239000012760 heat stabilizer Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 1
- 125000005525 methide group Chemical group 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- RJMRIDVWCWSWFR-UHFFFAOYSA-N methyl(tripropoxy)silane Chemical compound CCCO[Si](C)(OCCC)OCCC RJMRIDVWCWSWFR-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- FABOKLHQXVRECE-UHFFFAOYSA-N phenyl(tripropoxy)silane Chemical compound CCCO[Si](OCCC)(OCCC)C1=CC=CC=C1 FABOKLHQXVRECE-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- ZMYXZXUHYAGGKG-UHFFFAOYSA-N propoxysilane Chemical compound CCCO[SiH3] ZMYXZXUHYAGGKG-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 239000004447 silicone coating Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- XOAJIYVOSJHEQB-UHFFFAOYSA-N trimethyl trimethoxysilyl silicate Chemical group CO[Si](OC)(OC)O[Si](OC)(OC)OC XOAJIYVOSJHEQB-UHFFFAOYSA-N 0.000 description 1
- ZQTYRTSKQFQYPQ-UHFFFAOYSA-N trisiloxane Chemical compound [SiH3]O[SiH2]O[SiH3] ZQTYRTSKQFQYPQ-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明涉及一种玻璃构件，所述玻璃构件具有塑料涂布的玻璃板和至少一个固定在玻璃板上的安装元件，玻璃板的整个表面特别是用硅基弹性体涂布并且涂层同时与安装元件在玻璃板上的铺置部分形成粘合连接。
Description
本申请是中国专利申请201380012432.8的分案申请
技术领域
本发明涉及玻璃构件及其制备方法，所述玻璃构件具有塑料涂布的玻璃板和至少一个固定在玻璃板上的安装元件。
背景技术
全部或至少大部分由玻璃组成的外立面和屋顶是现代建筑的不可分割的一部分。它们大多由平面玻璃板形成，所述平面玻璃板在合适的(大多由钢组成的)承载结构中使用。这些玻璃板通常经着色和/或设置有功能涂层，从而例如在建筑内部远离红外线辐射或者实现一定的光学效果。
特别已知的是具有蒸镀薄层的玻璃板，所述薄层升高红外线范围内的反射能力并且也部分升高可见光范围和UV范围内的反射能力。为了制备具有不透明外观的高品质玻璃片，通常对玻璃进行复杂和昂贵的表面蚀刻处理。
例如由US 4,814,230或US 7,309,734 B2也已知，通过施涂含颜料的弹性体层制备不透明玻璃板或具有特别的光学性能的玻璃板，所述玻璃板完全可以满足高品质要求。为了解释改进的底漆组合物对硅树脂化合物的强度的影响，EP 0 347 049描述了一种实验室样品，其中玻璃板和由不同方式处理的铝组成的板状或筛状条带经由硅树脂粘合剂彼此结合。
发明内容
通过本发明提供具有权利要求1的特征的玻璃构件。还给出其多种制备方法。
本发明的一个方面在于，同时为了固定目的而使用设计作为构件的玻璃板的首先为了实现光学效果而设置的涂层。因此这特别意味着背离了本领域技术人员的常规手段，因为具有固定作用的层(特别是粘合剂层)通常仅在为了充分的力传递而需要的较大部件的局部区域中形成。然而所讨论类型的涂层通常为(尽管不是必要的)施涂在玻璃板的整个表面上的塑料层。同时为了安装元件在玻璃板上的材料锁合式固定的目的而利用该涂层也是出人意料和有利的想法。该想法有可能显著简化生产过程和节约成本，因为可以取消额外的并且通常局部精确限制的粘合剂施涂过程。
本发明的另一个优点在于，为了固定安装元件的目的而构造得相对厚的塑料层(特别是硅树脂基弹性体层)改进了玻璃构件的断裂行为并且易于遵守安全规定。弹性体层将碎片一定程度地保持与构件连接，因此有助于避免碎片掉落或飞走。
在本发明的一个实施方案中，所述的或每个安装元件的铺置(aufliegende)部分由带孔金属板(Lochblech)形成，所述带孔金属板的孔至少部分地被玻璃板的涂层渗透。由于使用市售大量可得的简单的带孔金属板，该实施方案在应用方面是灵活的并且是成本低廉的，并且有可能在玻璃板和安装元件之间实现特别紧密的形状锁合，即实现高的结合强度。
在本发明的另一个实施方案中，玻璃板的表面有多于四分之一，特别是主要的表面部分被安装元件的铺置部分或多个安装元件的铺置部分覆盖。这有可能以有利的方式在安装玻璃构件时实现良好的力的分布并且避免了最大负荷和由其造成的断裂危险。
在另一个实施方案中，所述安装元件或至少一个安装元件包括从铺置部分向上竖起的固定角。固定角以技术简单且成本低廉的方式通过优选使用的带孔金属板的卷边(Abkanten)形成并且(设置有相应的开口)可以灵活地用于不同的安装情况。
在本发明的另一个实施方案中，涂层具有在1和7mm之间的范围内，特别是在2和5mm之间的范围内的厚度。玻璃板涂层为厚层，其精确厚度根据玻璃板的厚度和尺寸和符合安装要求的安装元件的特定布置而确定。
在另一个实施方案中，涂层以这样的方式浓密着色或染色，使得玻璃构件在可见光范围内不透明并且所述安装元件或每个安装元件被遮蔽。这保证了用玻璃构件形成的外立面或重建结构等的视觉上高品质的外观，而与基础结构和所属的安装元件的具体构造无关。涂层可以在给定的优选厚度下特别地着色或染色成白色并且同时遮蔽每个基础结构；当然，黑色或彩色的着色或染色也是适用的。
玻璃构件的涂层特别为硅树脂基弹性体或硅树脂涂层，亦即涂层的起始材料为硅树脂组合物。
特别适合涂布的硅树脂组合物特别是缩合交联性的双组份硅树脂组合物。优选地，其为由组分A和组分B组成的双组份硅树脂组合物，组分A包含
-至少一种羟基封端的聚二有机硅氧烷P；和
组分B包含
-至少一种用于聚二有机硅氧烷的交联剂；以及
-至少一种用于聚二有机硅氧烷的交联的催化剂。
合适的聚二有机硅氧烷特别为式(I)的聚二有机硅氧烷P，
其中
基团R1、R2和R3彼此独立地表示具有1至12个碳原子的线性或支化的一价烃基，其任选具有一个或多个杂原子并且任选具有一个或多个C-C多重键和/或任选具有脂环族和/或芳族部分；
基团R4彼此独立地表示羟基或各自具有1至13个碳原子的烷氧基、酰氧基或酮肟基，其任选具有一个或多个杂原子，和任选具有一个或多个C-C多重键和/或任选具有脂环族和/或芳族部分；
指数p表示0、1或2的值；和
指数m这样选择，使得聚二有机硅氧烷P在23℃的温度下具有10至500000mPa·s的粘度。
特别地，基团R1和R2表示具有1至5，特别是1至3个碳原子的烷基，优选是甲基。
此外指数m特别这样选择，使得聚二有机硅氧烷P在23℃的温度下具有1000至100000mPa·s的粘度。粘度通常根据DIN 53018确定。
当双组份硅树脂组合物的组分A中的聚二有机硅氧烷P为羟基封端的聚二有机硅氧烷时，指数p通常表示2的值。羟基封端的聚二有机硅氧烷是已知的并且可市售获得。这种聚二有机硅氧烷的制备也以已知的方式进行。其例如描述在US 4,962,152中，其公开内容通过引用的方式并入本文。
当双组份硅树脂组合物的组分A中的聚二有机硅氧烷P为其中基团R4表示烷氧基、酰氧基或酮肟基的式(I)的聚二有机硅氧烷P时，其特别为烷氧基或酮肟基。指数p则特别表示0或1的值。
优选的烷氧基为甲氧基、乙氧基或异丙氧基。
优选的酮肟基为其烷基各自具有1至6个碳原子的二烷基酮肟基。优选地，二烷基酮肟基的两个烷基彼此独立地表示甲基、乙基、正丙基、异丙基、正丁基或异丁基。特别优选的是这样的情况，其中二烷基酮肟的一个烷基表示甲基而二烷基酮肟的另一个烷基表示甲基、乙基或异丁基。最优选地，酮肟基表示乙基-甲基酮肟基。
双组份硅树脂组合物的组分B包含至少一种用于聚二有机硅氧烷的交联剂。特别地，交联剂为式(II)的硅烷。
在此基团R6彼此独立地表示具有1至12个碳原子的线性或支化的一价烃基，其任选具有一个或多个杂原子，并且任选具有一个或多个C-C多重键和/或任选具有脂环族和/或芳族部分。
基团R7彼此独立地表示氢原子或具有1至12个碳原子的烷基或具有1至12个碳原子的肟基或具有1至12个碳原子的酰基。特别地，基团R7表示具有1至5，特别是1至3个碳原子的烷基，优选甲基或乙基。
指数s表示0至4的值，特别是0、1或2的值，优选0的值。
对于作为用于聚二有机硅氧烷的交联剂的式(II)硅烷的选择来说，对硅树脂组合物的不同要求可能是决定性的。一方面硅烷的反应性起重要作用，其中原则上优选较高反应性的硅烷。另一方面，毒性原因也可能对于交联剂的选择是决定性的。因此，例如相比于四甲氧基硅烷，优选四乙氧基硅烷作为交联剂。
合适的式(II)的硅烷的实例为甲基三甲氧基硅烷、氯甲基三甲氧基硅烷、乙基三甲氧基硅烷、丙基三甲氧基硅烷、乙烯基三甲氧基硅烷、甲基三乙氧基硅烷、乙烯基三乙氧基硅烷、苯基三乙氧基硅烷、甲基三丙氧基硅烷、苯基三丙氧基硅烷、四甲氧基硅烷、四乙氧基硅烷、四正丙氧基硅烷或四正丁氧基硅烷。
特别优选地，式(II)的硅烷为乙烯基三甲氧基硅烷或四乙氧基硅烷或其混合物。
此外，硅烷也可以已经部分(一部分R7＝H)或完全水解(所有R7＝H)地存在。由于部分或完全水解的硅烷的剧烈升高的反应性，优选使用其作为交联剂。本领域技术人员已知，在使用部分或完全水解的硅烷用于形成低聚硅氧烷时，特别可能造成由于水解硅烷的缩合形成的二聚物和/或三聚物。因此也可以使用低聚硅氧烷作为用于双组份硅树脂组合物的交联剂。
例如，合适的低聚硅氧烷为六甲氧基二硅氧烷、六乙氧基二硅氧烷、六正丙氧基二硅氧烷、六正丁氧基二硅氧烷、八乙氧基三硅氧烷、八正丁氧基三硅氧烷和十乙氧基四硅氧烷。
当然也可以使用上述硅烷的任意混合物作为用于双组份硅树脂组合物的交联剂。
用于聚二有机硅氧烷的交联剂的份额为整个硅树脂组合物的优选0.1至20重量％，特别是1至15重量％，优选2至10重量％。
用于聚二有机硅氧烷的交联的催化剂特别是有机锡化合物或钛酸盐或其组合。
优选的有机锡化合物为二烷基锡化合物，例如选自二-2-乙基己酸二甲基锡、二月桂酸二甲基锡、二乙酸二正丁基锡、二-2-乙基己酸二正丁基锡、二辛酸二正丁基锡、二-2,2-二甲基辛酸二正丁基锡、二月桂酸二正丁基锡、二硬脂酸二正丁基锡、二马来酸二正丁基锡、二油酸二正丁基锡、二乙酸二正丁基锡、二-2-乙基己酸二正辛基锡、二-2,2-二甲基辛酸二正辛基锡、二马来酸二正辛基锡和二月桂酸二正辛基锡。
钛酸盐或有机钛酸盐表示具有至少一个通过氧原子连接在钛原子上的配体的化合物。适合作为通过氧-钛键连接在钛原子上的配体的为选自烷氧基、磺酸基、羧酸基、二烷基磷酸基、二烷基焦磷酸基和乙酰丙酮化物基的那些。优选的钛酸盐为例如四丁基钛酸盐或四异丙基钛酸盐。
此外，合适的钛酸盐具有至少一个多齿配体(也被称为螯合配体)。特别地，多齿配体为二齿配体。
合适的钛酸盐例如通过商标名AA、GBA、GBO、AA-75、AA-65、AA-105、DC、BEAT、IBAY从DuPont公司(USA)市售获得。
当然，在一定情况下有可能甚至优选使用不同的催化剂的混合物。例如，催化剂为有机锡化合物与钛酸盐的混合物。
用于聚二有机硅氧烷的交联的催化剂的份额为整个双组份硅树脂组合物的优选0.001至10重量％，特别是0.005至4重量％，优选0.01至3重量％。
双组份硅树脂组合物还可以任选包含其它成分。
这种额外成分特别为增塑剂、无机和/或有机填料、固化促进剂、颜料、助粘剂、加工助剂、流变改性剂、稳定剂、染料、抑制剂、热稳定剂、抗静电剂、阻燃剂、杀生物剂、蜡、流控剂、触变剂和本领域技术人员已知的其它常见原料和添加剂。
双组份硅树脂组合物中可以包含的其它合适的成分，特别是助粘剂和增塑剂，例如描述于专利申请US 2010/063190 A1第[0051]至[0055]段，其全部公开内容以引用的方式并入本文。
在使用这种任选成分时，重要的是注意：可能通过彼此反应或与其它内容物的反应影响组合物的储存稳定性的成分需要彼此分离地储存。
此外优选的是，这样选择在双组份硅树脂组合物中任选存在的所有提及的成分，使得双组份硅树脂组合物的两种组分的储存稳定性不受所述成分的存在的负面影响，亦即组合物的性能，特别是应用性能和固化性能在储存时不改变或仅略微改变。这意味着在储存的过程中不明显出现造成所述双组份硅树脂组合物的化学固化的反应。
特别适合作为增塑剂的是三烷基甲硅烷基封端的聚二烷基硅氧烷，特别是三甲基甲硅烷基封端的聚二甲基硅氧烷。优选粘度在1和10000mPa·s(再次根据DIN 53 018测得)之间的三甲基甲硅烷基封端的聚二甲基硅氧烷。特别优选地，粘度在10和1000mPa·s之间。然而也可以使用三甲基甲硅烷基封端的聚二甲基硅氧烷，其中一些甲基被其它有机基团(例如苯基、乙烯基或三氟丙基)替代。尽管特别优选使用线性三甲基甲硅烷基封端的聚二甲基硅氧烷作为增塑剂，也可以使用所述化合物的支化形式。这种支化的化合物这样形成：在用于其制备的起始材料中使用少量的三官能或四官能的硅烷。代替聚硅氧烷增塑剂，也有可能使用其它有机化合物，例如特定的烃或其混合物作为增塑剂。这种烃可以为芳族的或脂族的。在选择时特别注意：烃具有低挥发性和与硅树脂组合物的其它成分的足够的相容性。
增塑剂的份额为整个双组份硅树脂组合物的优选2至15重量％，特别是5至10重量％。
此外，组合物还可以包含至少一种填料。填料不仅影响未固化组合物的流变性能而且影响经固化组合物的机械性能和表面性质。还可以通过填料影响硅树脂组合物特别是在经固化状态下的外观。
合适的填料为例如任选涂布有脂肪酸(特别是硬脂酸)的天然、研磨或沉淀的碳酸钙，煅烧高岭土，氧化铝，氢氧化铝，二氧化硅，特别是得自热解过程的高度分散二氧化硅，炭黑，特别是工业制得的炭黑(“Carbon Black”)，硅酸铝，硅酸镁铝，硅酸锆，石英粉末，方晶石粉末，硅藻土，云母，氧化铁，氧化钛，氧化锆，石膏，Annal in，硫酸钡(BaSO4，也被称为重土或重晶石)，碳化硼，氮化硼，石墨，碳纤维，玻璃纤维或玻璃空心球，其表面任选用疏水剂处理。优选的填料为碳酸钙、煅烧高岭土、炭黑、高度分散二氧化硅以及阻燃填料，例如氢氧化物或水合物，特别是铝的氢氧化物或水合物，优选氢氧化铝。
在一个优选的实施方案中，硅树脂组合物包含得自热解过程的高度分散的二氧化硅或碳酸钙作为填料。
因此有可能和甚至有利的是，使用不同的填料的混合物。
合适量的填料例如在1至40重量％，特别是5至30重量％，优选10至20重量％的范围内，以整个双组份硅树脂组合物计。
在一个同样优选的实施方案中，双组份硅树脂组合物不包含或仅包含少量的填料。
在一个特别优选的实施方案中，双组份硅树脂组合物包含用于使组合物着色的试剂，其中所述试剂特别为着色糊剂或颜料。
在应用双组份硅树脂组合物时，组分A和B例如通过搅拌、捏合、辊压等或在混合器中或通过静态混合器彼此混合，这造成组合物的固化。双组份硅树脂组合物的固化特别在室温下进行。
特别地，这样使用双组份硅树脂组合物，使得组分A与组分B的重量比例≥1:1，特别是3:1至15:1，优选10:1至13:1。
在所提出方法的一个变体形式中，将涂层的起始材料以液体状态浇注或喷射在玻璃板上，使得通过流平形成平坦表面。在另一个实施方案中，将涂层的起始材料以液体状态或糊剂状态刮涂在玻璃板上。也有可能基本上自流平地浇注或喷射仍为(浓稠)液体的组合物并且结合随后的刮涂从而弥补仍然存在的水平缺陷。
或者，所述方法也可以这样设计，将涂层的起始材料以糊剂状态辊涂在玻璃板上，其中特别在起始材料的表面和涂布辊的表面之间置入塑料薄膜，并且在施涂之后和在涂层固化之前再除去塑料薄膜。由此避免了材料粘附在辊表面上。
在所述实施方案的一个改良方案中，在施涂至玻璃板之前至少尤其通过调节预反应时间从而调节起始材料的液体状态或糊剂状态。应理解，除此之外的其它参数例如溶剂份额、温度等是重要的。
与弹性体起始材料的具体施涂方式无关，将所述待固定的安装元件或每个待固定的安装元件“浮动地”放置在所形成的层上(或任选略微挤压)，只要起始材料仍未发生反应。取决于组合物及其反应过程，特别选择这样的安装过程，所述安装过程提供足够的时间储备从而在玻璃板和安装元件之间借助弹性体层建立紧密的材料锁合式连接。合意的是，可以在将安装元件放置在仍为(浓稠)液体或糊剂的起始材料层时保持侧面固定安装元件，直至随着层的持续固化使得安装元件本身通过层而充分固定。
根据涂层的组成，涂层的固化可以足够快地通过空气干燥而进行，但是也可以使用红外线加热器，任选引入潮湿空气或蒸汽或其它本身已知的用于促进该过程的试剂。
Claims (10)
1.玻璃构件，所述玻璃构件具有塑料涂布的玻璃板和至少一个固定在玻璃板上的安装元件，
其中玻璃板的整个表面被涂布，特别是用硅树脂基弹性体涂布，并且涂层同时与安装元件在玻璃板上的铺置部分形成粘合连接。
2.根据权利要求1所述的玻璃构件，其中所述安装元件或每个安装元件的铺置部分由带孔金属板形成，所述带孔金属板的孔至少部分地被玻璃板的涂层渗透。
3.根据权利要求1或2所述的玻璃构件，其中玻璃板的表面有多于四分之一，特别是主要的表面部分，被安装元件的铺置部分或多个安装元件的铺置部分覆盖。
4.根据前述权利要求任一项所述的玻璃构件，其中所述安装元件或至少一个安装元件包括从铺置部分向上竖起的固定角。
5.根据前述权利要求任一项所述的玻璃构件，其中涂层具有在1和7mm之间的范围内，特别是在2和5mm之间的范围内的厚度。
6.根据前述权利要求任一项所述的玻璃构件，其中涂层以这样的方式浓密着色，使得玻璃构件在可见光范围内不透明并且安装元件被遮蔽。
7.根据前述权利要求任一项所述的玻璃构件，其中涂层的起始材料为缩合交联性的双组份硅树脂组合物。
8.根据权利要求7所述的玻璃构件，其中双组份硅树脂组合物由组分A和组分B组成，组分A包含
-至少一种羟基封端的聚二有机硅氧烷P；和
组分B包含
-至少一种用于聚二有机硅氧烷的交联剂；以及
-至少一种用于聚二有机硅氧烷的交联的催化剂。
9.根据权利要求7或8所述的玻璃构件，其中双组份硅树脂组合物还包含至少一种着色糊剂或着色颜料。
10.用于制备根据前述权利要求任一项所述的玻璃构件的方法，其中以这样的方式将涂层的起始材料以液体状态或糊剂状态浇注或喷射在玻璃板上，使得通过流平形成平坦表面，或者将涂层的起始材料以液体状态或糊剂状态刮涂或辊涂在玻璃板上。
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| JPS59169323U (ja) * | 1983-04-28 | 1984-11-13 | 日本板硝子株式会社 | 板ガラスと他部材との接合体 |
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| JPS6294831U (zh) * | 1985-12-05 | 1987-06-17 | ||
| JPS63116326U (zh) * | 1987-01-23 | 1988-07-27 | ||
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| EP1894975A1 (de) | 2006-08-30 | 2008-03-05 | Sika Technology AG | Siliconzusammensetzung |
| FR2913262B1 (fr) * | 2007-03-02 | 2013-09-06 | Eurokera | Plaque vitroceramique et son procede de fabrication. |
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2012
- 2012-03-09 EP EP20120158888 patent/EP2636653A1/de not_active Withdrawn
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2013
- 2013-02-19 US US13/770,324 patent/US9789661B2/en active Active
- 2013-03-08 CN CN201380012432.8A patent/CN104159860A/zh active Pending
- 2013-03-08 DE DE202013012634.5U patent/DE202013012634U1/de not_active Expired - Lifetime
- 2013-03-08 KR KR1020207002297A patent/KR102178395B1/ko active IP Right Grant
- 2013-03-08 WO PCT/EP2013/054780 patent/WO2013132080A1/de active Application Filing
- 2013-03-08 CN CN201811605708.4A patent/CN109650739A/zh active Pending
- 2013-03-08 KR KR1020147025766A patent/KR20140145128A/ko not_active Application Discontinuation
- 2013-03-08 EP EP17201438.3A patent/EP3321239B1/de active Active
- 2013-03-08 EP EP13710340.4A patent/EP2822906B1/de active Active
- 2013-03-08 JP JP2014560401A patent/JP6396809B2/ja not_active Expired - Fee Related
-
2016
- 2016-12-09 US US15/374,361 patent/US10086591B2/en not_active Expired - Fee Related
-
2018
- 2018-05-23 JP JP2018098545A patent/JP2018158884A/ja active Pending
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| US4115356A (en) * | 1977-07-18 | 1978-09-19 | Dow Corning Corporation | Self adhering room temperature vulcanizable silicone elastomers |
| US4814230A (en) * | 1988-01-28 | 1989-03-21 | Vockler Larry D | Silicone-coated opaque glass |
| EP0347049A2 (en) * | 1988-06-15 | 1989-12-20 | Dow Corning Corporation | Improved primer compositions |
| US20050081993A1 (en) * | 2003-10-16 | 2005-04-21 | Ilkka Steven J. | Method of bonding glass |
| CN101472852A (zh) * | 2006-06-20 | 2009-07-01 | 陶氏环球技术公司 | 涂布的玻璃制品 |
Also Published As
| Publication number | Publication date |
|---|---|
| US9789661B2 (en) | 2017-10-17 |
| CN104159860A (zh) | 2014-11-19 |
| JP2018158884A (ja) | 2018-10-11 |
| DE202013012634U1 (de) | 2018-02-08 |
| KR20200014934A (ko) | 2020-02-11 |
| JP2015510862A (ja) | 2015-04-13 |
| EP3321239B1 (de) | 2021-04-07 |
| WO2013132080A1 (de) | 2013-09-12 |
| EP2822906B1 (de) | 2021-01-13 |
| EP3321239A1 (de) | 2018-05-16 |
| US20170087808A1 (en) | 2017-03-30 |
| EP2822906A1 (de) | 2015-01-14 |
| US20130236689A1 (en) | 2013-09-12 |
| KR20140145128A (ko) | 2014-12-22 |
| EP2636653A1 (de) | 2013-09-11 |
| JP6396809B2 (ja) | 2018-09-26 |
| KR102178395B1 (ko) | 2020-11-16 |
| US10086591B2 (en) | 2018-10-02 |
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