JP6168321B2 - 共重合体 - Google Patents
共重合体 Download PDFInfo
- Publication number
- JP6168321B2 JP6168321B2 JP2015549271A JP2015549271A JP6168321B2 JP 6168321 B2 JP6168321 B2 JP 6168321B2 JP 2015549271 A JP2015549271 A JP 2015549271A JP 2015549271 A JP2015549271 A JP 2015549271A JP 6168321 B2 JP6168321 B2 JP 6168321B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- copolymer
- ethylene
- sealing material
- olefin
- 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.)
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- 229920001577 copolymer Polymers 0.000 title claims description 48
- 229920005672 polyolefin resin Polymers 0.000 claims description 79
- -1 unsaturated silane compound Chemical class 0.000 claims description 79
- 238000004519 manufacturing process Methods 0.000 claims description 69
- 239000011342 resin composition Substances 0.000 claims description 33
- 125000003277 amino group Chemical group 0.000 claims description 31
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 25
- 229910052710 silicon Inorganic materials 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 15
- 150000002431 hydrogen Chemical class 0.000 claims description 12
- 125000002252 acyl group Chemical group 0.000 claims description 11
- 125000002947 alkylene group Chemical group 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910000077 silane Inorganic materials 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 125000004434 sulfur atom Chemical group 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 85
- 239000004711 α-olefin Substances 0.000 description 83
- 239000003566 sealing material Substances 0.000 description 81
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 50
- 239000005977 Ethylene Substances 0.000 description 50
- 239000004594 Masterbatch (MB) Substances 0.000 description 40
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 39
- 230000000052 comparative effect Effects 0.000 description 38
- 238000000034 method Methods 0.000 description 35
- 230000005693 optoelectronics Effects 0.000 description 35
- 229920005989 resin Polymers 0.000 description 31
- 239000011347 resin Substances 0.000 description 31
- 239000000758 substrate Substances 0.000 description 31
- 230000001070 adhesive effect Effects 0.000 description 29
- 239000000853 adhesive Substances 0.000 description 28
- 238000003475 lamination Methods 0.000 description 28
- 125000004432 carbon atom Chemical group C* 0.000 description 25
- 239000011521 glass Substances 0.000 description 19
- 239000008393 encapsulating agent Substances 0.000 description 17
- 239000010408 film Substances 0.000 description 15
- 230000008569 process Effects 0.000 description 15
- 239000000654 additive Substances 0.000 description 14
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 14
- 125000005372 silanol group Chemical group 0.000 description 12
- 238000002834 transmittance Methods 0.000 description 12
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 229910008051 Si-OH Inorganic materials 0.000 description 10
- 229910006358 Si—OH Inorganic materials 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 9
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 8
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 150000003973 alkyl amines Chemical class 0.000 description 7
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 239000005038 ethylene vinyl acetate Substances 0.000 description 6
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 6
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 6
- 238000005102 attenuated total reflection Methods 0.000 description 5
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 5
- 239000010432 diamond Substances 0.000 description 5
- 229910003460 diamond Inorganic materials 0.000 description 5
- 239000012760 heat stabilizer Substances 0.000 description 5
- 239000004611 light stabiliser Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000002411 adverse Effects 0.000 description 4
- 150000001412 amines Chemical group 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920002620 polyvinyl fluoride Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 description 3
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 125000004423 acyloxy group Chemical group 0.000 description 3
- 125000004414 alkyl thio group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 229920002313 fluoropolymer Polymers 0.000 description 3
- 239000004811 fluoropolymer Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000012780 transparent material Substances 0.000 description 3
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- 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 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000012963 UV stabilizer Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001343 alkyl silanes Chemical class 0.000 description 2
- 150000005840 aryl radicals Chemical class 0.000 description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 2
- ZICNIEOYWVIEQJ-UHFFFAOYSA-N (2-methylbenzoyl) 2-methylbenzenecarboperoxoate Chemical compound CC1=CC=CC=C1C(=O)OOC(=O)C1=CC=CC=C1C ZICNIEOYWVIEQJ-UHFFFAOYSA-N 0.000 description 1
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- RSGZQYVTVPJMTG-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhex-3-yn-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)C#CC(C)(C)OOC(=O)C1=CC=CC=C1 RSGZQYVTVPJMTG-UHFFFAOYSA-N 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- ZDKPIHMFWCOHRD-UHFFFAOYSA-N 1-[[4-[4-bis(2,4-ditert-butylphenoxy)phosphorylphenyl]phenyl]-(2,4-ditert-butylphenoxy)phosphoryl]oxy-2,4-ditert-butylbenzene Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(=O)(C=1C=CC(=CC=1)C=1C=CC(=CC=1)P(=O)(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C ZDKPIHMFWCOHRD-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- LAZHUUGOLCHESB-UHFFFAOYSA-N 2,3-dimethylbicyclo[2.2.1]hept-5-ene Chemical compound C1C2C(C)C(C)C1C=C2 LAZHUUGOLCHESB-UHFFFAOYSA-N 0.000 description 1
- UYZGVYVJIFOZPY-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)hex-3-yne Chemical compound CC(C)(C)OOC(C)C#CC(C)OOC(C)(C)C UYZGVYVJIFOZPY-UHFFFAOYSA-N 0.000 description 1
- JGBAASVQPMTVHO-UHFFFAOYSA-N 2,5-dihydroperoxy-2,5-dimethylhexane Chemical compound OOC(C)(C)CCC(C)(C)OO JGBAASVQPMTVHO-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- NGOCAPPEAVAHQM-UHFFFAOYSA-N 2-fluoroprop-1-ene Chemical compound CC(F)=C NGOCAPPEAVAHQM-UHFFFAOYSA-N 0.000 description 1
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- TXBZITDWMURSEF-UHFFFAOYSA-N 3,3-dimethylpent-1-ene Chemical compound CCC(C)(C)C=C TXBZITDWMURSEF-UHFFFAOYSA-N 0.000 description 1
- XVEASTGLHPVZNA-UHFFFAOYSA-N 3,4-dichlorobut-1-ene Chemical compound ClCC(Cl)C=C XVEASTGLHPVZNA-UHFFFAOYSA-N 0.000 description 1
- WFHXQNMTMDKVJG-UHFFFAOYSA-N 3,4-dimethylpent-1-ene Chemical compound CC(C)C(C)C=C WFHXQNMTMDKVJG-UHFFFAOYSA-N 0.000 description 1
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- MZWXWSVCNSPBLH-UHFFFAOYSA-N 3-(3-aminopropyl-methoxy-methylsilyl)oxypropan-1-amine Chemical compound NCCC[Si](C)(OC)OCCCN MZWXWSVCNSPBLH-UHFFFAOYSA-N 0.000 description 1
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- ZZFSVZSLTOWVQU-UHFFFAOYSA-N 3-silyloxyperoxypropan-1-amine Chemical compound NCCCOOO[SiH3] ZZFSVZSLTOWVQU-UHFFFAOYSA-N 0.000 description 1
- KLCNJIQZXOQYTE-UHFFFAOYSA-N 4,4-dimethylpent-1-ene Chemical compound CC(C)(C)CC=C KLCNJIQZXOQYTE-UHFFFAOYSA-N 0.000 description 1
- SUWJESCICIOQHO-UHFFFAOYSA-N 4-methylhex-1-ene Chemical compound CCC(C)CC=C SUWJESCICIOQHO-UHFFFAOYSA-N 0.000 description 1
- UDOJACSDSIHAAT-UHFFFAOYSA-N 5-benzylbicyclo[2.2.1]hept-2-ene Chemical compound C1C(C=C2)CC2C1CC1=CC=CC=C1 UDOJACSDSIHAAT-UHFFFAOYSA-N 0.000 description 1
- QHJIJNGGGLNBNJ-UHFFFAOYSA-N 5-ethylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CC)CC1C=C2 QHJIJNGGGLNBNJ-UHFFFAOYSA-N 0.000 description 1
- PCBPVYHMZBWMAZ-UHFFFAOYSA-N 5-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C)CC1C=C2 PCBPVYHMZBWMAZ-UHFFFAOYSA-N 0.000 description 1
- JIUFYGIESXPUPL-UHFFFAOYSA-N 5-methylhex-1-ene Chemical compound CC(C)CCC=C JIUFYGIESXPUPL-UHFFFAOYSA-N 0.000 description 1
- AKHDGSRSWWFVIZ-UHFFFAOYSA-N 5-propylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCC)CC1C=C2 AKHDGSRSWWFVIZ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
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Description
lは、1または2の整数であり、
R3は、ケイ素原子に結合している−OSiR6 mR7 (2−m)R8を示し、
R6及びR7は、それぞれ独立に、ケイ素原子に結合しているハロゲン、アミン基、−R9R10または−R10を示し、R9は、酸素または硫黄原子であり、R10は、水素、アルキル基、アリール基、アラルキル基またはアシル基を示し、
R8は、ケイ素原子に結合している−(CH2)nNR11R12を示し、R11及びR12は、それぞれ独立に、窒素原子に結合している水素またはR13NH2を示し、R13は、アルキレンを示し、
前記mは、1または2の整数であり、nは、0以上の整数である。
また、前記アリール基の炭素数は、6〜20、6〜18または6〜12であることができ、例えば、フェニル基またはナフチル基であることができるが、これに制限されるものではない。
前記アルキレン基は、炭素数1〜16、炭素数1〜12、炭素数1〜6または炭素数1〜4の直鎖または分枝鎖状アルキレン基であることができ、例えば、エチレン基またはプロピレン基であることができるが、これに制限されない。
R14及びR15は、それぞれ独立に、ケイ素原子に結合しているハロゲン、アミン基、−R16R17または−R17を示し、R16は、酸素または硫黄原子であり、R17は、水素、アルキル基、アリール基、アラルキル基またはアシル基を示し、oは、1〜3の整数である。
1つの例示で、前記共重合体は、オレフィン樹脂、不飽和シラン化合物、アミノシラン化合物及びラジカル開始剤を含むオレフィン樹脂組成物を反応器内に添加し、前記オレフィン樹脂組成物を押出反応させる段階を含む。
また、前記R19は、非反応性官能基であることができ、これに関する説明は、前述した非反応性官能基と同一なので省略する。
特に別途規定しない限り、見た明細書で単位重量部は、重量比率を意味する。
好ましくは、前記式1で、α1は、1.5〜4であり、β1は、50〜150であり、より好ましくは、α1は、2.5〜3.3であり、β1は、70〜130である。
[製造例1]
密度が0.870g/cm3であり、MFRが190℃、2.16kgの荷重下で5g/10分のエチレン/α−オレフィン共重合体95.01重量部、ビニルトリメトキシシラン(vinyltrimethoxysilane;VTMS)4.79重量部、3−アミノプロピルトリメトキシシラン(3−aminopropyltrimethoxysilane;APTMS)0.1重量部及び2,5−ビス(t−ブチルペルオキシ)−2,5−ジメチルヘキサン(2,5−Bis(tert−butylperoxy)−2,5−dimethylhexane、Luperox(登録商標)101)0.1重量部を二軸押出器を使用して220℃の温度で180rpmでグラフト反応押出(加熱溶融撹拌)して、変性エチレン/α−オレフィン共重合体のマスターバッチを製造した。(全体100重量部を基準として、それぞれの重量部はwt%を示す。)
製造例1で使用したビニルトリメトキシシラン及び3−アミノプロピルトリメトキシシランの含量を表1に示したように変更したことを除いて製造例1と同一に実施し、変性エチレン/α−オレフィン共重合体のマスターバッチを製造した。
製造例3で使用した3−アミノプロピルトリメトキシシランの代わりに、それぞれ3−アミノプロピルトリエトキシシラン(3−aminopropyltriethoxysilane;APTES)及びN−[3−(トリメトキシシリル)プロピル]エチレンジアミン(N−[3−(Trimethoxysilyl)propyl]ethylenediamine;DAS)を使用したことを除いて製造例3と同一に実施し、変性エチレン/α−オレフィン共重合体のマスターバッチを製造した。
それぞれ製造例1及び3で使用したエチレン/α−オレフィン共重合体の代わりに、密度が0.882g/cm3であり、MFRが190℃、2.16kgの荷重下で3g/10分のエチレン/α−オレフィン共重合体を使用したことを除いてそれぞれ製造例1及び3と同一に実施し、変性エチレン/α−オレフィン共重合体のマスターバッチを製造した。
それぞれ製造例1及び3で使用したエチレン/α−オレフィン共重合体の代わりに、密度が0.902g/cm3であり、MFRが190℃、2.16kgの荷重下で3g/10分のエチレン/α−オレフィン共重合体を使用したことを除いてそれぞれ製造例1及び3と同一に実施し、変性エチレン/α−オレフィン共重合体のマスターバッチを製造した。
製造例1で使用した3−アミノプロピルトリメトキシシランを使用せず、ビニルトリメトキシシランを4.89重量部で使用したことを除いて製造例1と同一に実施し、シラン変性エチレン/α−オレフィン共重合体のマスターバッチを製造した。
製造例3で使用した3−アミノプロピルトリメトキシシランの代わりに、それぞれドデシルアミン(dodecylamine;DA)及びトリメトキシプロピルシラン(Trimethoxypropylsilane;TMS)を使用したことを除いて製造例3と同一に実施し、シラン変性エチレン/α−オレフィン共重合体のマスターバッチを製造した。
比較製造例1で使用したエチレン/α−オレフィン共重合体の代わりに、密度が0.882g/cm3であり、MFRが190℃、2.16kgの荷重下で3g/10分のエチレン/α−オレフィン共重合体を使用したことを除いて比較製造例1と同一に実施し、シラン変性エチレン/α−オレフィン共重合体のマスターバッチを製造した。
比較製造例1で使用したエチレン/α−オレフィン共重合体の代わりに、密度が0.902g/cm3であり、MFRが190℃、2.16kgの荷重下で3g/10分のエチレン/α−オレフィン共重合体を使用したことを除いて比較製造例1と同一に実施し、シラン変性エチレン/α−オレフィン共重合体のマスターバッチを製造した。
製造例1で使用したビニルトリメトキシシランを使用せず、3−アミノプロピルトリメトキシシランをそれぞれ4.89重量部及び0.49重量部で使用したことを除いて製造例1と同一に実施し、エチレン/α−オレフィン共重合体のマスターバッチを製造した。
製造例1で使用したビニルトリメトキシシラン4.79重量部及び3−アミノプロピルトリメトキシシラン0.1重量部の代わりに、ビニルトリメトキシシラン2.44重量部と3−アミノプロピルトリメトキシシランを2.45重量部で使用したことを除いて製造例1と同一に実施し、変性エチレン/α−オレフィン共重合体のマスターバッチを製造した。
[実施例1〜5]
それぞれ前記製造例1〜5で製造された変性エチレン/α−オレフィン共重合体のマスターバッチと密度が0.870g/cm3であり、MFRが190℃、2.16kgの荷重下で5g/10分のエチレン/α−オレフィン共重合体をそれぞれ200g及び400g準備し、1:2の比率で混合した樹脂に、最終シート内で光安定剤(Uvinul 5050H)1000ppm、UV吸収剤(TINUVIN UV531)1000ppm、酸化防止剤1(Irganox 1010)500ppm及び酸化防止剤2(Irgafos 168)500ppmを含むようにする添加剤マスターバッチ18gを添加して混合した後、これを二軸押出器(φ19mm)及びTダイス(幅:200mm)を有するフィルム成形器のホッパーに投入し、押出温度180℃、取出速度3m/分で加工し、厚さ約500μmのシート状封止材を製造した。
実施例1で使用した変性エチレン/α−オレフィン共重合体のマスターバッチとエチレン/α−オレフィン共重合体の混合樹脂の代わりに、それぞれ前記製造例6及び7で製造された変性エチレン/α−オレフィン共重合体のマスターバッチと密度が0.882g/cm3であり、MFRが190℃、2.16kgの荷重下で3g/10分のエチレン/α−オレフィン共重合体をそれぞれ200g及び400gを準備し、1:2の比率で混合した樹脂を使用したことを除いて実施例1と同一に実施し、シート状封止材及び光電池モジュールを製作した。
実施例1で使用した変性エチレン/α−オレフィン共重合体のマスターバッチとエチレン/α−オレフィン共重合体の混合樹脂の代わりに、それぞれ前記製造例8及び9で製造された変性エチレン/α−オレフィン共重合体のマスターバッチと密度が0.902g/cm3であり、MFRが190℃、2.16kgの荷重下で3g/10分のエチレン/α−オレフィン共重合体をそれぞれ200g及び400g準備し、1:2の比率で混合した樹脂を使用したことを除いて実施例1と同一に実施し、シート状封止材及び光電池モジュールを製作した。
実施例1で使用した変性エチレン/α−オレフィン共重合体のマスターバッチとエチレン/α−オレフィン共重合体の混合樹脂の代わりに、製造例3で製造された変性エチレン/α−オレフィン共重合体のマスターバッチと密度が0.870g/cm3であり、MFRが190℃、2.16kgの荷重下で5g/10分のエチレン/α−オレフィン共重合体をそれぞれ100g及び500gを準備し、1:5の比率で混合した樹脂を使用したことを除いて実施例1と同一に実施し、シート状封止材及び光電池モジュールを製作した。
実施例1で使用した変性エチレン/α−オレフィン共重合体のマスターバッチとエチレン/α−オレフィン共重合体の混合樹脂の代わりに、製造例3で製造された変性エチレン/α−オレフィン共重合体のマスターバッチと密度が0.870g/cm3であり、MFRが190℃、2.16kgの荷重下で5g/10分のエチレン/α−オレフィン共重合体をそれぞれ54.5g及び545.5gを準備し、1:10の比率で混合した樹脂を使用したことを除いて実施例1と同一に実施し、シート状封止材及び光電池モジュールを製作した。
実施例1で使用した変性エチレン/α−オレフィン共重合体のマスターバッチとエチレン/α−オレフィン共重合体の混合樹脂の代わりに、前記製造例10で製造された変性エチレン/α−オレフィン共重合体のマスターバッチと密度が0.870g/cm3であり、MFRが190℃、2.16kgの荷重下で3g/10分のエチレン/α−オレフィン共重合体をそれぞれ200g及び400gを準備し、1:2の比率で混合した樹脂を使用したことを除いて実施例1と同一に実施し、シート状封止材及び光電池モジュールを製作した。
実施例1で使用した変性エチレン/α−オレフィン共重合体のマスターバッチの代わりに、それぞれ前記比較製造例1〜比較製造例3で製造されたシラン変性エチレン/α−オレフィン共重合体のマスターバッチを使用したことを除いて実施例1と同一に実施し、シート状封止材及び光電池モジュールを製作した。
実施例1で使用した変性エチレン/α−オレフィン共重合体のマスターバッチとエチレン/α−オレフィン共重合体の混合樹脂の代わりに、前記比較製造例4で製造されたシラン変性エチレン/α−オレフィン共重合体のマスターバッチと密度が0.882g/cm3であり、MFRが190℃、2.16kgの荷重下で3g/10分のエチレン/α−オレフィン共重合体をそれぞれ200g及び400gを準備し、1:2の比率で混合した樹脂を使用したことを除いて実施例1と同一に実施し、シート状封止材及び光電池モジュールを製作した。
実施例1で使用した変性エチレン/α−オレフィン共重合体のマスターバッチとエチレン/α−オレフィン共重合体の混合樹脂の代わりに、前記比較製造例5で製造されたシラン変性エチレン/α−オレフィン共重合体のマスターバッチと密度が0.902g/cm3であり、MFRが190℃、2.16kgの荷重下で3g/10分のエチレン/α−オレフィン共重合体をそれぞれ200g及び400gを準備し、1:2の比率で混合した樹脂を使用したことを除いて実施例1と同一に実施し、シート状封止材及び光電池モジュールを製作した。
実施例1で使用した変性エチレン/α−オレフィン共重合体のマスターバッチの代わりに、それぞれ前記比較製造例6及び比較製造例7で製造されたエチレン/α−オレフィン共重合体のマスターバッチを使用したことを除いて実施例1と同一に実施し、シート状封止材及び光電池モジュールを製作した。
実施例1で使用した変性エチレン/α−オレフィン共重合体のマスターバッチとエチレン/α−オレフィン共重合体の混合樹脂の代わりに、前記比較製造例8で製造された変性エチレン/α−オレフィン共重合体のマスターバッチと密度が0.870g/cm3であり、MFRが190℃、2.16kgの荷重下で3g/10分のエチレン/α−オレフィン共重合体をそれぞれ200g及び400gを準備し、1:2の比率で混合した樹脂を使用したことを除いて実施例1と同一に実施し、シート状封止材及び光電池モジュールを製作した。
[1.90度剥離強度の測定]
前記実施例1〜12、比較例1〜8で製造された封止材の剥離強度を測定するために、製造された光電池モジュールと類似の試験片を別に製造した。試験片は、板ガラス(厚さ:約3mm)、前記で製造された厚さ500μmの封止材及び裏面シート(厚さ20μmのポリフッ化ビニル樹脂シート、厚さ250μmのポリエチレンテレフタレート及び厚さ20μmのポリフッ化ビニル樹脂シートの積層シート;PVDF/PET/PVDF)を順に積層し、真空ラミネータで150℃に15分30秒間ラミネーションして製造した。製造された試験片の下部ガラス板を固定した後、ASTM D1897に準拠して、裏面シートにのみ接着された封止材を裏面シートと同時に15mm幅の矩形、50mm/分の引張速度及び90度の剥離角度で剥離しながら測定した剥離強度を表3に示した。
すなわち、前記実施例1〜12及び比較例1〜比較例8とそれに対する実験例を通じて、ビニルシラン、アルキルアミン、アミノシランまたはアルキルシランを単独で使用した場合よりビニルシラン及びアミノシランをすべて使用して変性させたエチレン/α−オレフィン共重合体のマスターバッチを非変性エチレン/α−オレフィン共重合体と特定含量範囲で使用する場合に、封止材上部の裏面シート及び下部のガラス基板と接着強度が優れていることを確認することができる。
実験例1で実施例1及び実施例3の封止材を使用して製造した光電池モジュールと類似の試験片の製作時にラミネーション条件を表5に示したように変更し、110℃、130℃、140℃、150℃、160℃でそれぞれ6分30秒、10分30秒、15分30秒間行ったことを除いて実験例1と同一に実施して測定した90度剥離強度を表5に示し、ラミネーション温度による接着強度を測定したグラフを図3に示した。
また、実験例1で比較例1の封止材を使用して製造した光電池モジュールと類似の試験片の製作時にラミネーション条件を表5に示したように変更し、110℃、130℃、140℃、150℃、160℃でそれぞれ6分30秒、10分30秒、15分30秒間行ったことを除いて実験例1と同一に実施して測定した90度剥離強度を表5に示し、ラミネーション温度による接着強度を測定したグラフを図3に示した。
実施例及び比較例で製造された光電子装置用封止材フィルムを、ASTM 1925に準拠して、Colorflex(Hunter lab)を利用して400nm〜700nm領域の反射率を測定し、これを利用して、YI値(黄色指数、Yellowness Index)を得た(下記式2参照)。
変性マスターバッチ内で一部のシリル基の炭化水素基がヒドロキシ基に転換された部分を含みながらも、アミン官能基を有する部分も一緒に含む分枝鎖を検出し、前記封止材フィルムのラミネーション過程で、アミノシラン化合物によって加水分解が促進され、メトキシシリル基(Si−O−CH3)がシラノール基(Si−OH)に転換された程度を測定するために、製造例1〜3及び比較製造例1の変性マスターバッチと実施例1〜3及び比較例1で製造された封止材フィルムに対して、前記変性マスターバッチ及び封止材内のメチレン基(CH2)とシラノール基(Si−OH)及びアミン基(NH2)の各ピークの面積をそれぞれ測定した。前記各ピークの面積は、次のような方法及び下記条件で測定した。
照射回数:32
分解能:4
前記実施例3及び比較例1で製造された封止材の光透過度を測定するために、別途の試験片を別に製造した。試験片は、2個の光学顕微鏡用スライドガラス(厚さ:約1mm)の間に前記で製造された厚さ500μmの封止材を2枚重ねて入れ、真空ラミネータでラミネーション温度を表9の条件のように異ならせてラミネーションして製造し、且つガイドを使用して2枚の重なった封止材シートの厚さの和が約500±50μmとなるように製造し、ヘイズメーター(Hazemeter)を使用して前記試験片の550nmの波長の光に対する電光線透過率及びヘイズ値を測定し、表9に示した。この場合、透過率及びヘイズ値は、前記試験片を試験片ホルダーに入れて3回測定した後、これらの平均値を求め、JIS K 7105の規格条件で測定された。ラミネーション工程時間は、5分 真空/30秒 圧力/10分 残留圧力に固定した。
Slit width:32nm
Detector unit:External(2D detectors)
Time constant:0.2秒
12、22 裏面シート
13、23 光起電力素子
14、24 封止材
Claims (4)
- オレフィン樹脂、不飽和シラン化合物、アミノシラン化合物及びラジカル開始剤を含むオレフィン樹脂組成物を反応器内に添加し、前記オレフィン樹脂組成物を押出反応させる段階を含み、前記アミノシラン化合物が、前記組成物中のシラン化合物100重量部に対して1〜40重量部の含量で含まれる、共重合体の製造方法。
- 不飽和シラン化合物は、下記化学式3で表示される化合物である、請求項1に記載の共重合体の製造方法:
DSiR18 pR19 (3−p) 化学式3
前記化学式3で、Dは、ケイ素原子に結合しているアルケニルを示し、
R18は、ケイ素原子に結合しているヒドロキシ基、ハロゲン、アミン基または−R20R21を示し、
R20は、酸素または硫黄原子であり、
R21は、アルキル基、アリール基またはアシル基を示し、
R19は、ケイ素原子に結合している水素、アルキル基、アリール基またはアラルキル基を示し、
pは、1〜3の整数である。 - 不飽和シラン化合物は、ビニルアルコキシシランである、請求項1に記載の共重合体の製造方法。
- 前記アミノシラン化合物は、下記化学式4で表示される化合物である、請求項1に記載の共重合体の製造方法:
SiR22 qR23 (4−q) 化学式4
前記化学式4で、
R22は、ケイ素原子に結合している−(CH2)rNR24R25を示し、
R24及びR25は、それぞれ独立に、窒素原子に結合している水素またはR26NH2を示し、
R26は、アルキレンを示し、
R23は、ケイ素原子に結合しているハロゲン、アミン基−R27R28または−R28を示し、
R27は、酸素または硫黄原子であり、
R28は、水素、アルキル基、アリール基、アラルキル基またはアシル基を示し、
qは、1〜4の整数であり、rは、0以上の整数である。
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