WO2014088180A1 - Adhesive composition for solar cell module, adhesive member for solar cell module formed therefrom, and solar cell module comprising same - Google Patents
Adhesive composition for solar cell module, adhesive member for solar cell module formed therefrom, and solar cell module comprising same Download PDFInfo
- Publication number
- WO2014088180A1 WO2014088180A1 PCT/KR2013/006465 KR2013006465W WO2014088180A1 WO 2014088180 A1 WO2014088180 A1 WO 2014088180A1 KR 2013006465 W KR2013006465 W KR 2013006465W WO 2014088180 A1 WO2014088180 A1 WO 2014088180A1
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- WIPO (PCT)
- Prior art keywords
- formula
- solar cell
- polysilsesquioxane
- cell module
- compound
- Prior art date
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- 239000000853 adhesive Substances 0.000 title claims abstract description 98
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 98
- 239000000203 mixture Substances 0.000 title claims abstract description 80
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims abstract description 110
- 150000001875 compounds Chemical class 0.000 claims abstract description 103
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 63
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims abstract description 30
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000003377 silicon compounds Chemical class 0.000 claims description 40
- 229940126062 Compound A Drugs 0.000 claims description 30
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 24
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 21
- 229910052736 halogen Inorganic materials 0.000 claims description 21
- 150000002367 halogens Chemical class 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 17
- 239000003963 antioxidant agent Substances 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 239000002683 reaction inhibitor Substances 0.000 claims description 9
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- 238000012643 polycondensation polymerization Methods 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 18
- 229920001296 polysiloxane Polymers 0.000 description 15
- 238000003756 stirring Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- -1 siloxane compound Chemical class 0.000 description 8
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical group O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 7
- 230000005484 gravity Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 description 6
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 4
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 3
- KNVOCSQDAIHOPP-UHFFFAOYSA-N 2-ethynylcyclohexan-1-ol Chemical compound OC1CCCCC1C#C KNVOCSQDAIHOPP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 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
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- 102100020895 Ammonium transporter Rh type A Human genes 0.000 description 2
- 101100301844 Arabidopsis thaliana RH50 gene Proteins 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 101150107345 Rhag gene Proteins 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000004148 curcumin Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000005055 methyl trichlorosilane Substances 0.000 description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000004825 One-part adhesive Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- PJRAPCLCRHFXNV-UHFFFAOYSA-N [SiH4].[Pt] Chemical compound [SiH4].[Pt] PJRAPCLCRHFXNV-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- ZPECUSGQPIKHLT-UHFFFAOYSA-N bis(ethenyl)-dimethoxysilane Chemical compound CO[Si](OC)(C=C)C=C ZPECUSGQPIKHLT-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000004956 cell adhesive effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XMKVMJPCDLDMTQ-UHFFFAOYSA-N ethenyl(diethoxy)silane Chemical compound CCO[SiH](C=C)OCC XMKVMJPCDLDMTQ-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 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
- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- QYRRPQSBTOLXQR-UHFFFAOYSA-N methoxy-[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(O[SiH2]OC)(C)C QYRRPQSBTOLXQR-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/02—Polysilicates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/14—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Definitions
- An adhesive composition for a solar cell module, an adhesive member for a solar cell module formed therefrom, and a solar cell module having the same are provided.
- the solar cell module can produce a desired output by connecting several solar cells to each other, and is made of a structure that can protect the battery from long-term natural environments and external shocks.
- a glass substrate with excellent light transmittance is used, and on the back, a back sheet made of a material having excellent moisture permeation prevention and electrical insulation properties is provided.
- the solar cell module is manufactured by sealing and compressing a glass substrate, a back sheet, a solar cell, and a frame accommodating the solar cell using an adhesive member.
- the adhesive member is generally formed by using a one-component adhesive composition containing a silsesquioxane oligomer, a filler, and the like in which a vinyl group, hydrogen and a hydroxyl group coexist in one molecule.
- the above-described adhesive composition may not only be stored at a low temperature because the crosslinking reaction may occur during storage at room temperature, and the uniformity and adhesion of the cured coating film formed from the adhesive composition may not reach satisfactory levels.
- Agent A containing a polysilsesquioxane compound having a C2-C10 alkenyl group and a C1-C10 alkyl group at the terminal and side chain according to one aspect of the present invention
- an adhesive composition for a solar cell module comprising a B agent containing a polycelsesquioxane compound having hydrogen and a C1-C10 alkyl group at its terminal and side chains.
- an adhesive member for a solar cell module including a curing reaction product of the adhesive composition for a solar cell module described above.
- the adhesive composition for a solar cell module according to an embodiment of the present invention is excellent in storage stability, and by using this, an adhesive member for a solar cell module having improved adhesion and mechanical properties may be manufactured.
- the adhesive composition for a solar cell module includes A containing a polysilsesquioxane compound having a C2-C10 alkenyl group and a C1-C10 alkyl group (hereinafter referred to as "polysilsesquioxane A”) at its terminal and side chains.
- Agent, and a B agent containing a polycelsesquioxane compound having a hydrogen and a C1-C10 alkyl group hereinafter referred to as "polysilsesquioxane B" at the terminal and side chain.
- the solar cell module adhesive composition is a two-component composition, unlike the conventional one-component adhesive composition is very excellent in storage stability and can be stored at room temperature.
- the adhesive composition for the solar cell module does not use high specific gravity fillers such as silicon oxide (SiO 2 ) and calcium carbonate (CaCO 3 ), thereby improving workability by weight reduction. And using such an adhesive composition it can be produced an adhesive member for a solar cell module with improved mechanical properties and adhesion such as durability.
- the agent A further includes at least one selected from an adhesion improving agent and a catalyst.
- the agent B further includes one or more selected from antioxidants and reaction inhibitors.
- the polysilsesquioxane compound A is a polysilsesquioxane compound having a C2-C10 alkenyl group, a C1-C10 alkyl group, and a hydroxyl group at the terminal and side chain (hereinafter, “the first sesquioxane compound ”) Is obtained by removing a hydroxyl group from the first polysilsesquioxane compound by reacting with a silicon compound represented by the following formula (4), a silicon compound represented by the following formula (5), and a silazane compound: .
- R 3 is a C1-C10 alkyl group
- Y 4 is a C1-C10 alkoxy group or a halogen element
- n is an integer of 1 to 3
- R ⁇ 4> is a C1-C10 alkyl group and Y ⁇ 5> is a C1-C10 alkoxy group or a halogen element.
- the first polysilsesquioxane compound may be prepared by subjecting a silicon compound represented by the following Chemical Formula 1, a silicon compound represented by the following Chemical Formula 2, and a silicon compound represented by the following Chemical Formula 3 to a hydrolysis polycondensation reaction. have.
- R 1 is a C2-C10 alkenyl group
- Y 1 is a C1-C10 alkoxy group or a halogen element
- n 1 to 3
- R 2 is a C1-C10 alkyl group
- Y 2 is a C1-C10 alkoxy group or a halogen element
- n 1 to 3
- Y 3 in Formula 3 is a C1-C10 alkoxy group or a halogen element.
- polysilsesquioxane B is a polysilsesquioxane compound having a hydrogen, a C1-C10 alkyl group and a hydroxyl group at the terminal and side chain (hereinafter referred to as "second polysilsesquioxane compound")
- second polysilsesquioxane compound a polysilsesquioxane compound having a hydrogen, a C1-C10 alkyl group and a hydroxyl group at the terminal and side chain
- R 3 is a C1-C10 alkyl group
- Y 4 is a C1-C10 alkoxy group or a halogen element
- R ⁇ 4> is a C1-C10 alkyl group and Y ⁇ 5> is a C1-C10 alkoxy group or a halogen element.
- the second polysilsesquioxane-based compound may be obtained by carrying out a reaction for hydrolytic condensation polymerization of a silicone compound represented by the following formula (2), a silicone compound represented by the following formula (3) and a silicone compound represented by the following formula (6): have.
- R 2 in Formula 2 is a C2-C10 alkenyl group
- Y 2 is a C1-C10 alkoxy group or a halogen element
- n 1 to 3
- Y 3 in Formula 3 is a C1-C10 alkoxy group or a halogen element
- Y 6 in Formula 6 is a C1-C10 alkoxy group or a halogen element
- n 1 to 3.
- Silazane compounds used in the preparation of the first polysilsesquioxane compound include hexadimethylsilazane, hexadiethylsilazane, and hexadiphenylsilazane.
- the number average molecular weight of the first polysilsesquioxane compound and the second polysilsesquioxane compound is 10,000 to 30,000.
- the polysilsesquioxane compound A and the polysilsesquioxane compound B are hydroxy groups of the first polysilsesquioxane compound and the second polysilsesquioxane compound, a silicone compound and a silazane compound. It is a polymer modified and hydrophobized by using one selected from among the viscosity is 50,000 to 100,000 mPas, the number average molecular weight is 10,000 to 30,000.
- the viscosity is evaluated according to the method of expressing the average value for the measured viscosity at 10 ⁇ 100RPM by rotating viscometer (Brook-Filed) at 25 °C, RH50% conditions.
- the viscosity of the polysilsesquioxane-based compound A and the polysilsesquioxane-based compound B is in the above range, the flowability of the adhesive composition is appropriate, so that an operation of manufacturing the adhesive member can be easily performed.
- the C2-C10 alkenyl group includes a vinyl group or an allyl group
- the C1-C10 alkyl group includes a methyl, ethyl, n-propyl, n-pentyl, isopentyl or butyl group.
- the C1-C10 alkoxy group includes a methoxy group, ethoxy group, propoxy group or pentyloxy, and the halogen element includes fluorine, chlorine, or iodine.
- the first polysilsesquioxane-based compound includes a unit represented by the following formula (7) or represented by the following formula (7).
- R 1 is a C2-C10 alkenyl group
- R 2 is a C1-C10 alkyl group.
- R 1 is a vinyl group
- R 2 is a methyl group
- the polysilsesquioxane compound A is represented by the following formula (8) or includes a unit represented by the following formula (8).
- R 1 is a C2-C10 alkenyl group
- R 2 is a C1-C10 alkyl group
- R 3 is a C1-C10 alkyl group.
- R 1 is a vinyl group
- R 2 is a methyl group
- R 3 is a methyl group.
- the second polysilsesquioxane compound includes a unit represented by the following formula (9) or represented by the following formula (9).
- R 2 in Formula 9 is a C1-C10 alkyl group.
- the polysilsesquioxane B is represented by the following formula (10) or includes a unit represented by the formula (10).
- R ⁇ 2> is a C1-C10 alkyl group and R ⁇ 3> is a C1-C10 alkyl group.
- the polysilsesquioxane compound A includes a compound represented by the following formula (11) or (12).
- x, y, z ' is independently a number greater than 0, for example, the number of 1 to 200,
- x, y, z, w is independently a number greater than 0, for example 1 to 200.
- the polymerization degree x, y, z of Formula 11 and the polymerization degree x, y, z, w of Formula 12 are selected such that the number average molecular weight of the compound represented by Formula 11 or Formula 12 is in the range of 10,000 to 30,000.
- the polysilsesquioxane B includes a compound represented by the following Formula 13 or Formula 14.
- x, y, z ' is independently a number greater than 0, for example, a number of 1 to 200,
- x, y, z and w are each independently a number greater than 0, for example, 1 to 200.
- X, y, z of Formula 13 and x, y, z, w of Formula 14 are selected such that the number average molecular weight of the compound represented by Formula 13 or Formula 14 is in the range of 10,000 to 30,000.
- the polysilsesquioxane B made of B is used in an amount of 5 to 45 parts by weight based on 100 parts by weight of the polysilsesquioxane compound A made of the A.
- the content of the polysilsesquioxane B is within the above range, it is possible to manufacture an adhesive member for a solar cell module having excellent durability.
- the agent B further includes a polysilsesquioxane compound A.
- a polysilsesquioxane compound A As such, when the polysilsesquioxane-based compound A is further added to the agent B, the viscosity of the agent A and the agent B is controlled to almost the same range, so that the agent A and the agent B are mixed evenly when sprayed from the nozzle of the filling cartridge, thereby making a perfect cured product. There is an advantage that can form.
- the content of the polysilsesquioxane compound A of agent B is 30 to 80 parts by weight based on 100 parts by weight of the polysilsesquioxane compound A of agent A.
- the agent A may include an adhesion improving agent and a catalyst.
- the adhesion improving agent is a 3-aminopropyl triethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-methoglyoxypropyl trimethoxysilane as components added to improve the adhesion of the adhesive member formed from the adhesive composition. , N- ( ⁇ -aminoethyl) - ⁇ -aminopropyl trimethoxysilane, ⁇ -glycidoxypropyl triethoxy silane and ⁇ -glycidoxy trimethyldimethoxysilane.
- the adhesion improving agent is 1 to 15 parts by weight based on 100 parts by weight of the polysilsesquioxane compound A in Agent A.
- the content of the adhesion improving agent is in the above range, the adhesion of the adhesive member formed from the composition to the substrate is excellent.
- the catalyst serves to promote the reaction between the polysilsesquioxane compound A and the polysilsesquioxane compound B.
- the catalyst may also serve as a flame retardant.
- a Speyer catalyst hereinafter, H 2 PtCl 6
- the catalyst is used in 0.0001 to 0.5 moles based on 1 mole of the polysilsesquioxane compound A.
- the content of the catalyst is in the above range, the reaction rate of the curing reaction of the polysilsesquioxane compound A and the polysilsesquioxane compound B is increased, thereby reducing the reaction time.
- the B agent may include an antioxidant and a reaction inhibitor.
- the antioxidant prevents the adhesive composition and the adhesive member formed from the adhesive composition from being oxidized by ultraviolet rays and heat, and prevents oxygen from being promoted by binding oxygen in the air to the ends of the broken molecules.
- Such antioxidants include phenolic compounds, monophenolic compounds or bisphenolic compounds, and include, but are not limited to, isotridecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propio Nate, benzene propanoic acid 3, 3-bis (1, 1- dimethylethyl) -4-hydroxy, C7-9- isoalkyl ester, etc. are mentioned.
- the antioxidant is used in 0.0001 to 0.5 moles based on 1 mole of polysilsesquioxane compound B. When the content of the antioxidant is in the above range, yellowing of the solar cell adhesive member formed using the adhesive composition does not occur.
- the reaction inhibitor inhibits the reaction of the components constituting the agent B before the agent A and the agent B are mixed.
- the reaction refers to, for example, a hydrosilylation reaction.
- the reaction inhibitor includes 1-ethynylcyclohexanol or 2-methyl-3-butyn-2-ol.
- the reaction inhibitor is used in an amount of 0.0001 to 0.5 moles based on 1 mole of the polysilsesquioxane compound B.
- a silane mixture is obtained by mixing the silicon compound represented by Chemical Formula 1, the silicon compound represented by Chemical Formula 2, and the silicon compound represented by Chemical Formula 3. The mixing is performed by stirring at room temperature for 0.5 to 1 hour.
- the rotational speed per minute during the stirring is 300 to 500 rpm.
- room temperature means 20 to 25 °C.
- the silicone compound represented by Formula 2 is used in an amount of 10 to 100 parts by weight based on 100 parts by weight of the silicon compound represented by Formula 1, and the silicon compound represented by Formula 3 is 100 weight of the silicon compound represented by Formula 1 It is used in 10 to 120 parts by weight based on parts.
- Acid and solvent are added and mixed to the silane mixture.
- the acid includes sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or acetic acid, and the acid is used in an amount of 0.01 to 2 moles based on 1 mole of the silicon compound represented by Formula 1.
- the solvent includes water or an alcohol, and the amount of the solvent is 50 to 2000 parts by weight based on 100 parts by weight of the silicone compound represented by Formula 1.
- the silicon compound represented by Formula 2 includes methyltrimethoxysilane (CH 3 Si (OCH 3 ) 3 ), or methyltriethoxysilane (CH 3 Si (OCH 2 CH 3 ) 3 ).
- the silicon compound represented by Chemical Formula 3 includes tetraethylorthosilicate (Si (OCH 2 CH 3 ) 4 ), or tetramethylorthosilicate (Si (OCH 3 ) 4 ).
- reaction mixture obtained according to the above process is heat-treated to perform hydrolysis and polycondensation reaction of the silicon compound.
- the heat treatment temperature is 80 to 100 °C.
- the heat treatment temperature is within the above range, the reactivity of the hydrolysis polycondensation reaction of the silicone compound is excellent.
- the reaction mixture is cooled to 50 ° C. or lower, for example, 10 to 45 ° C., and a polysilsesquioxane compound having a C 2 -C 10 alkenyl group, C 1 -C 10 alkyl group and a hydroxyl group at the terminal and side chain ( 1 polysilsesquioxane compound) is prepared.
- the first polysilsesquioxane compound and a solvent are mixed to obtain a mixture.
- the solvent is tetrahydrofuran, pyridine, propylene glycol monomethylether acetate, or propylene glycol methyl ether, and the solvent is used at 30 to 2000 parts by weight based on 100 parts by weight of the first polysilsesquioxane compound.
- the mixing may be performed by stirring at room temperature for 1 to 5 hours.
- One selected from the silicone compound represented by Formula 4, the silicone compound represented by Formula 5, and silazane is used in an amount of 5 to 100 parts by weight based on 100 parts by weight of the first polysilsesquioxane compound.
- the content of one selected from the silicon compound represented by Formula 4, the silicon compound represented by Formula 5, and silazane is within the above range, a polysilsesquioxane compound having controlled hydrophobicity may be obtained.
- reaction mixture is heat-treated to perform a silanol capping reaction of the first polysilsesquioxane compound.
- the heat treatment temperature is 80 to 100 °C.
- the silanol capping reactivity of the first polysilsesquioxane compound is excellent.
- the silicone compound represented by Chemical Formula 4 includes methyltrichlorosilane, dimethyldichlorosilane or trimethylchlorosilane.
- the silicon compound represented by Chemical Formula 5 includes (CH 3 SiCl 2 ) 2 O.
- the resultant of the silanol capping reaction is evaporated under reduced pressure to remove low boiling water, and then cooled to 50 ° C. or lower, for example, 10 to 45 ° C., to obtain polysilsesquioxane compound A.
- polysilsesquioxane compound B is prepared according to the following procedure.
- the silicon compound represented by Chemical Formula 2 the silicon compound represented by Chemical Formula 3, and the silicon compound represented by Chemical Formula 6 are stirred at room temperature for 0.5 to 1 hour to perform a mixing process.
- the rotational speed per minute during the stirring is 300 to 500 rpm.
- the type of the solvent is as described in the preparation of the first polysilsesquioxane compound.
- the acid is used in an amount of 0.01 to 2 moles based on 1 mole of the silicon compound represented by Formula 2.
- the solvent is used in an amount of 500 to 2000 parts by weight based on 100 parts by weight of the silicone compound represented by Formula 2.
- the silicon compound represented by Chemical Formula 6 includes H-SiCH 3 (OCH 3 ) 2 or H-Si (OCH 3 ) 3 .
- the silicone compound represented by Formula 3 is used in 10 to 150 parts by weight based on 100 parts by weight of the silicone compound represented by Formula 2, and the silicon compound represented by Formula 6 is 100 weight of the silicon compound represented by Formula 2 It is used in 10 to 150 parts by weight based on parts.
- the heat treatment temperature is as described in the preparation of the first polysilsesquioxane compound.
- the second polysilsesquioxane-based compound is dissolved in a solvent, and one or more selected from the silicon compound represented by the formula (4), the siloxane compound represented by the formula (5), and the silazane are added thereto, mixed, and heat-treated to obtain a second compound.
- the silanol capping reaction which removes a hydroxyl group from a polysilsesquioxane type compound is performed.
- the heat treatment temperature is the same as the manufacturing process of the polysilsesquioxane A.
- the amount of one selected from the silicone compound represented by Formula 4, the siloxane compound represented by Formula 5, and silazane is 5 to 100 parts by weight based on 100 parts by weight of the second polysilsesquioxane compound.
- the type of the solvent is the same as the preparation of the polysilsesquioxane compound A.
- the content of the solvent is 30 to 2000 parts by weight based on 100 parts by weight of the second polysilsesquioxane compound.
- the reaction product of the silanol capping reaction is evaporated under reduced pressure to remove low boiling water, and then cooled to 50 ° C. or lower, for example, 10 to 45 ° C. to obtain silsesquioxane compound B.
- the mixing is according to the stirring process for 300 to 500 rpm, 0.5 to 3 hours at room temperature.
- the mixing is carried out at the same temperature, stirring time and rotational speed conditions as in the case of preparation of agent A.
- the polysilsesquioxane compound A can be further added to the agent B.
- agent A and agent B are mixed to obtain an adhesive composition for a two-component solar cell module.
- the weight ratio of the agent A and agent B is 1: 1 to 20: 1.
- the weight of agent B to agent A is in the above range, the unreacted cured product of agent A and agent B is not formed and the hardness of the cured product is excellent.
- Adhesive composition for a solar cell module is a weight ratio of agent A and agent B is 1: 1.
- the viscosity of the agent A and the agent B is different, so that the mixing is easy, so that a complicated weighing process can be omitted during the operation and the curing time is short.
- the adhesive composition for a solar cell module obtained according to the above production method has a viscosity of about 80,000 to 120,000 cPs (80,000 to 120,000 mPa.s).
- the viscosity of the adhesive composition is lower than the above range, the discharge pressure is too low to contaminate the adhesive due to the adhesive outside the working area. If the viscosity is higher than the above range, the discharge pressure of the composition may be high, the adhesive force may be lowered, and the worker's fatigue may be increased. Workability may be degraded.
- the adhesive composition can be packaged using a two-component cartridge.
- the composition is an additional curing type adhesive composition, unlike conventional adhesive compositions, does not generate by-products such as water and hydrogen when cured, has high reliability and durability for mechanical properties, and does not have thickening and partial curing during storage, thereby improving storage stability at room temperature. Can be stored. In addition, since it does not contain a filler such as calcium carbonate, the fatigue of the worker is reduced and workability is improved by lightening.
- an adhesive member including a cured product of the adhesive composition for a solar cell module and a solar cell module having the same.
- the curing reaction of the composition includes a hydrogenation reaction in which hydrogen contained in the polysilsesquioxane compound B agent B is added to a double bond of the alkenyl group of the polysilsesquioxane compound A agent A.
- the product obtained by the curing reaction of the composition is a hydrophobic polysilsesquioxane-based compound having random and ladder types, unlike when using an adhesive composition containing a conventional silsesquioxane oligomer.
- the adhesive member includes a hydrophobic polysilsesquioxane-based compound, and the use of the adhesive member can prevent the frame corrosion in advance and prevent the solar cell from malfunctioning or reducing the life cycle of the solar cell due to the contamination. have.
- Methyltrimethoxysilane (hereinafter referred to as MTMS) in an approximately 1 liter round bottom flask equipped with a condenser, stirrer, temperature control system (including circulator, heating mantle and thermocouple) ) 124 parts by weight, 162 parts by weight of vinyltrimethoxysilane (hereinafter referred to as VTMS), and 169 parts by weight of tetraethylorthosilicate (hereinafter referred to as TEOS) were added and stirred at room temperature at about 400 RPM for 30 minutes.
- VTMS vinyltrimethoxysilane
- TEOS tetraethylorthosilicate
- the stirred solution was refluxed at about 90 ° C. for 3 hours and then distilled under reduced pressure to remove low boiling water.
- the resultant from which the low-boiling water was removed was cooled to about 45 ° C. to prepare a first polysilsesquioxane compound represented by a colorless transparent formula (7) having a number average molecular weight (Mn) of about 20,000 including methyl and vinyl groups.
- R 1 is a vinyl group
- R 2 is a methyl group
- THF tetrahydrofuran
- MTCS methyltrichlorosilane
- the reaction mixture was stirred for about 3 hours and then distilled under reduced pressure at 100 ° C. to remove low boiling water.
- the reaction product from which low boiling water was removed was cooled to about 45 ° C., and the viscosity was about 80,000 mPa .
- Polysilsesquioxane compound A represented by Chemical Formula 8 of s was prepared.
- R ⁇ 1> is a vinyl group
- R ⁇ 2> is a methyl group
- R ⁇ 3> is a methyl group
- Mn number average molecular weight
- R 2 is a methyl group.
- R 2 is a methyl group
- R 3 is a methyl group
- Vi PSQ a polysilsesquioxane compound represented by Formula 8 (hereinafter referred to as Vi PSQ) prepared according to Synthesis Example 2 in a vessel No. 1, 3-glycidoxypropyl trimethoxysilane (hereinafter referred to as GPTMS) 10 parts by weight, 1 part by weight of a Speyer catalyst (Speier catalyst) (H 2 PtCl 6 ) in order, and then stirred at about 400 rpm at room temperature for 30 minutes to prepare a agent A.
- GPTMS 3-glycidoxypropyl trimethoxysilane
- H PSQ polysilsesquioxane compound represented by Chemical Formula 10
- isotridecyl-3- (3,5 10 parts by weight of di- t -butyl-4-hydroxyphenyl) propionate and 1 part by weight of 2-ethynylcyclohexanol (1-ETCH) were added in this order, followed by stirring at room temperature at about 400 rpm for 30 minutes.
- H PSQ polysilsesquioxane compound represented by Chemical Formula 10
- Agent A and agent B were mixed in a 1: 1 weight ratio to prepare an adhesive composition for a two-component solar cell module.
- Example 1 As shown in Table 1, except that the content of the constituent components of the adhesive composition was changed, it was carried out in the same manner as in Example 1 to obtain an adhesive composition for a solar cell module.
- Vi PSQ The content of the stage in the embodiment 2-4-vinyl content of the polysilsesquioxane (hereinafter referred to as Vi PSQ) in the A and B is 100 parts by weight of the vinyl polysilsesquioxane (hereinafter referred to as Vi PSQ) is carried out in 60 parts by weight of Example 2, 50 parts by weight of Example 3, and 40 parts by weight of Example 4.
- Silsesquioxane oligomer (OSQ), ⁇ , ⁇ -vinyl terminated polydimethylsiloxane ( Vi PDMS), ⁇ , ⁇ -hydrogen terminated polydimethylsiloxane ( H PDMS), SiO 2 , CaCO 3 , triethylphosphate (TEP) , GPTMS and isotridecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and DBTDL were mixed in the composition of Table 1 to prepare a one-part adhesive composition.
- OSQ Silsesquioxane oligomer
- Vi PDMS Vi PDMS
- H PDMS ⁇ -hydrogen terminated polydimethylsiloxane
- SiO 2 SiO 2
- CaCO 3 triethylphosphate
- TEP triethylphosphate
- GPTMS and isotridecyl-3- (3,5-di-t-butyl-4-hydroxy
- Specimens were prepared according to the following method and the physical properties of each specimen were evaluated as follows.
- each of the adhesive composition of Example 1-4 and the adhesive composition of Comparative Example 1-2 was each 2 ⁇ m in one portion (20 ⁇ 10 mm) of an aluminum (Al) specimen (size: 20 ⁇ 50 ⁇ 2 mm). After the coating with a thickness of another aluminum (Al) by attaching a specimen attached to stand at 100 °C, 1 hour to prepare an adhesive specimen (B).
- Adhesion was measured according to the test method KSF1107A with UTM at 25 ° C. and RH 50% under the conditions of the adhesive specimen (B).
- the specimen (C) was measured at 25 °C, RH 50% condition by contacting the surface with a finger and the time the adhesive does not appear.
- the specimen D was measured at 25 ° C. and RH 50% at a Brook-Filed viscometer (10 rpm, Sp # 4 condition) to measure the intrinsic viscosity, and measured the change with time over time of the viscosity to double the initial viscosity. This time was determined as port life.
- Specimen (A) was prepared to measure hardness, tensile strength, elongation, modulus, and the like, and specimen (A) was cut to 10 ⁇ 10 mm size, 5EA was made, and tweezers were placed in a chamber of an electronic hydrometer to measure specific gravity. Each 5EA was measured in turn and the average value was determined as the specific gravity.
- Table 2 The physical property evaluation results are shown in Table 2 below.
- the specimen using the adhesive composition of Example 1-4 is not only improved hardness, tensile strength, elongation, modulus characteristics, Scotch time compared to the specimen using the adhesive composition of Comparative Example 1-2 It was found that the pot life and adhesion properties were improved.
- the test piece produced using the adhesive composition of Comparative Example 1-2 showed an increasing characteristic compared with the case of Example 1-4.
- the viscosity is increased, the discharge pressure and specific gravity are increased when using the cartridge containing the adhesive composition, and as a result, the product becomes heavy and the worker's fatigue is increased and the working speed is slowed. Therefore, when using the adhesive composition of Example 1-4 it can be seen that the workability is improved by reducing the worker fatigue compared to the case of Comparative Example 1-2.
- the adhesive composition for a solar cell module according to an embodiment of the present invention is excellent in storage stability, and by using this, an adhesive member for a solar cell module having improved adhesion and mechanical properties may be manufactured.
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Abstract
Provided are an adhesive composition for a solar cell module, an adhesive member for a solar cell module formed therefrom, and the solar cell module comprising the same, the adhesive composition for a solar cell module comprising: an agent A which contains a polysilsesquioxane-based compound having C2-C10 alkenyl groups and C1-C10 alkyl groups at an end and a side chain thereof; and an agent B which contains a polysilsesquioxane-based compound having hydrogen and C1-C10 alkyl groups at an end and a side chain thereof. The adhesive composition has excellent storage stability, and an adhesive member for a solar cell module which has improved adhesion and improved mechanical properties can be produced when using the adhesive composition.
Description
태양전지 모듈용 접착 조성물, 이로부터 형성된 태양전지 모듈용 접착 부재 및 이를 구비한 태양전지 모듈을 제시한다.An adhesive composition for a solar cell module, an adhesive member for a solar cell module formed therefrom, and a solar cell module having the same are provided.
태양전지 모듈은 여러 개의 태양전지를 서로 연결하여 원하는 출력을 낼 수 있으며, 장기간의 자연환경 및 외부충격으로부터 전지를 보호할 수 있는 구조로 만들어진다. 태양전지 모듈 전면에는 빛의 투과율이 우수한 유리기판을 사용하고 뒷면에는 수분 침투 방지와 전기적 절연 특성이 우수한 재질로 된 백 시트가 구비된다. 상기 태양전지 모듈은 유리기판, 백 시트, 태양전지 및 상기 태양전지를 수용하는 프레임을 접착 부재를 이용하여 밀봉, 압축하여 제조된다.The solar cell module can produce a desired output by connecting several solar cells to each other, and is made of a structure that can protect the battery from long-term natural environments and external shocks. On the front of the solar cell module, a glass substrate with excellent light transmittance is used, and on the back, a back sheet made of a material having excellent moisture permeation prevention and electrical insulation properties is provided. The solar cell module is manufactured by sealing and compressing a glass substrate, a back sheet, a solar cell, and a frame accommodating the solar cell using an adhesive member.
상기 접착 부재는 한분자내에 비닐기, 수소 및 하이드록시기가 공존하는 실세스퀴옥산 올리고머, 필러 등을 포함하는 일액형 접착 조성물을 사용하여 형성하는 것이 일반적이다. The adhesive member is generally formed by using a one-component adhesive composition containing a silsesquioxane oligomer, a filler, and the like in which a vinyl group, hydrogen and a hydroxyl group coexist in one molecule.
그런데 상술한 접착 조성물은 상온 보관시 자체 가교 반응이 일어날 수 있어 저온에서 보관해야 할 뿐만 아니라, 상기 접착 조성물로부터 형성된 경화 도막의 균일성 및 접착력이 만족할만한 수준에 이르지 못하여 개선의 여지가 많다.
However, the above-described adhesive composition may not only be stored at a low temperature because the crosslinking reaction may occur during storage at room temperature, and the uniformity and adhesion of the cured coating film formed from the adhesive composition may not reach satisfactory levels.
접착력, 기계적 물성 및 저장 안정성이 우수한 태양전지 모듈용 접착 부재를 형성할 수 있는 태양전지 모듈용 접착 조성물, 이로부터 형성된 태양전지 모듈용 접착 부재 및 이를 구비한 태양전지 모듈을 제공하는 것이다. It is to provide a solar cell module adhesive composition capable of forming an adhesive member for a solar cell module excellent in adhesion, mechanical properties and storage stability, a solar cell module adhesive member formed therefrom and a solar cell module having the same.
본 발명의 한 측면에 따라 말단 및 측쇄에 C2-C10의 알케닐기와 C1-C10 알킬기를 갖는 폴리실세스퀴옥산계 화합물을 함유하는 A제; 및Agent A containing a polysilsesquioxane compound having a C2-C10 alkenyl group and a C1-C10 alkyl group at the terminal and side chain according to one aspect of the present invention; And
말단 및 측쇄에 수소와 C1-C10 알킬기를 갖는 폴리셀세스퀴옥산계 화합물을 함유하는 B제를 포함하는 태양전지 모듈용 접착 조성물을 제공한다.Provided is an adhesive composition for a solar cell module comprising a B agent containing a polycelsesquioxane compound having hydrogen and a C1-C10 alkyl group at its terminal and side chains.
본 발명의 다른 측면에 따라 상술한 태양전지 모듈용 접착 조성물의 경화 반응 생성물을 포함하는 태양전지 모듈용 접착 부재를 제공한다.According to another aspect of the present invention, there is provided an adhesive member for a solar cell module including a curing reaction product of the adhesive composition for a solar cell module described above.
본 발명의 또 다른 측면에 따라 상술한 접착 부재를 구비하는 태양전지 모듈을 제공한다.According to still another aspect of the present invention, there is provided a solar cell module having the adhesive member described above.
본 발명의 일구현예에 따른 태양전지 모듈용 접착 조성물은 저장 안정성이 우수하며 이를 이용하면 접착력과 기계적 물성이 개선된 태양전지 모듈용 접착 부재를 제작할 수 있다.The adhesive composition for a solar cell module according to an embodiment of the present invention is excellent in storage stability, and by using this, an adhesive member for a solar cell module having improved adhesion and mechanical properties may be manufactured.
이하, 본 발명의 일구현예에 따른 태양전지 모듈용 접착 조성물, 그 제조방법 이를 이용하여 제조된 접착부재 및 이를 구비한 태양전지용 모듈을 상세하게 설명하기로 하지만 본 발명이 후술하는 내용에 제한되는 것은 아니며 해당분야에서 통상의 지식을 가진 자라면 본 발명의 기술적 사상을 벗어나지 않는 범위내에서 본 발명을 다양한 다른 형태로 구현할 수 있을 것이다.Hereinafter, an adhesive composition for a solar cell module and a method for manufacturing the same according to an embodiment of the present invention will be described in detail with respect to the adhesive member prepared by using the same and a solar cell module having the same. Those skilled in the art will appreciate that the present invention may be embodied in various other forms without departing from the spirit of the invention.
상기 태양전지 모듈용 접착 조성물은 말단 및 측쇄에 C2-C10의 알케닐기와 C1-C10 알킬기를 갖는 폴리실세스퀴옥산계 화합물(이하, “폴리실세스퀴옥산 A”라고 함)를 함유하는 A제와 말단 및 측쇄에 수소와 C1-C10 알킬기를 갖는 폴리셀세스퀴옥산계 화합물(이하, “폴리실세스퀴옥산 B”라고 함)을 함유하는 B제를 포함한다.The adhesive composition for a solar cell module includes A containing a polysilsesquioxane compound having a C2-C10 alkenyl group and a C1-C10 alkyl group (hereinafter referred to as "polysilsesquioxane A") at its terminal and side chains. Agent, and a B agent containing a polycelsesquioxane compound having a hydrogen and a C1-C10 alkyl group (hereinafter referred to as "polysilsesquioxane B") at the terminal and side chain.
상기 태양전지 모듈용 접착 조성물은 이액형 조성물로서 종래의 일액형 접착 조성물과 달리 저장 안정성이 매우 우수하여 상온에서 보관 가능하다. 그리고 상기 태양전지 모듈용 접착 조성물은 실리콘 산화물(SiO2), 탄산칼슘(CaCO3)과 같은 고비중 필러를 사용하지 않아 경량화에 의하여 작업성이 개선된다. 그리고 이러한 접착 조성물을 이용하면 내구성과 같은 기계적 물성 및 접착력이 향상된 태양전지 모듈용 접착 부재를 제조할 수 있다.The solar cell module adhesive composition is a two-component composition, unlike the conventional one-component adhesive composition is very excellent in storage stability and can be stored at room temperature. In addition, the adhesive composition for the solar cell module does not use high specific gravity fillers such as silicon oxide (SiO 2 ) and calcium carbonate (CaCO 3 ), thereby improving workability by weight reduction. And using such an adhesive composition it can be produced an adhesive member for a solar cell module with improved mechanical properties and adhesion such as durability.
상기 A제는 접착 개선제 및 촉매 중에서 선택된 하나 이상을 더 포함한다.The agent A further includes at least one selected from an adhesion improving agent and a catalyst.
상기 B제는 산화 방지제 및 반응억제제 중에서 선택된 하나 이상을 더 포함한다.The agent B further includes one or more selected from antioxidants and reaction inhibitors.
상기 A제에서 폴리실세스퀴옥산계 화합물 A는 말단 및 측쇄에 C2-C10 알케닐기, C1-C10 알킬기 및 하이드록시기를 갖는 폴리실세스퀴옥산계 화합물 (이하, “제1세스퀴옥산계 화합물”라고 함)을 하기 화학식 4로 표시되는 실리콘 화합물, 하기 화학식 5로 표시되는 실리콘 화합물 및 실라잔 화합물 중에서 선택된 하나와 반응하여 상기 제1폴리실세스퀴옥산계 화합물로부터 하이드록시기를 제거하여 얻은 것이다.In the agent A, the polysilsesquioxane compound A is a polysilsesquioxane compound having a C2-C10 alkenyl group, a C1-C10 alkyl group, and a hydroxyl group at the terminal and side chain (hereinafter, “the first sesquioxane compound ”) Is obtained by removing a hydroxyl group from the first polysilsesquioxane compound by reacting with a silicon compound represented by the following formula (4), a silicon compound represented by the following formula (5), and a silazane compound: .
화학식 4 
Formula 4
상기 화학식 4중, R3은 C1-C10 알킬기이고, Y4은 C1-C10 알콕시기 또는 할로겐 원소이고, n은 1 내지 3의 정수이고,In Formula 4, R 3 is a C1-C10 alkyl group, Y 4 is a C1-C10 alkoxy group or a halogen element, n is an integer of 1 to 3,
화학식 5 
Formula 5
상기 화학식 5중, R4는 C1-C10 알킬기이고, Y5는 C1-C10 알콕시기 또는 할로겐 원소이다.In said Formula (5), R <4> is a C1-C10 alkyl group and Y <5> is a C1-C10 alkoxy group or a halogen element.
상기 제1폴리실세스퀴옥산계 화합물은 하기 화학식 1로 표시되는 실리콘 화합물, 하기 화학식 2로 표시되는 실리콘 화합물 및 하기 화학식 3으로 표시되는 실리콘 화합물을 가수분해 축중합하는 반응을 실시하여 제조할 수 있다.The first polysilsesquioxane compound may be prepared by subjecting a silicon compound represented by the following Chemical Formula 1, a silicon compound represented by the following Chemical Formula 2, and a silicon compound represented by the following Chemical Formula 3 to a hydrolysis polycondensation reaction. have.
화학식 1 
Formula 1
상기 화학식 1중 R1은 C2-C10 알케닐기이고, Y1은 C1-C10 알콕시기 또는 할로겐 원소이고,In Formula 1, R 1 is a C2-C10 alkenyl group, Y 1 is a C1-C10 alkoxy group or a halogen element,
n은 1 내지 3이고, n is 1 to 3,
화학식 2 
Formula 2
상기 화학식 2중 R2은 C1-C10 알킬기이고, Y2은 C1-C10 알콕시기 또는 할로겐 원소이고,In Formula 2, R 2 is a C1-C10 alkyl group, Y 2 is a C1-C10 alkoxy group or a halogen element,
n은 1 내지 3이고, n is 1 to 3,
화학식 3 
Formula 3
상기 화학식 3중 Y3은 C1-C10 알콕시기 또는 할로겐 원소이다. Y 3 in Formula 3 is a C1-C10 alkoxy group or a halogen element.
상기 B제에서 폴리실세스퀴옥산 B는 말단 및 측쇄에 수소, C1-C10 알킬기 및 하이드록시기를 갖는 폴리실세스퀴옥산계 화합물 (이하,“제2폴리실세스퀴옥산계 화합물”이라고 함)을 하기 화학식 4로 표시되는 실리콘 화합물, 하기 화학식 5로 표시되는 실록산 화합물, 실라잔 화합물 중에서 선택된 하나와 반응하여 상기 제2폴리실세스퀴옥산계 화합물로부터 하이드록시기를 제거하여 얻는다.In the B agent, polysilsesquioxane B is a polysilsesquioxane compound having a hydrogen, a C1-C10 alkyl group and a hydroxyl group at the terminal and side chain (hereinafter referred to as "second polysilsesquioxane compound") To react with one selected from a silicon compound represented by the formula (4), a siloxane compound represented by the following formula (5), a silazane compound is obtained by removing a hydroxyl group from the second polysilsesquioxane-based compound.
[화학식 4][Formula 4]
상기 화학식 4중, R3은 C1-C10 알킬기이고, Y4은 C1-C10 알콕시기 또는 할로겐 원소이고,In Formula 4, R 3 is a C1-C10 alkyl group, Y 4 is a C1-C10 alkoxy group or a halogen element,
[화학식 5][Formula 5]
상기 화학식 5중, R4는 C1-C10 알킬기이고, Y5는 C1-C10 알콕시기 또는 할로겐 원소이다.In said Formula (5), R <4> is a C1-C10 alkyl group and Y <5> is a C1-C10 alkoxy group or a halogen element.
상기 제2폴리실세스퀴옥산계 화합물은, 하기 화학식 2로 표시되는 실리콘 화합물, 하기 화학식 3으로 표시되는 실리콘 화합물 및 하기 화학식 6으로 표시되는 실리콘 화합물을 가수분해 축중합하는 반응을 실시하여 얻을 수 있다.The second polysilsesquioxane-based compound may be obtained by carrying out a reaction for hydrolytic condensation polymerization of a silicone compound represented by the following formula (2), a silicone compound represented by the following formula (3) and a silicone compound represented by the following formula (6): have.
[화학식 2][Formula 2]
상기 화학식 2중 R2은 C2-C10 알케닐기이고, Y2는 C1-C10 알콕시기 또는 할로겐 원소이고,R 2 in Formula 2 is a C2-C10 alkenyl group, Y 2 is a C1-C10 alkoxy group or a halogen element,
n은 1 내지 3이고, n is 1 to 3,
[화학식 3][Formula 3]
상기 화학식 3중 Y3은 C1-C10 알콕시기 또는 할로겐 원소이고,Y 3 in Formula 3 is a C1-C10 alkoxy group or a halogen element,
화학식 6 
Formula 6
상기 화학식 6중 Y6은 C1-C10 알콕시기 또는 할로겐 원소이고,Y 6 in Formula 6 is a C1-C10 alkoxy group or a halogen element,
n은 1 내지 3이다. n is 1 to 3.
상기 제1폴리실세스퀴옥산계 화합물 제조시 사용되는 실라잔 화합물은 헥사디메틸실라잔, 헥사디에틸실라잔, 헥사디페닐실라잔을 포함한다.Silazane compounds used in the preparation of the first polysilsesquioxane compound include hexadimethylsilazane, hexadiethylsilazane, and hexadiphenylsilazane.
상기 제1폴리실세스퀴옥산계 화합물 및 제2폴리실세스퀴옥산계 화합물의 수평균 분자량은 10,000 내지 30,000이다. The number average molecular weight of the first polysilsesquioxane compound and the second polysilsesquioxane compound is 10,000 to 30,000.
상기 폴리실세스퀴옥산계 화합물 A 및 폴리실세스퀴옥산계 화합물 B는, 상기 제1폴리실세스퀴옥산계 화합물 및 제2폴리실세스퀴옥산계 화합물의 하이드록시기를 실리콘 화합물 및 실라잔 화합물 중에서 선택된 하나를 이용하여 개질하여 소수화시킨 고분자로서 점도가 50,000 내지 100,000 mPas이고, 수평균 분자량은 10,000 내지 30,000이다.The polysilsesquioxane compound A and the polysilsesquioxane compound B are hydroxy groups of the first polysilsesquioxane compound and the second polysilsesquioxane compound, a silicone compound and a silazane compound. It is a polymer modified and hydrophobized by using one selected from among the viscosity is 50,000 to 100,000 mPas, the number average molecular weight is 10,000 to 30,000.
상기 점도는 25℃, RH50% 조건에서 회전식점도계(Brook-Filed)로 10~100RPM에서의 측정점도에 대한 평균값을 표기한 방법에 따라 평가한 것이다.The viscosity is evaluated according to the method of expressing the average value for the measured viscosity at 10 ~ 100RPM by rotating viscometer (Brook-Filed) at 25 ℃, RH50% conditions.
상기 폴리실세스퀴옥산계 화합물 A 및 폴리실세스퀴옥산계 화합물 B의 점도가 상기 범위일 때 접착 조성물의 흐름성이 적절하여 접착 부재를 제조하는 작업을 용이하게 수행할 수 있다. When the viscosity of the polysilsesquioxane-based compound A and the polysilsesquioxane-based compound B is in the above range, the flowability of the adhesive composition is appropriate, so that an operation of manufacturing the adhesive member can be easily performed.
제1폴리실세스퀴옥산계 화합물, 제2폴리실세스퀴옥산계 화합물, 폴리실세스퀴옥산계 화합물 A 및 폴리실세스퀴옥산계 화합물 B의 수평균 분자량이 상기 범위일 때 접착 조성물의 점도가 태양전지 모듈 제작시 접착 부재로서 유용하다.Viscosity of the adhesive composition when the number average molecular weight of the first polysilsesquioxane compound, the second polysilsesquioxane compound, the polysilsesquioxane compound A and the polysilsesquioxane compound B is in the above range It is useful as an adhesive member when manufacturing a solar cell module.
본 발명에서 C2-C10 알케닐기는 비닐기 또는 알릴기를 포함하며, C1-C10 알킬기로는 메틸, 에틸, n-프로필, n-펜틸, 이소펜틸 또는 부틸기를 포함한다.In the present invention, the C2-C10 alkenyl group includes a vinyl group or an allyl group, and the C1-C10 alkyl group includes a methyl, ethyl, n-propyl, n-pentyl, isopentyl or butyl group.
상기 C1-C10 알콕시기는 메톡시기, 에톡시기, 프로폭시기 또는 펜틸옥시를 포함하며, 할로겐 원소는 불소, 염소, 또는 요오드를 포함한다.The C1-C10 alkoxy group includes a methoxy group, ethoxy group, propoxy group or pentyloxy, and the halogen element includes fluorine, chlorine, or iodine.
상기 제1폴리실세스퀴옥산계 화합물은 하기 화학식 7로 표시되거나 또는 하기 화학식 7로 표시되는 유닛을 포함한다.The first polysilsesquioxane-based compound includes a unit represented by the following formula (7) or represented by the following formula (7).
화학식 7 
Formula 7
상기 화학식 7중 R1은 C2-C10 알케닐기이고, R2은 C1-C10 알킬기이다.In Formula 7, R 1 is a C2-C10 alkenyl group, and R 2 is a C1-C10 alkyl group.
일구현예에 의하면, 상기 화학식 7에서 R1은 비닐기이고, R2는 메틸기이다.According to one embodiment, in Formula 7 R 1 is a vinyl group, R 2 is a methyl group.
상기 폴리실세스퀴옥산계 화합물 A은 하기 화학식 8로 표시되거나 또는 하기 화학식 8로 표시되는 유닛을 포함한다.The polysilsesquioxane compound A is represented by the following formula (8) or includes a unit represented by the following formula (8).
화학식 8 
Formula 8
상기 화학식 8중 R1은 C2-C10 알케닐기이고, R2은 C1-C10 알킬기이고, In Formula 8, R 1 is a C2-C10 alkenyl group, R 2 is a C1-C10 alkyl group,
R3은 C1-C10 알킬기이다.R 3 is a C1-C10 alkyl group.
일구현예에 의하면, 상기 화학식 8에서 R1은 비닐기이고, R2는 메틸기이고, R3은 메틸기이다.According to an embodiment, in Formula 8, R 1 is a vinyl group, R 2 is a methyl group, R 3 is a methyl group.
상기 제2폴리실세스퀴옥산계 화합물은 하기 화학식 9로 표시되거나 또는 하기 화학식 9로 표시되는 유닛을 포함한다.The second polysilsesquioxane compound includes a unit represented by the following formula (9) or represented by the following formula (9).
화학식 9 
Formula 9
상기 화학식 9중 R2은 C1-C10 알킬기이다.R 2 in Formula 9 is a C1-C10 alkyl group.
상기 폴리실세스퀴옥산 B는 하기 화학식 10으로 표시되거나 또는 화학식 10으로 표시되는 유닛을 포함한다.The polysilsesquioxane B is represented by the following formula (10) or includes a unit represented by the formula (10).
화학식 10 
Formula 10
상기 화학식 10중, R2은 C1-C10 알킬기이고, R3은 C1-C10 알킬기이다.In said Formula (10), R <2> is a C1-C10 alkyl group and R <3> is a C1-C10 alkyl group.
상기 폴리실세스퀴옥산계 화합물 A는 하기 화학식 11 또는 화학식 12로 표시되는 화합물을 포함한다.The polysilsesquioxane compound A includes a compound represented by the following formula (11) or (12).
화학식 11 
Formula 11
상기 화학식 11 중, x, y, z 는 서로 독립적으로 0보다 큰 수, 예를 들어 1 내지 200의 수이고,In Formula 11, x, y, z 'is independently a number greater than 0, for example, the number of 1 to 200,
화학식 12 
Formula 12
상기 화학식 12 중, x, y, z, w는 서로 독립적으로 0보다 큰 수, 예를 들어 1 내지 200의 수이다.In Formula 12, x, y, z, w is independently a number greater than 0, for example 1 to 200.
상기 화학식 11의 중합도 x, y, z 및 화학식 12의 중합도 x, y, z, w는 상기 화학식 11 또는 화학식 12로 표시되는 화합물의 수평균 분자량이 10,000 내지 30,000 범위가 되도록 선택된다.The polymerization degree x, y, z of Formula 11 and the polymerization degree x, y, z, w of Formula 12 are selected such that the number average molecular weight of the compound represented by Formula 11 or Formula 12 is in the range of 10,000 to 30,000.
상기 폴리실세스퀴옥산 B는 하기 화학식 13 또는 화학식 14로 표시되는 화합물을 포함한다.The polysilsesquioxane B includes a compound represented by the following Formula 13 or Formula 14.
화학식 13 
Formula 13
상기 화학식 13 중 x, y, z 는 서로 독립적으로 0보다 큰 수, 예를 들어 1 내지 200의 수이고,In Formula 13, x, y, z 'is independently a number greater than 0, for example, a number of 1 to 200,
화학식 14 
Formula 14
상기 화학식 14 중, x, y, z, w는 서로 독립적으로 0보다 큰 수, 예를 들어 1 내지 200의 수이다.In Formula 14, x, y, z and w are each independently a number greater than 0, for example, 1 to 200.
상기 화학식 13의 x, y, z 및 화학식 14의 x, y, z, w는 상기 화학식 13 또는 화학식 14로 표시되는 화합물의 수평균 분자량이 10,000 내지 30,000 범위가 되도록 선택된다.X, y, z of Formula 13 and x, y, z, w of Formula 14 are selected such that the number average molecular weight of the compound represented by Formula 13 or Formula 14 is in the range of 10,000 to 30,000.
상기 B제의 폴리실세스퀴옥산 B는 상기 A제의 폴리실세스퀴옥산계 화합물 A 100 중량부를 기준으로 하여 5 내지 45 중량부로 사용한다. 상기 폴리실세스퀴옥산 B의 함량이 상기 범위일 때 내구성이 우수한 태양전지 모듈용 접착부재를 제조할 수 있다.The polysilsesquioxane B made of B is used in an amount of 5 to 45 parts by weight based on 100 parts by weight of the polysilsesquioxane compound A made of the A. When the content of the polysilsesquioxane B is within the above range, it is possible to manufacture an adhesive member for a solar cell module having excellent durability.
상기 B제는 폴리실세스퀴옥산계 화합물 A를 더 포함한다. 이와 같이 폴리실세스퀴옥산계 화합물 A를 B제에 더 부가하는 경우에는 A제와 B제의 점도가 거의 동일한 범위로 제어되어 충진 카트리지의 노즐로부터 분사시 A제와 B제가 골고루 혼합되어 완벽한 경화체를 형성시킬 수 있는 이점이 있다. The agent B further includes a polysilsesquioxane compound A. As such, when the polysilsesquioxane-based compound A is further added to the agent B, the viscosity of the agent A and the agent B is controlled to almost the same range, so that the agent A and the agent B are mixed evenly when sprayed from the nozzle of the filling cartridge, thereby making a perfect cured product. There is an advantage that can form.
상기 B제의 폴리실세스퀴옥산계 화합물 A의 함량은 상기 A제의 폴리실세스퀴옥산계 화합물 A 100 중량부를 기준으로 하여 30 내지 80 중량부이다. The content of the polysilsesquioxane compound A of agent B is 30 to 80 parts by weight based on 100 parts by weight of the polysilsesquioxane compound A of agent A.
일구현예에 의하면, 상기 A제는 접착 개선제와 촉매를 포함할 수 있다.According to one embodiment, the agent A may include an adhesion improving agent and a catalyst.
상기 접착 개선제는 접착 조성물로부터 형성된 접착부재의 접착력을 향상시키기 위하여 부가되는 성분으로서 3-아미노프로필 트리에톡시실란, 3-글리시독시프로필 트리메톡시실란, 3-메타글리옥시프로필 트리메톡시실란, N-(β-아미노에틸)-γ-아미노프로필 트리메톡시실란, γ-글리시독시프로필 트리에톡시 실란 및 γ-글리시독시 트리메틸디메톡시실란 중에서 선택된 하나 이상이다. The adhesion improving agent is a 3-aminopropyl triethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-methoglyoxypropyl trimethoxysilane as components added to improve the adhesion of the adhesive member formed from the adhesive composition. , N- (β-aminoethyl) -γ-aminopropyl trimethoxysilane, γ-glycidoxypropyl triethoxy silane and γ-glycidoxy trimethyldimethoxysilane.
상기 접착개선제는 A제에서 폴리실세스퀴옥산계 화합물 A 100 중량부를 기준으로 하여 1 내지 15 중량부이다. 접착 개선제이 함량이 상기 범위일 때 상기 조성물로부터 형성된 접착 부재의 기재에 대한 접착력이 우수하다. The adhesion improving agent is 1 to 15 parts by weight based on 100 parts by weight of the polysilsesquioxane compound A in Agent A. When the content of the adhesion improving agent is in the above range, the adhesion of the adhesive member formed from the composition to the substrate is excellent.
상기 촉매는 폴리실세스퀴옥산계 화합물 A와 폴리실세스퀴옥산계 화합물 B의 반응을 촉진하는 역할을 한다. 상기 촉매는 난연제 역할도 수행할 수 있다. The catalyst serves to promote the reaction between the polysilsesquioxane compound A and the polysilsesquioxane compound B. The catalyst may also serve as a flame retardant.
상기 촉매는 백금계 촉매로서, 슈파이어 촉매(Speier catalyst)(이하 H2PtCl6), 백금 실란 리간드 촉매(Pt(CH2=CH-Si(CH3))2) 등을 포함한다.The catalyst is a platinum-based catalyst, and includes a Speyer catalyst (hereinafter, H 2 PtCl 6 ), a platinum silane ligand catalyst (Pt (CH 2 = CH-Si (CH 3 )) 2 ), and the like.
상기 촉매는 폴리실세스퀴옥산계 화합물 A 1몰을 기준으로 하여 0.0001 내지 0.5몰로 사용한다. 촉매의 함량이 상기 범위일 때 폴리실세스퀴옥산계 화합물 A와 폴리실세스퀴옥산계 화합물 B의 경화 반응의 반응속도가 빨라져서 반응시간이 감소된다.The catalyst is used in 0.0001 to 0.5 moles based on 1 mole of the polysilsesquioxane compound A. When the content of the catalyst is in the above range, the reaction rate of the curing reaction of the polysilsesquioxane compound A and the polysilsesquioxane compound B is increased, thereby reducing the reaction time.
상기 B제는 산화방지제 및 반응억제제를 포함할 수 있다.The B agent may include an antioxidant and a reaction inhibitor.
상기 산화방지제는 접착 조성물 및 접착 조성물로부터 형성된 접착 부재가 자외선, 열에 의하여 산화되는 것을 방지하고 끊어진 분자의 말단에 공기중 산소가 결합되어 산화가 촉진되는 것을 차단한다. 상기 산화방지제는 페놀계 화합물, 모노페놀계 화합물 또는 비스페놀계 화합물을 포함하며, 비제한적인 예로서 이소트리데실-3-(3,5-디-t-부틸-4-하이드록시페닐)프로피오네이트, 벤젠프로피온산(benzene propanoic acid) 3,3-비스(1,1-디메틸에틸)-4-하이드록시, C7-9-이소알킬에스테르 등을 들 수 있다.The antioxidant prevents the adhesive composition and the adhesive member formed from the adhesive composition from being oxidized by ultraviolet rays and heat, and prevents oxygen from being promoted by binding oxygen in the air to the ends of the broken molecules. Such antioxidants include phenolic compounds, monophenolic compounds or bisphenolic compounds, and include, but are not limited to, isotridecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propio Nate, benzene propanoic acid 3, 3-bis (1, 1- dimethylethyl) -4-hydroxy, C7-9- isoalkyl ester, etc. are mentioned.
상기 산화방지제는 폴리실세스퀴옥산계 화합물 B 1몰을 기준으로 하여 0.0001 내지 0.5몰로 사용된다. 상기 산화방지제의 함량이 상기 범위일 때 접착 조성물을 이용하여 형성된 태양전지용 접착 부재의 황변이 발생하지 않는다.The antioxidant is used in 0.0001 to 0.5 moles based on 1 mole of polysilsesquioxane compound B. When the content of the antioxidant is in the above range, yellowing of the solar cell adhesive member formed using the adhesive composition does not occur.
상기 반응억제제는 A제와 B제가 혼합하기 이전, B제를 이루는 구성성분의 반응이 일어나는 것을 억제하는 역할을 한다. 상기 반응은 예를 들어 수소규소화반응(Hydrosilylation) 반응을 말한다.The reaction inhibitor inhibits the reaction of the components constituting the agent B before the agent A and the agent B are mixed. The reaction refers to, for example, a hydrosilylation reaction.
상기 반응억제제는 1-에티닐사이클로헥사놀 또는 2-메틸-3-부틴-2-올을 포함한다.The reaction inhibitor includes 1-ethynylcyclohexanol or 2-methyl-3-butyn-2-ol.
상기 반응억제제의 함량은 폴리실세스퀴옥산계 화합물 B 1몰을 기준으로 하여 0.0001 내지 0.5몰로 사용된다.The reaction inhibitor is used in an amount of 0.0001 to 0.5 moles based on 1 mole of the polysilsesquioxane compound B.
이하, 상술한 태양전지 모듈용 접착 조성물 제조시 필요한 폴리실세스퀴옥산계 화합물 A 및 폴리실세스퀴옥산계 화합물 B의 제조방법을 살펴보기로 한다.Hereinafter, a method of preparing the polysilsesquioxane compound A and the polysilsesquioxane compound B necessary for preparing the adhesive composition for a solar cell module will be described.
먼저 상기 화학식 1로 표시되는 실리콘 화합물, 상기 화학식 2로 표시되는 실리콘 화합물 및 상기 화학식 3으로 표시되는 실리콘 화합물을 혼합하여 실란 혼합물을 얻는다. 상기 혼합은 상온에서 0.5 내지 1시간 동안 교반하여 실시한다.First, a silane mixture is obtained by mixing the silicon compound represented by Chemical Formula 1, the silicon compound represented by Chemical Formula 2, and the silicon compound represented by Chemical Formula 3. The mixing is performed by stirring at room temperature for 0.5 to 1 hour.
상기 교반시 분당 회전수는 300 내지 500 rpm이다.The rotational speed per minute during the stirring is 300 to 500 rpm.
본 발명에서 상온은 20 내지 25℃를 의미한다.In the present invention, room temperature means 20 to 25 ℃.
상기 화학식 2로 표시되는 실리콘 화합물은 상기 화학식 1로 표시되는 실리콘 화합물 100 중량부를 기준으로 하여 10 내지 100 중량부로 사용하며, 상기 화학식 3으로 표시되는 실리콘 화합물은 상기 화학식 1로 표시되는 실리콘 화합물 100 중량부를 기준으로 하여 10 내지 120 중량부로 사용한다.The silicone compound represented by Formula 2 is used in an amount of 10 to 100 parts by weight based on 100 parts by weight of the silicon compound represented by Formula 1, and the silicon compound represented by Formula 3 is 100 weight of the silicon compound represented by Formula 1 It is used in 10 to 120 parts by weight based on parts.
상기 실란 혼합물에 산 및 용매를 부가 및 혼합한다. Acid and solvent are added and mixed to the silane mixture.
상기 산은 황산, 염산, 질산, 인산 또는 아세트산을 포함하며, 산은 화학식 1로 표시되는 실리콘 화합물 1몰을 기준으로 하여 0.01 내지 2몰로 사용한다.The acid includes sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or acetic acid, and the acid is used in an amount of 0.01 to 2 moles based on 1 mole of the silicon compound represented by Formula 1.
상기 용매는 물, 또는 알코올을 포함하며, 상기 용매의 사용량은 화학식 1로 표시되는 실리콘 화합물 100 중량부를 기준으로 하여 50 내지 2000 중량부이다.The solvent includes water or an alcohol, and the amount of the solvent is 50 to 2000 parts by weight based on 100 parts by weight of the silicone compound represented by Formula 1.
상기 화학식 1로 표시되는 실리콘 화합물은 비닐트리메톡시실란 (CH2=CH-Si(OCH3)3), 디비닐디메톡시실란((CH2=CH)2Si(OCH3)2), 디비닐디에톡시실란((CH2=CH)2Si(OCH2CH3)2), 또는 비닐트리에톡시실란(CH2=CH-Si(OCH2CH3)3) 을 포함한다.The silicon compound represented by Chemical Formula 1 may include vinyltrimethoxysilane (CH 2 = CH-Si (OCH 3 ) 3 ), divinyldimethoxysilane ((CH 2 = CH) 2 Si (OCH 3 ) 2 ), di Vinyldiethoxysilane ((CH 2 = CH) 2 Si (OCH 2 CH 3 ) 2 ), or vinyltriethoxysilane (CH 2 = CH-Si (OCH 2 CH 3 ) 3 ).
상기 화학식 2로 표시되는 실리콘 화합물은 메틸트리메톡시실란(CH3Si(OCH3)3), 또는 메틸트리에톡시실란(CH3Si(OCH2CH3)3)을 포함한다.The silicon compound represented by Formula 2 includes methyltrimethoxysilane (CH 3 Si (OCH 3 ) 3 ), or methyltriethoxysilane (CH 3 Si (OCH 2 CH 3 ) 3 ).
상기 화학식 3으로 표시되는 실리콘 화합물은 테트라에틸오르토실리케이트(Si(OCH2CH3)4), 또는 테트라메틸오르토실리케이트(Si(OCH3)4)을 포함한다.The silicon compound represented by Chemical Formula 3 includes tetraethylorthosilicate (Si (OCH 2 CH 3 ) 4 ), or tetramethylorthosilicate (Si (OCH 3 ) 4 ).
상기 반응 혼합물의 반응이 진행되면 교반중인 플라스크의 반응 혼합물에서는 50~80℃의 발열 반응이 일어난다.When the reaction of the reaction mixture proceeds, the exothermic reaction of 50 ~ 80 ℃ occurs in the reaction mixture of the stirring flask.
이어서 상기 과정에 따라 얻은 반응 혼합물을 열처리하여 상기 실리콘 화합물의 가수분해 및 축중합 반응을 실시한다.Subsequently, the reaction mixture obtained according to the above process is heat-treated to perform hydrolysis and polycondensation reaction of the silicon compound.
상기 열처리온도는 80 내지 100℃이다. 열처리 온도가 상기 범위일 때 실리콘 화합물의 가수분해 축중합 반응의 반응성이 우수하다.The heat treatment temperature is 80 to 100 ℃. When the heat treatment temperature is within the above range, the reactivity of the hydrolysis polycondensation reaction of the silicone compound is excellent.
상술한 반응후 반응 혼합물을 50℃ 이하, 예를 들어 10 내지 45 ℃로 냉각하여 말단 및 측쇄에 C2-C10의 알케닐기, C1-C10 알킬기 및 하이드록시기를 갖는 폴리실세스퀴옥산계 화합물(제1폴리실세스퀴옥산계 화합물)을 제조한다.After the reaction described above, the reaction mixture is cooled to 50 ° C. or lower, for example, 10 to 45 ° C., and a polysilsesquioxane compound having a C 2 -C 10 alkenyl group, C 1 -C 10 alkyl group and a hydroxyl group at the terminal and side chain ( 1 polysilsesquioxane compound) is prepared.
이어서 상기 제1폴리실세스퀴옥산계 화합물 및 용매를 혼합하여 혼합물을 얻는다.Subsequently, the first polysilsesquioxane compound and a solvent are mixed to obtain a mixture.
상기 용매는 테트라하이드로퓨란, 피리딘, 프로필렌 글리콜 모노메틸에테르 아세테이트, 또는 프로필렌 글리콜 메틸 에테르를 사용하며, 용매는 제1폴리실세스퀴옥산계 화합물 100 중량부를 기준으로 하여 30 내지 2000 중량부로 사용된다.The solvent is tetrahydrofuran, pyridine, propylene glycol monomethylether acetate, or propylene glycol methyl ether, and the solvent is used at 30 to 2000 parts by weight based on 100 parts by weight of the first polysilsesquioxane compound.
상기 혼합은 상온에서 1 내지 5시간 동안 교반하여 수행할 수 있다.The mixing may be performed by stirring at room temperature for 1 to 5 hours.
상기 혼합물에 상기 화학식 4로 표시되는 실리콘 화합물, 상기 화학식 5로 표시되는 실리콘 화합물 및 실라잔 중에서 선택된 하나를 적가한다.To the mixture is added dropwise one selected from the silicon compound represented by Formula 4, the silicon compound represented by Formula 5, and silazane.
상기 화학식 4로 표시되는 실리콘 화합물, 상기 화학식 5로 표시되는 실리콘 화합물 및 실라잔 중에서 선택된 하나는 상기 제1폴리실세스퀴옥산계 화합물 100 중량부를 기준으로 하여 5 내지 100 중량부로 사용된다. 상기 화학식 4로 표시되는 실리콘 화합물, 상기 화학식 5로 표시되는 실리콘 화합물 및 실라잔 중에서 선택된 하나의 함량이 상기 범위일 때 소수성이 제어된 폴리실세스퀴옥산계 화합물을 얻을 수 있다.One selected from the silicone compound represented by Formula 4, the silicone compound represented by Formula 5, and silazane is used in an amount of 5 to 100 parts by weight based on 100 parts by weight of the first polysilsesquioxane compound. When the content of one selected from the silicon compound represented by Formula 4, the silicon compound represented by Formula 5, and silazane is within the above range, a polysilsesquioxane compound having controlled hydrophobicity may be obtained.
그 후 상기 반응 혼합물을 열처리하여 제1폴리실세스퀴옥산계 화합물의 실라놀 캡핑 반응(silanol capping reaction)을 실시한다. Thereafter, the reaction mixture is heat-treated to perform a silanol capping reaction of the first polysilsesquioxane compound.
상기 열처리온도는 80 내지 100℃이다. 열처리 온도가 상기 범위일 때 제1폴리실세스퀴옥산계 화합물의 실라놀 캡핑 반응성이 우수하다. The heat treatment temperature is 80 to 100 ℃. When the heat treatment temperature is in the above range, the silanol capping reactivity of the first polysilsesquioxane compound is excellent.
상기 화학식 4로 표시되는 실리콘 화합물은 메틸트리클로로실란, 디메틸디클로로실란 또는 트리메틸클로로실란을 포함한다.The silicone compound represented by Chemical Formula 4 includes methyltrichlorosilane, dimethyldichlorosilane or trimethylchlorosilane.
상기 화학식 5로 표시되는 실리콘 화합물은 (CH3SiCl2)2O을 포함한다.The silicon compound represented by Chemical Formula 5 includes (CH 3 SiCl 2 ) 2 O.
상기 실라놀 캡핑 반응의 결과물을 감압 증발하여 저비물을 제거한 후 50℃ 이하, 예를 들어 10 내지 45 ℃로 냉각하여 폴리실세스퀴옥산계 화합물 A를 얻는다.The resultant of the silanol capping reaction is evaporated under reduced pressure to remove low boiling water, and then cooled to 50 ° C. or lower, for example, 10 to 45 ° C., to obtain polysilsesquioxane compound A.
이와 별도로 폴리실세스퀴옥산계 화합물 B를 하기 과정에 따라 제조한다.Separately, polysilsesquioxane compound B is prepared according to the following procedure.
먼저, 상기 화학식 2로 표시되는 실리콘 화합물, 상기 화학식 3으로 표시되는 실리콘 화합물 및 하기 화학식 6으로 표시되는 실리콘 화합물을 상온에서 0.5 내지 1 시간 동안 교반하여 혼합과정을 실시한다.First, the silicon compound represented by Chemical Formula 2, the silicon compound represented by Chemical Formula 3, and the silicon compound represented by Chemical Formula 6 are stirred at room temperature for 0.5 to 1 hour to perform a mixing process.
상기 교반시 분당 회전수는 300 내지 500 rpm이다.The rotational speed per minute during the stirring is 300 to 500 rpm.
상기 반응 혼합물에 산 및 용매를 부가하고 열처리하여 상기 실리콘 화합물의 가수분해 축중합 반응을 실시하여 제2폴리실세스퀴옥산계 화합물을 얻는다. An acid and a solvent are added to the reaction mixture, followed by heat treatment to carry out a hydrolysis polycondensation reaction of the silicone compound to obtain a second polysilsesquioxane compound.
상기 용매의 종류는 상기 제1폴리실세스퀴옥산계 화합물의 제조과정에서 설명한 바와 같다.The type of the solvent is as described in the preparation of the first polysilsesquioxane compound.
상기 산은 화학식 2로 표시되는 실리콘 화합물 1몰을 기준으로 하여 0.01 내지 2몰로 사용한다.The acid is used in an amount of 0.01 to 2 moles based on 1 mole of the silicon compound represented by Formula 2.
상기 용매는 화학식 2로 표시되는 실리콘 화합물 100 중량부를 기준으로 하여 500 내지 2000 중량부로 사용한다.The solvent is used in an amount of 500 to 2000 parts by weight based on 100 parts by weight of the silicone compound represented by Formula 2.
상기 화학식 6으로 표시되는 실리콘 화합물은 H-SiCH3(OCH3)2 또는 H-Si(OCH3)3를 포함한다.The silicon compound represented by Chemical Formula 6 includes H-SiCH 3 (OCH 3 ) 2 or H-Si (OCH 3 ) 3 .
상기 화학식 3으로 표시되는 실리콘 화합물은 상기 화학식 2로 표시되는 실리콘 화합물 100 중량부를 기준으로 하여 10 내지 150 중량부로 사용하고, 상기 화학식 6으로 표시되는 실리콘 화합물은 상기 화학식 2로 표시되는 실리콘 화합물 100 중량부를 기준으로 하여 10 내지 150 중량부로 사용한다. The silicone compound represented by Formula 3 is used in 10 to 150 parts by weight based on 100 parts by weight of the silicone compound represented by Formula 2, and the silicon compound represented by Formula 6 is 100 weight of the silicon compound represented by Formula 2 It is used in 10 to 150 parts by weight based on parts.
상기 열처리온도는 상기 제1폴리실세스퀴옥산계 화합물의 제조과정에서 설명한 바와 같다.The heat treatment temperature is as described in the preparation of the first polysilsesquioxane compound.
상기 제2폴리실세스퀴옥산계 화합물을 용매에 용해하고 여기에 상기 화학식 4로 표시되는 실리콘 화합물, 상기 화학식 5로 표시되는 실록산 화합물, 실라잔 중에서 선택된 하나를 부가 및 혼합하고 이를 열처리하여 제2폴리실세스퀴옥산계 화합물로부터 하이드록시기를 제거하는 실라놀 캡핑 반응을 실시한다.The second polysilsesquioxane-based compound is dissolved in a solvent, and one or more selected from the silicon compound represented by the formula (4), the siloxane compound represented by the formula (5), and the silazane are added thereto, mixed, and heat-treated to obtain a second compound. The silanol capping reaction which removes a hydroxyl group from a polysilsesquioxane type compound is performed.
상기 열처리 온도는 상기 폴리실세스퀴옥산 A의 제조과정과 동일하다.The heat treatment temperature is the same as the manufacturing process of the polysilsesquioxane A.
상기 화학식 4로 표시되는 실리콘 화합물, 상기 화학식 5로 표시되는 실록산 화합물, 실라잔 중에서 선택된 하나의 사용량은 제2폴리실세스퀴옥산계 화합물 100 중량부를 기준으로 하여 5 내지 100 중량부이다.The amount of one selected from the silicone compound represented by Formula 4, the siloxane compound represented by Formula 5, and silazane is 5 to 100 parts by weight based on 100 parts by weight of the second polysilsesquioxane compound.
상기 용매의 종류는 폴리실세스퀴옥산계 화합물 A의 제조과정과 동일하다.The type of the solvent is the same as the preparation of the polysilsesquioxane compound A.
상기 용매의 함량은 제2폴리실세스퀴옥산계 화합물 100 중량부를 기준으로 하여 30 내지 2000 중량부이다.The content of the solvent is 30 to 2000 parts by weight based on 100 parts by weight of the second polysilsesquioxane compound.
상기 실라놀 캡핑 반응의 반응 결과물을 감압 증발하여 저비물을 제거한 후 50℃ 이하, 예를 들어 10 내지 45 ℃로 냉각하여 실세스퀴옥산계 화합물 B를 얻는다.The reaction product of the silanol capping reaction is evaporated under reduced pressure to remove low boiling water, and then cooled to 50 ° C. or lower, for example, 10 to 45 ° C. to obtain silsesquioxane compound B.
상기 폴리실세스퀴옥산계 화합물 A 및 폴리실세스퀴옥산계 화합물 B를 이용하여 태양전지 모듈용 접착 조성물을 제조하는 방법을 살펴 보면 다음과 같다.Looking at the method for producing an adhesive composition for a solar cell module using the polysilsesquioxane-based compound A and polysilsesquioxane-based compound B as follows.
상기 폴리실세스퀴옥산계 화합물 A, 접착 개선제 및 촉매 중에서 선택된 하나 이상, 예를 들어 접착 개선제 및 촉매를 혼합하여 A제를 얻는다.At least one selected from the polysilsesquioxane compound A, an adhesion improving agent and a catalyst, for example, an adhesion improving agent and a catalyst is mixed to obtain an agent A.
상기 혼합은 300 내지 500 rpm, 상온에서 0.5 내지 3시간동안 교반하는 과정에 따른다. The mixing is according to the stirring process for 300 to 500 rpm, 0.5 to 3 hours at room temperature.
이와 별도로 상기 폴리실세스옥산계 화합물 B, 산화 방지제 및 반응 억제제 중에서 선택된 하나 이상, 예를 들어 산화 방지제 및 반응억제제를 혼합하여 B제를 얻는다.Separately, at least one selected from the polysilsesoxane compound B, an antioxidant, and a reaction inhibitor, for example, an antioxidant and a reaction inhibitor, is mixed to obtain a B agent.
상기 혼합은 A제 제조시와 마찬가지의 온도, 교반시간 및 회전수 조건에서 실시한다.The mixing is carried out at the same temperature, stirring time and rotational speed conditions as in the case of preparation of agent A.
상기 B제에는 폴리실세스퀴옥산계 화합물 A를 더 부가할 수 있다.The polysilsesquioxane compound A can be further added to the agent B.
상기 A제와 B제를 혼합하여 이액형 태양전지 모듈용 접착제 조성물을 얻는다.The agent A and agent B are mixed to obtain an adhesive composition for a two-component solar cell module.
상기 A제와 B제의 중량비는 1:1 내지 20:1이다. A제에 대한 B제의 중량이 상기 범위일 때 A제와 B제의 미반응 경화체가 형성되지 않고 경화체의 경도가 우수하다. The weight ratio of the agent A and agent B is 1: 1 to 20: 1. When the weight of agent B to agent A is in the above range, the unreacted cured product of agent A and agent B is not formed and the hardness of the cured product is excellent.
일구현예에 따른 태양전지 모듈용 접착제 조성물은 A제와 B제의 중량비가 1:1이다. 이와 같은 동일한 중량비를 갖는 조성물을 이용하면, A제와 B제의 점도가 상이하여 혼합이 용이하여 작업시 복잡한 계량 과정을 생략할 수 있고 경화시간이 짧은 이점이 있다.Adhesive composition for a solar cell module according to one embodiment is a weight ratio of agent A and agent B is 1: 1. When the composition having the same weight ratio is used, the viscosity of the agent A and the agent B is different, so that the mixing is easy, so that a complicated weighing process can be omitted during the operation and the curing time is short.
상기 제조방법에 따라 얻은 태양전지 모듈용 접착 조성물은 점도가 약 8만~12만 cPs (8만~12만 mPa.s)이다. 접착 조성물의 점도가 상기 범위보다 낮으면 토출압이 너무 낮아 작업 부위 외 다른 곳에 접착제가 묻어 오염될 수 있고 상기 점도 범위 보다 높으면 조성물의 토출압이 높아 접착력이 저하될 수 있고 작업자의 피로도가 증가하여 작업성이 저하될 수 있다.The adhesive composition for a solar cell module obtained according to the above production method has a viscosity of about 80,000 to 120,000 cPs (80,000 to 120,000 mPa.s). When the viscosity of the adhesive composition is lower than the above range, the discharge pressure is too low to contaminate the adhesive due to the adhesive outside the working area. If the viscosity is higher than the above range, the discharge pressure of the composition may be high, the adhesive force may be lowered, and the worker's fatigue may be increased. Workability may be degraded.
상기 접착 조성물은 이액형 카트리지를 사용하여 포장 가능하다. 상기 접착 The adhesive composition can be packaged using a two-component cartridge. The adhesion
조성물은 부가경화 타입 접착 조성물로서 종래의 접착 조성물과 달리 경화시 물, 수소와 같은 부산물이 발생하지 않고 내구성 및 기계적 물성에 대한 신뢰도가 높고 저장중 증점 및 부분 경화가 없어 저장 안정성이 향상되어 상온에서 보관 가능하다. 또한 탄산칼슘과 같은 필러를 함유하고 있지 않아 작업자의 피로도가 감소될 뿐만 아니라 경량화로 작업성이 개선된다. The composition is an additional curing type adhesive composition, unlike conventional adhesive compositions, does not generate by-products such as water and hydrogen when cured, has high reliability and durability for mechanical properties, and does not have thickening and partial curing during storage, thereby improving storage stability at room temperature. Can be stored. In addition, since it does not contain a filler such as calcium carbonate, the fatigue of the worker is reduced and workability is improved by lightening.
본 발명의 다른 측면에 따라 상술한 태양전지 모듈용 접착 조성물의 경화 생성물을 포함하는 접착 부재 및 이를 구비한 태양전지 모듈을 제공한다.According to another aspect of the present invention, there is provided an adhesive member including a cured product of the adhesive composition for a solar cell module and a solar cell module having the same.
상기 태양전지 모듈용 접착 조성물을 이액형 카트리지에 포장한 후 이를 원하는 영역에 가하면 상온에서 상기 조성물의 경화 반응이 진행되어 상기 접착 조성물의 경화 반응 생성물(경화체)을 포함하는 접착 부재를 제조할 수 있다. When the adhesive composition for a solar cell module is packaged in a two-component cartridge and then applied to a desired region, a curing reaction of the composition proceeds at room temperature, thereby preparing an adhesive member including a curing reaction product (cured product) of the adhesive composition. .
상기 조성물의 경화 반응은 A제의 폴리실세스퀴옥산계 화합물 A의 알케닐기의 이중결합에 B제의 폴리실세스퀴옥산계 화합물 B가 갖고 있는 수소가 부가되는 수소 첨가 반응을 포함한다.The curing reaction of the composition includes a hydrogenation reaction in which hydrogen contained in the polysilsesquioxane compound B agent B is added to a double bond of the alkenyl group of the polysilsesquioxane compound A agent A.
상기 조성물의 경화 반응으로 얻어진 생성물은 종래의 실세스퀴옥산 올리고머를 함유하는 접착 조성물을 이용한 경우와 달리 랜덤(random) 및 래더(ladder) 타입을 갖는 소수성 폴리실세스퀴옥산계 화합물이다.The product obtained by the curing reaction of the composition is a hydrophobic polysilsesquioxane-based compound having random and ladder types, unlike when using an adhesive composition containing a conventional silsesquioxane oligomer.
상기 접착 부재는 소수성 폴리실세스퀴옥산계 화합물을 포함하며 이러한 접착부재를 이용하면 프레임 부식을 미연에 방지할 수 있고 오염으로 인하여 태양전지가 오작동되거나 태양전지의 라이프 사이클이 감소되는 것을 억제할 수 있다.The adhesive member includes a hydrophobic polysilsesquioxane-based compound, and the use of the adhesive member can prevent the frame corrosion in advance and prevent the solar cell from malfunctioning or reducing the life cycle of the solar cell due to the contamination. have.
이하, 하기 실시예를 들어 설명하기로 하되, 본 발명이 하기 실시예로 한정되는 것을 의미하는 것은 아니다.Hereinafter, the following examples will be described, but the present invention is not meant to be limited to the following examples.
합성예 1: 화학식 7로 표시되는 제1폴리실세스퀴옥산계 화합물(화학식 7에서 R1=비닐기, R2=메틸기임)의 제조 Synthesis Example 1 Preparation of First Polysilsesquioxane Compound Represented by Formula 7 (In Formula 7, R 1 = Vinyl Group and R 2 = Methyl Group)
콘덴서, 교반기, 온도 제어 시스템(써큘레이터(Circulator), 히팅맨틀(Heating mantle) 및 써모커플(Thermocouple) 포함)이 장착된 약 1리터 용량의 둥근 바닥 플라스크에 메틸트리메톡시실란(이하 MTMS이라 함) 124 중량부, 비닐트리메톡시실란(이하 VTMS이라 함) 162 중량부, 테트라에틸오르토실리케이트(이하 TEOS이라 함) 169 중량부를 넣고, 약 400RPM으로 30분간 상온 교반하였다. Methyltrimethoxysilane (hereinafter referred to as MTMS) in an approximately 1 liter round bottom flask equipped with a condenser, stirrer, temperature control system (including circulator, heating mantle and thermocouple) ) 124 parts by weight, 162 parts by weight of vinyltrimethoxysilane (hereinafter referred to as VTMS), and 169 parts by weight of tetraethylorthosilicate (hereinafter referred to as TEOS) were added and stirred at room temperature at about 400 RPM for 30 minutes.
1N의 질산 25ml와 정제된 물 136 중량부를 미리 혼합한 후, 이를 교반중인 플라스크에 미리 설치한 드로핑 펀넬(Dropping funnel)을 사용하여 반응 혼합물에 30분에 걸쳐 적가하였다. After mixing 25 ml of 1 N nitric acid and 136 parts by weight of purified water, it was added dropwise to the reaction mixture over 30 minutes using a dropping funnel pre-installed in a stirring flask.
반응 혼합물의 반응이 진행되면 교반중인 플라스크의 반응 혼합물에서는 약 70℃의 발열 반응이 일어 났고, 교반 초기에는 백색의 혼탁한 용액이었지만 교반을 지속한 결과 무색 투명한 용액이 되었다. When the reaction mixture proceeded, an exothermic reaction of about 70 ° C. occurred in the reaction mixture of the stirring flask, and it was a white cloudy solution at the beginning of stirring, but the solution was continued as a colorless transparent solution.
상기 교반 용액을 약 90℃에서 3시간 동안 환류한 후 이를 감압 증류하여 저비물을 제거하였다. 저비물이 제거된 결과물을 약 45℃로 냉각하여 메틸기 및 비닐기를 포함한 수평균분자량(Mn) 약 20,000인 무색투명한 화학식 7로 표시되는 제1폴리실세스퀴옥산계 화합물을 제조하였다. The stirred solution was refluxed at about 90 ° C. for 3 hours and then distilled under reduced pressure to remove low boiling water. The resultant from which the low-boiling water was removed was cooled to about 45 ° C. to prepare a first polysilsesquioxane compound represented by a colorless transparent formula (7) having a number average molecular weight (Mn) of about 20,000 including methyl and vinyl groups.
화학식 7Formula 7
상기 화학식 7에서 R1는 비닐기, R2는 메틸기이다.In Formula 7, R 1 is a vinyl group, and R 2 is a methyl group.
합성예 2: 화학식 8로 표시되는 폴리실세스퀴옥산계 화합물 A(화학식 8에서 R1은 비닐기이고, R2는 메틸기이고, R3은 메틸기임)의 제조Synthesis Example 2 Preparation of Polysilsesquioxane Compound A represented by Formula 8 (In Formula 8, R 1 is a vinyl group, R 2 is a methyl group, and R 3 is a methyl group.)
콘덴서, 교반기 및 온도 제어 시스템(써큘레이터(Circulator), 히팅맨틀 및 써모커플 포함)이 장착된 약 1리터 용량의 둥근 바닥 플라스크에 합성예 1에 따라 얻은 화학식 7로 표시되는 제1폴리실세스퀴옥산계 화합물(화학식 7에서 R1=비닐기, R2=메틸기임) 100중량부, 테트라하이드로퓨란 (이하 THF이라 함) 50중량부를 넣고, 약 400 RPM으로 30분간 상온 교반하였다. A first polysilsesqui, represented by Formula 7 obtained according to Synthesis Example 1 in a round bottom flask of about 1 liter capacity equipped with a condenser, agitator and temperature control system (including circulator, heating mantle and thermocouple) 100 parts by weight of an oxane compound (wherein R 1 = vinyl group and R 2 = methyl group) and 50 parts by weight of tetrahydrofuran (hereinafter referred to as THF) were added, followed by stirring at room temperature at about 400 RPM for 30 minutes.
메틸트리클로로실란(이하 MTCS이라 함) 50중량부를 교반중인 반응 플라스크에 미리 설치한 드로핑 펀넬을 사용하여 30분간 천천히 적가하였다. 50 parts by weight of methyltrichlorosilane (hereinafter referred to as MTCS) was slowly added dropwise to the reaction flask under stirring using a dropping funnel pre-installed for 30 minutes.
상기 반응 혼합물을 약 3시간 동안 교반한 후 이를 100℃에서 감압 증류하여 저비물을 제거하였다. 저비물이 제거된 반응 결과물을 약 45℃로 냉각하여 점도 약 80,000 mPa.s의 화학식 8로 표시되는 폴리실세스퀴옥산계 화합물 A를 제조하였다. The reaction mixture was stirred for about 3 hours and then distilled under reduced pressure at 100 ° C. to remove low boiling water. The reaction product from which low boiling water was removed was cooled to about 45 ° C., and the viscosity was about 80,000 mPa . Polysilsesquioxane compound A represented by Chemical Formula 8 of s was prepared.
화학식 8Formula 8
상기 화학식 8중, R1은 비닐기이고, R2는 메틸기이고, R3은 메틸기이다.In said Formula (8), R <1> is a vinyl group, R <2> is a methyl group and R <3> is a methyl group.
합성예 3: 화학식 9로 표시되는 제2폴리실세스퀴옥산계 화합물(화학식 9에서 R2=메틸기임)의 제조 Synthesis Example 3: Preparation of second polysilsesquioxane compound represented by Formula 9 (wherein R 2 = methyl group in Formula 9 )
비닐트리메톡시실란 162 중량부 대신 트리메톡시실란 128 중량부를 사용한 것을 제외하고는, 합성예 1과 동일한 방법에 따라 실시하여 수평균분자량(Mn) 약 200,000의 무색투명한 화학식 9로 표시되는 제2폴리실세스퀴옥산계 화합물을 제조하였다.A second color represented by a colorless transparent chemical formula 9 having a number average molecular weight (Mn) of about 200,000 according to the same method as in Synthesis Example 1, except that 128 parts by weight of trimethoxysilane was used instead of 162 parts by weight of vinyltrimethoxysilane. A polysilsesquioxane compound was prepared.
화학식 9Formula 9
상기 화학식 9에서 R2는 메틸기이다.In Formula 9, R 2 is a methyl group.
합성예 4: 화학식 10으로 표시되는 폴리실세스퀴옥산계 화합물 B(화학식 10에서 R1은 메틸기이고, R3은 메틸기임)의 제조 Synthesis Example 4 Preparation of Polysilsesquioxane Compound B represented by Formula 10 (In Formula 10, R 1 is a methyl group and R 3 is a methyl group.)
합성예 1에 따라 얻은 화학식 7로 표시되는 폴리실세스퀴옥산계 화합물 100 중량부 대신 합성예 3에 따라 얻은 화학식 9로 표시되는 제2폴리실세스퀴옥산계 화합물 100 중량부를 사용한 것을 제외하고는, 합성예 2과 동일한 방법에 따라 실시하여 점도 약 50,000 mPa.s의 화학식 10으로 표시되는 폴리실세스퀴옥산계 화합물 B을 제조하였다. 100 parts by weight of the second polysilsesquioxane compound represented by Formula 9 instead of 100 parts by weight of the polysilsesquioxane compound represented by Formula 7 obtained according to Synthesis Example 1 was used. And viscosities of about 50,000 mPa in the same manner as in Synthesis example 2 . Polysilsesquioxane compound B represented by Chemical Formula 10 of s was prepared.
화학식 10Formula 10
상기 화학식 10중 R2은 메틸기이고, R3은 메틸기이다.In Formula 10, R 2 is a methyl group, and R 3 is a methyl group.
실시예 1: 태양전지 모듈용 접착제 조성물 제조Example 1 Preparation of Adhesive Composition for Solar Cell Module
1번 용기에 합성예 2에 따라 제조된 화학식 8로 표시되는 폴리실세스퀴옥산계 화합물(이하 ViPSQ 이라 함) 100중량부, 3-글리시독시프로필 트리메톡시실란(이하 GPTMS이라 함) 10중량부, 슈파이어 촉매(Speier catalyst)(H2PtCl6) 1중량부를 순서대로 투입 후 상온에서 약 400rpm으로 30분간 교반하여 A제를 제조하였다.100 parts by weight of a polysilsesquioxane compound represented by Formula 8 (hereinafter referred to as Vi PSQ) prepared according to Synthesis Example 2 in a vessel No. 1, 3-glycidoxypropyl trimethoxysilane (hereinafter referred to as GPTMS) 10 parts by weight, 1 part by weight of a Speyer catalyst (Speier catalyst) (H 2 PtCl 6 ) in order, and then stirred at about 400 rpm at room temperature for 30 minutes to prepare a agent A.
2번 용기에 ViPSQ 70중량부, 합성예 4에 따라 제조된 화학식 10으로 표시되는 폴리실세스퀴옥산계 화합물(이하 HPSQ 이라 함) 30중량부, 이소트리데실-3-(3,5-디-t-부틸-4-하이드록시페닐)프로피오네이트 10중량부, 2-에티닐사이클로헥사놀(1-ETCH) 1중량부를 순서대로 투입 후 상온에서 약 400rpm으로 30분간 교반하여 B제를 제조하였다.70 parts by weight of Vi PSQ in a container No. 2, 30 parts by weight of a polysilsesquioxane compound represented by Chemical Formula 10 (hereinafter referred to as H PSQ) prepared according to Synthesis Example 4, isotridecyl-3- (3,5 10 parts by weight of di- t -butyl-4-hydroxyphenyl) propionate and 1 part by weight of 2-ethynylcyclohexanol (1-ETCH) were added in this order, followed by stirring at room temperature at about 400 rpm for 30 minutes. Was prepared.
상기 A제와 B제를 1:1 중량비로 혼합하여 이액형 태양전지 모듈용 접착제 조성물을 제조하였다.Agent A and agent B were mixed in a 1: 1 weight ratio to prepare an adhesive composition for a two-component solar cell module.
실시예 2-4Example 2-4
하기 표 1에 나타난 바와 같이, 접착 조성물의 구성 성분의 함량을 변화시킨 것을 제외하고는, 실시예 1과 동일하게 실시하여 태양전지 모듈용 접착제 조성물을 얻었다.As shown in Table 1, except that the content of the constituent components of the adhesive composition was changed, it was carried out in the same manner as in Example 1 to obtain an adhesive composition for a solar cell module.
단 실시예 2-4에서 A제에서 비닐폴리실세스퀴옥산(이하 ViPSQ 이라 함)의 함량은 100 중량부이고 B제에서 비닐폴리실세스퀴옥산(이하 ViPSQ 이라 함)의 함량은 실시예 2의 경우 60 중량부, 실시예 3의 경우 50 중량부, 실시예 4의 경우 40 중량부였다. The content of the stage in the embodiment 2-4-vinyl content of the polysilsesquioxane (hereinafter referred to as Vi PSQ) in the A and B is 100 parts by weight of the vinyl polysilsesquioxane (hereinafter referred to as Vi PSQ) is carried out in 60 parts by weight of Example 2, 50 parts by weight of Example 3, and 40 parts by weight of Example 4.
비교예 1-2Comparative Example 1-2
실세스퀴옥산 올리고머(OSQ), α,ω-비닐 말단 폴리디메틸실록산 (ViPDMS), α,ω-하이드로겐 말단 폴리디메틸실록산(HPDMS), SiO2, CaCO3, 트리에틸포스페이트 (TEP), GPTMS 및 이소트리데실-3-(3,5-디-t-부틸-4-하이드록시페닐)프로피오네이트, DBTDL을 하기 표 1의 조성으로 혼합하여 일액형 접착제 조성물을 제조하였다.Silsesquioxane oligomer (OSQ), α, ω-vinyl terminated polydimethylsiloxane ( Vi PDMS), α, ω-hydrogen terminated polydimethylsiloxane ( H PDMS), SiO 2 , CaCO 3 , triethylphosphate (TEP) , GPTMS and isotridecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and DBTDL were mixed in the composition of Table 1 to prepare a one-part adhesive composition.
표 1
Table 1
| 성분명 | 실시예1 | 실시예2 | 실시예3 | 실시예4 | 비교예1 | 비교예2 | |
| 조성 | ViPSQ 1 | 170 | 160 | 150 | 140 | ||
| HPSQ 2 | 30 | 40 | 50 | 60 | |||
| OSQ 3 | 60 | 70 | |||||
| ViPDMS 4 | 40 | 35 | |||||
| HPDMS 5 | 10 | 5 | |||||
| SiO2 6 | 40 | 40 | |||||
| CaCO3 7 | 50 | 50 | |||||
| TEP 8 | 10 | 10 | |||||
| GPTMS 9 | 10 | 10 | 10 | 10 | |||
| Isotridecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate 10 | 10 | 10 | 10 | 10 | 10 | 10 | |
| 1-ETCH 11 | 1 | 1 | 1 | 1 | |||
| DBTDL 12 | 2 | 2 | |||||
| Speier Catalyst 13 | 1 | 1 | 1 | 1 |
| Ingredient Name | Example 1 | Example 2 | Example 3 | Example 4 | Comparative Example 1 | Comparative Example 2 | |
| Furtherance | Vi PSQ 1 | 170 | 160 | 150 | 140 | ||
| H PSQ 2 | 30 | 40 | 50 | 60 | |||
| OSQ 3 | 60 | 70 | |||||
| Vi PDMS 4 | 40 | 35 | |||||
| H PDMS 5 | 10 | 5 | |||||
| SiO 2 6 | 40 | 40 | |||||
| CaCO 3 7 | 50 | 50 | |||||
| TEP 8 | 10 | 10 | |||||
| GPTMS 9 | 10 | 10 | 10 | 10 | |||
| Isotridecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 10 | 10 | 10 | 10 | 10 | 10 | 10 | |
| 1-ETCH 11 | One | One | One | One | |||
| DBTDL 12 | 2 | 2 | |||||
| Speier Catalyst 13 | One | One | One | One |
*1: 삼성정밀화학(SFC) 제조* 1: Samsung Fine Chemicals (SFC)
*2: SFC 제조 * 2: SFC manufacturing
*3: Silsesquioxane Oligomer, SFC 제조* 3: Silsesquioxane Oligomer, manufactured by SFC
*4: α,ω-Vinyl terminated polydimehtylsioxane, 상품명 DMS-V46, (美)Gelest * 4: α, ω-Vinyl terminated polydimehtylsioxane, trade name DMS-V46, (Gelest)
*5: α,ω-Hydrogen terminated polydimehylsiloxane, 상품명 DMS-H41, (美)Gelest * 5: α, ω-Hydrogen terminated polydimehylsiloxane, trade name DMS-H41, (Gelest)
*6: 상품명 Aerosil 200, (美)Evonik * 6 trade name Aerosil 200, Evonik
*7: Fatty acid coated CaCO3, 상품명 5T, (英)OMYA * 7: Fatty acid coated CaCO 3 , trade name 5T, (OM) OMYA
*8: Triethylphosphate, (韓)Chempia * 8: Triethylphosphate, (Chempia)
*9: 3-Glycidoxypropyl trimethoxysilane, 상품명 A-187, (美)Dow-Corning* 9: 3-Glycidoxypropyl trimethoxysilane, trade name A-187, (Dow-Corning)
*10: 상품명 SONGNOX 1077LQ, (韓)송원산업 * 10: Trade name SONGNOX 1077LQ, (Songwon Industrial Co., Ltd.)
*11: 1-Ethynylcyclohexanol,(美)Aldrich* 11: 1-Ethynylcyclohexanol, Aldrich
*12: Dibutyl tin dilaurate, (美)Aldrich* 12: Dibutyl tin dilaurate, Aldrich
*13: H2PtCl6, (日)Tanaka * 13: H 2 PtCl 6 , (day) Tanaka
평가예 1: 물성 측정 Evaluation Example 1: Measurement of Physical Properties
하기 방법에 따라 시편을 제작하였고 각 시편의 물성을 다음과 같이 평가하였다.Specimens were prepared according to the following method and the physical properties of each specimen were evaluated as follows.
i) 경도, 인장강도, 신율 및 모듈러스 i) hardness, tensile strength, elongation and modulus
상기 실시예 1-4의 접착 조성물 및 비교예 1-2의 접착 조성물 각각 50g을 테프론 금형에 충진 후 이를 100℃로 승온시켜 1시간 동안 방치하여 두께 2㎜의 시트(A)를 제작하였다. 50 g of the adhesive composition of Example 1-4 and 50 g of the adhesive composition of Comparative Example 1-2 were respectively filled in a Teflon mold and then heated to 100 ° C. and left for 1 hour to prepare a sheet (A) having a thickness of 2 mm.
상기 시트(A)를 25℃ RH50% 조건에서 Universal testing machine(이하 The sheet (A) at 25 ℃ RH50% conditions Universal Testing Machine
UTM 이라 함)으로 시험법 KSM6518에 따라 경도(Hardness), 인장강도(Tensile UTM) Hardness, Tensile according to Test Method KSM6518
strength), 신율(Elongation) 및 모듈러스(Modulus at E100%)를 측정하였다. strength, elongation and modulus (Modulus at E100%) were measured.
ii) 접착력ii) adhesion
상기 실시예 1-4의 접착 조성물 및 비교예 1-2의 접착 조성물 각각 0.5g을 각각 알루미늄(Al) 시편(사이즈: 20×50×2 ㎜)의 한쪽 부분(20×10 ㎜)에 2㎛의 두께로 코팅 후 다른 알루미늄(Al) 시편을 붙여 연결하여 100℃, 1시간 동안 방치하여 접착시편(B)를 제작하였다. 0.5 g of each of the adhesive composition of Example 1-4 and the adhesive composition of Comparative Example 1-2 was each 2 μm in one portion (20 × 10 mm) of an aluminum (Al) specimen (size: 20 × 50 × 2 mm). After the coating with a thickness of another aluminum (Al) by attaching a specimen attached to stand at 100 ℃, 1 hour to prepare an adhesive specimen (B).
상기 접착시편(B)를 25℃, RH 50% 조건에서 UTM으로 시험법 KSF1107A에 따라 접착력(Adhesion)을 측정하였다.Adhesion was measured according to the test method KSF1107A with UTM at 25 ° C. and RH 50% under the conditions of the adhesive specimen (B).
iii) 스카치 타임 iii) Scotch Time
상기 실시예 1-4의 접착 조성물 및 비교예 1-2의 접착 조성물 각각을 알루미늄 디쉬(dish)에 1g 적하하여 스카치 타임(Scotch time) 측정용 시편(C)를 제작하였다. 1 g of each of the adhesive composition of Example 1-4 and the adhesive composition of Comparative Example 1-2 was added dropwise to an aluminum dish to prepare a specimen (C) for scotch time measurement.
상기 시편(C)를 25℃, RH 50% 조건에서 손가락으로 표면에 접촉하여 접착제가 묻어나지 않는 시간을 측정하였다. The specimen (C) was measured at 25 ℃, RH 50% condition by contacting the surface with a finger and the time the adhesive does not appear.
iv) 점도 및 포트 라이프(Pot life) iv) viscosity and pot life
상기 실시예 1-4의 접착 조성물 및 비교예 1-2의 접착 조성물 각각 100g을 와이드 마우스 플라스크(Wide-mouth flask) 또는 비이커에 담아 점도 및 포트 라이프(Pot life) 측정용 시편(D)를 제작하였다.100 g of each of the adhesive composition of Example 1-4 and the adhesive composition of Comparative Example 1-2 was put in a wide-mouth flask or beaker to prepare a specimen (D) for measuring viscosity and pot life. It was.
상기 시편(D)를 25℃, RH 50% 조건에서 Brook-Filed 점도계(10rpm, Sp#4 조건)로 고유 점도를 측정하고, 점도의 시간에 대한 경시변화를 측정하여 초기 점도의 2배가 되는 시간을 확인하여 이 시간을 포트 라이프로 정하였다. The specimen D was measured at 25 ° C. and RH 50% at a Brook-Filed viscometer (10 rpm, Sp # 4 condition) to measure the intrinsic viscosity, and measured the change with time over time of the viscosity to double the initial viscosity. This time was determined as port life.
v) 비중v) specific gravity
시편(A)를 제조하여 경도, 인장강도, 신율, 모듈러스 등을 측정한 후 시편(A)를 10×10㎜ 규격으로 절단, 5EA를 만들어 전자 비중계의 챔버에 핀셋으로 집어 넣어 비중을 측정하였다. 5EA를 각각 차례대로 측정하여 평균값을 비중으로 정하였다. 상기 물성 평가 결과를 하기 표 2에 나타내었다.Specimen (A) was prepared to measure hardness, tensile strength, elongation, modulus, and the like, and specimen (A) was cut to 10 × 10 mm size, 5EA was made, and tweezers were placed in a chamber of an electronic hydrometer to measure specific gravity. Each 5EA was measured in turn and the average value was determined as the specific gravity. The physical property evaluation results are shown in Table 2 below.
표 2
TABLE 2
| 구 분 | 실시예1 | 실시예2 | 실시예3 | 실시예4 | 비교예1 | 비교예2 |
| 경도(Shore A) | 41 | 42 | 44 | 46 | 40 | 38 |
| 인장강도(MPa) | 7.9 | 8.1 | 7.7 | 7.7 | 5.5 | 5.1 |
| 신율(%) | 610 | 570 | 550 | 540 | 520 | 480 |
| 모듈러스(MPa/E100%) | 2.4 | 2.6 | 2.3 | 2.3 | 1.8 | 1.6 |
| 점도(mPa.s/25℃, RH 50%) | 88K | 85K | 83K | 82K | 110K | 120K |
| 비중(@25℃, RH 50%) | 1.26 | 1.26 | 1.26 | 1.26 | 1.82 | 1.82 |
| 포트 라이프 (hr/25℃, RH 50%) | 15 | 13 | 10 | 8 | 3 | 3 |
| 스카치 타임(min) | 32 | 30 | 28 | 27 | 36 | 38 |
| 접착력(kgf/㎠ @Al) | 26 | 28 | 28 | 26 | 20 | 16 |
| division | Example 1 | Example 2 | Example 3 | Example 4 | Comparative Example 1 | Comparative Example 2 |
| Shore A | 41 | 42 | 44 | 46 | 40 | 38 |
| Tensile Strength (MPa) | 7.9 | 8.1 | 7.7 | 7.7 | 5.5 | 5.1 |
| % Elongation | 610 | 570 | 550 | 540 | 520 | 480 |
| Modulus (MPa / E100%) | 2.4 | 2.6 | 2.3 | 2.3 | 1.8 | 1.6 |
| Viscosity (mPa. S / 25 ℃, RH 50%) | 88K | 85 K | 83 K | 82 K | 110 K | 120 K |
| Specific gravity (@ 25 ℃, RH 50%) | 1.26 | 1.26 | 1.26 | 1.26 | 1.82 | 1.82 |
| Pot Life (hr / 25 ℃, RH 50%) | 15 | 13 | 10 | 8 | 3 | 3 |
| Scotch Time (min) | 32 | 30 | 28 | 27 | 36 | 38 |
| Adhesive force (kg f / ㎠ @Al) | 26 | 28 | 28 | 26 | 20 | 16 |
상기 표 2을 참조하여, 실시예 1-4의 접착 조성물을 이용한 시편은 비교예 1-2의 접착 조성물을 이용한 시편과 비교하여 경도, 인장강도, 연신율, 모듈러스 특성이 향상될 뿐만 아니라, 스카치 타임, 포트 라이프 및 접착력 특성이 개선됨을 알 수 있었다.Referring to Table 2, the specimen using the adhesive composition of Example 1-4 is not only improved hardness, tensile strength, elongation, modulus characteristics, Scotch time compared to the specimen using the adhesive composition of Comparative Example 1-2 It was found that the pot life and adhesion properties were improved.
점도 및 비중에 있어서는 비교예 1-2의 접착 조성물을 이용하여 제작된 시편이 실시예 1-4의 경우와 비교하여 증가하는 특성을 나타냈다. 이와 같이 점도가 증가되면 상기 접착 조성물을 함유한 카트리지 사용시 토출압 및 비중이 증가하게 되고 이로써 제품이 무거워져서 작업자의 피로가 증가되며 작업속도가 느려지는 것으로 나타났다. 따라서 실시예 1-4의 접착 조성물을 이용하면 비교예 1-2의 경우와 비교하여 작업자 피로도가 감소되어 작업성이 개선됨을 알 수 있었다.In terms of viscosity and specific gravity, the test piece produced using the adhesive composition of Comparative Example 1-2 showed an increasing characteristic compared with the case of Example 1-4. As such, when the viscosity is increased, the discharge pressure and specific gravity are increased when using the cartridge containing the adhesive composition, and as a result, the product becomes heavy and the worker's fatigue is increased and the working speed is slowed. Therefore, when using the adhesive composition of Example 1-4 it can be seen that the workability is improved by reducing the worker fatigue compared to the case of Comparative Example 1-2.
본 발명의 일구현예에 따른 태양전지 모듈용 접착 조성물은 저장 안정성이 우수하며 이를 이용하면 접착력과 기계적 물성이 개선된 태양전지 모듈용 접착 부재를 제작할 수 있다.The adhesive composition for a solar cell module according to an embodiment of the present invention is excellent in storage stability, and by using this, an adhesive member for a solar cell module having improved adhesion and mechanical properties may be manufactured.
상기에서 바람직한 제조예를 참조하여 설명하였지만, 해당 기술 분야의 숙련된 당업자는 하기의 특허청구범위에 기재된 사상 및 영역으로부터 벗어나지 않는 범위내에서 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다.Although described with reference to the preferred manufacturing examples above, those skilled in the art will understand that various modifications and changes can be made without departing from the spirit and scope described in the claims below.
Claims (13)
- 말단 및 측쇄에 C2-C10의 알케닐기와 C1-C10 알킬기를 갖는 폴리실세스퀴옥산계 화합물(이하, 폴리실세스퀴옥산계 화합물 A)을 함유하는 A제; 및A agent containing the polysilsesquioxane type compound (Hereinafter, polysilsesquioxane type compound A) which has a C2-C10 alkenyl group and a C1-C10 alkyl group in a terminal and a side chain; And말단 및 측쇄에 수소와 C1-C10 알킬기를 갖는 폴리실세스퀴옥산계 화합물 (이하, 폴리실세스퀴옥산계 화합물 B)을 함유하는 B제를 포함하는 태양전지 모듈용 접착 조성물.Adhesive composition for solar cell modules containing B agent containing the polysilsesquioxane type compound (henceforth polysilsesquioxane type compound B) which has hydrogen and a C1-C10 alkyl group at the terminal and side chains.
- 제1항에 있어서, The method of claim 1,상기 A제가 촉매 및 접착 개선제 중에서 선택된 하나 이상을 포함하는 태양전지 모듈용 접착 조성물.The adhesive composition for solar cell modules, wherein the agent A includes at least one selected from a catalyst and an adhesion improving agent.
- 제1항에 있어서, The method of claim 1,상기 B제가 산화방지제 및 반응억제제 중에서 선택된 하나 이상을 포함하는 태양전지 모듈용 접착 조성물.Adhesive composition for a solar cell module, wherein the B agent comprises at least one selected from an antioxidant and a reaction inhibitor.
- 제1항에 있어서, The method of claim 1,상기 폴리실세스퀴옥산계 화합물 A는 말단 및 측쇄에 C2-C10 알케닐기, C1-C10 알킬기 및 하이드록시기를 갖는 폴리실세스퀴옥산계 화합물(이하, 제1폴리실세스퀴옥산계 화합물)을 하기 화학식 4로 표시되는 실리콘 화합물, 하기 화학식 5로 표시되는 실리콘 화합물 및 실라잔 화합물 중에서 선택된 하나와 반응하여 얻은 것인 태양전지 모듈용 접착 조성물:The polysilsesquioxane compound A is a polysilsesquioxane compound having a C2-C10 alkenyl group, a C1-C10 alkyl group and a hydroxyl group at the terminal and side chain (hereinafter, referred to as a first polysilsesquioxane compound). An adhesive composition for a solar cell module obtained by reacting with a silicon compound represented by Formula 4, a silicon compound represented by Formula 5, and a silazane compound:화학식 4Formula 4
상기 화학식 4중, R3은 C1-C10 알킬기이고, Y4은 C1-C10 알콕시기 또는 할로겐 원소이고, n은 1 내지 3의 정수이고,In Formula 4, R 3 is a C1-C10 alkyl group, Y 4 is a C1-C10 alkoxy group or a halogen element, n is an integer of 1 to 3,화학식 5Formula 5
상기 화학식 5중, R4는 C1-C10 알킬기이고, Y5는 C1-C10 알콕시기 또는 할로겐 원소이다.In said Formula (5), R <4> is a C1-C10 alkyl group and Y <5> is a C1-C10 alkoxy group or a halogen element. - 제4항에 있어서, The method of claim 4, wherein상기 제1폴리실세스퀴옥산계 화합물이 하기 화학식 1로 표시되는 실리콘 화합물, 하기 화학식 2로 표시되는 실리콘 화합물 및 하기 화학식 3으로 표시되는 실리콘 화합물을 가수분해 축중합하여 얻는 것인 태양전지 모듈용 접착 조성물.:Adhesion for a solar cell module, wherein the first polysilsesquioxane compound is obtained by hydrolysis-condensation polymerization of a silicon compound represented by the following Chemical Formula 1, a silicon compound represented by the following Chemical Formula 2, and a silicon compound represented by the following Chemical Formula 3 Composition .:화학식 1Formula 1
상기 화학식 1중 R1은 C2-C10 알케닐기이고, Y1은 C1-C10 알콕시기 또는 할로겐 원소이고,In Formula 1, R 1 is a C2-C10 alkenyl group, Y 1 is a C1-C10 alkoxy group or a halogen element,n은 1 내지 3이고, n is 1 to 3,화학식 2Formula 2
상기 화학식 2중 R2은 C1-C10 알킬기이고, Y2은 C1-C10 알콕시기 또는 할로겐 원소이고,In Formula 2, R 2 is a C1-C10 alkyl group, Y 2 is a C1-C10 alkoxy group or a halogen element,n은 1 내지 3이고, n is 1 to 3,화학식 3Formula 3
상기 화학식 3중 Y3은 C1-C10 알콕시기 또는 할로겐 원소이다. Y 3 in Formula 3 is a C1-C10 alkoxy group or a halogen element. - 제1항에 있어서,The method of claim 1,상기 폴리실세스퀴옥산계 화합물 B는 말단 및 측쇄에 수소, C1-C10 알킬기 및 하이드록시기를 갖는 폴리실세스퀴옥산계 화합물(이하, 제2폴리실세스퀴옥산계 화합물)을 하기 화학식 4로 표시되는 실리콘 화합물, 하기 화학식 5로 표시되는 실리콘 화합물, 실라잔 화합물 중에서 선택된 하나와 반응하여 얻은 것인 태양전지 모듈용 접착 조성물:The polysilsesquioxane compound B is a polysilsesquioxane compound (hereinafter referred to as a second polysilsesquioxane compound) having hydrogen, a C1-C10 alkyl group, and a hydroxyl group at the terminal and side chain thereof. An adhesive composition for a solar cell module obtained by reacting with a silicon compound represented, one selected from a silicon compound represented by Formula 5, and a silazane compound:화학식 4Formula 4
상기 화학식 4중, R3은 C1-C10 알킬기이고, Y4은 C1-C10 알콕시기 또는 할로겐 원소이고, n은 1 내지 3의 정수이고,In Formula 4, R 3 is a C1-C10 alkyl group, Y 4 is a C1-C10 alkoxy group or a halogen element, n is an integer of 1 to 3,화학식 5Formula 5
상기 화학식 5중, R4는 C1-C10 알킬기이고, Y5는 C1-C10 알콕시기 또는 할로겐 원소이다.In said Formula (5), R <4> is a C1-C10 alkyl group and Y <5> is a C1-C10 alkoxy group or a halogen element. - 제6항에 있어서, The method of claim 6,상기 제2폴리실세스퀴옥산계 화합물은 하기 화학식 2로 표시되는 실리콘 화합물, 하기 화학식 3으로 표시되는 실리콘 화합물 및 하기 화학식 6으로 표시되는 실리콘 화합물을 가수분해 축중합하여 얻은 것인 태양전지 모듈용 접착 조성물:The second polysilsesquioxane compound is a solar cell module adhesive obtained by hydrolytic condensation polymerization of a silicon compound represented by the following Chemical Formula 2, a silicon compound represented by the following Chemical Formula 3, and a silicon compound represented by the following Chemical Formula 6 Composition:화학식 2Formula 2
상기 화학식 1중 R2은 C2-C10 알케닐기이고, Y2는 C1-C10 알콕시기 또는 할로겐 원소이고,R 2 in Formula 1 is a C2-C10 alkenyl group, Y 2 is a C1-C10 alkoxy group or a halogen element,n은 1 내지 3이고, n is 1 to 3,화학식 3Formula 3
상기 화학식 3중 Y3은 C1-C10 알콕시기 또는 할로겐 원소이고,Y 3 in Formula 3 is a C1-C10 alkoxy group or a halogen element,화학식 6Formula 6
상기 화학식 6중 Y6은 C1-C10 알콕시기 또는 할로겐 원소이고,Y 6 in Formula 6 is a C1-C10 alkoxy group or a halogen element,n은 1 내지 3이다. n is 1 to 3. - 제1항에 있어서, The method of claim 1,상기 B제의 폴리실세스퀴옥산계 화합물 B는 상기 A제의 폴리실세스퀴옥산계 화합물 A 100 중량부를 기준으로 하여 5 내지 45 중량부로 사용하는 태양전지 모듈용 접착 조성물.The polysilsesquioxane compound B of the agent B is used for the solar cell module 5 to 45 parts by weight based on 100 parts by weight of the polysilsesquioxane compound A of the agent A.
- 제1항에 있어서, The method of claim 1,상기 B제가 폴리실세스퀴옥산계 화합물 A를 더 포함하는 태양전지 모듈용 접착 조성물.Adhesive composition for solar cell modules which said agent B further contains polysilsesquioxane type compound A.
- 제2항에 있어서, The method of claim 2,상기 촉매의 함량은 상기 A제의 폴리실세스퀴옥산계 화합물 A 1몰을 기준으로 하여 0.0001 내지 0.5몰이고,The content of the catalyst is 0.0001 to 0.5 mol based on 1 mol of the polysilsesquioxane compound A of agent A,상기 접착 개선제의 함량은 상기 폴리실세스퀴옥산계 화합물 A 100 중량부를 기준으로 하여 1 내지 15 중량부인 태양전지 모듈용 접착 조성물.The adhesion improving agent is a solar cell module adhesive composition of 1 to 15 parts by weight based on 100 parts by weight of the polysilsesquioxane compound A.
- 제3항에 있어서, The method of claim 3,상기 산화방지제 및 반응억제제의 함량은 각각 상기 B제의 폴리실세스퀴옥산계 화합물 B 1몰을 기준으로 하여 0.0001 내지 0.5몰인 태양전지 모듈용 접착 조성물.The amount of the antioxidant and the reaction inhibitor is 0.0001 to 0.5 mole based on 1 mole of the polysilsesquioxane compound B of the B agent, respectively.
- 제1항 내지 제11항 중 어느 한 항의 태양전지 모듈용 접착 조성물의 경화 반Hardening half of the adhesive composition for solar cell modules of any one of Claims 1-11.응 생성물을 포함하는 태양전지 모듈용 접착 부재.An adhesive member for a solar cell module comprising a product.
- 제12항의 접착 부재를 구비하는 태양전지 모듈. A solar cell module comprising the adhesive member of claim 12.
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| KR1020120142314A KR20140075865A (en) | 2012-12-07 | 2012-12-07 | Adhesion composition for solar cell module, adhesive member for solar cell module formed therefrom the composition and solar cell module employing the adhesive member |
| KR10-2012-0142314 | 2012-12-07 |
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| US20110018235A1 (en) * | 2006-12-27 | 2011-01-27 | Bluestar Silicones France | Adhesive silicone composition and adhesion method using the same |
-
2012
- 2012-12-07 KR KR1020120142314A patent/KR20140075865A/en not_active Application Discontinuation
-
2013
- 2013-07-19 WO PCT/KR2013/006465 patent/WO2014088180A1/en active Application Filing
- 2013-11-18 TW TW102141811A patent/TW201422751A/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070219312A1 (en) * | 2006-03-17 | 2007-09-20 | Jennifer Lynn David | Silicone adhesive composition and method for preparing the same |
| US20070244249A1 (en) * | 2006-04-06 | 2007-10-18 | General Electric Company | Two-part translucent silicone rubber-forming composition |
| US20080081863A1 (en) * | 2006-09-19 | 2008-04-03 | Shin-Etsu Chemical Co., Ltd. | Two part adhesive for silicone rubber which cures by addition reaction |
| US20110018235A1 (en) * | 2006-12-27 | 2011-01-27 | Bluestar Silicones France | Adhesive silicone composition and adhesion method using the same |
Non-Patent Citations (1)
| Title |
|---|
| KETOLA, BARRY ET AL.: "Silicones for photovoltaic encapsulation.", 23RD EUROPEAN PHOTOVOLTAIC SOLAR ENERGY CONFERENCE., 2008, VALENCIA, pages 2969 - 2973 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530994A (en) * | 2014-12-30 | 2015-04-22 | 苏州度辰新材料有限公司 | PID-resistant encapsulation adhesive film used for photovoltaic cell |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201422751A (en) | 2014-06-16 |
| KR20140075865A (en) | 2014-06-20 |
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