KR101632374B1 - Curable resin composition - Google Patents
Curable resin composition Download PDFInfo
- Publication number
- KR101632374B1 KR101632374B1 KR1020127010743A KR20127010743A KR101632374B1 KR 101632374 B1 KR101632374 B1 KR 101632374B1 KR 1020127010743 A KR1020127010743 A KR 1020127010743A KR 20127010743 A KR20127010743 A KR 20127010743A KR 101632374 B1 KR101632374 B1 KR 101632374B1
- Authority
- KR
- South Korea
- Prior art keywords
- meth
- acrylate
- component
- adhesive
- resin composition
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 72
- 239000000853 adhesive Substances 0.000 claims abstract description 118
- 230000001070 adhesive effect Effects 0.000 claims abstract description 118
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 111
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 36
- 239000011737 fluorine Substances 0.000 claims abstract description 35
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 229920000728 polyester Polymers 0.000 claims abstract description 16
- 229920001971 elastomer Polymers 0.000 claims abstract description 12
- 239000000806 elastomer Substances 0.000 claims abstract description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 11
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 11
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 11
- 125000003709 fluoroalkyl group Chemical group 0.000 claims abstract description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 125000002897 diene group Chemical class 0.000 claims abstract 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 2
- -1 phenoxyethyl Chemical group 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 239000011521 glass Substances 0.000 claims description 20
- 229920002313 fluoropolymer Polymers 0.000 claims description 14
- 239000004811 fluoropolymer Substances 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 150000002978 peroxides Chemical class 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 11
- 239000005062 Polybutadiene Substances 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 150000001993 dienes Chemical class 0.000 claims description 10
- 229920002857 polybutadiene Polymers 0.000 claims description 10
- 230000009477 glass transition Effects 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 150000002148 esters Chemical group 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 229920001195 polyisoprene Polymers 0.000 claims description 5
- XXHDHAPOSIFMIG-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]-1-phenoxyethanol Chemical compound OCCOCCOCCOCC(O)OC1=CC=CC=C1 XXHDHAPOSIFMIG-UHFFFAOYSA-N 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- HLIQLHSBZXDKLV-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol Chemical compound OCCOCC(O)OC1=CC=CC=C1 HLIQLHSBZXDKLV-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000000088 plastic resin Substances 0.000 claims description 3
- WLDMPODMCFGWAA-UHFFFAOYSA-N 3a,4,5,6,7,7a-hexahydroisoindole-1,3-dione Chemical compound C1CCCC2C(=O)NC(=O)C21 WLDMPODMCFGWAA-UHFFFAOYSA-N 0.000 claims 1
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- 125000004185 ester group Chemical group 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 82
- 239000011347 resin Substances 0.000 description 50
- 229920005989 resin Polymers 0.000 description 50
- 238000001723 curing Methods 0.000 description 44
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 33
- 239000012790 adhesive layer Substances 0.000 description 25
- 238000011156 evaluation Methods 0.000 description 21
- 239000002033 PVDF binder Substances 0.000 description 19
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 19
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 18
- 239000004926 polymethyl methacrylate Substances 0.000 description 18
- 238000004383 yellowing Methods 0.000 description 16
- 238000002156 mixing Methods 0.000 description 15
- 238000000016 photochemical curing Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 229920000139 polyethylene terephthalate Polymers 0.000 description 14
- 239000005020 polyethylene terephthalate Substances 0.000 description 14
- 238000003851 corona treatment Methods 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 8
- 208000028659 discharge Diseases 0.000 description 7
- 230000001678 irradiating effect Effects 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 7
- 229920002799 BoPET Polymers 0.000 description 6
- 229910001335 Galvanized steel Inorganic materials 0.000 description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- 239000008397 galvanized steel Substances 0.000 description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229920002725 thermoplastic elastomer Polymers 0.000 description 5
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 4
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 125000006226 butoxyethyl group Chemical group 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000004455 differential thermal analysis Methods 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- MHCLJIVVJQQNKQ-UHFFFAOYSA-N ethyl carbamate;2-methylprop-2-enoic acid Chemical compound CCOC(N)=O.CC(=C)C(O)=O MHCLJIVVJQQNKQ-UHFFFAOYSA-N 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920002620 polyvinyl fluoride Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- NKVCQMYWYHDOOF-UHFFFAOYSA-N 1-phenoxyethane-1,2-diol Chemical compound OCC(O)OC1=CC=CC=C1 NKVCQMYWYHDOOF-UHFFFAOYSA-N 0.000 description 2
- CDXFIRXEAJABAZ-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CDXFIRXEAJABAZ-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002959 polymer blend Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 1
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 description 1
- QERNPKXJOBLNFM-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluoropentane Chemical compound CC(F)(F)C(F)(F)C(F)(F)C(F)F QERNPKXJOBLNFM-UHFFFAOYSA-N 0.000 description 1
- JAEZSIYNWDWMMN-UHFFFAOYSA-N 1,1,3-trimethylthiourea Chemical compound CNC(=S)N(C)C JAEZSIYNWDWMMN-UHFFFAOYSA-N 0.000 description 1
- SBUBPFHJZHQNNT-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene hydrogen peroxide Chemical compound OO.OO.CC(C)C1=CC=CC=C1C(C)C SBUBPFHJZHQNNT-UHFFFAOYSA-N 0.000 description 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- FGTYTUFKXYPTML-UHFFFAOYSA-N 2-benzoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 FGTYTUFKXYPTML-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- MYISVPVWAQRUTL-UHFFFAOYSA-N 2-methylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3SC2=C1 MYISVPVWAQRUTL-UHFFFAOYSA-N 0.000 description 1
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 description 1
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 1
- GYUPEJSTJSFVRR-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,6-nonafluorohexyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)CCOC(=O)C=C GYUPEJSTJSFVRR-UHFFFAOYSA-N 0.000 description 1
- XFFRBHGLJSLAIF-UHFFFAOYSA-N 3a,4,5,6,7,7a-hexahydroisoindole-1,3-dione;ethyl prop-2-enoate Chemical compound CCOC(=O)C=C.C1CCCC2C(=O)NC(=O)C21 XFFRBHGLJSLAIF-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- NWDBBJVMYVHDIW-UHFFFAOYSA-N C=CC.C1(C2C(C(N1)=O)CCCC2)=O Chemical group C=CC.C1(C2C(C(N1)=O)CCCC2)=O NWDBBJVMYVHDIW-UHFFFAOYSA-N 0.000 description 1
- VRIQBNPWJSSBFQ-UHFFFAOYSA-N CC(C=O)C.C(C)(C)C1=CC=2C(C3=CC=CC=C3SC2C(=C1)C(C)C)=O Chemical compound CC(C=O)C.C(C)(C)C1=CC=2C(C3=CC=CC=C3SC2C(=C1)C(C)C)=O VRIQBNPWJSSBFQ-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N DEAEMA Natural products CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- FEXQDZTYJVXMOS-UHFFFAOYSA-N Isopropyl benzoate Chemical compound CC(C)OC(=O)C1=CC=CC=C1 FEXQDZTYJVXMOS-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- LFOXEOLGJPJZAA-UHFFFAOYSA-N [(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphoryl]-(2,6-dimethoxyphenyl)methanone Chemical compound COC1=CC=CC(OC)=C1C(=O)P(=O)(CC(C)CC(C)(C)C)C(=O)C1=C(OC)C=CC=C1OC LFOXEOLGJPJZAA-UHFFFAOYSA-N 0.000 description 1
- NBICYCZLCAMSBG-UHFFFAOYSA-L [Co+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O Chemical compound [Co+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O NBICYCZLCAMSBG-UHFFFAOYSA-L 0.000 description 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- VRAIHTAYLFXSJJ-UHFFFAOYSA-N alumane Chemical compound [AlH3].[AlH3] VRAIHTAYLFXSJJ-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229930006711 bornane-2,3-dione Natural products 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- UPIWXMRIPODGLE-UHFFFAOYSA-N butyl benzenecarboperoxoate Chemical group CCCCOOC(=O)C1=CC=CC=C1 UPIWXMRIPODGLE-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
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000007613 environmental effect Effects 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
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical class OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
Images
Classifications
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- 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
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
-
- 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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polymerisation Methods In General (AREA)
Abstract
According to the present invention, there is provided a curable resin composition containing the following components (A) to (C) and exhibiting high adhesive strength. (A) a polymer having at least one (meth) acryloyl group at the terminal or side chain of the (a-1) molecule and having a dienic or hydrogenated diene skeleton, (a-2) an elastomer and (a- 3) at least one member selected from the group consisting of copolymerized polyesters, (B) a (meth) acrylate having fluorine, and (C) a polymerization initiator. The curable resin composition may further contain (D) a (meth) acrylate other than the component (A) and the component (B) and the (E) silane coupling agent. (B) is preferably a (meth) acrylic acid ester having an ester residue of a fluoroalkyl group having 2 to 8 carbon atoms.
Description
The present invention relates to a curable resin composition. For example, a curable resin composition which exhibits high adhesion to a photo-curable or room temperature curable fluoropolymer and has high heat resistance and light resistance, and an adhesive composition using the curable resin composition and a composite coated or bonded thereto by the adhesive composition, To a back sheet and a front sheet for a solar cell to which a film layer is bonded.
Solar cells that convert sunlight energy into electrical energy using photovoltaic effects such as semiconductor P-N junction diodes have attracted attention as a clean energy source in the background of serious global environmental problems.
(A) a fluorine-based film is used on the surface, or (b) an aluminum (aluminum) film is used as a backing sheet Foil is used for the intermediate layer in many cases. On the other hand, there is a back sheet constituted by using a polyethylene terephthalate film as a constitution considering the price and the environment.
As disclosed in Patent Document 1, urethane-based adhesives are used for bonding various films when producing back sheets using these materials. BACKGROUND OF THE INVENTION [0002] Backs sheets made using urethane-based adhesives have problems in adhesion durability (hydrolysis resistance, heat resistance, light resistance) and are not suitable for prolonged use. The urethane-based adhesive is often harmful to the human body because many solvents are used, and it takes time to volatilize the solvent, and there are many problems in workability and productivity.
Since various film materials used in the backsheet are often made of an adhesive material such as a fluorine-based polymer or polyethylene terephthalate as described above, in order to avoid the above-described problems of the urethane-based adhesive, And thus it has been difficult to find an alternative adhesive.
The present invention has been made in view of the above problems related to the adhesive used for the back sheet of the solar cell module.
Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, they have reached the present invention.
That is, the present invention is, in one aspect, a curable resin composition containing the following components (A) to (C).
(A) is a polymer having at least one (meth) acryloyl group at the terminal or side chain of the (a-1) molecule and having a dienic or hydrogenated diene skeleton, (a-2) an elastomer and a-3) copolymerized polyester,
(B) is a (meth) acrylate having fluorine,
(C) is a polymerization initiator.
The curable resin composition according to the present invention further comprises (meth) acrylate other than the component (A) and the component (B) as the component (D) in one embodiment.
The curable resin composition according to the present invention further contains a silane coupling agent as a component (E) in one embodiment.
In the curable resin composition of the present invention, (a-1) is selected as the component (A) and the diene-based or hydrogenated diene-based skeleton is selected from the group consisting of polybutadiene, polyisoprene, polybutadiene, Isoprene and hydrogenated products of isoprene.
In the curable resin composition of the present invention, (a-1) is selected as the component (A) in the embodiment, and the number average molecular weight of the polymer is 500 to 50000.
In the curable resin composition of the present invention, (a-2) is selected as the component (A) in one embodiment, and the elastomer is a diene-based copolymer.
In the curable resin composition of the present invention, (a-3) is selected as the component (A) in one embodiment, and the (a-3) copolymerized polyester has a glass transition temperature of -20 캜 to 90 캜.
The curable resin composition according to the present invention is a (meth) acrylic acid ester in which, in one embodiment, the component (B) is a fluoroalkyl group having 2 to 8 carbon atoms in the ester residue.
In one embodiment, the curable resin composition of the present invention is a composition wherein the component (D) is at least one member selected from the group consisting of phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) At least one selected from the group consisting of polyethylene glycol (meth) acrylate, hexahydrophthalimideethyl (meth) acrylate and ethyl (meth) acrylate.
In one embodiment, the curable resin composition of the present invention is a silane coupling agent in which the component (E) has an epoxy group and / or a (meth) acrylic group.
In the curable resin composition of the present invention, the component (C) is a photopolymerization initiator in one embodiment.
In the curable resin composition of the present invention, the component (C) is peroxide in one embodiment.
The curable resin composition according to the present invention further comprises a reducing agent as component (F) in one embodiment.
The curable resin composition according to the present invention is a two-component curable resin composition according to one embodiment, wherein the first agent comprises at least (C) a peroxide and the second agent contains at least (F) a reducing agent.
Another aspect of the present invention is an adhesive composition comprising the curable resin composition according to the present invention.
The present invention is, in another aspect, a cured product of the adhesive composition according to the present invention.
The present invention is a composite in which an adherend is covered or bonded by a cured product according to the present invention in another aspect.
In the composite according to the present invention, in the embodiment, the adherend of the composite is at least one selected from the group consisting of fluoropolymer, general-purpose plastic resin, glass and metal.
The present invention is, in one aspect, a back sheet for a solar cell in which each film layer is formed by an adhesive composition according to the present invention.
In one aspect, the present invention is a front sheet for a solar cell in which each film layer is formed by an adhesive composition according to the present invention.
In one aspect, the present invention is a solar cell module using a back sheet according to the present invention.
In one aspect, the present invention is a solar cell module using a front sheet according to the present invention.
The curable resin composition of the present invention exhibits high adhesive strength.
BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional explanatory view showing one embodiment of the layer structure of the back sheet of the present invention. Fig.
2 is a cross-sectional view showing an embodiment of a solar cell module manufactured using the back sheet of the present invention.
The component (A) of the present invention is a polymer having at least one (meth) acryloyl group at the terminal or side chain of the (a-1) molecule and having a dienic or hydrogenated dienic skeleton, (a-2) An elastomer and (a-3) a copolymer polyester.
The main chain skeleton of the polymer of the component (a-1) of the present invention is a diene-based or hydrogenated diene-based skeleton. Examples of the diene-based or hydrogenated diene-based skeleton include at least one skeleton selected from the group consisting of hydrogenated products of polybutadiene, polyisoprene, polybutadiene, and hydrogenated polyisoprene. Of these, at least one selected from the group consisting of hydrogenated products of polybutadiene and polybutadiene is preferable, and polybutadiene is more preferable.
The polymer of the component (a-1) has at least one (meth) acryloyl group at the terminal or side chain of the main chain skeleton. Among them, it is preferable to have a (meth) acryloyl group at both ends of the main chain skeleton.
The polymer of the component (a-1) preferably has a number average molecular weight of from 500 to 50,000, more preferably from 8,000 to 45,000. When the number average molecular weight is 500 or more, since the hardness of the cured product obtained by irradiating the energy ray to the curable resin composition of the present invention is high, the adhesive layer can be easily formed. When the number average molecular weight is 50000 or less, the viscosity of the curable resin composition obtained is small, and therefore, workability in mixing in the production process and workability in using the curable resin composition in practical use are good.
As the component (a-1), "UC-203" (a maleic anhydride adduct of an isoprene polymer and an ester oligomer of 2-hydroxyethyl methacrylate) produced by Kuraray Co., Ltd., "TEAI- Added 1,2-polybutadiene-terminated urethane methacrylate), "TE-2000" (1,2-polybutadiene-terminated urethane methacrylate) manufactured by Nippon Soda Co., Ltd., and the like.
The elastomer of the component (a-2) of the present invention means a polymeric material having rubber-like elasticity at room temperature and is preferably capable of dissolving or dispersing in (meth) acrylate. The use of the elastomer makes it possible to impart strength to the cured resin, thereby further improving the peel adhesion strength and the impact bonding strength, and in addition, it is possible to prevent the brittle fracture of the adhesive caused at low temperatures. (a-2) refers to components other than the component (a-1) and components other than the component (a-3).
Examples of the elastomer of the component (a-2) include various synthetic rubbers such as acrylonitrile-butadiene rubber, styrene-butadiene rubber, chloroprene rubber and butadiene rubber, natural rubbers, styrene-butadiene- , Caprolactone type, adipate type and PTMG type, polyester type thermoplastic elastomers such as polybutylene terephthalate-polytetramethylene glycol multi-block polymer, and polyamide type thermoplastic elastomers such as 1,2-polybutadiene A thermoplastic elastomer, a vinyl chloride thermoplastic elastomer, an olefin thermoplastic elastomer, and an elastomer comprising a (meth) acrylic acid ester block copolymer. These elastomer components may be used singly or in combination of two or more as long as they have good compatibility.
Of these, a diene-based copolymer is preferable, and an acrylonitrile-butadiene rubber is more preferable because it has good solubility in (meth) acrylate and has a large effect of improving peel adhesion strength and impact adhesion strength.
The copolymerized polyester of the component (a-3) of the present invention is not limited as far as it is crystalline or amorphous, but amorphous copolymerized polyester is preferable.
The glass transition temperature (Tg) of the copolymer polyester of the component (a-3) of the present invention is preferably -20 to 90 占 폚, more preferably 0 to 60 占 폚 in that good adhesion strength to the adherend is exhibited , And most preferably from 10 to 40 占 폚.
Glass warfare refers to a change in a substance such as glass which is liquid at a high temperature, rapidly increases its viscosity in a certain temperature range due to temperature drop, and becomes almost amorphous solid by losing fluidity. The method of measuring the glass transition temperature is not particularly limited, but generally includes thermogravimetry, differential scanning calorimetry, differential thermal analysis, differential thermal analysis, and glass transition temperature calculated by dynamic viscoelasticity measurement. In the examples, the glass transition temperature was measured by differential thermal analysis.
The number average molecular weight of the copolymer polyester of the component (a-3) of the present invention is preferably 2,000 or more, more preferably 4,000 or more. The number average molecular weight of the copolymer polyester of the component (a-3) of the present invention is preferably 40,000 or less, more preferably 30,000 or less. If the number average molecular weight is 2000 or more, the cohesive force increases and the adhesive strength tends to increase. When the number average molecular weight is 40,000 or less, the viscosity of the curable resin composition is lowered and the application to the substrate tends to be facilitated.
Component (B) of the present invention is (meth) acrylate having fluorine. When the fluorine atom is present at any one of the molecular structures of the (meth) acrylate, there is no restriction on the introduction position of the fluorine. For example, a (meth) acrylate ester having a fluoroalkyl group in an ester residue may be used. Examples of the fluorine-containing (meth) acrylate include monofunctional (meth) acrylates having one (meth) acryloyl group and polyfunctional (meth) acrylates having two (meth) acryloyl groups. Examples of polyfunctional (meth) acrylates having two or more (meth) acryloyl groups include polymerizable fluorinated surfactants having two or more (meth) acryloyl groups as described in Japanese Patent Application Laid-Open No. 2007-246696 Specific examples thereof include a perfluoroalkyl group-lipophilic group-containing oligomer ("RS-75" manufactured by DIC Corporation), and the like.
Examples of the monofunctional (meth) acrylate having fluorine include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,2 (Perfluorobutyl) 2-hydroxypropyl (meth) acrylate, 2, 3-pentafluoropropyl (meth) acrylate, 2- (Perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorohexyl) 2-hydroxypropyl (meth) acrylate, 2- 1H, 3H-perfluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 1H, 1H, 5H octafluoropentyl (Meth) acrylate, 1H-1- (trifluoromethyl) trifluoromethyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl 3-methyl Naphthyl) and the like can be mentioned 2-hydroxypropyl (meth) acrylate. Among them, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,2,3,3-pentafluoro (Meth) acrylate such as propyl (meth) acrylate, 1H, 1H, 5H octafluoropentyl acrylate, 2- (perfluorohexyl) ethyl (Meth) acrylic acid esters having a fluoroalkyl group in the ester moiety are preferable, and 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) A fluoroalkyl group having 2 to 3 carbon atoms such as acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate and 2,2,2,3,3-pentafluoropropyl (meth) (Meth) acrylic acid ester is more preferable, and 2,2,2-trifluoroethyl (meth) acrylate is most preferable.
The ratio of the component (A) to the component (B) is preferably from 0.01 to 97 parts by mass, more preferably from 3 to 99.99 parts by mass, of the component (A) and the component (B) in a total amount of 100 parts by mass of the components (A) More preferably from 30 to 99 parts by mass, further preferably from 1 to 70 parts by mass, further preferably from 40 to 95 parts by mass, still more preferably from 5 to 60 parts by mass, and most preferably from 45 to 90 parts by mass,
Component (C) of the present invention is a polymerization initiator. The polymerization initiator is not particularly limited as long as it is capable of initiating polymerization of (meth) acrylate having fluorine as the component (B). Of these, photopolymerization initiators and / or peroxides are preferred.
Examples of the photopolymerization initiator include an ultraviolet polymerization initiator and a visible light polymerization initiator. Examples of the ultraviolet polymerization initiator include benzoin, benzophenone, and acetophenone. Examples of the visible light polymerization initiator include acylphosphine oxide-based, thioxanthone-based, metallocene-based, quinone-based, and -aminoalkylphenone based.
Examples of the photopolymerization initiator include benzophenone, 4-phenylbenzophenone, benzoylbenzoic acid, 2,2-diethoxyacetophenone, bisdiethylaminobenzophenone, benzyl, benzoin, benzoylisopropylether, benzyldimethylketal, 1-hydroxycyclo Hexylphenyl ketone, thioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone 2-methylpropan-1-one, 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy- 2-methyl-1-phenylpropan-1-one, camphorquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6 2-dimethylamino-1- (4-methylthio) phenyl) -2-morpholinopropane- (Morpholin-4-yl-phenyl) -butan-1-one, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, and the like. Of these, benzyl dimethyl ketal is preferred.
As the peroxide of the present invention, an organic peroxide is preferable. Examples of the organic peroxide include cumene hydroperoxide, paramethane hydroperoxide, tertiary butyl hydroperoxide, diisopropylbenzene dihydroperoxide, methyl ethyl ketone peroxide, benzoyl peroxide, and tertiary butyl peroxybenzoate. . Of these, cumene hydroperoxide is preferable in view of reactivity.
The amount of the component (C) to be used is preferably 0.05 to 10 parts by mass, more preferably 0.5 to 7 parts by mass per 100 parts by mass of the total of the components (A), (B) and (D) This adhesive has a high adhesive strength.
In the case of using a peroxide as a polymerization initiator in the present invention, the curable resin composition of the present invention contains a peroxide and a reducing agent on one side and the other component on the other side, Can be used as a resin composition. In this case, the amount of the peroxide used in the preparation of the 2 formulation is the amount of the above-mentioned mass part.
The curable resin composition of the present invention may contain a (meth) acrylate other than the component (A) and the component (B) as the component (D) for the purpose of further improving the adhesion. Examples of the (meth) acrylate other than the component (A) and the component (B) include a monofunctional (meth) acrylate and a bifunctional or higher polyfunctional (meth) acrylate. Of these, monofunctional (meth) acrylates are preferred.
Among the (meth) acrylates used as the component (D) of the present invention, monofunctional monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) Isobutyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl Acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (Meth) acrylate having a straight-chain or branched alkyl group having 1 to 20 carbon atoms such as heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, Ah (Meth) acrylate having a dicyclopentenyl group such as dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyloxypropyl (meth) acrylate and dicyclopentenyl (meth) acrylate, (Meth) acrylate such as hexahydrophthalimidoethyl (meth) acrylate (for example, product name: M-140, manufactured by TOAGOSEI CO., LTD.) Or hexahydrophthalimide propylene (meth) (Meth) acrylate including (meta) acrylate having a cyclic imide group such as tetrahydrophthalimide alkyl (meth) acrylate such as tetrahydrophthalimide ethyl (meth) acrylate, 2-hydroxyethyl (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (Meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, Acrylate, phenoxyethyleneglycol (meth) acrylate, phenoxyethyleneglycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxyethyl (Meth) acrylate, butoxy ethyl (meth) acrylate, butoxy ethyl (meth) acrylate, butoxy ethyl (meth) acrylate, (Meth) acrylate, 2-ethylhexylpolyethylene glycol (meth) acrylate, nonylphenylpolypropylene glycol (meth) acrylate, methoxy (Meth) acrylate, glycidyl (meth) acrylate, glycerol (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, epichlorohydrin EO modified phenoxy (meth) acrylate, ethylene oxide (hereinafter abbreviated as EO) modified phthalic acid (meth) acrylate, EO modified succinic acid (meth) acrylate, caprolactone (Meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, morpholino (Meth) acrylate, and the like.
The (meth) acrylate used as the component (D) of the present invention is excellent in the mixing property with the component (A) or the component (B) and further improves the adhesion to the polyester base material such as polyethylene terephthalate (Meth) acrylate is preferable from the viewpoint that it can be used in the present invention and monofunctional (meth) acrylate is preferable, and phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (Meth) acrylate, hexahydrophthalimideethyl (meth) acrylate, and ethyl (meth) acrylate.
When the component (D) is contained in the curable resin composition of the present invention, the amount of component (D) to be used is from 100 parts by mass to 100 parts by mass of the total of components (A), (B) (A), 5 to 40 parts by weight of the component (B), 5 to 40 parts by weight of the component (D), and 3 to 5 parts by weight of the component (D) To 80 parts by mass is more preferable, and 10 to 55 parts by mass of the component (A), 10 to 35 parts by mass of the component (B), and 7 to 75 parts by mass of the component (D) are most preferable.
The use amount of the component (D) in this range has a high adhesive strength.
In addition, for the purpose of adjusting the viscosity and fluidity, polymers, fine powdered silicas, paraffins, polymerization inhibitors, antioxidants, plasticizers, fillers, colorants and rust preventives can be used.
In the present invention, a silane coupling agent may be further used as the component (E). Examples of the silane coupling agent include silane coupling agents having an epoxy group such as? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane and? -Glycidoxypropyltrimethoxysilane,? - (meth) acryloxypropyltrimethoxysilane (Meth) acrylate, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (? -Methoxyethoxy) silane coupling agents such as? -Chloropropyltrimethoxysilane, vinyltrimethoxysilane, ) Silane,? -Mercaptopropyltrimethoxysilane,? -Aminopropyltriethoxysilane, N -? - (aminoethyl) -? - aminopropyltrimethoxysilane, N -? - -Aminopropylmethyldimethoxysilane,? -Ureidopropyltriethoxysilane, and the like. Among them, a silane coupling agent having an epoxy group and / or a (meth) acrylic group is preferable from the viewpoint of the effect of improving adhesion durability.
When the curable resin composition of the present invention contains the component (E), the amount of the component (E) used is preferably 0.1 to 100 parts by mass based on the total amount of the component (A), the component (B) To 15 parts by mass is preferable, and 0.3 parts by mass to 5 parts by mass is more preferable.
When a peroxide is used as the polymerization initiator of the component (C) of the present invention, it is possible to use a reducing agent in combination as the component (F).
As the reducing agent of the present invention, a thioamide compound such as trimethyl thiourea or ethylene thiourea, a transition metal salt such as cobalt naphthenate, copper naphthenate, vanadyl acetylacetonate, cobalt octenoate, cobalt octylate or copper acetylacetonate, . It is also possible to use one or more of these. Of these, transition metal salts are preferable, and cobalt octylate is more preferable.
The amount of the reducing agent used as the component (F) is preferably 0.1 to 10 parts by mass, more preferably 0.15 to 5 parts by mass, per 100 parts by mass of the total of the components (A), (B) Do. When the amount is more than 0.1 part by mass, the polymerization reaction proceeds sufficiently, so that the bonding strength is increased. When the amount is less than 10 parts by mass, the side reaction is not caused and the bonding strength is increased. The used amount is the amount used for the component (A), the component (B) and the component (D), and is the amount of the above-mentioned mass portion when the used amount is one of the two formulations.
As the embodiment of the present invention, when the curable resin composition of the present invention is used as a room-temperature-curable two-part adhesive composition, it is preferably used as a two-part type curable resin composition. That is, the essential component of the curable resin composition of the present invention can contain a peroxide on one side and a reducing agent on the other side, and the other components can be appropriately compounded in two agents. The adhesive can be used by contacting two agents immediately before use and curing them.
The curable resin composition of the present invention can be used as an adhesive composition. The cured product of the adhesive composition exhibits a high adhesive strength to an adherend such as a general-purpose plastic resin such as polyethylene terephthalate, polycarbonate, or polyolefin, a fluorine-based polymer, glass and metal, and has a higher adhesive strength to the fluorine- .
Examples of the fluorine-based polymer as the adherend of the present invention include polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoro Propylene copolymers, tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymers, tetrafluoroethylene-ethylene copolymers, polychlorotrifluoroethylene, chlorotrifluoroethylene-ethylene copolymers and the like And fluorine-containing polymers. Polymer blends of these fluorine-containing polymers and fluorine-free polymers are also included in the fluorine-based polymers of the present invention. For example, a polymer blend of polyvinylidene fluoride and polymethyl methacrylate corresponds to the fluoropolymer of the present invention.
Examples of the polyester as the adherend of the present invention include polyethylene terephthalate and polybutylene terephthalate. Examples of the polycarbonate as an adherend of the present invention include bisphenol A-polycarbonate and the like.
The adherend of the present invention may be used as it is or may be subjected to a surface treatment such as a corona discharge treatment, a plasma treatment, a wet treatment by various chemicals, a sand blast treatment or the like, if necessary. It is preferable that the surface treatment is carried out because adhesion is improved in many cases. The surface treatment is preferably a corona discharge treatment.
Example
Hereinafter, the present invention will be described in more detail with reference to experimental examples, but the present invention is not limited thereto. The following compounds were selected as the respective components in the curable resin composition described in Experimental Example.
(Experimental Examples 1 to 15)
The raw materials of the kind shown in Table 1 were mixed in the composition shown in Table 1 to prepare a curable resin composition. Various physical properties of the obtained composition were measured. These results are shown in Table 1.
(Materials used)
(A)
As a polymer having at least one (meth) acryloyl group at the terminal or side chain of the molecule and also having a dienic or hydrogenated dienic skeleton
(A-1) 1,2-polybutadiene terminated urethane methacrylate ("TE-2000" manufactured by Nippon Soda Co., Ltd.) (number average molecular weight 2000 converted to polystyrene by GPC)
As an elastomer
(A-2) Acrylonitrile butadiene rubber (NBR) ("N-220SH" manufactured by Zeon Corporation) (Mooney viscosity 41)
And as a copolymerized polyester
(A-3) An amorphous copolymer polyester having a glass transition temperature of 15 DEG C (VYLON GK-590, product of Toyo Seiki Seisakusho Co., Ltd.) having a number average molecular weight of 7000 in terms of polystyrene as measured by GPC and having a glass transition temperature )
(Meth) acrylate containing fluorine as the component (B)
(B-1) 2,2,2-trifluoroethyl methacrylate ("V-3 FM" manufactured by Osaka Organic Chemical Industry Co., Ltd.)
(B-2) 2- (perfluorobutyl) ethyl acrylate ("CHEMNOX FAAC-4" manufactured by UNIMATECH CORPORATION)
(B-3) Perfluoroalkyl group-lipophilic group-containing oligomer ("RS-75" manufactured by DIC)
(B-4) 2- (perfluorohexyl) ethyl methacrylate ("M-1620"
(C) as a photopolymerization initiator
(C-1) benzyl dimethyl ketal
(Meth) acrylate of the component (D)
(D-1) phenoxyethyl methacrylate ("PO" manufactured by Kyowa Chemical Industry Co., Ltd.)
(D-2) phenoxyethyl acrylate ("PO-A" manufactured by Kyowa Chemical Industry Co., Ltd.)
(D-3) Phenoxypolyethylene glycol acrylate ("P-200A" manufactured by Kyowa Chemical Industry Co., Ltd.)
(D-4) hexahydrophthalimide ethyl acrylate ("M-140" manufactured by Toagosei Co., Ltd.)
(D-5) Ethyl methacrylate ("Light Ester E" manufactured by Kyowa Chemical Industry Co., Ltd.)
As the silane coupling agent of component (E)
(E-1)? -Methacryloxypropyltrimethoxysilane
(E-2)? -Glycidoxypropyltrimethoxysilane
Various physical properties were measured as follows.
[Photocuring property] The temperature was measured at 23 ° C. Regarding the photo-curability, a fluorine resin film (DENKA DX film,
[Evaluation of fluoropolymer adhesiveness (peel adhesion strength between fluoropolymer test pieces)] A fluororesin film (DENKA DX film, average thickness of 50 占 퐉) having an 8: 2 mixture of polyvinylidene fluoride resin and polymethyl methacrylate resin Manufactured by Denki Kagaku Kogyo K.K.) were bonded to each other with a curing resin composition as an adhesive so that the adhesive layer had a thickness of 30 μm and an adhesive surface area of 40 mm × 10 mm. After curing by light irradiation, the two end portions of the film which were not adhered to the test piece adhered with the adhesive were pulled to peel off the portions where the films adhered to each other, and the initial 180 ° peel adhesion strength was measured. The light irradiation conditions were according to the method described in [Photocuring property]. The peel adhesion strength (unit: N / cm) was measured with a tensile tester at a tensile speed of 10 mm / min under an environment of a temperature of 23 캜 and a humidity of 50%.
(Peel adhesion strength between polyethylene terephthalate test pieces) A test piece (biaxially oriented PET film (Lumirror T60, average thickness 190 占 퐉, manufactured by Toray Industries, Inc.) (
(Tensile Adhesive Strength Between Heat-Resistant Glass Test Specimens) Heat-resistant glass test pieces (25 mm x 25 mm x 2.0 mm) were laminated together using a Teflon (registered trademark) tape having a thickness of 80 m, a width of 11.5 mm, (Adhesive area: 3.125 cm < 2 >). The light irradiation conditions were according to the method described in [Photocuring property]. After curing the adhesive under the above conditions, a galvanized steel sheet (100 mm in length x 25 mm in width x 2.0 mm in thickness, manufactured by Engineering Test Service Co., Ltd.) was adhered to both surfaces of the test piece by using adhesive "G-55" manufactured by Denki Kagaku Kogyo Co., . After curing, the initial tensile shear bond strength was measured by chucking the galvanized steel sheet using the test specimens bonded with an adhesive. The tensile shear bond strength (unit: MPa) was measured at a tensile speed of 10 mm / min under an environment of a temperature of 23 DEG C and a humidity of 50% using a tensile tester.
(Evaluation of Light fastness) A test piece of a fluorine resin film (DENKA DX film, average thickness of 50 m, manufactured by Denki Kagaku Kogyo Co., Ltd.) having an 8: 2 mixture of polyvinylidene fluoride resin and polymethyl methacrylate resin × 10 mm in width × 0.05 mm in thickness) were bonded to each other with a curing resin composition as an adhesive so that the adhesive layer had a thickness of 30 μm and a bonding area of 40 mm × 10 mm. The light irradiation conditions were according to the method described in [Photocuring property]. After curing, the test specimens adhered with an adhesive were irradiated with ultraviolet ray deterioration tester (EYE Super UV Tester SUV-W131, Iwasaki Electric Co., Ltd.) for 30 days under the environment of 60 캜 x 50% RH at a UV irradiation amount of 100 mW / cm 2. By using the test piece after irradiation, the two end portions of the film that were not closely adhered were pulled to peel off the portion where the films adhered to each other, and the 180 degree peel adhesion strength was measured. In addition, the appearance of the adhered area was visually observed to determine whether it was yellowing. The peel adhesion strength (unit: N / cm) was measured with a tensile tester at a tensile speed of 10 mm / min under an environment of a temperature of 23 캜 and a humidity of 50%.
[Evaluation of heat resistance] A test piece of a fluorine resin film (DENKA DX film,
(Evaluation of Humidity and Heat Resistance) A test piece of a fluorine resin film (DENKA DX film,
(Appearance Observation (yellowing degree)) TEMPAX glass (25 mm x 25 mm x 2 mm) was adhered and cured by using a curable resin composition as an adhesive composition with an adhesive layer thickness of 100 m and an adhesive area of 1.0 mm < 2 >. The light irradiation conditions were according to the method described in [Photocuring property]. After curing, the test piece after exposure was exposed to light resistance, heat resistance, or resistance to humidity and humidity, and the Δb value of the test piece was measured in a color measuring device ("UV-VISIBLE SPECTROPOHOTOMETER" manufactured by SHIMADZU).
(Continuation of Table 1)
(Experimental Example 16)
The raw materials of the kind shown in Table 2 were mixed in the composition shown in Table 2 to prepare a curing resin composition of room temperature curing property at room temperature. Further, the agent containing the cumene hydroperoxide and the agent containing the cobalt octylate was referred to as B-agent. A and B were sampled in the same amount and mixed, and after mixing, various kinds of physical properties were measured immediately after application to various test pieces. These results are shown in Table 2. In addition, various physical properties were measured as follows.
(Materials used)
As the peroxide of component (C)
(C-2) cumene hydroperoxide (product name: PH-80, manufactured by Nippon Oil & Fats Co., Ltd.)
(F) as a reducing agent
(F-1) Cobalt octylate (product name: Oct.Co, manufactured by Shinto Dyes Co., Ltd.)
[Evaluation of fluoropolymer adhesiveness (peel adhesion strength between fluoropolymer test pieces)] A fluororesin film (DENKA DX film, average thickness of 50 占 퐉) having an 8: 2 mixture of polyvinylidene fluoride resin and polymethyl methacrylate resin (10 mm in length x 10 mm in thickness, 0.05 mm in length) of a test piece (product of Denki Kagaku Kogyo K.K.) were used as an adhesive, and a curing resin composition of room temperature curing property was applied as an adhesive to form an adhesive layer having a thickness of 30 μm and an adhesive surface area of 40 mm × 10 mm Respectively. The adhesives were prepared by mixing the A and B materials in the same mass and curing them by leaving the specimens bonded at 23 ℃ for 24 hours. Thereafter, the two unfouled film ends of the test piece adhered with the adhesive were pulled out to peel off the portions where the films adhered to each other, and the initial 180 ° peel adhesion strength was measured. The peel adhesion strength (unit: N / cm) was measured with a tensile tester at a tensile speed of 10 mm / min under an environment of a temperature of 23 캜 and a humidity of 50%.
(Peel adhesion strength between polyethylene terephthalate test pieces) A test piece (biaxially oriented PET film (Lumirror T60, average thickness 190 占 퐉, manufactured by Toray Industries, Inc.) (
(Tensile Adhesive Strength Between Heat-Resistant Glass Test Specimens) A heat-resistant glass test piece (25 mm long × 25 mm × 2.0 mm thick) was coated with a Teflon (registered trademark) tape having a thickness of 80 μm, a width of 11.5 mm and a length of 25 mm as a spacer (Adhesive area: 3.125 cm < 2 >). The adhesives were prepared by mixing the A and B materials at the same mass and curing by letting the test specimens coalesce at 23 ℃ for 24 hours. Thereafter, a galvanized steel sheet (100 mm in length x 25 mm in width x 2.0 mm in thickness, manufactured by Engineering Test Service Co., Ltd.) was adhered to both sides of the test piece by using adhesive "G-55" manufactured by Denki Kagaku Kogyo Co., After curing, the initial tensile shear bond strength was measured by chucking the galvanized steel sheet using the test specimens bonded with an adhesive. The tensile shear bond strength (unit: MPa) was measured at a tensile speed of 10 mm / min under an environment of a temperature of 23 DEG C and a humidity of 50% using a tensile tester.
(Evaluation of Light fastness) A test piece of a fluorine resin film (DENKA DX film, average thickness of 50 m, manufactured by Denki Kagaku Kogyo Co., Ltd.) having an 8: 2 mixture of polyvinylidene fluoride resin and polymethyl methacrylate resin × 10 mm in width × 0.05 mm in thickness) were bonded to each other with an adhesive area thickness of 30 μm and a bonding area of 40 mm × 10 mm by using a curable resin composition of room temperature curing type 2 as a bonding agent. The adhesives were prepared by mixing the A and B materials at the same mass and curing by letting the test specimens coalesce at 23 ℃ for 24 hours. Then, the test piece adhered with an adhesive was irradiated with ultraviolet ray deterioration tester (EYE Super UV Tester SUV-W131, Iwasaki Electric Co., Ltd.) for 30 days under an environment of 60 캜 x 50% RH at a UV irradiation amount of 100 mW / cm 2. By using the test piece after irradiation, the two end portions of the film that were not closely adhered were pulled to peel off the portion where the films adhered to each other, and the 180 degree peel adhesion strength was measured. In addition, the appearance of the adhered area was visually observed to determine whether it was yellowing. The peel adhesion strength (unit: N / cm) was measured with a tensile tester at a tensile speed of 10 mm / min under an environment of a temperature of 23 캜 and a humidity of 50%.
[Evaluation of heat resistance] A test piece of a fluorine resin film (DENKA DX film,
(Evaluation of Humidity and Heat Resistance) A test piece of a fluorine resin film (DENKA DX film,
(Appearance Observation (yellowing degree)) TEMPAX glass (25 mm x 25 mm x 2 mm) was adhered and cured by using a curable resin composition as an adhesive composition with an adhesive layer thickness of 100 m and an adhesive area of 1.0 mm < 2 >. The curing conditions and methods of use were the same as those described in Experimental Example 16 (Evaluation of Glass Adhesion (Tensile Adhesion Strength Between Heat Resistance Glass Specimens)). After curing, the corresponding test piece after the light resistance, heat resistance or humidity resistance thermostability test was measured in a color measurement apparatus ("UV-VISIBLE SPECTROPOHOTOMETER" manufactured by SHIMADZU Co., Ltd.).
(Experimental Example 17)
A test piece for evaluation of physical properties was prepared by applying a urethane resin adhesive (Takelac A511, a main product of Mitsui Takeda Chemical Co., Ltd., hardening agent A50 = 10/1) to various substrate films so as to have a coating amount of 5 g / m 2 and bonding them. Respectively. These results are shown in Table 3. The preparation of various test pieces and the measurement of various physical properties were carried out as follows.
[Evaluation of fluoropolymer adhesiveness (peel adhesion strength between fluoropolymer test pieces)] A fluororesin film (DENKA DX film, average thickness of 50 占 퐉) having an 8: 2 mixture of polyvinylidene fluoride resin and polymethyl methacrylate resin Manufactured by Denki Kagaku Kogyo Co., Ltd.) were bonded to each other with an adhesive layer thickness of 30 μm and a bonding area of 40 mm × 10 mm by using a urethane resin adhesive. The adhesive was prepared by mixing the main agent and the curing agent in a ratio of 10/1 (mass ratio). Thereafter, the two unfouled film ends of the test piece adhered with the adhesive were pulled out to peel off the portions where the films adhered to each other, and the initial 180 ° peel adhesion strength was measured. The peel adhesion strength (unit: N / cm) was measured with a tensile tester at a tensile speed of 10 mm / min under an environment of a temperature of 23 캜 and a humidity of 50%.
(Peel adhesion strength between polyethylene terephthalate test pieces) A test piece (biaxially oriented PET film (Lumirror T60, average thickness 190 占 퐉, manufactured by Toray Industries, Inc.) (
(Tensile Adhesive Strength Between Heat-Resistant Glass Test Specimens) [0086] A heat-resistant glass test piece (25 x 25 x 2.0 mm) was coated with a urethane (Adhesion area: 3.125 cm < 2 >). The adhesive was prepared by mixing the main agent and the curing agent in a ratio of 10/1 (mass ratio). Thereafter, a galvanized steel sheet (100 mm in length x 25 mm in width x 2.0 mm in thickness, manufactured by Engineering Test Service Co., Ltd.) was adhered to both sides of the test piece by using adhesive "G-55" manufactured by Denki Kagaku Kogyo Co., After curing, the initial tensile shear bond strength was measured by chucking the galvanized steel sheet using the test specimens bonded with an adhesive. The tensile shear bond strength (unit: MPa) was measured at a tensile speed of 10 mm / min under an environment of a temperature of 23 DEG C and a humidity of 50% using a tensile tester.
(Evaluation of Light fastness) A test piece of a fluorine resin film (DENKA DX film, average thickness of 50 m, manufactured by Denki Kagaku Kogyo Co., Ltd.) having an 8: 2 mixture of polyvinylidene fluoride resin and polymethyl
[Evaluation of heat resistance] A test piece of a fluorine resin film (DENKA DX film,
(Evaluation of Humidity and Heat Resistance) A test piece of a fluorine resin film (DENKA DX film,
(Experimental Example 18)
The curable resin composition used in Experimental Example 2 was applied as an adhesive to a fluorine resin film (Tedlar, manufactured by DuPont Co., Ltd.) having a thickness of 38 mu m so as to have an adhesive thickness of 20 mu m, followed by bonding to an aluminum foil having a thickness of 20 mu m, The composition was applied as an adhesive and bonded to a fluororesin film. As shown in FIG. 1, the fluororesin film 11 (38 μm) / the adhesive layer 12 (20 μm) / the aluminum foil 13 (20 μm) / the adhesive layer 14 (20 μm) / the fluororesin film 15 ) (38 탆) (on the side of the solar cell element). The
The
The produced solar cell module was subjected to measurement and evaluation of the output test of the battery after 500 hours of storage under the environment of 85 ° C-90% RH. As a result, the output deteriorated to within 5%.
(Experimental Example 19)
Using a biaxially oriented PET film (Lumirror T60, average thickness 190 占 퐉, manufactured by Toray), the curable resin composition of Experimental Example 3 was applied as an adhesive so as to have an adhesive thickness of 20 占 퐉, (Tedlar, product of DuPont Co., Ltd.) to prepare a front sheet (surface protective sheet) of Experimental Example 19. [ The photo-curing was performed by irradiating UV light having a wavelength of 365 nm from the PET film side for 15 seconds under a condition of an integrated light quantity of 2000 mJ / cm 2 using a curing device manufactured by Fusion Corporation using an electrodeless discharge lamp.
The prepared front sheet was stored for 3,000 hours under an environment of 85 ° C × 85% RH, and the appearance of the front sheet was observed. As a result, peeling of each layer of the sheet did not occur and no yellowing was observed.
The
The produced solar cell module was subjected to measurement and evaluation of the output test of the battery after 500 hours of storage under the environment of 85 ° C-90% RH. As a result, the output deteriorated to within 5%.
(Experimental Examples 20 to 30)
The raw materials of the kind shown in Table 4 were mixed in the composition shown in Table 4 to prepare a curable resin composition. Various physical properties of the obtained composition were measured. These results are shown in Table 4. In addition, various physical properties were measured as follows.
[Evaluation of fluoropolymer adhesiveness (peel adhesion strength between fluoropolymer test pieces)] A fluororesin film (DENKA DX film, average thickness of 50 占 퐉) having an 8: 2 mixture of polyvinylidene fluoride resin and polymethyl methacrylate resin (
(Peel adhesion strength between polyethylene terephthalate test pieces) A test piece (biaxially oriented PET film (Lumirror T60, average thickness 190 占 퐉, manufactured by Toray Industries, Inc.) (
[Evaluation of light fastness] A fluorine resin film (DENKA DX film, average thickness of 50 mu m, dengan) having an 8: 2 mixture (ratio by weight) of polyvinylidene fluoride resin treated by corona discharge treatment as described above and polymethyl methacrylate resin (50 mm in length x 10 mm in width x 0.05 mm in thickness) of an adhesive layer (product of Kikagaku Kogyo Co., Ltd.) were bonded to each other with an adhesive layer thickness of 30 m and a bonding area of 40 mm x 10 mm by using a curable resin composition as an adhesive. Then, the adhesive portion was cured by irradiating light according to the method described in the above-mentioned [Photocurability], and then the test piece adhered with the adhesive was irradiated with ultraviolet rays by UV light with a UV tester (EYE Super UV Tester SUV-W131, Iwasaki Electric Co., Ltd.) And irradiated for 30 days at an irradiation dose of 100 mW / cm 2 under an environment of 60 ° C × 50% RH. By using the test piece after irradiation, the two end portions of the film that were not closely adhered were pulled to peel off the portion where the films adhered to each other, and the 180 degree peel adhesion strength was measured. In addition, the appearance of the adhered area was visually observed to determine whether it was yellowing. The peel adhesion strength (unit: N / cm) was measured with a tensile tester at a tensile speed of 10 mm / min under an environment of a temperature of 23 캜 and a humidity of 50%.
[Evaluation of heat resistance] A fluorine resin film (DENKA DX film, average thickness of 50 占 퐉, dengan (weight ratio)) of 8: 2 mixture (ratio by mass) of polyvinylidene fluoride resin subjected to corona discharge treatment as described above and polymethyl methacrylate resin (50 mm in length x 10 mm in width x 0.05 mm in thickness) of an adhesive layer (product of Kikagaku Kogyo Co., Ltd.) were bonded to each other with an adhesive layer thickness of 30 m and a bonding area of 40 mm x 10 mm by using a curable resin composition as an adhesive. Next, after the adhesive portion is cured by irradiating light according to the method described in the above-mentioned [Photocuring Properties], the test piece adhered with the adhesive is heated at a temperature of 85 ° C and a humidity of 5% RH for 1000 hours Exposing. By using the test piece after the exposure, the two end portions of the film which did not adhered were pulled out to peel off the portion where the films adhered to each other to measure the 180 degree peel adhesion strength. In addition, the appearance of the adhered area was visually observed to determine whether it was yellowing. The peel adhesion strength (unit: N / cm) was measured with a tensile tester at a tensile speed of 10 mm / min under an environment of a temperature of 23 캜 and a humidity of 50%.
(Evaluation of Humidity and Heat Resistance) A fluorine resin film (DENKA DX film, average thickness of 50 占 퐉, average thickness of 50 占 퐉) having an 8: 2 mixture (ratio by mass) of polyvinylidene fluoride resin treated by corona discharge treatment as described above and polymethyl methacrylate resin (50 mm in length x 10 mm in width x 0.05 mm in thickness) of an adhesive layer (manufactured by Denki Kagaku Kogyo Co., Ltd.) were bonded to each other with an adhesive layer thickness of 30 m and a bonding area of 40 mm x 10 mm by using a curable resin composition as an adhesive. Next, after the adhesive portion is cured by irradiating light according to the method described in the above-mentioned [Photocuring property], the test piece adhered with the adhesive is heat-treated at a temperature of 85 ° C and a relative humidity of 85% Exposing. By using the test piece after the exposure, the two end portions of the film which did not adhered were pulled out to peel off the portion where the films adhered to each other to measure the 180 degree peel adhesion strength. In addition, the appearance of the adhered area was visually observed to determine whether it was yellowing. The peel adhesion strength (unit: N / cm) was measured with a tensile tester at a tensile speed of 10 mm / min under an environment of a temperature of 23 캜 and a humidity of 50%.
From Table 1, the following are recognized. The curable resin composition of the present invention exhibits high adhesiveness to fluoropolymer, polyethylene terephthalate and glass, and exhibits high adhesion durability even after exposure to high temperature and high humidity, high temperature exposure and ultraviolet light (Experimental Examples 1 to 12). (Comparative Example 1, Experimental Example 2 and Experimental Example 3).
It can be seen from Table 2 that the curable resin composition of room temperature curing type 2 of the present invention exhibits high adhesiveness to fluoropolymer, polyethylene terephthalate and glass and exhibits high adhesion durability even after exposure to high temperature and high humidity, Able to know.
Further, from the comparison between Table 1 and Table 2 and Table 3, the curable resin composition of the present invention exhibited higher adhesiveness to various adherends than the urethane resin adhesive and at the same time, after the high temperature and high humidity exposure, the high temperature exposure and the ultraviolet exposure, Indicating high adhesion durability.
From Examples 18 and 19, it can be seen that when the curable resin composition of the present invention is used, a back sheet and a front sheet for a solar cell having high durability can be obtained, and a solar cell module can be manufactured using the back sheet and the front sheet .
From Examples 20 to 30, it is also found that the curable resin composition of the present invention exhibits high adhesion and adhesion durability even for various adherends subjected to corona discharge treatment. From the comparison of Experimental Examples 20 to 30 and Experimental Examples 1 to 15, it can be seen that the use of an adherend subjected to a corona discharge treatment exhibits higher adhesiveness and adhesion durability than an untreated adherend.
The curable resin composition of the present invention has high adhesion durability (hydrolysis resistance, heat resistance, light resistance) while exhibiting sufficient adhesive strength to a hard-to-stick material such as a fluorine-based polymer or polyethylene terephthalate or glass, particularly a fluorine-based polymer. A multilayer film in which various films such as a fluorine-based polymer and polyethylene terephthalate are laminated is applied to a back sheet or a front sheet (front film) of a solar cell module. The curable resin composition of the present invention is a fluorine-based polymer or a polyethylene terephthalate Is industrially very effective in that it can be used as an adhesive for lamination of various films.
1 solar cell module
10 back sheet
11, 15 fluorine resin film
12, 14 adhesive layer
13 Aluminum foil
20 EVA
30 solar cell element
40 glass plate or front sheet
50 spacer
Claims (22)
(A) is a polymer having at least one (meth) acryloyl group at the terminal or side chain of the (a-1) molecule and having a dienic or hydrogenated diene skeleton, (a-2) an elastomer and a-3) copolymerized polyester,
(B) is a (meth) acrylate having fluorine,
(C) is a polymerization initiator,
The component (D) is at least one member selected from the group consisting of phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, hexahydrophthalimide (Meth) acrylate other than the component (A) and the component (B) which are at least one member selected from the group consisting of ethyl (meth) acrylate and ethyl (meth) acrylate.
And a silane coupling agent as a component (E).
(A-1) is selected as the component (A), and the diene-based or hydrogenated diene skeleton is at least one selected from the group consisting of hydrogenated products of polybutadiene, polyisoprene, polybutadiene and hydrogenated polyisoprene Wherein the curable resin composition is a skeleton.
(A-1) is selected as the component (A), and the number average molecular weight of the polymer is 500 to 50,000.
(A-2) is selected as the component (A), and the elastomer is a diene-based copolymer.
(A-3) is selected as the component (A), and the copolymerizable polyester has a glass transition temperature of -20 占 폚 to 90 占 폚.
Wherein the component (B) is a (meth) acrylic acid ester having an ester residue of a fluoroalkyl group having 2 to 8 carbon atoms.
Wherein the component (E) is a silane coupling agent having an epoxy group and / or a (meth) acrylic group.
(C) is a photopolymerization initiator.
(C) is a peroxide.
And a reducing agent as a component (F).
A curable resin composition which is a two-component type curable resin composition, wherein the first agent comprises at least (C) a peroxide and the second agent contains at least (F) a reducing agent.
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| JP2009225646 | 2009-09-29 | ||
| JPJP-P-2009-225646 | 2009-09-29 |
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| JP (1) | JP5767971B2 (en) |
| KR (1) | KR101632374B1 (en) |
| CN (1) | CN102574962B (en) |
| TW (1) | TWI518127B (en) |
| WO (1) | WO2011040407A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US8921490B2 (en) * | 2009-06-30 | 2014-12-30 | Henkel US IP LLC | Ultrafast heat/room temperature adhesive composition for bonding applications |
| CN103113538B (en) * | 2013-01-24 | 2015-02-25 | 常州大学 | Fluorine-containing large-molecule coupling agent, and preparation method and application thereof |
| WO2014157624A1 (en) * | 2013-03-29 | 2014-10-02 | 株式会社クラレ | Polymer, method for producing same, and resin composition containing said polymer |
| CN104497944B (en) * | 2014-11-18 | 2016-06-29 | 惠晶显示科技（苏州）有限公司 | One can develop UV solidify hydrofluoric acid resistant protection glue |
| JP6979153B2 (en) * | 2015-03-24 | 2021-12-08 | セメダイン株式会社 | Curable composition |
| JP2017037923A (en) * | 2015-08-07 | 2017-02-16 | 大日本印刷株式会社 | Shock absorbing type glass substrate for solar cell module, and solar cell module using the same |
| KR20190027855A (en) * | 2016-07-07 | 2019-03-15 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Adhesive for light direction conversion film |
| US11466183B2 (en) | 2018-07-18 | 2022-10-11 | Threebond Co., Lid. | Adhesive composition, cured product, and bonded body |
| JP7319766B2 (en) * | 2018-08-10 | 2023-08-02 | 日東電工株式会社 | Adhesive sheet |
| JP7355559B2 (en) * | 2019-08-28 | 2023-10-03 | 住友理工株式会社 | Radical curable sealing material for fuel cells |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002164360A (en) * | 2000-11-27 | 2002-06-07 | Sumitomo Bakelite Co Ltd | Die-attach paste and semiconductor device |
| JP2002184793A (en) | 2000-04-10 | 2002-06-28 | Sumitomo Bakelite Co Ltd | Die attachment paste and semiconductor device |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4383878A (en) * | 1980-05-20 | 1983-05-17 | Minnesota Mining And Manufacturing Company | Transfer process |
| JPS6189264A (en) * | 1984-10-08 | 1986-05-07 | Dainippon Toryo Co Ltd | Coating resin composition |
| JPS62146278A (en) * | 1985-12-19 | 1987-06-30 | Sumitomo Bakelite Co Ltd | Ultraviolet-curing type plating base |
| JPS63189411A (en) * | 1987-01-30 | 1988-08-05 | Asahi Glass Co Ltd | Polyester resin composition |
| JP3214186B2 (en) * | 1993-10-07 | 2001-10-02 | 三菱電機株式会社 | Method for manufacturing semiconductor device |
| TWI282811B (en) * | 2000-04-10 | 2007-06-21 | Sumitomo Bakelite Co | Die-attaching paste and semiconductor device |
| JP2007266382A (en) | 2006-03-29 | 2007-10-11 | Toppan Printing Co Ltd | Backseat for solar cell module and solar cell module using same |
| JP5237565B2 (en) * | 2007-02-09 | 2013-07-17 | 株式会社ブリヂストン | Photo-curable liquid rubber composition |
| CN101431107A (en) * | 2007-11-07 | 2009-05-13 | E.I.内穆尔杜邦公司 | Laminated film and solar cell panel employing the same |
| JPWO2009063945A1 (en) * | 2007-11-15 | 2011-03-31 | 日立化成工業株式会社 | Optical waveguide resin composition and optical waveguide |
| JP2009235205A (en) * | 2008-03-26 | 2009-10-15 | Tomoegawa Paper Co Ltd | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet using the same |
| CN101290950B (en) * | 2008-05-23 | 2011-02-02 | 浙江工业大学 | Back film of solar cell and preparing technique thereof |
-
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- 2010-09-28 CN CN201080043623.7A patent/CN102574962B/en active Active
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002184793A (en) | 2000-04-10 | 2002-06-28 | Sumitomo Bakelite Co Ltd | Die attachment paste and semiconductor device |
| JP2002164360A (en) * | 2000-11-27 | 2002-06-07 | Sumitomo Bakelite Co Ltd | Die-attach paste and semiconductor device |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20120106725A (en) | 2012-09-26 |
| JP5767971B2 (en) | 2015-08-26 |
| WO2011040407A1 (en) | 2011-04-07 |
| CN102574962A (en) | 2012-07-11 |
| TWI518127B (en) | 2016-01-21 |
| TW201120126A (en) | 2011-06-16 |
| JPWO2011040407A1 (en) | 2013-02-28 |
| CN102574962B (en) | 2016-05-04 |
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