WO2022163166A1 - アクリル系粘着剤シート、アクリル系粘着剤組成物、粘着フィルム、及び、フレキシブルデバイス - Google Patents
アクリル系粘着剤シート、アクリル系粘着剤組成物、粘着フィルム、及び、フレキシブルデバイス Download PDFInfo
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- WO2022163166A1 WO2022163166A1 PCT/JP2021/045483 JP2021045483W WO2022163166A1 WO 2022163166 A1 WO2022163166 A1 WO 2022163166A1 JP 2021045483 W JP2021045483 W JP 2021045483W WO 2022163166 A1 WO2022163166 A1 WO 2022163166A1
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- WIPO (PCT)
- Prior art keywords
- sensitive adhesive
- weight
- acrylate
- meth
- monomer
- Prior art date
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 130
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 239000000203 mixture Substances 0.000 title claims abstract description 55
- 239000010410 layer Substances 0.000 claims abstract description 45
- 230000001070 adhesive effect Effects 0.000 claims abstract description 36
- 239000000853 adhesive Substances 0.000 claims abstract description 26
- 229920001721 polyimide Polymers 0.000 claims abstract description 18
- 238000003860 storage Methods 0.000 claims abstract description 12
- 239000011521 glass Substances 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims description 191
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 153
- 125000000217 alkyl group Chemical group 0.000 claims description 120
- 229920001519 homopolymer Polymers 0.000 claims description 68
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 53
- 230000009477 glass transition Effects 0.000 claims description 46
- 229920000058 polyacrylate Polymers 0.000 claims description 46
- 239000002313 adhesive film Substances 0.000 claims description 44
- 125000004432 carbon atom Chemical group C* 0.000 claims description 43
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 9
- 239000003522 acrylic cement Substances 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 230000000694 effects Effects 0.000 description 72
- 229920005989 resin Polymers 0.000 description 49
- 239000011347 resin Substances 0.000 description 49
- -1 alkali metal salts Chemical class 0.000 description 42
- 239000003431 cross linking reagent Substances 0.000 description 29
- 239000010408 film Substances 0.000 description 28
- 238000000034 method Methods 0.000 description 28
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 24
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 24
- 239000012790 adhesive layer Substances 0.000 description 24
- 239000000758 substrate Substances 0.000 description 24
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 24
- 150000002148 esters Chemical group 0.000 description 22
- 239000000463 material Substances 0.000 description 22
- 238000004519 manufacturing process Methods 0.000 description 21
- 239000002585 base Substances 0.000 description 20
- 229920000642 polymer Polymers 0.000 description 19
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 15
- 239000012948 isocyanate Substances 0.000 description 14
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 13
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 13
- 230000001771 impaired effect Effects 0.000 description 13
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 239000003505 polymerization initiator Substances 0.000 description 11
- 238000005452 bending Methods 0.000 description 10
- 238000004132 cross linking Methods 0.000 description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000470 constituent Substances 0.000 description 9
- 150000002978 peroxides Chemical class 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 150000002513 isocyanates Chemical class 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 7
- 239000004642 Polyimide Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 5
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 5
- 235000019439 ethyl acetate Nutrition 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 238000000691 measurement method Methods 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 229920001646 UPILEX Polymers 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 235000006708 antioxidants Nutrition 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- 229920001228 polyisocyanate Polymers 0.000 description 4
- 239000005056 polyisocyanate Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000003505 terpenes Chemical class 0.000 description 4
- 235000007586 terpenes Nutrition 0.000 description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 3
- RTEZVHMDMFEURJ-UHFFFAOYSA-N 2-methylpentan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCCC(C)(C)OOC(=O)C(C)(C)C RTEZVHMDMFEURJ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
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- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
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- 150000003839 salts Chemical class 0.000 description 3
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- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- AGKBXKFWMQLFGZ-UHFFFAOYSA-N (4-methylbenzoyl) 4-methylbenzenecarboperoxoate Chemical compound C1=CC(C)=CC=C1C(=O)OOC(=O)C1=CC=C(C)C=C1 AGKBXKFWMQLFGZ-UHFFFAOYSA-N 0.000 description 2
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 2
- VBQCFYPTKHCPGI-UHFFFAOYSA-N 1,1-bis(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1(OOC(C)(C)CCC)CCCCC1 VBQCFYPTKHCPGI-UHFFFAOYSA-N 0.000 description 2
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 2
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 2
- DPGYCJUCJYUHTM-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yloxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)CC(C)(C)C DPGYCJUCJYUHTM-UHFFFAOYSA-N 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- KANZWHBYRHQMKZ-UHFFFAOYSA-N 2-ethenylpyrazine Chemical compound C=CC1=CN=CC=N1 KANZWHBYRHQMKZ-UHFFFAOYSA-N 0.000 description 2
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
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- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
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- 239000004793 Polystyrene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 230000005260 alpha ray Effects 0.000 description 2
- 125000001204 arachidyl 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])C([H])([H])[H] 0.000 description 2
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- NSGQRLUGQNBHLD-UHFFFAOYSA-N butan-2-yl butan-2-yloxycarbonyloxy carbonate Chemical compound CCC(C)OC(=O)OOC(=O)OC(C)CC NSGQRLUGQNBHLD-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- 125000002704 decyl 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])* 0.000 description 2
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- 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 2
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 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 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
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- 238000010556 emulsion polymerization method Methods 0.000 description 1
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- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- XCLDSQRVMMXWMS-UHFFFAOYSA-N ethyl 4-methyl-3-oxopentanoate Chemical compound CCOC(=O)CC(=O)C(C)C XCLDSQRVMMXWMS-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- UKFXDFUAPNAMPJ-UHFFFAOYSA-N ethylmalonic acid Chemical compound CCC(C(O)=O)C(O)=O UKFXDFUAPNAMPJ-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- NDOGLIPWGGRQCO-UHFFFAOYSA-N hexane-2,4-dione Chemical compound CCC(=O)CC(C)=O NDOGLIPWGGRQCO-UHFFFAOYSA-N 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- ZIYVHBGGAOATLY-UHFFFAOYSA-L methylmalonate(2-) Chemical compound [O-]C(=O)C(C)C([O-])=O ZIYVHBGGAOATLY-UHFFFAOYSA-L 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical class C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
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- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
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- 238000007363 ring formation reaction Methods 0.000 description 1
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- 235000010378 sodium ascorbate Nutrition 0.000 description 1
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 1
- 229960005055 sodium ascorbate Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 125000000542 sulfonic acid group Chemical group 0.000 description 1
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- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
- DLSMLZRPNPCXGY-UHFFFAOYSA-N tert-butylperoxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOOC(C)(C)C DLSMLZRPNPCXGY-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229940042596 viscoat Drugs 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- 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
- C09J139/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Adhesives based on derivatives of such polymers
- C09J139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
Definitions
- the present invention relates to acrylic pressure-sensitive adhesive sheets, acrylic pressure-sensitive adhesive compositions, pressure-sensitive adhesive films, and flexible devices.
- Adhesive films are used to reinforce and protect the surfaces of members of various shapes.
- thermocompression bonding is usually performed using an anisotropic conductive film (ACF).
- ACF anisotropic conductive film
- an adhesive film may be adhered to the back side of the substrate of the semiconductor element in advance to reinforce the substrate (for example, Patent Document 1).
- a release layer and a flexible film substrate are formed on a support substrate such as glass, A TFT substrate is formed on the film substrate, and an organic EL layer is formed thereon. Then, the support substrate is peeled off to manufacture the flexible device.
- the flexible display layer is very thin, the device may be defective due to handling or the like. Therefore, in some cases, an adhesive film is adhered to the back side for reinforcement (for example, Patent Document 2).
- Semiconductor element substrates and flexible devices may be repeatedly bent, and if the adhesive film laminated to the substrate, etc., has poor bending properties, the recovery after bending will deteriorate, and in the worst case, it will break due to repeated bending. It can be chilling. Specifically, when an adhesive film is attached to a bent portion (for example, a movable bent portion of a folding member), for example, the following problems occur.
- a bent portion for example, a movable bent portion of a folding member
- the thickness of the area where the adhesive film is bent or pulled will change significantly, and even in such a state, wrinkles will easily appear or the film will float. do. For example, when the adhesive film is pulled, the thickness of the adhesive film is significantly reduced, and the film tends to be lifted from the adherend.
- One approach to solving the above problems is to improve elasticity by reducing the thickness of the adhesive layer.
- the thickness of the pressure-sensitive adhesive layer is reduced, there is a problem that it becomes difficult to maintain the adhesive force.
- An object of the present invention is to provide an acrylic pressure-sensitive adhesive sheet and an acrylic pressure-sensitive adhesive composition forming the acrylic pressure-sensitive adhesive sheet, which can achieve both excellent adhesiveness and excellent elasticity even if the thickness of the pressure-sensitive adhesive layer is reduced. , an adhesive film having an adhesive layer composed of the acrylic adhesive sheet, and a flexible device having the adhesive film.
- the acrylic pressure-sensitive adhesive sheet according to the embodiment of the present invention is At 23 ° C., at a peeling speed of 300 mm / min and a peeling angle of 180 degrees, the adhesive strength to the polyimide film is 5.5 N / 25 mm or more, and the adhesive strength to glass is 5.5 N / 25 mm or more,
- the storage modulus G′ at ⁇ 20° C. is 200 kPa or less,
- the thickness is 25 ⁇ m or less.
- the acrylic pressure-sensitive adhesive composition according to the embodiment of the present invention is An acrylic pressure-sensitive adhesive composition for forming an acrylic pressure-sensitive adhesive sheet according to an embodiment of the present invention, Contains acrylic polymers (P) and oligomers.
- the acrylic polymer (P) is obtained by polymerizing a monomer component (M), and the monomer component (M) contains a monomer (m5) having a polar group other than a hydroxyl group.
- the content of the monomer (m5) having a polar group other than the hydroxyl group in the monomer component (M) is 0.1% by weight to 5.0% by weight.
- the monomer (m5) having a polar group other than a hydroxyl group is a monomer (1) represented by general formula (1), a monomer (2) represented by general formula (2), and It contains at least one selected from the group consisting of N-vinyl-2-pyrrolidone.
- R 1 is an alkyl group having 1 to 10 carbon atoms
- R 2 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a —COOR group
- R is a carbon It is an alkyl group of numbers 1 to 10.
- R 3 is an alkylene group having 1 to 10 carbon atoms
- R 4 is an alkyl group having 1 to 10 carbon atoms
- R 5 is a hydrogen atom or a methyl group.
- the content of the oligomer in the acrylic pressure-sensitive adhesive composition is 0.1 to 6.5 parts by weight with respect to 100 parts by weight of the acrylic polymer (P). .
- the oligomer has a weight average molecular weight Mw of 1,000 to 30,000.
- the monomer component (M) contains an alkyl (meth)acrylate.
- the alkyl (meth)acrylate homopolymer has a glass transition temperature Tg of -10°C or lower.
- the content of the alkyl (meth)acrylate in the monomer component (M) is 50% by weight to 99% by weight.
- the monomer component (M) contains a hydroxyl group-containing monomer (m4).
- the content of the hydroxyl group-containing monomer (m4) in the monomer component (M) is 0.01% by weight to 30% by weight.
- the adhesive film according to the embodiment of the invention has an adhesive layer composed of the acrylic adhesive sheet according to the embodiment of the invention.
- a flexible device according to an embodiment of the present invention comprises an adhesive film according to an embodiment of the present invention.
- an acrylic pressure-sensitive adhesive sheet and an acrylic pressure-sensitive adhesive composition forming the acrylic pressure-sensitive adhesive sheet which can achieve both excellent adhesiveness and excellent elasticity even if the thickness of the pressure-sensitive adhesive layer is thin.
- a pressure-sensitive adhesive film having a pressure-sensitive adhesive layer composed of the acrylic pressure-sensitive adhesive sheet and a flexible device provided with the pressure-sensitive adhesive film.
- FIG. 1 is a schematic cross-sectional view showing one embodiment of the flexible device of the present invention, showing one usage pattern of the adhesive film according to the embodiment of the present invention.
- (meth) acrylic when used in this specification, it means “acrylic and/or methacrylic", and when the expression “(meth) acrylate” is used, “acrylate and/or methacrylate ", and the expression “(meth)allyl” means “allyl and/or methallyl”, and the expression “(meth)acrolein” means “acrolein and/or methacrolein”. means rain.
- the expression “acid (salt)” in this specification means “acid and/or its salt”. Examples of salts include alkali metal salts and alkaline earth metal salts, and specific examples include sodium salts and potassium salts.
- An acrylic pressure-sensitive adhesive sheet according to an embodiment of the present invention is a sheet-like acrylic pressure-sensitive adhesive. Therefore, it may be a sheet that can be handled independently as an acrylic pressure-sensitive adhesive sheet, or it may be recognized as one of the constituent members like an acrylic pressure-sensitive adhesive layer.
- the acrylic pressure-sensitive adhesive sheet according to the embodiment of the present invention preferably has an adhesive strength of 5.5 N/25 mm or more, more preferably 5.5 N/25 mm or more, to a polyimide film at a peel speed of 300 mm/min and a peel angle of 180 degrees at 23°C. is 6.0 N/25 mm or more, more preferably 6.5 N/25 mm or more, still more preferably 7.0 N/25 mm or more, particularly preferably 7.5 N/25 mm or more, most preferably 8 0 N/25 mm or more.
- the upper limit of the adhesive strength is preferably as high as possible, but it is preferably 30 N/25 mm or less in consideration of the balance with other adhesive properties.
- the acrylic pressure-sensitive adhesive sheet according to the embodiment of the present invention preferably has an adhesive force to a glass plate of 5.5 N/25 mm or more at 23° C., a peel speed of 300 mm/min, and a peel angle of 180 degrees, and more preferably. is 6.0 N/25 mm or more, more preferably 6.5 N/25 mm or more, still more preferably 7.0 N/25 mm or more, particularly preferably 7.5 N/25 mm or more, most preferably 8 0 N/25 mm or more.
- the upper limit of the adhesive strength is preferably as high as possible, but it is preferably 30 N/25 mm or less in consideration of the balance with other adhesive properties. By adjusting the adhesive strength within the above range, sufficient adhesiveness to various adherends such as flexible devices such as foldable devices and rollable devices can be exhibited. The measurement of the adhesive force will be described later.
- the acrylic pressure-sensitive adhesive sheet according to the embodiment of the present invention typically has an adhesive strength to a polyimide film at 23° C., a peel speed of 300 mm/min, and a peel angle of 180 degrees within the above range, and glass is within the above range.
- the fact that the acrylic pressure-sensitive adhesive sheet according to the embodiment of the present invention has such adhesive properties means that the adhesion properties of the acrylic pressure-sensitive adhesive sheet according to the embodiment of the present invention are less dependent on the adherend. .
- the acrylic pressure-sensitive adhesive sheet according to the embodiment of the present invention preferably has a storage modulus G' at -20°C of 200 kPa or less, more preferably 180 kPa or less, still more preferably 160 kPa or less, and still more preferably It is 150 kPa or less, more preferably 140 kPa or less, particularly preferably 130 kPa or less, and most preferably 120 kPa or less.
- the lower limit of the storage elastic modulus G' is preferably 70 kPa or more in consideration of the balance with other adhesive properties.
- the thickness of the acrylic pressure-sensitive adhesive sheet according to the embodiment of the present invention is preferably 25 ⁇ m or less, more preferably 23 ⁇ m or less, still more preferably 20 ⁇ m or less, still more preferably 18 ⁇ m or less, and particularly preferably. is 15 ⁇ m or less, most preferably 13 ⁇ m or less.
- the lower limit of the thickness is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, It is more preferably 5 ⁇ m or more, particularly preferably 7 ⁇ m or more, and most preferably 9 ⁇ m or more. If the thickness of the acrylic pressure-sensitive adhesive sheet is within the above range, the thickness of the acrylic pressure-sensitive adhesive sheet can be reduced.
- the acrylic pressure-sensitive adhesive sheet according to the embodiment of the present invention it is more preferable to adjust all of the adhesive strength to the polyimide film, the storage elastic modulus G' at -20°C, and the thickness within the above ranges. By adjusting in this way, the acrylic pressure-sensitive adhesive sheet according to the embodiment of the present invention can achieve both excellent adhesiveness and excellent elasticity even when the thickness of the pressure-sensitive adhesive layer is reduced.
- the acrylic pressure-sensitive adhesive sheet according to the embodiment of the present invention is preferably formed from an acrylic pressure-sensitive adhesive composition.
- the acrylic pressure-sensitive adhesive sheet can thus be defined as being formed from the acrylic pressure-sensitive adhesive composition. This is because the acrylic pressure-sensitive adhesive sheet becomes an acrylic pressure-sensitive adhesive sheet when the acrylic pressure-sensitive adhesive composition undergoes a cross-linking reaction or the like by heating or ultraviolet irradiation. Since it is impossible to specify directly and there are circumstances that make it impractical ("impossible and impractical circumstances"), the definition of "things formed from acrylic pressure-sensitive adhesive compositions" properly specified the acrylic pressure-sensitive adhesive sheet as a "thing".
- any method for forming such an acrylic pressure-sensitive adhesive sheet may be used as long as the effects of the present invention are not impaired.
- any suitable method can be adopted.
- an acrylic pressure-sensitive adhesive composition is applied onto any appropriate substrate, heated and dried as necessary, and cured as necessary. and forming an acrylic pressure-sensitive adhesive sheet on the substrate. Any appropriate means can be adopted as such means for coating as long as the effects of the present invention are not impaired.
- coating means examples include a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, an air knife coater, a spray coater, a comma coater, a direct coater, and a roll brush coater. mentioned.
- Any appropriate means can be employed for heating and drying the acrylic pressure-sensitive adhesive composition as long as the effects of the present invention are not impaired.
- heating/drying means for example, heating at about 60° C. to 180° C. can be mentioned.
- Any appropriate means can be employed for curing the acrylic pressure-sensitive adhesive composition as long as the effects of the present invention are not impaired.
- curing means examples include ultraviolet irradiation, laser beam irradiation, ⁇ -ray irradiation, ⁇ -ray irradiation, ⁇ -ray irradiation, X-ray irradiation, and electron beam irradiation.
- the acrylic pressure-sensitive adhesive composition according to the embodiment of the invention is an acrylic pressure-sensitive adhesive composition that forms the acrylic pressure-sensitive adhesive sheet according to the embodiment of the invention.
- the acrylic pressure-sensitive adhesive composition according to the embodiment of the invention preferably contains an acrylic polymer (P). Only one type of acrylic polymer (P) may be used, or two or more types may be used. By including the acrylic polymer (P) in the acrylic pressure-sensitive adhesive composition according to the embodiment of the present invention, the effects of the present invention can be exhibited more.
- any appropriate weight-average molecular weight Mw can be adopted as the weight-average molecular weight Mw of the acrylic polymer (P) as long as it does not impair the effects of the present invention.
- the content of the acrylic polymer (P) in the acrylic pressure-sensitive adhesive composition according to the embodiment of the present invention is preferably 50% by weight or more, more preferably 70% by weight or more, and still more preferably 90% by weight. or more, particularly preferably 95% by weight or more, and most preferably 97% by weight or more.
- the upper limit of the content ratio is preferably 99.9% by weight or less.
- the acrylic polymer (P) is preferably obtained by polymerizing the monomer component (M).
- the acrylic polymer (P) can thus be defined as one obtained by polymerizing the monomer component (M). This is because the acrylic polymer (P) becomes the acrylic polymer (P) by causing a polymerization reaction of the monomer component (M), and it is impossible to directly specify the acrylic polymer (P) by its structure. , In addition, due to the existence of circumstances that are almost impractical ("impossible / impractical circumstances"), the acrylic polymer (P) is defined as "obtained by polymerizing the monomer component (M)" is properly identified as a "thing".
- the monomer component (M) preferably contains a monomer (m5) having a polar group other than a hydroxyl group.
- the number of monomers (m5) having a polar group other than a hydroxyl group may be one, or two or more.
- the content of the monomer (m5) having a polar group other than a hydroxyl group in the monomer component (M) is preferably 0.01% by weight to 40% by weight, and more It is preferably 0.05 wt% to 20 wt%, more preferably 0.1 wt% to 10 wt%, still more preferably 0.3 wt% to 5.0 wt%, particularly preferably 0 .4 wt % to 4.0 wt %, most preferably 0.5 wt % to 3.5 wt %.
- the monomer (m5) having a polar group other than a hydroxyl group any appropriate monomer having a polar group other than a hydroxyl group can be employed as long as the effects of the present invention are not impaired.
- the monomer (m5) having a polar group other than a hydroxyl group is preferably a monomer having a polar group other than a hydroxyl group whose homopolymer has a glass transition temperature Tg of 100° C. or less.
- Tg is preferably 95° C. or lower, more preferably 90° C. or lower.
- the lower limit of Tg is preferably -30°C or higher, more preferably -10°C or higher.
- the glass transition temperature Tg of the homopolymer of the monomer (m5) having a polar group other than a hydroxyl group can affect the adhesive properties and bending properties of the acrylic polymer (P).
- the monomer (m5) having a polar group other than a hydroxyl group by adopting a monomer having a polar group other than a hydroxyl group whose homopolymer has a glass transition temperature Tg within the above range, an acrylic polymer ( The tackiness and elasticity of P) can be adjusted appropriately, and the effects of the present invention can be further expressed.
- the monomer (m5) having a polar group other than a hydroxyl group is preferably a hydroxyl group whose homopolymer has a glass transition temperature Tg of 50° C. to 100° C. from the viewpoint that the effects of the present invention can be further exhibited.
- Essentially contains a monomer having a polar group other than The glass transition temperature Tg of a homopolymer (homopolymer) of this monomer is preferably 60°C to 95°C, more preferably 70°C to 90°C.
- the glass transition temperature Tg of the homopolymer (homopolymer) in the monomer (m5) having a polar group other than a hydroxyl group is 50 ° C. to 100 ° C. (preferably 60 ° C. to 95 ° C., more preferably 70 ° C. to 90 ° C. ) is preferably 30% by weight to 100% by weight, more preferably 50% by weight to 100% by weight, from the viewpoint that the effects of the present invention can be further expressed. more preferably 70% to 100% by weight, particularly preferably 90% to 100% by weight, and most preferably 95% to 100% by weight.
- the glass transition temperature Tg of the homopolymer (homopolymer) of the monomer (m5) having a polar group other than a hydroxyl group that can be contained in the monomer component (M) a value described in a known document can be adopted.
- numerical values described in "Polymer Handbook” (3rd edition, John Wiley & Sons, Inc., 1989) can be used.
- the conventional value is adopted.
- the monomer (m5) having a polar group other than a hydroxyl group that is not described in the "Polymer Handbook” above the catalog value of the monomer manufacturing company is used.
- the Tg of the alkyl (meth)acrylate homopolymer which is not described in the above "Polymer Handbook” and is not provided with the catalog value of the monomer manufacturing company, is the value obtained by the measurement method described in JP-A-2007-51271. shall be used.
- the monomer (m5) having a polar group other than a hydroxyl group is preferably a monomer (1) represented by general formula (1), a monomer (2) represented by general formula (2), and N-vinyl- It contains at least one selected from the group consisting of 2-pyrrolidone.
- R 1 is an alkyl group having 1 to 10 carbon atoms
- R 2 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a —COOR group
- R is a carbon It is an alkyl group of numbers 1 to 10.
- R 3 is an alkylene group having 1 to 10 carbon atoms
- R 4 is an alkyl group having 1 to 10 carbon atoms
- R 5 is a hydrogen atom or a methyl group.
- the number of monomers (1) represented by general formula (1) may be one, or two or more.
- the monomer (1) represented by the general formula (1) has two polymerizable double bonds at its terminals and a structure (C—CH 2 —O— CH 2 —C) and further having an alkyl ester group (COOR 1 group) on at least one of the carbon atoms second from the end of the two terminal polymerizable double bonds, thereby promoting cyclization polymerization , it is possible to introduce an alkyl ester group into the structure constructed by cyclopolymerization, and these characteristics give the obtained acrylic pressure-sensitive adhesive better flexibility against bending motion and better Both resilience can be expressed.
- the number of monomers (2) represented by general formula (2) may be one, or two or more.
- R 1 is an alkyl group having 1 to 10 carbon atoms. an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, particularly preferably a methyl group or an ethyl group, most preferably is a methyl group.
- R 2 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a -COOR group.
- R 2 is preferably an alkyl group having 1 to 8 carbon atoms, more preferably 1 to 1 carbon atoms, in that the effects of the present invention can be more exhibited.
- 6 alkyl group more preferably an alkyl group having 1 to 3 carbon atoms.
- R is preferably an alkyl group having 1 to 10 carbon atoms, and from the viewpoint that the effects of the present invention can be more expressed, R is preferably an alkyl group having 1 to 8 carbon atoms.
- R 2 is preferably a hydrogen atom in that the effects of the present invention can be expressed more effectively.
- R 3 is an alkylene group having 1 to 10 carbon atoms, and from the viewpoint that the effects of the present invention can be more expressed, R 3 preferably has a number of carbon atoms. an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, still more preferably an alkylene group having 1 to 3 carbon atoms, and particularly preferably a methylene group ( --CH.sub.2--) or ethylene a group (--CH 2 CH 2 --), most preferably an ethylene group (--CH 2 CH 2 --).
- R 4 is an alkyl group having 1 to 10 carbon atoms. an alkyl group having 2 to 8 carbon atoms, more preferably an alkyl group having 3 to 6 carbon atoms, more preferably an alkyl group having 3 to 5 carbon atoms, particularly preferably a butyl group, most preferably n- butyl group.
- R 5 is a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint that the effects of the present invention can be exhibited more.
- the content of at least one is preferably 0.01% by weight to 30% by weight, more preferably 0.05% by weight to 10% by weight, from the viewpoint that the effects of the present invention can be more expressed. preferably 0.1 wt% to 5.0 wt%, more preferably 0.3 wt% to 4.0 wt%, particularly preferably 0.4 wt% to 3.5 wt%, Most preferably 0.5% to 3.0% by weight.
- the content of the monomer (1) represented by the general formula (1) in the monomer component (M) is It is preferably 0.01% to 20% by weight, more preferably 0.1% to 10% by weight, and still more preferably 0.2% to 5% by weight, in order to further express the effects of the invention.
- the content of the monomer (2) represented by the general formula (2) in the monomer component (M) is It is preferably 0.01% by weight to 20% by weight, more preferably 0.05% by weight to 10% by weight, and still more preferably 0.1% by weight to 8% by weight, in order to further express the effects of the invention.
- 0 wt% more preferably 1.0 wt% to 6.0 wt%, particularly preferably 1.2 wt% to 4.0 wt%, most preferably 1.5 wt% to 3.0% by weight.
- the content of N-vinyl-2-pyrrolidone in the monomer component (M) is preferable in that the effect of the present invention can be exhibited more.
- the monomer (m5) having a polar group other than a hydroxyl group the monomer (1) represented by the general formula (1), the monomer (2) represented by the general formula (2), other than N-vinyl-2-pyrrolidone
- carboxy group-containing monomers nitrogen-containing monomers other than N-vinyl-2-pyrrolidone, sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, cyano group-containing monomers, acid anhydride group-containing monomers, vinyl esters
- examples include vinyl acetate (VAc), vinyl propionate, vinyl laurate), aromatic vinyl compounds, amide group-containing monomers, epoxy group-containing monomers, (meth)acryloylmorpholine, and vinyl ethers.
- carboxy group-containing monomers examples include acrylic acid (AA), methacrylic acid (MAA), carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid. mentioned.
- Nitrogen-containing monomers other than N-vinyl-2-pyrrolidone include, for example, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole, vinylmorpholine, (meth) Nitrogen-containing vinyl monomers such as acryloylmorpholine, N-vinylcarboxylic acid amides and N-vinylcaprolactam; cyano group-containing acrylic monomers such as acrylonitrile and methacrylonitrile;
- the monomer component (M) preferably contains an alkyl (meth)acrylate.
- the alkyl group of the ester moiety is preferably an alkyl group having 1 to 16 carbon atoms.
- the alkyl group of the ester moiety as used herein does not include an alkyl group containing a polar group such as a hydroxyl group.
- alkyl (meth)acrylate Only one type of alkyl (meth)acrylate may be used, or two or more types may be used.
- the content of the alkyl (meth)acrylate in the monomer component (M) is preferably 50% to 99% by weight, more preferably 70% to 98% by weight, from the viewpoint of being able to exhibit the effects of the present invention. %, more preferably 80 wt % to 97 wt %, particularly preferably 85 wt % to 96 wt %, most preferably 90 wt % to 96 wt %.
- alkyl (meth)acrylate Any appropriate alkyl (meth)acrylate can be employed as the alkyl (meth)acrylate as long as the effects of the present invention are not impaired.
- an alkyl (meth)acrylate for example, a compound represented by the following formula (1) can be preferably used.
- CH2 C( R1 ) COOR2 (1)
- R 1 in the above formula (1) is a hydrogen atom or a methyl group
- R 2 is a C 1-20 alkyl group.
- R 2 is preferably an alkyl group having 1 to 16 carbon atoms, more preferably an alkyl group having 2 to 14 carbon atoms, still more preferably a carbon It is an alkyl group having 4 to 14 carbon atoms, particularly preferably an alkyl group having 4 to 12 carbon atoms.
- the above-mentioned alkyl group is preferably a chain alkyl group in that the effects of the present invention can be exhibited more effectively.
- chain as used herein means a straight-chain or branched chain.
- alkyl (meth)acrylates in which R 2 is a chain alkyl group having 1 to 20 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n - butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) ) acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (me
- the alkyl (meth)acrylate that can be contained in the monomer component (M) has a homopolymer glass transition temperature Tg of preferably ⁇ 10° C. or lower. more preferably -12°C or lower, more preferably -15°C or lower, particularly preferably -18°C or lower, and most preferably -20°C or lower.
- the lower limit of the glass transition temperature Tg is preferably -80°C or higher.
- the glass transition temperature Tg of the alkyl (meth)acrylate homopolymer (homopolymer) that can be contained in the monomer component (M) can affect the adhesive properties and bending properties of the acrylic polymer (P).
- an acrylic polymer (The tackiness and elasticity of P) can be adjusted appropriately, and the effects of the present invention can be further expressed.
- the glass transition temperature Tg of the alkyl (meth)acrylate homopolymer (homopolymer) that can be contained in the monomer component (M) is known as the above-mentioned monomer (m5) having a polar group other than a hydroxyl group.
- Values described in materials can be adopted, for example, numerical values described in "Polymer Handbook” (3rd edition, John Wiley & Sons, Inc., 1989) can be used. In addition, when multiple numerical values are described in the above “Polymer Handbook", the conventional value is adopted. For alkyl (meth)acrylates not listed in the above “Polymer Handbook", the catalog values of monomer manufacturing companies are used.
- the Tg of the alkyl (meth)acrylate homopolymer which is not described in the above "Polymer Handbook” and is not provided with the catalog value of the monomer manufacturing company, is the value obtained by the measurement method described in JP-A-2007-51271. shall be used.
- Tg of the alkyl (meth)acrylate homopolymer that can be contained in the monomer component (M) are as follows. 2-ethylhexyl acrylate (2EHA): -70°C Lauryl acrylate (LA): -23°C n-butyl acrylate (BA): -55°C
- the monomer component (M) is an alkyl (meth)acrylate having a homopolymer glass transition temperature Tg of ⁇ 80° C. to ⁇ 60° C. in the point that the effect of the present invention can be more expressed. preferably contains an alkyl (meth)acrylate (m1) in When the monomer component (M) contains the alkyl (meth)acrylate (m1), the content of the alkyl (meth)acrylate (m1) in the monomer component (M) is It is preferably 40% to 99% by weight, more preferably 45% to 90% by weight, still more preferably 50% to 80% by weight, particularly preferably 55% to 75% by weight. , most preferably 60% to 70% by weight.
- the glass transition temperature Tg of the alkyl (meth)acrylate homopolymer (homopolymer) that can be contained in the monomer component (M) can affect the adhesive properties and bending properties of the acrylic polymer (P). . Then, as the alkyl (meth)acrylate that can be contained in the monomer component (M), the alkyl (meth)acrylate (m1) is adjusted so that the content ratio in the monomer component (M) is within the above range and adopted. By doing so, the adhesiveness and elasticity of the acrylic polymer (P) can be appropriately adjusted, and the effects of the present invention can be exhibited more effectively.
- 2EHA 2-ethylhexyl acrylate
- the monomer component (M) is an alkyl (meth)acrylate having a homopolymer glass transition temperature Tg of ⁇ 40° C. to ⁇ 10° C. from the point of view that the effect of the present invention can be more expressed. preferably contains an alkyl (meth)acrylate (m2) in When the monomer component (M) contains the alkyl (meth)acrylate (m2), the content of the alkyl (meth)acrylate (m2) in the monomer component (M) is It is preferably 5% to 50% by weight, more preferably 7% to 40% by weight, still more preferably 10% to 30% by weight, particularly preferably 13% to 25% by weight. , most preferably between 15% and 22% by weight.
- the glass transition temperature Tg of the alkyl (meth)acrylate homopolymer (homopolymer) that can be contained in the monomer component (M) can affect the adhesiveness and elasticity of the acrylic polymer (P). Then, as the alkyl (meth)acrylate that can be contained in the monomer component (M), the alkyl (meth)acrylate (m2) is adjusted so that the content ratio in the monomer component (M) is within the above range and adopted. By doing so, the adhesiveness and elasticity of the acrylic polymer (P) can be appropriately adjusted, and the effects of the present invention can be exhibited more effectively.
- alkyl (meth)acrylate (m2) examples include lauryl acrylate (LA) (the glass transition temperature Tg of its homopolymer (homopolymer) is -23°C).
- the monomer component (M) is an alkyl (meth)acrylate, and the glass transition temperature Tg of its homopolymer (homopolymer) is more than -60°C and less than -40°C in that the effect of the present invention can be more expressed.
- the glass transition temperature Tg of the alkyl (meth)acrylate homopolymer (homopolymer) that can be contained in the monomer component (M) can affect the adhesiveness and elasticity of the acrylic polymer (P). Then, as the alkyl (meth)acrylate that can be contained in the monomer component (M), the alkyl (meth)acrylate (m3) is adjusted so that the content ratio in the monomer component (M) is within the above range and adopted. By doing so, the adhesiveness and elasticity of the acrylic polymer (P) can be appropriately adjusted, and the effects of the present invention can be exhibited more effectively.
- the monomer component (M) is selected from the group consisting of alkyl (meth)acrylates (m1), alkyl (meth)acrylates (m2), and alkyl (meth)acrylates (m3) in order to further develop the effects of the present invention. It is preferable to include at least one selected, and at least two selected from the group consisting of alkyl (meth)acrylate (m1), alkyl (meth)acrylate (m2), and alkyl (meth)acrylate (m3) may be included. More preferably, it contains all of alkyl (meth)acrylate (m1), alkyl (meth)acrylate (m2), and alkyl (meth)acrylate (m3).
- the monomer component (M) typically contains at least one selected from the group consisting of 2-ethylhexyl acrylate, lauryl acrylate, and n-butyl acrylate in order to further develop the effects of the present invention. It preferably contains at least two selected from the group consisting of 2-ethylhexyl acrylate, lauryl acrylate, and n-butyl acrylate, and more preferably contains all of 2-ethylhexyl acrylate, lauryl acrylate, and n-butyl acrylate. .
- the monomer component (M) preferably contains a hydroxyl group-containing monomer (m4). Only one kind of hydroxyl group-containing monomer (m4) may be used, or two or more kinds thereof may be used.
- the hydroxyl group-containing monomer (m4) that can be contained in the monomer component (M) has a homopolymer glass transition temperature Tg of preferably ⁇ 10° C. or lower. , more preferably -15°C or lower, still more preferably -20°C or lower, particularly preferably -25°C or lower, and most preferably -30°C or lower.
- the lower limit of the glass transition temperature Tg is preferably -80°C or higher.
- the glass transition temperature Tg of the homopolymer (homopolymer) of the hydroxyl group-containing monomer (m4) that can be contained in the monomer component (M) can affect the adhesiveness and elasticity of the acrylic polymer (P).
- hydroxyl group-containing monomer (m4) that can be contained in the monomer component (M), by adopting a hydroxyl group-containing monomer (m4) whose homopolymer (homopolymer) has a glass transition temperature Tg within the above range, acrylic Adhesiveness and elasticity of the polymer (P) can be appropriately adjusted, and the effects of the present invention can be exhibited more.
- the glass transition temperature Tg of the homopolymer (homopolymer) of the hydroxyl group-containing monomer (m4) that can be contained in the monomer component (M) the monomer (m5) having a polar group other than the hydroxyl group and the alkyl (
- values described in publicly known documents can be adopted, for example, values described in "Polymer Handbook” (3rd edition, John Wiley & Sons, Inc., 1989) can be used.
- the conventional value is adopted.
- the hydroxyl group-containing monomer (m4) not listed in the "Polymer Handbook” above the catalog value of the monomer manufacturing company is used.
- Tg of the homopolymer of the hydroxyl group-containing monomer (m4) which is not described in the above "Polymer Handbook" and is not provided by the catalog value of the monomer manufacturing company, is obtained by the measurement method described in JP-A-2007-51271. values shall be used.
- glass transition temperature Tg of the homopolymer (homopolymer) of the hydroxyl group-containing monomer (m4) that can be contained in the monomer component (M) are as follows. 2-hydroxyethyl acrylate: -15°C 4-hydroxybutyl acrylate: -40°C
- the content ratio of the hydroxyl group-containing monomer (m4) in the monomer component (M) is preferably 0.00, from the viewpoint that the effects of the present invention can be exhibited more effectively.
- hydroxyl group-containing monomers (m4) examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy hydroxyalkyl (meth)acrylates such as butyl (meth)acrylate; polypropylene glycol mono(meth)acrylate; N-hydroxyethyl (meth)acrylamide;
- the hydroxyl group-containing monomer (m4) preferably contains a hydroxyalkyl (meth)acrylate, more preferably a linear alkyl group having 2 to 4 carbon atoms in the alkyl group portion.
- hydroxyalkyl (meth)acrylate group examples include 2-hydroxyethyl acrylate (HEA) and 4-hydroxybutyl acrylate (4HBA). Butyl acrylate.
- the monomer component (M) is preferably selected from alkyl (meth)acrylate (m1), alkyl (meth)acrylate (m2), and alkyl (meth)acrylate (m3) in order to further develop the effects of the present invention.
- At least one selected from the group consisting of, and a hydroxyl group-containing monomer (m4) more preferably alkyl (meth)acrylate (m1), alkyl (meth)acrylate (m2), alkyl (meth)acrylate (m3)
- At least two selected from the group consisting of and a hydroxyl group-containing monomer (m4) more preferably alkyl (meth)acrylate (m1), alkyl (meth)acrylate (m2), alkyl (meth)acrylate (m3 ) and a hydroxyl group-containing monomer (m4).
- the monomer component (M) is typically preferably at least one selected from the group consisting of 2-ethylhexyl acrylate, lauryl acrylate, and n-butyl acrylate. and a hydroxyl group-containing monomer (m4), more preferably at least two selected from the group consisting of 2-ethylhexyl acrylate, lauryl acrylate, n-butyl acrylate, and a hydroxyl group-containing monomer (m4), more preferably includes any of 2-ethylhexyl acrylate, lauryl acrylate, n-butyl acrylate, and a hydroxyl group-containing monomer (m4).
- the content ratio of the total amount of the monomer (m4) is preferably 60% by weight to 99.9% by weight, more preferably 70% by weight to 99.8% by weight, still more preferably 80% by weight to 99.8% by weight. 7% by weight, particularly preferably 90% to 99.6% by weight, most preferably 95% to 99.5% by weight.
- the monomer component (M) is other monomers other than the monomer (m5) having a polar group other than the hydroxyl group, the alkyl (meth)acrylate, and the hydroxyl group-containing monomer (m4), as long as the effect of the present invention is not impaired.
- may contain Other monomers can be used, for example, for the purpose of adjusting the glass transition temperature (Tg) of the acrylic polymer (P), adjusting the adhesion performance, and the like. Only one kind of other monomer may be used, or two or more kinds thereof may be used.
- the content of other monomers in the monomer component (M) is preferably 20% by weight or less, more preferably 10% by weight or less, still more preferably 5% by weight or less, and particularly preferably 3% by weight or less. and most preferably 1% by weight or less.
- acrylic polymer (P) As a method for obtaining the acrylic polymer (P), various polymerization methods known as methods for synthesizing acrylic polymers, such as solution polymerization method, emulsion polymerization method, bulk polymerization method, suspension polymerization method, etc., are appropriately used. can be adopted. Among these polymerization methods, the solution polymerization method can be preferably used. As a method of supplying the monomer during solution polymerization, a batch charging method, a continuous supply (dropping) method, a divided supply (dropping) method, or the like, in which the entire amount of the monomer component is supplied at once, can be appropriately adopted.
- a batch charging method As a method of supplying the monomer during solution polymerization, a batch charging method, a continuous supply (dropping) method, a divided supply (dropping) method, or the like, in which the entire amount of the monomer component is supplied at once, can be appropriately adopted.
- the polymerization temperature can be appropriately selected depending on the type of monomer and solvent used, the type of polymerization initiator, etc., and is preferably 20°C or higher, more preferably 30°C or higher, and even more preferably 40°C. above, preferably 170° C. or lower, more preferably 160° C. or lower, and even more preferably 140° C. or lower.
- Methods for obtaining acrylic polymers include photopolymerization by irradiating with light such as UV (typically carried out in the presence of a photopolymerization initiator), and irradiation with radiation such as ⁇ rays and ⁇ rays. Active energy ray irradiation polymerization such as radiation polymerization carried out using a method may also be employed.
- the solvent (polymerization solvent) used for solution polymerization can be appropriately selected from any suitable organic solvent.
- suitable organic solvent examples include aromatic compounds such as toluene (typically aromatic hydrocarbons), acetic esters such as ethyl acetate, and aliphatic or alicyclic hydrocarbons such as hexane and cyclohexane.
- the initiator (polymerization initiator) used for polymerization can be appropriately selected from any suitable polymerization initiator depending on the type of polymerization method. Only one polymerization initiator may be used, or two or more polymerization initiators may be used.
- polymerization initiators examples include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis(2-methylpropionic acid) dimethyl, 4,4'-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis[2-(5-methyl- 2-imidazolin-2-yl)propane]dihydrochloride, 2,2′-azobis(2-methylpropionamidine) disulfate, 2,2′-azobis(N,N′-dimethyleneisobutyramidine), 2, 2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] hydrate (VA-057, manufactured by Wako Pure Chemical Industries, Ltd.) and other azo initiators; potassium persulfate, ammonium persulfate and other peroxides Sul
- the amount of the polymerization initiator used is preferably 0.005 to 1 part by weight, more preferably 0.01 to 1 part by weight, relative to 100 parts by weight of the monomer component (M).
- Any other suitable additive may be included in the polymerization as long as it does not impair the effects of the present invention.
- Acrylic pressure-sensitive adhesive compositions according to embodiments of the present invention preferably contain oligomers. Only one type of oligomer may be used, or two or more types may be used. By including an oligomer in the acrylic pressure-sensitive adhesive composition according to the embodiment of the present invention, the effects of the present invention can be exhibited more.
- the weight average molecular weight Mw of the oligomer is preferably 1,000 to 30,000, more preferably 1,500 to 10,000, even more preferably 2,000 to 8,000, and particularly preferably 2,000 to 5,000.
- Acrylic oligomers are preferable as oligomers because they are easily compatible with acrylic polymers.
- the glass transition temperature Tg of the acrylic oligomer is preferably 20°C or higher, more preferably 40°C or higher, still more preferably 60°C or higher, particularly preferably 80°C or higher, and most preferably 100°C. That's it.
- the upper limit of the glass transition temperature Tg of the acrylic oligomer is preferably 200° C. or lower, more preferably 180° C. or lower, and still more preferably 160° C. or lower.
- the glass transition temperature Tg of the acrylic oligomer is obtained from the Fox formula based on the Tg of the homopolymer of each constituent monomer (homopolymer) and the weight fraction (copolymerization ratio based on weight) of the monomer. It means the desired value.
- Tg is the glass transition temperature of the copolymer (unit: K)
- Wi is the weight fraction of the monomer i in the copolymer (weight-based copolymerization ratio)
- Tgi is the homopolymer of the monomer i. represents the glass transition temperature (unit: K).
- Tg of the homopolymer the values described in known materials can be adopted, for example, the values described in "Polymer Handbook” (3rd edition, John Wiley & Sons, Inc., 1989) can be used. . If multiple numerical values are listed in the above "Polymer Handbook", the conventional value is adopted. For monomers not listed in the above “Polymer Handbook", the catalog values of the monomer manufacturing companies are used.
- Acrylic oligomers contain alicyclic alkyl (meth)acrylates as the main constituent monomer components. Only one kind of alicyclic alkyl (meth)acrylate may be used, or two or more kinds thereof may be used.
- alicyclic alkyl (meth)acrylates include cycloalkyl (meth)acrylates such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, cyclooctyl (meth)acrylate; ) acrylates and other bicyclic aliphatic hydrocarbon ring-containing (meth)acrylic acid esters; dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth) (Meth) acrylic having a tricyclic or higher aliphatic hydrocarbon ring such as acrylate, 1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate acid esters.
- cycloalkyl (meth)acrylates such as cycl
- alicyclic alkyl (meth)acrylate dicyclopentanyl acrylate, dicyclopentanyl methacrylate, cyclohexyl acrylate, and cyclohexyl methacrylate are preferable in that the effects of the present invention can be further expressed.
- the content of the alicyclic alkyl (meth)acrylate with respect to the total amount of the constituent monomer components of the acrylic oligomer is preferably 10% by weight to 99% by weight, more preferably 30% by weight, from the viewpoint that the effects of the present invention can be further expressed. % to 98% by weight, more preferably 40% to 97% by weight, particularly preferably 50% to 96% by weight.
- the acrylic oligomer may contain a chain alkyl (meth)acrylate having a chain alkyl group as a constituent monomer component, and the chain alkyl (meth)acrylate having a chain alkyl group is only one. may be used, or two or more may be used.
- chain as used herein means a straight-chain or branched chain.
- the chain alkyl (meth)acrylate is preferably a chain alkyl (meth)acrylate having a chain alkyl group having 1 to 20 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (Meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate , heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodec
- methyl methacrylate is preferable in that the effects of the present invention can be exhibited more effectively.
- the content of the chain alkyl (meth)acrylate with respect to the total amount of the constituent monomer components of the acrylic oligomer is preferably 10% by weight to 90% by weight, more preferably 20% by weight, in order to further express the effects of the present invention. % to 80% by weight, more preferably 30% to 70% by weight.
- the acrylic oligomer may contain (meth)acrylic acid as a constituent monomer component, and the number of (meth)acrylic acids may be one, or two or more.
- acrylic acid is preferable in that the effects of the present invention can be expressed more.
- the content of (meth)acrylic acid with respect to the total amount of the constituent monomer components of the acrylic oligomer is preferably 0.1% by weight to 20% by weight, more preferably 1% by weight, from the viewpoint that the effects of the present invention can be further expressed. % to 10% by weight, more preferably 3% to 7% by weight.
- Oligomers are obtained by polymerizing constituent monomer components by various polymerization methods. Any appropriate additive may be used in the polymerization of the oligomer as long as the effects of the present invention are not impaired. Examples of such additives include polymerization initiators and chain transfer agents.
- the content ratio of the oligomer in the acrylic pressure-sensitive adhesive composition is preferably 0.1 parts by weight to 6.5 parts by weight with respect to 100 parts by weight of the acrylic polymer (P) in order to further express the effects of the present invention.
- parts more preferably 0.5 to 5.5 parts by weight, still more preferably 1.0 to 4.5 parts by weight, still more preferably 1.0 to 4.0 parts by weight parts by weight, more preferably 1.0 to 3.5 parts by weight, particularly preferably 1.0 to 3.0 parts by weight, and most preferably 1.5 to 2.0 parts by weight. 5 parts by weight.
- the acrylic pressure-sensitive adhesive composition according to the embodiment of the invention may contain a cross-linking agent.
- the number of cross-linking agents may be one, or two or more.
- the cross-linking agent may be included in the acrylic pressure-sensitive adhesive in a form after cross-linking reaction, a form before cross-linking reaction, a form in which partial cross-linking reaction has occurred, an intermediate or composite form thereof, and the like.
- the cross-linking agent is typically contained in the acrylic pressure-sensitive adhesive in the form after the cross-linking reaction.
- the content ratio of the cross-linking agent in the acrylic pressure-sensitive adhesive composition is preferably 0.005 parts by weight to 10 parts by weight with respect to 100 parts by weight of the acrylic polymer (P) in order to further express the effects of the present invention.
- parts more preferably 0.01 to 7 parts by weight, still more preferably 0.01 to 5 parts by weight, still more preferably 0.01 to 1 part by weight, and further It is preferably 0.01 to 0.5 parts by weight, particularly preferably 0.01 to 0.35 parts by weight, most preferably 0.01 to 0.1 parts by weight.
- cross-linking agents examples include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, silicone-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, silane-based cross-linking agents, alkyl-etherified melamine-based cross-linking agents, and metal chelate-based cross-linking agents.
- Peroxides and other cross-linking agents preferably isocyanate-based cross-linking agents, epoxy-based cross-linking agents, or peroxides, more preferably isocyanate-based cross-linking agents, in that the effects of the present invention can be more expressed. agent, peroxide.
- isocyanate-based cross-linking agent a compound having two or more isocyanate groups (including an isocyanate-regenerating polar group temporarily protected by a blocking agent or by quantification of the isocyanate group) in one molecule can be used.
- isocyanate-based cross-linking agents include aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate; alicyclic isocyanates such as isophorone diisocyanate; and aliphatic isocyanates such as hexamethylene diisocyanate.
- isocyanate-based crosslinking agents include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate; and 2,4-tolylene diisocyanate.
- 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, aromatic diisocyanates such as polymethylene polyphenyl isocyanate; trimethylolpropane/tolylene diisocyanate trimer adduct (for example, manufactured by Tosoh Corporation, trade name Coronate L), Trimethylolpropane/hexamethylene diisocyanate trimer adduct (for example, manufactured by Tosoh Corporation, trade name: Coronate HL), isocyanurate of hexamethylene diisocyanate (for example, manufactured by Tosoh Corporation, trade name: Coronate HX), etc.
- trimethylolpropane/tolylene diisocyanate trimer adduct for example, manufactured by Tosoh Corporation, trade name Coronate L
- Trimethylolpropane/hexamethylene diisocyanate trimer adduct for example, manufactured by Tosoh Corporation, trade name: Coronat
- trimethylolpropane adduct of xylylene diisocyanate e.g., Mitsui Chemicals, trade name: Takenate D110N
- xylylene diisocyanate trimethylolpropane adduct e.g., Mitsui Chemicals, trade name: Takenate D120N
- Trimethylolpropane adduct of isophorone diisocyanate e.g., Mitsui Chemicals, trade name: Takenate D140N
- hexamethylene diisocyanate trimethylolpropane adduct e.g., Mitsui Chemicals, trade name: Takenate D160N
- polyisocyanates polyfunctionalized with isocyanurate bonds, biuret bonds, allophanate bonds, and the like.
- the aromatic isocyanate and the like
- epoxy-based cross-linking agent a polyfunctional epoxy compound having two or more epoxy groups in one molecule can be used.
- epoxy-based cross-linking agents include N,N,N',N'-tetraglycidyl-m-xylenediamine, diglycidylaniline, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, penta erythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyg
- peroxides examples include dibenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butyl hydroperoxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxine)hexyne-3, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 2,5 -dimethyl-2,5-mono(t-butylperoxy)-hexane, ⁇ , ⁇ '-bis(t-butylperoxy-m-isopropyl)benzene, di(2-ethylhexyl)peroxydicarbonate, di( 4-t-butyl cyclohexyl)peroxydicarbonate, di-sec-butyl peroxydicarbonate, t-butyl per
- the acrylic pressure-sensitive adhesive composition according to the embodiment of the present invention may contain a tackifier resin in order to adjust adhesive properties and bending properties. Only one kind of tackifying resin may be used, or two or more kinds thereof may be used.
- tackifying resins include rosin-based tackifying resins, terpene-based tackifying resins, hydrocarbon-based tackifying resins, epoxy-based tackifying resins, polyamide-based tackifying resins, elastomer-based tackifying resins, and phenol-based tackifying resins. , and ketone-based tackifying resins.
- the amount of the tackifying resin used is preferably 5 parts by weight to 70 parts by weight, more preferably 10 parts by weight, with respect to 100 parts by weight of the acrylic polymer (P), in order to further express the effects of the present invention.
- the tackifying resin preferably contains a tackifying resin TL having a softening point of less than 105°C, in order to achieve the effects of the present invention.
- the tackifying resin TL can effectively contribute to improving the deformability of the pressure-sensitive adhesive layer in the plane direction (shearing direction).
- the softening point of the tackifier resin used as the tackifier resin TL is preferably 50° C. to 103° C., more preferably 60° C. to 100° C., and still more preferably 65°C to 95°C, particularly preferably 70°C to 90°C, most preferably 75°C to 85°C.
- the softening point of the tackifying resin is defined as a value measured based on the softening point test method (ring and ball method) specified in JIS K5902 and JIS K2207. Specifically, the sample is melted as quickly as possible at the lowest possible temperature and carefully filled into a ring placed on a flat metal plate to avoid the formation of bubbles. After it cools down, cut off the raised part from the plane including the top of the ring with a slightly heated knife. Next, a supporter (ring base) is placed in a glass container (heating bath) having a diameter of 85 mm or more and a height of 127 mm or more, and glycerin is poured to a depth of 90 mm or more.
- the steel ball (diameter 9.5 mm, weight 3.5 g) and the ring filled with the sample are immersed in the glycerin without touching each other, and the temperature of the glycerin is kept at 20° C. ⁇ 5° C. for 15 minutes. .
- a steel ball is then centered on the surface of the sample in the ring and placed in position on the support.
- the distance from the upper end of the ring to the glycerin surface is kept at 50 mm, a thermometer is placed, the center of the mercury ball of the thermometer is set at the same height as the center of the ring, and the container is heated.
- the Bunsen burner flame used for heating is directed halfway between the center and the rim of the bottom of the vessel to ensure even heating.
- the rate at which the bath temperature rises after reaching 40° C. from the start of heating must be 5.0 ⁇ 0.5° C. per minute.
- the temperature at which the sample gradually softens and flows down the ring until it finally touches the bottom plate is read and taken as the softening point. Two or more softening points are measured at the same time, and the average value is adopted.
- the amount of the tackifier resin TL to be used is preferably 5 parts by weight to 50 parts by weight, more preferably 5 parts by weight to 50 parts by weight, with respect to 100 parts by weight of the acrylic polymer (P), from the point of view that the effects of the present invention can be further expressed. 10 to 45 parts by weight, more preferably 15 to 40 parts by weight, particularly preferably 20 to 35 parts by weight, most preferably 25 to 32 parts by weight.
- tackifier resin TL one or more selected from among the tackifier resins exemplified above having a softening point of less than 105°C may be employed.
- the tackifying resin TL preferably contains a rosin-based resin.
- Rosin-based resins that can be preferably employed as the tackifying resin TL include, for example, rosin esters such as unmodified rosin esters and modified rosin esters.
- Modified rosin esters include, for example, hydrogenated rosin esters.
- the tackifying resin TL preferably contains a hydrogenated rosin ester in that it can further express the effects of the present invention.
- the hydrogenated rosin ester preferably has a softening point of less than 105°C, more preferably 50°C to 100°C, and even more preferably 60°C to 90°C, in order to further exhibit the effects of the present invention. , particularly preferably 70°C to 85°C, most preferably 75°C to 85°C.
- the tackifying resin TL may contain a non-hydrogenated rosin ester.
- the non-hydrogenated rosin ester is a concept that comprehensively refers to those other than the hydrogenated rosin ester among the rosin esters described above.
- Non-hydrogenated rosin esters include unmodified rosin esters, disproportionated rosin esters and polymerized rosin esters.
- the non-hydrogenated rosin ester preferably has a softening point of less than 105° C., more preferably 50° C. to 100° C., and even more preferably 60° C. to 90° C., from the viewpoint that the effect of the present invention can be exhibited more effectively.
- °C particularly preferably 70°C to 85°C, most preferably 75°C to 85°C.
- the tackifier resin TL may contain other tackifier resins in addition to the rosin-based resin.
- the other tackifying resin one or more selected from those having a softening point of less than 105° C. among the tackifying resins exemplified above can be employed.
- the tackifying resin TL may contain, for example, a rosin-based resin and a terpene resin.
- the content of the rosin-based resin in the entire tackifying resin TL is preferably more than 50% by weight, more preferably 55% to 100% by weight, and even more preferably, from the viewpoint that the effects of the present invention can be further expressed. is 60% to 99% by weight, particularly preferably 65% to 97% by weight, most preferably 75% to 97% by weight.
- the tackifying resin may contain a combination of a tackifying resin TL and a tackifying resin TH having a softening point of 105° C. or higher (preferably 105° C. to 170° C.) in order to further express the effects of the present invention. good.
- the tackifying resin TH may contain at least one selected from rosin-based tackifying resins (eg, rosin esters) and terpene-based tackifying resins (eg, terpene phenolic resins).
- rosin-based tackifying resins eg, rosin esters
- terpene-based tackifying resins eg, terpene phenolic resins
- the acrylic pressure-sensitive adhesive composition according to the embodiment of the present invention may optionally contain a leveling agent, a cross-linking aid, a plasticizer, a softening agent, a filler, an antistatic agent, an antioxidant, an ultraviolet absorber, and an antioxidant. , a light stabilizer, a cross-linking catalyst, a cross-linking retarder, and the like, which are commonly used in the field of pressure-sensitive adhesives. As for such various additives, conventionally known ones can be used in a conventional manner.
- cross-linking catalysts include Nasem ferric iron, tetra-n-butyl titanate, tetraisopropyl titanate, butyltin oxide, dioctyltin dilaurate, and the like.
- crosslinking retarders include compounds that cause keto-enol tautomerism, and specific examples include ⁇ -diketones such as acetylacetone and 2,4-hexanedione; methyl acetoacetate and ethyl acetoacetate.
- propionyl acetate esters such as ethyl propionyl acetate
- isobutyryl acetate esters such as ethyl isobutyryl acetate
- malonic esters such as methyl malonate and ethyl malonate
- a pressure-sensitive adhesive film according to an embodiment of the invention has a pressure-sensitive adhesive layer composed of an acrylic pressure-sensitive adhesive sheet according to an embodiment of the invention.
- the adhesive film according to the embodiment of the present invention may be a substrate-less film consisting only of an adhesive layer, or may be a substrate-attached film having a substrate layer and an adhesive layer.
- the pressure-sensitive adhesive film of the present invention may have any appropriate other layer in addition to the substrate layer and the pressure-sensitive adhesive layer as long as the effects of the present invention are not impaired.
- the base material layer may be one layer, or may be two or more layers.
- the substrate layer is preferably a single layer in that the effect of the present invention can be exhibited more effectively.
- the adhesive layer may be one layer, or two or more layers.
- the pressure-sensitive adhesive layer is preferably a single layer in that the effects of the present invention can be exhibited more effectively.
- the pressure-sensitive adhesive film according to the embodiment of the present invention may be provided with any appropriate release liner on the surface of the pressure-sensitive adhesive layer opposite to the base layer for protection before use.
- the release liner includes, for example, a release liner in which the surface of a base material (liner base material) such as paper or plastic film is treated with silicone, or a base material (liner base material) such as paper or plastic film whose surface is coated with a polyolefin resin.
- a base material such as paper or plastic film
- a base material such as paper or plastic film whose surface is coated with a polyolefin resin.
- Examples include laminated release liners.
- plastic films as liner substrates include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, Polyurethane films, ethylene-vinyl acetate copolymer films and the like are included.
- the thickness of the release liner is preferably 1 ⁇ m to 500 ⁇ m, more preferably 3 ⁇ m to 450 ⁇ m, still more preferably 5 ⁇ m to 400 ⁇ m, particularly preferably 10 ⁇ m to 300 ⁇ m.
- the thickness of the adhesive film according to the embodiment of the present invention is preferably 1 ⁇ m to 500 ⁇ m, more preferably 5 ⁇ m to 200 ⁇ m, even more preferably 10 ⁇ m to 150 ⁇ m, particularly preferably 20 ⁇ m to 100 ⁇ m, most preferably 30 ⁇ m to 80 ⁇ m. If the thickness of the adhesive film according to the embodiment of the present invention is within the above range, the effects of the present invention can be exhibited more effectively.
- the adhesive film according to the embodiment of the present invention preferably has a total light transmittance of 20% or more, more preferably 30% or more, still more preferably 40% or more, and particularly preferably 50% or more. , most preferably 60% or more. If the total light transmittance of the pressure-sensitive adhesive film of the present invention is within the above range, excellent transparency can be exhibited.
- the adhesive film according to the embodiment of the present invention preferably has a haze of 15% or less, more preferably 13% or less, still more preferably 10% or less, particularly preferably 8% or less, and most preferably is 6% or less. If the haze of the pressure-sensitive adhesive film of the present invention is within the above range, more excellent transparency can be exhibited.
- the adhesive film according to the embodiment of the present invention can achieve both excellent adhesiveness and excellent elasticity, it can be preferably employed in flexible devices such as foldable devices and rollable devices.
- the thickness of the substrate layer is preferably 1 ⁇ m to 500 ⁇ m, more preferably 5 ⁇ m to 300 ⁇ m, still more preferably 10 ⁇ m to 100 ⁇ m, particularly preferably 15 ⁇ m to 80 ⁇ m, most preferably 20 ⁇ m to 60 ⁇ m. . If the thickness of the base material layer is within the above range, the effects of the present invention can be exhibited more effectively.
- the base layer preferably has a Young's modulus at 23° C. of 6.0 ⁇ 10 7 Pa or more, more preferably 1.0 ⁇ 10 8 Pa or more, and still more preferably 5.0 ⁇ 10 8 Pa or more. , particularly preferably 8.0 ⁇ 10 8 Pa or more, and most preferably 1.0 ⁇ 10 9 Pa or more.
- the upper limit of Young's modulus of the substrate layer at 23° C. is typically preferably 1.0 ⁇ 10 11 Pa or less. If the Young's modulus of the base material layer at 23° C. is within the above range, the effects of the present invention can be exhibited more effectively. If the Young's modulus of the base layer at 23° C.
- the pressure-sensitive adhesive film is bent at an angle, the tension on the outer diameter side may not be sufficiently maintained against the compression on the inner diameter side, and the thickness will change. It becomes easier, and there is a possibility that lifting from the adherend may easily occur. If the Young's modulus of the substrate layer at 23° C. is too high, the adhesive film may not be easily deformable. A method for measuring Young's modulus will be described in detail later.
- any appropriate material can be adopted as the material of the base material layer as long as it does not impair the effects of the present invention.
- a typical example of the material for such a base material layer is a resin material.
- resin materials for the substrate layer include polyimide (PI), polyetheretherketone (PEEK), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), and polymethyl methacrylate.
- PI polyimide
- PEEK polyetheretherketone
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- PBT polybutylene terephthalate
- polymethyl methacrylate examples include polymethyl methacrylate.
- PMMA polycarbonate, triacetyl cellulose (TAC), polysulfone, polyarylate, polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA) , polyamide (nylon), wholly aromatic polyamide (aramid), polyvinyl chloride (PVC), polyvinyl acetate, polyphenylene sulfide (PPS), fluorine resin, and cyclic olefin polymer.
- the thickness of the adhesive layer can refer to the thickness of the acrylic adhesive sheet according to the embodiment of the present invention. Therefore, the thickness of the adhesive layer is preferably 25 ⁇ m or less, more preferably 23 ⁇ m or less, still more preferably 20 ⁇ m or less, still more preferably 18 ⁇ m or less, particularly preferably 15 ⁇ m or less, and most preferably. is 13 ⁇ m or less.
- the thinner the thickness, the better, but in consideration of the balance with other adhesive properties, in reality, the lower limit of the thickness is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, It is more preferably 5 ⁇ m or more, particularly preferably 7 ⁇ m or more, and most preferably 9 ⁇ m or more.
- the adhesive layer is one form of an acrylic adhesive sheet.
- any appropriate forming method can be adopted as long as the effects of the present invention are not impaired.
- an acrylic pressure-sensitive adhesive composition is applied onto any appropriate substrate, heated and dried as necessary, cured as necessary, and coated on the substrate.
- a method of forming an acrylic pressure-sensitive adhesive layer in Any appropriate means can be adopted as such means for coating as long as the effects of the present invention are not impaired.
- coating means examples include a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, an air knife coater, a spray coater, a comma coater, a direct coater, and a roll brush coater. mentioned.
- Any appropriate means can be employed for heating and drying the acrylic pressure-sensitive adhesive composition as long as the effects of the present invention are not impaired.
- heating/drying means for example, heating to about 60° C. to 180° C. can be mentioned.
- Any appropriate means can be employed for curing the acrylic pressure-sensitive adhesive composition as long as the effects of the present invention are not impaired.
- curing means examples include ultraviolet irradiation, laser beam irradiation, ⁇ -ray irradiation, ⁇ -ray irradiation, ⁇ -ray irradiation, X-ray irradiation, and electron beam irradiation.
- the pressure-sensitive adhesive film of the present invention can achieve both excellent adhesiveness and excellent elasticity, it can be used as a bendable device (a device that can be bent), a foldable device (a device that can be folded), or a rollable device that has a movable bending portion. Flexible devices such as devices (rollable devices) can be conveniently provided.
- the flexible device according to the embodiment of the present invention includes the adhesive film according to the embodiment of the present invention.
- a flexible device of the present invention comprises an adhesive film according to embodiments of the present invention.
- a foldable device of the present invention may include any suitable other member as long as it comprises an adhesive film according to embodiments of the present invention.
- FIG. 1 is a schematic cross-sectional view showing one embodiment of the flexible device of the present invention as a representative example of one usage pattern of the adhesive film according to the embodiment of the present invention.
- a foldable device 1000 according to an embodiment of the present invention includes a cover film 10, an adhesive layer 20, a polarizing plate 30, an adhesive layer 40, a touch sensor 50, an adhesive layer 60, an OLED 70, and an embodiment of the present invention.
- the pressure-sensitive adhesive film 100 is provided by The adhesive film 100 according to the embodiment of the present invention is composed of an adhesive layer 80 and a substrate layer 90 in FIG.
- the adhesive layer 20, the adhesive layer 40, and the adhesive layer 60 may be adhesive layers containing an adhesive having the same composition as the adhesive layer 80 constituting the adhesive film 100 according to the embodiment of the present invention, or may be different. It may be a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive of the composition.
- R 1 is a methyl group and R 2 is a hydrogen atom.
- R 2 is a hydrogen atom.
- Glass transition temperature of its homopolymer (homopolymer) Tg about 80°C)
- V#216 2-butyl carbamoyloxyethyl acrylate (Viscoat #216, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
- R 3 is —CH 2 CH 2 — and R 4 is n-butyl group, and R 5 is a hydrogen atom.
- MMA methyl methacrylate
- HEA hydroxyethyl acrylate
- AIBN 2,2'-azobisisobutyronitrile
- Irgacure 184 photopolymerization initiator (manufactured by BASF)
- Irgacure 651 photopolymerization initiator (manufactured by BASF)
- DCPMA Dicyclopolymerization initiator (manufactured by BASF)
- a 25 ⁇ m-thick polyimide base material (trade name “Upilex 25RN”, manufactured by Ube Industries, Ltd.) is pasted together, and an adhesive film with a polyimide base material is attached. was made. Cut the adhesive film with a polyimide base material into width 25 mm ⁇ length 100 mm, peel off the separator (JT-50Wa) to expose the adhesive, and apply 2 kg to the polyimide film (trade name "Upilex 50S", manufactured by Ube Industries). A sample for evaluation was obtained by adhering with one reciprocation of the roller.
- the obtained evaluation sample was stored at room temperature for 30 minutes, and then measured with a tensile tester.
- a tensile tester As the tensile tester, a trade name "Autograph AG-Xplus HS 6000 mm/min high speed model (AG-50NX plus)" manufactured by Shimadzu Corporation was used. After setting the evaluation sample in the tensile tester, the tensile test was started. The conditions of the tensile test were a peeling angle of 180 degrees and a peeling speed (pulling speed) of 300 mm/min. The load when the adhesive film was peeled off from the polyimide film (Upilex 50S) was measured, and the average load at that time was defined as the adhesive strength.
- the storage elastic modulus G' corresponds to the portion stored as elastic energy when the material is deformed, and is an index representing the degree of hardness. Only the adhesive layer was taken out from the adhesive film, laminated to a thickness of about 1 mm, and punched out into a ⁇ 9 mm cylindrical pellet to prepare a sample for measurement. Using a dynamic viscoelasticity measuring device (manufactured by Rheometrics Co., Ltd., ARES), the obtained measurement sample was fixed to a ⁇ 8 mm parallel plate jig, and the storage elastic modulus G′ was calculated. The measurement conditions are as follows. Measurement: Shear mode Temperature range: -60°C to 210°C Heating rate: 5°C/min Frequency: 1Hz
- ⁇ Weight average molecular weight Mw> A weight average molecular weight was measured by a gel permeation chromatography (GPC) method. Specifically, "Agilent 1260 Infinity" (manufactured by Agilent Technologies) was used as a GPC measurement device, and a tetrahydrofuran solution containing 0.1% by weight of an amine-based component was prepared in consideration of the polymer concentration of the sample. After allowing to stand and filtering through a 0.45 ⁇ m membrane filter, the filtrate was subjected to GPC measurement. It was measured under the following conditions and calculated from standard polystyrene conversion values.
- GPC gel permeation chromatography
- Example concentration 0.1% by weight (tetrahydrofuran solution with amine component added)
- sample injection volume 100 ⁇ L
- Eluent tetrahydrofuran with amine-based component
- Flow rate 0.5 mL/min
- Detector Differential refractometer (RI)
- Column temperature (measurement temperature): 40°C ⁇ Standard sample: polystyrene (PS)
- Acrylic polymer (1) 100 parts by weight, C/HX as a cross-linking agent: 0.09 parts by weight, Acrylic oligomer (A): 2 parts by weight, Irganox 1010 as an antioxidant: 0.3 parts by weight, catalyst As Nasem ferric: 0.01 parts by weight, mixed well and diluted with ethyl acetate to give a total solids content of 21% by weight and acetylacetone to give a solvent content of 2% by weight. , to obtain a coating solution of the acrylic pressure-sensitive adhesive composition (1).
- a release sheet (product name: JT-50Wa, manufactured by Nitto Denko Co., Ltd.) made of a polyester resin having a thickness of 50 ⁇ m and having one surface subjected to silicone treatment is applied to the obtained coating solution of the acrylic pressure-sensitive adhesive composition (1). It was applied to the treated surface so that the thickness after drying was 13 ⁇ m, and dried under the conditions of a drying temperature of 130° C. and a drying time of 1 minute.
- the silicone-treated surface of a release sheet product name: MRQ50T100J, manufactured by Mitsubishi Chemical Co., Ltd.
- MRQ50T100J manufactured by Mitsubishi Chemical Co., Ltd.
- Examples 2 to 9 Except for changing the raw material composition and various conditions as shown in Table 2, the same procedure as in Example 1 was performed, and the coating solutions of the acrylic adhesive compositions (2) to (9) and the adhesive films (2) to (9) were prepared. got This was aged at 50° C. for 3 days and various evaluations were made. Table 3 shows the results.
- the acrylic pressure-sensitive adhesive sheet and the like according to the embodiment of the present invention can be used for so-called flexible devices such as foldable devices and rollable devices.
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Abstract
Description
23℃における、剥離速度300mm/分、剥離角度180度での、ポリイミドフィルムに対する粘着力が5.5N/25mm以上であり、ガラスに対する粘着力が5.5N/25mm以上であり、
-20℃における貯蔵弾性率G’が200kPa以下であり、
厚みが25μm以下である。
本発明の実施形態によるアクリル系粘着剤シートを形成するアクリル系粘着剤組成物であって、
アクリル系ポリマー(P)とオリゴマーを含む。
本発明の実施形態によるアクリル系粘着剤シートは、シート状のアクリル系粘着剤である。したがって、アクリル系粘着剤シートとして独立して扱うことができるものであってもよいし、アクリル系粘着剤層のように構成部材の1つとして認識されるものであってもよい。
本発明の実施形態によるアクリル系粘着剤組成物は、本発明の実施形態によるアクリル系粘着剤シートを形成するアクリル系粘着剤組成物である。
本発明の実施形態によるアクリル系粘着剤組成物は、好ましくは、アクリル系ポリマー(P)を含む。アクリル系ポリマー(P)は、1種のみであってもよいし、2種以上であってもよい。本発明の実施形態によるアクリル系粘着剤組成物がアクリル系ポリマー(P)を含むことにより、本発明の効果がより発現し得る。
CH2=C(R1)COOR2 (1)
2-エチルヘキシルアクリレート(2EHA):-70℃
ラウリルアクリレート(LA): -23℃
n-ブチルアクリレート(BA): -55℃
2-ヒドロキシエチルアクリレート: -15℃
4-ヒドロキシブチルアクリレート: -40℃
本発明の実施形態によるアクリル系粘着剤組成物は、好ましくは、オリゴマーを含む。オリゴマーは、1種のみであってもよいし、2種以上であってもよい。本発明の実施形態によるアクリル系粘着剤組成物がオリゴマーを含むことにより、本発明の効果がより発現し得る。
1/Tg=Σ(Wi/Tgi)
本発明の実施形態によるアクリル系粘着剤組成物は架橋剤を含んでいてもよい。架橋剤は、1種のみであってもよいし、2種以上であってもよい。
本発明の実施形態によるアクリル系粘着剤組成物は、粘着特性や屈曲特性を調整する等のために、粘着付与樹脂を含んでいてもよい。粘着付与樹脂は、1種のみであってもよいし、2種以上であってもよい。
本発明の実施形態によるアクリル系粘着剤組成物は、必要に応じて、レベリング剤、架橋助剤、可塑剤、軟化剤、充填剤、帯電防止剤、老化防止剤、紫外線吸収剤、酸化防止剤、光安定剤、架橋触媒、架橋遅延剤等の、粘着剤の分野において一般的な各種の添加剤を含有してもよい。このような各種添加剤については、従来公知のものを常法により使用することができる。
本発明の実施形態による粘着フィルムは、本発明の実施形態によるアクリル系粘着剤シートから構成される粘着剤層を有する。
基材層の厚みは、好ましくは1μm~500μmであり、より好ましくは5μm~300μmであり、さらに好ましくは10μm~100μmであり、特に好ましくは15μm~80μmであり、最も好ましくは20μm~60μmである。基材層の厚みが上記範囲内にあれば、本発明の効果がより発現し得る。
粘着剤層の厚みは、本発明の実施形態によるアクリル系粘着剤シートの厚みを援用し得る。したがって、粘着剤層の厚みは、好ましくは25μm以下であり、より好ましくは23μm以下であり、さらに好ましくは20μm以下であり、さらに好ましくは18μm以下であり、特に好ましくは15μm以下であり、最も好ましくは13μm以下である。上記厚みは薄ければ薄いほど良いが、他の粘着剤特性とのバランス等を勘案すると、現実的には、上記厚みの下限は、好ましくは1μm以上であり、より好ましくは3μm以上であり、さらに好ましくは5μm以上であり、特に好ましくは7μm以上であり、最も好ましくは9μm以上である。
本発明の粘着フィルムは、優れた粘着性と優れた弾性を両立できるので、可動屈曲部を有するベンダブルデバイス(曲げることが可能なデバイス)やフォルダブルデバイス(折りたたむことが可能なデバイス)やローラブルデバイス(丸めることが可能なデバイス)などのフレキシブルデバイスに好適に備えられ得る。
2EHA:アクリル酸2-エチルヘキシル(その単独重合体(ホモポリマー)のガラス転移温度Tg=-70℃)
LA:アクリル酸ラウリル(その単独重合体(ホモポリマー)のガラス転移温度Tg=-23℃)
BA:アクリル酸n-ブチル(その単独重合体(ホモポリマー)のガラス転移温度Tg=-55℃)
4HBA:アクリル酸4-ヒドロキシブチル(その単独重合体(ホモポリマー)のガラス転移温度Tg=-32℃)
NVP:N-ビニル-2-ピロリドン(その単独重合体(ホモポリマー)のガラス転移温度Tg=約80℃)
AOMA(登録商標):日本触媒社製の環化重合性モノマー(一般式(1)において、R1がメチル基、R2が水素原子。)(その単独重合体(ホモポリマー)のガラス転移温度Tg=約80℃)
V#216:アクリル酸-2-ブチルカルバモイルオキシエチルエステル(ビスコート#216、大阪有機化学工業社製)(一般式(2)において、R3が-CH2CH2-、R4がn-ブチル基、R5が水素原子。)(その単独重合体(ホモポリマー)のガラス転移温度Tg=0℃)
MMA:メタクリル酸メチル
HEA:アクリル酸ヒドロキシエチル
AIBN:2,2’-アゾビスイソブチロニトリル
イルガキュア184:光重合開始剤(BASF社製)
イルガキュア651:光重合開始剤(BASF社製)
DCPMA:メタクリル酸ジシクロペンタニル
CHMA:メタクリル酸シクロヘキシル
AA:アクリル酸
C/HX:コロネートHX(東ソー社製、イソシアネート系架橋剤)
D110N:タケネートD110N(三井化学社製、イソシアネート系架橋剤)
HDDA:1,6-ヘキサンジオールジアクリレート
BPO:過酸化物(ナイパーBMT-40SV、日本油脂社製)
ナーセム第二鉄:鉄触媒(日本化学産業社製)
イルガノックス1010:酸化防止剤(BASF社製)
KBM403:シランカップリング剤(信越化学工業社製)
粘着フィルムのセパレーターのうち、剥離力の小さいセパレーター(MRQ50T100J)を剥がしたのち、厚さ25μmのポリイミド基材(商品名「ユーピレックス25RN」、宇部興産社製)を貼り合わせ、ポリイミド基材付き粘着フィルムを作製した。ポリイミド基材付き粘着フィルムを幅25mm×長さ100mmにカットし、セパレーター(JT-50Wa)を剥がして粘着剤を露出させ、ポリイミドフィルム(商品名「ユーピレックス50S」、宇部興産社製)へ2kgハンドローラー1往復にて貼着し、評価用試料を得た。
得られた評価用試料を、室温で30分間保管後、引っ張り試験機にて測定した。引っ張り試験機としては、島津製作所社製の商品名「オートグラフAG-Xplus HS 6000mm/min高速モデル(AG-50NX plus)」を用いた。引っ張り試験機に評価用試料をセットした後、引っ張り試験を開始した。引っ張り試験の条件は、剥離角度:180度、剥離速度(引っ張り速度):300mm/分とした。上記ポリイミドフィルム(ユーピレックス50S)から粘着フィルムを剥離した時の荷重を測定し、その際の平均荷重を粘着力とした。
ポリイミド基材付き粘着フィルムを幅25mm×長さ100mmにカットし、セパレーター(JT-50Wa)を剥がして粘着剤を露出させ、ポリイミドフィルム(商品名「ユーピレックス50S」、宇部興産社製)へ2kgハンドローラー1往復にて貼着する代わりに、ポリイミド基材付き粘着フィルムを幅25mm×長さ100mmにカットし、セパレーター(JT-50Wa)を剥がして粘着剤を露出させ、ガラス(品名:S2004U8、松浪硝子工業社製)の非スズ面へ2kgハンドローラー1往復にて貼着した以外は、上記の<ポリイミドフィルムに対する粘着力>の測定方法と同様に行った。
貯蔵弾性率G’は、材料が変形する際に弾性エネルギーとして貯蔵される部分に相当し、硬さの程度を表す指標である。
粘着フィルムからから粘着剤層のみを取り出し、積層して約1mmの厚みとし、これをφ9mmに打ち抜き、円柱状のペレットを作製して測定用サンプルとした。
動的粘弾性測定装置(レオメトリックス社製、ARES)を用い、得られた測定サンプルをφ8mmパラレルプレートの治具に固定し、貯蔵弾性率G’を算出した。測定条件は下記の通りである。
測定:せん断モード
温度範囲:-60℃~210℃
昇温速度:5℃/分
周波数:1Hz
重量平均分子量は、ゲルパーミエーションクロマトグラフ(GPC)法により測定した。具体的には、GPC測定装置として「Agilent 1260 Infinity」(アジレントテクノロジー社製)を用い、試料のポリマー濃度を考慮し、0.1重量%のアミン系成分添加テトラヒドロフラン溶液に調製して、20時間放置し、0.45μmメンブランフィルターにてろ過後、ろ液についてGPC測定を行った。
下記の条件にて測定し、標準ポリスチレン換算値により算出した。
(分子量測定条件)
・サンプル濃度:0.1重量%(アミン系成分添加テトラヒドロフラン溶液)
・サンプル注入量:100μL
・カラム:商品名「TSKgel GMH-H(S)」(東ソー社製)
・溶離液:アミン系成分添加テトラヒドロフラン
・流速:0.5mL/min
・検出器:示差屈折計(RI)
・カラム温度(測定温度):40℃
・標準試料:ポリスチレン(PS)
攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた四つ口フラスコに、2EHA:68.0重量部、LA:19.4重量部、BA:7.8重量部、4HBA:3.9重量部、AOMA(登録商標):1.0重量部、重合開始剤としてAIBN:0.1重量部を入れ、これらの合計の濃度が42重量%となるように酢酸エチルを仕込み、緩やかに攪拌しながら1時間かけて系内を窒素置換し、フラスコ内の液温を58℃付近に保って5時間重合反応を行い、反応終了後、酢酸エチルを加えて、ポリマー濃度が32重量%となるように調整し、アクリル系ポリマー(1)の溶液を得た。結果を表1に示した。
モノマー成分、各種条件を表1に記載の通りに変更した以外は、製造例1と同様に行い、アクリル系ポリマー(2)~(6)、(8)の溶液を得た。結果を表1に示した。
BA:99.0重量部と4HBA:1.0重量部をモノマー成分として得られるアクリル系樹脂(綜研化学社製、商品名「SK2137」)をアクリル系ポリマー(7)とした。結果を表1に示した。
モノマー成分としてDCPMA:60重量部およびMMA:40重量部、連鎖移動剤としてα-チオグリセロール:3.5重量部、および、重合溶媒としてトルエン100重量部を混合し、窒素雰囲気下にて70℃で1時間撹拌した。次に、熱重合開始剤としてAIBN:0.2重量部を投入し、70℃で2時間反応させた後、80℃に昇温して2時間反応させ、アクリル系オリゴマー(A)を得た。アクリル系オリゴマー(A)の重量平均分子量Mwは5100、ガラス転移温度(Tg)は130℃であった。
モノマー成分としてCHMA:95重量部およびAA:5重量部、連鎖移動剤としてα-メチルスチレンダイマー(日本油脂社製、商品名「ノフマ-MSD」):10重量部、熱重合開始剤としてAIBN:10重量部、これらの原料濃度が50重量%となるようにトルエンを混合し、窒素雰囲気下にて85℃で2時間反応させた。次に、86℃に昇温して1.5時間反応させ、アクリル系オリゴマー(B)を得た。アクリル系オリゴマー(B)の重量平均分子量は4000、ガラス転移温度(Tg)は67℃であった。
アクリル系ポリマー(1):100重量部、架橋剤としてC/HX:0.09重量部、アクリル系オリゴマー(A):2重量部、酸化防止剤としてイルガノックス1010:0.3重量部、触媒としてナーセム第二鉄:0.01重量部を混合し、十分に撹拌して、全体の固形分が21重量%となるように酢酸エチルおよび溶剤分の2重量%となるアセチルアセトンで希釈することにより、アクリル系粘着剤組成物(1)の塗布溶液を得た。得られたアクリル系粘着剤組成物(1)の塗布溶液を、一方の面にシリコーン処理を施した厚さ50μmのポリエステル樹脂からなる剥離シート(品名:JT-50Wa、日東電工社製)のシリコーン処理面に、乾燥後の厚みが13μmとなるよう塗布し、乾燥温度130℃、乾燥時間1分の条件で乾燥した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ50μmのポリエステル樹脂からなる剥離シート(品名:MRQ50T100J、三菱ケミカル社製)のシリコーン処理面が接触するように貼合せて、粘着フィルム(1)を得た。これを50℃で3日間エージングを行い、各種評価を行った。結果を表3に示した。
原料組成、各種条件を表2のように変更した以外は、実施例1と同様に行い、アクリル系粘着剤組成物(2)~(9)の塗布溶液、粘着フィルム(2)~(9)を得た。これを50℃で3日間エージングを行い、各種評価を行った。結果を表3に示した。
原料組成、各種条件を表2のように変更した以外は、実施例1と同様に行い、アクリル系粘着剤組成物(C1)~(C5)の塗布溶液、粘着フィルム(C1)~(C5)を得た。これを50℃で3日間エージングを行い、各種評価を行った。結果を表3に示した。
100 粘着フィルム
10 カバーフィルム
20 粘着剤層
30 偏光板
40 粘着剤層
50 タッチセンサー
60 粘着剤層
70 OLED
80 粘着剤層
90 基材層
Claims (14)
- 23℃における、剥離速度300mm/分、剥離角度180度での、ポリイミドフィルムに対する粘着力が5.5N/25mm以上であり、ガラスに対する粘着力が5.5N/25mm以上であり、
-20℃における貯蔵弾性率G’が200kPa以下であり、
厚みが25μm以下である、
アクリル系粘着剤シート。 - 請求項1に記載のアクリル系粘着剤シートを形成するアクリル系粘着剤組成物であって、
アクリル系ポリマー(P)とオリゴマーを含む、
アクリル系粘着剤組成物。 - 前記アクリル系ポリマー(P)は、モノマー成分(M)を重合して得られ、該モノマー成分(M)は、水酸基以外の極性基を有するモノマー(m5)を含む、請求項2に記載のアクリル系粘着剤組成物。
- 前記モノマー成分(M)中の前記水酸基以外の極性基を有するモノマー(m5)の含有割合が、0.1重量%~5.0重量%である、請求項3に記載のアクリル系粘着剤組成物。
- 前記アクリル系粘着剤組成物中の前記オリゴマーの含有割合が、前記アクリル系ポリマー(P)100重量部に対して、0.1重量部~6.5重量部である、請求項2から5までのいずれかに記載のアクリル系粘着剤組成物。
- 前記オリゴマーの重量平均分子量Mwが1000~30000である、請求項2から6までのいずれかに記載のアクリル系粘着剤組成物。
- 前記モノマー成分(M)がアルキル(メタ)アクリレートを含む、請求項3から7までのいずれかに記載のアクリル系粘着剤組成物。
- 前記アルキル(メタ)アクリレートの単独重合体のガラス転移温度Tgが-10℃以下である、請求項8に記載のアクリル系粘着剤組成物。
- 前記モノマー成分(M)中の前記アルキル(メタ)アクリレートの含有割合が50重量%~99重量%である、請求項8または9に記載のアクリル系粘着剤組成物。
- 前記モノマー成分(M)が水酸基含有モノマー(m4)を含む、請求項3から10までのいずれかに記載のアクリル系粘着剤組成物。
- 前記モノマー成分(M)中の前記水酸基含有モノマー(m4)の含有割合が0.01重量%~30重量%である、請求項11に記載のアクリル系粘着剤組成物。
- 請求項1に記載のアクリル系粘着剤シートから構成される粘着剤層を有する、粘着フィルム。
- 請求項13に記載の粘着フィルムを備えるフレキシブルデバイス。
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Citations (6)
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JP2018168305A (ja) * | 2017-03-30 | 2018-11-01 | リンテック株式会社 | 粘着シート、積層体、及びデバイス |
JP2020122140A (ja) * | 2019-01-30 | 2020-08-13 | 日東電工株式会社 | 粘着シート、粘着層付き光学フィルム、積層体、および画像表示装置 |
JP2020139035A (ja) * | 2019-02-27 | 2020-09-03 | リンテック株式会社 | 粘着シート、繰り返し屈曲積層部材および繰り返し屈曲デバイス |
JP2020139037A (ja) * | 2019-02-27 | 2020-09-03 | リンテック株式会社 | 繰り返し屈曲デバイス用粘着剤、粘着シート、繰り返し屈曲積層部材および繰り返し屈曲デバイス |
JP2020535245A (ja) * | 2017-12-11 | 2020-12-03 | エルジー・ケム・リミテッド | フォルダブルディスプレイ用粘着剤組成物およびこれを含むフォルダブルディスプレイ |
JP2021175806A (ja) * | 2020-04-28 | 2021-11-04 | 三菱ケミカル株式会社 | 粘着剤組成物、粘着剤および粘着シート |
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JPS593469Y2 (ja) | 1979-06-15 | 1984-01-31 | 株式会社山武 | シリンダ−形近接スイツチのシ−ル装置 |
JPH0214764Y2 (ja) | 1986-10-31 | 1990-04-20 |
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2021
- 2021-12-10 CN CN202180092058.1A patent/CN116802244A/zh active Pending
- 2021-12-10 JP JP2022578119A patent/JPWO2022163166A1/ja active Pending
- 2021-12-10 WO PCT/JP2021/045483 patent/WO2022163166A1/ja active Application Filing
- 2021-12-10 KR KR1020237028642A patent/KR20230137959A/ko unknown
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Patent Citations (6)
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JP2018168305A (ja) * | 2017-03-30 | 2018-11-01 | リンテック株式会社 | 粘着シート、積層体、及びデバイス |
JP2020535245A (ja) * | 2017-12-11 | 2020-12-03 | エルジー・ケム・リミテッド | フォルダブルディスプレイ用粘着剤組成物およびこれを含むフォルダブルディスプレイ |
JP2020122140A (ja) * | 2019-01-30 | 2020-08-13 | 日東電工株式会社 | 粘着シート、粘着層付き光学フィルム、積層体、および画像表示装置 |
JP2020139035A (ja) * | 2019-02-27 | 2020-09-03 | リンテック株式会社 | 粘着シート、繰り返し屈曲積層部材および繰り返し屈曲デバイス |
JP2020139037A (ja) * | 2019-02-27 | 2020-09-03 | リンテック株式会社 | 繰り返し屈曲デバイス用粘着剤、粘着シート、繰り返し屈曲積層部材および繰り返し屈曲デバイス |
JP2021175806A (ja) * | 2020-04-28 | 2021-11-04 | 三菱ケミカル株式会社 | 粘着剤組成物、粘着剤および粘着シート |
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CN116802244A (zh) | 2023-09-22 |
KR20230137959A (ko) | 2023-10-05 |
TW202239928A (zh) | 2022-10-16 |
JPWO2022163166A1 (ja) | 2022-08-04 |
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