JP2016037533A - Adhesive composition and adhesive film - Google Patents
Adhesive composition and adhesive film Download PDFInfo
- Publication number
- JP2016037533A JP2016037533A JP2014160622A JP2014160622A JP2016037533A JP 2016037533 A JP2016037533 A JP 2016037533A JP 2014160622 A JP2014160622 A JP 2014160622A JP 2014160622 A JP2014160622 A JP 2014160622A JP 2016037533 A JP2016037533 A JP 2016037533A
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- meth
- sensitive adhesive
- adhesive layer
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 239000002313 adhesive film Substances 0.000 title claims abstract description 38
- 239000000853 adhesive Substances 0.000 title claims abstract description 36
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 106
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 99
- 239000012790 adhesive layer Substances 0.000 claims abstract description 44
- -1 isocyanate compound Chemical class 0.000 claims abstract description 38
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 31
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 30
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 23
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 20
- 125000003118 aryl group Chemical group 0.000 claims abstract description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012948 isocyanate Substances 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 229920001577 copolymer Polymers 0.000 claims abstract description 8
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 110
- 239000010410 layer Substances 0.000 claims description 66
- 239000010408 film Substances 0.000 claims description 54
- 239000012788 optical film Substances 0.000 claims description 28
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 13
- 238000004132 cross linking Methods 0.000 claims description 11
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 9
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 4
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 239000010409 thin film Substances 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 description 15
- 230000003287 optical effect Effects 0.000 description 15
- 239000012298 atmosphere Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 125000000524 functional group Chemical group 0.000 description 10
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002347 octyl 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])[H] 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- MBNRBJNIYVXSQV-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propane-1-thiol Chemical compound CCO[Si](C)(OCC)CCCS MBNRBJNIYVXSQV-UHFFFAOYSA-N 0.000 description 1
- UDWIZRDPCQAYRF-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C=C UDWIZRDPCQAYRF-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- MCDBEBOBROAQSH-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C=C MCDBEBOBROAQSH-UHFFFAOYSA-N 0.000 description 1
- DGBFOBNYTYHFPN-UHFFFAOYSA-N 3-[ethoxy(dimethyl)silyl]propyl prop-2-enoate Chemical compound CCO[Si](C)(C)CCCOC(=O)C=C DGBFOBNYTYHFPN-UHFFFAOYSA-N 0.000 description 1
- ZCRUJAKCJLCJCP-UHFFFAOYSA-N 3-[methoxy(dimethyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(C)CCCOC(=O)C=C ZCRUJAKCJLCJCP-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- JSCDRVVVGGYHSN-UHFFFAOYSA-N 8-hydroxyoctyl prop-2-enoate Chemical compound OCCCCCCCCOC(=O)C=C JSCDRVVVGGYHSN-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 241001070941 Castanea Species 0.000 description 1
- 235000014036 Castanea Nutrition 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 125000004122 cyclic group Chemical group 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 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 1
- ASGKDLGXPOIMTM-UHFFFAOYSA-N diethoxy-methyl-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](C)(OCC)OCC)CCC2OC21 ASGKDLGXPOIMTM-UHFFFAOYSA-N 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- SLQTWNAJXFHMHM-UHFFFAOYSA-N dimethoxy-methyl-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](C)(OC)OC)CCC2OC21 SLQTWNAJXFHMHM-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 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 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- DTPZJXALAREFEY-UHFFFAOYSA-N n-methyl-3-triethoxysilylpropan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCNC DTPZJXALAREFEY-UHFFFAOYSA-N 0.000 description 1
- DVYVMJLSUSGYMH-UHFFFAOYSA-N n-methyl-3-trimethoxysilylpropan-1-amine Chemical compound CNCCC[Si](OC)(OC)OC DVYVMJLSUSGYMH-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001400 nonyl 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])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- LTOKKZDSYQQAHL-UHFFFAOYSA-N trimethoxy-[4-(oxiran-2-yl)butyl]silane Chemical compound CO[Si](OC)(OC)CCCCC1CO1 LTOKKZDSYQQAHL-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl 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])[H] 0.000 description 1
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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- 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
Abstract
Description
本発明は、偏光板などの光学部材の貼り合わせに用いられる粘着剤組成物及び粘着フィルムに関する。 The present invention relates to a pressure-sensitive adhesive composition and a pressure-sensitive adhesive film used for bonding optical members such as polarizing plates.
粘着剤層を介して偏光板、位相差板などの光学部材を液晶セルなどの被着体に貼合するため、種々の粘着フィルムが提案されている（例えば特許文献１〜２参照）。
特許文献１には、ブチルアクリレートなどを主成分のモノマーとし、アクリルアミド化合物などを含有する光学用粘着剤組成物が記載されている。
特許文献２には、炭素数４〜８のアルキル基を有する（メタ）アクリレートを主成分のモノマーとし、カルボキシル基含有モノマー、及び窒素含有ビニルモノマーを含有する光学用粘着剤組成物が記載されている。
また、粘着剤層の屈折率を高めるために、種々の工夫をした粘着フィルムが提案されている（例えば特許文献３〜８参照）。
特許文献３には、芳香族環を有し、屈折率１．５１〜１．７５のタッキファイヤーを含有する光学用粘着剤組成物が記載されている。
特許文献４には、芳香族環を含有するアクリル酸変性モノマーの共重合性ポリマーを含む粘着剤組成物を含有する粘着シートが記載されている。
特許文献５には、芳香族環を有する粘着付与樹脂と、芳香族リン酸エステル系可塑剤を含有する光学用粘着剤組成物が記載されている。
特許文献６には、アクリル系樹脂と、エチレン性不飽和基を１つ含有する芳香族化合物を含有する粘着剤組成物が硬化されてなる粘着剤が記載されている。
特許文献７には、芳香族モノマーを含有するアクリル系の粘着剤を介して、位相差フィルム及び複屈折板を互いに固着してなる光学部品が記載されている。
特許文献８には、芳香族ジイソシアネートと、芳香族ポリエステルジオールを反応させてなるウレタン樹脂を含む粘着剤組成物が記載されている。
Various adhesive films have been proposed for bonding optical members such as a polarizing plate and a retardation plate to an adherend such as a liquid crystal cell via an adhesive layer (see, for example, Patent Documents 1 and 2).
Patent Document 1 describes an optical pressure-sensitive adhesive composition containing acrylamide compound or the like, using butyl acrylate or the like as a main monomer.
Patent Document 2 describes an optical pressure-sensitive adhesive composition containing a (meth) acrylate having a C 4-8 alkyl group as a main component monomer, a carboxyl group-containing monomer, and a nitrogen-containing vinyl monomer. Yes.
Moreover, in order to raise the refractive index of an adhesive layer, the adhesive film which carried out various devices is proposed (for example, refer patent documents 3-8).
Patent Document 3 describes an optical pressure-sensitive adhesive composition having an aromatic ring and containing a tackifier having a refractive index of 1.51 to 1.75.
Patent Document 4 describes a pressure-sensitive adhesive sheet containing a pressure-sensitive adhesive composition containing a copolymerizable polymer of an acrylic acid-modified monomer containing an aromatic ring.
Patent Document 5 describes an optical pressure-sensitive adhesive composition containing a tackifier resin having an aromatic ring and an aromatic phosphate ester plasticizer.
Patent Document 6 describes a pressure-sensitive adhesive obtained by curing a pressure-sensitive adhesive composition containing an acrylic resin and an aromatic compound containing one ethylenically unsaturated group.
Patent Document 7 describes an optical component in which a retardation film and a birefringent plate are fixed to each other via an acrylic pressure-sensitive adhesive containing an aromatic monomer.
Patent Document 8 describes a pressure-sensitive adhesive composition containing a urethane resin obtained by reacting an aromatic diisocyanate and an aromatic polyester diol.
近年において、光学部材の層間を貼合するのに用いる粘着フィルムに対して要求されている事項は、光学部材の薄膜化を図るために、粘着剤層の厚さを薄くした粘着フィルムとすることである。
一般に、粘着剤層の粘着力は、粘着剤層の厚さに略比例していることから、粘着剤層の厚さを薄くすると、それに伴って粘着力が低下してしまう。
In recent years, what is required for the adhesive film used for laminating the layers of the optical member is to make the adhesive film with a thinner adhesive layer in order to reduce the thickness of the optical member. It is.
In general, since the adhesive strength of the pressure-sensitive adhesive layer is substantially proportional to the thickness of the pressure-sensitive adhesive layer, when the thickness of the pressure-sensitive adhesive layer is reduced, the adhesive strength is reduced accordingly.
しかし、近年求められている粘着フィルムは、粘着剤層の厚さを薄くしても、従来の粘着フィルム（粘着剤層の厚さが約３０μｍと厚い）と同等の粘着力を有しており、且つ、高温・高湿度の雰囲気下に長時間放置した後の耐久性についても、従来の粘着フィルムと同等以上の性能を有することが求められている。
また、粘着剤層の厚さを薄くできること、及び、エージング処理（恒温で養生を行うこと）を施す必要がない粘着剤層を形成できることから、粘着フィルムの基材を省いた粘着剤層のみからなる、「離型フィルム／粘着剤層／離型フィルム」の部材構成をした、ＮＣＦ（Ｎｏｎ Ｃａｒｒｉｅｒ Ｆｉｌｍ）の形態とすることが求められている。
However, the pressure-sensitive adhesive film required in recent years has the same adhesive strength as the conventional pressure-sensitive adhesive film (thickness of the pressure-sensitive adhesive layer is about 30 μm) even if the thickness of the pressure-sensitive adhesive layer is reduced. In addition, the durability after being left for a long time in an atmosphere of high temperature and high humidity is also required to have performance equal to or higher than that of a conventional adhesive film.
In addition, since the thickness of the pressure-sensitive adhesive layer can be reduced and a pressure-sensitive adhesive layer that does not need to be subjected to aging treatment (curing at constant temperature) can be formed, only from the pressure-sensitive adhesive layer without the base material of the pressure-sensitive adhesive film Therefore, it is required to be in the form of NCF (Non Carrier Film) having a member configuration of “release film / adhesive layer / release film”.
また、従来の粘着フィルムでは、被着体に粘着フィルムを貼り合せた後に、エージング処理が施されるために、被着体と粘着剤層との密着性の向上を図ることができた。
しかしながら、ＮＣＦの形態をした粘着フィルムは、すでに粘着剤層のエージングを終了させていることから、被着体と粘着剤層との密着力が不足する。そのため、被着体の表面に対して、コロナ処理などの表面処理をする必要があるという問題があった。
これらの要求事項および問題を克服した粘着フィルムが、必要とされている。
Moreover, in the conventional adhesive film, since an aging process is performed after bonding an adhesive film to an adherend, the adhesiveness of an adherend and an adhesive layer was able to be improved.
However, since the adhesive film in the form of NCF has already finished the aging of the adhesive layer, the adhesion between the adherend and the adhesive layer is insufficient. Therefore, there has been a problem that the surface of the adherend needs to be subjected to a surface treatment such as a corona treatment.
There is a need for an adhesive film that overcomes these requirements and problems.
本発明は、上記事情に鑑みてなされたものであり、薄膜にも拘わらず、優れたリワーク性と高い密着性の性能を有する粘着剤層を形成することが可能な粘着剤組成物及びそれを用いた粘着フィルムを提供することを課題とする。 The present invention has been made in view of the above circumstances, and a pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive layer having excellent reworkability and high adhesion performance in spite of a thin film, and It aims at providing the used adhesive film.
上記の課題を解決するため、本発明に係わる粘着剤組成物は、ブチルアクリレートを必須モノマーとし、官能基含有モノマーとしてはカルボキシル基含有共重合性ビニルモノマーを用いず、水酸基含有共重合性ビニルモノマーを用いた、重量平均分子量１００万以上の共重合体に対して、架橋剤としてイソシアネート化合物を用いること、さらに好ましくは、シランカップリング剤を併用することを特徴とする。 In order to solve the above-mentioned problems, the pressure-sensitive adhesive composition according to the present invention uses butyl acrylate as an essential monomer, and does not use a carboxyl group-containing copolymerizable vinyl monomer as a functional group-containing monomer. An isocyanate compound is used as a crosslinking agent for a copolymer having a weight average molecular weight of 1,000,000 or more, and more preferably a silane coupling agent is used in combination.
また、上記の課題を解決するため、本発明は、（１）主成分の（メタ）アクリレートモノマーとして、アルキル基の炭素数がＣ１〜Ｃ１４のアルキル（メタ）アクリレートモノマー及び芳香族基を有する（メタ）アクリレートモノマーからなるモノマー群の中から選択された少なくとも１種以上を含有し、前記主成分の（メタ）アクリレートモノマーの合計１００重量部の内、ブチルアクリレートを少なくとも３０重量部以上と、カルボキシル基含有共重合性ビニルモノマーを含まず、前記主成分の（メタ）アクリレートモノマーの合計１００重量部に対して、（２）水酸基含有共重合性ビニルモノマーを０．１〜３．５重量部と、を含有し、酸価が０．１以下で、重量平均分子量が１００万以上の共重合体であるアクリル系ポリマーと、前記主成分の（メタ）アクリレートモノマーの合計１００重量部に対して、（３）架橋剤としてイソシアネート化合物を０．０１〜０．８重量部と、を含有してなる粘着剤組成物を提供する。 Moreover, in order to solve said subject, this invention has the alkyl (meth) acrylate monomer and C1-C14 alkyl (meth) acrylate monomer and aromatic group as (1) main component (meth) acrylate monomer ( It contains at least one selected from the group of monomers consisting of (meth) acrylate monomers, and contains at least 30 parts by weight of butyl acrylate in a total of 100 parts by weight of the main component (meth) acrylate monomers, carboxyl 0.1 to 3.5 parts by weight of (2) hydroxyl group-containing copolymerizable vinyl monomer with respect to a total of 100 parts by weight of the main component (meth) acrylate monomer, excluding the group-containing copolymerizable vinyl monomer. An acrylic polymer which is a copolymer having an acid value of 0.1 or less and a weight average molecular weight of 1 million or more, 100 parts by weight of the total of the main component of the (meth) acrylate monomer, provides (3) comprising and a 0.01 to 0.8 parts by weight of an isocyanate compound as a crosslinking agent pressure-sensitive adhesive composition.
さらに、前記主成分の（メタ）アクリレートモノマーの合計１００重量部に対して、（４）シランカップリング剤を０．０１〜０．５重量部含有することが好ましい。 Furthermore, it is preferable to contain 0.01-0.5 weight part of (4) silane coupling agents with respect to a total of 100 weight part of the (meth) acrylate monomer of the said main component.
また、前記イソシアネート化合物が、トリレンジイソシアネートのトリメチロールプロパンアダクト体であることが好ましい。 The isocyanate compound is preferably a trimethylolpropane adduct of tolylene diisocyanate.
また、前記（２）水酸基含有共重合性ビニルモノマーが、８−ヒドロキシオクチル（メタ）アクリレート、６−ヒドロキシヘキシル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、からなる化合物群の中から選択された少なくとも一種以上であることが好ましい。 The (2) hydroxyl group-containing copolymerizable vinyl monomer is selected from the group consisting of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. Preferably, at least one selected from the group of compounds consisting of
また、本発明は、前記粘着剤組成物を架橋させた粘着剤層であり、架橋後のゲル分率が４０〜７５％であり、厚さ２５μｍの粘着剤層の粘着力が１．５〜６．０Ｎ／２５ｍｍであることを特徴とする粘着剤層を提供する。 Moreover, this invention is the adhesive layer which bridge | crosslinked the said adhesive composition, the gel fraction after bridge | crosslinking is 40 to 75%, and the adhesive force of the 25-micrometer-thick adhesive layer is 1.5- The pressure-sensitive adhesive layer is characterized by being 6.0 N / 25 mm.
また、前記粘着剤層を被着体に貼り合わせ後、７０℃×１０日後の粘着力が１．５〜１０Ｎ／２５ｍｍであることが好ましい。 Moreover, after bonding the said adhesive layer to a to-be-adhered body, it is preferable that the adhesive force after 70 degreeC x 10 days is 1.5-10N / 25mm.
また、本発明は、基材の片面上に、前記粘着剤層が積層されたことを特徴とする粘着フィルムを提供する。 Moreover, this invention provides the adhesive film characterized by the said adhesive layer being laminated | stacked on the single side | surface of a base material.
また、本発明は、前記粘着フィルムが用いられた、偏光板とディスプレイパネルとの貼り合せに用いられる粘着フィルムを提供する。 Moreover, this invention provides the adhesive film used for bonding of a polarizing plate and a display panel using the said adhesive film.
また、本発明は、粘着剤層付き偏光板の粘着剤層として用いられた前記粘着剤層を提供する。 Moreover, this invention provides the said adhesive layer used as an adhesive layer of a polarizing plate with an adhesive layer.
また、本発明は、偏光板の構成材料として、λ／４又はλ／２の位相差を持つ位相差フィルムが用いられた粘着剤層付き偏光板の粘着剤層として用いられた前記粘着剤層を提供する。 Further, the present invention provides the pressure-sensitive adhesive layer used as a pressure-sensitive adhesive layer of a polarizing plate with a pressure-sensitive adhesive layer in which a retardation film having a phase difference of λ / 4 or λ / 2 is used as a constituent material of the polarizing plate. I will provide a.
また、本発明は、光学フィルムの少なくとも一方の面に、前記粘着剤層が積層されている粘着剤層付き光学フィルムを提供する。 Moreover, this invention provides the optical film with an adhesive layer by which the said adhesive layer is laminated | stacked on the at least one surface of the optical film.
本発明によれば、従来の粘着剤層よりも、架橋剤量および官能基量を減らしつつ、架橋後のゲル分率の高い粘着剤層になることが特徴であり、柔軟性、堅剛性、耐久性、及びリワーク性を兼ね備えた粘着剤層、及びそれを用いた粘着フィルムが得られる。
本発明の粘着フィルムは、薄膜にも関わらず、優れたリワーク性と高い密着性の性能を有する。
According to the present invention, it is characterized in that the pressure-sensitive adhesive layer has a high gel fraction after crosslinking while reducing the amount of the crosslinking agent and the amount of functional groups as compared with the conventional pressure-sensitive adhesive layer. A pressure-sensitive adhesive layer having durability and reworkability, and a pressure-sensitive adhesive film using the same are obtained.
The adhesive film of the present invention has excellent reworkability and high adhesion performance in spite of a thin film.
以下、好適な実施の形態に基づいて本発明を説明する。
本発明の粘着剤組成物は、（１）主成分の（メタ）アクリレートモノマーとして、アルキル基の炭素数がＣ１〜Ｃ１４のアルキル（メタ）アクリレートモノマー及び芳香族基を有する（メタ）アクリレートモノマーからなるモノマー群の中から選択された少なくとも１種以上を含有し、前記主成分の（メタ）アクリレートモノマーの合計１００重量部の内、ブチルアクリレートを少なくとも３０重量部以上と、カルボキシル基含有共重合性ビニルモノマーを含まず、前記主成分の（メタ）アクリレートモノマーの合計１００重量部に対して、（２）水酸基含有共重合性ビニルモノマーを０．１〜３．５重量部と、を含有し、酸価が０．１以下で、重量平均分子量が１００万以上の共重合体であるアクリル系ポリマーと、前記主成分の（メタ）アクリレートモノマーの合計１００重量部に対して、（３）架橋剤としてイソシアネート化合物を０．０１〜０．８重量部と、を含有してなることを特徴とする。
Hereinafter, the present invention will be described based on preferred embodiments.
The pressure-sensitive adhesive composition of the present invention comprises (1) an alkyl (meth) acrylate monomer having a C1-C14 alkyl group and a (meth) acrylate monomer having an aromatic group as the main component (meth) acrylate monomer. At least one selected from the monomer group consisting of, and a total of 100 parts by weight of the main component (meth) acrylate monomer, at least 30 parts by weight of butyl acrylate, and carboxyl group-containing copolymerization (2) 0.1 to 3.5 parts by weight of a hydroxyl group-containing copolymerizable vinyl monomer with respect to a total of 100 parts by weight of the main component (meth) acrylate monomer, without vinyl monomers, An acrylic polymer which is a copolymer having an acid value of 0.1 or less and a weight average molecular weight of 1,000,000 or more, and (meth) of the main component 100 parts by weight of the total of chestnut rates monomer, characterized by containing a, and 0.01 to 0.8 parts by weight of an isocyanate compound (3) a crosslinking agent.
本発明に係わる粘着剤組成物において、アルキル基の炭素数がＣ１〜Ｃ１４のアルキル（メタ）アクリレートモノマーとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、デシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、トリデシル（メタ）アクリレート、テトラデシル（メタ）アクリレート、シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレートなどの少なくとも１種以上が挙げられる。アルキル（メタ）アクリレートモノマーのアルキル基は、直鎖、分枝状、環状のいずれでもよい。
主成分の（メタ）アクリレートモノマーの合計１００重量部の内、アルキル基の炭素数がＣ１〜Ｃ１４のアルキル（メタ）アクリレートモノマーの合計は、７０重量部以上が好ましく、１００重量部でもよい。アルキル基の炭素数がＣ１〜Ｃ１４のアルキル（メタ）アクリレートモノマーは、粘着剤組成物のアクリル系ポリマー（共重合体）１００重量部に対する割合が、５０〜９９．９重量部であることが好ましい。本発明では、ブチルアクリレートを必須のモノマーとする。主成分の（メタ）アクリレートモノマーの合計１００重量部の内、ブチルアクリレートを少なくとも３０重量部以上含むことが好ましい。
また、本発明においては、粘着剤組成物が、アルキル基の炭素数がＣ１〜Ｃ１４のアルキル（メタ）アクリレートモノマーの１種以上からなる主成分の（メタ）アクリレートモノマーの合計１００重量部の内、メチルアクリレートのモノマーを２０重量部以上の割合で含有することにより、粘着剤層の屈折率を、１．４７以上に高めることができる。
In the pressure-sensitive adhesive composition according to the present invention, the alkyl (meth) acrylate monomer having an alkyl group having C1 to C14 may be methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) ) Acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) ) Acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate DOO, tetradecyl (meth) acrylate, cyclopentyl (meth) acrylate, and at least one kind such as cyclohexyl (meth) acrylate. The alkyl group of the alkyl (meth) acrylate monomer may be linear, branched or cyclic.
Of the total 100 parts by weight of the main component (meth) acrylate monomer, the total of the alkyl (meth) acrylate monomers having C1-C14 alkyl groups is preferably 70 parts by weight or more, and may be 100 parts by weight. The alkyl (meth) acrylate monomer having an alkyl group with C1 to C14 preferably has a ratio of 50 to 99.9 parts by weight based on 100 parts by weight of the acrylic polymer (copolymer) in the pressure-sensitive adhesive composition. . In the present invention, butyl acrylate is an essential monomer. Of the total 100 parts by weight of the main component (meth) acrylate monomer, it is preferable to contain at least 30 parts by weight of butyl acrylate.
In the present invention, the pressure-sensitive adhesive composition contains 100 parts by weight or more of the main component (meth) acrylate monomer composed of one or more alkyl (meth) acrylate monomers having an alkyl group with C1 to C14 carbon atoms. By containing the methyl acrylate monomer in a proportion of 20 parts by weight or more, the refractive index of the pressure-sensitive adhesive layer can be increased to 1.47 or more.
本発明に係わる粘着剤組成物には、さらに、主成分の（メタ）アクリレートモノマーとして、芳香族基を有する（メタ）アクリレートモノマーの１種以上を含有させることができる。芳香族基を有する（メタ）アクリレートモノマーとしては、ベンジル（メタ）アクリレート、ナフチル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシブチル（メタ）アクリレート、２−（１−ナフチルオキシ）エチル（メタ）アクリレート、２−（２−ナフチルオキシ）エチル（メタ）アクリレート、６−（１−ナフチルオキシ）ヘキシル（メタ）アクリレート、６−（２−ナフチルオキシ）ヘキシル（メタ）アクリレート、８−（１−ナフチルオキシ）オクチル（メタ）アクリレート、８−（２−ナフチルオキシ）オクチル（メタ）アクリレートなどが挙げられる。屈折率が高い粘着剤層を得るためには、芳香族基を有する（メタ）アクリレートモノマーの少なくとも１種以上を配合することが好ましい。 The pressure-sensitive adhesive composition according to the present invention may further contain one or more (meth) acrylate monomers having an aromatic group as the main component (meth) acrylate monomer. Examples of the (meth) acrylate monomer having an aromatic group include benzyl (meth) acrylate, naphthyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxybutyl (meth) acrylate, 2- (1-naphthyloxy) ethyl (meth) ) Acrylate, 2- (2-naphthyloxy) ethyl (meth) acrylate, 6- (1-naphthyloxy) hexyl (meth) acrylate, 6- (2-naphthyloxy) hexyl (meth) acrylate, 8- (1- Naphtyloxy) octyl (meth) acrylate, 8- (2-naphthyloxy) octyl (meth) acrylate, and the like. In order to obtain a pressure-sensitive adhesive layer having a high refractive index, it is preferable to blend at least one (meth) acrylate monomer having an aromatic group.
これらの芳香族基を有する（メタ）アクリレートモノマーを、主成分のモノマーであるアルキル基の炭素数がＣ１〜Ｃ１４のアルキル（メタ）アクリレートモノマーと混合することにより、得られる粘着剤層の屈折率を上昇させて調整でき、光学部材間の屈折率差を少なくして、全反射を低減させることにより全光線透過率を向上させることができる。本発明に係わる粘着剤層において、粘着剤組成物に芳香族基を有する（メタ）アクリレートモノマーを含有させる場合は、主成分の（メタ）アクリレートモノマーの合計１００重量部の内、５〜３０重量部の割合で含有させるのが好ましい。
また、芳香族基を有する（メタ）アクリレートモノマーを共重合させることにより、上記の主成分の（メタ）アクリレートモノマーの合計１００重量部の内、メチルアクリレートのモノマーを２０重量部以上の割合で含有させて粘着剤層の屈折率を高める効果よりも、さらに粘着剤層の屈折率を高めることができる。
また、上記のとおり、粘着剤層の屈折率を高める方法として、主成分の（メタ）アクリレートモノマーの合計１００重量部の内、メチルアクリレートのモノマーを２０重量部以上の割合で含有させる方法と、芳香族基を有する（メタ）アクリレートモノマーを共重合させる方法との２つの方法があり、それぞれの方法を単独で採用できるが、その２つの方法を併用することがより好ましい。
The refractive index of the pressure-sensitive adhesive layer obtained by mixing these aromatic group-containing (meth) acrylate monomers with an alkyl (meth) acrylate monomer having a C1-C14 alkyl group as the main component monomer. The total light transmittance can be improved by decreasing the refractive index difference between the optical members and reducing the total reflection. In the pressure-sensitive adhesive layer according to the present invention, when the pressure-sensitive adhesive composition contains a (meth) acrylate monomer having an aromatic group, 5 to 30 weights in a total of 100 parts by weight of the main component (meth) acrylate monomer. It is preferable to make it contain in the ratio of a part.
Moreover, by copolymerizing the (meth) acrylate monomer having an aromatic group, the methyl acrylate monomer is contained in a proportion of 20 parts by weight or more in the total 100 parts by weight of the main component (meth) acrylate monomer. The refractive index of the pressure-sensitive adhesive layer can be further increased than the effect of increasing the refractive index of the pressure-sensitive adhesive layer.
As described above, as a method for increasing the refractive index of the pressure-sensitive adhesive layer, a method of containing a methyl acrylate monomer in a proportion of 20 parts by weight or more in a total of 100 parts by weight of the main component (meth) acrylate monomer, There are two methods, a method of copolymerizing a (meth) acrylate monomer having an aromatic group, and each method can be employed alone, but it is more preferable to use the two methods in combination.
本発明の粘着剤組成物において、アクリル系ポリマーは、官能基含有モノマーとしては、カルボキシル基含有共重合性ビニルモノマーを含まず、水酸基含有共重合性ビニルモノマーを含有する。官能基含有モノマーとして、水酸基含有共重合性ビニルモノマーのみを用いてもよい。 In the pressure-sensitive adhesive composition of the present invention, the acrylic polymer does not contain a carboxyl group-containing copolymerizable vinyl monomer as a functional group-containing monomer, but contains a hydroxyl group-containing copolymerizable vinyl monomer. Only the hydroxyl group-containing copolymerizable vinyl monomer may be used as the functional group-containing monomer.
水酸基含有共重合性ビニルモノマーとしては、例えば、８−ヒドロキシオクチル（メタ）アクリレート、６−ヒドロキシヘキシル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート等の水酸基含有アルキル（メタ）アクリレート類や、Ｎ−ヒドロキシ（メタ）アクリルアミド、Ｎ−ヒドロキシメチル（メタ）アクリルアミド、Ｎ−ヒドロキシエチル（メタ）アクリルアミド等の水酸基含有（メタ）アクリルアミド類などの少なくとも１種以上が挙げられる。
中でも、水酸基含有共重合性ビニルモノマーが、８−ヒドロキシオクチル（メタ）アクリレート、６−ヒドロキシヘキシル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、からなる化合物群の中から選択された少なくとも一種以上であることが好ましい。
また、本発明に係わる粘着剤層において、粘着剤組成物に含有させる水酸基含有共重合性ビニルモノマーは、得られる粘着剤層が透明導電性フィルムのＩＴＯ表面などの腐食し易い被着体に対する腐食性に影響を与えるとされる、カルボキシル基含有共重合性ビニルモノマーの含有量を減らすための共重合性モノマーとして使用できる。そのため、水酸基含有共重合性ビニルモノマーは、粘着剤層の粘着力を向上させ、且つ、腐食性を低減させることに役立てることができる。本発明に係わる粘着剤層において、粘着剤組成物に含有させる水酸基含有共重合性ビニルモノマーは、主成分の（メタ）アクリレートモノマーの合計１００重量部の内、０．１〜３．５重量部であることが好ましい。
Examples of the hydroxyl group-containing copolymerizable vinyl monomer include hydroxyl groups such as 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. At least one or more kinds of hydroxyl-containing (meth) acrylamides such as containing alkyl (meth) acrylates, N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and N-hydroxyethyl (meth) acrylamide Can be mentioned.
Among them, the compound in which the hydroxyl group-containing copolymerizable vinyl monomer is 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate It is preferably at least one selected from the group.
Moreover, in the pressure-sensitive adhesive layer according to the present invention, the hydroxyl group-containing copolymerizable vinyl monomer contained in the pressure-sensitive adhesive composition is used to corrode the adherend that is easily corroded such as the ITO surface of the transparent conductive film. It can be used as a copolymerizable monomer for reducing the content of a carboxyl group-containing copolymerizable vinyl monomer, which is said to affect the properties. Therefore, the hydroxyl group-containing copolymerizable vinyl monomer can be used for improving the adhesive strength of the pressure-sensitive adhesive layer and reducing the corrosivity. In the pressure-sensitive adhesive layer according to the present invention, the hydroxyl group-containing copolymerizable vinyl monomer to be contained in the pressure-sensitive adhesive composition is 0.1 to 3.5 parts by weight in a total of 100 parts by weight of the main component (meth) acrylate monomer. It is preferable that
本発明の粘着剤層に用いる粘着剤組成物のアクリル系ポリマーは、（１）主成分の（メタ）アクリレートモノマーとして、アルキル基の炭素数がＣ１〜Ｃ１４のアルキル（メタ）アクリレートモノマー及び芳香族基を有する（メタ）アクリレートモノマーからなるモノマー群の中から選択された少なくとも１種以上を含有し、前記主成分の（メタ）アクリレートモノマーの合計１００重量部の内、ブチルアクリレートを少なくとも３０重量部以上と、カルボキシル基含有共重合性ビニルモノマーを含まず、前記主成分の（メタ）アクリレートモノマーの合計１００重量部に対して、（２）水酸基含有共重合性ビニルモノマーを０．１〜３．５重量部と、を含有し、酸価が０．１以下で、重量平均分子量が１００万以上の共重合体である。 The acrylic polymer of the pressure-sensitive adhesive composition used for the pressure-sensitive adhesive layer of the present invention is (1) as a main component (meth) acrylate monomer, an alkyl (meth) acrylate monomer having a C1-C14 alkyl group and an aromatic group. Containing at least one selected from the group consisting of (meth) acrylate monomers having a group, and at least 30 parts by weight of butyl acrylate in a total of 100 parts by weight of the main component (meth) acrylate monomers In addition to the above, the carboxyl group-containing copolymerizable vinyl monomer is not included, and the total amount of (2) hydroxyl group-containing copolymerizable vinyl monomer is 0.1-3. 5 parts by weight, a copolymer having an acid value of 0.1 or less and a weight average molecular weight of 1,000,000 or more.
共重合体の重合方法は、特に限定されるものではなく、溶液重合法、乳化重合法等、適宜、公知の重合方法が使用可能である。前記アクリル系ポリマーは、（メタ）アクリレートモノマーや（メタ）アクリルアミド類などのアクリル系モノマーを５０〜１００重量％含むことが好ましい。 The polymerization method of the copolymer is not particularly limited, and a known polymerization method such as a solution polymerization method and an emulsion polymerization method can be used as appropriate. The acrylic polymer preferably contains 50 to 100% by weight of an acrylic monomer such as a (meth) acrylate monomer or (meth) acrylamide.
前記粘着剤組成物は、上記のアクリル系ポリマーに、架橋剤や、適宜任意の添加剤を配合することで、必要とされる物性値などの特性を調整することができる。
（３）架橋剤としては、例えば、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、ジフェニルメタンジイソシアネート、トリレンジイソシアネート、キシリレンジイソシアネート等のジイソシアネート類のビュレット変性体やイソシアヌレート変性体、トリメチロールプロパンや、グリセリン等の３価以上のポリオールとのアダクト体などのポリイソシアネート化合物の少なくとも１種以上が挙げられる。アクリル系ポリマーが、架橋剤のイソシアネート化合物と架橋反応可能な官能基として、水酸基を有することが好ましく、また、これらの官能基を側鎖に有するモノマーを含有することが好ましい。また、粘着剤組成物が、主成分の（メタ）アクリレートモノマーの合計１００重量部に対してイソシアネート化合物を０．０１〜０．８重量部を、含有することが好ましい。（３）架橋剤として、イソシアネート化合物のみを用いてもよい。イソシアネート化合物として、トリレンジイソシアネートのアダクト体が好ましく、特に、トリレンジイソシアネートのトリメチロールプロパンアダクト体が好ましい。
The pressure-sensitive adhesive composition can adjust properties such as required physical property values by blending the acrylic polymer with a crosslinking agent or an appropriate additive as appropriate.
(3) Examples of the crosslinking agent include burette-modified products, isocyanurate-modified products, trimethylolpropane, glycerin and the like of diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, and xylylene diisocyanate. Examples include at least one polyisocyanate compound such as an adduct with a polyol having a valence higher than that. The acrylic polymer preferably has a hydroxyl group as a functional group capable of undergoing a crosslinking reaction with the isocyanate compound of the crosslinking agent, and preferably contains a monomer having such a functional group in the side chain. Moreover, it is preferable that an adhesive composition contains 0.01-0.8 weight part of isocyanate compounds with respect to a total of 100 weight part of the (meth) acrylate monomer of a main component. (3) You may use only an isocyanate compound as a crosslinking agent. As the isocyanate compound, an adduct of tolylene diisocyanate is preferable, and a trimethylolpropane adduct of tolylene diisocyanate is particularly preferable.
前記粘着剤組成物は、さらに、（４）シランカップリング剤を含有することが好ましい。（４）シランカップリング剤としては、１分子中に、少なくとも１つの有機官能基と、少なくとも１つの加水分解性基を有し、前記加水分解性基が、ケイ素原子に結合したアルコキシ基等である化合物が挙げられる。前記シランカップリング剤が、エポキシ基、（メタ）アクリロキシ基、メルカプト基、アミノ基からなる群から選択された少なくとも一種類の、有機官能基を有することが好ましい。ここで、（メタ）アクリロキシ基とは、アクリロキシ基（ＣＨ２＝ＣＨＣＯＯ−）、又は、メタクリロキシ基（ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ−）を意味する。 The pressure-sensitive adhesive composition preferably further contains (4) a silane coupling agent. (4) As a silane coupling agent, it has at least one organic functional group and at least one hydrolyzable group in one molecule, and the hydrolyzable group is an alkoxy group bonded to a silicon atom, or the like. There are certain compounds. It is preferable that the silane coupling agent has at least one organic functional group selected from the group consisting of an epoxy group, a (meth) acryloxy group, a mercapto group, and an amino group. Here, the (meth) acryloxy group means an acryloxy group (CH 2 ═CHCOO—) or a methacryloxy group (CH 2 ═C (CH 3 ) COO—).
エポキシ基を有するシランカップリング剤としては、例えば、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、３−グリシドキシプロピルトリエトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルメチルジメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルメチルジエトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリエトキシシラン、５，６−エポキシヘキシルトリメトキシシラン、５，６−エポキシヘキシルメチルジメトキシシラン、５，６−エポキシヘキシルメチルジエトキシシラン、５，６−エポキシヘキシルトリエトキシシランなどが挙げられる。
（メタ）アクリロキシ基を有するシランカップリング剤としては、例えば、３−（メタ）アクリロキシプロピルトリメトキシシラン、３−（メタ）アクリロキシプロピルメチルジメトキシシラン、３−（メタ）アクリロキシプロピルトリエトキシシラン、３−（メタ）アクリロキシプロピルメチルジエトキシシラン、３−（メタ）アクリロキシプロピルジメチルエトキシシラン、３−（メタ）アクリロキシプロピルジメチルメトキシシランなどが挙げられる。
メルカプト基を有するシランカップリング剤としては、例えば、３−メルカプトプロピルメチルジメトキシシラン、３−メルカプトプロピルトリメトキシシラン、３−メルカプトプロピルメチルジエトキシシラン、３−メルカプトプロピルトリエトキシシランなどが挙げられる。
アミノ基を有するシランカップリング剤としては、例えば、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、Ｎ−フェニル−３−アミノプロピルトリメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルメチルジメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルメチルジエトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルトリメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルトリエトキシシラン、３−（メチルアミノ）プロピルトリメトキシシラン、３−（メチルアミノ）プロピルトリエトキシシランなどが挙げられる。
また、前記有機官能基を含み、オリゴマー化したアルコキシオリゴマー（シリコーンアルコキシオリゴマー）なども、シランカップリング剤として用いることができる。
Examples of the silane coupling agent having an epoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropyl. Triethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 5,6-epoxyhexyltrimethoxysilane, 5,6-epoxyhexylmethyldimethoxysilane, 5,6-epoxyhexylmethyldiethoxysilane, 5,6- Epoxy hex Such as triethoxy silane.
Examples of the silane coupling agent having a (meth) acryloxy group include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, and 3- (meth) acryloxypropyltriethoxy. Examples thereof include silane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyldimethylethoxysilane, and 3- (meth) acryloxypropyldimethylmethoxysilane.
Examples of the silane coupling agent having a mercapto group include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, and 3-mercaptopropyltriethoxysilane.
Examples of the silane coupling agent having an amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-2- (aminoethyl)- 3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) ) -3-aminopropyltriethoxysilane, 3- (methylamino) propyltrimethoxysilane, 3- (methylamino) propyltriethoxysilane and the like.
Moreover, the oligomerized alkoxy oligomer (silicone alkoxy oligomer) containing the said organic functional group etc. can also be used as a silane coupling agent.
（４）シランカップリング剤の含有量は、主成分の（メタ）アクリレートモノマーの合計１００重量部に対して、シランカップリング剤０．０１〜０．５重量部が好ましい。 (4) As for content of a silane coupling agent, 0.01-0.5 weight part of silane coupling agents are preferable with respect to a total of 100 weight part of the (meth) acrylate monomer of a main component.
その他任意の成分として、酸化防止剤、界面活性剤、硬化促進剤、可塑剤、充填剤、架橋触媒、架橋遅延剤、硬化遅延剤、加工助剤、老化防止剤などの公知の添加剤を適宜に配合することができる。これらは、単独で、もしくは２種以上併せて用いてもよい。 As other optional components, known additives such as an antioxidant, a surfactant, a curing accelerator, a plasticizer, a filler, a crosslinking catalyst, a crosslinking retarder, a curing retarder, a processing aid, and an antiaging agent are appropriately used. Can be blended. These may be used alone or in combination of two or more.
本発明の粘着剤層は、前記粘着剤組成物を基材や離型フィルムに塗布した後、粘着剤組成物を架橋することで得ることができる。架橋後の粘着剤層のゲル分率は、４０〜７５％であることが好ましい。
光学部材の層間の貼合などに用いる場合、薄い粘着剤層であることが望ましく、前記粘着剤層の厚さは、１μｍ〜２５μｍが好ましく、５μｍ〜２５μｍがより好ましい。また、一般に、粘着剤層の粘着力は、粘着剤層の厚さに略比例しているが、厚さが２５μｍの粘着剤層の粘着力が１．５〜６．０Ｎ／２５ｍｍであることが好ましい。さらに、粘着剤層を被着体に貼り合わせ後、７０℃×１０日後の粘着力が１．５〜１０Ｎ／２５ｍｍであることが好ましい。被着体としては、無アルカリガラス等のガラス板、樹脂フィルム等が挙げられる。
The pressure-sensitive adhesive layer of the present invention can be obtained by crosslinking the pressure-sensitive adhesive composition after applying the pressure-sensitive adhesive composition to a substrate or a release film. The gel fraction of the pressure-sensitive adhesive layer after crosslinking is preferably 40 to 75%.
When used for bonding between layers of an optical member, it is desirable that it is a thin pressure-sensitive adhesive layer, and the thickness of the pressure-sensitive adhesive layer is preferably 1 μm to 25 μm, and more preferably 5 μm to 25 μm. In general, the adhesive strength of the adhesive layer is substantially proportional to the thickness of the adhesive layer, but the adhesive strength of the adhesive layer having a thickness of 25 μm is 1.5 to 6.0 N / 25 mm. Is preferred. Furthermore, after the adhesive layer is bonded to the adherend, the adhesive strength after 70 ° C. × 10 days is preferably 1.5 to 10 N / 25 mm. Examples of the adherend include glass plates such as non-alkali glass and resin films.
本発明に係わる粘着剤層を、光学部材の層間の貼合などに用いる場合、粘着剤層と光学部材との界面での光線の反射を低減させるため、屈折率の差がなるべく小さいことが望ましい。このため、前記粘着剤層の屈折率が１．４７〜１．５０であることが好ましい。 When the pressure-sensitive adhesive layer according to the present invention is used for bonding between layers of an optical member, it is desirable that the difference in refractive index is as small as possible in order to reduce the reflection of light rays at the interface between the pressure-sensitive adhesive layer and the optical member. . For this reason, it is preferable that the refractive index of the said adhesive layer is 1.47-1.50.
本発明の粘着フィルムは、本発明の粘着剤層を、基材又は離型フィルムの片面上に形成することで製造することができる。
粘着剤層の形成に用いる基材フィルムや、粘着面を保護する離型フィルム（セパレーター）としては、ポリエステルフィルムなどの樹脂フィルム等を用いることができる。
基材フィルムには、樹脂フィルムの粘着剤層が形成された側とは反対面に、シリコーン系、フッ素系の離型剤やコート剤、シリカ微粒子等による防汚処理、帯電防止剤の塗布や練り込み等による帯電防止処理を施すことができる。
The pressure-sensitive adhesive film of the present invention can be produced by forming the pressure-sensitive adhesive layer of the present invention on one side of a substrate or a release film.
As the base film used for forming the pressure-sensitive adhesive layer and the release film (separator) for protecting the pressure-sensitive adhesive surface, a resin film such as a polyester film can be used.
On the base film, on the side opposite to the side where the adhesive layer of the resin film is formed, antifouling treatment with silicone-based, fluorine-based release agent or coating agent, silica fine particles, etc., application of antistatic agent, An antistatic treatment such as kneading can be performed.
離型フィルムには、粘着剤層の粘着面と合わされる側の面に、シリコーン系、フッ素系の離型剤などにより離型処理が施される。
１つの粘着剤層の両面に、それぞれ離型フィルムの離型処理が施された面を合わせることで、「離型フィルム／粘着剤層／離型フィルム」の構成とすることもできる。この場合、両側の離型フィルムを、順次、あるいは同時に剥離して粘着面を表出することにより、光学フィルム等の光学部材と貼合可能になる。光学フィルムとしては、偏光フィルム、位相差フィルム、反射防止フィルム、防眩（アンチグレア）フィルム、紫外線吸収フィルム、赤外線吸収フィルム、光学補償フィルム、輝度向上フィルム等が挙げられる。
The release film is subjected to release treatment with a silicone-based or fluorine-based release agent or the like on the surface of the pressure-sensitive adhesive layer that is to be combined with the pressure-sensitive adhesive surface.
A structure of “release film / adhesive layer / release film” can also be obtained by combining the surfaces of the release layer with the release film subjected to the release treatment. In this case, the release films on both sides can be bonded to an optical member such as an optical film by separating the release films sequentially or simultaneously to expose the adhesive surface. Examples of the optical film include a polarizing film, a retardation film, an antireflection film, an antiglare (antiglare) film, an ultraviolet absorption film, an infrared absorption film, an optical compensation film, and a brightness enhancement film.
本発明の粘着フィルムは、偏光板を主とする液晶表示装置の周辺部材用の各種光学フィルム、タッチパネル用の各種光学フィルム、電子ペーパー用の各種光学フィルム、有機ＥＬ用の各種光学フィルム等の貼り合せに用いることができる。
また、これらの光学フィルムの少なくとも一方の面に、前記粘着剤層が積層されている粘着剤層付き光学フィルムとすることができる。具体的には、「光学フィルム／粘着剤層／光学フィルム」、「光学フィルム／粘着剤層／離型フィルム」、「光学フィルム／粘着剤層」、「光学フィルム／粘着剤層／光学フィルム／粘着剤層／光学フィルム」、「光学フィルム／粘着剤層／光学フィルム／粘着剤層／離型フィルム」、「離型フィルム／粘着剤層／光学フィルム／粘着剤層／離型フィルム」等の構成が挙げられる。
例えば、「光学フィルム／粘着剤層／離型フィルム」のように、離型フィルムで保護された粘着剤層を有する場合、離型フィルムを剥がして、「光学フィルム／粘着剤層」のように粘着剤層を表出させ、他の光学フィルムと貼合することにより、粘着剤層が層間の貼合に用いられた「光学フィルム／粘着剤層／光学フィルム」のような構成が得られる。
本発明の粘着フィルムは、偏光板とディスプレイパネルとの貼り合せに好適に用いられる。例えば、粘着剤層付き偏光板の粘着剤層として用いられる。偏光板の構成材料として、λ／４又はλ／２の位相差を持つ位相差フィルムが用いられてもよい。
The adhesive film of the present invention is applied to various optical films for peripheral members of liquid crystal display devices mainly comprising polarizing plates, various optical films for touch panels, various optical films for electronic paper, various optical films for organic EL, etc. Can be used together.
Moreover, it can be set as the optical film with an adhesive layer by which the said adhesive layer is laminated | stacked on the at least one surface of these optical films. Specifically, “optical film / pressure-sensitive adhesive layer / optical film”, “optical film / pressure-sensitive adhesive layer / release film”, “optical film / pressure-sensitive adhesive layer”, “optical film / pressure-sensitive adhesive layer / optical film / “Adhesive layer / optical film”, “optical film / adhesive layer / optical film / adhesive layer / release film”, “release film / adhesive layer / optical film / adhesive layer / release film”, etc. A configuration is mentioned.
For example, when having a pressure-sensitive adhesive layer protected by a release film such as “optical film / pressure-sensitive adhesive layer / release film”, the release film is peeled off, and “optical film / pressure-sensitive adhesive layer” By exposing the pressure-sensitive adhesive layer and pasting with another optical film, a configuration such as “optical film / pressure-sensitive adhesive layer / optical film” in which the pressure-sensitive adhesive layer is used for bonding between layers is obtained.
The adhesive film of this invention is used suitably for bonding of a polarizing plate and a display panel. For example, it is used as an adhesive layer of a polarizing plate with an adhesive layer. As a constituent material of the polarizing plate, a retardation film having a retardation of λ / 4 or λ / 2 may be used.
以下、実施例をもって本発明を具体的に説明する。 Hereinafter, the present invention will be specifically described with reference to examples.
＜アクリル系ポリマーの製造＞
［実施例１］
撹拌機、温度計、還流冷却器及び窒素導入管を備えた反応装置に、窒素ガスを導入して、反応装置内の空気を窒素ガスで置換した。その後、反応装置にブチルアクリレート１００重量部、８−ヒドロキシオクチルアクリレート０．２重量部とともに溶剤（酢酸エチル）を６０重量部加えた。その後、重合開始剤としてアゾビスイソブチロニトリル０．１重量部を２時間かけて滴下させ、６５℃で６時間反応させ、重量平均分子量が１００万以上の、実施例１に用いるアクリル系ポリマー溶液１を得た。アクリル系ポリマーの一部を採取し、後述する酸価の測定試料として用いた。
［実施例２〜５及び比較例１〜３］
モノマーの組成を各々、表１の（１）群及び（２）群の記載のようにする以外は、上記の実施例１に用いるアクリル系ポリマー溶液１と同様にして、実施例２〜５及び比較例１〜３に用いるアクリル系ポリマー溶液を得た。なお、特に測定結果を示さないが、実施例２〜５及び比較例１〜３のアクリル系ポリマー溶液に含まれるアクリル系ポリマーの重量平均分子量は、１００万以上である。
<Manufacture of acrylic polymer>
[Example 1]
Nitrogen gas was introduced into a reactor equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube, and the air in the reactor was replaced with nitrogen gas. Thereafter, 100 parts by weight of butyl acrylate and 0.2 parts by weight of 8-hydroxyoctyl acrylate as well as 60 parts by weight of a solvent (ethyl acetate) were added to the reactor. Thereafter, 0.1 part by weight of azobisisobutyronitrile as a polymerization initiator is dropped over 2 hours, reacted at 65 ° C. for 6 hours, and an acrylic polymer used in Example 1 having a weight average molecular weight of 1 million or more. Solution 1 was obtained. A part of the acrylic polymer was collected and used as an acid value measurement sample described later.
[Examples 2 to 5 and Comparative Examples 1 to 3]
Examples 2 to 5 and Examples 2 to 5 were carried out in the same manner as in the acrylic polymer solution 1 used in Example 1 except that the monomer compositions were as described in groups (1) and (2) in Table 1. An acrylic polymer solution used in Comparative Examples 1 to 3 was obtained. In addition, although a measurement result is not shown especially, the weight average molecular weight of the acrylic polymer contained in the acrylic polymer solution of Examples 2-5 and Comparative Examples 1-3 is 1 million or more.
＜粘着剤組成物、粘着剤層及び粘着フィルムの製造＞
［実施例１］
上記のとおり製造した実施例１のアクリル系ポリマー溶液１に対して、コロネートＬ（トリレンジイソシアネート（ＴＤＩ）化合物のトリメチロールプロパン（ＴＭＰ）アダクト体）０．２重量部、ＫＢＭ−４０３（３−グリシドキシプロピルトリメトキシシラン）０．０５重量部を加えて撹拌混合して実施例１の粘着剤組成物を得た。この粘着剤組成物をシリコーン樹脂コートされたポリエチレンテレフタレート（ＰＥＴ）フィルムからなる離型フィルムの上に塗布後、９０℃で乾燥することによって溶剤を除去した後、２３℃、５０％ＲＨの雰囲気下で７日間エージングすることにより、粘着剤組成物を架橋してなる厚さ２５μｍの粘着剤層を、離型フィルムの片面上に有する、実施例１の粘着フィルムを得た。
［実施例２〜５及び比較例１〜３］
添加剤の組成を各々、表１の（３）群及び（４）群の記載のようにする以外は、上記の実施例１の粘着フィルムと同様にして、実施例２〜５及び比較例１〜３の粘着フィルムを得た。
<Manufacture of an adhesive composition, an adhesive layer, and an adhesive film>
[Example 1]
Coronate L (trimethylolpropane (TMP) adduct body of tolylene diisocyanate (TDI) compound) 0.2 parts by weight, KBM-403 (3- The pressure-sensitive adhesive composition of Example 1 was obtained by adding 0.05 part by weight of glycidoxypropyltrimethoxysilane) and stirring and mixing. The pressure-sensitive adhesive composition was applied on a release film composed of a polyethylene terephthalate (PET) film coated with a silicone resin, and then the solvent was removed by drying at 90 ° C., and then in an atmosphere of 23 ° C. and 50% RH. By aging for 7 days, the pressure-sensitive adhesive film of Example 1 having a pressure-sensitive adhesive layer having a thickness of 25 μm formed by crosslinking the pressure-sensitive adhesive composition on one side of the release film was obtained.
[Examples 2 to 5 and Comparative Examples 1 to 3]
Examples 2 to 5 and Comparative Example 1 were carried out in the same manner as the adhesive film of Example 1 except that the compositions of the additives were as described in groups (3) and (4) of Table 1. -3 adhesive films were obtained.
表１では、（１）群の合計を１００重量部として求めた、（２）群から（４）群までの添加割合として、重量部の数値を括弧で囲んで示す。
また、表１に用いた各成分の略記号の化合物名を、表２に示す。なお、コロネート（登録商標）Ｌは日本ポリウレタン工業株式会社の商品名であり、Ｄ−１１０Ｎは三井化学株式会社の商品名であり、ＫＢＭ−４０３及びＫＢＭ−８０３は信越化学工業株式会社の商品名である。ＴＤＩはトリレンジイソシアネートを意味し、ＴＭＰはトリメチロールプロパンを意味し、ＸＤＩはキシリレンジイソシアネートを意味する。表１及び表２中、カルボキシル基含有共重合性ビニルモノマーは、水酸基含有共重合性ビニルモノマーとともに（２）群に記載した。
In Table 1, the numerical values of parts by weight are shown in parentheses as addition ratios from group (2) to group (4), where the total of group (1) was determined as 100 parts by weight.
In addition, Table 2 shows the names of the abbreviations of each component used in Table 1. Coronate (registered trademark) L is a trade name of Nippon Polyurethane Industry Co., Ltd., D-110N is a trade name of Mitsui Chemicals, Inc., and KBM-403 and KBM-803 are trade names of Shin-Etsu Chemical Co., Ltd. It is. TDI means tolylene diisocyanate, TMP means trimethylolpropane, and XDI means xylylene diisocyanate. In Table 1 and Table 2, the carboxyl group-containing copolymerizable vinyl monomer is described in the group (2) together with the hydroxyl group-containing copolymerizable vinyl monomer.
＜試験方法及び評価＞
実施例１〜５及び比較例１〜３における粘着フィルムから、離型フィルム（シリコーン樹脂コートされたＰＥＴフィルム）を剥がして、粘着剤層を表出させ、偏光板（フィルム）の片面に粘着剤層を転写した。
<Test method and evaluation>
From the adhesive films in Examples 1 to 5 and Comparative Examples 1 to 3, the release film (PET film coated with silicone resin) was peeled off to expose the adhesive layer, and the adhesive on one side of the polarizing plate (film) The layer was transferred.
＜粘着力の測定方法＞
厚さ１８０μｍの偏光板（フィルム）の片面に、厚さ２５μｍの粘着剤層を転写して、試料となる粘着フィルム（粘着剤層付き光学フィルム）を得た。
得られた粘着フィルムを、無アルカリガラスのアセトンで洗浄した非錫面に圧着ロールで貼り合わせ、５０℃、０．５ＭＰａ×２０分間の条件でオートクレーブ処理した後、２３℃×５０％ＲＨの雰囲気下に戻し、１時間経過させた。その後の粘着フィルムの剥離強度を、引張試験機によって、ＪＩＳ Ｚ０２３７「粘着テープ・粘着シート試験方法」に準拠して測定し、１８０°方向に３００ｍｍ／ｍｉｎの速度で剥離した時の剥離強度を、粘着フィルムの粘着剤層の粘着力（Ｎ／２５ｍｍ）とした。
<Measurement method of adhesive strength>
A pressure-sensitive adhesive layer having a thickness of 25 μm was transferred to one side of a polarizing plate (film) having a thickness of 180 μm to obtain a pressure-sensitive adhesive film (optical film with a pressure-sensitive adhesive layer) as a sample.
The obtained adhesive film was bonded to a non-tin surface washed with non-alkali glass acetone with a pressure roll and autoclaved under conditions of 50 ° C. and 0.5 MPa × 20 minutes, and then an atmosphere of 23 ° C. × 50% RH. Returned to 1 hour. The peel strength of the subsequent adhesive film was measured with a tensile tester in accordance with JIS Z0237 “Test method for adhesive tape / adhesive sheet”, and the peel strength when peeled at a rate of 300 mm / min in the 180 ° direction was It was set as the adhesive force (N / 25mm) of the adhesive layer of an adhesive film.
＜酸価の測定方法＞
アクリル系ポリマーの酸価は、試料を溶剤（ジエチルエーテルとエタノールを体積比２：１で混合したもの）に溶かし、電位差自動滴定装置（京都電子工業製、ＡＴ−６１０）を用いて、０．１上記電位差滴定装置を用い、濃度が約０．１ｍｏｌ／ｌの水酸化カリウムエタノール溶液で電位差滴定を行い、試料を中和するために必要な水酸化カリウムエタノール溶液の量を測定した。そして、下記式より、酸価を求めた。
酸価＝（Ｂ×ｆ×５．６１１）／Ｓ
Ｂ＝滴定に用いた０．１ｍｏｌ／ｌ水酸化カリウムエタノール溶液の量（ｍｌ）
ｆ＝０．１ｍｏｌ／ｌ水酸化カリウムエタノール溶液のファクター
Ｓ＝試料の固形分の質量（ｇ）
<Method for measuring acid value>
The acid value of the acrylic polymer was determined by dissolving the sample in a solvent (diethyl ether and ethanol mixed at a volume ratio of 2: 1) and using an automatic potentiometric titrator (AT-610, manufactured by Kyoto Electronics Industry). 1 Using the above potentiometric titrator, potentiometric titration was performed with a potassium hydroxide ethanol solution having a concentration of about 0.1 mol / l, and the amount of potassium hydroxide ethanol solution necessary to neutralize the sample was measured. And the acid value was calculated | required from the following formula.
Acid value = (B × f × 5.611) / S
B = Amount of 0.1 mol / l potassium hydroxide ethanol solution used for titration (ml)
f = factor of 0.1 mol / l potassium hydroxide ethanol solution S = mass (g) of solid content of sample
＜ゲル分率の測定方法＞
エージング終了後、偏光板に貼り合わせる前の測定試料の質量を正確に測定し、トルエン中に２４時間浸漬後、２００メッシュの金網で濾過する。その後、濾過物を１００℃、１時間乾燥した後、残渣の質量を正確に測定して、以下の式から粘着剤層（架橋後の粘着剤）のゲル分率を算出した。
ゲル分率（％）＝不溶部分質量（ｇ）／粘着剤質量（ｇ）×１００
<Method for measuring gel fraction>
After the aging is completed, the mass of the measurement sample before being bonded to the polarizing plate is accurately measured, immersed in toluene for 24 hours, and then filtered through a 200 mesh wire net. Then, after drying a filtered material at 100 degreeC for 1 hour, the mass of the residue was measured correctly and the gel fraction of the adhesive layer (adhesive after bridge | crosslinking) was computed from the following formula | equation.
Gel fraction (%) = insoluble partial mass (g) / adhesive mass (g) × 100
＜耐久性の試験方法＞
粘着力の測定と同様の方法で作成した１０ｃｍ角の粘着フィルムを、同様の方法で無アルカリガラスの非錫面に貼り合わせて作成した試料を、所定の雰囲気（８０℃ｄｒｙ雰囲気、または６０℃×９０％ＲＨの雰囲気）下に２５０時間放置後、２３℃×５０％ＲＨ雰囲気下に取り出し、１時間後に粘着フィルムの状態を目視で観察して耐久性を判断した。
○・・粘着フィルムの剥がれ及び発泡が全くない。
△・・粘着フィルムの一部に剥がれ及び発泡が発生している。
×・・粘着フィルムの全体に剥がれ及び発泡が発生している。
<Durability test method>
A sample prepared by laminating a 10 cm square adhesive film prepared by the same method as the measurement of adhesive strength on the non-tin surface of non-alkali glass by the same method was used in a predetermined atmosphere (80 ° C. dry atmosphere or 60 ° C. In an atmosphere of 90% RH for 250 hours, it was taken out in an atmosphere of 23 ° C. and 50% RH, and after 1 hour, the state of the adhesive film was visually observed to determine durability.
○ ・ ・ There is no peeling or foaming of the adhesive film.
Δ ·· Peeling and foaming occurred on part of the adhesive film.
× ·· Peeling and foaming occurred on the entire adhesive film.
＜リワーク性の試験方法＞
粘着力の測定と同様の方法で作成した１０ｃｍ角の粘着フィルムを、同様の方法で無アルカリガラスの非錫面に貼り合わせて作成した試料を、７０℃の雰囲気下に１０日間放置後、２３℃の雰囲気下に取り出し、１時間放置後の粘着フィルムの粘着力を測定してリワーク性を判断した。
○・・７０℃×１０日後の粘着力が１．５〜１０Ｎ／２５ｍｍである。
△・・７０℃×１０日後の粘着力が１０Ｎ／２５ｍｍより大きいが、２０Ｎ／２５ｍｍ以下である。
×・・７０℃×１０日後の粘着力が２０Ｎ／２５ｍｍより大きい（剥がすことができない）。
<Test method for reworkability>
A sample prepared by laminating a 10 cm square adhesive film prepared by the same method as the measurement of adhesive strength on the non-tin surface of non-alkali glass by the same method was left in an atmosphere of 70 ° C. for 10 days, and then 23 Reworkability was judged by measuring the adhesive strength of the adhesive film after taking out in an atmosphere at 0 ° C. and leaving it for 1 hour.
○ ·· Adhesive strength after 10 days at 70 ° C. is 1.5 to 10 N / 25 mm.
Δ ·· 70 ° C. × 10 days later, the adhesive strength is greater than 10 N / 25 mm, but 20 N / 25 mm or less.
× · The adhesive strength after 70 ° C. × 10 days is greater than 20 N / 25 mm (cannot be removed).
表３に、評価結果を示す。酸価については、カルボキシル基含有共重合性ビニルモノマーを含まない、実施例１〜５及び比較例２，３のアクリル系ポリマーの酸価が０．１以下であり、カルボキシル基含有共重合性ビニルモノマーを含む、比較例１のアクリル系ポリマーの酸価が０．１より大きいことを確認した。 Table 3 shows the evaluation results. Regarding the acid value, the acid value of the acrylic polymers of Examples 1 to 5 and Comparative Examples 2 and 3, which do not include a carboxyl group-containing copolymerizable vinyl monomer, is 0.1 or less, and the carboxyl group-containing copolymerizable vinyl. It confirmed that the acid value of the acrylic polymer of the comparative example 1 containing a monomer was larger than 0.1.
実施例１〜５の粘着フィルムは、厚さ２５μｍの粘着剤層の粘着力が１．５〜６．０Ｎ／２５ｍｍの範囲であり、架橋後の粘着剤層のゲル分率が４０〜７５％であり、密着性及び耐久性が優れていた。また、被着体に貼り合わせ後、７０℃×１０日後の粘着力が１．５〜１０Ｎ／２５ｍｍの範囲であることにより、リワーク性にも優れていた。すなわち、実施例１〜５の粘着フィルムでは、要求事項および問題を克服することができた。 In the adhesive films of Examples 1 to 5, the adhesive force of the adhesive layer having a thickness of 25 μm is in the range of 1.5 to 6.0 N / 25 mm, and the gel fraction of the adhesive layer after crosslinking is 40 to 75%. It was excellent in adhesion and durability. Moreover, after bonding together to a to-be-adhered body, it was excellent also in rework property because the adhesive force after 70 degreeC x 10 days is the range of 1.5-10N / 25mm. That is, the requirements and problems could be overcome with the adhesive films of Examples 1 to 5.
比較例１の粘着フィルムは、主成分の（メタ）アクリレートモノマーとして、ブチルアクリレートを含まず、官能基含有モノマーとして、カルボキシル基含有共重合性ビニルモノマーを含み、ゲル分率が高いためか、厚さ２５μｍの粘着剤層の粘着力が強く、６０℃×９０％ＲＨの雰囲気下での耐久性、及びリワーク性に劣っていた。
比較例２の粘着フィルムは、粘着剤組成物に水酸基含有共重合性ビニルモノマーの配合量が多すぎて、ゲル分率が高いためか、６０℃×９０％ＲＨの雰囲気下での耐久性に劣り、８０℃ｄｒｙ雰囲気下での耐久性、及びリワーク性にも、やや劣っていた。
比較例３の粘着フィルムは、粘着剤組成物にカルボキシル基含有共重合性ビニルモノマーも水酸基含有共重合性ビニルモノマーも含まないため、アクリル系ポリマーが架橋せず、ゲル分率は０であり、厚さ２５μｍの粘着剤層の粘着力が非常に強い。その結果、耐久性、及びリワーク性に劣っていた。
このように、比較例１〜３の粘着フィルムでは、従来の要求事項および問題を克服することができなかった。
The adhesive film of Comparative Example 1 does not contain butyl acrylate as the main component (meth) acrylate monomer, contains a carboxyl group-containing copolymerizable vinyl monomer as the functional group-containing monomer, and has a high gel fraction. The pressure-sensitive adhesive layer having a thickness of 25 μm was strong, and was inferior in durability and reworkability in an atmosphere of 60 ° C. × 90% RH.
The pressure-sensitive adhesive film of Comparative Example 2 has a durability in an atmosphere of 60 ° C. × 90% RH because the amount of the hydroxyl group-containing copolymerizable vinyl monomer is too large in the pressure-sensitive adhesive composition and the gel fraction is high. It was inferior, and it was a little inferior also in durability in 80 degreeC dry atmosphere, and rework property.
Since the pressure-sensitive adhesive film of Comparative Example 3 contains neither a carboxyl group-containing copolymerizable vinyl monomer nor a hydroxyl group-containing copolymerizable vinyl monomer in the pressure-sensitive adhesive composition, the acrylic polymer is not crosslinked, and the gel fraction is 0. The adhesive force of the 25 μm thick adhesive layer is very strong. As a result, it was inferior to durability and reworkability.
As described above, the adhesive films of Comparative Examples 1 to 3 could not overcome the conventional requirements and problems.
Claims (11)
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014160622A JP6644971B2 (en) | 2014-08-06 | 2014-08-06 | Adhesive layer and adhesive film |
| KR1020150066513A KR101717087B1 (en) | 2014-08-06 | 2015-05-13 | Adhesive composition and adhesive film |
| CN201510249734.8A CN106189942B (en) | 2014-08-06 | 2015-05-15 | adhesive composition and adhesive film |
| TW104117120A TWI668282B (en) | 2014-08-06 | 2015-05-28 | Adhesive composition and adhesive film |
| KR1020170030360A KR101812077B1 (en) | 2014-08-06 | 2017-03-10 | Adhesive composition and adhesive film |
| KR1020170174765A KR101962116B1 (en) | 2014-08-06 | 2017-12-19 | Adhesive composition and adhesive film |
| KR1020190031538A KR102053981B1 (en) | 2014-08-06 | 2019-03-20 | Adhesive composition and adhesive film |
| KR1020190159289A KR102196223B1 (en) | 2014-08-06 | 2019-12-03 | Adhesive film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014160622A JP6644971B2 (en) | 2014-08-06 | 2014-08-06 | Adhesive layer and adhesive film |
Related Child Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2018165334A Division JP7022668B2 (en) | 2018-09-04 | 2018-09-04 | Manufacturing method of optical film with adhesive layer |
| JP2018165333A Division JP6720255B2 (en) | 2018-09-04 | 2018-09-04 | Adhesive layer and adhesive film |
| JP2018165335A Division JP7022669B2 (en) | 2018-09-04 | 2018-09-04 | Manufacturing method of optical film with adhesive layer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2016037533A true JP2016037533A (en) | 2016-03-22 |
| JP6644971B2 JP6644971B2 (en) | 2020-02-12 |
Family
ID=55448055
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014160622A Active JP6644971B2 (en) | 2014-08-06 | 2014-08-06 | Adhesive layer and adhesive film |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6644971B2 (en) |
| KR (5) | KR101717087B1 (en) |
| CN (1) | CN106189942B (en) |
| TW (1) | TWI668282B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017110074A (en) * | 2015-12-15 | 2017-06-22 | 住友化学株式会社 | Optical film with adhesive layer and optical laminate |
| JP2017110077A (en) * | 2015-12-15 | 2017-06-22 | 住友化学株式会社 | Adhesive composition |
| WO2017104350A1 (en) * | 2015-12-15 | 2017-06-22 | 住友化学株式会社 | Adhesive composition |
| JP2017110075A (en) * | 2015-12-15 | 2017-06-22 | 住友化学株式会社 | Adhesive composition |
| JP2019189764A (en) * | 2018-04-25 | 2019-10-31 | 藤森工業株式会社 | Adhesive composition and adhesive film |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6725448B2 (en) * | 2017-04-07 | 2020-07-15 | 藤森工業株式会社 | Adhesive composition and adhesive film |
| JP6720255B2 (en) * | 2018-09-04 | 2020-07-08 | 藤森工業株式会社 | Adhesive layer and adhesive film |
| JP7121171B2 (en) * | 2020-05-07 | 2022-08-17 | 藤森工業株式会社 | Adhesive layer and optical film with adhesive layer |
| JP7132402B2 (en) * | 2020-05-07 | 2022-09-06 | 藤森工業株式会社 | Adhesive layer and optical film with adhesive layer |
| JP7001765B2 (en) * | 2020-06-16 | 2022-01-20 | 藤森工業株式会社 | Adhesive layer and adhesive film |
| JP7339323B2 (en) | 2020-06-16 | 2023-09-05 | 藤森工業株式会社 | Optical film with adhesive layer |
| KR102384903B1 (en) | 2020-07-01 | 2022-04-11 | 판테크내진 주식회사 | Hanger for plumbing pipes with damping function |
| JP7001770B2 (en) * | 2020-07-27 | 2022-01-20 | 藤森工業株式会社 | Adhesive film |
| JP7339322B2 (en) | 2020-07-27 | 2023-09-05 | 藤森工業株式会社 | Optical film with adhesive layer |
| JP7001771B2 (en) | 2020-07-27 | 2022-01-20 | 藤森工業株式会社 | Adhesive layer and adhesive film |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006009250A1 (en) * | 2004-07-22 | 2006-01-26 | Soken Chemical & Engineering Co., Ltd. | Adhesive composition for polarizing plate and polarizing plate |
| JP2009120805A (en) * | 2007-10-22 | 2009-06-04 | Nitto Denko Corp | Pressure-sensitive adhesive composition for optical film, pressure-sensitive adhesive layer for optical film, production method thereof, pressure-sensitive adhesive optical film and image display |
| JP2009215528A (en) * | 2008-02-15 | 2009-09-24 | Nitto Denko Corp | Pressure-sensitive adhesive composition for optical films, pressure-sensitive adhesive optical film and image display |
| JP2010150396A (en) * | 2008-12-25 | 2010-07-08 | Cheil Industries Inc | Adhesive composition and optical member using the same |
| JP2010196000A (en) * | 2009-02-27 | 2010-09-09 | Soken Chem & Eng Co Ltd | Acrylic pressure-sensitive adhesive, pressure-sensitive adhesive sheet for polarizing film using the same, and pressure-sensitive adhesion-type polarizing film |
| JP2011504537A (en) * | 2007-11-22 | 2011-02-10 | チェイル インダストリーズ インコーポレイテッド | Adhesive composition, optical member, surface protective sheet |
| JP2012102276A (en) * | 2010-11-12 | 2012-05-31 | Lintec Corp | Acrylic adhesive composition, acrylic adhesive, and optical member with adhesive layer |
| JP2012111939A (en) * | 2010-11-02 | 2012-06-14 | Nippon Synthetic Chem Ind Co Ltd:The | Acrylic resin composition, acrylic adhesive, adhesive sheet, double-sided adhesive sheet, adhesive for transparent electrode, touch panel and image display device, and method of manufacturing adhesive layer containing laminate |
| JP2012208247A (en) * | 2011-03-29 | 2012-10-25 | Sumitomo Chemical Co Ltd | Liquid crystal display device |
| JP2012247574A (en) * | 2011-05-26 | 2012-12-13 | Nitto Denko Corp | Adhesion type polarizing plate and image display device |
| JP2012247517A (en) * | 2011-05-26 | 2012-12-13 | Nitto Denko Corp | Adhesive layer-equipped polarization plate, and image display device |
| JP2012255172A (en) * | 2009-04-30 | 2012-12-27 | Nitto Denko Corp | Adhesive composition for optical film, adhesive layer for optical film, adhesive type optical film, and image display device |
| JP2014152317A (en) * | 2013-02-13 | 2014-08-25 | Lintec Corp | Pressure-sensitive adhesive composition, pressure-sensitive adhesive and pressure-sensitive adhesive sheet |
Family Cites Families (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006293281A (en) | 2005-03-17 | 2006-10-26 | Seiko Epson Corp | Optical component and projector |
| JP4800722B2 (en) | 2005-09-26 | 2011-10-26 | 日東電工株式会社 | Optical pressure-sensitive adhesive composition, optical pressure-sensitive adhesive layer, optical member with a pressure-sensitive adhesive layer, method for producing the same, and image display device |
| EP1956064B1 (en) * | 2005-11-21 | 2010-10-13 | Soken Chemical & Engineering Co. Ltd., | Adhesive composition for optical film, adhesive sheet, and optical member using such adhesive composition |
| JP2009091522A (en) | 2007-10-12 | 2009-04-30 | Toyo Ink Mfg Co Ltd | Adhesive composition and laminate obtained by using the same |
| JP5524640B2 (en) | 2010-01-26 | 2014-06-18 | 大王製紙株式会社 | Adhesive sheet |
| JP2012021148A (en) | 2010-06-16 | 2012-02-02 | Nippon Synthetic Chem Ind Co Ltd:The | Pressure-sensitive adhesive, pressure-sensitive adhesive for optical member, optical member with pressure-sensitive adhesive layer and image display device |
| JP5725760B2 (en) * | 2010-08-19 | 2015-05-27 | 大同化成工業株式会社 | Acrylic polymer compounds used in pressure-sensitive adhesive compositions for touch panels |
| KR20120038633A (en) * | 2010-10-14 | 2012-04-24 | 동우 화인켐 주식회사 | Adhesive composition, polarizing plate and liquid crystal display device comprising the same |
| JP5583048B2 (en) | 2011-02-14 | 2014-09-03 | リンテック株式会社 | Optical pressure-sensitive adhesive composition, optical pressure-sensitive adhesive layer, and optical pressure-sensitive adhesive laminate |
| JP5614328B2 (en) | 2011-02-25 | 2014-10-29 | 藤倉化成株式会社 | Adhesive composition, adhesive film, and optical component |
| JP5760571B2 (en) | 2011-03-24 | 2015-08-12 | Dic株式会社 | Colored adhesive tape for fixing polarizing film |
| KR20130013995A (en) * | 2011-07-29 | 2013-02-06 | 동우 화인켐 주식회사 | Adhesive composition, polarizing plate and liquid crystal display device comprising the same |
| JP5851166B2 (en) * | 2011-09-20 | 2016-02-03 | 藤森工業株式会社 | Adhesive composition and adhesive film |
| JP6013898B2 (en) * | 2012-12-17 | 2016-10-25 | 藤森工業株式会社 | Adhesive layer and adhesive film |
| JP6057693B2 (en) * | 2012-12-17 | 2017-01-11 | 藤森工業株式会社 | Adhesive layer and adhesive film |
| JP5901548B2 (en) * | 2013-01-17 | 2016-04-13 | 藤森工業株式会社 | Adhesive layer and adhesive film |
| JP6391916B2 (en) * | 2013-06-21 | 2018-09-19 | 日東電工株式会社 | Optical pressure-sensitive adhesive layer, optical film with pressure-sensitive adhesive layer, and image display device |
| JP6343836B2 (en) * | 2013-10-31 | 2018-06-20 | 藤森工業株式会社 | Light diffusion adhesive layer and light diffusion adhesive film |
| JP6343837B2 (en) * | 2013-12-10 | 2018-06-20 | 藤森工業株式会社 | Light diffusion adhesive layer and light diffusion adhesive film |
| JP6066937B2 (en) * | 2014-01-28 | 2017-01-25 | 藤森工業株式会社 | Light diffusion adhesive layer and light diffusion adhesive film |
-
2014
- 2014-08-06 JP JP2014160622A patent/JP6644971B2/en active Active
-
2015
- 2015-05-13 KR KR1020150066513A patent/KR101717087B1/en active IP Right Grant
- 2015-05-15 CN CN201510249734.8A patent/CN106189942B/en active Active
- 2015-05-28 TW TW104117120A patent/TWI668282B/en active
-
2017
- 2017-03-10 KR KR1020170030360A patent/KR101812077B1/en active IP Right Grant
- 2017-12-19 KR KR1020170174765A patent/KR101962116B1/en active IP Right Grant
-
2019
- 2019-03-20 KR KR1020190031538A patent/KR102053981B1/en active IP Right Grant
- 2019-12-03 KR KR1020190159289A patent/KR102196223B1/en active IP Right Grant
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006009250A1 (en) * | 2004-07-22 | 2006-01-26 | Soken Chemical & Engineering Co., Ltd. | Adhesive composition for polarizing plate and polarizing plate |
| JP2009120805A (en) * | 2007-10-22 | 2009-06-04 | Nitto Denko Corp | Pressure-sensitive adhesive composition for optical film, pressure-sensitive adhesive layer for optical film, production method thereof, pressure-sensitive adhesive optical film and image display |
| JP2011504537A (en) * | 2007-11-22 | 2011-02-10 | チェイル インダストリーズ インコーポレイテッド | Adhesive composition, optical member, surface protective sheet |
| JP2009215528A (en) * | 2008-02-15 | 2009-09-24 | Nitto Denko Corp | Pressure-sensitive adhesive composition for optical films, pressure-sensitive adhesive optical film and image display |
| JP2010150396A (en) * | 2008-12-25 | 2010-07-08 | Cheil Industries Inc | Adhesive composition and optical member using the same |
| JP2010196000A (en) * | 2009-02-27 | 2010-09-09 | Soken Chem & Eng Co Ltd | Acrylic pressure-sensitive adhesive, pressure-sensitive adhesive sheet for polarizing film using the same, and pressure-sensitive adhesion-type polarizing film |
| JP2012255172A (en) * | 2009-04-30 | 2012-12-27 | Nitto Denko Corp | Adhesive composition for optical film, adhesive layer for optical film, adhesive type optical film, and image display device |
| JP2012111939A (en) * | 2010-11-02 | 2012-06-14 | Nippon Synthetic Chem Ind Co Ltd:The | Acrylic resin composition, acrylic adhesive, adhesive sheet, double-sided adhesive sheet, adhesive for transparent electrode, touch panel and image display device, and method of manufacturing adhesive layer containing laminate |
| JP2012102276A (en) * | 2010-11-12 | 2012-05-31 | Lintec Corp | Acrylic adhesive composition, acrylic adhesive, and optical member with adhesive layer |
| JP2012208247A (en) * | 2011-03-29 | 2012-10-25 | Sumitomo Chemical Co Ltd | Liquid crystal display device |
| JP2012247574A (en) * | 2011-05-26 | 2012-12-13 | Nitto Denko Corp | Adhesion type polarizing plate and image display device |
| JP2012247517A (en) * | 2011-05-26 | 2012-12-13 | Nitto Denko Corp | Adhesive layer-equipped polarization plate, and image display device |
| JP2014152317A (en) * | 2013-02-13 | 2014-08-25 | Lintec Corp | Pressure-sensitive adhesive composition, pressure-sensitive adhesive and pressure-sensitive adhesive sheet |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017110074A (en) * | 2015-12-15 | 2017-06-22 | 住友化学株式会社 | Optical film with adhesive layer and optical laminate |
| JP2017110077A (en) * | 2015-12-15 | 2017-06-22 | 住友化学株式会社 | Adhesive composition |
| WO2017104350A1 (en) * | 2015-12-15 | 2017-06-22 | 住友化学株式会社 | Adhesive composition |
| JP2017110076A (en) * | 2015-12-15 | 2017-06-22 | 住友化学株式会社 | Adhesive composition |
| WO2017104348A1 (en) * | 2015-12-15 | 2017-06-22 | 住友化学株式会社 | Adhesive layer-equipped optical film, and optical laminate |
| WO2017104349A1 (en) * | 2015-12-15 | 2017-06-22 | 住友化学株式会社 | Adhesive composition |
| JP2017110075A (en) * | 2015-12-15 | 2017-06-22 | 住友化学株式会社 | Adhesive composition |
| WO2017104351A1 (en) * | 2015-12-15 | 2017-06-22 | 住友化学株式会社 | Adhesive composition |
| JP2019189764A (en) * | 2018-04-25 | 2019-10-31 | 藤森工業株式会社 | Adhesive composition and adhesive film |
| KR20210040928A (en) * | 2018-04-25 | 2021-04-14 | 후지모리 고교 가부시키가이샤 | Adhesive composition and adhesive film |
| KR102383869B1 (en) | 2018-04-25 | 2022-04-08 | 후지모리 고교 가부시키가이샤 | Adhesive composition and adhesive film |
| JP7166783B2 (en) | 2018-04-25 | 2022-11-08 | 藤森工業株式会社 | Adhesive composition solution, method for producing adhesive film, method for producing optical film with adhesive layer, method for producing polarizing plate with adhesive layer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6644971B2 (en) | 2020-02-12 |
| KR102196223B1 (en) | 2020-12-29 |
| CN106189942A (en) | 2016-12-07 |
| KR101812077B1 (en) | 2017-12-27 |
| TWI668282B (en) | 2019-08-11 |
| TW201606015A (en) | 2016-02-16 |
| KR20190137749A (en) | 2019-12-11 |
| KR20190033501A (en) | 2019-03-29 |
| KR20160017598A (en) | 2016-02-16 |
| CN106189942B (en) | 2018-11-20 |
| KR102053981B1 (en) | 2019-12-09 |
| KR20180001535A (en) | 2018-01-04 |
| KR20170031677A (en) | 2017-03-21 |
| KR101962116B1 (en) | 2019-03-26 |
| KR101717087B1 (en) | 2017-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6620325B2 (en) | Adhesive layer and adhesive film | |
| JP6644971B2 (en) | Adhesive layer and adhesive film | |
| JP6703086B2 (en) | Adhesive layer and adhesive film | |
| JP6703087B2 (en) | Adhesive layer and adhesive film | |
| JP6912628B2 (en) | Adhesive layer and optical film with adhesive layer | |
| JP6720255B2 (en) | Adhesive layer and adhesive film | |
| JP6912627B2 (en) | Adhesive layer and optical film with adhesive layer | |
| JP7132402B2 (en) | Adhesive layer and optical film with adhesive layer | |
| JP2024019685A (en) | Adhesive layer and adhesive film | |
| JP7022669B2 (en) | Manufacturing method of optical film with adhesive layer | |
| JP7022668B2 (en) | Manufacturing method of optical film with adhesive layer | |
| JP7339323B2 (en) | Optical film with adhesive layer | |
| JP7339322B2 (en) | Optical film with adhesive layer | |
| JP7121171B2 (en) | Adhesive layer and optical film with adhesive layer | |
| JP7001765B2 (en) | Adhesive layer and adhesive film | |
| JP7486551B2 (en) | Pressure-sensitive adhesive layer, polarizing plate with pressure-sensitive adhesive layer, and optical film with pressure-sensitive adhesive layer | |
| JP7001770B2 (en) | Adhesive film | |
| JP7486553B2 (en) | Pressure-sensitive adhesive layer, polarizing plate with pressure-sensitive adhesive layer, and optical film with pressure-sensitive adhesive layer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20160422 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20170131 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170321 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20170426 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170720 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20171212 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180208 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20180605 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180904 |
|
| C60 | Trial request (containing other claim documents, opposition documents) |
Free format text: JAPANESE INTERMEDIATE CODE: C60 Effective date: 20180904 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20180911 |
|
| C21 | Notice of transfer of a case for reconsideration by examiners before appeal proceedings |
Free format text: JAPANESE INTERMEDIATE CODE: C21 Effective date: 20180918 |
|
| A912 | Re-examination (zenchi) completed and case transferred to appeal board |
Free format text: JAPANESE INTERMEDIATE CODE: A912 Effective date: 20181005 |
|
| C211 | Notice of termination of reconsideration by examiners before appeal proceedings |
Free format text: JAPANESE INTERMEDIATE CODE: C211 Effective date: 20181016 |
|
| C22 | Notice of designation (change) of administrative judge |
Free format text: JAPANESE INTERMEDIATE CODE: C22 Effective date: 20190416 |
|
| C22 | Notice of designation (change) of administrative judge |
Free format text: JAPANESE INTERMEDIATE CODE: C22 Effective date: 20190528 |
|
| C13 | Notice of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: C13 Effective date: 20190611 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20190808 |
|
| C23 | Notice of termination of proceedings |
Free format text: JAPANESE INTERMEDIATE CODE: C23 Effective date: 20191105 |
|
| C03 | Trial/appeal decision taken |
Free format text: JAPANESE INTERMEDIATE CODE: C03 Effective date: 20191210 |
|
| C30A | Notification sent |
Free format text: JAPANESE INTERMEDIATE CODE: C3012 Effective date: 20191210 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20191212 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6644971 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |