JP2022105711A - Adhesive composition, adhesive film, film for touch panels, film for electronic paper, and film for organic el - Google Patents
Adhesive composition, adhesive film, film for touch panels, film for electronic paper, and film for organic el Download PDFInfo
- Publication number
- JP2022105711A JP2022105711A JP2022085979A JP2022085979A JP2022105711A JP 2022105711 A JP2022105711 A JP 2022105711A JP 2022085979 A JP2022085979 A JP 2022085979A JP 2022085979 A JP2022085979 A JP 2022085979A JP 2022105711 A JP2022105711 A JP 2022105711A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- acrylate
- film
- pressure
- sensitive adhesive
- 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 43
- 239000002313 adhesive film Substances 0.000 title claims abstract description 19
- 239000000853 adhesive Substances 0.000 title abstract description 16
- 230000001070 adhesive effect Effects 0.000 title abstract description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 106
- 239000000178 monomer Substances 0.000 claims abstract description 63
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 38
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 30
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 25
- 239000012298 atmosphere Substances 0.000 claims abstract description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 14
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 12
- 229920001577 copolymer Polymers 0.000 claims abstract description 11
- 125000000524 functional group Chemical group 0.000 claims abstract description 10
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims abstract description 6
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 5
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 92
- -1 2-ethoxyethyl Chemical group 0.000 claims description 70
- 239000010410 layer Substances 0.000 claims description 44
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 24
- 239000003431 cross linking reagent Substances 0.000 claims description 12
- 150000001875 compounds Chemical group 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 2
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 claims description 2
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 claims description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 claims description 2
- 239000012790 adhesive layer Substances 0.000 abstract description 20
- 239000004971 Cross linker Substances 0.000 abstract 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 abstract 1
- 239000010408 film Substances 0.000 description 68
- 239000012788 optical film Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 13
- 239000011521 glass Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000005259 measurement Methods 0.000 description 9
- 230000001681 protective effect Effects 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- 229920006243 acrylic copolymer Polymers 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 238000005187 foaming Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 230000002265 prevention Effects 0.000 description 7
- 229920002799 BoPET Polymers 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- 229920002050 silicone resin Polymers 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920002284 Cellulose triacetate Polymers 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 150000003926 acrylamides Chemical class 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 230000035939 shock Effects 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
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-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
- 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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- PBGPBHYPCGDFEZ-UHFFFAOYSA-N 1-ethenylpiperidin-2-one Chemical compound C=CN1CCCCC1=O PBGPBHYPCGDFEZ-UHFFFAOYSA-N 0.000 description 1
- WLPAQAXAZQUXBG-UHFFFAOYSA-N 1-pyrrolidin-1-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCCC1 WLPAQAXAZQUXBG-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-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
- OCIFJWVZZUDMRL-UHFFFAOYSA-N 6-hydroxyhexyl prop-2-enoate Chemical compound OCCCCCCOC(=O)C=C OCIFJWVZZUDMRL-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 101100433727 Caenorhabditis elegans got-1.2 gene Proteins 0.000 description 1
- 229920008347 Cellulose acetate propionate Polymers 0.000 description 1
- 239000004985 Discotic Liquid Crystal Substance Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241001248531 Euchloe <genus> Species 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000005529 alkyleneoxy group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 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
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 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
- 238000012662 bulk polymerization Methods 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
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 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
- 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
- 230000006866 deterioration Effects 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction 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
- 239000006260 foam Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 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
- 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
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 230000001771 impaired effect Effects 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
- 239000012948 isocyanate Substances 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
- 150000003951 lactams Chemical class 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
- 230000007257 malfunction Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 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
- RKSYJNCKPUDQET-UHFFFAOYSA-N n,n-dipropylprop-2-enamide Chemical compound CCCN(CCC)C(=O)C=C RKSYJNCKPUDQET-UHFFFAOYSA-N 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 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
- 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 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003050 poly-cycloolefin Polymers 0.000 description 1
- 229920006267 polyester film 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
- 229920002451 polyvinyl alcohol Polymers 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
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 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 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
Description
本発明は、粘着剤層を厚塗りされた粘着フィルムを、高温・高湿度の雰囲気下に長期間放置しても白濁することのない、白濁防止性能を有する粘着剤組成物、及び粘着フィルムに関する。さらに詳細には、水酸基を含有しない窒素含有ビニルモノマーまたはアルコキシ基含有（メタ）アクリル酸エステルモノマーを含有する粘着剤組成物に関し、粘着剤層の厚みを厚塗りにした際にも透明性を損なわず、さらには高温・高湿度の雰囲気下に長期間放置した後の、白濁防止性能にも優れた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に関するものである。 The present invention relates to an adhesive composition having anti-whitening performance and an adhesive film, which does not become cloudy even when the pressure-sensitive adhesive film thickly coated with the pressure-sensitive adhesive layer is left in an atmosphere of high temperature and high humidity for a long period of time. .. More specifically, with respect to a pressure-sensitive adhesive composition containing a hydroxyl group-free nitrogen-containing vinyl monomer or an alkoxy group-containing (meth) acrylic acid ester monomer, the transparency is impaired even when the thickness of the pressure-sensitive adhesive layer is thickened. Further, the present invention relates to a pressure-sensitive adhesive composition having excellent anti-white turbidity performance after being left in an atmosphere of high temperature and high humidity for a long period of time, and a pressure-sensitive adhesive film using the same.
近年、ＰＤＰ（プラズマディスプレイ）、液晶パネル、有機ＥＬパネルなどの各種ディスプレイにおいては、ディスプレイ前面に各種光学フィルムや保護板が貼り付けられている。
例えば、ＰＤＰにおいては、電磁波のシールドフィルム以外に、近赤外線の波長領域を使用している各種のリモコンスイッチの誤作動を防ぐための近赤外線吸収フィルム、その近赤外線吸収フィルムに使用されている近赤外線吸収剤の経時劣化を防ぐための紫外線吸収フィルム、さらには可視光領域の色調調整のためのネオン光カットフィルム、光学フィルターの表面に外光が映り込むのを防ぐための反射防止フィルム等が、ディスプレイ前面に貼り付けられている。これらのフィルムを、ディスプレイ用光学フィルターとして用いることにより、画像の映り具合の改善が図られている。
In recent years, in various displays such as PDPs (plasma displays), liquid crystal panels, and organic EL panels, various optical films and protective plates are attached to the front surface of the displays.
For example, in PDP, in addition to the electromagnetic shielding film, a near-infrared absorbing film for preventing malfunction of various remote control switches using the near-infrared wavelength region, and a near-infrared absorbing film used for the near-infrared absorbing film. Ultraviolet absorbing film to prevent deterioration of infrared absorber over time, neon light cut film to adjust color tone in visible light region, antireflection film to prevent external light from being reflected on the surface of optical filter, etc. , Attached to the front of the display. By using these films as optical filters for displays, the appearance of images is improved.
また、液晶パネルが、表示ディスプレイとして使用されている携帯電話では、液晶パネルの前面に衝撃吸収用の保護板が、液晶パネルの割れ防止のために空気層を介して取り付けられている。しかし、最近では、軽量化と薄型化、及び視認性の向上を図るため、携帯電話の液晶パネルの前面に空気層を設けないで、粘着剤層を用いて直接に薄い保護板を貼り合せることが行なわれている。
また、ＰＤＰでも、軽量化と薄型化、及び視認性の向上を図るため、ＰＤＰパネルに直接、光学フィルター用のフィルムを貼合することが、ダイレクトカラーフィルター方式として検討されている。
Further, in a mobile phone in which a liquid crystal panel is used as a display, a protective plate for shock absorption is attached to the front surface of the liquid crystal panel via an air layer to prevent the liquid crystal panel from cracking. However, recently, in order to reduce the weight and thickness and improve the visibility, a thin protective plate is directly attached using an adhesive layer without providing an air layer on the front surface of the liquid crystal panel of the mobile phone. Is being done.
Further, also in PDP, in order to reduce the weight and thickness and improve the visibility, it is considered as a direct color filter method to directly bond a film for an optical filter to a PDP panel.
上記の光学フィルムや保護板は、粘着剤層を使用してディスプレイの前面に貼り合せられているが、粘着剤層を使用して各種の光学フィルムをディスプレイに貼り合せる時に、気泡を巻き込んでしまい粘着剤層に微小気泡が生じるという問題があった。
また、ディスプレイ表示装置の、出荷前に行なわれるディスプレイの性能試験では、オーブンを使用して行われる高温・高湿度での環境条件下における耐久試験に合格する必要がある。しかし、白濁防止性能が改善されていない粘着剤層を用いた光学フィルムの場合、オーブンから取り出した後、粘着剤層が白濁してしまい、ディスプレイの商品価値を損なうという問題があった。
The above optical film and protective plate are attached to the front surface of the display using an adhesive layer, but when various optical films are attached to the display using the adhesive layer, air bubbles are trapped. There was a problem that fine bubbles were generated in the pressure-sensitive adhesive layer.
In addition, in the performance test of the display of the display display device, which is performed before shipment, it is necessary to pass the durability test under environmental conditions at high temperature and high humidity, which is performed using an oven. However, in the case of an optical film using an adhesive layer whose anti-whitening performance has not been improved, there is a problem that the adhesive layer becomes cloudy after being taken out from the oven, which impairs the commercial value of the display.
このように、粘着テープを使用して、光学フィルムをディスプレイに貼り合せた時に、粘着剤層に微小気泡が生じるという問題や、また、ディスプレイを、オーブンを使用して高温・高湿度の環境条件下で耐久性試験を行った時、およびオーブンから取り出した後に、粘着剤層に白濁が生じるという問題を解決するために、従来から様々な取り組みが行なわれている。 In this way, when the optical film is attached to the display using the adhesive tape, there is a problem that fine bubbles are generated in the adhesive layer, and the display is exposed to high temperature and high humidity environmental conditions using an oven. Various efforts have been made in the past to solve the problem of white turbidity in the adhesive layer when the durability test is performed underneath and after removal from the oven.
例えば、特許文献１には、粘着剤層の表面に窪みが生じた場合の修復性能を改善して気泡の巻き込みを防止する、粘着剤層を用いた粘着型光学フィルムが開示されている。具体的には、アルキル基の炭素数が７～１８のアルキル（メタ）アクリレートと、水酸基含有モノマーとの重量比率が１００：０．０１～５で含有するポリマー、及び水酸基と反応する官能基を２つ以上有する化合物、を含有する組成物の架橋物により形成された粘着剤層である。この粘着剤層（厚さ２０μｍ）を用いた光学フィルムをガラスに貼り合せた後、５０℃×０．０５ＭＰａ雰囲気下に５分間放置し、粘着剤層での微小気泡の発生の有無を目視にて確認する方法により気泡の有無を検査しているが、微小気泡の発生が防止できているとしている。
For example, Patent Document 1 discloses an adhesive optical film using an adhesive layer, which improves repair performance when a dent is formed on the surface of the adhesive layer and prevents air bubbles from being entrained. Specifically, a polymer containing an alkyl (meth) acrylate having an alkyl group having 7 to 18 carbon atoms and a hydroxyl group-containing monomer having a weight ratio of 100: 0.01 to 5 and a functional group that reacts with the hydroxyl group are used. It is a pressure-sensitive adhesive layer formed by a crosslinked product of a composition containing two or more compounds. An optical film using this pressure-sensitive adhesive layer (
また、特許文献２には、画像表示装置等の保護に必要な衝撃吸収のための、アクリル酸系誘導体、アクリル酸系誘導体ポリマー、及び高分子量架橋剤を含有した樹脂組成物が開示されている。画像表示用パネルの割れ防止あるいは応力及び衝撃の緩和に有用で、透明性に優れているとしている。
吸湿試験として、深さ０．５ｍｍの枠で成形した樹脂シートを６０℃、９０％ＲＨの高温・高湿試験槽に５０時間入れることで行い、目視観察で評価を行なう方法で確認した結果、この樹脂組成物であれば発泡が少なく透明性に優れているとしている。
Further, Patent Document 2 discloses a resin composition containing an acrylic acid-based derivative, an acrylic acid-based derivative polymer, and a high-molecular-weight cross-linking agent for shock absorption necessary for protection of an image display device or the like. .. It is said to be useful for preventing cracks in image display panels or for alleviating stress and impact, and has excellent transparency.
As a moisture absorption test, a resin sheet molded in a frame with a depth of 0.5 mm was placed in a high-temperature / high-humidity test tank at 60 ° C. and 90% RH for 50 hours, and the results were confirmed by visual observation. It is said that this resin composition has less foaming and is excellent in transparency.
また、特許文献３には、優れた耐湿熱性を有する電子ディスプレイ用粘着剤層が開示されている。具体的には、（メタ）アクリル酸アルキルエステルモノマーと、カルボキシル基含有モノマーとの共重合体および／または混合物を含む電子ディスプレイ用粘着剤組成物であって、さらに、アルキレンオキシ基を有するモノマー、および、ヒドロキシル基含有（メタ）アクリル酸エステルモノマーを含むことを特徴とする電子ディスプレイ用粘着剤組成物である。
吸湿試験として、樹脂フィルムに積層した粘着剤層（厚さ２００μｍ）を介してガラス板に貼り合せた積層体を、６０℃、９０％ＲＨの環境下に１２０時間放置した後、常温（２５℃）下で３０分間放置した後、ヘイズ値を測定して積層体の透明性を判定している。この粘着剤組成物によれば、高温・高湿下で放置された後でも、発泡が少なくて高い透明性を維持できるとしている。
Further, Patent Document 3 discloses a pressure-sensitive adhesive layer for an electronic display having excellent moisture resistance and heat resistance. Specifically, a pressure-sensitive adhesive composition for an electronic display containing a copolymer and / or a mixture of a (meth) acrylic acid alkyl ester monomer and a carboxyl group-containing monomer, and further, a monomer having an alkyleneoxy group. A pressure-sensitive adhesive composition for an electronic display, which comprises a hydroxyl group-containing (meth) acrylic acid ester monomer.
As a moisture absorption test, a laminate bonded to a glass plate via an adhesive layer (thickness 200 μm) laminated on a resin film was left at 60 ° C. and 90% RH for 120 hours, and then at room temperature (25 ° C.). ) After leaving it for 30 minutes underneath, the haze value is measured to determine the transparency of the laminate. According to this pressure-sensitive adhesive composition, even after being left at high temperature and high humidity, there is little foaming and high transparency can be maintained.
光学用粘着剤フィルムに対して、近年求められている要求事項は、粘着剤層を厚塗りした時においても、高い透明性を確保し、且つ、高温・高湿度の雰囲気下に長期間放置した後、室温環境に取り出しても白濁しないことである。
しかし、粘着剤層の厚みを厚塗りにした際の、高い透明性は達成することができても、高温・高湿時の白濁防止性能はなかなか達成できないことが多かった。また、白濁防止性能を改良するために、水酸基含有モノマーの添加量を増やすなどの試みは成され、白濁防止性能は改善されてきたが、その代わりに、耐久性などの性能を保持できないなどの欠点が多かった。これらの欠点を、同時に克服できる粘着剤が必要とされている。
The requirements for optical pressure-sensitive adhesive films in recent years are that even when the pressure-sensitive adhesive layer is thickly applied, high transparency is ensured and the film is left in a high-temperature, high-humidity atmosphere for a long period of time. After that, it does not become cloudy even if it is taken out to a room temperature environment.
However, although high transparency can be achieved when the thickness of the pressure-sensitive adhesive layer is thickened, it is often difficult to achieve white turbidity prevention performance at high temperature and high humidity. In addition, in order to improve the white turbidity prevention performance, attempts have been made to increase the amount of the hydroxyl group-containing monomer added, and the white turbidity prevention performance has been improved, but instead, the performance such as durability cannot be maintained. There were many drawbacks. There is a need for adhesives that can overcome these shortcomings at the same time.
すなわち、本発明の目的は、粘着剤層を厚塗りされた粘着フィルムを、高温・高湿度の雰囲気下に長期間放置しても白濁することのない、白濁防止性能を有する粘着剤組成物、及び粘着フィルムを提供することである。 That is, an object of the present invention is an adhesive composition having anti-white turbidity performance, which does not cause white turbidity even when the adhesive film thickly coated with the adhesive layer is left in an atmosphere of high temperature and high humidity for a long period of time. And to provide an adhesive film.
前記課題を解決するため、本発明は、水酸基を含有しない窒素含有ビニルモノマーまたはアルコキシ基含有アルキル（メタ）アクリレートモノマーの少なくとも１種と、官能基にカルボキシル基を含有せず水酸基を含有する共重合性ビニルモノマーの少なくとも１種とを含むことを特徴とする粘着剤組成物を提供する。
また、本発明の粘着剤組成物は、（Ａ）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またはフェノキシ基含有アルキル（メタ）アクリレートモノマーの少なくとも１種が５０～９５重量部、（Ｂ）前記水酸基を含有しない窒素含有ビニルモノマーまたはアルコキシ基含有アルキル（メタ）アクリレートモノマーの少なくとも１種が５～５０重量部、（Ｃ）前記官能基にカルボキシル基を含有せず水酸基を含有する共重合性ビニルモノマーの少なくとも１種が０．５～１０重量部、からなる重量平均分子量が２０万～２００万の共重合体、および、（Ｄ）架橋剤が０．０１～５重量部、を、前記（Ａ）と前記（Ｂ）との合計が１００重量部となる割合で含有することが好ましい。
前記粘着剤組成物によって形成された、塗工厚み２５０μｍの粘着剤層が、全光線透過率が９０％以上、ヘイズ値が１．０％以下であることが好ましい。
前記粘着剤組成物によって形成された、塗工厚み２５０μｍの粘着剤層を、６０℃、９０％ＲＨの雰囲気下で２４０時間放置後、室温環境に取り出した際のヘイズ値が、４．０％以下であることが好ましい。
また、本発明は、基材の片面上に、前記粘着剤組成物からなる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。
また、本発明は、前記粘着フィルムが用いられた、タッチパネル用フィルムを提供する。
また、本発明は、前記粘着フィルムが用いられた、電子ペーパー用フィルムを提供する。
また、本発明は、前記粘着フィルムが用いられた、有機ＥＬ用フィルムを提供する。
また、本発明は、光学フィルムの少なくとも一方の面に、前記粘着剤組成物からなる粘着剤層が積層されている粘着剤付き光学フィルムを提供する。
In order to solve the above problems, the present invention presents a copolymerization of at least one of a hydroxyl group-free nitrogen-containing vinyl monomer or an alkoxy group-containing alkyl (meth) acrylate monomer and a hydroxyl group-free functional group. Provided is a pressure-sensitive adhesive composition comprising at least one of a sex vinyl monomer.
Further, in the pressure-sensitive adhesive composition of the present invention, at least one of (A) an alkyl (meth) acrylate monomer having an alkyl group having C1 to C14 and an alkyl (meth) acrylate monomer containing a phenoxy group is 50 to 95 parts by weight. , (B) At least one of the hydroxyl group-free nitrogen-containing vinyl monomer or alkoxy group-containing alkyl (meth) acrylate monomer is 5 to 50 parts by weight, and (C) the functional group does not contain a carboxyl group and contains a hydroxyl group. At least one of the copolymerizable vinyl monomers is 0.5 to 10 parts by weight, a copolymer having a weight average molecular weight of 200,000 to 2 million, and (D) a cross-linking agent is 0.01 to 5 parts by weight. , Are preferably contained in a proportion such that the total of the above (A) and the above (B) is 100 parts by weight.
It is preferable that the pressure-sensitive adhesive layer having a coating thickness of 250 μm formed by the pressure-sensitive adhesive composition has a total light transmittance of 90% or more and a haze value of 1.0% or less.
The haze value when the pressure-sensitive adhesive layer having a coating thickness of 250 μm formed by the pressure-sensitive adhesive composition was left in an atmosphere of 60 ° C. and 90% RH for 240 hours and then taken out to a room temperature environment was 4.0%. The following is preferable.
The present invention also provides a pressure-sensitive adhesive film in which a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is laminated on one side of a base material.
The present invention also provides a touch panel film using the adhesive film.
The present invention also provides a film for electronic paper in which the pressure-sensitive adhesive film is used.
The present invention also provides a film for organic EL in which the pressure-sensitive adhesive film is used.
The present invention also provides an optical film with a pressure-sensitive adhesive, in which a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is laminated on at least one surface of the optical film.
本発明によれば、粘着剤層の厚みが２５０μｍ以上の厚塗り時において、透明性に優れていることは勿論のこと、高温・高湿時の白濁防止性能を改善することが可能になる。 According to the present invention, when the pressure-sensitive adhesive layer is thickly coated with a thickness of 250 μm or more, it is possible to improve not only excellent transparency but also white turbidity prevention performance at high temperature and high humidity.
以下、好適な実施の形態に基づき、本発明を説明する。
本発明の粘着剤組成物は、（Ｂ）窒素含有ビニルモノマーまたはアルコキシ基含有アルキル（メタ）アクリレートモノマーの少なくとも１種と、（Ｃ）官能基にカルボキシル基を含有せず水酸基を含有する共重合性ビニルモノマーとを含む。
Hereinafter, the present invention will be described based on a preferred embodiment.
The pressure-sensitive adhesive composition of the present invention is a copolymerization of (B) at least one of a nitrogen-containing vinyl monomer or an alkoxy group-containing alkyl (meth) acrylate monomer, and (C) a functional group containing a hydroxyl group without containing a carboxyl group. Contains sex vinyl monomers.
本発明に用いる粘着剤ポリマーとしては、アクリル系ポリマーが好ましく、特に、（Ａ）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少なくとも１種を主成分とする共重合組成物が好ましい。 As the pressure-sensitive adhesive polymer used in the present invention, an acrylic polymer is preferable, and in particular, a copolymer composition containing at least one of (A) an alkyl (meth) acrylate monomer having an alkyl group having C1 to C14 as a main component. Is preferable.
（Ａ）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、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、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。
（Ａ）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一部に代えて、２－フェノキシエチル（メタ）アクリレート等のフェノキシ基含有アルキル（メタ）アクリレートモノマーを併用することもできる。
(A) As the alkyl (meth) acrylate monomer having an alkyl group having C1 to C14 carbon atoms, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 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) Examples thereof include acrylate, decyl (meth) acrylate, cyclopentyl (meth) acrylate, and cyclohexyl (meth) acrylate. The alkyl group of the alkyl (meth) acrylate monomer may be linear, branched or cyclic.
(A) A phenoxy group-containing alkyl (meth) acrylate monomer such as 2-phenoxyethyl (meth) acrylate may be used in combination with a part of the alkyl (meth) acrylate monomer having an alkyl group having C1 to C14 carbon atoms. can.
（Ｂ）のうち、窒素含有ビニルモノマーとしては、Ｎ－ビニル－２－ピロリドン、Ｎ－ビニルカプロラクタム、Ｎ－アクリロイルモルホリンなどの環状窒素ビニル化合物；Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド、Ｎ，Ｎ－ジプロピルアクリルアミド、Ｎ，Ｎ－ジイソプロピル（メタ）アクリルアミド、Ｎ，Ｎ－ジブチル（メタ）アクリルアミド、Ｎ－エチル－Ｎ－メチル（メタ）アクリルアミド、Ｎ－メチル－Ｎ－プロピル（メタ）アクリルアミド、Ｎ－メチル－Ｎ－イソプロピル（メタ）アクリルアミド等のジアルキル置換（メタ）アクリルアミド；Ｎ，Ｎ－ジメチルアミノメチル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノイソプロピル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノブチル（メタ）アクリレート、Ｎ－エチル－Ｎ－メチルアミノエチル（メタ）アクリレート、Ｎ－メチル－Ｎ－プロピルアミノエチル（メタ）アクリレート、Ｎ－メチル－Ｎ－イソプロピルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジブチルアミノエチル（メタ）アクリレートなどのジアルキルアミノ（メタ）アクリレート；Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ－ジプロピルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ－ジイソプロピルアミノプロピル（メタ）アクリルアミド、Ｎ－エチル－Ｎ－メチルアミノプロピル（メタ）アクリルアミド、Ｎ－メチル－Ｎ－プロピルアミノプロピル（メタ）アクリルアミド、Ｎ－メチル－Ｎ－イソプロピルアミノプロピル（メタ）アクリルアミドなどのＮ，Ｎ－ジアルキル置換アミノプロピル（メタ）アクリルアミドなどが挙げられる。
（Ｂ）の窒素含有ビニルモノマーとしては、水酸基を含有しないものが好ましく、水酸基およびカルボキシル基を含有しないものがより好ましい。このようなモノマーとしては、上に例示したモノマー、例えば、Ｎ，Ｎ－ジアルキル置換アミノ基やＮ，Ｎ－ジアルキル置換アミド基を含有するアクリル系モノマー；Ｎ－ビニル－２－ピロリドン、Ｎ－ビニルカプロラクタム、Ｎ－ビニル－２－ピペリドンなどのＮ－ビニル置換ラクタム類；Ｎ－（メタ）アクリロイルモルホリンやＮ－（メタ）アクリロイルピロリジンなどのＮ－（メタ）アクリロイル置換環状アミン類が好ましい。
Among (B), the nitrogen-containing vinyl monomer includes cyclic nitrogen vinyl compounds such as N-vinyl-2-pyrrolidone, N-vinylcaprolactam, and N-acryloylmorpholin; N, N-dimethyl (meth) acrylamide, N, N. -Diethyl (meth) acrylamide, N, N-dipropylacrylamide, N, N-diisopropyl (meth) acrylamide, N, N-dibutyl (meth) acrylamide, N-ethyl-N-methyl (meth) acrylamide, N-methyl Dialkyl-substituted (meth) acrylamides such as -N-propyl (meth) acrylamide, N-methyl-N-isopropyl (meth) acrylamide; N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) ) Acrylamide, N, N-dimethylaminopropyl (meth) acrylate, N, N-dimethylaminoisopropyl (meth) acrylate, N, N-dimethylaminobutyl (meth) acrylate, N-ethyl-N-methylaminoethyl (meth) ) Acrylamide, N-methyl-N-propylaminoethyl (meth) acrylate, N-methyl-N-isopropylaminoethyl (meth) acrylate, N, N-dibutylaminoethyl (meth) acrylate and other dialkylamino (meth) acrylates. N, N-dimethylaminopropyl (meth) acrylamide, N, N-dipropylaminopropyl (meth) acrylamide, N, N-dipropylaminopropyl (meth) acrylamide, N, N-diisopropylaminopropyl (meth) acrylamide, N N, N-dialkyl substituted aminopropyls such as -ethyl-N-methylaminopropyl (meth) acrylamide, N-methyl-N-propylaminopropyl (meth) acrylamide, N-methyl-N-isopropylaminopropyl (meth) acrylamide, etc. Examples include (meth) acrylamide.
As the nitrogen-containing vinyl monomer (B), those containing no hydroxyl group are preferable, and those containing no hydroxyl group and a carboxyl group are more preferable. Examples of such a monomer include the monomers exemplified above, for example, an acrylic monomer containing an N, N-dialkyl substituted amino group or an N, N-dialkyl substituted amide group; N-vinyl-2-pyrrolidone, N-vinyl. N-vinyl-substituted lactams such as caprolactam and N-vinyl-2-piperidone; N- (meth) acryloyl-substituted cyclic amines such as N- (meth) acryloylmorpholine and N- (meth) acryloylpyrrolidine are preferred.
（Ｂ）のうち、アルコキシ基含有アルキル（メタ）アクリレートモノマーとしては、２－メトキシエチル（メタ）アクリレート、２－エトキシエチル（メタ）アクリレート、２－プロポキシエチル（メタ）アクリレート、２－イソプロポキシエチル（メタ）アクリレート、２－ブトキシエチル（メタ）アクリレート、２－メトキシプロピル（メタ）アクリレート、２－エトキシプロピル（メタ）アクリレート、２－プロポキシプロピル（メタ）アクリレート、２－イソプロポキシプロピル（メタ）アクリレート、２－ブトキシプロピル（メタ）アクリレート、３－メトキシプロピル（メタ）アクリレート、３－エトキシプロピル（メタ）アクリレート、３－プロポキシプロピル（メタ）アクリレート、３－イソプロポキシプロピル（メタ）アクリレート、３－ブトキシプロピル（メタ）アクリレート、４－メトキシブチル（メタ）アクリレート、４－エトキシブチル（メタ）アクリレート、４－プロポキシブチル（メタ）アクリレート、４－イソプロポキシブチル（メタ）アクリレート、４－ブトキシブチル（メタ）アクリレートなどが挙げられる。
これらのアルコキシ基含有アルキル（メタ）アクリレートモノマーは、アルキル（メタ）アクリレートにおけるアルキル基の原子がアルコキシ基で置換された構造を有する。
Among (B), the alkoxy group-containing alkyl (meth) acrylate monomer includes 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, and 2-isopropoxyethyl. (Meta) acrylate, 2-butoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 2-ethoxypropyl (meth) acrylate, 2-propoxypropyl (meth) acrylate, 2-isopropoxypropyl (meth) acrylate , 2-butoxypropyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 3-propoxypropyl (meth) acrylate, 3-isopropoxypropyl (meth) acrylate, 3-butoxy Propyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, 4-ethoxybutyl (meth) acrylate, 4-propoxybutyl (meth) acrylate, 4-isopropoxybutyl (meth) acrylate, 4-butoxybutyl (meth) Examples include acrylate.
These alkoxy group-containing alkyl (meth) acrylate monomers have a structure in which the atom of the alkyl group in the alkyl (meth) acrylate is substituted with an alkoxy group.
（Ｃ）官能基にカルボキシル基を含有せず水酸基を含有する共重合性ビニルモノマーとしては、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（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、６－ヒドロキシヘキシル（メタ）アクリレート、８－ヒドロキシオクチル（メタ）アクリレート等の水酸基含有（メタ）アクリル酸エステル類や、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が挙げられ、これらの化合物群の中から選択された、少なくとも１種以上であることが好ましい。
なお、水酸基含有（メタ）アクリルアミド類は窒素を含有するが、本発明においては、（Ｂ）群ではなく、（Ｃ）群に属するものとする。
(C) Examples of the copolymerizable vinyl monomer containing a hydroxyl group and not a carboxyl group in the functional group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate. , 4-Hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate and other hydroxyl group-containing (meth) acrylic acid esters, N-hydroxy (meth) acrylamide, N- Examples thereof include hydroxyl group-containing (meth) acrylamides such as hydroxymethyl (meth) acrylamide and N-hydroxyethyl (meth) acrylamide, and at least one selected from these compound groups is preferable.
The hydroxyl group-containing (meth) acrylamides contain nitrogen, but in the present invention, they belong to the group (C), not the group (B).
上記以外の共重合性ビニルモノマーとしては、（メタ）アクリル酸、イタコン酸、クロトン酸、マレイン酸、フマル酸、カルボキシエチル（メタ）アクリレート、カルボキシペンチル（メタ）アクリレートなどのカルボキシル基を含有する共重合性ビニルモノマー、ベンジル（メタ）アクリレート等の芳香族基含有（メタ）アクリル酸エステル類、スチレン、アクリルアミド、アクリロニトリル、メチルビニルエーテル、エチルビニルエーテル、酢酸ビニル、塩化ビニルなどの各種ビニルモノマーが挙げられる。 Examples of the copolymerizable vinyl monomer other than the above include copolymers containing carboxyl groups such as (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, carboxyethyl (meth) acrylate, and carboxypentyl (meth) acrylate. Examples thereof include polymerizable vinyl monomers, aromatic group-containing (meth) acrylic acid esters such as benzyl (meth) acrylate, and various vinyl monomers such as styrene, acrylamide, acrylonitrile, methyl vinyl ether, ethyl vinyl ether, vinyl acetate, and vinyl chloride.
上記（Ａ）、（Ｂ）および（Ｃ）のモノマーは、アクリル系共重合体として、粘着剤の主剤となる粘着剤ポリマーを構成する。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、塊状重合、懸濁重合、乳化重合等、適宜の重合方法が使用可能である。
粘着剤ポリマーの平均分子量は、特に限定されるものではないが、例えば重量平均分子量２０万～２００万の範囲内が挙げられる。
The above-mentioned monomers (A), (B) and (C) constitute an pressure-sensitive adhesive polymer which is a main component of a pressure-sensitive adhesive as an acrylic copolymer. The polymerization method of the copolymer is not particularly limited, and an appropriate polymerization method such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization can be used.
The average molecular weight of the pressure-sensitive adhesive polymer is not particularly limited, and examples thereof include a weight average molecular weight in the range of 200,000 to 2,000,000.
本発明に用いられる粘着剤ポリマーは、（Ａ）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またはフェノキシ基含有アルキル（メタ）アクリレートモノマーの少なくとも１種が５０～９５重量部、（Ｂ）水酸基を含有しない窒素含有ビニルモノマーまたはアルコキシ基含有アルキル（メタ）アクリレートモノマーの少なくとも１種が５～５０重量部、（Ｃ）官能基にカルボキシル基を含有せず水酸基を含有する共重合性ビニルモノマーの少なくとも１種が０．５～１０重量部、からなる共重合体であることが好ましい。ここで、（Ａ）～（Ｃ）の重量部は、（Ａ）と（Ｂ）との合計が１００重量部となるように規定する。 The pressure-sensitive adhesive polymer used in the present invention comprises (A) at least 50 to 95 parts by weight of an alkyl (meth) acrylate monomer having an alkyl group having C1 to C14 or an alkyl (meth) acrylate monomer containing a phenoxy group. (B) Copolymerization in which at least one of a nitrogen-containing vinyl monomer or an alkoxy group-containing alkyl (meth) acrylate monomer containing no hydroxyl group is 5 to 50 parts by weight, and (C) the functional group does not contain a carboxyl group and contains a hydroxyl group. It is preferable that at least one of the sex vinyl monomers is a copolymer composed of 0.5 to 10 parts by weight. Here, the parts by weight of (A) to (C) are specified so that the total of (A) and (B) is 100 parts by weight.
本発明の粘着剤組成物は、粘着剤層を形成する際に粘着剤ポリマーを架橋することが好ましい。架橋をするため、粘着剤組成物が既知の架橋剤を含んでも良く、紫外線（ＵＶ）など光架橋で架橋しても良い。架橋剤としては、２官能以上のイソシアネート化合物、２官能以上のエポキシ化合物、２官能以上のアクリレート化合物、金属キレート化合物などが挙げられる。架橋剤の含有量は、特に限定されるものではないが、０．０１～５重量部が挙げられる。 The pressure-sensitive adhesive composition of the present invention preferably crosslinks the pressure-sensitive adhesive polymer when forming the pressure-sensitive adhesive layer. For cross-linking, the pressure-sensitive adhesive composition may contain a known cross-linking agent, or may be cross-linked by optical cross-linking such as ultraviolet rays (UV). Examples of the cross-linking agent include a bifunctional or higher functional isocyanate compound, a bifunctional or higher functional epoxy compound, a bifunctional or higher acrylate compound, and a metal chelate compound. The content of the cross-linking agent is not particularly limited, but may be 0.01 to 5 parts by weight.
（Ｄ）架橋剤としては、前記（Ｃ）のモノマーに含まれる水酸基と反応してアクリル系共重合体を架橋し得るものが好ましい。このような架橋剤としては、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（１分子中に２個のＮＣＯ基を有する化合物）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（１分子中に少なくとも３個以上のＯＨ基を有する化合物）とのアダクト体（ポリオール変性体）などのポリイソシアネート化合物などが挙げられる。また紫外線（ＵＶ）など光架橋で架橋しても良い。
なお、本発明に用いられる共重合体は、架橋剤と反応する官能基モノマーとして、前記（Ｃ）の水酸基含有ビニルモノマーを含むことから、カルボキシル基含有ビニルモノマーを含まないものとすることができる。
As the cross-linking agent (D), one capable of cross-linking the acrylic copolymer by reacting with the hydroxyl group contained in the monomer (C) is preferable. Examples of such a cross-linking agent include a bullet-modified product of diisocyanates (compounds having two NCO groups in one molecule) such as hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, and xylylene diisocyanate, and isocyanurate. Examples thereof include modified products, polyisocyanate compounds such as adducts (polyisocyanate modified products) with trivalent or higher polyols (compounds having at least 3 or more OH groups in one molecule) such as trimethylol propane and glycerin. Further, it may be crosslinked by optical cross-linking such as ultraviolet rays (UV).
Since the copolymer used in the present invention contains the hydroxyl group-containing vinyl monomer (C) described above as the functional group monomer that reacts with the cross-linking agent, it can be said that the copolymer does not contain the carboxyl group-containing vinyl monomer. ..
本発明の粘着剤組成物は、（Ａ）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またはフェノキシ基含有アルキル（メタ）アクリレートモノマーの少なくとも１種が５０～９５重量部、（Ｂ）水酸基を含有しない窒素含有ビニルモノマーまたはアルコキシ基含有アルキル（メタ）アクリレートモノマーの少なくとも１種が５～５０重量部、（Ｃ）官能基にカルボキシル基を含有せず水酸基を含有する共重合性ビニルモノマーの少なくとも１種が０．５～１０重量部、からなる重量平均分子量が２０万～２００万の共重合体、および、（Ｄ）架橋剤が０．０１～５重量部、を、前記（Ａ）と前記（Ｂ）との合計が１００重量部となる割合で含有することが好ましい。 In the pressure-sensitive adhesive composition of the present invention, at least one of (A) an alkyl (meth) acrylate monomer having an alkyl group having C1 to C14 or an alkyl (meth) acrylate monomer containing a phenoxy group is 50 to 95 parts by weight, (A). B) At least one of a nitrogen-containing vinyl monomer or an alkoxy group-containing alkyl (meth) acrylate monomer containing no hydroxyl group is 5 to 50 parts by weight, and (C) copolymerizability containing a hydroxyl group without containing a carboxyl group in the functional group. A copolymer consisting of at least one vinyl monomer of 0.5 to 10 parts by weight, a weight average molecular weight of 200,000 to 2 million, and (D) a cross-linking agent of 0.01 to 5 parts by weight, described above. It is preferable that the mixture of (A) and (B) is contained in a proportion of 100 parts by weight.
本発明の粘着剤組成物は、さらに、その他成分としてシランカップリング剤、酸化防止剤、界面活性剤、硬化促進剤、可塑剤、充填剤、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種以上を併せて用いることができる。 The pressure-sensitive adhesive composition of the present invention further contains other components such as a silane coupling agent, an antioxidant, a surfactant, a curing accelerator, a plasticizer, a filler, a curing retarder, a processing aid, and an antiaging agent. Known additives can be appropriately blended. These can be used alone or in combination of two or more.
本発明の粘着剤組成物によれば、粘着剤層の厚みを厚塗りとした時の、優れた透明性は勿論のこと、高温・高湿時の白濁防止性能を改善することが可能になる。前記粘着剤組成物によって形成された、塗工厚み２５０μｍの粘着剤層が、全光線透過率が９０％以上、ヘイズ値が１．０％以下であることが好ましい。また、前記粘着剤組成物によって形成された、塗工厚み２５０μｍの粘着剤層を、６０℃、９０％ＲＨの雰囲気下で２４０時間放置後、室温環境に取り出した際のヘイズ値が４．０％以下であることが好ましい。 According to the pressure-sensitive adhesive composition of the present invention, it is possible to improve not only excellent transparency when the thickness of the pressure-sensitive adhesive layer is thickened, but also white turbidity prevention performance at high temperature and high humidity. .. It is preferable that the pressure-sensitive adhesive layer having a coating thickness of 250 μm formed by the pressure-sensitive adhesive composition has a total light transmittance of 90% or more and a haze value of 1.0% or less. Further, the haze value when the pressure-sensitive adhesive layer having a coating thickness of 250 μm formed by the pressure-sensitive adhesive composition was left in an atmosphere of 60 ° C. and 90% RH for 240 hours and then taken out to a room temperature environment was 4.0. % Or less is preferable.
本発明の粘着フィルムは、基材フィルムの片面上に、本発明の粘着剤組成物からなる粘着剤層が積層されたものである。本発明の粘着フィルムは、タッチパネル用、電子ペーパー用、有機ＥＬ用、光学部材用、表面保護用等の各種用途に用いることができる。粘着剤層の厚みは、特に限定されるものではないが、例えば、１００～２０００μｍである。粘着剤層の厚みが薄すぎると、衝撃吸収性能が悪くなるが、粘着剤層の厚みが厚過ぎるとコストが上昇する点で不利である。特に、粘着剤層の厚みが、２５０μｍ以上の厚塗りであると、本発明の効果が高いため、好ましい。 The pressure-sensitive adhesive film of the present invention is obtained by laminating a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition of the present invention on one side of a base film. The adhesive film of the present invention can be used for various purposes such as for touch panels, electronic paper, organic EL, optical members, and surface protection. The thickness of the pressure-sensitive adhesive layer is not particularly limited, but is, for example, 100 to 2000 μm. If the thickness of the pressure-sensitive adhesive layer is too thin, the shock absorption performance deteriorates, but if the thickness of the pressure-sensitive adhesive layer is too thick, the cost increases, which is disadvantageous. In particular, it is preferable that the thickness of the pressure-sensitive adhesive layer is 250 μm or more because the effect of the present invention is high.
粘着剤層の基材フィルムや、粘着面を保護する剥離フィルム（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。
剥離フィルムには、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。
偏光板用の表面保護フィルムなどの、光学用の表面保護フィルムの場合は、基材フィルム及び粘着剤層は、十分な透明性を有することが好ましい。
また、粘着剤層を介して、各種フィルムを積層した積層フィルムに用いることができる。このようなフィルムとしては、タッチパネル用フィルム、電子ペーパー用フィルム、有機ＥＬ用フィルム、光学用フィルム等が挙げられる。
As the base film of 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 or fluorine-based mold release agent or coating agent, silica fine particles, etc., application of antistatic agent, etc. Antistatic treatment such as kneading can be applied.
The release film is subjected to a mold release treatment with a silicone-based or fluorine-based mold release agent or the like on the surface of the pressure-sensitive adhesive layer that is combined with the adhesive surface.
In the case of an optical surface protective film such as a surface protective film for a polarizing plate, it is preferable that the base film and the pressure-sensitive adhesive layer have sufficient transparency.
Further, it can be used for a laminated film in which various films are laminated via an adhesive layer. Examples of such a film include a touch panel film, an electronic paper film, an organic EL film, an optical film, and the like.
また、本発明の粘着剤組成物は、光学フィルムの少なくとも一方の面に粘着剤層が積層されてなる、粘着剤付き光学フィルムに利用することもできる。
粘着剤付き光学フィルムにおいては、基材フィルムとして、偏光板フィルム、位相差板フィルム、レンズフィルム、位相差板兼用の偏光板フィルム、レンズフィルム兼用の偏光板フィルム等の光学フィルムを用いることができる。
粘着剤付き光学フィルムは、光学フィルムの片面または両面に粘着剤層を積層してなるものであって、画像表示装置のガラス板等との貼り合わせに用いることができる。これらの粘着剤付き光学フィルムは、粘着剤層を介してガラス基板等と貼り合わされて、画像表示装置等に組み込むことができる。粘着剤付き偏光板などの粘着剤付き光学フィルムに用いられる粘着剤層は、十分な透明性を有することが好ましい。
また、基材フィルムとして使用する偏光板は、一般的に、ポリビニルアルコール系偏光子の両面に、トリアセチルセルロース系保護フィルムで挟まれた３層構造を有している。
保護フィルムの表面に、ディスコティック液晶がコートされている偏光板、もしくは、トリアセチルセルロース系フィルムの替わりに、延伸トリアセチルセルロース系フィルム、延伸ポリシクロオレフィン系フィルム、または延伸セルロースアセテートプロピオネートフィルム等で貼り合わされた構造となっている。更に、これらの偏光板フィルムは、液晶表示用パネルの表面基材であるガラス基板に、粘着剤層を介して貼り合わされる。
Further, the pressure-sensitive adhesive composition of the present invention can also be used for an optical film with a pressure-sensitive adhesive, in which a pressure-sensitive adhesive layer is laminated on at least one surface of the optical film.
In the optical film with an adhesive, as the base film, an optical film such as a polarizing plate film, a retardation plate film, a lens film, a polarizing plate film that also serves as a retardation plate, and a polarizing plate film that also serves as a lens film can be used. ..
The optical film with an adhesive is formed by laminating an adhesive layer on one side or both sides of the optical film, and can be used for bonding to a glass plate or the like of an image display device. These optical films with an adhesive can be bonded to a glass substrate or the like via an adhesive layer and incorporated into an image display device or the like. The pressure-sensitive adhesive layer used for the pressure-sensitive optical film such as a polarizing plate with a pressure-sensitive adhesive preferably has sufficient transparency.
Further, the polarizing plate used as the base film generally has a three-layer structure sandwiched between both sides of a polyvinyl alcohol-based polarizing element and a triacetyl cellulose-based protective film.
Instead of a polarizing plate or a triacetyl cellulose-based film on which the surface of the protective film is coated with a discotic liquid crystal, a stretched triacetyl cellulose-based film, a stretched polycycloolefin-based film, or a stretched cellulose acetate propionate film. It has a structure that is pasted together by such means. Further, these polarizing plate films are bonded to a glass substrate, which is a surface base material of a liquid crystal display panel, via an adhesive layer.
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.
＜アクリル共重合体の製造＞
［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、２－エチルヘキシルアクリレート９５重量部、Ｎ－ビニル－２－ピロリドン５重量部、６－ヒドロキシヘキシルアクリレート１．０重量部とともに、溶剤（酢酸エチル）を１００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８時間反応させ、重量平均分子量８０万の、実施例１のアクリル共重合体溶液１を得た。
［実施例２～７及び比較例１～２］
単量体の組成を、各々、表１の記載のようにする以外は、上記の実施例１に用いるアクリル共重合体溶液１と同様にして、実施例２～７及び比較例１～２に用いるアクリル共重合体溶液を得た。
<Manufacturing of acrylic copolymer>
[Example 1]
Nitrogen gas was introduced into a reactor equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube, and the air in the reactor was replaced with nitrogen gas. Then, 100 parts of a solvent (ethyl acetate) was added to the reaction apparatus together with 95 parts by weight of 2-ethylhexyl acrylate, 5 parts by weight of N-vinyl-2-pyrrolidone, and 1.0 part by weight of 6-hydroxyhexyl acrylate. Then, 0.1 part by weight of azobisisobutyronitrile was added dropwise over 2 hours as a polymerization initiator, and the mixture was reacted at 65 ° C. for 8 hours to obtain an acrylic copolymer solution of Example 1 having a weight average molecular weight of 800,000. I got 1.
[Examples 2 to 7 and Comparative Examples 1 to 2]
Examples 2 to 7 and Comparative Examples 1 to 2 have the same composition as the acrylic copolymer solution 1 used in Example 1 above, except that the composition of the monomers is as shown in Table 1. The acrylic copolymer solution to be used was obtained.
＜粘着剤組成物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、アクリル共重合体溶液１（そのうち（Ａ）群＋（Ｂ）群が１００重量部）に対して、コロネートＨＸ（ヘキサメチレンジイソシアネート化合物のイソシアヌレート体）０．５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）フィルムからなる剥離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、粘着剤層の厚さが２５０μｍである粘着フィルムを得た。
その後、ポリエチレンテレフタレート（ＰＥＴ）フィルムに粘着シートを転写させ、「ＰＥＴフィルム／粘着剤層／剥離フィルム（シリコーン樹脂コートされたＰＥＴフィルム）」の積層構成を有する、実施例１の粘着フィルムを得た。
［実施例２～７及び比較例１～２］
架橋剤の組成を、各々、表１の（Ｄ）の記載のようにする以外は、上記の実施例１の表面保護フィルムと同様にして、実施例２～７及び比較例１～２の粘着フィルムを得た。
<Manufacturing of adhesive composition and adhesive film>
[Example 1]
0.5 part by weight of Coronate HX (isocyanurate form of hexamethylene diisocyanate compound) is added to 1 part of acrylic copolymer solution 1 (of which 100 parts by weight is group (A) + group (B)) produced as described above. In addition, the mixture was stirred and mixed to obtain the pressure-sensitive adhesive composition of Example 1. This pressure-sensitive adhesive composition is applied onto a release film made of a polyethylene terephthalate (PET) film coated with a silicone resin, and then dried at 90 ° C. to remove the solvent, and the thickness of the pressure-sensitive adhesive layer is 250 μm. An adhesive film was obtained.
Then, the pressure-sensitive adhesive sheet was transferred to a polyethylene terephthalate (PET) film to obtain a pressure-sensitive adhesive film of Example 1 having a laminated structure of "PET film / pressure-sensitive adhesive layer / release film (PET film coated with silicone resin)". ..
[Examples 2 to 7 and Comparative Examples 1 to 2]
Adhesion of Examples 2 to 7 and Comparative Examples 1 and 2 is the same as that of the surface protective film of Example 1 above, except that the composition of the cross-linking agent is as shown in (D) of Table 1. I got a film.
表１において、各成分の配合比は、（Ａ）群＋（Ｂ）群の合計を１００重量部として求めた、重量部の数値を括弧で囲んで示す。表１のＭｗは、重量平均分子量を意味する。
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。また、表２の（Ｄ）群において、ＨＤＩは、ヘキサメチレンジイソシアネートを、ＸＤＩは、キシリレンジイソシアネートを意味する。
なお、コロネート（登録商標）ＨＸ、同ＨＬ及び同Ｌ－４５は、日本ポリウレタン工業株式会社の商品名であり、デュラネート（登録商標）２４Ａ―１００は、旭化成ケミカルズ株式会社の商品名であり、タケネート（登録商標）Ｄ－１１０Ｎは、三井化学株式会社の商品名である。
In Table 1, the compounding ratio of each component is obtained by taking the total of the group (A) + the group (B) as 100 parts by weight, and the numerical values of the parts by weight are shown in parentheses. Mw in Table 1 means the weight average molecular weight.
The compound names of the abbreviations of each component used in Table 1 are shown in Table 2. Further, in the group (D) of Table 2, HDI means hexamethylene diisocyanate and XDI means xylylene diisocyanate.
Coronate (registered trademark) HX, HL and L-45 are trade names of Nippon Polyurethane Industry Co., Ltd., and Duranate (registered trademark) 24A-100 is a trade name of Asahi Kasei Chemicals Co., Ltd. (Registered trademark) D-110N is a trade name of Mitsui Kagaku Co., Ltd.
＜試験方法及び評価＞
実施例１～７及び比較例１～２の粘着フィルムを、２３℃、５０％ＲＨの雰囲気下で７日間エージングした後、剥離フィルム（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たものを、全光線透過率の測定試料とした。
また、実施例１～７及び比較例１～２の粘着フィルムを、２３℃、５０％ＲＨの雰囲気下で７日間エージングした後、剥離フィルム（シリコーン樹脂コートされたＰＥＴフィルム）で粘着剤層の両面を覆ったままのものを、ヘイズ値の測定試料とした。
また、実施例１～７及び比較例１～２の粘着フィルムを、２３℃、５０％ＲＨの雰囲気下で７日間エージングした後、オーブンによる６０℃、９０％ＲＨの雰囲気下で２４０時間放置後にオーブンから室温環境（２３℃、５０％ＲＨ）に取り出した後、剥離フィルム（シリコーン樹脂コートされたＰＥＴフィルム）で粘着剤層の両面を覆ったままのものを、湿熱後ヘイズ値の測定試料とした。
また、粘着剤層を表出させた粘着フィルムを、粘着剤層を介して無アルカリガラス板の表面に貼り合わせ、１日放置した後、５０℃、５気圧、２０分間オートクレーブ処理し、室温でさらに１２時間放置したものを、粘着力の測定試料とした。
また、粘着剤層を表出させた粘着フィルムを、粘着剤層を介して無アルカリガラス板の表面に貼り合わせ、耐久性の測定試料とした。
<Test method and evaluation>
The adhesive films of Examples 1 to 7 and Comparative Examples 1 and 2 were aged in an atmosphere of 23 ° C. and 50% RH for 7 days, and then the release film (the PET film coated with a silicone resin) was peeled off to remove the adhesive layer. Was used as a sample for measuring the total light transmittance.
Further, the pressure-sensitive adhesive films of Examples 1 to 7 and Comparative Examples 1 and 2 were aged at 23 ° C. and 50% RH for 7 days, and then the pressure-sensitive adhesive layer was coated with a release film (a PET film coated with a silicone resin). The sample with both sides covered was used as the haze value measurement sample.
Further, the adhesive films of Examples 1 to 7 and Comparative Examples 1 and 2 were aged in an atmosphere of 23 ° C. and 50% RH for 7 days, and then left in an oven at 60 ° C. and 90% RH for 240 hours. After taking it out of the oven to a room temperature environment (23 ° C, 50% RH), the adhesive layer covered on both sides with a release film (PET film coated with silicone resin) was used as a sample for measuring the haze value after moist heat. did.
Further, the pressure-sensitive adhesive film on which the pressure-sensitive adhesive layer was exposed was attached to the surface of a non-alkali glass plate via the pressure-sensitive adhesive layer, left to stand for 1 day, and then autoclaved at 50 ° C., 5 atm, and 20 minutes at room temperature. The sample left for another 12 hours was used as a sample for measuring the adhesive strength.
Further, the pressure-sensitive adhesive film on which the pressure-sensitive adhesive layer was exposed was attached to the surface of the non-alkali glass plate via the pressure-sensitive adhesive layer to prepare a sample for measuring durability.
＜全光線透過率＞
上記で得られた、全光線透過率の測定試料について、ヘイズメータ（製造者：日本電色株式会社、型式：Ｈａｚｅ Ｍｅｔｅｒ、ＮＤＨ２０００）を用いて、ＪＩＳＫ７１０５に準じて、粘着剤層の全光線透過率を測定した。
<Total light transmittance>
For the measurement sample of the total light transmittance obtained above, using a haze meter (manufacturer: Nippon Denshoku Co., Ltd., model: Haze Meter, NDH2000), the total light transmittance of the pressure-sensitive adhesive layer is according to JIS K7105. Was measured.
＜ヘイズ値及び湿熱後ヘイズ値＞
上記で得られた、ヘイズ値及び湿熱後ヘイズ値の測定試料について、ヘイズメータ（製造者：日本電色株式会社、型式：Ｈａｚｅ Ｍｅｔｅｒ、ＮＤＨ２０００）を用いて、粘着剤層のヘイズ値を測定した。
なお、上記の測定試料では、剥離フィルム（シリコーン樹脂コートされたＰＥＴフィルム）で粘着剤層の両面を覆ったままのものを、ヘイズ値及び湿熱後ヘイズ値の測定試料としたが、剥離フィルム自体のヘイズ値は、無視できる程度に小さいことを確認した。
<Haze value and haze value after moist heat>
The haze value of the pressure-sensitive adhesive layer was measured using a haze meter (manufacturer: Nippon Denshoku Co., Ltd., model: Haze Meter, NDH2000) for the measurement samples of the haze value and the haze value after moist heat obtained above.
In the above measurement sample, a release film (a PET film coated with a silicone resin) with both sides of the pressure-sensitive adhesive layer covered was used as a measurement sample for the haze value and the haze value after moist heat, but the release film itself. It was confirmed that the haze value of was so small that it could be ignored.
＜ガラス板に対する粘着力＞
上記で得られた、粘着力の測定試料（２５ｍｍ幅の粘着フィルムを、無アルカリガラス板の表面に貼り合わせたもの）を、１８０°方向に引張試験機を用いて０．３ｍ／ｍｉｎの引張速度において剥がして、測定した剥離強度を粘着力とした。
<Adhesive strength to glass plate>
The adhesive strength measurement sample (a 25 mm wide adhesive film bonded to the surface of a non-alkali glass plate) obtained above is tensioned at 0.3 m / min in the 180 ° direction using a tensile tester. It was peeled off at a speed, and the measured peeling strength was taken as the adhesive strength.
＜耐久性＞
上記で得られた、耐久性の測定試料を、８０℃（Ｄｒｙ）の雰囲気下に２５０時間放置後、室温に取り出し、被着体からの剥がれ、発泡等を目視にて確認した。評価基準は、剥がれ・発泡が全く確認されない場合を「○」、剥がれ・発泡が僅かに確認された場合を「△」、剥がれ・発泡が明確に確認された場合を「×」と評価した。
<Durability>
The durability measurement sample obtained above was left in an atmosphere of 80 ° C. (Dry) for 250 hours, then taken out to room temperature, and peeling from the adherend, foaming, etc. were visually confirmed. The evaluation criteria were "○" when no peeling / foaming was confirmed, "Δ" when peeling / foaming was slightly confirmed, and "×" when peeling / foaming was clearly confirmed.
表３に、測定結果及び評価結果を示す。 Table 3 shows the measurement results and the evaluation results.
実施例１～７の粘着フィルムは、粘着剤層が厚塗り（２５０μｍ）時の透明性（全光線透過率が９０％以上、ヘイズ値が１．０％以下）は勿論のこと、高温・高湿度の雰囲気下に長期間放置しても白濁の小さい、白濁防止性能（６０℃、９０％ＲＨ、２４０時間放置後のヘイズ値が４．０％以下）を有し、白濁防止性能を改善することができた。さらに、高温の雰囲気下に長期間放置しても、剥がれや発泡することがなかった。
比較例１～２の粘着フィルムは、高温・高湿度の雰囲気下に長期間放置すると、ヘイズ値の増大が見られ、白濁防止性能に問題があるものとなった。また、高温の雰囲気下に長期間放置すると、剥がれや発泡が見られ、耐久性に問題があるものとなった。さらに、比較例１では、高温・高湿度の雰囲気下に放置する前から、透明性（全光線透過率・ヘイズ値）の測定結果が悪いものとなった。
The adhesive films of Examples 1 to 7 have high temperature and high temperature as well as transparency (total light transmittance of 90% or more and haze value of 1.0% or less) when the adhesive layer is thickly coated (250 μm). It has anti-white turbidity performance (60 ° C, 90% RH, haze value of 4.0% or less after being left for 240 hours) with little white turbidity even when left in a humid atmosphere for a long period of time, and improves the white turbidity prevention performance. I was able to. Furthermore, even if it was left in a high temperature atmosphere for a long period of time, it did not peel off or foam.
When the adhesive films of Comparative Examples 1 and 2 were left in an atmosphere of high temperature and high humidity for a long period of time, an increase in haze value was observed, and there was a problem in the white turbidity prevention performance. In addition, when left in a high temperature atmosphere for a long period of time, peeling and foaming were observed, and there was a problem in durability. Further, in Comparative Example 1, the measurement result of transparency (total light transmittance / haze value) was poor even before being left in an atmosphere of high temperature and high humidity.
＜高温・高湿度の環境から取り出した後のヘイズ値の変化＞
また、実施例１及び比較例１の粘着フィルムを、２３℃、５０％ＲＨの雰囲気下で７日間エージングした後、オーブンによる６０℃、９０％ＲＨの雰囲気下で２４０時間放置後に、オーブンから室温環境（２３℃、５０％ＲＨ）に取り出し、取り出した直後から６０分経過までヘイズ値を測定した。得られた、高温・高湿度の環境から取り出した後のヘイズ値の変化を、図１に示す。
図１において、本発明に係わる実施例１は、オーブンから取り出した直後から１分程度で、ヘイズ値が最大値（３．５％）に達するが、オーブンから取り出して１時間経過しても、ヘイズ値が４．０％を超えることはなく、優れた白濁防止性能を有することが分かる。一方、比較例１においては、オーブンから取り出した直後から数分でヘイズ値が最大値として約２５％に上昇した後、放置時間の経過と共に、徐々にヘイズ値が低下する傾向を示すが、白濁の著しい状態が６０分以上も継続することが分かる。
なお、実施例１及び比較例１のいずれの場合も、高温・高湿度の環境において発生した、上記の白濁は、室温において数時間放置することにより、徐々に消滅して、最終的に粘着フィルムは透明（ヘイズ値が１．０％以下）となった。
本評価は、粘着剤層の両面が、剥離フィルムの間で覆われている状態で実施した場合に起こる変化であり、白濁が消滅するまでの時間が比較的短いが、ガス透過性の悪いガラス同士やアクリル板とガラスなどと貼り合わせたサンプルの場合は、白濁するタイミングは同じであるが、白濁が消滅するまでの時間が、数日かかることもある。
<Changes in haze value after removal from high temperature / humidity environment>
Further, the adhesive films of Example 1 and Comparative Example 1 were aged in an atmosphere of 23 ° C. and 50% RH for 7 days, left in an oven at 60 ° C. and 90% RH for 240 hours, and then left at room temperature from the oven. It was taken out to the environment (23 ° C., 50% RH), and the haze value was measured from immediately after taking out to the lapse of 60 minutes. FIG. 1 shows the changes in the haze value obtained after taking out from the high temperature and high humidity environment.
In FIG. 1, in Example 1 according to the present invention, the haze value reaches the maximum value (3.5%) in about 1 minute immediately after being taken out of the oven, but even after 1 hour has passed since being taken out of the oven. It can be seen that the haze value does not exceed 4.0% and has excellent anti-whitening performance. On the other hand, in Comparative Example 1, the haze value rises to about 25% as the maximum value within a few minutes immediately after being taken out from the oven, and then the haze value tends to gradually decrease with the lapse of the leaving time, but it becomes cloudy. It can be seen that the remarkable state of is continued for 60 minutes or more.
In both Examples 1 and Comparative Example 1, the white turbidity generated in a high temperature and high humidity environment gradually disappears by being left at room temperature for several hours, and finally the adhesive film is formed. Was transparent (haze value was 1.0% or less).
This evaluation is a change that occurs when both sides of the pressure-sensitive adhesive layer are covered between the release films, and the time until the white turbidity disappears is relatively short, but the glass has poor gas permeability. In the case of samples that are bonded together or with an acrylic plate and glass, the timing of clouding is the same, but it may take several days for the clouding to disappear.
Claims (5)
前記アクリル系ポリマーが、
（Ａ）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またはフェノキシ基含有アルキル（メタ）アクリレートモノマーの少なくとも１種の合計が５０～９５重量部と、
（Ｂ）水酸基及びカルボキシル基を含有しない窒素含有ビニルモノマーまたはアルコキシ基含有アルキル（メタ）アクリレートモノマーの少なくとも１種が５～５０重量部、
（Ｃ）官能基にカルボキシル基を含有せず水酸基を含有する共重合性ビニルモノマーである、水酸基含有（メタ）アクリル酸エステルの少なくとも１種の合計が０．５～１０重量部、
からなる重量平均分子量が２０万～２００万の共重合体、
前記（Ｂ）アルコキシ基含有アルキル（メタ）アクリレートモノマーが、２－メトキシエチル（メタ）アクリレート、２－エトキシエチル（メタ）アクリレート、２－プロポキシエチル（メタ）アクリレート、２－イソプロポキシエチル（メタ）アクリレート、２－ブトキシエチル（メタ）アクリレート、２－メトキシプロピル（メタ）アクリレート、２－エトキシプロピル（メタ）アクリレート、２－プロポキシプロピル（メタ）アクリレート、２－イソプロポキシプロピル（メタ）アクリレート、２－ブトキシプロピル（メタ）アクリレート、３－メトキシプロピル（メタ）アクリレート、３－エトキシプロピル（メタ）アクリレート、３－プロポキシプロピル（メタ）アクリレート、３－イソプロポキシプロピル（メタ）アクリレート、３－ブトキシプロピル（メタ）アクリレート、４－メトキシブチル（メタ）アクリレート、４－エトキシブチル（メタ）アクリレート、４－プロポキシブチル（メタ）アクリレート、４－イソプロポキシブチル（メタ）アクリレート、４－ブトキシブチル（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１種以上であり、
前記（Ｃ）官能基にカルボキシル基を含有せず水酸基を含有する共重合性ビニルモノマーが、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（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、６－ヒドロキシヘキシル（メタ）アクリレート、８－ヒドロキシオクチル（メタ）アクリレート、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）アクリルアミドからなる化合物群から選択した１種以上であり、
前記（Ａ）と前記（Ｂ）との合計が１００重量部となる割合で含有してなり、
前記粘着剤組成物が、前記（Ａ）と前記（Ｂ）との合計１００重量部に対して、（Ｄ）架橋剤を０．０１～５重量部の割合で含有してなり、
前記粘着剤組成物によって形成された、塗工厚み２５０μｍの粘着剤層を、６０℃、９０％ＲＨの雰囲気下で２４０時間放置後、室温環境に取り出した際のヘイズ値が、４．０％以下であることを特徴とする粘着剤組成物。 A pressure-sensitive adhesive composition containing an acrylic polymer and a cross-linking agent.
The acrylic polymer is
(A) The total amount of at least one of an alkyl (meth) acrylate monomer having an alkyl group having C1 to C14 and an alkyl (meth) acrylate monomer containing a phenoxy group is 50 to 95 parts by weight.
(B) At least one of a nitrogen-containing vinyl monomer containing no hydroxyl group and a carboxyl group or an alkoxy group-containing alkyl (meth) acrylate monomer is 5 to 50 parts by weight.
(C) A total of 0.5 to 10 parts by weight of at least one hydroxyl group-containing (meth) acrylic acid ester, which is a copolymerizable vinyl monomer containing a hydroxyl group without containing a carboxyl group in the functional group.
A copolymer consisting of a weight average molecular weight of 200,000 to 2 million,
The (B) alkoxy group-containing alkyl (meth) acrylate monomer is 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 2-isopropoxyethyl (meth). Acrylate, 2-butoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 2-ethoxypropyl (meth) acrylate, 2-propoxypropyl (meth) acrylate, 2-isopropoxypropyl (meth) acrylate, 2- Butoxypropyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 3-propoxypropyl (meth) acrylate, 3-isopropoxypropyl (meth) acrylate, 3-butoxypropyl (meth) ) Acrylate, 4-methoxybutyl (meth) acrylate, 4-ethoxybutyl (meth) acrylate, 4-propoxybutyl (meth) acrylate, 4-isopropoxybutyl (meth) acrylate, 4-butoxybutyl (meth) acrylate. One or more selected from the compound group,
The copolymerizable vinyl monomer (C) which does not contain a carboxyl group but contains a hydroxyl group is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, or 3-hydroxypropyl (meth) acrylate. , 4-Hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl ( Meta) One or more selected from the group of compounds consisting of acrylamide,
The content is such that the total of the above (A) and the above (B) is 100 parts by weight.
The pressure-sensitive adhesive composition contains 0.01 to 5 parts by weight of the (D) cross-linking agent with respect to 100 parts by weight of the total of (A) and (B).
The haze value when the pressure-sensitive adhesive layer having a coating thickness of 250 μm formed by the pressure-sensitive adhesive composition was left in an atmosphere of 60 ° C. and 90% RH for 240 hours and then taken out to a room temperature environment was 4.0%. A pressure-sensitive adhesive composition comprising the following.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022085979A JP7328403B2 (en) | 2020-04-01 | 2022-05-26 | Adhesive composition, adhesive film, touch panel film, electronic paper film, organic EL film |
| JP2023127211A JP2023133566A (en) | 2020-04-01 | 2023-08-03 | Adhesive composition, adhesive film, film for touch panel, film for electronic paper and film for organic el |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020065847A JP6898491B2 (en) | 2018-03-14 | 2020-04-01 | Adhesive film |
| JP2021097217A JP7082232B2 (en) | 2020-04-01 | 2021-06-10 | Adhesive film |
| JP2022085979A JP7328403B2 (en) | 2020-04-01 | 2022-05-26 | Adhesive composition, adhesive film, touch panel film, electronic paper film, organic EL film |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2021097217A Division JP7082232B2 (en) | 2020-04-01 | 2021-06-10 | Adhesive film |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2023127211A Division JP2023133566A (en) | 2020-04-01 | 2023-08-03 | Adhesive composition, adhesive film, film for touch panel, film for electronic paper and film for organic el |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2022105711A true JP2022105711A (en) | 2022-07-14 |
| JP7328403B2 JP7328403B2 (en) | 2023-08-16 |
Family
ID=87761058
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2022085979A Active JP7328403B2 (en) | 2020-04-01 | 2022-05-26 | Adhesive composition, adhesive film, touch panel film, electronic paper film, organic EL film |
| JP2023127211A Pending JP2023133566A (en) | 2020-04-01 | 2023-08-03 | Adhesive composition, adhesive film, film for touch panel, film for electronic paper and film for organic el |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2023127211A Pending JP2023133566A (en) | 2020-04-01 | 2023-08-03 | Adhesive composition, adhesive film, film for touch panel, film for electronic paper and film for organic el |
Country Status (1)
| Country | Link |
|---|---|
| JP (2) | JP7328403B2 (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001123136A (en) * | 1999-10-28 | 2001-05-08 | Soken Chem & Eng Co Ltd | Moisture-resistant adhesive sheet and its use |
| JP2003329838A (en) * | 2002-05-15 | 2003-11-19 | Nitto Denko Corp | Pressure-sensitive adhesive optical film, pressure- sensitive adhesive composition for optical film and image display device |
| JP2007138057A (en) * | 2005-11-21 | 2007-06-07 | Soken Chem & Eng Co Ltd | Adhesive composition for optical film and adhesive sheet, and optical member using the same |
| JP2009079203A (en) * | 2007-09-06 | 2009-04-16 | Nitto Denko Corp | Pressure-sensitive adhesive composition, pressure-sensitive adhesive product and display using it |
| 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 |
| KR20100018414A (en) * | 2008-08-06 | 2010-02-17 | 동우 화인켐 주식회사 | Anti- static and anti-light leakage adhesive composition and polarizing plate using the composition |
| JP2010077287A (en) * | 2008-09-26 | 2010-04-08 | Nitto Denko Corp | Adhesive sheet for bonding optical component material |
| JP2010229246A (en) * | 2009-03-26 | 2010-10-14 | Daio Paper Corp | Pressure-sensitive adhesive sheet |
| JP2010285548A (en) * | 2009-06-11 | 2010-12-24 | Nitto Denko Corp | Adhesive tape for optical member |
| JP2011511100A (en) * | 2008-01-11 | 2011-04-07 | エルジー・ケム・リミテッド | Adhesive composition, polarizing plate containing the same, and liquid crystal display device |
| WO2011111575A1 (en) * | 2010-03-10 | 2011-09-15 | 日東電工株式会社 | Adhesive sheet for optical use |
| JP2011195651A (en) * | 2010-03-18 | 2011-10-06 | Saiden Chemical Industry Co Ltd | Self-adhesive composition for optical use |
-
2022
- 2022-05-26 JP JP2022085979A patent/JP7328403B2/en active Active
-
2023
- 2023-08-03 JP JP2023127211A patent/JP2023133566A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001123136A (en) * | 1999-10-28 | 2001-05-08 | Soken Chem & Eng Co Ltd | Moisture-resistant adhesive sheet and its use |
| JP2003329838A (en) * | 2002-05-15 | 2003-11-19 | Nitto Denko Corp | Pressure-sensitive adhesive optical film, pressure- sensitive adhesive composition for optical film and image display device |
| JP2007138057A (en) * | 2005-11-21 | 2007-06-07 | Soken Chem & Eng Co Ltd | Adhesive composition for optical film and adhesive sheet, and optical member using the same |
| JP2009079203A (en) * | 2007-09-06 | 2009-04-16 | Nitto Denko Corp | Pressure-sensitive adhesive composition, pressure-sensitive adhesive product and display using it |
| JP2011511100A (en) * | 2008-01-11 | 2011-04-07 | エルジー・ケム・リミテッド | Adhesive composition, polarizing plate containing the same, and liquid crystal display device |
| 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 |
| KR20100018414A (en) * | 2008-08-06 | 2010-02-17 | 동우 화인켐 주식회사 | Anti- static and anti-light leakage adhesive composition and polarizing plate using the composition |
| JP2010077287A (en) * | 2008-09-26 | 2010-04-08 | Nitto Denko Corp | Adhesive sheet for bonding optical component material |
| JP2010229246A (en) * | 2009-03-26 | 2010-10-14 | Daio Paper Corp | Pressure-sensitive adhesive sheet |
| JP2010285548A (en) * | 2009-06-11 | 2010-12-24 | Nitto Denko Corp | Adhesive tape for optical member |
| WO2011111575A1 (en) * | 2010-03-10 | 2011-09-15 | 日東電工株式会社 | Adhesive sheet for optical use |
| JP2011195651A (en) * | 2010-03-18 | 2011-10-06 | Saiden Chemical Industry Co Ltd | Self-adhesive composition for optical use |
Also Published As
| Publication number | Publication date |
|---|---|
| JP7328403B2 (en) | 2023-08-16 |
| JP2023133566A (en) | 2023-09-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5851166B2 (en) | Adhesive composition and adhesive film | |
| JP6463859B2 (en) | Adhesive composition and adhesive film | |
| KR102027126B1 (en) | Adhesive layer and adhesive film | |
| JP6796151B2 (en) | Adhesive film | |
| JP6687655B2 (en) | Adhesive composition and adhesive film | |
| JP6646374B2 (en) | Adhesive composition and adhesive film | |
| JP6898491B2 (en) | Adhesive film | |
| JP7082232B2 (en) | Adhesive film | |
| JP7328403B2 (en) | Adhesive composition, adhesive film, touch panel film, electronic paper film, organic EL film | |
| JP7125462B2 (en) | adhesive film | |
| JP6920483B2 (en) | Adhesive layer and adhesive film | |
| JP6270972B2 (en) | Adhesive layer and adhesive film | |
| JP7065229B2 (en) | Adhesive layer and adhesive film | |
| JP7092823B2 (en) | Adhesive layer and adhesive film | |
| CN111849361B (en) | Adhesive composition for optical use, and adhesive film and adhesive sheet each using the same | |
| TWI840551B (en) | Optical adhesive composition, and adhesive film, adhesive sheet using the same | |
| JP6810185B2 (en) | Adhesive layer and adhesive film | |
| JP6793233B2 (en) | Light diffusion adhesive film | |
| JP2018016801A (en) | Adhesive layer and adhesive film | |
| JP2021042392A (en) | Adhesive layer and adhesive film | |
| JP2021011589A (en) | Light diffusion adhesive film | |
| JP2017222879A (en) | Adhesive layer and adhesive film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20220526 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20230418 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20230616 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20230704 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20230803 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7328403 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |