JP2021102681A - Adhesive composition and adhesive film - Google Patents
Adhesive composition and adhesive film Download PDFInfo
- Publication number
- JP2021102681A JP2021102681A JP2019233900A JP2019233900A JP2021102681A JP 2021102681 A JP2021102681 A JP 2021102681A JP 2019233900 A JP2019233900 A JP 2019233900A JP 2019233900 A JP2019233900 A JP 2019233900A JP 2021102681 A JP2021102681 A JP 2021102681A
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- sensitive adhesive
- meth
- acrylate
- adhesive composition
- 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
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- 239000000203 mixture Substances 0.000 title claims abstract description 90
- 239000000853 adhesive Substances 0.000 title claims abstract description 28
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 28
- 239000002313 adhesive film Substances 0.000 title abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 166
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 73
- 239000000178 monomer Substances 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000004132 cross linking Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 190
- 239000010410 layer Substances 0.000 claims description 96
- 125000000217 alkyl group Chemical group 0.000 claims description 82
- -1 isocyanate compound Chemical class 0.000 claims description 49
- 238000002834 transmittance Methods 0.000 claims description 21
- 229920002554 vinyl polymer Polymers 0.000 claims description 21
- 150000001875 compounds Chemical group 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000002723 alicyclic group Chemical group 0.000 claims description 11
- 229920001903 high density polyethylene Polymers 0.000 claims description 10
- 239000004700 high-density polyethylene Substances 0.000 claims description 10
- 229920006267 polyester film Polymers 0.000 claims description 7
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 claims description 5
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 abstract description 40
- 230000035699 permeability Effects 0.000 abstract description 18
- 239000012790 adhesive layer Substances 0.000 abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 7
- 239000010408 film Substances 0.000 description 64
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 26
- 239000007789 gas Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 18
- 239000012788 optical film Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- 238000000691 measurement method Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000003926 acrylamides Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 239000010409 thin film 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
- JSCDRVVVGGYHSN-UHFFFAOYSA-N 8-hydroxyoctyl prop-2-enoate Chemical compound OCCCCCCCCOC(=O)C=C JSCDRVVVGGYHSN-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
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 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 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000825 pharmaceutical preparation Substances 0.000 description 2
- 229940127557 pharmaceutical product Drugs 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- ATZHWSYYKQKSSY-UHFFFAOYSA-N tetradecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C(C)=C ATZHWSYYKQKSSY-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical compound CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- MMEJYPZZFYTVLJ-WAYWQWQTSA-N (z)-2-(2-prop-2-enoyloxyethyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(C(O)=O)\CCOC(=O)C=C MMEJYPZZFYTVLJ-WAYWQWQTSA-N 0.000 description 1
- KCZQSKKNAGZQSZ-UHFFFAOYSA-N 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazin-2,4,6-trione Chemical compound O=C=NCCCCCCN1C(=O)N(CCCCCCN=C=O)C(=O)N(CCCCCCN=C=O)C1=O KCZQSKKNAGZQSZ-UHFFFAOYSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- NQUXRXBRYDZZDL-UHFFFAOYSA-N 1-(2-prop-2-enoyloxyethyl)cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1(CCOC(=O)C=C)C(O)=O NQUXRXBRYDZZDL-UHFFFAOYSA-N 0.000 description 1
- PWMLMBQHHBLIQM-UHFFFAOYSA-N 1-(3-prop-2-enoyloxypropyl)cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1(CCCOC(=O)C=C)C(O)=O PWMLMBQHHBLIQM-UHFFFAOYSA-N 0.000 description 1
- ZWJFRNCFFGAVHP-UHFFFAOYSA-N 1-methyl-1-(1-methylcycloheptyl)cycloheptane Chemical group CC1(CCCCCC1)C1(CCCCCC1)C ZWJFRNCFFGAVHP-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- RESPXSHDJQUNTN-UHFFFAOYSA-N 1-piperidin-1-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCCCC1 RESPXSHDJQUNTN-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
- STFXXRRQKFUYEU-UHFFFAOYSA-N 16-methylheptadecyl prop-2-enoate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)C=C STFXXRRQKFUYEU-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- YDRQKFSCVSLQKI-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethyl)cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1(CCOC(=O)C=C)C(O)=O YDRQKFSCVSLQKI-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
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- UXTGJIIBLZIQPK-UHFFFAOYSA-N 3-(2-prop-2-enoyloxyethyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(CCOC(=O)C=C)=C1C(O)=O UXTGJIIBLZIQPK-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-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
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-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
- 229920002799 BoPET Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical group C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 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
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 238000007718 adhesive strength test Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 150000008378 aryl ethers Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 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
- 230000001588 bifunctional effect Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- ARUKYTASOALXFG-UHFFFAOYSA-N cycloheptylcycloheptane Chemical group C1CCCCCC1C1CCCCCC1 ARUKYTASOALXFG-UHFFFAOYSA-N 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
- NLUNLVTVUDIHFE-UHFFFAOYSA-N cyclooctylcyclooctane Chemical group C1CCCCCCC1C1CCCCCCC1 NLUNLVTVUDIHFE-UHFFFAOYSA-N 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
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000009826 distribution Methods 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
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 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
- ZNAOFAIBVOMLPV-UHFFFAOYSA-N hexadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(C)=C ZNAOFAIBVOMLPV-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
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
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- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
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- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
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- 239000012466 permeate Substances 0.000 description 1
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- 229920006255 plastic film Polymers 0.000 description 1
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- 125000003367 polycyclic group Chemical group 0.000 description 1
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- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
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- 150000003077 polyols Chemical class 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XZHNPVKXBNDGJD-UHFFFAOYSA-N tetradecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C=C XZHNPVKXBNDGJD-UHFFFAOYSA-N 0.000 description 1
- 238000000427 thin-film deposition 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
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- 239000012780 transparent material Substances 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
- 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
- 229920001567 vinyl ester resin Polymers 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- 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
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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]
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J2433/00—Presence of (meth)acrylic polymer
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
Description
本発明は、水蒸気透過率が低く、水蒸気バリア性に優れた粘着剤層を形成することができる粘着剤組成物、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。 The present invention relates to a pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive layer having a low water vapor permeability and an excellent water vapor barrier property, and a pressure-sensitive adhesive film using the same.
従来から、特定の医薬品、有機ＥＬ（有機エレクトロルミネッセンス）ディスプレイ、電子ペーパーなどでは、大気中の水分及び酸素が、内容物の医薬品、発光素子などに悪影響を及ぼすことを避けるために、ガスバリア性フィルムを用いて内容物を密封することが行われている。
また、近年、自ら発光する発光素子を用いた有機ＥＬディスプレイが、液晶ディスプレイに比べて画像が鮮明であることから、テレビ、スマートフォン、デジタルサイネージなどのディスプレイとして、徐々に普及しつつある。
特に、有機ＥＬディスプレイの発光素子は、耐湿性が低い有機物で形成されているため、大気中の水分に対して極めて脆弱である。そこで、従来は、発光素子の基材及び封止部材として、ガスバリア性と耐熱性を有する薄いガラス基板が用いられてきた。ところが、近年、有機ＥＬディスプレイのフレキシブル化が進められ、薄いガラス基板を代替する透明な基材として、ガスバリア性フィルムが用いられている。また、ガスバリア性フィルムを貼り合せるために、ガスバリア性を有する粘着剤層が用いられている。
例えば、特許文献１には、高いガスバリア性が必要とされる食品、医薬品の包装用途や太陽電池、電子ペーパー、有機ＥＬディスプレイなどの電子部材の用途に使用される、ガスバリア性フィルムが開示されている。
Conventionally, in specific pharmaceutical products, organic EL (organic electroluminescence) displays, electronic papers, etc., gas barrier films have been used to prevent moisture and oxygen in the atmosphere from adversely affecting the pharmaceutical products and light emitting elements of the contents. The contents are sealed using.
Further, in recent years, an organic EL display using a light emitting element that emits light by itself has a clearer image than a liquid crystal display, and thus is gradually becoming widespread as a display for televisions, smartphones, digital signage, and the like.
In particular, the light emitting element of the organic EL display is extremely vulnerable to moisture in the atmosphere because it is made of an organic substance having low moisture resistance. Therefore, conventionally, a thin glass substrate having gas barrier properties and heat resistance has been used as a base material and a sealing member for a light emitting element. However, in recent years, the flexibility of organic EL displays has been promoted, and gas barrier films have been used as transparent base materials to replace thin glass substrates. Further, in order to bond the gas barrier film, a pressure-sensitive adhesive layer having a gas barrier property is used.
For example, Patent Document 1 discloses a gas barrier film used for packaging foods and pharmaceuticals requiring high gas barrier properties and for electronic members such as solar cells, electronic papers, and organic EL displays. There is.
従来のプラズマＣＶＤ法によりケイ素酸化物を主成分とした蒸着膜によるガスバリア層を形成する方法では、有機ＥＬディスプレイや電子ペーパー用途で必要とされる水蒸気透過率１×１０−３ｇ／（ｍ２・ｄａｙ）以下の高いガスバリア性を得るためには、蒸着膜を厚膜化する必要がある。ところが、形成されたガスバリア層が非常に緻密かつ高硬度な層であるため、このような厚膜の蒸着膜の場合には、ガスバリア性フィルムを曲げたときに、蒸着膜にクラックが発生し、ガスバリア性が低下するという課題があった。 In the method of forming a gas barrier layer by a thin-film deposition film containing silicon oxide as a main component by the conventional plasma CVD method, the water vapor transmittance required for organic EL displays and electronic paper applications is 1 × 10 -3 g / (m 2). -In order to obtain a high gas barrier property of day) or less, it is necessary to thicken the vapor-deposited film. However, since the formed gas barrier layer is a very dense and high-hardness layer, in the case of such a thick-film vapor-deposited film, cracks occur in the vapor-deposited film when the gas-barrier film is bent. There was a problem that the gas barrier property was lowered.
そこで、特許文献１に係わる発明のガスバリア性フィルムは、高分子フィルム基材の少なくとも片面に、蒸着膜からなるガスバリア層を有するガスバリアフィルムであって、前記ガスバリア層は高分子フィルム基材の側から、周期律表第３族から第１４族に属する金属元素のうち少なくとも１つの元素を含む化合物を主成分とする第１の層と、ケイ素化合物を主成分とする第２の層がこの順に積層されている。さらに、各層の厚みを特定の範囲にすることにより、高温環境や屈曲に対してもガスバリア性が低下し難い、高度なガスバリア性を有するガスバリア性フィルムが得られるとしている。 Therefore, the gas barrier film of the invention according to Patent Document 1 is a gas barrier film having a gas barrier layer made of a vapor-deposited film on at least one side of the polymer film base material, and the gas barrier layer is from the side of the polymer film base material. , A first layer containing a compound containing at least one of the metal elements belonging to Groups 3 to 14 of the Periodic Table as a main component and a second layer containing a silicon compound as a main component are laminated in this order. Has been done. Furthermore, by setting the thickness of each layer within a specific range, it is said that a gas barrier film having a high degree of gas barrier property can be obtained, in which the gas barrier property is unlikely to decrease even in a high temperature environment or bending.
また、特許文献２には、有機ＥＬ素子等のディスプレイデバイスなど、電子デバイスの封止に好適に用いられる粘着性組成物および該組成物から得られる粘着性シートが開示されている。特許文献２の発明に係わる粘着剤組成物によれば、特定分子量のポリイソブチレン系樹脂とポリブテン樹脂とを使用したことにより、目的の粘着物性を発現させるとともに、水蒸気透過率を低下させることができ、外部からの水分の浸入を防止することができるとしている。 Further, Patent Document 2 discloses an adhesive composition preferably used for sealing an electronic device such as a display device such as an organic EL element, and an adhesive sheet obtained from the composition. According to the pressure-sensitive adhesive composition according to the invention of Patent Document 2, by using a polyisobutylene-based resin having a specific molecular weight and a polybutene resin, the desired sticky physical properties can be exhibited and the water vapor permeability can be reduced. , It is said that it is possible to prevent the ingress of moisture from the outside.
また、特許文献３には、湿熱条件下においても白化せず、透明性やガスバリア性に優れる粘着剤組成物が開示されている。特許文献３の発明に係わる粘着剤組成物によれば、粘着付与樹脂を含有する粘着剤組成物とすることにより、ガスバリア性が顕著に向上し、相溶性が良好となるとしている。 Further, Patent Document 3 discloses a pressure-sensitive adhesive composition which does not whiten even under moist heat conditions and has excellent transparency and gas barrier properties. According to the pressure-sensitive adhesive composition according to the invention of Patent Document 3, the pressure-sensitive adhesive composition containing the pressure-sensitive adhesive resin remarkably improves the gas barrier property and improves the compatibility.
しかし、特許文献１に記載の発明に係わるガスバリア性フィルムは、基材の片面にスパッタ・ＣＶＤ装置を使用して金属薄膜層の蒸着膜を形成することによりガスバリア性を発揮させている。そのため、例えば、厚みが１８８μｍのポリエステルフィルムのような、相当な剛性を有する基材を使用する必要があり、適度な柔軟性を有する粘着剤層に、蒸着膜を積層してガスバリア性を持たせることには適用できなかった。
また、特許文献２に記載の発明に係わる粘着剤組成物は、オレフィン系樹脂であるポリブテン樹脂を含有しているため、紫外線による劣化により黄変することを、酸化防止剤により防止するとしても、潜在的に時間の経過と共に変色することが避けられないという問題がある。このため、紫外線による変色が起こらない粘着剤組成物が求められていた。
また、特許文献３に記載の発明に係わる粘着剤組成物を用いた粘着シートにおいて、厚みが１００μｍの粘着剤層が形成された実施例１〜６の粘着シートでは、水蒸気透過率が７０〜１１０ｇ／（ｍ２・ｄａｙ）である。しかし、厚みが１００μｍの粘着剤層では厚膜であることにより、適用範囲に制約を受ける。このため、粘着剤層が薄膜でも、優れた水蒸気バリア性を有することが求められている。さらに、各種ディスプレイに用いられる光学用粘着フィルムでは、視認性を向上させるために高透明性が必要とされている。
However, the gas barrier film according to the invention described in Patent Document 1 exhibits gas barrier properties by forming a vapor-deposited film of a metal thin film layer on one side of a base material using a sputtering / CVD device. Therefore, for example, it is necessary to use a base material having considerable rigidity such as a polyester film having a thickness of 188 μm, and a vapor-deposited film is laminated on an adhesive layer having appropriate flexibility to provide gas barrier properties. It couldn't be applied to that.
Further, since the pressure-sensitive adhesive composition according to the invention described in Patent Document 2 contains a polybutene resin which is an olefin resin, even if an antioxidant is used to prevent yellowing due to deterioration due to ultraviolet rays, There is a potential problem that discoloration is unavoidable over time. Therefore, there has been a demand for an adhesive composition that does not cause discoloration due to ultraviolet rays.
Further, in the pressure-sensitive adhesive sheet using the pressure-sensitive adhesive composition according to the invention described in Patent Document 3, the pressure-sensitive adhesive sheets of Examples 1 to 6 in which the pressure-sensitive adhesive layer having a thickness of 100 μm is formed have a water vapor transmittance of 70 to 110 g. a / (m 2 · day). However, the pressure-sensitive adhesive layer having a thickness of 100 μm is limited in the applicable range because it is a thick film. Therefore, even if the pressure-sensitive adhesive layer is a thin film, it is required to have an excellent water vapor barrier property. Further, the optical adhesive film used for various displays is required to have high transparency in order to improve visibility.
上記の問題に鑑み、本発明は、一般的な構造を有するアクリル系モノマーのみを含有した粘着剤組成物であるにも拘らず、水蒸気透過率が低く、水蒸気バリア性に優れた粘着剤層を得ることができる粘着剤組成物、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。 In view of the above problems, the present invention provides a pressure-sensitive adhesive layer having a low water vapor permeability and an excellent water vapor barrier property, even though it is a pressure-sensitive adhesive composition containing only an acrylic monomer having a general structure. It is an object of the present invention to provide a pressure-sensitive adhesive composition that can be obtained and a pressure-sensitive adhesive film using the same.
低い透湿度である粘着剤組成物に関して、一般的に、アクリル系ポリマーから得られる厚みが１００μｍの粘着剤層においては、水蒸気透過率を測定すると３００ｇ／（ｍ２・ｄａｙ）以上の高い数値を示している。また、粘着剤層の厚さが薄いほど水蒸気バリア性は低下するため、粘着剤層を薄膜にすると、水蒸気透過率の値は、さらに高い値を示すことになる。前記の課題を解決した、本発明の粘着剤組成物は、粘着剤層の厚さが２５μｍのときの水蒸気透過率が、１００ｇ／（ｍ２・ｄａｙ）以下であり、優れた水蒸気バリア性を有する粘着剤層が得られることを特徴としている。 Regarding the pressure-sensitive adhesive composition having a low moisture permeability, in general, in a pressure-sensitive adhesive layer having a thickness of 100 μm obtained from an acrylic polymer, the water vapor permeability is measured to be as high as 300 g / (m 2 · day) or more. Shown. Further, the thinner the pressure-sensitive adhesive layer, the lower the water vapor barrier property. Therefore, when the pressure-sensitive adhesive layer is made into a thin film, the value of the water vapor transmittance becomes even higher. The pressure-sensitive adhesive composition of the present invention, which solves the above-mentioned problems, has a water vapor permeability of 100 g / (m 2 · day) or less when the thickness of the pressure-sensitive adhesive layer is 25 μm, and has excellent water vapor barrier properties. It is characterized in that a pressure-sensitive adhesive layer is obtained.
本発明は、粘着剤組成物として、少なくとも、
（Ａ−１）アルキル基の炭素数がＣ１４以上〜Ｃ２０以下のアルキル（メタ）アクリレートの少なくとも１種以上と、
（Ｂ）水酸基を含有する（メタ）アクリレートの少なくとも１種以上とを、カルボキシ基を含有するビニルモノマー、及びアミノ基等の窒素含有ビニルモノマーを含有させずに共重合させたアクリル系ポリマーと、
（Ｃ）架橋剤として３官能以上のイソシアネート化合物とを含有する粘着剤組成物を用いて、該粘着剤組成物を架橋させた粘着剤層とすることを技術思想としている。その結果、一般的な構造を有するアクリル系モノマーのみを含有した粘着剤組成物であるにも拘らず、従来にない低い透湿度を有する粘着剤層が得られることを見い出し、本発明を完成させることができた。
The present invention, as a pressure-sensitive adhesive composition, at least
(A-1) At least one type of alkyl (meth) acrylate having an alkyl group having a carbon number of C14 or more and C20 or less.
(B) An acrylic polymer obtained by copolymerizing at least one (meth) acrylate containing a hydroxyl group without containing a vinyl monomer containing a carboxy group and a nitrogen-containing vinyl monomer such as an amino group.
(C) The technical idea is to use a pressure-sensitive adhesive composition containing a trifunctional or higher functional isocyanate compound as a cross-linking agent to form a cross-linked pressure-sensitive pressure-sensitive adhesive layer. As a result, it has been found that a pressure-sensitive adhesive layer having an unprecedentedly low moisture permeability can be obtained even though the pressure-sensitive adhesive composition contains only an acrylic monomer having a general structure, and completes the present invention. I was able to.
前記の課題を解決するため、本発明は、モノマー成分として（メタ）アクリレートのみを共重合させてなるアクリル系ポリマーと、（Ｃ）架橋剤とを含有する粘着剤組成物であって、前記粘着剤組成物を架橋してなる粘着剤層の厚さを２５μｍとしたときの、該粘着剤層の水蒸気透過率が、ＪＩＳ Ｋ７１２９に準拠した赤外線センサ法を用いて測定したとき、３２℃×９０％ＲＨ雰囲気下において１００ｇ／（ｍ２・ｄａｙ）以下であることを特徴とする粘着剤組成物を提供する。 In order to solve the above-mentioned problems, the present invention is a pressure-sensitive adhesive composition containing an acrylic polymer obtained by copolymerizing only (meth) acrylate as a monomer component and (C) a cross-linking agent. When the thickness of the pressure-sensitive adhesive layer formed by cross-linking the agent composition is 25 μm, the water vapor permeability of the pressure-sensitive adhesive layer is 32 ° C. × 90 when measured using an infrared sensor method based on JIS K7129. Provided is a pressure-sensitive adhesive composition characterized by being 100 g / (m 2 · day) or less under a% RH atmosphere.
前記粘着剤組成物に含まれる前記アクリル系ポリマーが、
（Ａ−１）アルキル基の炭素数がＣ１４以上〜Ｃ２０以下のアルキル（メタ）アクリレートの少なくとも１種以上の合計を１００重量部、又は、（Ａ−２）アルキル基の炭素数がＣ１４以上〜Ｃ２０以下のアルキル（メタ）アクリレートの少なくとも１種以上の合計を８５〜１００重量部と、アルキル基の炭素数がＣ１以上〜Ｃ１３以下のアルキル（メタ）アクリレート、脂環式炭化水素基を含有する（メタ）アクリレート、芳香環構造を含有する（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１種以上の合計を１５〜０．０重量部との合計を１００重量部と、
（Ｂ）水酸基を含有する（メタ）アクリレートの少なくとも１種以上の合計を０．１〜５．０重量部と、
をカルボキシ基を含有するビニルモノマー、及び窒素含有ビニルモノマーを含有させないで共重合させた重量平均分子量５万〜１５０万のアクリル系ポリマーであり、
前記粘着剤組成物が、前記アクリル系ポリマーの１００重量部に対して、前記（Ｃ）架橋剤として３官能以上のイソシアネート化合物を０．０１〜２．０重量部の割合で含有してなることが好ましい。
The acrylic polymer contained in the pressure-sensitive adhesive composition
The total of at least one type of alkyl (meth) acrylate having (A-1) alkyl groups of C14 or more and C20 or less is 100 parts by weight, or (A-2) alkyl groups have C14 or more. A total of at least one or more alkyl (meth) acrylates having a C20 or less is contained in an amount of 85 to 100 parts by weight, an alkyl (meth) acrylate having an alkyl group having a carbon number of C1 or more and C13 or less, and an alicyclic hydrocarbon group. The total of at least one selected from the compound group consisting of (meth) acrylate and (meth) acrylate containing an aromatic ring structure is 15 to 0.0 parts by weight, and the total is 100 parts by weight.
(B) The total of at least one (meth) acrylate containing a hydroxyl group is 0.1 to 5.0 parts by weight.
Is a vinyl monomer containing a carboxy group and an acrylic polymer having a weight average molecular weight of 50,000 to 1.5 million obtained by copolymerizing without containing a nitrogen-containing vinyl monomer.
The pressure-sensitive adhesive composition contains 0.01 to 2.0 parts by weight of a trifunctional or higher functional isocyanate compound as the (C) cross-linking agent with respect to 100 parts by weight of the acrylic polymer. Is preferable.
前記アクリル系ポリマーのＳＰ値が９．０（ｃａｌ／ｃｍ３）０．５以下であることが好ましい。 The SP value of the acrylic polymer is preferably 9.0 (cal / cm 3 ) 0.5 or less.
前記粘着剤組成物を架橋してなる厚みが２５μｍの粘着剤層を、厚みが５０μｍのポリエステルフィルムの基材の片面に積層した粘着フィルムとし、ＪＩＳ Ｚ０２３７に準拠して前記粘着剤層の粘着力を測定したとき、高密度ポリエチレン樹脂に対する、前記粘着剤層の粘着力が１０Ｎ／２５ｍｍ以上であることが好ましい。 A pressure-sensitive adhesive layer having a thickness of 25 μm obtained by cross-linking the pressure-sensitive adhesive composition is formed into a pressure-sensitive adhesive film laminated on one side of a base material of a polyester film having a thickness of 50 μm, and the adhesive strength of the pressure-sensitive adhesive layer is in accordance with JIS Z0237. The adhesive strength of the pressure-sensitive adhesive layer to the high-density polyethylene resin is preferably 10 N / 25 mm or more.
前記アクリル系ポリマーが、前記アクリル系ポリマーの１００重量部に対して、アルキル基の炭素数がＣ１４以上〜Ｃ２０以下のアルキル（メタ）アクリレートの少なくとも１種以上の合計を８０重量部以上の割合で含有してなることが好ましい。 The acrylic polymer is a total of at least one type of alkyl (meth) acrylate having an alkyl group having C14 or more and C20 or less in a ratio of 80 parts by weight or more with respect to 100 parts by weight of the acrylic polymer. It is preferably contained.
前記（Ｂ）水酸基を含有する（メタ）アクリレートが、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−ヒドロキシプロピル（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ばれた少なくとも１種であることが好ましい。 The (meth) acrylate containing the (B) hydroxyl group is 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, It is preferably at least one selected from the group of compounds consisting of 2-hydroxyethyl (meth) acrylate.
前記粘着剤組成物を架橋してなる粘着剤層の、厚さが２５μｍのときの全光線透過率が９０％以上、且つヘイズ値が１．０％以下であることが好ましい。 When the thickness of the pressure-sensitive adhesive layer formed by cross-linking the pressure-sensitive adhesive composition is 25 μm, the total light transmittance is preferably 90% or more and the haze value is preferably 1.0% or less.
また、本発明は、前記粘着剤組成物を架橋してなる粘着剤層を、基材の少なくとも片面に形成してなる粘着フィルムを提供する。 The present invention also provides a pressure-sensitive adhesive film in which a pressure-sensitive adhesive layer formed by cross-linking the pressure-sensitive adhesive composition is formed on at least one surface of a base material.
本発明の粘着剤組成物は、一般的な構造を有するアクリル系モノマーのみを含有した粘着剤組成物であるにも拘らず、水蒸気透過率が低く、水蒸気バリア性に優れた粘着剤層を得ることができる。 Although the pressure-sensitive adhesive composition of the present invention is a pressure-sensitive adhesive composition containing only an acrylic monomer having a general structure, a pressure-sensitive adhesive layer having a low water vapor permeability and an excellent water vapor barrier property can be obtained. be able to.
以下、好適な実施形態に基づいて、本発明を説明する。 Hereinafter, the present invention will be described based on preferred embodiments.
本実施形態の粘着剤組成物は、モノマー成分として（メタ）アクリレートのみを共重合させてなるアクリル系ポリマーと、（Ｃ）架橋剤とを含有する粘着剤組成物であって、前記粘着剤組成物を架橋してなる粘着剤層の厚さを２５μｍとしたときの、該粘着剤層の水蒸気透過率が、ＪＩＳ Ｋ７１２９に準拠した赤外線センサ法を用いて測定したとき、３２℃×９０％ＲＨ雰囲気下において１００ｇ／（ｍ２・ｄａｙ）以下であることを特徴とする。 The pressure-sensitive adhesive composition of the present embodiment is a pressure-sensitive adhesive composition containing an acrylic polymer obtained by copolymerizing only (meth) acrylate as a monomer component and (C) a cross-linking agent. When the thickness of the pressure-sensitive adhesive layer formed by cross-linking an object is 25 μm, the water vapor permeability of the pressure-sensitive adhesive layer is 32 ° C. × 90% RH when measured using an infrared sensor method compliant with JIS K7129. It is characterized in that it is 100 g / (m 2 · day) or less in an atmosphere.
前記アクリル系ポリマーは、粘着剤組成物の主剤として機能する。前記アクリル系ポリマーを構成するモノマー成分としては、（メタ）アクリレートが好ましい。（メタ）アクリレートは、アクリレートの１種以上でもよく、メタクリレートの１種以上でもよく、アクリレートの１種以上とメタクリレートの１種以上との混合物でもよい。また、本発明の粘着剤組成物は、一般的な構造を有するアクリル系モノマーのみを含有した粘着剤組成物とするため、前記アクリル系ポリマーは、（メタ）アクリレート以外の共重合性モノマー成分、例えば（メタ）アクリルアミド等のアミド系モノマー、（メタ）アクリロニトリル等のニトリル系モノマー、スチレン等のオレフィン系モノマー、酢酸ビニル等のビニルエステル等を含有しないことが好ましい。さらに、粘着剤層の被着体が、酸化インジウム錫（ＩＴＯ）などの金属表面である場合には、前記アクリル系ポリマーが、詳しくは後述するが、カルボキシ基を有する（メタ）アクリレートエステルモノマー、及び、（メタ）アクリル酸、（メタ）アクリル酸塩等の、該金属表面を腐食させる原因となる化合物を含有しないことが好ましい。 The acrylic polymer functions as a main component of the pressure-sensitive adhesive composition. As the monomer component constituting the acrylic polymer, (meth) acrylate is preferable. The (meth) acrylate may be one or more of acrylate, one or more of methacrylate, or a mixture of one or more of acrylate and one or more of methacrylate. Further, since the pressure-sensitive adhesive composition of the present invention is a pressure-sensitive adhesive composition containing only an acrylic monomer having a general structure, the acrylic polymer is a copolymerizable monomer component other than (meth) acrylate. For example, it is preferable not to contain an amide-based monomer such as (meth) acrylamide, a nitrile-based monomer such as (meth) acrylonitrile, an olefin-based monomer such as styrene, and a vinyl ester such as vinyl acetate. Further, when the adherend of the pressure-sensitive adhesive layer is a metal surface such as indium tin oxide (ITO), the acrylic polymer is a (meth) acrylate ester monomer having a carboxy group, which will be described in detail later. Further, it is preferable not to contain a compound such as (meth) acrylic acid or (meth) acrylate that causes corrosion of the metal surface.
前記モノマー成分の主成分となる（メタ）アクリレートとしては、（Ａ−１）アルキル基の炭素数がＣ１４以上〜Ｃ２０以下のアルキル（メタ）アクリレートの少なくとも１種以上、又は、（Ａ−２）アルキル基の炭素数がＣ１４以上〜Ｃ２０以下のアルキル（メタ）アクリレートの少なくとも１種以上と、アルキル基の炭素数がＣ１以上〜Ｃ１３以下のアルキル（メタ）アクリレート、脂環式炭化水素基を含有する（メタ）アクリレート、芳香環構造を含有する（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１種以上とが挙げられる。 As the (meth) acrylate which is the main component of the monomer component, at least one or more of (A-1) alkyl (meth) acrylates having an alkyl group having C14 or more and C20 or less carbon atoms, or (A-2). Contains at least one type of alkyl (meth) acrylate having an alkyl group having a carbon number of C14 to C20, an alkyl (meth) acrylate having an alkyl group having a carbon number of C1 to C13, and an alicyclic hydrocarbon group. At least one selected from the group of compounds consisting of (meth) acrylates and (meth) acrylates containing an aromatic ring structure can be mentioned.
前記（Ａ−１）及び（Ａ−２）に共通して用いられる、アルキル基の炭素数がＣ１４以上〜Ｃ２０以下のアルキル（メタ）アクリレートの具体例としては、テトラデシル（メタ）アクリレート、イソテトラデシル（メタ）アクリレート、ミリスチル（メタ）アクリレート、イソミリスチル（メタ）アクリレート等の、アルキル基の炭素数がＣ１４であるアルキル（メタ）アクリレート；ペンタデシル（メタ）アクリレート、イソペンタデシル（メタ）アクリレート等の、アルキル基の炭素数がＣ１５であるアルキル（メタ）アクリレート；ヘキサデシル（メタ）アクリレート、イソヘキサデシル（メタ）アクリレート、セチル（メタ）アクリレート、イソセチル（メタ）アクリレート等の、アルキル基の炭素数がＣ１６であるアルキル（メタ）アクリレート；ヘプタデシル（メタ）アクリレート、イソヘプタデシル（メタ）アクリレート等の、アルキル基の炭素数がＣ１７であるアルキル（メタ）アクリレート；オクタデシル（メタ）アクリレート、イソオクタデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレート等の、アルキル基の炭素数がＣ１８であるアルキル（メタ）アクリレート；ノナデシル（メタ）アクリレート、イソノナデシル（メタ）アクリレート等のアルキル基の炭素数がＣ１９であるアルキル（メタ）アクリレート；イコシル（メタ）アクリレート、イソイコシル（メタ）アクリレート等の、アルキル基の炭素数がＣ２０であるアルキル（メタ）アクリレートからなる群から選択される、少なくとも１種以上が挙げられる。 Specific examples of the alkyl (meth) acrylate having an alkyl group having a carbon number of C14 or more and C20 or less, which is commonly used in (A-1) and (A-2), are tetradecyl (meth) acrylate and isotetra. Alkyl (meth) acrylate having an alkyl group having C14 carbon atoms such as decyl (meth) acrylate, myristyl (meth) acrylate, and isomyristyl (meth) acrylate; pentadecyl (meth) acrylate, isopentadecyl (meth) acrylate, etc. Alkyl (meth) acrylate in which the number of carbon atoms of the alkyl group is C15; the number of carbon atoms of the alkyl group such as hexadecyl (meth) acrylate, isohexadecyl (meth) acrylate, cetyl (meth) acrylate, and isosetyl (meth) acrylate. Alkyl (meth) acrylate having C16; alkyl (meth) acrylate having an alkyl group having C17 carbon atoms such as heptadecyl (meth) acrylate and isoheptadecyl (meth) acrylate; octadecyl (meth) acrylate, isooctadecil (meth) Alkyl (meth) acrylates such as acrylates, stearyl (meth) acrylates and isostearyl (meth) acrylates having an alkyl group having a C18 carbon number; Alkyl (meth) acrylate having C19; at least one selected from the group consisting of alkyl (meth) acrylates having an alkyl group having C20 carbon atoms, such as icosyl (meth) acrylate and isoicosyl (meth) acrylate. Can be mentioned.
前記（Ａ−２）のうち、アルキル基の炭素数がＣ１以上〜Ｃ１３以下のアルキル（メタ）アクリレートとしては、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、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｓ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、イソペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、イソヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、イソヘプチル（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、イソデシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、イソウンデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、イソドデシル（メタ）アクリレート、トリデシル（メタ）アクリレート、イソトリデシル（メタ）アクリレート等が挙げられる。 Among the above (A-2), examples of the alkyl (meth) acrylate having an alkyl group having C1 or more and C13 or less have methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and isopropyl (meth). ) Acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate , Isohexyl (meth) acrylate, heptyl (meth) acrylate, isoheptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate , Decyl (meth) acrylate, Isodecyl (meth) acrylate, Undecyl (meth) acrylate, Isoundecyl (meth) acrylate, Dodecyl (meth) acrylate, Isododecyl (meth) acrylate, Tridecyl (meth) acrylate, Isotridecyl (meth) acrylate, etc. Can be mentioned.
前記（Ａ−２）のうち、脂環式炭化水素基を含有する（メタ）アクリレートの具体例としては、シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート等の、単環式の脂環式炭化水素基を含有する（メタ）アクリレート；イソボルニル（メタ）アクリレート、ビシクロヘプチル（メタ）アクリレート、ビシクロオクチル（メタ）アクリレート、ジメチルビシクロヘプチル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート等の、多環式の脂環式炭化水素基を含有する（メタ）アクリレートからなる群から選択される、少なくとも１種以上が挙げられる。 Among the above (A-2), specific examples of the (meth) acrylate containing an alicyclic hydrocarbon group include monocyclic alicyclic hydrocarbons such as cyclopentyl (meth) acrylate and cyclohexyl (meth) acrylate. Hydrocarbon-containing (meth) acrylates; isobornyl (meth) acrylates, bicycloheptyl (meth) acrylates, bicyclooctyl (meth) acrylates, dimethylbicycloheptyl (meth) acrylates, dicyclopentanyl (meth) acrylates, dicyclopentenyl At least one selected from the group consisting of (meth) acrylates containing polycyclic alicyclic hydrocarbon groups such as (meth) acrylate and dicyclopentenyloxyethyl (meth) acrylate can be mentioned.
前記（Ａ−２）のうち、芳香環構造を含有する（メタ）アクリレートとしては、ベンジル（メタ）アクリレート、ナフチル（メタ）アクリレート、フェニル（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、フェノキシエトキシエチル（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）アクリレート等の少なくとも１種以上が挙げられる。芳香環構造を含有する（メタ）アクリレートは、水酸基、カルボキシ基、窒素原子を含有しない（メタ）アクリレートであることが好ましい。例えば、芳香族炭化水素基を含有する（メタ）アクリレート、芳香族炭化水素基を含有するアルキル（メタ）アクリレート、芳香族エーテル基を含有するアルキル（メタ）アクリレートなどが挙げられる。 Among the above (A-2), examples of the (meth) acrylate containing an aromatic ring structure include benzyl (meth) acrylate, naphthyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, and phenoxybutyl (. Meta) acrylate, phenoxyethoxyethyl (meth) acrylate, 2- (1-naphthyloxy) ethyl (meth) acrylate, 2- (2-naphthyloxy) ethyl (meth) acrylate, 6- (1-naphthyloxy) hexyl ( At least one of meta) acrylate, 6- (2-naphthyloxy) hexyl (meth) acrylate, 8- (1-naphthyloxy) octyl (meth) acrylate, 8- (2-naphthyloxy) octyl (meth) acrylate, etc. The above can be mentioned. The (meth) acrylate containing an aromatic ring structure is preferably a (meth) acrylate containing no hydroxyl group, carboxy group, or nitrogen atom. For example, (meth) acrylate containing an aromatic hydrocarbon group, alkyl (meth) acrylate containing an aromatic hydrocarbon group, alkyl (meth) acrylate containing an aromatic ether group, and the like can be mentioned.
前記（Ａ−１）が、アルキル基の炭素数がＣ１４以上〜Ｃ２０以下のアルキル（メタ）アクリレートの２種以上の合計が１００重量部から構成されてもよい。また、前記（Ａ−２）の合計１００重量部のうち、アルキル基の炭素数がＣ１４以上〜Ｃ２０以下のアルキル（メタ）アクリレートの少なくとも１種以上の合計を８５〜１００重量部と、アルキル基の炭素数がＣ１以上〜Ｃ１３以下のアルキル（メタ）アクリレート、脂環式炭化水素基を含有する（メタ）アクリレート、芳香環構造を含有する（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１種以上の合計を１５〜０．０重量部とから構成されてもよい。
また、前記（Ａ−２）の合計１００重量部のうち、アルキル基の炭素数がＣ１４以上〜Ｃ２０以下のアルキル（メタ）アクリレートの少なくとも１種以上の合計を８５〜１００重量部と、アルキル基の炭素数がＣ１以上〜Ｃ１３以下のアルキル（メタ）アクリレート、脂環式炭化水素基を含有する（メタ）アクリレート、芳香環構造を含有する（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１種以上の特定の（メタ）アクリレートを、特定の割合範囲で含有することが、粘着剤層の水蒸気透過率を低減させる点において好ましい。
In (A-1), the total of two or more kinds of alkyl (meth) acrylates having an alkyl group having C14 or more and C20 or less may be composed of 100 parts by weight. Further, out of the total of 100 parts by weight of (A-2), the total of at least one kind of alkyl (meth) acrylate having an alkyl group having C14 or more and C20 or less is 85 to 100 parts by weight, and the alkyl group. Was selected from a group of compounds consisting of alkyl (meth) acrylates having a carbon number of C1 or more and C13 or less, (meth) acrylates containing an alicyclic hydrocarbon group, and (meth) acrylates containing an aromatic ring structure. A total of at least one or more may be composed of 15 to 0.0 parts by weight.
Further, out of the total of 100 parts by weight of (A-2), the total of at least one kind of alkyl (meth) acrylate having an alkyl group having C14 or more and C20 or less is 85 to 100 parts by weight, and the alkyl group. Was selected from a group of compounds consisting of an alkyl (meth) acrylate having a carbon number of C1 or more and C13 or less, a (meth) acrylate containing an alicyclic hydrocarbon group, and a (meth) acrylate containing an aromatic ring structure. It is preferable to contain at least one specific (meth) acrylate in a specific ratio range in terms of reducing the water vapor permeability of the pressure-sensitive adhesive layer.
例えば、前記アクリル系ポリマーの１００重量部に対して、アルキル基の炭素数がＣ１４以上〜Ｃ２０以下のアルキル（メタ）アクリレートの１種以上の合計を８０重量部以上の割合で含有してなることが好ましく、８５重量部以上の割合で含有してなることがより好ましく、９０重量部以上の割合で含有してなることが特に好ましい。また、前記アクリル系ポリマーの１００重量部に対して、アルキル基の炭素数がＣ１以上〜Ｃ１３以下のアルキル（メタ）アクリレート、脂環式炭化水素基を含有する（メタ）アクリレート又は芳香環構造を含有する（メタ）アクリレートから選択される少なくとも１種以上の合計を、２０重量部以下の割合で含有してなることが好ましく、１５重量部以下の割合で含有してなることがより好ましく、１０重量部以下の割合で含有してなることが特に好ましい。また、紫外線等の影響を抑制するため、脂環式炭化水素基を含有する（メタ）アクリレート及び芳香環構造を含有する（メタ）アクリレートとしては、前記アクリル系ポリマーの側鎖部分にオレフィン系二重結合を有しない化合物を選択することが好ましい。 For example, the total content of one or more alkyl (meth) acrylates having an alkyl group having C14 or more and C20 or less is contained in an amount of 80 parts by weight or more with respect to 100 parts by weight of the acrylic polymer. It is more preferable that the content is 85 parts by weight or more, and it is particularly preferable that the content is 90 parts by weight or more. Further, an alkyl (meth) acrylate having an alkyl group having C1 or more and C13 or less, a (meth) acrylate containing an alicyclic hydrocarbon group, or an aromatic ring structure is provided with respect to 100 parts by weight of the acrylic polymer. The total of at least one selected from the contained (meth) acrylates is preferably contained in a proportion of 20 parts by weight or less, more preferably 15 parts by weight or less, and 10 parts by weight or less. It is particularly preferable that the content is in a proportion of parts by weight or less. Further, in order to suppress the influence of ultraviolet rays and the like, the (meth) acrylate containing an alicyclic hydrocarbon group and the (meth) acrylate containing an aromatic ring structure include an olefin-based double bond in the side chain portion of the acrylic polymer. It is preferable to select a compound having no double bond.
ところで、本発明に係わる粘着剤組成物を使用して得られる粘着剤層が、優れたガスバリア性を有する理由は、今のところ明確ではないが、次のように推測される。つまり、アクリル系ポリマーの１００重量部のうち、長鎖アルキル基を有する（メタ）アクリレートである、アルキル基の炭素数がＣ１４以上〜Ｃ２０以下のアルキル（メタ）アクリレートを８０重量部以上の割合で含有させたことにより、該アクリル系ポリマーの親水性が抑制されて疎水性が強くなり、粘着剤層に侵入した水分が、粘着剤層に吸収され難く、且つ、粘着剤層を透過し難くなり、粘着剤層の水蒸気透過率が低減されるものと推測される。
したがって、さらに、長鎖アルキル基の炭素数を２０よりも多くして、アルキル（メタ）アクリレートの分子構造を長大化させると、アクリル系ポリマーの疎水性がより強くなると考えられる。しかし、この場合、アクリル系ポリマーを溶解させた粘着剤組成物の粘度が増大することから、基材に塗布して粘着剤層を積層することが困難になるという問題が発生する。よって、本実施形態に係わる粘着剤組成物は、アクリル系ポリマーの１００重量部のうち、アルキル基の炭素数がＣ１４以上〜Ｃ２０以下のアルキル（メタ）アクリレートの少なくとも１種以上の合計を８０〜１００重量部の割合で含有させることが、本発明の課題を解決するための実用的な粘着剤組成物が得られることから好ましい。
By the way, the reason why the pressure-sensitive adhesive layer obtained by using the pressure-sensitive adhesive composition according to the present invention has excellent gas barrier properties is not clear at present, but is presumed as follows. That is, out of 100 parts by weight of the acrylic polymer, 80 parts by weight or more of the alkyl (meth) acrylate having a long-chain alkyl group and having an alkyl group having C14 or more and C20 or less carbon atoms is used. By containing the acrylic polymer, the hydrophilicity of the acrylic polymer is suppressed and the hydrophobicity becomes stronger, and the moisture that has entered the pressure-sensitive adhesive layer is difficult to be absorbed by the pressure-sensitive adhesive layer and is difficult to permeate through the pressure-sensitive adhesive layer. It is presumed that the water vapor permeability of the pressure-sensitive adhesive layer is reduced.
Therefore, it is considered that if the number of carbon atoms of the long-chain alkyl group is increased to more than 20, and the molecular structure of the alkyl (meth) acrylate is lengthened, the hydrophobicity of the acrylic polymer becomes stronger. However, in this case, since the viscosity of the pressure-sensitive adhesive composition in which the acrylic polymer is dissolved increases, there arises a problem that it becomes difficult to apply the pressure-sensitive adhesive composition to the base material and laminate the pressure-sensitive adhesive layer. Therefore, in the pressure-sensitive adhesive composition according to the present embodiment, the total of at least one or more alkyl (meth) acrylates having an alkyl group having C14 or more and C20 or less in 100 parts by weight of the acrylic polymer is 80 to 80. It is preferable to contain it in a ratio of 100 parts by weight because a practical pressure-sensitive adhesive composition for solving the problem of the present invention can be obtained.
前記（Ｂ）水酸基を含有する（メタ）アクリレートの具体例としては、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、３−ヒドロキシプロピル（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、２−ヒドロキシエチル（メタ）アクリレート、２，３−ジヒドロキシプロピル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、その他のポリアルキレングリコールモノ（メタ）アクリレート等の少なくとも１種以上が挙げられる。 Specific examples of the (meth) acrylate containing the (B) hydroxyl group include 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 3-hydroxypropyl (meth). Meta) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. At least one kind or more such as polyalkylene glycol mono (meth) acrylate of.
前記（Ｂ）水酸基を含有する（メタ）アクリレートは、前記（Ａ−１）又は（Ａ−２）の合計１００重量部に対して、０．１〜５．０重量部の割合で含有することが好ましく、０．６〜５．０重量部の割合で含有することがより好ましく、１．２〜５．０重量部の割合で含有することが特に好ましい。また、前記（Ｂ）水酸基を含有する（メタ）アクリレートは、アルキル基の炭素数がＣ２以上〜Ｃ８以下である水酸基置換アルキル（メタ）アクリレートが好ましく、中でも、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−ヒドロキシプロピル（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ばれた少なくとも１種であることが好ましい。さらに、前記（Ｂ）水酸基を含有する（メタ）アクリレートは、アルキル基の炭素数がＣ４以上〜Ｃ８以下である水酸基置換アルキル（メタ）アクリレートがより好ましく、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）アクリレートからなる化合物群の中から選ばれた少なくとも１種であることが、粘着剤層の凝集力を増大させ、ひいては粘着力を増大できることから特に好ましい。 The (meth) acrylate containing the (B) hydroxyl group shall be contained in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the total of (A-1) or (A-2). Is more preferable, and it is more preferably contained in a proportion of 0.6 to 5.0 parts by weight, and particularly preferably contained in a proportion of 1.2 to 5.0 parts by weight. The (meth) acrylate containing the (B) hydroxyl group is preferably a hydroxyl group-substituted alkyl (meth) acrylate having an alkyl group having C2 or more to C8 or less, and among them, 8-hydroxyoctyl (meth) acrylate. At least one selected from the group of compounds consisting of 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. Is preferable. Further, as the (meth) acrylate containing the (B) hydroxyl group, a hydroxyl group-substituted alkyl (meth) acrylate having an alkyl group having C4 or more and C8 or less carbon atoms is more preferable, and 8-hydroxyoctyl (meth) acrylate, 6 At least one selected from the compound group consisting of −hydroxyhexyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate can increase the cohesive force of the pressure-sensitive adhesive layer, and thus the adhesive force. Is particularly preferable.
前記アクリル系ポリマーは、カルボキシ基を含有するビニルモノマーを含有させないで共重合させたアクリル系ポリマーであることが好ましい。カルボキシ基を含有する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、フマル酸等のエステル基を有しないカルボキシ基含有モノマー；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、２−（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、２−（メタ）アクリロイロキシプロピルヘキサヒドロフタル酸、２−（メタ）アクリロイロキシエチルフタル酸、２−（メタ）アクリロイロキシエチルコハク酸、２−（メタ）アクリロイロキシエチルマレイン酸、カルボキシポリカプロラクトンモノ（メタ）アクリレート、２−（メタ）アクリロイロキシエチルテトラヒドロフタル酸等のカルボキシ基を有する（メタ）アクリレートエステルモノマーが挙げられるが、これらに限定されるものではない。 The acrylic polymer is preferably an acrylic polymer copolymerized without containing a vinyl monomer containing a carboxy group. Examples of the carboxy group-containing vinyl monomer include carboxy group-containing monomers having no ester group such as (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, and phthalic acid; carboxyethyl (meth) acrylate and carboxypentyl (meth). ) Ester, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxypropyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloy (Meta) acrylate ester monomer having a carboxy group such as loxyethyl succinic acid, 2- (meth) acryloyloxyethyl maleic acid, carboxypolycaprolactone mono (meth) acrylate, 2- (meth) acryloyloxyethyl tetrahydrophthalic acid However, the present invention is not limited to these.
前記アクリル系ポリマーは、窒素含有ビニルモノマーを含有させないで共重合させたアクリル系ポリマーであることが好ましい。窒素含有ビニルモノマーとしては、Ｎ−（メタ）アクリロイルモルホリン、Ｎ−（メタ）アクリロイルピロリジン、Ｎ−（メタ）アクリロイルピペリジン等の環状（メタ）アクリルアミド類；Ｎ−ビニルピロリドン等のＮ−ビニル基含有環状モノマー；（メタ）アクリルアミド、Ｎ−アルキル（メタ）アクリルアミド、Ｎ，Ｎ−ジアルキル（メタ）アクリルアミド等の非環状（メタ）アクリルアミド類；Ｎ，Ｎ−ジアルキルアミノアルキル（メタ）アクリレート等の置換アミノ基含有（メタ）アクリレート類；Ｎ，Ｎ−ジアルキルアミノアルキル（メタ）アクリルアミド等の置換アミノ基含有（メタ）アクリルアミド類；（メタ）アクリロニトリル等のニトリル基含有ビニルモノマー；イソシアネート基含有ビニルモノマー；（メタ）アクリロイルオキシアルキルトリメチルアンモニウム塩等の４級アンモニウム基含有ビニルモノマー等が挙げられるが、これらに限定されるものではない。 The acrylic polymer is preferably an acrylic polymer copolymerized without containing a nitrogen-containing vinyl monomer. Examples of the nitrogen-containing vinyl monomer include cyclic (meth) acrylamides such as N- (meth) acryloylmorpholin, N- (meth) acryloylpyrrolidin, and N- (meth) acryloylpiperidin; and N-vinyl groups such as N-vinylpyrrolidone. Cyclic monomer; Acryloyl (meth) acrylamides such as (meth) acrylamide, N-alkyl (meth) acrylamide, N, N-dialkyl (meth) acrylamide; Substituted aminos such as N, N-dialkylaminoalkyl (meth) acrylate Group-containing (meth) acrylates; substituted amino group-containing (meth) acrylamides such as N, N-dialkylaminoalkyl (meth) acrylamide; nitrile group-containing vinyl monomers such as (meth) acryloylnitrile; isocyanate group-containing vinyl monomers; Meta) Examples thereof include, but are not limited to, quaternary ammonium group-containing vinyl monomers such as acryloyloxyalkyltrimethylammonium salt.
なお、前記の特許文献３に記載の発明に係わる粘着シートは、アクリル系ポリマーにアミド基含有モノマーを共重合させることを必須要件としているが、本実施形態の粘着剤組成物は、アミド基含有モノマーを必須成分としていない。このため、本実施形態によれば、モノマー成分として（メタ）アクリレートのみを共重合させてなるアクリル系ポリマーを含有する粘着剤組成物であっても、水蒸気透過率が低く、水蒸気バリア性に優れた粘着剤層を得ることができる。 The pressure-sensitive adhesive sheet according to the invention described in Patent Document 3 requires that an amide group-containing monomer be copolymerized with an acrylic polymer, but the pressure-sensitive adhesive composition of the present embodiment contains an amide group. Monomer is not an essential ingredient. Therefore, according to the present embodiment, even a pressure-sensitive adhesive composition containing an acrylic polymer obtained by copolymerizing only (meth) acrylate as a monomer component has a low water vapor permeability and an excellent water vapor barrier property. A pressure-sensitive adhesive layer can be obtained.
前記アクリル系ポリマーとして使用され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、重量平均分子量５万〜１５０万のアクリル系ポリマーであることが好ましく、重量平均分子量１５万〜１５０万のアクリル系ポリマーであることがより好ましく、重量平均分子量３０万〜１５０万のアクリル系ポリマーであることが特に好ましい。 The polymerization method of the copolymer used as the acrylic polymer is not particularly limited, and known polymerization methods such as a solution polymerization method and an emulsion polymerization method can be used as appropriate. The acrylic polymer is preferably an acrylic polymer having a weight average molecular weight of 50,000 to 1.5 million, more preferably an acrylic polymer having a weight average molecular weight of 150,000 to 1.5 million, and a weight average molecular weight of 300,000 to 150. It is particularly preferable that it is an acrylic polymer of 10,000.
前記アクリル系ポリマーは、酸価が０のアクリル系ポリマーであることが好ましい。前記アクリル系ポリマーが、カルボキシ基を含有するビニルモノマー以外にも、例えば、スルホン酸基を含有するビニルモノマー、ホスホン酸基を含有するビニルモノマー等の酸性モノマーを含有させないで共重合させたアクリル系ポリマーであることが好ましい。カルボキシ基等の酸性基は親水性が高いため、前記アクリル系ポリマーに酸性モノマーを共重合させると、水蒸気透過率が増加し、水蒸気バリア性が低下するおそれがある。
また、被着体が酸化インジウム錫（ＩＴＯ）などの金属表面である場合には、カルボキシ基を含有するビニルモノマーを共重合させたアクリル系ポリマーを含有する粘着剤層が、該金属表面を腐食して透明導電膜の抵抗値を変化させる原因となる。このため、前記アクリル系ポリマーは、金属表面を腐食させる原因となる化合物である、カルボキシ基を含有するビニルモノマーを含有させないで共重合させたアクリル系ポリマーであることが好ましい。
The acrylic polymer is preferably an acrylic polymer having an acid value of 0. In addition to the vinyl monomer containing a carboxy group, the acrylic polymer is copolymerized without containing an acidic monomer such as a vinyl monomer containing a sulfonic acid group or a vinyl monomer containing a phosphonic acid group. It is preferably a polymer. Since an acidic group such as a carboxy group has high hydrophilicity, when an acidic monomer is copolymerized with the acrylic polymer, the water vapor transmittance may increase and the water vapor barrier property may decrease.
When the adherend has a metal surface such as indium tin oxide (ITO), the pressure-sensitive adhesive layer containing an acrylic polymer copolymerized with a vinyl monomer containing a carboxy group corrodes the metal surface. This causes a change in the resistance value of the transparent conductive film. Therefore, the acrylic polymer is preferably an acrylic polymer copolymerized without containing a vinyl monomer containing a carboxy group, which is a compound that causes corrosion of the metal surface.
前記（Ｃ）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、これらのビュレット変性体、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。ポリイソシアネート化合物は、カルボキシ基を含有するビニルモノマーを含有させないで共重合させたアクリル系ポリマーであっても、（Ｂ）水酸基を含有する（メタ）アクリレートと反応して、粘着剤組成物を架橋させることができる。前記粘着剤組成物が、前記アクリル系ポリマーの１００重量部に対して、前記（Ｃ）架橋剤として３官能以上のイソシアネート化合物を０．０１〜２．０重量部の割合で含有してなることが好ましい。ポリイソシアネート化合物が３官能以上である場合、２官能の場合に比べて、より高密度の架橋が可能になる。前記（Ｃ）架橋剤の使用量が多すぎる場合、前記アクリル系ポリマーの高分子鎖間に隙間が生じ、水蒸気透過率が増加し、水蒸気バリア性が低下するおそれがある。 Examples of the (C) cross-linking agent include diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, and xylylene diisocyanate, bullet-modified products, isocyanurate-modified products, trimethylolpropane, and glycerin. At least one or more of polyisocyanate compounds such as adducts with trivalent or higher valent polyols such as. Even if the polyisocyanate compound is an acrylic polymer copolymerized without containing a vinyl monomer containing a carboxy group, it reacts with (B) a (meth) acrylate containing a hydroxyl group to crosslink the pressure-sensitive adhesive composition. Can be made to. The pressure-sensitive adhesive composition contains 0.01 to 2.0 parts by weight of a trifunctional or higher functional isocyanate compound as the (C) cross-linking agent with respect to 100 parts by weight of the acrylic polymer. Is preferable. When the polyisocyanate compound is trifunctional or higher, higher density cross-linking is possible as compared with the case of bifunctional. If the amount of the cross-linking agent (C) used is too large, gaps may occur between the polymer chains of the acrylic polymer, the water vapor transmittance may increase, and the water vapor barrier property may decrease.
前記粘着剤組成物は、任意の成分として、シランカップリング剤、酸化防止剤、帯電防止剤、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種類以上を併せて用いてもよい。
なお、前記特許文献３の粘着シートは、テルペンフェノール樹脂等の粘着付与樹脂を必須成分としているが、本実施形態の粘着剤組成物は、粘着付与樹脂を必須成分としていない。このため、本実施形態によれば、前記アクリル系ポリマーのみを樹脂成分とした粘着剤組成物であり、一般的な構造を有するアクリル系モノマーのみを含有した粘着剤組成物であっても、水蒸気透過率が低く、水蒸気バリア性に優れた粘着剤層を得ることができる。このため、本実施形態の粘着剤組成物は、高品質の光学部材にも貼合可能である、高品質の粘着剤層を製造することができる。
The pressure-sensitive adhesive composition contains, as optional components, a silane coupling agent, an antioxidant, an antistatic agent, a surfactant, a curing accelerator, a plasticizer, a filler, a cross-linking catalyst, a cross-linking retarder, a curing retarder, and the like. Known additives such as processing aids and antistatic agents can be appropriately blended. These may be used alone or in combination of two or more.
The pressure-sensitive adhesive sheet of Patent Document 3 contains a pressure-imparting resin such as a terpene phenol resin as an essential component, but the pressure-sensitive adhesive composition of the present embodiment does not contain a pressure-imparting resin as an essential component. Therefore, according to the present embodiment, the pressure-sensitive adhesive composition containing only the acrylic polymer as a resin component, and even the pressure-sensitive adhesive composition containing only the acrylic monomer having a general structure is water vapor. A pressure-sensitive adhesive layer having a low transmittance and an excellent water vapor barrier property can be obtained. Therefore, the pressure-sensitive adhesive composition of the present embodiment can produce a high-quality pressure-sensitive adhesive layer that can be bonded to a high-quality optical member.
本実施形態に係わる粘着剤層は、前記粘着剤組成物を基材や離型フィルムに塗布した後、前記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、場合により、４０〜８５％、６０〜９０％、又は９５〜１００％であることが好ましい。前記（Ｃ）架橋剤の反応を進行させるため、前記粘着剤層を所定の温度条件に保管して、エージングすることが好ましい。粘着剤層の厚さは、用途等にも依存して適宜設定できるが、例えば、１〜５０μｍの厚さが挙げられ、１〜２５μｍの厚さが好ましい。 The pressure-sensitive adhesive layer according to the present embodiment can be obtained by applying the pressure-sensitive adhesive composition to a base material or a release film, and then cross-linking the pressure-sensitive adhesive composition. The gel fraction of the pressure-sensitive adhesive layer after cross-linking is preferably 40 to 85%, 60 to 90%, or 95 to 100%, depending on the case. In order to allow the reaction of the (C) cross-linking agent to proceed, it is preferable to store the pressure-sensitive adhesive layer at a predetermined temperature condition for aging. The thickness of the pressure-sensitive adhesive layer can be appropriately set depending on the application and the like, but for example, a thickness of 1 to 50 μm is mentioned, and a thickness of 1 to 25 μm is preferable.
前記粘着剤組成物は、該粘着剤組成物を架橋してなる粘着剤層の厚さを２５μｍとしたときの、該粘着剤層の水蒸気透過率が、ＪＩＳ Ｋ７１２９に準拠した赤外線センサ法を用いて測定したとき、３２℃×９０％ＲＨ雰囲気下において１００ｇ／（ｍ２・ｄａｙ）以下であることが好ましく、９０ｇ／（ｍ２・ｄａｙ）以下であることがより好ましい。水蒸気透過率の測定方法の詳細は、２００８年改正のＪＩＳ Ｋ７１２９「プラスチック−フィルム及びシート−水蒸気透過度の求め方（機器測定法）」のＢ法、又は２０１９年制定のＪＩＳ Ｋ７１２９−２「プラスチック−フィルム及びシート−水蒸気透過度の求め方−第２部：赤外線センサ法」に記載されている。 The pressure-sensitive adhesive composition uses an infrared sensor method in which the water vapor transmittance of the pressure-sensitive adhesive layer when the thickness of the pressure-sensitive adhesive layer formed by cross-linking the pressure-sensitive adhesive composition is 25 μm is based on JIS K7129. It is preferably 100 g / (m 2 · day) or less, and more preferably 90 g / (m 2 · day) or less in an atmosphere of 32 ° C. × 90% RH. For details on the method of measuring the water vapor transmission rate, refer to the JIS K7129 "Plastic-Film and Sheet-How to obtain the water vapor transmission rate (equipment measurement method)" revised in 2008, or the JIS K7129-2 "Plastic" established in 2019. -Films and sheets-How to determine water vapor permeability-Part 2: Infrared sensor method ".
前記アクリル系ポリマーのＳＰ値（溶解度パラメータ）が、９．０（ｃａｌ／ｃｍ３）０．５以下であることが好ましい。また、本実施形態に係わる粘着剤組成物において使用される高分子のＳＰ値は、高分子を混合する場合の相溶性の良否を判断する尺度であるＦｅｄｏｒｓの式を使って算出される数値である。Ｆｅｄｏｒｓの式によれば、分子を構成する原子、原子団、官能基等の構成単位ごとに提案された凝集エネルギーΔＥｉ（ｃａｌ／ｍｏｌ）及びモル体積ΔＶｉ（ｃｍ３／ｍｏｌ）の値を用いて、次の式によりＳＰ値が算出される。なお、０．５乗（又は１／２乗）は、平方根と同義である。
ＳＰ＝（ΣΔＥｉ／ΣΔＶｉ）０．５
The SP value (solubility parameter) of the acrylic polymer is preferably 9.0 (cal / cm 3 ) 0.5 or less. Further, the SP value of the polymer used in the pressure-sensitive adhesive composition according to the present embodiment is a numerical value calculated using the Fedors formula, which is a scale for judging the quality of compatibility when the polymer is mixed. is there. According to the Fedors formula, the values of the aggregation energy ΔE i (cal / mol) and the molar volume ΔV i (cm 3 / mol) proposed for each structural unit such as atoms, atomic groups, and functional groups constituting the molecule are calculated. Using, the SP value is calculated by the following formula. Note that 0.5 (or 1/2) is synonymous with the square root.
SP = (ΣΔE i / ΣΔV i ) 0.5
Ｆｅｄｏｒｓの式において、添え字ｉは、各構成単位に付される番号を表し、Σは、添え字ｉに関する総和を表す。分子中に同一の構成単位が複数個存在する場合は、添え字ｉに対応する個数をｎｉとして、ΣΔＥｉの代わりにΣ（ｎｉ×ΔＥｉ）、ΣΔＶｉの代わりにΣ（ｎｉ×ΔＶｉ）を用いることができる。各構成単位の存在割合を整数比で表し難い場合は、ｎｉとして、非整数の割合（モル分率等）を用いてもよい。 In the Fedors formula, the subscript i represents the number assigned to each structural unit, and Σ represents the sum of the subscript i. If the same structural unit is plurally present in the molecule, the number corresponding to the index i as n i, instead Σ (n i × ΔE i) of ShigumaderutaE i, instead of .SIGMA..DELTA.V i sigma (n i × ΔV i ) can be used. If hardly represent the existence ratio of each structural unit by an integer ratio, a n i, may be used the ratio of the non-integer (mole fraction, etc.).
前記粘着剤組成物は、該粘着剤組成物を架橋してなる厚みが２５μｍの粘着剤層を、厚みが５０μｍのポリエステルフィルムの基材の片面に積層した粘着フィルムとし、ＪＩＳ Ｚ０２３７に準拠して前記粘着剤層の粘着力を測定したとき、高密度ポリエチレン樹脂に対する、前記粘着剤層の粘着力が１０Ｎ／２５ｍｍ以上であることが好ましい。粘着力の試験に使用される被着体としては、高密度ポリエチレン等のポリエチレン樹脂が挙げられる。ポリエチレンのＳＰ値は７．７〜８．４程度であるため、前記アクリル系ポリマーのＳＰ値が９．０より大きいと、被着体であるポリエチレン樹脂に対する粘着力が低下する要因となる。 The pressure-sensitive adhesive composition is a pressure-sensitive adhesive film obtained by laminating a pressure-sensitive adhesive layer having a thickness of 25 μm obtained by cross-linking the pressure-sensitive adhesive composition on one side of a base material of a polyester film having a thickness of 50 μm, in accordance with JIS Z0237. When the adhesive strength of the pressure-sensitive adhesive layer is measured, the adhesive strength of the pressure-sensitive adhesive layer with respect to the high-density polyethylene resin is preferably 10 N / 25 mm or more. Examples of the adherend used for the adhesive strength test include polyethylene resins such as high-density polyethylene. Since the SP value of polyethylene is about 7.7 to 8.4, if the SP value of the acrylic polymer is larger than 9.0, it causes a decrease in the adhesive strength to the polyethylene resin as an adherend.
前記粘着剤層を、光学フィルム、光学ガラス等の光学部材を貼合するために用いる場合、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。前記粘着剤層の屈折率は、芳香環構造を含有する（メタ）アクリレート等のモノマー成分の添加割合等により調整することができる。
前記アクリル系ポリマーは、前記（Ａ−２）の合計１００重量部のうち、芳香環構造を含有する（メタ）アクリレートモノマーを、３〜３０重量部の割合で含有することにより、前記粘着剤層の屈折率を１．４７〜１．５０の値とすることが可能となる。
When the pressure-sensitive adhesive layer is used for bonding optical members such as an optical film and optical glass, 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. Is desirable. Therefore, the refractive index of the pressure-sensitive adhesive layer is preferably 1.47 to 1.50. The refractive index of the pressure-sensitive adhesive layer can be adjusted by the addition ratio of a monomer component such as (meth) acrylate containing an aromatic ring structure.
The acrylic polymer contains the (meth) acrylate monomer containing an aromatic ring structure in a proportion of 3 to 30 parts by weight in a total of 100 parts by weight of the above (A-2), thereby forming the pressure-sensitive adhesive layer. The refractive index of can be set to a value of 1.47 to 1.50.
前記粘着剤層を、有機ＥＬディスプレイ、液晶ディスプレイ、電子ペーパー等の表示装置に用いる場合は、透明性に優れる粘着剤層であることが好ましい。具体的には、前記粘着剤組成物は、該粘着剤組成物を架橋してなる粘着剤層の、厚さが２５μｍのときの全光線透過率が９０％以上であることが好ましく、９２％以上であることがより好ましく、９４％以上であることが特に好ましい。また、前記粘着剤組成物は、該粘着剤組成物を架橋してなる粘着剤層の、厚さが２５μｍのときのヘイズ値が１．０％以下であることが好ましく、０．８％以下であることがより好ましく、０．６％以下であることが特に好ましい。本実施形態の粘着剤組成物によれば、フィラー等の添加物を添加しなくても、水蒸気透過率が低く、水蒸気バリア性に優れた粘着剤層が得られる。このため、添加物による光の散乱等が抑制され、全光線透過率が高く、ヘイズ値が低く、透明性に優れた粘着剤層を得ることができる。 When the pressure-sensitive adhesive layer is used in a display device such as an organic EL display, a liquid crystal display, or electronic paper, it is preferably a pressure-sensitive adhesive layer having excellent transparency. Specifically, the pressure-sensitive adhesive composition preferably has a total light transmittance of 90% or more when the thickness of the pressure-sensitive adhesive layer formed by cross-linking the pressure-sensitive adhesive composition is 25 μm, preferably 92%. The above is more preferable, and 94% or more is particularly preferable. Further, in the pressure-sensitive adhesive composition, the haze value of the pressure-sensitive adhesive layer formed by cross-linking the pressure-sensitive adhesive composition when the thickness is 25 μm is preferably 1.0% or less, preferably 0.8% or less. Is more preferable, and 0.6% or less is particularly preferable. According to the pressure-sensitive adhesive composition of the present embodiment, a pressure-sensitive adhesive layer having a low water vapor permeability and an excellent water vapor barrier property can be obtained without adding an additive such as a filler. Therefore, it is possible to obtain a pressure-sensitive adhesive layer in which light scattering and the like due to additives are suppressed, the total light transmittance is high, the haze value is low, and the transparency is excellent.
本実施形態の粘着フィルムは、前記粘着剤組成物を架橋してなる粘着剤層を、基材の少なくとも片面に形成してなる。前記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 embodiment is formed by forming a pressure-sensitive adhesive layer formed by cross-linking the pressure-sensitive adhesive composition on at least one side of a base material. 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 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.
離型フィルムには、前記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。前記粘着剤層の両面に離型フィルムの離型処理が施された面を貼り合せることで、「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、離型フィルムを粘着剤層から剥離するために必要な剥離力が、前記粘着剤層の両面で同一でもよく、あるいは互いに異なってもよい。 The release film is subjected to a 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 combined with the adhesive surface. A "release film / adhesive layer / release film" can also be formed by laminating the release-treated surfaces of the release film on both sides of the pressure-sensitive adhesive layer. In this case, the peeling force required to peel the release film from the pressure-sensitive adhesive layer may be the same on both sides of the pressure-sensitive adhesive layer, or may be different from each other.
前記粘着フィルムから離型フィルムの少なくとも１つを剥離して、前記粘着剤層の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、有機ＥＬディスプレイにおける発光素子の基材フィルム等が挙げられる。前記光学フィルムは、有機ＥＬディスプレイの各種光学フィルム、液晶ディスプレイ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であってもよい。
本実施形態の粘着剤層又は粘着フィルムを貼り合せた光学フィルムは、例えば、有機ＥＬディスプレイ、液晶ディスプレイ、タッチパネル、電子ペーパー等に適用することができることから、本発明に係わる粘着剤組成物、及びそれを用いた粘着フィルムは、産業上の利用価値が大である。
By peeling at least one of the release films from the pressure-sensitive adhesive film to expose the pressure-sensitive surface of the pressure-sensitive adhesive layer, it can be bonded to an optical member such as an optical film. Examples of the optical film include a polarizing film, a retardation film, an antireflection film, an antiglare film, an ultraviolet absorbing film, an infrared absorbing film, an optical compensation film, a brightness improving film, and a base film for a light emitting element in an organic EL display. Can be mentioned. The optical film may be various optical films for an organic EL display, various optical films for a liquid crystal display, various optical films for a touch panel, and various optical films for electronic paper.
Since the pressure-sensitive adhesive layer or the optical film to which the pressure-sensitive adhesive film of the present embodiment is bonded can be applied to, for example, an organic EL display, a liquid crystal display, a touch panel, an electronic paper, etc., the pressure-sensitive adhesive composition according to the present invention and the pressure-sensitive adhesive film. Adhesive films using it have great industrial utility value.
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及び粘着剤組成物の製造＞
［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、反応装置にテトラデシルメタクリレートを９５重量部、ベンジルアクリレートを５重量部、８−ヒドロキシオクチルアクリレートを３．０重量部の割合で溶剤（酢酸エチル）と共に加えた。その後、重合開始剤としてアゾビスイソブチロニトリルを２時間かけて滴下した後、重合反応を継続して、実施例１のアクリル系ポリマーの溶液を得た。実施例１のアクリル系ポリマーの溶液に対して、架橋剤として、コロネート（登録商標）Ｌを０．４重量部の割合で添加した後、撹拌混合して実施例１の粘着剤組成物を得た。
<Manufacturing of acrylic polymers and adhesive compositions>
[Example 1]
Nitrogen gas was introduced into a reactor equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction pipe, and the air in the reactor was replaced with nitrogen gas. Then, 95 parts by weight of tetradecyl methacrylate, 5 parts by weight of benzyl acrylate, and 3.0 parts by weight of 8-hydroxyoctyl acrylate were added to the reaction apparatus together with the solvent (ethyl acetate). Then, azobisisobutyronitrile was added dropwise as a polymerization initiator over 2 hours, and then the polymerization reaction was continued to obtain a solution of the acrylic polymer of Example 1. Coronate (registered trademark) L was added as a cross-linking agent to the solution of the acrylic polymer of Example 1 at a ratio of 0.4 parts by weight, and then stirred and mixed to obtain the pressure-sensitive adhesive composition of Example 1. It was.
［実施例２〜６及び比較例１〜７］
モノマーの組成を各々、表１の（Ａ）群及び（Ｂ）群の記載のように用いた以外は、上記の実施例１のアクリル系ポリマーの溶液と同様にして、実施例２〜６及び比較例１〜７のアクリル系ポリマーの溶液を得た。また、架橋剤を、表１の（Ｃ）群の記載のように用いた以外は、上記の実施例１の粘着剤組成物と同様にして、実施例２〜６及び比較例１〜７の粘着剤組成物を得た。
[Examples 2 to 6 and Comparative Examples 1 to 7]
Examples 2 to 6 and Examples 2 to 6 and the same as the above-mentioned solution of the acrylic polymer of Example 1 except that the composition of the monomer was used as described in Group (A) and Group (B) of Table 1, respectively. A solution of the acrylic polymer of Comparative Examples 1 to 7 was obtained. In addition, Examples 2 to 6 and Comparative Examples 1 to 7 were made in the same manner as the pressure-sensitive adhesive composition of Example 1 above, except that the cross-linking agent was used as described in Group (C) of Table 1. A pressure-sensitive adhesive composition was obtained.
表１における実施例１、３、４、６及び比較例４〜７では、（Ａ）群のモノマーが、（Ａ−２）アルキル基の炭素数がＣ１４以上〜Ｃ２０以下のアルキル（メタ）アクリレートの少なくとも１種以上と、アルキル基の炭素数がＣ１以上〜Ｃ１３以下のアルキル（メタ）アクリレート、脂環式炭化水素基を含有する（メタ）アクリレート、芳香環構造を含有する（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１種以上とを含有している。また、実施例２、５では、（Ａ）群のモノマーが、（Ａ−１）アルキル基の炭素数がＣ１４以上〜Ｃ２０以下のアルキル（メタ）アクリレートの少なくとも１種以上である。また、実施例１〜７及び比較例４〜７では、アクリル系ポリマーの１００重量部に対して、アルキル基の炭素数がＣ１４以上〜Ｃ２０以下のアルキル（メタ）アクリレートの少なくとも１種以上の合計が８０重量部以上を含有している。また、比較例１〜３では、アクリル系ポリマーの１００重量部に対して、アルキル基の炭素数がＣ１４以上〜Ｃ２０以下のアルキル（メタ）アクリレートの少なくとも１種以上の合計が８０重量部未満である。 In Examples 1, 3, 4, 6 and Comparative Examples 4 to 7 in Table 1, the monomer of the group (A) is an alkyl (meth) acrylate having an alkyl group (A-2) having a carbon number of C14 or more and C20 or less. From alkyl (meth) acrylates having an alkyl group having C1 or more to C13 or less, (meth) acrylate containing an alicyclic hydrocarbon group, and (meth) acrylate containing an aromatic ring structure. Contains at least one selected from the group of compounds. Further, in Examples 2 and 5, the monomer of the group (A) is at least one kind of alkyl (meth) acrylate having the carbon number of the (A-1) alkyl group of C14 or more and C20 or less. Further, in Examples 1 to 7 and Comparative Examples 4 to 7, the total of at least one type of alkyl (meth) acrylate having an alkyl group having C14 or more and C20 or less has a carbon number of C14 or more and C20 or less with respect to 100 parts by weight of the acrylic polymer. Contains 80 parts by weight or more. Further, in Comparative Examples 1 to 3, the total of at least one type of alkyl (meth) acrylate having an alkyl group having C14 or more and C20 or less is less than 80 parts by weight with respect to 100 parts by weight of the acrylic polymer. is there.
表１において、（Ａ）群のモノマーの合計を１００重量部として求めた重量部の値を、化合物名に対応する略記号に添えて示す。さらに、（Ｂ）群及び（Ｃ）群では、アクリル系ポリマーを１００重量部として求めた重量部の数値を、括弧（ ）内に示す。
なお、表１で用いた化合物名に対応する略記号は、次のとおりである。
In Table 1, the value of the part by weight obtained by assuming that the total amount of the monomers of the group (A) is 100 parts by weight is shown by adding the abbreviation corresponding to the compound name. Further, in the groups (B) and (C), the numerical value of the part by weight obtained by assuming that the acrylic polymer is 100 parts by weight is shown in parentheses ().
The abbreviations corresponding to the compound names used in Table 1 are as follows.
また、表１において、（Ａ）群のうち、アルキル基の炭素数がＣ１４以上〜Ｃ２０以下のアルキル（メタ）アクリレートについては、テトラデシルメタクリレートを「ＴＤＭＡ」、テトラデシルアクリレートを「ＴＤＡ」、ペンタデシルアクリレートを「ＰＤＡ」、ヘキサデシルメタクリレートを「ＨＤＭＡ」、イソステアリルアクリレートを「ＩＳＴＡ」と表示した。
また、（Ａ）群のうち、脂環式炭化水素基を含有する（メタ）アクリレート及び芳香環構造を含有する（メタ）アクリレートについては、ベンジルアクリレートを「ＢＺＡ」、イソボルニルアクリレートを「ＩＢＯＡ」と表示した。
また、（Ａ）群のうち、アルキル基の炭素数がＣ１以上〜Ｃ１３以下のアルキル（メタ）アクリレート及び窒素含有ビニルモノマーについては、２−エチルヘキシルアクリレートを「２ＥＨＡ」、ｎ−ブチルアクリレートを「ＢＡ」、メチルアクリレートを「ＭＡ」、Ｎ，Ｎ−ジメチルアクリルアミドを「ＤＭＡＡ」と表示した。
Further, in Table 1, for the alkyl (meth) acrylate having an alkyl group having C14 or more and C20 or less carbon atoms in the group (A), tetradecyl methacrylate is “TDMA”, tetradecyl acrylate is “TDA”, and penta. The decyl acrylate was labeled as "PDA", the hexadecyl methacrylate was labeled as "HDMA", and the isostearyl acrylate was labeled as "ISTA".
Further, in the group (A), regarding the (meth) acrylate containing an alicyclic hydrocarbon group and the (meth) acrylate containing an aromatic ring structure, the benzyl acrylate is "BZA" and the isobornyl acrylate is "IBOA". Was displayed.
In the group (A), for alkyl (meth) acrylates having an alkyl group having C1 or more and C13 or less carbon atoms and nitrogen-containing vinyl monomers, 2-ethylhexyl acrylate is "2EHA" and n-butyl acrylate is "BA". , Methyl acrylate was labeled as "MA" and N, N-dimethylacrylamide was labeled as "DMAA".
また、表１において、（Ｂ）群については、８−ヒドロキシオクチルアクリレートを「８ＨＯＡ」、６−ヒドロキシヘキシルアクリレートを「６ＨＨＡ」、４−ヒドロキシブチルアクリレートを「４ＨＢＡ」、２−ヒドロキシエチルアクリレートを「ＨＥＡ」、アクリル酸を「ＡＡｃ」と表示した。 In Table 1, for group (B), 8-hydroxyoctyl acrylate is "8HOA", 6-hydroxyhexyl acrylate is "6HHA", 4-hydroxybutyl acrylate is "4HBA", and 2-hydroxyethyl acrylate is "2". "HEA" and acrylic acid are indicated as "AAc".
また、表１において、（Ｃ）群については、コロネート（登録商標）Ｌ（東ソー株式会社の商品名：ＴＤＩのＴＭＰアダクト体）を「Ｌ」、コロネート（登録商標）ＨＸ（東ソー株式会社の商品名：ＨＤＩのイソシアヌレート体）を「ＨＸ」、コロネート（登録商標）ＨＬ（東ソー株式会社の商品名：ＨＤＩアダクト体）を「ＨＬ」、タケネート（登録商標）Ｄ−１１０Ｎ（三井化学株式会社の商品名：ＸＤＩアダクト体）を「Ｄ−１１０Ｎ」と表示した。
ここで、「ＴＤＩ」はトリレンジイソシアネート、「ＴＭＰ」はトリメチロールプロパン、「ＨＤＩ」はヘキサメチレンジイソシアネート、「ＸＤＩ」はキシリレンジイソシアネートをそれぞれ意味する。
In Table 1, for group (C), Coronate (registered trademark) L (trademark of Tosoh Corporation: TMP adduct body of TDI) is "L", and Coronate (registered trademark) HX (product of Tosoh Corporation). Name: HDI isocyanurate) is "HX", Coronate (registered trademark) HL (trade name of Tosoh Corporation: HDI Adduct) is "HL", Takenate (registered trademark) D-110N (Mitsui Chemicals, Inc.) Product name: XDI Adduct body) was displayed as "D-110N".
Here, "TDI" means trimethylolpropane, "TMP" means trimethylolpropane, "HDI" means hexamethylene diisocyanate, and "XDI" means xylylene diisocyanate.
＜粘着剤層及び粘着フィルムの製造＞
実施例１〜６及び比較例１〜７の粘着剤組成物を、それぞれ離型フィルム（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）の表面に塗布した。塗布後に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日間エージングした。これにより、粘着剤組成物を架橋してなる厚さが２５μｍの粘着剤層を、離型フィルムの片面上に有する、実施例１〜６及び比較例１〜７の粘着フィルムを得た。
<Manufacturing of adhesive layer and adhesive film>
The pressure-sensitive adhesive compositions of Examples 1 to 6 and Comparative Examples 1 to 7 were applied to the surfaces of release films (silicone resin-coated polyethylene terephthalate (PET) films), respectively. After coating, the solvent was removed by drying at 90 ° C., and then aging was performed at 23 ° C. and 50% RH for 7 days. As a result, the pressure-sensitive adhesive films of Examples 1 to 6 and Comparative Examples 1 to 7 having a pressure-sensitive adhesive layer having a thickness of 25 μm formed by cross-linking the pressure-sensitive adhesive composition on one side of the release film were obtained.
＜試験方法及び評価＞
実施例１〜６及び比較例１〜７の粘着フィルムから、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た。
<Test method and evaluation>
The release film (silicone resin coated PET film) was peeled off from the pressure-sensitive adhesive films of Examples 1 to 6 and Comparative Examples 1 to 7 to expose the pressure-sensitive adhesive layer.
＜水蒸気透過率の測定方法＞
厚さを２５μｍとした粘着剤層の水蒸気透過率〔ｇ／（ｍ２・ｄａｙ）〕は、ＪＩＳ Ｋ７１２９のＢ法に準拠した赤外線センサ法により、株式会社日立ハイテクサイエンスのＭＯＣＯＮ（登録商標）水蒸気透過率測定装置 ＰＥＲＭＡＴＲＡＮ−Ｗ（登録商標）３／３４Ｇを使用し、３２℃×９０％ＲＨ雰囲気下において２４ｈに透過した水蒸気の量（ｇ）から面積１ｍ２当たりに換算して測定した。測定値が９００ｇ／（ｍ２・ｄａｙ）以上となる場合は、測定装置の測定上限界値に達するため、測定値を特定せずに「９００ｇ／（ｍ２・ｄａｙ）以上」とした。
<Measurement method of water vapor permeability>
Water vapor transmission rate of the thickness was 25μm adhesive layer [g / (m 2 · day)] is an infrared sensor method that conforms to B method JIS K7129, MOCON of Hitachi High-Tech Science ® steam transmittance measuring apparatus PERMATRAN-W using (R) 3 / 34G, was measured in terms of area 1 m 2 per the amount (g) of water vapor passing through the 24h under an atmosphere RH 32 ℃ × 90%. When the measured value is 900 g / (m 2 · day) or more, the measurement limit value is reached in the measuring device, so “900 g / (m 2 · day) or more” is set without specifying the measured value.
＜粘着力の測定方法＞
厚みが５０μｍのポリエステルフィルムの基材の片面に、厚さを２５μｍとした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、厚みが２ｍｍの高密度ポリエチレン樹脂の表面に圧着ロールで貼り合せて、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。前記高密度ポリエチレン樹脂の表面から粘着フィルムを剥離するときの粘着力を測定する方法として、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、粘着フィルムの剥離強度を測定し、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 base material of a polyester film having a thickness of 50 μm to obtain a sample pressure-sensitive adhesive film (optical film with a pressure-sensitive adhesive layer). The obtained adhesive film was attached to the surface of a high-density polyethylene resin having a thickness of 2 mm with a pressure-bonding roll, autoclaved at 50 ° C. for 0.5 MPa × 20 minutes, and then an atmosphere of 23 ° C. × 50% RH was applied. It was returned to the bottom and allowed to pass for 1 hour. As a method of measuring the adhesive strength when peeling the adhesive film from the surface of the high-density polyethylene resin, the peeling strength of the adhesive film is determined by a tensile tester in accordance with JIS Z0237 (adhesive tape / adhesive sheet test method). The peel strength when peeled at a speed of 300 mm / min in the 180 ° direction was taken as the adhesive strength (N / 25 mm) of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film.
＜全光線透過率の測定方法＞
厚さを２５μｍとした粘着剤層について、日本電色工業株式会社製ヘーズメーター（商品名：ＮＤＨ４０００）を使用して、ＪＩＳ Ｋ７３６１−１（プラスチック−透明材料の全光線透過率の試験方法−第１部：シングルビーム法）に準拠して、粘着剤層の全光線透過率（％）を測定した。
<Measurement method of total light transmittance>
For the pressure-sensitive adhesive layer having a thickness of 25 μm, using a haze meter (trade name: NDH4000) manufactured by Nippon Denshoku Industries Co., Ltd., JIS K7361-1 (Plastic-Test method for total light transmittance of transparent material-No. The total light transmittance (%) of the pressure-sensitive adhesive layer was measured according to (1 part: single beam method).
＜ヘイズ値の測定方法＞
厚さを２５μｍとした粘着剤層について、日本電色工業株式会社製ヘーズメーター（商品名：ＮＤＨ４０００）を使用して、ＪＩＳ Ｋ７１３６（プラスチック−透明材料のヘーズの求め方）に準拠して、粘着剤層のヘイズ値（％）を測定した。
<Measurement method of haze value>
Adhesive layer with a thickness of 25 μm is adhered using a haze meter (trade name: NDH4000) manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K7136 (How to obtain haze of plastic-transparent material). The haze value (%) of the agent layer was measured.
表２に、粘着剤層の評価に係わる測定結果を示す。さらに表２には、アクリル系ポリマーの重量平均分子量及びＳＰ値を、それぞれ「ポリマー分子量」及び「ポリマーＳＰ値」の欄に示した。 Table 2 shows the measurement results related to the evaluation of the pressure-sensitive adhesive layer. Further, in Table 2, the weight average molecular weight and the SP value of the acrylic polymer are shown in the columns of "polymer molecular weight" and "polymer SP value", respectively.
表２の試験結果によると、本発明の実施例１〜６の粘着フィルムは、厚さを２５μｍとした粘着剤層の水蒸気透過率が、ＪＩＳ Ｋ７１２９に準拠した赤外線センサ法を用いて測定したとき、３２℃×９０％ＲＨ雰囲気下において１００ｇ／（ｍ２・ｄａｙ）以下であり、粘着剤層の水蒸気バリア性に優れている。
また、本発明の実施例１〜６の粘着フィルムは、厚みを２５μｍとした粘着剤層を、厚みが５０μｍのポリエステルフィルムの基材の片面に積層した粘着フィルムとし、ＪＩＳ Ｚ０２３７に準拠して前記粘着剤層の粘着力を測定したとき、高密度ポリエチレン樹脂に対する、前記粘着剤層の粘着力が１０Ｎ／２５ｍｍ以上であり、粘着剤層の粘着力に優れている。
また、本発明の実施例１〜６の粘着フィルムは、厚さを２５μｍとした粘着剤層の全光線透過率が９０％以上、且つヘイズ値が１．０％以下であり、粘着剤層の透明性に優れている。
すなわち、本発明の実施例１〜６の粘着フィルムによれば、本発明の課題を解決することができている。
According to the test results in Table 2, in the adhesive films of Examples 1 to 6 of the present invention, when the water vapor transmittance of the adhesive layer having a thickness of 25 μm was measured by using an infrared sensor method based on JIS K7129. , 100 g / (m 2 · day) or less in an atmosphere of 32 ° C. × 90% RH, and the adhesive layer has excellent water vapor barrier properties.
Further, the pressure-sensitive adhesive films of Examples 1 to 6 of the present invention are pressure-sensitive adhesive films in which a pressure-sensitive adhesive layer having a thickness of 25 μm is laminated on one side of a base material of a polyester film having a thickness of 50 μm. When the adhesive strength of the pressure-sensitive adhesive layer was measured, the adhesive strength of the pressure-sensitive adhesive layer with respect to the high-density polyethylene resin was 10 N / 25 mm or more, and the adhesive strength of the pressure-sensitive adhesive layer was excellent.
Further, in the pressure-sensitive adhesive films of Examples 1 to 6 of the present invention, the total light transmittance of the pressure-sensitive adhesive layer having a thickness of 25 μm is 90% or more and the haze value is 1.0% or less. It has excellent transparency.
That is, according to the adhesive films of Examples 1 to 6 of the present invention, the problem of the present invention can be solved.
また、本発明の比較例１〜３の粘着フィルムは、アクリル系ポリマーが、アルキル基の炭素数が８、又は４のアルキル（メタ）アクリレートを主成分としているため、水蒸気透過率が高く、水蒸気バリア性に劣っている。また、本発明の比較例１〜３の粘着フィルムは、高密度ポリエチレン樹脂に対する粘着力が低かった。 Further, in the pressure-sensitive adhesive films of Comparative Examples 1 to 3 of the present invention, since the acrylic polymer contains an alkyl (meth) acrylate having an alkyl group having 8 or 4 carbon atoms as a main component, it has a high water vapor transmittance and water vapor. It is inferior in barrier properties. Further, the adhesive films of Comparative Examples 1 to 3 of the present invention had low adhesive strength to the high-density polyethylene resin.
また、本発明の比較例４及び６の粘着フィルムは、アクリル系ポリマーが、水酸基を含有する（メタ）アクリレートを含有せず、カルボキシ基を含有するビニルモノマーを含有しているため、水蒸気透過率が高く、水蒸気バリア性に劣っている。また、本発明の比較例４及び６の粘着フィルムは、高密度ポリエチレン樹脂に対する粘着力が低かった。 Further, in the pressure-sensitive adhesive films of Comparative Examples 4 and 6 of the present invention, since the acrylic polymer does not contain a (meth) acrylate containing a hydroxyl group but contains a vinyl monomer containing a carboxy group, the water vapor transmittance. Is high and the water vapor barrier property is inferior. Further, the adhesive films of Comparative Examples 4 and 6 of the present invention had low adhesive strength to the high-density polyethylene resin.
また、本発明の比較例５及び７の粘着フィルムは、アクリル系ポリマーを架橋する架橋剤が過多であるため、アクリル系ポリマーの架橋点が偏在して、アクリル系ポリマーの網目構造に隙間が多くなっていることが原因と考えられるが、粘着剤層の水蒸気透過率が高く、水蒸気バリア性に劣っている。また、高密度ポリエチレン樹脂に対する粘着力が低い。また、本発明の比較例５及び７の粘着フィルムは、前記のアクリル系ポリマーの架橋点が偏在していることが原因と考えられるが、粘着剤層のヘイズ値が高く、全光線透過率が低かった。
なお、本発明の比較例５の粘着フィルムは、本発明の比較例５のアクリル系ポリマーが、モノマー組成、重量平均分子量及びＳＰ値の点で、本発明の実施例１のアクリル系ポリマーと同一であり、いずれも架橋剤として３官能以上のイソシアネート化合物を用いて架橋したものであるが、実施例１及び比較例５の粘着フィルムでは、架橋剤の含有量の差異のみにより、両者の測定結果に顕著な差異が示された。
Further, in the adhesive films of Comparative Examples 5 and 7 of the present invention, since the cross-linking agent for cross-linking the acrylic polymer is excessive, the cross-linking points of the acrylic polymer are unevenly distributed, and there are many gaps in the network structure of the acrylic polymer. It is considered that the cause is that the pressure-sensitive adhesive layer has a high water vapor permeability and is inferior in water vapor barrier property. In addition, the adhesive strength to the high-density polyethylene resin is low. Further, it is considered that the pressure-sensitive adhesive films of Comparative Examples 5 and 7 of the present invention are caused by the uneven distribution of the cross-linking points of the acrylic polymer, but the haze value of the pressure-sensitive adhesive layer is high and the total light transmittance is high. It was low.
In the adhesive film of Comparative Example 5 of the present invention, the acrylic polymer of Comparative Example 5 of the present invention is the same as the acrylic polymer of Example 1 of the present invention in terms of monomer composition, weight average molecular weight and SP value. However, in the adhesive films of Example 1 and Comparative Example 5, the measurement results of both were measured only by the difference in the content of the cross-linking agent. A significant difference was shown in.
Claims (8)
前記粘着剤組成物を架橋してなる粘着剤層の厚さを２５μｍとしたときの、該粘着剤層の水蒸気透過率が、ＪＩＳ Ｋ７１２９に準拠した赤外線センサ法を用いて測定したとき、３２℃×９０％ＲＨ雰囲気下において１００ｇ／（ｍ２・ｄａｙ）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 obtained by copolymerizing only (meth) acrylate as a monomer component and (C) a cross-linking agent.
When the thickness of the pressure-sensitive adhesive layer formed by cross-linking the pressure-sensitive adhesive composition is 25 μm, the water vapor transmittance of the pressure-sensitive adhesive layer is 32 ° C. when measured using an infrared sensor method based on JIS K7129. A pressure-sensitive adhesive composition having a value of 100 g / (m 2 · day) or less under a 90% RH atmosphere.
（Ａ−１）アルキル基の炭素数がＣ１４以上〜Ｃ２０以下のアルキル（メタ）アクリレートの少なくとも１種以上の合計を１００重量部、又は、
（Ａ−２）アルキル基の炭素数がＣ１４以上〜Ｃ２０以下のアルキル（メタ）アクリレートの少なくとも１種以上の合計を８５〜１００重量部と、アルキル基の炭素数がＣ１以上〜Ｃ１３以下のアルキル（メタ）アクリレート、脂環式炭化水素基を含有する（メタ）アクリレート、芳香環構造を含有する（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１種以上の合計を１５〜０．０重量部との合計を１００重量部と、
（Ｂ）水酸基を含有する（メタ）アクリレートの少なくとも１種以上の合計を０．１〜５．０重量部と、
をカルボキシ基を含有するビニルモノマー、及び窒素含有ビニルモノマーを含有させないで共重合させた重量平均分子量５万〜１５０万のアクリル系ポリマーであり、
前記粘着剤組成物が、前記アクリル系ポリマーの１００重量部に対して、前記（Ｃ）架橋剤として３官能以上のイソシアネート化合物を０．０１〜２．０重量部の割合で含有してなることを特徴とする請求項１に記載の粘着剤組成物。 The acrylic polymer contained in the pressure-sensitive adhesive composition
(A-1) 100 parts by weight or 100 parts by weight of the total of at least one type of alkyl (meth) acrylate having an alkyl group having C14 or more and C20 or less carbon atoms.
(A-2) A total of 85 to 100 parts by weight of at least one type of alkyl (meth) acrylate having an alkyl group having a carbon number of C14 or more and C20 or less and an alkyl having an alkyl group having a carbon number of C1 or more to C13 or less The total of at least one selected from the compound group consisting of (meth) acrylate, (meth) acrylate containing an alicyclic hydrocarbon group, and (meth) acrylate containing an aromatic ring structure is 15 to 0. The total of 0 parts by weight is 100 parts by weight,
(B) The total of at least one (meth) acrylate containing a hydroxyl group is 0.1 to 5.0 parts by weight.
Is a vinyl monomer containing a carboxy group and an acrylic polymer having a weight average molecular weight of 50,000 to 1.5 million obtained by copolymerizing without containing a nitrogen-containing vinyl monomer.
The pressure-sensitive adhesive composition contains 0.01 to 2.0 parts by weight of a trifunctional or higher functional isocyanate compound as the (C) cross-linking agent with respect to 100 parts by weight of the acrylic polymer. The pressure-sensitive adhesive composition according to claim 1.
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| JP7173384B1 (en) | 2022-02-18 | 2022-11-16 | 王子ホールディングス株式会社 | Double-sided pressure-sensitive adhesive sheet, laminate, and method for producing laminate |
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| JP7173384B1 (en) | 2022-02-18 | 2022-11-16 | 王子ホールディングス株式会社 | Double-sided pressure-sensitive adhesive sheet, laminate, and method for producing laminate |
| JP2023120963A (en) * | 2022-02-18 | 2023-08-30 | 王子ホールディングス株式会社 | Double-sided adhesive sheet, laminate, and method for manufacturing laminate |
| JP2023120964A (en) * | 2022-02-18 | 2023-08-30 | 王子ホールディングス株式会社 | Double-sided adhesive sheet, laminate, and method for manufacturing laminate |
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