JP6896120B2 - Adhesive film and surface protection film - Google Patents
Adhesive film and surface protection film Download PDFInfo
- Publication number
- JP6896120B2 JP6896120B2 JP2020030456A JP2020030456A JP6896120B2 JP 6896120 B2 JP6896120 B2 JP 6896120B2 JP 2020030456 A JP2020030456 A JP 2020030456A JP 2020030456 A JP2020030456 A JP 2020030456A JP 6896120 B2 JP6896120 B2 JP 6896120B2
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- JP
- Japan
- Prior art keywords
- film
- pressure
- sensitive adhesive
- group
- meth
- 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.)
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- 239000002313 adhesive film Substances 0.000 title claims description 23
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 102
- 239000000203 mixture Substances 0.000 claims description 64
- 239000000178 monomer Substances 0.000 claims description 44
- 125000000217 alkyl group Chemical group 0.000 claims description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims description 31
- 239000002216 antistatic agent Substances 0.000 claims description 29
- 150000003839 salts Chemical class 0.000 claims description 29
- 230000001681 protective effect Effects 0.000 claims description 24
- 239000003431 cross linking reagent Substances 0.000 claims description 23
- 150000001875 compounds Chemical group 0.000 claims description 20
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 16
- 229920006243 acrylic copolymer Polymers 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 13
- 229920002554 vinyl polymer Polymers 0.000 claims description 13
- 230000001588 bifunctional effect Effects 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 239000012948 isocyanate Substances 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 230000002209 hydrophobic effect Effects 0.000 claims description 9
- 150000002513 isocyanates Chemical class 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 0.000 claims description 2
- 150000004714 phosphonium salts Chemical group 0.000 claims 1
- 239000010408 film Substances 0.000 description 102
- 239000010410 layer Substances 0.000 description 36
- -1 polyethylene terephthalate Polymers 0.000 description 36
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 29
- 239000012788 optical film Substances 0.000 description 24
- 230000003287 optical effect Effects 0.000 description 21
- 239000000853 adhesive Substances 0.000 description 20
- 230000001070 adhesive effect Effects 0.000 description 20
- 239000012790 adhesive layer Substances 0.000 description 20
- 238000007334 copolymerization reaction Methods 0.000 description 13
- 239000003822 epoxy resin Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229920000647 polyepoxide Polymers 0.000 description 9
- 238000011109 contamination Methods 0.000 description 8
- 239000004973 liquid crystal related substance Substances 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 239000013522 chelant Substances 0.000 description 5
- 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 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229920002050 silicone resin Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 230000003373 anti-fouling effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 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
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- UGAPHEBNTGUMBB-UHFFFAOYSA-N acetic acid;ethyl acetate Chemical compound CC(O)=O.CCOC(C)=O UGAPHEBNTGUMBB-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 210000002858 crystal cell Anatomy 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 125000005645 linoleyl group Chemical group 0.000 description 2
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000001117 oleyl 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])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 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
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 229920001296 polysiloxane 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
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-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
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OQFWMWOQWBLMJZ-UHFFFAOYSA-N CCCCCCCCP(CCCCCCCC)CCCCCCCC.ClCC1=CC=CC=C1 Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC.ClCC1=CC=CC=C1 OQFWMWOQWBLMJZ-UHFFFAOYSA-N 0.000 description 1
- 101100433727 Caenorhabditis elegans got-1.2 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- DQPBABKTKYNPMH-UHFFFAOYSA-M amino sulfate Chemical compound NOS([O-])(=O)=O DQPBABKTKYNPMH-UHFFFAOYSA-M 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant 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
- 239000012298 atmosphere Substances 0.000 description 1
- KHSLHYAUZSPBIU-UHFFFAOYSA-M benzododecinium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 KHSLHYAUZSPBIU-UHFFFAOYSA-M 0.000 description 1
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 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
- GEHMWSIEKHOKJZ-UHFFFAOYSA-M benzyl(trioctyl)azanium;chloride Chemical compound [Cl-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CC1=CC=CC=C1 GEHMWSIEKHOKJZ-UHFFFAOYSA-M 0.000 description 1
- DGLWIADPBVYUIM-UHFFFAOYSA-M benzyl(tris-decyl)azanium bromide Chemical compound [Br-].C(CCCCCCCCC)[N+](CC1=CC=CC=C1)(CCCCCCCCCC)CCCCCCCCCC DGLWIADPBVYUIM-UHFFFAOYSA-M 0.000 description 1
- BBBDQPZPPBITID-UHFFFAOYSA-M benzyl(tris-decyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCC[N+](CCCCCCCCCC)(CCCCCCCCCC)CC1=CC=CC=C1 BBBDQPZPPBITID-UHFFFAOYSA-M 0.000 description 1
- CDWCBHSRJGNQLM-UHFFFAOYSA-M benzyl(tris-decyl)phosphanium bromide Chemical compound [Br-].C(CCCCCCCCC)[P+](CC1=CC=CC=C1)(CCCCCCCCCC)CCCCCCCCCC CDWCBHSRJGNQLM-UHFFFAOYSA-M 0.000 description 1
- SCJPZKAHFISXQX-UHFFFAOYSA-M benzyl(tris-decyl)phosphanium chloride Chemical compound [Cl-].C(CCCCCCCCC)[P+](CC1=CC=CC=C1)(CCCCCCCCCC)CCCCCCCCCC SCJPZKAHFISXQX-UHFFFAOYSA-M 0.000 description 1
- VZWMKHUMEIECPK-UHFFFAOYSA-M benzyl-dimethyl-octadecylazanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 VZWMKHUMEIECPK-UHFFFAOYSA-M 0.000 description 1
- CSNHNGDROQRZKT-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 CSNHNGDROQRZKT-UHFFFAOYSA-M 0.000 description 1
- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 description 1
- DLNWMWYCSOQYSQ-UHFFFAOYSA-M benzyl-hexadecyl-dimethylazanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 DLNWMWYCSOQYSQ-UHFFFAOYSA-M 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- SXPWTBGAZSPLHA-UHFFFAOYSA-M cetalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SXPWTBGAZSPLHA-UHFFFAOYSA-M 0.000 description 1
- 229960000228 cetalkonium chloride Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical compound ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- WCOATMADISNSBV-UHFFFAOYSA-K diacetyloxyalumanyl acetate Chemical compound [Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WCOATMADISNSBV-UHFFFAOYSA-K 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 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
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000008040 ionic compounds Chemical group 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical class CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- HOTLAXCCXLLJAF-UHFFFAOYSA-M tetra(nonyl)azanium;bromide Chemical compound [Br-].CCCCCCCCC[N+](CCCCCCCCC)(CCCCCCCCC)CCCCCCCCC HOTLAXCCXLLJAF-UHFFFAOYSA-M 0.000 description 1
- WNYKNASIKRLGTN-UHFFFAOYSA-M tetra(nonyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCC[N+](CCCCCCCCC)(CCCCCCCCC)CCCCCCCCC WNYKNASIKRLGTN-UHFFFAOYSA-M 0.000 description 1
- DDFXAFPWFJDMPS-UHFFFAOYSA-M tetra(nonyl)phosphanium;bromide Chemical compound [Br-].CCCCCCCCC[P+](CCCCCCCCC)(CCCCCCCCC)CCCCCCCCC DDFXAFPWFJDMPS-UHFFFAOYSA-M 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 1
- AHNISXOXSNAHBZ-UHFFFAOYSA-M tetrakis-decylazanium;bromide Chemical compound [Br-].CCCCCCCCCC[N+](CCCCCCCCCC)(CCCCCCCCCC)CCCCCCCCCC AHNISXOXSNAHBZ-UHFFFAOYSA-M 0.000 description 1
- YUOPMAJOMPKKLZ-UHFFFAOYSA-M tetrakis-decylazanium;chloride Chemical compound [Cl-].CCCCCCCCCC[N+](CCCCCCCCCC)(CCCCCCCCCC)CCCCCCCCCC YUOPMAJOMPKKLZ-UHFFFAOYSA-M 0.000 description 1
- GBPSSGTXNRSVPE-UHFFFAOYSA-M tetrakis-decylphosphanium;bromide Chemical compound [Br-].CCCCCCCCCC[P+](CCCCCCCCCC)(CCCCCCCCCC)CCCCCCCCCC GBPSSGTXNRSVPE-UHFFFAOYSA-M 0.000 description 1
- AVZJTQJZWLALMI-UHFFFAOYSA-M tetrakis-decylphosphanium;chloride Chemical compound [Cl-].CCCCCCCCCC[P+](CCCCCCCCCC)(CCCCCCCCCC)CCCCCCCCCC AVZJTQJZWLALMI-UHFFFAOYSA-M 0.000 description 1
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 description 1
- SNNIPOQLGBPXPS-UHFFFAOYSA-M tetraoctylazanium;chloride Chemical compound [Cl-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC SNNIPOQLGBPXPS-UHFFFAOYSA-M 0.000 description 1
- QVBRLOSUBRKEJW-UHFFFAOYSA-M tetraoctylphosphanium;bromide Chemical compound [Br-].CCCCCCCC[P+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QVBRLOSUBRKEJW-UHFFFAOYSA-M 0.000 description 1
- AXTXARBFPWQUQA-UHFFFAOYSA-M tetraoctylphosphanium;chloride Chemical compound [Cl-].CCCCCCCC[P+](CCCCCCCC)(CCCCCCCC)CCCCCCCC AXTXARBFPWQUQA-UHFFFAOYSA-M 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000005040 tridecenyl group Chemical group C(=CCCCCCCCCCCC)* 0.000 description 1
Landscapes
- Polarising Elements (AREA)
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、帯電防止性能を有する粘着剤組成物、粘着フィルム及び表面保護フィルムに関する。さらに詳細には、帯電防止剤として、疎水性の４級オニウム塩を含有する粘着剤組成物に関し、粘着性能を損なわずに帯電防止性に優れた粘着剤組成物、それを用いた粘着フィルム及び表面保護フィルムを提供することに関するものである。 The present invention relates to an adhesive composition, an adhesive film and a surface protective film having antistatic properties. More specifically, with respect to a pressure-sensitive adhesive composition containing a hydrophobic quaternary onium salt as an antistatic agent, a pressure-sensitive adhesive composition having excellent antistatic properties without impairing the pressure-sensitive adhesive performance, a pressure-sensitive adhesive film using the same, and a pressure-sensitive adhesive composition. It relates to providing a surface protective film.
従来から、液晶ディスプレイを構成する部材である偏光板、位相差板、反射防止フィルムなどの光学部材の製造工程においては、光学部材の表面を一時的に保護するための表面保護フィルムが貼着される。このような表面保護フィルムは、光学部材を製造する工程のみに使用され、光学部材を液晶ディスプレイに組み込む時点で、光学部材から剥離して除去される。このような光学部材の表面を保護するための表面保護フィルムは、製造工程においてのみに使用されるため、一般には、工程フィルムと呼ばれることもある。 Conventionally, in the manufacturing process of optical members such as polarizing plates, retardation plates, and antireflection films, which are members constituting liquid crystal displays, a surface protective film for temporarily protecting the surface of the optical members is attached. To. Such a surface protective film is used only in the process of manufacturing the optical member, and is peeled off from the optical member and removed when the optical member is incorporated into the liquid crystal display. Since such a surface protective film for protecting the surface of the optical member is used only in the manufacturing process, it is also generally called a process film.
このように、光学部材を製造する工程において使用される表面保護フィルムは、光学的に透明性を有するポリエチレンテレフタレート（ＰＥＴ）樹脂フィルムの片面に粘着剤層が形成されているが、光学部材に貼り合わせるまで、その粘着剤層を保護するための剥離処理された剥離フィルムが、粘着剤層の上に貼り合わされている。
また、偏光板、位相差板、反射防止フィルムなどの光学部材は、表面保護フィルムを貼り合わされた状態で、液晶表示板の表示能力、色相、コントラスト、異物混入などの光学的評価を伴う製品検査を行うため、表面保護フィルムに対する要求性能としては、粘着剤層に気泡や異物が付着していないことが求められている。
また、近年では、偏光板、位相差板、反射防止フィルムなどの光学部材から表面保護フィルムを剥がすときに、粘着剤層を被着体が剥がす時に発生する静電気に伴って生じる剥離帯電が、液晶ディスプレイの電気制御回路の故障に影響することが懸念され、粘着剤層に対して優れた帯電防止性能が求められている。
また、偏光板、位相差板、反射防止フィルムなどの光学部材に表面保護フィルムを貼り合わせるときには、各種の理由により、一旦、表面保護フィルムを剥がして、再度、表面保護フィルムを貼り直すことがあり、そのときに被着体の光学部材から剥がし易いこと（リワーク性）が求められている。また、このとき、被着体を汚染しないこと、いわゆる糊残りが起こらないことが求められている。
また、最終的に偏光板、位相差、反射防止フィルム板などの光学部材から表面保護フィルムを剥がすときには、速やかに剥離できることが求められている。いわゆる、高速度での剥離によっても、速やかに剥離できるように、粘着力が剥離速度によっても変化が少ないことが求められている。
As described above, the surface protective film used in the process of manufacturing the optical member has an adhesive layer formed on one side of the optically transparent polyethylene terephthalate (PET) resin film, and is attached to the optical member. A release-treated release film for protecting the pressure-sensitive adhesive layer is bonded onto the pressure-sensitive adhesive layer until they are combined.
In addition, optical members such as polarizing plates, retardation plates, and antireflection films are inspected with optical evaluations such as display capability, hue, contrast, and foreign matter contamination of the liquid crystal display plate with the surface protective film attached. Therefore, as the required performance of the surface protective film, it is required that bubbles and foreign matters do not adhere to the pressure-sensitive adhesive layer.
Further, in recent years, when the surface protective film is peeled off from an optical member such as a polarizing plate, a retardation plate, or an antireflection film, the peeling charge generated by the static electricity generated when the adherend peels off the adhesive layer is a liquid crystal display. There is a concern that it may affect the failure of the electric control circuit of the display, and excellent antistatic performance is required for the adhesive layer.
Further, when the surface protective film is attached to an optical member such as a polarizing plate, a retardation plate, or an antireflection film, the surface protective film may be peeled off and then reattached for various reasons. At that time, it is required that it can be easily peeled off from the optical member of the adherend (reworkability). Further, at this time, it is required that the adherend is not contaminated, that is, so-called adhesive residue does not occur.
Further, when the surface protective film is finally peeled off from an optical member such as a polarizing plate, a phase difference, or an antireflection film plate, it is required to be able to peel off quickly. It is required that the adhesive strength does not change much depending on the peeling speed so that the peeling can be performed quickly even by the so-called peeling at a high speed.
例えば、優れた帯電防止性能については、表面保護フィルムに帯電防止性を付与させるための方法として、基材フィルムに帯電防止剤を練り込む方法などが示されている。
帯電防止剤としては、例えば、（ａ）第４級アンモニウム塩、ピリジニウム塩、第１〜３級アミノ基などのカチオン性基を有する各種のカチオン性帯電防止剤、（ｂ）スルホン酸塩基、硫酸エステル塩基、リン酸エステル塩基、ホスホン酸塩基などのアニオン性基を有するアニオン性帯電防止剤、（ｃ）アミノ酸系、アミノ硫酸エステル系などの両性帯電防止剤、（ｄ）アミノアルコール系、グリセリン系、ポリエチレングリコール系などのノニオン性帯電防止剤、（ｅ）上記の様な帯電防止剤を高分子量化した高分子型帯電防止剤、などが開示されている（特許文献１）。
また、近年では、このような帯電防止剤を基材フィルムに含有させたり、あるいは基材フィルムの表面に塗布するのではなく、直接に粘着剤層に含有させたりすることが提案されている。
For example, with regard to excellent antistatic performance, a method of kneading an antistatic agent into a base film has been shown as a method for imparting antistatic properties to a surface protective film.
Examples of the antistatic agent include (a) various cationic antistatic agents having a cationic group such as a quaternary ammonium salt, a pyridinium salt, and a primary to tertiary amino group, and (b) a sulfonic acid base and a sulfuric acid. Anionic antistatic agents having anionic groups such as ester bases, phosphate ester bases, and phosphonic acid bases, (c) amphoteric antistatic agents such as amino acid-based and aminosulfate-based, (d) aminoalcohol-based, and glycerin-based. , Nonionic antistatic agents such as polyethylene glycol type, (e) high molecular weight antistatic agents obtained by increasing the molecular weight of the above antistatic agents, and the like are disclosed (Patent Document 1).
Further, in recent years, it has been proposed that such an antistatic agent is contained in the base film, or is directly contained in the pressure-sensitive adhesive layer instead of being applied to the surface of the base film.
また、リワーク性能については、例えば、アクリル樹脂中に、イソシアネート系化合物の硬化剤と、特定のシリケートオリゴマーをアクリル系樹脂１００重量部に対して０．０００１〜１０重量部で配合した粘着剤組成物が提案されている（特許文献２）。
特許文献２では、アルキル基の炭素数が２〜１２程度のアクリル酸アルキルエステルやアルキル基の炭素数が４〜１２程度のメタクリル酸アルキルエステル等を主モノマー成分とし、例えば、カルボキシル基含有モノマーなどの他の官能基含有モノマー成分を含むことができるとしている。一般的には、上記主モノマーを５０重量％以上含有させることが好ましい、又、官能基含有モノマー成分の含有量は０．００１〜５０重量％であって、好ましくは０．００１〜２５重量％、更に好ましくは０．０１〜２５重量％であることが望まれる、としている。このような特許文献２に記載の粘着剤組成物は、高温下又は高温高湿下でも凝集力及び接着力の経時変化が小さく、かつ、曲面に対する接着力にも優れた効果を示すことから、リワーク性を有するとしている。
一般に、粘着剤層を柔らかい性状のものにすると、糊残りが発生し易くなり、リワーク性が低下し易い。すなわち、誤って貼合したときに剥離し難く、貼り直しが困難となり易い。このことから、カルボキシル基などの官能基を有するモノマーを主剤に架橋させて、粘着剤層を一定の硬さにすることが、リワーク性を持たせるためには必要と考えられる。
Regarding the rework performance, for example, a pressure-sensitive adhesive composition in which an isocyanate-based compound curing agent and a specific silicate oligomer are blended in an acrylic resin in an amount of 0.0001 to 10 parts by weight based on 100 parts by weight of the acrylic resin. Has been proposed (Patent Document 2).
In Patent Document 2, an acrylic acid alkyl ester having an alkyl group having about 2 to 12 carbon atoms, a methacrylate alkyl ester having an alkyl group having about 4 to 12 carbon atoms, or the like is used as a main monomer component, and for example, a carboxyl group-containing monomer or the like. Other functional group-containing monomer components can be included. Generally, it is preferable that the main monomer is contained in an amount of 50% by weight or more, and the content of the functional group-containing monomer component is 0.001 to 50% by weight, preferably 0.001 to 25% by weight. , More preferably 0.01 to 25% by weight. The pressure-sensitive adhesive composition described in Patent Document 2 has a small change in cohesive force and adhesive force with time even under high temperature or high temperature and high humidity, and exhibits an excellent effect on the adhesive force on a curved surface. It is said to have reworkability.
In general, when the pressure-sensitive adhesive layer has a soft property, adhesive residue is likely to occur, and the reworkability is likely to decrease. That is, when they are attached by mistake, they are difficult to peel off and reattachment is likely to be difficult. From this, it is considered necessary to crosslink a monomer having a functional group such as a carboxyl group with the main agent to make the pressure-sensitive adhesive layer have a certain hardness in order to have reworkability.
上述したように、粘着フィルムとして帯電防止機能を求められることが多く、色々な種類の帯電防止剤が試みられてきた。しかし、特に光学フィルムの用途においては、帯電防止機能は持たせることができるが、透明性が悪いなどの欠点があり、さらには帯電防止剤の粘着剤への相溶性不足などから帯電防止剤のブリードアウトや粘着フィルムを剥がした際に、被着体に汚染が生じてしまうなどのリワーク性が悪い等の欠点が多かった。これら、性能を満足できても、コストが高くなってしまうなどの問題もあり、低コストでこれら欠点を克服出来る帯電防止剤を含んだ粘着剤が必要とされて来た。 As described above, an antistatic function is often required as an adhesive film, and various types of antistatic agents have been tried. However, especially in the use of optical films, although it is possible to have an antistatic function, there are drawbacks such as poor transparency, and the antistatic agent has insufficient compatibility with the adhesive. When the bleed-out or the adhesive film was peeled off, there were many drawbacks such as poor reworkability such as contamination of the adherend. Even if these performances can be satisfied, there are problems such as high cost, and an adhesive containing an antistatic agent that can overcome these drawbacks at low cost has been required.
本発明は、上記の事情に鑑みてなされたものであり、優れた帯電防止性能を備え、粘着剤との相溶性に優れるためブリードアウトや粘着フィルムを剥がした際に、被着体に汚染が生じてしまうなどのリワーク性の欠点を改善した、粘着剤組成物、粘着フィルム、及び表面保護フィルムを提供することを課題とする。 The present invention has been made in view of the above circumstances, and has excellent antistatic performance and excellent compatibility with an adhesive. Therefore, when a bleed-out or an adhesive film is peeled off, the adherend is contaminated. It is an object of the present invention to provide an adhesive composition, an adhesive film, and a surface protective film, which have improved defects in reworkability such as occurrence.
前記課題を解決するため、本発明は、帯電防止性能を有する粘着剤組成物であって、帯電防止剤として、融点３０〜５０℃の疎水性の４級オニウム塩を含有す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 problems, the present invention is a pressure-sensitive adhesive composition having antistatic performance, and is characterized by containing a hydrophobic quaternary onium salt having a melting point of 30 to 50 ° C. as an antistatic agent. A pressure-sensitive adhesive composition is provided.
前記４級オニウム塩が、２５℃の水１００ｇに対する溶解度が５ｇ以下であることが好ましい。 The quaternary onium salt preferably has a solubility of 5 g or less in 100 g of water at 25 ° C.
粘着剤成分が、（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸アルキルエステルモノマーの少なくとも１種と、（Ｂ）水酸基および／またはカルボキシル基を含有する共重合性ビニルモノマーの少なくとも１種と、からなる共重合組成物であり、前記共重合組成物の１００重量部に対して、（Ｃ）前記４級オニウム塩を０．１〜１０重量部、を必須成分として含有することが好ましい。 The pressure-sensitive adhesive component is (A) at least one (meth) acrylic acid alkyl ester monomer having an alkyl group having C1 to C14 carbon atoms, and (B) a copolymerizable vinyl monomer containing a hydroxyl group and / or a carboxyl group. It is a copolymerization composition comprising at least one kind, and contains (C) 0.1 to 10 parts by weight of the quaternary onium salt as an essential component with respect to 100 parts by weight of the copolymerization composition. Is preferable.
粘着剤成分が、（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸アルキルエステルモノマーの少なくとも１種と、ビニル基を有する共重合性ビニルモノマーの少なくとも１種と、からなる共重合組成物であり、前記共重合組成物の１００重量部に対して、（Ｃ）前記４級オニウム塩を０．１〜１０重量部、を必須成分として含有することが好ましい。 The pressure-sensitive adhesive component is composed of (A) at least one kind of (meth) acrylic acid alkyl ester monomer having an alkyl group having C1 to C14 carbon atoms and at least one kind of copolymerizable vinyl monomer having a vinyl group. It is a polymerization composition, and it is preferable that 0.1 to 10 parts by weight of (C) the quaternary onium salt is contained as an essential component with respect to 100 parts by weight of the copolymerization composition.
粘着剤成分が、（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸アルキルエステルモノマーの少なくとも２種以上からなる共重合組成物であり、前記共重合組成物の１００重量部に対して、（Ｃ）前記４級オニウム塩を０．１〜１０重量部、を必須成分として含有することが好ましい。 The pressure-sensitive adhesive component is a copolymerization composition composed of at least two or more (A) alkyl group (meth) acrylic acid alkyl ester monomers having C1 to C14 carbon atoms, and is contained in 100 parts by weight of the copolymerization composition. On the other hand, (C) preferably contains 0.1 to 10 parts by weight of the quaternary onium salt as an essential component.
粘着剤成分が、（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸アルキルエステルモノマーの少なくとも１種と、芳香族系モノマーの少なくとも１種と、からなる共重合組成物であり、前記共重合組成物の１００重量部に対して、（Ｃ）前記４級オニウム塩を０．１〜１０重量部、を必須成分として含有することが好ましい。 The pressure-sensitive adhesive component is a copolymer composition comprising (A) at least one kind of (meth) acrylic acid alkyl ester monomer having C1 to C14 carbon atoms and at least one kind of aromatic monomer. It is preferable that 0.1 to 10 parts by weight of (C) the quaternary onium salt is contained as an essential component with respect to 100 parts by weight of the copolymer composition.
基材の片面上に、前記粘着剤組成物を積層して形成された粘着剤層において、前記粘着剤層の表面抵抗率が１．０×１０＋１２Ω／□以下であることが好ましい。 In the pressure-sensitive adhesive layer formed by laminating the pressure-sensitive adhesive composition on one surface of the base material, the surface resistivity of the pressure-sensitive adhesive layer is preferably 1.0 × 10 + 12 Ω / □ or less.
また、本発明は、基材の片面上に、前記粘着剤組成物を用いて粘着剤層が積層されたことを特徴とする粘着フィルムを提供する。 The present invention also provides a pressure-sensitive adhesive film in which a pressure-sensitive adhesive layer is laminated on one side of a base material using the pressure-sensitive adhesive composition.
また、本発明は、前記粘着剤組成物を用いて粘着剤層が積層されたことを特徴とする粘着フィルムを提供する。 The present invention also provides a pressure-sensitive adhesive film in which a pressure-sensitive adhesive layer is laminated using the pressure-sensitive adhesive composition.
また、本発明は、前記粘着フィルムが用いられた、表面保護フィルムを提供する。 The present invention also provides a surface protective film in which the pressure-sensitive adhesive film is used.
また、本発明は、前記粘着フィルムが用いられた、偏光板用の表面保護フィルムを提供する。 The present invention also provides a surface protective film for a polarizing plate using the pressure-sensitive adhesive film.
また、本発明は、前記粘着フィルムが用いられた、光学用の表面保護フィルムを提供する。 The present invention also provides an optical surface protective film using the pressure-sensitive adhesive film.
また、本発明は、前記粘着フィルムが用いられた偏光板とディスプレイパネルの貼り合わせ用フィルムを提供する。 The present invention also provides a film for bonding a polarizing plate and a display panel using the pressure-sensitive adhesive film.
また、本発明は、前記粘着フィルムが用いられた偏光板を構成する材料の貼り合わせ用フィルムを提供する。 The present invention also provides a film for bonding materials constituting a polarizing plate using the pressure-sensitive adhesive film.
また、本発明は、前記粘着フィルムが用いられたタッチパネル用フィルムを提供する。 The present invention also provides a touch panel film using the adhesive film.
また、本発明は、前記粘着フィルムが用いられた電子ペーパー用フィルムを提供する。 The present invention also provides a film for electronic paper in which the pressure-sensitive adhesive film is used.
本発明によれば、融点３０〜５０℃の疎水性の４級オニウム塩を帯電防止成分として粘着剤に併用することで、粘着剤との相溶性に優れるためブリードアウトや粘着フィルムを剥がした際に、被着体に汚染が生じてしまうなどのリワーク性の欠点である課題を改善することが可能となる。 According to the present invention, when a hydrophobic quaternary onium salt having a melting point of 30 to 50 ° C. is used in combination with an adhesive as an antistatic component, the compatibility with the adhesive is excellent, so that when the bleed-out or the adhesive film is peeled off. In addition, it is possible to improve the problem of reworkability such as contamination of the adherend.
以下、好適な実施の形態に基づいて本発明を説明する。
本発明の粘着剤組成物は、帯電防止性能を有する粘着剤組成物であって、帯電防止剤として、融点３０〜５０℃の疎水性の４級オニウム塩を含有することを特徴とする。
Hereinafter, the present invention will be described based on preferred embodiments.
The pressure-sensitive adhesive composition of the present invention is a pressure-sensitive adhesive composition having an antistatic property, and is characterized by containing a hydrophobic quaternary onium salt having a melting point of 30 to 50 ° C. as an antistatic agent.
本発明の粘着剤組成物に用いる粘着剤成分としては、アクリル系共重合体などの共重合組成物が好ましい。特に、（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸アルキルエステルモノマーの少なくとも１種を主成分とする共重合体が好ましい。
（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸アルキルエステルモノマーとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、デシル（メタ）アクリレート、シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート等のアルキル（メタ）アクリレートモノマーが挙げられる。アルキル（メタ）アクリレートモノマーのアルキル基は、直鎖、分枝状、環状のいずれでもよい。
As the pressure-sensitive adhesive component used in the pressure-sensitive adhesive composition of the present invention, a copolymer composition such as an acrylic copolymer is preferable. In particular, a copolymer containing at least one (meth) acrylic acid alkyl ester monomer having (A) alkyl groups having C1 to C14 as a main component is preferable.
Examples of the (meth) acrylic acid alkyl ester monomer having an alkyl group having C1 to C14 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (A). Meta) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate. Examples thereof include alkyl (meth) acrylate monomers such as meta) acrylate, decyl (meth) acrylate, cyclopentyl (meth) acrylate, and cyclohexyl (meth) acrylate. The alkyl group of the alkyl (meth) acrylate monomer may be linear, branched or cyclic.
本発明に用いる粘着剤成分の共重合組成物として、（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸アルキルエステルモノマーの少なくとも１種と、他の共重合性モノマーの少なくとも１種とからなる共重合組成物を採用することもできる。この場合、他の共重合性モノマーとしては、ビニル基を有する共重合性ビニルモノマーや、（Ｂ）水酸基および／またはカルボキシル基を含有する共重合性ビニルモノマー、芳香族系モノマーが挙げられる。 As the copolymerization composition of the pressure-sensitive adhesive component used in the present invention, at least one (meth) acrylic acid alkyl ester monomer having (A) alkyl groups having C1 to C14 carbon atoms and at least one of the other copolymerizable monomers. Copolymerization compositions consisting of seeds can also be adopted. In this case, examples of the other copolymerizable monomer include a copolymerizable vinyl monomer having a vinyl group, (B) a copolymerizable vinyl monomer containing a hydroxyl group and / or a carboxyl group, and an aromatic monomer.
水酸基を含有する共重合性ビニルモノマーとしては、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、６−ヒドロキシヘキシル（メタ）アクリレート、８−ヒドロキシオクチル（メタ）アクリレート等の水酸基含有（メタ）アクリル酸エステル類や、Ｎ−ヒドロキシ（メタ）アクリルアミド、Ｎ−ヒドロキシメチル（メタ）アクリルアミド、Ｎ−ヒドロキシエチル（メタ）アクリルアミド等の水酸基含有（メタ）アクリルアミド類などが挙げられ、これらの化合物群の中から選択された、少なくとも１種以上であることが好ましい。
カルボキシル基を含有する共重合性ビニルモノマーとしては、（メタ）アクリル酸、イタコン酸、クロトン酸、マレイン酸、フマル酸、カルボキシエチル（メタ）アクリレート、カルボキシペンチル（メタ）アクリレートからなどが挙げられ、これらの化合物群の中から選択された、少なくとも１種以上であることが好ましい。
芳香族系モノマーとしては、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート等の芳香族基含有（メタ）アクリル酸エステル類のほか、スチレン等が挙げられる。
上記以外の共重合性ビニルモノマーとしては、アクリルアミド、アクリロニトリル、メチルビニルエーテル、エチルビニルエーテル、酢酸ビニル、塩化ビニルなどの各種ビニルモノマーが挙げられる。
Examples of the copolymerizable vinyl monomer containing a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-. Hydroxyl-containing (meth) acrylic acid esters such as hydroxyhexyl (meth) acrylate and 8-hydroxyoctyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and N-hydroxyethyl ( Examples thereof include hydroxyl group-containing (meth) acrylamides such as meta) acrylamide, and at least one selected from these compound groups is preferable.
Examples of the copolymerizable vinyl monomer containing a carboxyl group include (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, carboxyethyl (meth) acrylate, and carboxypentyl (meth) acrylate. At least one selected from these compound groups is preferable.
Examples of the aromatic monomer include aromatic group-containing (meth) acrylic acid esters such as benzyl (meth) acrylate and phenoxyethyl (meth) acrylate, as well as styrene and the like.
Examples of copolymerizable vinyl monomers other than the above include various vinyl monomers such as acrylamide, acrylonitrile, methyl vinyl ether, ethyl vinyl ether, vinyl acetate, and vinyl chloride.
また、本発明に用いる粘着剤成分の共重合組成物として、
（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸アルキルエステルモノマーの少なくとも１種と、（Ｂ）水酸基および／またはカルボキシル基を含有する共重合性ビニルモノマーの少なくとも１種と、からなる共重合組成物、
（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸アルキルエステルモノマーの少なくとも１種と、ビニル基を有する共重合性ビニルモノマーの少なくとも１種と、からなる共重合組成物
（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸アルキルエステルモノマーの少なくとも１種と、芳香族系モノマーの少なくとも１種と、からなる共重合組成物、
（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸アルキルエステルモノマーの少なくとも１種と、（Ｂ）水酸基および／またはカルボキシル基を含有する共重合性ビニルモノマーの少なくとも１種と、芳香族系モノマーの少なくとも１種と、からなる共重合組成物、等が挙げられる。
また、（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸アルキルエステルモノマーの少なくとも２種以上からなる共重合組成物を採用することもできる。この場合、（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸アルキルエステルモノマー以外の共重合性ビニルモノマーを用いなくても共重合組成物とすることができる。
Further, as a copolymer composition of the pressure-sensitive adhesive component used in the present invention,
(A) At least one kind of (meth) acrylic acid alkyl ester monomer having an alkyl group having C1 to C14 carbon atoms, and (B) at least one kind of copolymerizable vinyl monomer containing a hydroxyl group and / or a carboxyl group. Copolymerization composition consisting of
(A) A copolymer composition (A) comprising at least one (meth) acrylic acid alkyl ester monomer having an alkyl group having C1 to C14 carbon atoms and at least one copolymerizable vinyl monomer having a vinyl group (A). A copolymer composition comprising at least one (meth) acrylic acid alkyl ester monomer having an alkyl group having C1 to C14 carbon atoms and at least one aromatic monomer.
(A) At least one kind of (meth) acrylic acid alkyl ester monomer having an alkyl group having C1 to C14 carbon atoms, and (B) at least one kind of copolymerizable vinyl monomer containing a hydroxyl group and / or a carboxyl group. Examples thereof include a copolymer composition comprising at least one kind of aromatic monomer and the like.
Further, a copolymer composition consisting of at least two or more kinds of (meth) acrylic acid alkyl ester monomers having (A) alkyl groups having C1 to C14 carbon atoms can also be adopted. In this case, the copolymerization composition can be obtained without using a copolymerizable vinyl monomer other than the (meth) acrylic acid alkyl ester monomer having (A) alkyl groups having C1 to C14 carbon atoms.
アクリル系共重合体等の共重合組成物の重合方法は、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。アクリル系共重合体の重量平均分子量は、２０万〜２００万であることが好ましい。 The polymerization method of the copolymer composition such as an acrylic copolymer is not particularly limited, and a known polymerization method such as a solution polymerization method and an emulsion polymerization method can be used as appropriate. The weight average molecular weight of the acrylic copolymer is preferably 200,000 to 2,000,000.
本発明の粘着剤組成物は、粘着剤層を形成する際に前記共重合組成物を架橋することが好ましい。架橋をするため、粘着剤組成物が既知の架橋剤を含んでも良く、紫外線（ＵＶ）など光架橋で架橋しても良い。架橋剤としては、２官能以上のイソシアネート系架橋剤、２官能以上のエポキシ系架橋剤、アルミニウムキレート系架橋剤からなる化合物群のうちから選択される１種以上の架橋剤が好ましい。架橋剤を用いる場合は、前記共重合組成物の１００重量部に対して、０．１〜５重量部含有することが好ましい。 The pressure-sensitive adhesive composition of the present invention preferably crosslinks the copolymerization composition when forming the pressure-sensitive adhesive layer. For cross-linking, the pressure-sensitive adhesive composition may contain a known cross-linking agent, or may be cross-linked by optical cross-linking such as ultraviolet rays (UV). As the cross-linking agent, one or more cross-linking agents selected from the compound group consisting of a bifunctional or higher functional isocyanate-based cross-linking agent, a bifunctional or higher functional epoxy-based cross-linking agent, and an aluminum chelate-based cross-linking agent are preferable. When a cross-linking agent is used, it is preferably contained in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the copolymer composition.
本発明の粘着剤組成物は、帯電防止性能を付与するため、帯電防止剤を含有する。帯電防止剤は、常温（例えば３０℃）で固体であることが好ましく、より具体的には、帯電防止剤の融点が、３０〜５０℃のイオン化合物である。本発明は、帯電防止剤として、融点３０〜５０℃の疎水性の４級オニウム塩を含有することを特徴とする。
これらの帯電防止剤は、融点が低いため、また、長鎖のアルキル基を有するため、アクリル系ポリマーとの親和性は高いと推測される。
The pressure-sensitive adhesive composition of the present invention contains an antistatic agent in order to impart antistatic performance. The antistatic agent is preferably a solid at room temperature (for example, 30 ° C.), and more specifically, it is an ionic compound having an antistatic agent having a melting point of 30 to 50 ° C. The present invention is characterized by containing a hydrophobic quaternary onium salt having a melting point of 30 to 50 ° C. as an antistatic agent.
Since these antistatic agents have a low melting point and have a long-chain alkyl group, it is presumed that they have a high affinity with an acrylic polymer.
融点３０〜５０℃の疎水性の４級オニウム塩である帯電防止剤としては、例えば、炭素数８〜１８のアルキル基を有するアルキルジメチルベンジルアンモニウム塩、炭素数８〜１８のアルキル基を有するジアルキルメチルベンジルアンモニウム塩、炭素数８〜１８のアルキル基を有するトリアルキルベンジルアンモニウム塩、炭素数８〜１８のアルキル基を有するテトラアルキルアンモニウム塩、炭素数８〜１８のアルキル基を有するアルキルジメチルベンジルホスホニウム塩、炭素数８〜１８のアルキル基を有するジアルキルメチルベンジルホスホニウム塩、炭素数８〜１８のアルキル基を有するトリアルキルベンジルホスホニウム塩、炭素数８〜１８のアルキル基を有するテトラアルキルホスホニウム塩、炭素数１４〜２０のアルキル基を有するアルキルトリメチルアンモニウム塩、炭素数１４〜２０のアルキル基を有するアルキルジメチルエチルアンモニウム塩などの、水に難溶性の４級オニウム塩の中から、融点３０〜５０℃のものを選択して用いることができる。これらのアルキル基は、不飽和結合を有するアルケニル基であってもよい。 Examples of the antistatic agent which is a hydrophobic quaternary onium salt having a melting point of 30 to 50 ° C. include an alkyldimethylbenzylammonium salt having an alkyl group having 8 to 18 carbon atoms and a dialkyl having an alkyl group having 8 to 18 carbon atoms. Methylbenzylammonium salt, trialkylbenzylammonium salt having an alkyl group having 8 to 18 carbon atoms, tetraalkylammonium salt having an alkyl group having 8 to 18 carbon atoms, alkyldimethylbenzylphosphonium having an alkyl group having 8 to 18 carbon atoms Salt, dialkylmethylbenzylphosphonium salt having an alkyl group having 8 to 18 carbon atoms, trialkylbenzylphosphonium salt having an alkyl group having 8 to 18 carbon atoms, tetraalkylphosphonium salt having an alkyl group having 8 to 18 carbon atoms, carbon Among quaternary onium salts that are sparingly soluble in water, such as alkyltrimethylammonium salts having an alkyl group of 14 to 20 and alkyldimethylethylammonium salts having an alkyl group of 14 to 20 carbon atoms, the melting point is 30 to 50 ° C. Can be selected and used. These alkyl groups may be alkenyl groups having an unsaturated bond.
炭素数８〜１８のアルキル基としては、オクチル基、ノニル基、デシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基などが挙げられる。天然油脂に由来する混合アルキル基であってもよい。炭素数８〜１８のアルケニル基としては、オクテニル基、ノネニル基、デセニル基、ドデセニル基、トリデセニル基、テトラデセニル基、ペンタデセニル基、ヘキサデセニル基、ヘプタデセニル基、オクタデセニル基、オレイル基、リノレイル基などが挙げられる。
炭素数１４〜２０のアルキル基としては、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基などが挙げられる。天然油脂に由来する混合アルキル基であってもよい。炭素数１４〜２０のアルケニル基としては、テトラデセニル基、ペンタデセニル基、ヘキサデセニル基、ヘプタデセニル基、オクタデセニル基、オレイル基、リノレイル基、ノナデセニル基、イコセニル基などが挙げられる。
Examples of the alkyl group having 8 to 18 carbon atoms include an octyl group, a nonyl group, a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group and an octadecyl group. It may be a mixed alkyl group derived from natural fats and oils. Examples of the alkenyl group having 8 to 18 carbon atoms include an octenyl group, a nonenyl group, a decenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, an oleyl group and a linoleyl group. ..
Examples of the alkyl group having 14 to 20 carbon atoms include a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecil group and an icosyl group. It may be a mixed alkyl group derived from natural fats and oils. Examples of the alkenyl group having 14 to 20 carbon atoms include a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, an oleyl group, a linoleyl group, a nonadesenyl group and an icosenyl group.
４級オニウム塩のカウンターアニオンとしては、クロリド（Ｃｌ−）、ブロミド（Ｂｒ−）、メチルサルフェート（ＣＨ３ＯＳＯ３ −）、エチルサルフェート（Ｃ２Ｈ５ＯＳＯ３ −）、パラトルエンスルホネート（ｐ−ＣＨ３Ｃ６Ｈ４ＳＯ３ −）等が挙げられる。 Counter anions for the quaternary onium salt include chloride (Cl − ), bromide (Br − ), methyl sulfate (CH 3 OSO 3 − ), ethyl sulfate (C 2 H 5 OSO 3 − ), and paratoluene sulfonate (p −). CH 3 C 6 H 4 SO 3 -) and the like.
４級オニウム塩の具体例としては、ドデシルジメチルベンジルアンモニウムクロリド、ドデシルジメチルベンジルアンモニウムブロミド、テトラデシルジメチルベンジルアンモニウムクロリド、テトラデシルジメチルベンジルアンモニウムブロミド、ヘキサデシルジメチルベンジルアンモニウムクロリド、ヘキサデシルジメチルベンジルアンモニウムブロミド、オクタデシルジメチルベンジルアンモニウムクロリド、オクタデシルジメチルベンジルアンモニウムブロミド、トリオクチルベンジルアンモニウムクロリド、トリオクチルベンジルアンモニウムブロミド、トリオクチルベンジルホスホニウムクロリド、トリオクチルベンジルホスホニウムブロミド、トリス（デシル）ベンジルアンモニウムクロリド、トリス（デシル）ベンジルアンモニウムブロミド、トリス（デシル）ベンジルホスホニウムクロリド、トリス（デシル）ベンジルホスホニウムブロミド、テトラオクチルアンモニウムクロリド、テトラオクチルアンモニウムブロミド、テトラオクチルホスホニウムクロリド、テトラオクチルホスホニウムブロミド、テトラノニルアンモニウムクロリド、テトラノニルアンモニウムブロミド、テトラノニルホスホニウムクロリド、テトラノニルホスホニウムブロミド、テトラキス（デシル）アンモニウムクロリド、テトラキス（デシル）アンモニウムブロミド、テトラキス（デシル）ホスホニウムクロリド、テトラキス（デシル）ホスホニウムブロミド、等が挙げられる。
なお、「トリス（デシル）」、「テトラキス（デシル）」は、炭素数１０のアルキル基であるデシル基を３個又は４個有することを意味し、炭素数１３のアルキル基であるトリデシル基や、炭素数１４のアルキル基であるテトラデシル基とは区別される。
Specific examples of the quaternary onium salt include dodecyldimethylbenzylammonium chloride, dodecyldimethylbenzylammonium bromide, tetradecyldimethylbenzylammonium chloride, tetradecyldimethylbenzylammonium bromide, hexadecyldimethylbenzylammonium chloride, hexadecyldimethylbenzylammonium bromide, Octadecyldimethylbenzylammonium chloride, octadecyldimethylbenzylammonium bromide, trioctylbenzylammonium chloride, trioctylbenzylammonium bromide, trioctylbenzylphosphonium chloride, trioctylbenzylphosphonium bromide, tris (decyl) benzylammonium chloride, tris (decyl) benzylammonium Bromid, Tris (decyl) benzylphosphonium chloride, Tris (decyl) benzylphosphonium bromide, Tetraoctylammonium chloride, Tetraoctylammonium bromide, Tetraoctylphosphonium chloride, Tetraoctylphosphonium bromide, Tetranonylammonium chloride, Tetranonylammonium bromide, Tetranonyl Examples thereof include phosphonium chloride, tetranonyl phosphonium bromide, tetrakis (decyl) ammonium chloride, tetrakis (decyl) ammonium bromide, tetrakis (decyl) phosphonium chloride, and tetrakis (decyl) phosphonium bromide.
In addition, "tris (decyl)" and "tetrakis (decyl)" mean having 3 or 4 decyl groups which are alkyl groups having 10 carbon atoms, and tridecyl groups which are alkyl groups having 13 carbon atoms and , Is distinguished from the tetradecyl group, which is an alkyl group having 14 carbon atoms.
前記４級オニウム塩が、２５℃の水１００ｇに対する溶解度が５ｇ以下であることが好ましい。前記４級オニウム塩は、共重合組成物の１００重量部に対して、（Ｃ）前記４級オニウム塩を０．１〜１０重量部、を必須成分として含有することが好ましい。 The quaternary onium salt preferably has a solubility of 5 g or less in 100 g of water at 25 ° C. The quaternary onium salt preferably contains (C) 0.1 to 10 parts by weight of the quaternary onium salt as an essential component with respect to 100 parts by weight of the copolymer composition.
粘着剤組成物に帯電防止剤を添加して帯電防止性能を持たせる場合、前記粘着剤組成物を積層して形成された粘着剤層において、前記粘着剤層の表面抵抗率が１．０×１０＋１２Ω／□以下であることが好ましい。表面抵抗率が大きいと、剥離時に帯電で発生した静電気を逃がす性能に劣る。そのため、表面抵抗率を十分に小さくすることにより、粘着剤層を被着体が剥がす時に発生する、静電気に伴って生じる剥離帯電圧が低減され、被着体の制御用電子回路等に影響することを抑制することができる。 When an antistatic agent is added to the pressure-sensitive adhesive composition to provide antistatic performance, the surface resistivity of the pressure-sensitive adhesive layer is 1.0 × in the pressure-sensitive adhesive layer formed by laminating the pressure-sensitive adhesive composition. It is preferably 10 + 12 Ω / □ or less. If the surface resistivity is large, the performance of releasing static electricity generated by charging at the time of peeling is inferior. Therefore, by sufficiently reducing the surface resistivity, the peeling band voltage generated when the adherend peels off the pressure-sensitive adhesive layer due to static electricity is reduced, which affects the electronic circuit for controlling the adherend and the like. Can be suppressed.
本発明の粘着剤組成物は、粘着剤層を形成する際に共重合組成物を架橋させることが好ましい。粘着剤層の共重合組成物を架橋させるために、粘着剤組成物が既知の架橋剤を含んでいることが好ましい。本発明で使用される架橋剤は、２官能以上のイソシアネート系架橋剤、２官能以上のエポキシ系架橋剤、アルミニウムキレート系架橋剤からなる化合物群のうちから選択される１種以上の架橋剤であることが好ましい。架橋剤は、１種類を単独で使用してもよいし、２種類以上を組み合わせて併用してもよい。 The pressure-sensitive adhesive composition of the present invention preferably crosslinks the copolymerization composition when forming the pressure-sensitive adhesive layer. In order to crosslink the copolymerization composition of the pressure-sensitive adhesive layer, it is preferable that the pressure-sensitive adhesive composition contains a known cross-linking agent. The cross-linking agent used in the present invention is one or more cross-linking agents selected from the compound group consisting of a bifunctional or higher functional isocyanate-based cross-linking agent, a bifunctional or higher functional epoxy-based cross-linking agent, and an aluminum chelate-based cross-linking agent. It is preferable to have. One type of cross-linking agent may be used alone, or two or more types may be used in combination.
２官能以上のイソシアネート系化合物としては、１分子中に少なくとも２個以上のイソシアネート（ＮＣＯ）基を有するポリイソシアネート化合物であればよく、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、ジフェニルメタンジイソシアネート、トリレンジイソシアネート、キシリレンジイソシアネート等のジイソシアネート類（１分子中に２個のＮＣＯ基を有する化合物）のビュレット変性体やイソシアヌレート変性体、トリメチロールプロパンやグリセリン等の３価以上のポリオール（１分子中に少なくとも３個以上のＯＨ基を有する化合物）とのアダクト体（ポリオール変性体）などが挙げられる。
また、３官能以上のイソシアネート化合物が、１分子中に少なくとも３個以上のイソシアネート（ＮＣＯ）基を有するポリイソシアネート化合物であり、特にヘキサメチレンジイソシアネート化合物のイソシアヌレート体、イソホロンジイソシアネート化合物のイソシアヌレート体、ヘキサメチレンジイソシアネート化合物のアダクト体、イソホロンジイソシアネート化合物のアダクト体、ヘキサメチレンジイソシアネート化合物のビュレット体、イソホロンジイソシアネート化合物のビュレット体からなる化合物群の中から選択された、少なくとも一種以上であることが好ましい。
２官能以上のイソシアネート系架橋剤は、アクリル系共重合体の１００重量部に対して、０．０１〜５．０重量部含まれることが好ましく、さらに好ましくは０．０２〜３．０重量部含まれるのがよい。
The bifunctional or higher functional isocyanate compound may be a polyisocyanate compound having at least two or more isocyanate (NCO) groups in one molecule, and may be hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, or xylylene diisocyanate. Bullet-modified or isocyanurate-modified compounds of diisocyanates such as isocyanate (compounds having two NCO groups in one molecule), trivalent or higher polyols such as trimethylolpropane and glycerin (at least three or more in one molecule) Examples thereof include an adduct form (polypolymodified form) with a compound having an OH group of.
Further, the trifunctional or higher functional isocyanate compound is a polyisocyanate compound having at least three or more isocyanate (NCO) groups in one molecule, particularly, an isocyanurate form of a hexamethylene diisocyanate compound, an isocyanurate form of an isophorone diisocyanate compound, and the like. It is preferably at least one selected from the compound group consisting of an adduct body of a hexamethylene diisocyanate compound, an adduct body of an isophorone diisocyanate compound, a bullet body of a hexamethylene diisocyanate compound, and a bullet body of an isophorone diisocyanate compound.
The bifunctional or higher functional isocyanate-based cross-linking agent is preferably contained in an amount of 0.01 to 5.0 parts by weight, more preferably 0.02 to 3.0 parts by weight, based on 100 parts by weight of the acrylic copolymer. It should be included.
２官能以上のエポキシ系化合物としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂等のビスフェノール型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、グリシジルエーテル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂等のなどのエポキシ樹脂が挙げられる。これらの中でも、２官能のビスフェノールＡ型およびビスフェノールＦ型等のビスフェノール型エポキシ樹脂が、低粘度の液状であり取り扱い易いことからより好ましい。
また、２官能以上のエポキシ系化合物は、具体的には、グリセリンポリ（例えばジ、トリ）グリシジルエーテル、ソルビトールポリグリシジルエーテル、ペンタエリスリトールポリ（例えばジ、トリ、テトラ）グリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル等が挙げられる。
２官能以上のエポキシ系化合物は、アクリル系共重合体の１００重量部に対して、０．０１〜５．０重量部含まれることが好ましく、さらに好ましくは０．０２〜３．０重量部含まれるのが良い。
Examples of the bifunctional or higher functional epoxy compound include bisphenol type epoxy resin such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, glycidyl ether type epoxy resin, and glycidyl amine. Examples thereof include epoxy resins such as type epoxy resins. Among these, bisphenol type epoxy resins such as bifunctional bisphenol A type and bisphenol F type are more preferable because they are low-viscosity liquids and easy to handle.
Specific examples of the bifunctional or higher functional epoxy compound include glycerin poly (for example, di, tri) glycidyl ether, sorbitol polyglycidyl ether, pentaerythritol poly (for example, di, tri, tetra) glycidyl ether, and trimethylolpropane poly. Examples include glycidyl ether and the like.
The bifunctional or higher functional epoxy compound is preferably contained in an amount of 0.01 to 5.0 parts by weight, more preferably 0.02 to 3.0 parts by weight, based on 100 parts by weight of the acrylic copolymer. It is good to be.
共重合組成物がカルボキシル基または水酸基を有している場合には、これらの官能基とアルミニウムキレート系化合物との架橋を生じる。このため、アルミニウムキレート系化合物を架橋剤として使用することができる。
本発明で使用できるアルミニウムキレート系化合物としては、アセチルアセトンアルミニウム塩、アセト酢酸エチルアルミニウム塩などのケトエノール互変異性体アルミニウム塩が好ましく、ケトエノール互変異性体アルミニウム塩の中でもアセチルアセトンアルミニウム塩は、架橋剤としての機能に優れるものとして好適に用いられる。
ケトエノール互変異性体アルミニウム塩に用いられる、ケトエノール互変異性体としては、アセチルアセトン等のβ−ジケトンや、アセト酢酸エチル、アセト酢酸メチル、アセト酢酸オレイル、アセト酢酸アルキル等のβ−ケトカルボン酸エステル等が挙げられる。
ケトエノール互変異性体アルミニウム塩としては、具体的には、アルミニウムトリス（アセチルアセトネート）、アルミニウムトリス（エチルアセトアセテート）、アルミニウムモノアセチルアセトネートビス（エチルアセトアセテート）、アルミニウムモノアセチルアセトネートビスオレイルアセトアセテート、エチルアセトアセテートアルミニウムジイソプロピレート、アルキルアセトアセテートアルミニウムジイソプロピレート等が挙げられる。
When the copolymerization composition has a carboxyl group or a hydroxyl group, cross-linking between these functional groups and an aluminum chelate compound occurs. Therefore, an aluminum chelate compound can be used as a cross-linking agent.
As the aluminum chelate compound that can be used in the present invention, keto-enol tautomer aluminum salts such as acetylacetone aluminum salt and ethyl acetoacetate aluminum salt are preferable, and among the keto-enol tautomer aluminum salts, acetylacetone aluminum salt is used as a cross-linking agent. It is preferably used as having excellent functions.
Examples of the keto-enol tautomer used for the keto-enol tautomer aluminum salt include β-diketone such as acetylacetone and β-ketocarboxylic acid ester such as ethyl acetoacetate, methyl acetoacetate, oleyl acetoacetic acid and alkyl acetoacetic acid. Can be mentioned.
Specific examples of the keto-enol tautomer aluminum salt include aluminum tris (acetylacetoneate), aluminumtris (ethylacetate acetate), aluminum monoacetylacetone bis (ethylacetacetate), and aluminum monoacetylacetone bisoleyl. Examples thereof include acetoacetate, ethylacetateacetate aluminum diisopropyrate, and alkylacetate acetate aluminum diisopropyrate.
さらに、その他の成分として、シランカップリング剤、酸化防止剤、界面活性剤、硬化促進剤、可塑剤、充填剤、硬化遅延剤、加工助剤、老化防止剤などの公知の添加剤を適宜に配合することができる。これらは、単独でもしくは２種以上併せて用いることができる。 Further, as other components, known additives such as a silane coupling agent, an antioxidant, a surfactant, a curing accelerator, a plasticizer, a filler, a curing retarder, a processing aid, and an antiaging agent are appropriately added. Can be blended. These can be used alone or in combination of two or more.
本発明の粘着フィルムは、本発明の粘着剤組成物からなる粘着剤層を、基材又は離型フィルムの片面上に形成することで製造することができる。また、本発明の粘着フィルムは、本発明の粘着剤組成物からなる粘着剤層を、基材の両面に形成することもできる。
粘着剤層の形成に用いる基材フィルムや、粘着面を保護する離型フィルム（セパレーター）としては、ポリエステルフィルムなどの樹脂フィルム等を用いることができる。
基材フィルムには、樹脂フィルムの粘着剤層が形成された側とは反対面に、シリコーン系、フッ素系の離型剤やコート剤、シリカ微粒子等による防汚処理、帯電防止剤の塗布や練り込み等による帯電防止処理を施すことができる。
剥離フィルムには、粘着剤層の粘着面と合わされる側の面に、シリコーン系、フッ素系の離型剤などにより離型処理が施される。
偏光板や位相差フィルムなどの各種光学フィルムを、液晶セルなどの光学部品及び他の光学フィルムに貼り合せる、粘着フィルムの粘着剤層は、十分な透明性を有することが好ましい。また、偏光板用の表面保護フィルムなどの光学用の表面保護フィルムの場合は、基材フィルム及び粘着剤層は、十分な透明性を有することが好ましい。
The pressure-sensitive adhesive film of the present invention can be produced by forming a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition of the present invention on one side of a base material or a release film. Further, in the pressure-sensitive adhesive film of the present invention, a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition of the present invention can be formed on both sides 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.
The release film is subjected to a mold release treatment with a silicone-based or fluorine-based mold release agent or the like on the surface of the pressure-sensitive adhesive layer that is combined with the adhesive surface.
The pressure-sensitive adhesive layer of the pressure-sensitive adhesive film, which adheres various optical films such as a polarizing plate and a retardation film to an optical component such as a liquid crystal cell and another optical film, preferably has sufficient transparency. Further, in the case of an optical surface protective film such as a surface protective film for a polarizing plate, it is preferable that the base film and the pressure-sensitive adhesive layer have sufficient transparency.
粘着フィルムが基材フィルムを有する場合、本発明の粘着フィルムは、例えば、表面保護フィルム、偏光板用の表面保護フィルム、光学用の表面保護フィルム、粘着剤付き光学フィルム、粘着剤付き偏光板などに好適に用いることができる。 When the adhesive film has a base film, the adhesive film of the present invention may be, for example, a surface protective film, a surface protective film for a polarizing plate, a surface protective film for optical use, an optical film with an adhesive, a polarizing plate with an adhesive, or the like. Can be suitably used for.
粘着フィルムが基材フィルムを有しない場合、１つの粘着剤層の両面に、それぞれ離型フィルムの離型処理が施された面を合わせることで、「離型フィルム／粘着剤層／離型フィルム」の構成とすることもできる。この場合、両側の離型フィルムを、順次、あるいは同時に剥離して粘着面を露出することにより、光学フィルム等の光学部材と貼合可能になる。光学フィルムとしては、偏光フィルム、位相差フィルム、反射防止フィルム、防眩（アンチグレア）フィルム、紫外線吸収フィルム、赤外線吸収フィルム、光学補償フィルム、輝度向上フィルム等が挙げられる。
この場合、本発明の粘着フィルムは、偏光板とディスプレイパネルの貼り合わせに用いることができる。ディスプレイパネルとしては液晶表示装置や有機ＥＬ等が挙げられるが、これらに限定されるものではない。
また、本発明の粘着フィルムは、偏光板を構成する材料の貼り合わせ用粘着フィルム、偏光板を主とする液晶表示装置の周辺部材用の各種光学フィルム、タッチパネル用フィルム、電子ペーパー用フィルム、有機ＥＬ用フィルム等に用いることができる。
When the pressure-sensitive adhesive film does not have a base film, the release-treated surfaces of the release film are aligned on both sides of one pressure-sensitive adhesive layer to form a "release film / pressure-sensitive adhesive layer / release film". It can also be configured as. In this case, the release films on both sides are peeled off sequentially or at the same time to expose the adhesive surface, so that the release films 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, and a brightness improving film.
In this case, the adhesive film of the present invention can be used for bonding the polarizing plate and the display panel. Examples of the display panel include, but are not limited to, a liquid crystal display device, an organic EL, and the like.
The adhesive film of the present invention includes an adhesive film for bonding materials constituting a polarizing plate, various optical films for peripheral members of a liquid crystal display device mainly a polarizing plate, a film for a touch panel, a film for electronic paper, and an organic film. It can be used for EL films and the like.
また、これらの光学フィルムの少なくとも一方の面に、前記粘着剤層が積層されてなる粘着剤層付き光学フィルムとすることができる。具体的には、「光学フィルム／粘着剤層／光学フィルム」、「光学フィルム／粘着剤層／離型フィルム」、「光学フィルム／粘着剤層」、「光学フィルム／粘着剤層／光学フィルム／粘着剤層／光学フィルム」、「光学フィルム／粘着剤層／光学フィルム／粘着剤層／離型フィルム」、「離型フィルム／粘着剤層／光学フィルム／粘着剤層／離型フィルム」等の構成が挙げられる。
例えば、「光学フィルム／粘着剤層／離型フィルム」のように、離型フィルムで保護された粘着剤層を有する場合、離型フィルムを剥がして、「光学フィルム／粘着剤層」のように粘着剤層を露出させ、他の光学フィルムと貼合することにより、粘着剤層が層間の貼合に用いられた「光学フィルム／粘着剤層／光学フィルム」のような構成が得られる。
Further, an optical film with an adhesive layer obtained by laminating the adhesive layer on at least one surface of these optical films can be obtained. Specifically, "optical film / adhesive layer / optical film", "optical film / adhesive layer / release film", "optical film / adhesive layer", "optical film / adhesive layer / optical film /""Adhesive film / optical film", "optical film / adhesive layer / optical film / adhesive layer / release film", "release film / adhesive layer / optical film / adhesive layer / release film", etc. The configuration can be mentioned.
For example, when having an adhesive layer protected by a release film such as "optical film / adhesive layer / release film", the release film is peeled off to form "optical film / adhesive layer". By exposing the pressure-sensitive adhesive layer and bonding it with another optical film, a configuration such as "optical film / pressure-sensitive adhesive layer / optical film" in which the pressure-sensitive adhesive layer is used for bonding between layers can be obtained.
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.
＜アクリル系共重合体の製造＞
［実施例１］
撹拌機、温度計、還流冷却器及び窒素導入管を備えた反応装置に、窒素ガスを導入して、反応装置内の空気を窒素ガスで置換した。その後、反応装置に２−エチルヘキシルアクリレート１００重量部、６−ヒドロキシヘキシルアクリレート１．５重量部とともに溶剤（酢酸エチル）を１００部加えた。その後、重合開始剤としてアゾビスイソブチロニトリル０．１重量部を２時間かけて滴下させ、６５℃で８時間反応させ、重量平均分子量５０万の、実施例１のアクリル系共重合体溶液１を得た。
［実施例２〜６及び比較例１〜３］
単量体の組成を各々、表１の（Ａ）、（Ａ′）、及び（Ｂ）の記載のようにする以外は、上記の実施例１に用いるアクリル系共重合体溶液１と同様にして、実施例２〜６及び比較例１〜３に用いるアクリル系共重合体溶液を得た。
<Manufacturing of acrylic copolymer>
[Example 1]
Nitrogen gas was introduced into a reactor equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction pipe, and the air in the reactor was replaced with nitrogen gas. Then, 100 parts by weight of 2-ethylhexyl acrylate and 1.5 parts by weight of 6-hydroxyhexyl acrylate and 100 parts of solvent (ethyl acetate) were added to the reaction apparatus. Then, 0.1 part by weight of azobisisobutyronitrile as a polymerization initiator was added dropwise over 2 hours and reacted at 65 ° C. for 8 hours to obtain an acrylic copolymer solution of Example 1 having a weight average molecular weight of 500,000. I got 1.
[Examples 2 to 6 and Comparative Examples 1 to 3]
The composition of the monomer is the same as that of the acrylic copolymer solution 1 used in Example 1 above, except that the compositions of the monomers are as described in (A), (A'), and (B) of Table 1, respectively. Then, the acrylic copolymer solutions used in Examples 2 to 6 and Comparative Examples 1 to 3 were obtained.
＜粘着剤組成物及び粘着フィルムの製造＞
［実施例１］
上記のとおり製造したアクリル系共重合体溶液１（そのうちアクリル系共重合体が１００重量部）に対して、コロネートＨＸ １．５重量部と、トリオクチルホスホニウムベンジルクロリド２．０重量部を加えて撹拌混合して実施例１の粘着剤組成物を得た。この粘着剤組成物をシリコーン樹脂コートされたポリエチレンテレフタレート（ＰＥＴ）フィルムからなる剥離フィルムの上に塗布後、９０℃で乾燥することによって溶剤を除去し、粘着剤層の厚さが２５μｍである粘着フィルムを得た。
その後、一方の面に帯電防止及び防汚処理されたポリエチレンテレフタレート（ＰＥＴ）フィルムの帯電防止及び防汚処理された面とは反対の面に粘着フィルムを転写させ、「帯電防止及び防汚処理されたＰＥＴフィルム／粘着剤層／剥離フィルム（シリコーン樹脂コートされたＰＥＴフィルム）」の積層構成を有する実施例１の粘着フィルムを得た。
［実施例２〜６及び比較例１〜３］
添加剤の組成を各々、表１の「架橋剤」及び（Ｃ）の記載のようにする以外は、上記の実施例１の粘着フィルムと同様にして、実施例２〜６及び比較例１〜３の粘着フィルムを得た。
<Manufacturing of adhesive composition and adhesive film>
[Example 1]
To 1.5 parts by weight of the acrylic copolymer solution 1 (of which 100 parts by weight is the acrylic copolymer) produced as described above, 1.5 parts by weight of coronate HX and 2.0 parts by weight of trioctylphosphonium benzyl chloride were added. The pressure-sensitive adhesive composition of Example 1 was obtained by stirring and mixing. This pressure-sensitive adhesive composition is applied onto a release film made of a polyethylene terephthalate (PET) film coated with a silicone resin, and then dried at 90 ° C. to remove the solvent, and the pressure-sensitive adhesive layer has a thickness of 25 μm. I got a film.
After that, the adhesive film is transferred to the surface opposite to the antistatic and antifouling treated polyethylene terephthalate (PET) film on one surface, and "antistatic and antifouling treated". An adhesive film of Example 1 having a laminated structure of "PET film / adhesive layer / release film (PET film coated with silicone resin)" was obtained.
[Examples 2 to 6 and Comparative Examples 1 to 3]
Examples 2 to 6 and Comparative Examples 1 to 6 are the same as the pressure-sensitive adhesive film of Example 1 above, except that the composition of the additive is as described in "Crosslinking Agent" and (C) of Table 1, respectively. An adhesive film of 3 was obtained.
表１において、各成分の配合比は、（Ａ）と（Ａ′）との合計量を１００重量部として求めた重量部の数値を括弧で囲んで示す。また、表１に用いた各成分の略記号の化合物名を、表２に示す。また、表２（Ｃ）群には、帯電防止剤の２５℃における水１００ｇへの溶解度（ｇ）、及び融点（℃）を合わせて示した。
なお、コロネート（登録商標）ＨＸ、同ＨＬは日本ポリウレタン工業株式会社の商品名であり、ＴＥＴＲＡＤ（登録商標）−Ｘは三菱ガス化学株式会社の商品名であり、デュラネート（登録商標）２４Ａ−１００は旭化成ケミカルズ株式会社の商品名である。
In Table 1, the compounding ratio of each component is shown by enclosing the numerical value of the part by weight obtained by assuming that the total amount of (A) and (A') is 100 parts by weight. Table 2 shows the compound names of the abbreviations of each component used in Table 1. Further, in Group 2 (C), the solubility (g) of the antistatic agent in 100 g of water at 25 ° C. and the melting point (° C.) are also shown.
Coronate (registered trademark) HX and HL are trade names of Nippon Polyurethane Industry Co., Ltd., TETRAD (registered trademark) -X is a trade name of Mitsubishi Gas Chemical Company, Inc., and Duranate (registered trademark) 24A-100. Is the trade name of Asahi Kasei Chemicals Co., Ltd.
＜試験方法及び評価＞
実施例１〜６及び比較例１〜３における粘着フィルムを２３℃、５０％ＲＨの雰囲気下で７日間エージングした後、剥離フィルム（シリコーン樹脂コートされたＰＥＴフィルム）を剥がして、粘着剤層を露出させた粘着フィルムを、表面抵抗率の測定試料とした。
さらに、この粘着剤層を露出させた粘着フィルムを、粘着剤層を介して液晶セルに貼られた偏光板の表面に貼り合わせ、１日放置した後、５０℃、５気圧、２０分間オートクレーブ処理し、室温でさらに１２時間放置したものを、粘着力の測定試料とした。
<Test method and evaluation>
The pressure-sensitive adhesive films of Examples 1 to 6 and Comparative Examples 1 to 3 were aged at 23 ° C. and 50% RH for 7 days, and then the release film (silicone resin-coated PET film) was peeled off to remove the pressure-sensitive adhesive layer. The exposed adhesive film was used as a sample for measuring the surface resistance.
Further, the pressure-sensitive adhesive film with the pressure-sensitive adhesive layer exposed is attached to the surface of the polarizing plate attached to the liquid crystal cell via the pressure-sensitive adhesive layer, left for one day, and then autoclaved at 50 ° C., 5 atmospheres, and 20 minutes. Then, the sample left at room temperature for another 12 hours was used as a sample for measuring the adhesive strength.
＜粘着剤層の表面抵抗率＞
エージングした後、偏光板に貼り合わせる前に、剥離フィルム（シリコーン樹脂コートされたＰＥＴフィルム）を剥がして粘着剤層を露出させ、抵抗率計ハイレスタＵＰ−ＨＴ４５０（三菱化学アナリテック製）を用いて粘着剤層の表面抵抗率（Ω／□）を測定した。
<Surface resistivity of adhesive layer>
After aging, before sticking to the polarizing plate, the release film (PET film coated with silicone resin) is peeled off to expose the adhesive layer, and the resistivity meter Hiresta UP-HT450 (manufactured by Mitsubishi Chemical Analytech) is used. The surface resistivity (Ω / □) of the pressure-sensitive adhesive layer was measured.
＜粘着力＞
上記で得られた粘着剤層を露出させた粘着フィルムを、２５ｍｍ幅の粘着フィルムに裁断し、偏光板の表面に貼り合わせた後、１８０°方向に引張試験機を用いて３０ｍ／ｍｉｎの剥離速度において剥がして測定した剥離強度を粘着力（Ｎ／２５ｍｍ）とした。
<Adhesive strength>
The pressure-sensitive adhesive film obtained above with the pressure-sensitive adhesive layer exposed is cut into a pressure-sensitive adhesive film having a width of 25 mm, attached to the surface of the polarizing plate, and then peeled off at 30 m / min in the 180 ° direction using a tensile tester. The peeling strength measured by peeling at a speed was defined as the adhesive strength (N / 25 mm).
＜耐汚染性＞
上記で得られた粘着剤層を露出させた粘着フィルムを、偏光板に貼り合せた後、６０℃９０％ＲＨの雰囲気下に２５０時間放置後、室温に取り出し、さらに１２時間放置した後、試料を３０ｍ／ｍｉｎの引張速度で１８０°剥離した際に偏光板表面に汚染移行の無いことを確認した。評価目標基準は、偏光板に汚染移行の無い場合を「○」、少なくとも一部汚染移行が確認された場合を「△」、全面に汚染移行が確認された場合を「×」と評価した。
<Stain resistance>
The pressure-sensitive adhesive film obtained above with the pressure-sensitive adhesive layer exposed was attached to a polarizing plate, left in an atmosphere of 60 ° C. and 90% RH for 250 hours, taken out to room temperature, left for another 12 hours, and then a sample. It was confirmed that there was no contamination transfer on the surface of the polarizing plate when the film was peeled off by 180 ° at a tensile speed of 30 m / min. The evaluation target criteria were evaluated as "○" when there was no contamination transfer on the polarizing plate, "Δ" when at least a partial contamination transfer was confirmed, and "x" when contamination transfer was confirmed on the entire surface.
表３に、評価結果を示す。なお、粘着剤層の表面抵抗率は、「ｍ×１０＋ｎ」を「ｍＥ＋ｎ」とする方式（ただし、ｍは任意の実数値、ｎは正の整数）により表記した。 Table 3 shows the evaluation results. The surface resistivity of the pressure-sensitive adhesive layer is expressed by a method in which "m × 10 + n " is set to "mE + n" (where m is an arbitrary real value and n is a positive integer).
実施例１〜６の粘着剤組成物及び粘着フィルムは、粘着剤組成物の中に帯電防止剤として融点３０〜５０℃の疎水性の４級オニウム塩を含有するため、表面抵抗率が十分に低く、耐汚染性が良好であった。帯電防止性については、表３に示すとおり、表面抵抗率がいずれも、１．０×１０＋１２Ω／□以下となっており、剥離帯電圧の低減効果を有している。
また、比較例１の粘着剤組成物及び粘着フィルムは、粘着剤組成物の中に帯電防止剤を含まないため、表面抵抗率が高く、しかも、耐汚染性に問題があった。
比較例２、３の粘着剤組成物及び粘着フィルムは、粘着剤組成物の中の帯電防止剤として、融点が５０℃を越える親水性の４級オニウム塩を含有するため、表面抵抗率が高く、しかも、耐汚染性に問題があった。
Since the pressure-sensitive adhesive compositions and pressure-sensitive adhesive films of Examples 1 to 6 contain a hydrophobic quaternary onium salt having a melting point of 30 to 50 ° C. as an antistatic agent in the pressure-sensitive adhesive composition, the surface resistivity is sufficient. It was low and had good stain resistance. As for the antistatic property, as shown in Table 3, the surface resistivity is 1.0 × 10 + 12 Ω / □ or less, and has the effect of reducing the peeling band voltage.
Further, since the pressure-sensitive adhesive composition and the pressure-sensitive adhesive film of Comparative Example 1 do not contain an antistatic agent in the pressure-sensitive adhesive composition, they have a high surface resistivity and have a problem in stain resistance.
The pressure-sensitive adhesive compositions and pressure-sensitive adhesive films of Comparative Examples 2 and 3 contain a hydrophilic quaternary onium salt having a melting point of more than 50 ° C. as an antistatic agent in the pressure-sensitive adhesive composition, and therefore have a high surface resistivity. Moreover, there was a problem in stain resistance.
本発明の粘着剤組成物は、疎水性の４級オニウム塩を帯電防止成分として粘着剤に併用することで、粘着剤との相溶性に優れるためブリードアウトや粘着フィルムを剥がした際に、被着体に汚染が生じてしまうなどのリワーク性の欠点である課題を改善することができ、産業上の利用価値が大である。 The pressure-sensitive adhesive composition of the present invention has excellent compatibility with the pressure-sensitive adhesive by using a hydrophobic quaternary onium salt as an antistatic component in combination with the pressure-sensitive adhesive. It is possible to improve the problem of reworkability such as contamination of the body, and it has great industrial utility value.
Claims (4)
前記アクリル系共重合体が、（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸アルキルエステルモノマーの少なくとも１種と、（Ｂ）水酸基および／またはカルボキシル基を含有する共重合性ビニルモノマーの少なくとも１種と、を共重合させた共重合体であり、
前記帯電防止剤が、融点３０〜５０℃の４級オニウム塩であり、前記４級オニウム塩が、２５℃の水１００ｇに対する溶解度が５ｇ以下である疎水性を有してなり、
前記４級オニウム塩が、４級アンモニウム塩または４級ホスホニウム塩の化合物群から選択した１種であり、
前記架橋剤が、２官能以上のイソシアネート系架橋剤、２官能以上のエポキシ系架橋剤からなる化合物群のうちから選択される１種以上であり、
前記粘着剤組成物が、前記アクリル系共重合体の１００重量部に対して、前記架橋剤の合計を０．１〜５重量部の割合で含有してなり、
前記４級オニウム塩のカウンターアニオンが、クロリド（Ｃｌ−）、ブロミド（Ｂｒ−）、メチルサルフェート（ＣＨ３ＯＳＯ３ −）、エチルサルフェート（Ｃ２Ｈ５ＯＳＯ３ −）、パラトルエンスルホネート（ｐ−ＣＨ３Ｃ６Ｈ４ＳＯ３ −）からなる群より選択した１種であることを特徴とする粘着フィルム。 A pressure-sensitive adhesive film obtained by laminating an pressure-sensitive adhesive composition containing an acrylic copolymer, a cross-linking agent, and an antistatic agent on one side of a base material.
The acrylic copolymer, copolymerizable containing at least one and, (B) a hydroxyl and / or carboxyl groups of the (A) carbon atoms in the alkyl group thereof C1 to C14 (meth) acrylic acid alkyl ester monomer and at least one vinyl monomer, a copolymer obtained by copolymerizing,
The antistatic agent is a quaternary onium salt having a melting point of 30 to 50 ° C., and the quaternary onium salt has a hydrophobic property of 5 g or less in solubility in 100 g of water at 25 ° C.
The quaternary onium salt is one selected from the compound group of the quaternary ammonium salt or the quaternary phosphonium salt.
The cross-linking agent is at least one selected from the compound group consisting of a bifunctional or higher functional isocyanate-based cross-linking agent and a bifunctional or higher functional epoxy-based cross-linking agent.
The pressure-sensitive adhesive composition contains the total amount of the cross-linking agent in a ratio of 0.1 to 5 parts by weight with respect to 100 parts by weight of the acrylic copolymer.
The counter anions of the quaternary onium salt are chloride (Cl − ), bromide (Br − ), methyl sulfate (CH 3 OSO 3 − ), ethyl sulfate (C 2 H 5 OSO 3 − ), and paratoluene sulfonate (p −). adhesive film, characterized in that) is one selected from the group consisting of - CH 3 C 6 H 4 SO 3.
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| JP4756626B2 (en) * | 2004-05-24 | 2011-08-24 | 日東電工株式会社 | Optical film with surface protective film and image display device |
| JP4971826B2 (en) * | 2007-02-23 | 2012-07-11 | 帝人デュポンフィルム株式会社 | Surface protective adhesive film |
| JP2010001360A (en) * | 2008-06-19 | 2010-01-07 | Teijin Dupont Films Japan Ltd | Adhesive film for surface protection |
| JP2013041037A (en) * | 2011-08-12 | 2013-02-28 | Fuji Xerox Co Ltd | Laminate film for electrophotography, image forming method, and information recording medium |
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2020
- 2020-02-26 JP JP2020030456A patent/JP6896120B2/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021193193A (en) * | 2020-02-26 | 2021-12-23 | 藤森工業株式会社 | Adhesive film and surface protective film |
| JP7239660B2 (en) | 2020-02-26 | 2023-03-14 | 藤森工業株式会社 | Adhesive film and surface protection film |
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| JP2020100833A (en) | 2020-07-02 |
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