JP5963113B2 - UV curable adhesive composition for optics and adhesive layer - Google Patents
UV curable adhesive composition for optics and adhesive layer Download PDFInfo
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- JP5963113B2 JP5963113B2 JP2012212018A JP2012212018A JP5963113B2 JP 5963113 B2 JP5963113 B2 JP 5963113B2 JP 2012212018 A JP2012212018 A JP 2012212018A JP 2012212018 A JP2012212018 A JP 2012212018A JP 5963113 B2 JP5963113 B2 JP 5963113B2
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- component
- meth
- acrylate
- weight
- sensitive adhesive
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- 239000000203 mixture Substances 0.000 title claims description 84
- 239000012790 adhesive layer Substances 0.000 title claims description 31
- 239000000853 adhesive Substances 0.000 title claims description 30
- 230000001070 adhesive effect Effects 0.000 title claims description 30
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 64
- -1 ethylene Compound Chemical class 0.000 claims description 50
- 239000002904 solvent Substances 0.000 claims description 31
- 239000000178 monomer Substances 0.000 claims description 24
- 230000003287 optical effect Effects 0.000 claims description 24
- 229920000058 polyacrylate Polymers 0.000 claims description 24
- 239000010410 layer Substances 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 5
- 238000005227 gel permeation chromatography Methods 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- 238000001723 curing Methods 0.000 claims description 3
- 238000003848 UV Light-Curing Methods 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 106
- 239000010408 film Substances 0.000 description 27
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 18
- 239000011521 glass Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 12
- 125000000524 functional group Chemical group 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 229920006267 polyester film Polymers 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000007259 addition reaction Methods 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 238000005187 foaming Methods 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 4
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 4
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 4
- VSYIJNDEXXBJFH-UHFFFAOYSA-N 5-isocyanato-2-methylpent-1-en-3-one Chemical compound CC(=C)C(=O)CCN=C=O VSYIJNDEXXBJFH-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 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 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- FOMNBFSRHKJALH-UHFFFAOYSA-N 5-isocyanatopent-1-en-3-one Chemical compound C=CC(=O)CCN=C=O FOMNBFSRHKJALH-UHFFFAOYSA-N 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 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 3
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 238000001035 drying Methods 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 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 3
- 238000003756 stirring Methods 0.000 description 3
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 2
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000007718 adhesive strength test Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 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
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 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
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- XPEMPJFPRCHICU-UHFFFAOYSA-N (1-tert-butylcyclohexyl) prop-2-enoate Chemical compound C=CC(=O)OC1(C(C)(C)C)CCCCC1 XPEMPJFPRCHICU-UHFFFAOYSA-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
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- XDWRKTULOHXYGN-UHFFFAOYSA-N 1,3-bis(ethenoxy)-2,2-bis(ethenoxymethyl)propane Chemical compound C=COCC(COC=C)(COC=C)COC=C XDWRKTULOHXYGN-UHFFFAOYSA-N 0.000 description 1
- CZAVRNDQSIORTH-UHFFFAOYSA-N 1-ethenoxy-2,2-bis(ethenoxymethyl)butane Chemical compound C=COCC(CC)(COC=C)COC=C CZAVRNDQSIORTH-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 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
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- PUBNJSZGANKUGX-UHFFFAOYSA-N 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=C(C)C=C1 PUBNJSZGANKUGX-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- MWDGNKGKLOBESZ-UHFFFAOYSA-N 2-oxooctanal Chemical compound CCCCCCC(=O)C=O MWDGNKGKLOBESZ-UHFFFAOYSA-N 0.000 description 1
- FYRWKWGEFZTOQI-UHFFFAOYSA-N 3-prop-2-enoxy-2,2-bis(prop-2-enoxymethyl)propan-1-ol Chemical compound C=CCOCC(CO)(COCC=C)COCC=C FYRWKWGEFZTOQI-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 description 1
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- ZGFPUTOTEJOSAY-UHFFFAOYSA-N FC1=C([Ti])C(F)=CC=C1N1C=CC=C1 Chemical compound FC1=C([Ti])C(F)=CC=C1N1C=CC=C1 ZGFPUTOTEJOSAY-UHFFFAOYSA-N 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical group CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000002511 behenyl 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])C([H])([H])C([H])([H])[H] 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- KOMDZQSPRDYARS-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical class [Ti].C1C=CC=C1.C1C=CC=C1 KOMDZQSPRDYARS-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 238000001514 detection method Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- PODOEQVNFJSWIK-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethoxyphenyl)methanone Chemical compound COC1=CC(OC)=CC(OC)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 PODOEQVNFJSWIK-UHFFFAOYSA-N 0.000 description 1
- 230000005674 electromagnetic induction Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- CVDUUPMTIHXQKC-UHFFFAOYSA-N ethene 1,3,5-triazinane-2,4,6-trione Chemical group C=C.O=C1NC(=O)NC(=O)N1 CVDUUPMTIHXQKC-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、光学用紫外線硬化型粘着剤組成物及び粘着層に関する。 The present invention relates to an optical ultraviolet curable pressure-sensitive adhesive composition and a pressure-sensitive adhesive layer.
近年、車両搭載用、屋外計器用、パソコンなどのディスプレイやテレビなどの表示装置は、軽量化、薄型化が求められることから、液晶表示装置が広く使用されるようになり、その需要はますます増加傾向にある。そして、特に最近では、銀行などの金融機関のＡＴＭ、自動販売機、携帯電話、携帯情報端末、デジタルオーディオプレーヤー、携帯ゲーム機、電子辞書、コピー機、ファックス、カーナビなどのデジタル情報機器には、液晶表示装置を用いたタッチパネルが多く使用されている。 In recent years, display devices such as on-vehicle equipment, outdoor instruments, and displays such as personal computers and televisions are required to be lighter and thinner, so liquid crystal display devices have become widely used, and the demand is increasing. It is increasing. And especially recently, digital information devices such as ATMs of financial institutions such as banks, vending machines, mobile phones, personal digital assistants, digital audio players, portable game machines, electronic dictionaries, photocopiers, fax machines, car navigation systems, A touch panel using a liquid crystal display device is often used.
上記タッチパネルは、表示装置と位置入力装置を組み合わせた電子部品であり、外部から受けた画像情報を液晶ディスプレイに表示するとともに、触れられた画面位置情報を感知し、外部へ情報信号として出力する機能を有する。タッチパネルの位置入力装置には主に、抵抗膜方式、静電容量方式、電磁誘導方式、光学方式、音響方式などの制御方式があり、なかでも抵抗膜方式、静電容量方式が一般的な制御方法となっている。 The touch panel is an electronic component that combines a display device and a position input device. The touch panel displays image information received from the outside on a liquid crystal display, senses the touched screen position information, and outputs it as an information signal to the outside. Have There are mainly control methods such as resistive film type, electrostatic capacity method, electromagnetic induction method, optical method, and acoustic method for touch panel position input devices. It has become a method.
上記抵抗膜方式、静電容量方式タッチパネルは、最前面保護フィルム、ガラス及び酸化インジウム（以下、ＩＴＯと記載）膜などの透明導電層を設けたフィルム、ガラス、液晶などの表示装置、その他機能性シートから構成される。これらのうち、フィルム、ガラス及び機能性シートは通常、光学用粘着剤により貼り合わせる。 The above resistive film type and capacitive type touch panel is a front protective film, glass and a film provided with a transparent conductive layer such as indium oxide (hereinafter referred to as ITO) film, glass, liquid crystal display device, and other functionalities. Consists of sheets. Among these, a film, glass, and a functional sheet are usually bonded together with an optical pressure-sensitive adhesive.
上記のとおり、タッチパネル用途に使用される光学用粘着剤は、最前面保護フィルムやガラスと透明導電層と設けたフィルムやガラスとの貼り合わせ、透明導電層を設けたフィルムやガラスと液晶などの表示装置との貼り合わせなどに用いられるため、透明性や耐候性などの光学的性能が求められる。 As mentioned above, the optical pressure-sensitive adhesive used for the touch panel application is such as bonding of the frontmost protective film or glass and a film or glass provided with a transparent conductive layer, or a film or glass provided with a transparent conductive layer or liquid crystal. Since it is used for bonding with a display device, optical performance such as transparency and weather resistance is required.
このような光学用粘着剤として、各種高分子量アクリルポリマーと各種架橋剤からなる光学用粘着剤組成物が提案されている（特許文献１及び２参照）。 As such an optical pressure-sensitive adhesive, an optical pressure-sensitive adhesive composition comprising various high molecular weight acrylic polymers and various crosslinking agents has been proposed (see Patent Documents 1 and 2).
一方、最近では、タッチパネルの耐衝撃性向上や、最前面保護フィルムやガラスの印刷段差の吸収のため、１００μｍ以上の厚い粘着剤層が求められるようになってきている。このような１００μｍ以上の粘着剤層を得る場合、上記光学用粘着剤組成物を２５μｍや５０μｍの粘着剤層を重ね貼りする場合、工程数が多いためコストもかかる、貼り合わせることで透明性が低いなどの問題点もあった。一方、１回の塗工で１００μｍ以上の厚膜の粘着剤層を形成しようとすると、塗工溶剤乾燥の際に発泡してしまい、塗膜に気泡が発生し、光学用としての性能を満たせないという課題があった。 On the other hand, recently, a thick adhesive layer of 100 μm or more has been demanded for improving the impact resistance of the touch panel and absorbing the printing step of the frontmost protective film or glass. When obtaining such a pressure-sensitive adhesive layer of 100 μm or more, when the above-mentioned optical pressure-sensitive adhesive composition is laminated with a 25 μm or 50 μm pressure-sensitive adhesive layer, the number of steps is large, so it takes a lot of cost. There were also problems such as low. On the other hand, if a thick adhesive layer with a thickness of 100 μm or more is formed by a single coating, foaming occurs when the coating solvent is dried, bubbles are generated in the coating film, and the optical performance can be satisfied. There was no problem.
また、発泡させることなく１回の塗工で厚膜の粘着層を得る方法としては、無溶剤型粘着剤組成物の使用が考えられる。無溶剤型粘着剤組成物としては、各種（メタ）アクリレートオリゴマー、（メタ）アクリレートモノマーを含む紫外線硬化性の無溶剤型粘着剤組成物が提案されている（特許文献３参照）。 Further, as a method for obtaining a thick film adhesive layer by one coating without foaming, use of a solventless pressure-sensitive adhesive composition can be considered. As the solventless pressure-sensitive adhesive composition, an ultraviolet curable solventless pressure-sensitive adhesive composition containing various (meth) acrylate oligomers and (meth) acrylate monomers has been proposed (see Patent Document 3).
しかし、上記無溶剤型粘着剤組成物では、透明性、粘着力、加熱、加湿条件下における耐久性、貼り合わせ時に位置ズレを起こした際、剥離時に糊が残る等、粘着剤としての性能に課題があった。 However, with the above solvent-free pressure-sensitive adhesive composition, transparency, adhesive strength, durability under heating and humidifying conditions, and when misalignment occurs at the time of bonding, adhesive remains at the time of peeling, etc. There was a problem.
本発明は、タッチパネルなどに使用する光学用粘着剤組成物であって、溶剤含有量が１重量％未満であり実質的に無溶剤のため溶剤乾燥が不要であり、厚膜の粘着剤層を１回の塗工で形成することが可能で、透明性、粘着力、加熱、加湿条件下における耐久性に優れ、さらには貼り合わせ後、糊残りなく剥離可能な光学用紫外線硬化型粘着剤組成物を提供することである。 The present invention is an optical pressure-sensitive adhesive composition used for a touch panel and the like, and the solvent content is less than 1% by weight and is substantially solvent-free, so solvent drying is not required. UV curable pressure-sensitive adhesive composition for optical use that can be formed by a single coating, has excellent durability under transparency, adhesive strength, heating and humidification conditions, and can be peeled off without adhesive residue after bonding. Is to provide things.
本発明者は鋭意検討した結果、光学用紫外線硬化型粘着剤組成物において、溶剤含有量が１重量％未満、２５℃における粘度が１００〜１０，０００ｍＰａ・ｓ、色調がガードナーカラー１以下であり、（Ａ）重量平均分子量（ゲルパーミエテーションクロマトグラフィーによるポリスチレン換算値）が３００，０００〜１，２００，０００であるエチレン性不飽和結合含有アクリル系ポリマー、（Ｂ）エチレン性不飽和結合を１つ含有し、かつ炭素数が４〜１８の鎖状アルキル基を有するモノマー、（Ｃ）エチレン性不飽和結合を１つ含有し、かつ炭素数が４〜１８の環状アルキル基を有するモノマー、（Ｄ）エチレン性不飽和基を３つ以上含有する化合物、（Ｅ）光重合開始剤を含む光学用紫外線硬化型粘着剤組成物により上記課題を解決できることを見出した。 As a result of intensive studies, the present inventors have found that in an optical ultraviolet curable pressure-sensitive adhesive composition, the solvent content is less than 1% by weight, the viscosity at 25 ° C. is 100 to 10,000 mPa · s, and the color tone is 1 or less Gardner color. , (A) an ethylenically unsaturated bond-containing acrylic polymer having a weight average molecular weight (polystyrene conversion value by gel permeation chromatography) of 300,000 to 1,200,000, and (B) an ethylenically unsaturated bond. 1 and a monomer having a chain alkyl group having 4 to 18 carbon atoms, (C) a monomer having one ethylenically unsaturated bond and having a cyclic alkyl group having 4 to 18 carbon atoms, (D) A compound containing three or more ethylenically unsaturated groups and (E) an ultraviolet curable pressure-sensitive adhesive composition containing a photopolymerization initiator solves the above problem. It was found to be able to.
また、本発明者は、組成物により、上記課題を解決した粘着層を提供できることも見出した。 Moreover, this inventor also discovered that the adhesion layer which solved the said subject can be provided with a composition.
すなわち本発明は、溶剤含有量が１重量％未満、２５℃における粘度が１００〜１０，０００ｍＰａ・ｓ、色調がガードナーカラー１以下であり、かつ（（Ａ）重量平均分子量（ゲルパーミエテーションクロマトグラフィーによるポリスチレン換算値）が３００，０００〜１，２００，０００であるエチレン性不飽和結合含有アクリル系ポリマー、（Ｂ）エチレン性不飽和結合を１つ含有し、かつ炭素数が４〜１８の鎖状アルキル基を有するモノマー、（Ｃ）エチレン性不飽和結合を１つ含有し、かつ炭素数が４〜１８の環状アルキル基を有するモノマー、（Ｄ）エチレン性不飽和基を３つ以上含有する化合物、（Ｅ）光重合開始剤剤を含む光学用紫外線硬化型粘着剤組成物である。 That is, the present invention has a solvent content of less than 1% by weight, a viscosity at 25 ° C. of 100 to 10,000 mPa · s, a color tone of Gardner color 1 or less, and ((A) weight average molecular weight (gel permeation chromatography). (Equivalent polystyrene-based value) 300,000 to 1,200,000 ethylenically unsaturated bond-containing acrylic polymer, (B) one ethylenically unsaturated bond, and 4 to 18 carbon atoms Monomer having a chain alkyl group, (C) a monomer having one ethylenically unsaturated bond and a cyclic alkyl group having 4 to 18 carbon atoms, (D) containing three or more ethylenically unsaturated groups And (E) an ultraviolet curable pressure-sensitive adhesive composition containing a photopolymerization initiator.
本発明２は、本発明１において、光学用紫外線硬化型粘着剤組成物１００重量％に対して、（Ａ）成分を５〜５０重量％、（Ｂ）成分を５〜８０重量％、（Ｃ）成分を５〜８０重量％、（Ｄ）成分を０．００５〜５重量％及び（Ｅ）成分を０．１〜１０重量％含有する光学用紫外線硬化型粘着剤組成物である。 Invention 2 is the invention 1, wherein the component (A) is 5 to 50% by weight, the component (B) is 5 to 80% by weight, and (C) with respect to 100% by weight of the optical ultraviolet curable pressure-sensitive adhesive composition. The composition is an ultraviolet curable pressure-sensitive adhesive composition for optical use containing 5 to 80% by weight of component, 0.005 to 5% by weight of component (D) and 0.1 to 10% by weight of component (E).
本発明３は、本発明１の光学用紫外線硬化型粘着剤組成物を硬化させて得られる粘着層である。 The present invention 3 is an adhesive layer obtained by curing the optical ultraviolet curable adhesive composition of the present invention 1.
本発明４は、本発明３において、厚みが平均１０〜１０００μｍである粘着層である。 The present invention 4 is the pressure-sensitive adhesive layer having an average thickness of 10 to 1000 μm in the present invention 3.
本発明によれば、タッチパネルやプラズマディスプレイパネルなどに光学用粘着剤組成物として使用でき、実質的に無溶剤のため溶剤乾燥が不要であり、厚膜の粘着剤層を１回の塗工で形成することが可能となる。また、本発明の粘着層は、粘着性、剥離時に糊残りがない、透明性及び耐久性に優れているため、タッチパネルやプラズマディスプレイパネルなどの光学用に使用する粘着層として好適である。 According to the present invention, it can be used as an optical pressure-sensitive adhesive composition for a touch panel, a plasma display panel, etc., and is substantially solvent-free, so that solvent drying is unnecessary, and a thick-film pressure-sensitive adhesive layer can be applied once. It becomes possible to form. In addition, the pressure-sensitive adhesive layer of the present invention is suitable as a pressure-sensitive adhesive layer used for optics such as a touch panel and a plasma display panel because it has adhesiveness, no adhesive residue at the time of peeling, and excellent transparency and durability.
本発明は、溶剤含有量が１重量％未満、２５℃における粘度が１００〜１０，０００ｍＰａ・ｓ、色調がガードナーカラー１以下であり、かつ（Ａ）重量平均分子量（ゲルパーミエテーションクロマトグラフィーによるポリスチレン換算値）が３００，０００〜１，２００，０００であるエチレン性不飽和結合含有アクリル系ポリマー、（Ｂ）エチレン性不飽和結合を１つ含有し、かつ炭素数が４〜１８の鎖状アルキル基を有するモノマー、（Ｃ）エチレン性不飽和結合を１つ含有し、かつ炭素数が４〜１８の環状アルキル基を有するモノマー、（Ｄ）エチレン性不飽和基を３つ以上含有する化合物、（Ｅ）光重合開始剤を含む光学用紫外線硬化型粘着剤組成物である。 The present invention has a solvent content of less than 1% by weight, a viscosity at 25 ° C. of 100 to 10,000 mPa · s, a color tone of Gardner color 1 or less, and (A) a weight average molecular weight (by gel permeation chromatography). (Equivalent polystyrene value) is 300,000 to 1,200,000 ethylenically unsaturated bond-containing acrylic polymer, (B) one chain containing ethylenically unsaturated bonds and having 4 to 18 carbon atoms A monomer having an alkyl group, (C) a monomer containing one ethylenically unsaturated bond and a cyclic alkyl group having 4 to 18 carbon atoms, and (D) a compound containing three or more ethylenically unsaturated groups (E) An ultraviolet curable pressure-sensitive adhesive composition containing an optical polymerization initiator.
上記溶剤含有量が１重量％を超えると、厚膜の粘着剤層を形成しようする際、塗工溶剤乾燥、硬化の際に発泡してしまい、塗膜に気泡が発生してしまうなどの問題がある。また、硬化して粘着層を形成する工程において、乾燥工程を省略することができる。 When the solvent content exceeds 1% by weight, when forming a thick adhesive layer, foaming occurs when the coating solvent is dried and cured, and bubbles are generated in the coating film. There is. Further, the drying step can be omitted in the step of forming the adhesive layer by curing.
上記粘度が１００〜１０，０００ｍＰａ・ｓの範囲外の粘度の場合、常温、常圧での厚膜塗工が困難である。 When the viscosity is outside the range of 100 to 10,000 mPa · s, it is difficult to apply a thick film at room temperature and pressure.
上記粘着剤組成物の色調がガードナーカラーで１以下とすることで、粘着層として色調に優れ、透明性に優れたものとすることができ、光学用粘着剤組成物として好適に使用することができる。 When the color tone of the pressure-sensitive adhesive composition is 1 or less in Gardner color, the pressure-sensitive adhesive layer can be excellent in color tone and excellent in transparency, and can be suitably used as an optical pressure-sensitive adhesive composition. it can.
上記（Ａ）成分は、側鎖に反応性官能基を有するアクリル系ポリマー（ａ１）（以下、（ａ１）成分という）と反応性官能基とエチレン性不飽和結合とを有する化合物（ａ２）（以下、（ａ２）成分という）との反応により得られる。 The component (A) is a compound (a2) having an acrylic polymer (a1) having a reactive functional group in the side chain (hereinafter referred to as component (a1)), a reactive functional group, and an ethylenically unsaturated bond ( Hereinafter, it is obtained by a reaction with (a2) component).
上記の側鎖に反応性官能基を有するアクリル系ポリマー（ａ１）は、アルキル（メタ）アクリレートモノマー（ａ３）（以下、（ａ３）成分という）とエチレン性不飽和結合と反応性官能基を有するモノマー（ａ４）（以下、（ａ４）成分という）と、必要に応じてさらに他のエチレン性不飽和結合を有するモノマー（ａ５）（以下、（ａ５）成分という）をラジカル共重合することにより得られる。 The acrylic polymer (a1) having a reactive functional group in the side chain has an alkyl (meth) acrylate monomer (a3) (hereinafter referred to as component (a3)), an ethylenically unsaturated bond, and a reactive functional group. It is obtained by radical copolymerization of monomer (a4) (hereinafter referred to as component (a4)) and, if necessary, monomer (a5) having another ethylenically unsaturated bond (hereinafter referred to as component (a5)). It is done.
（ａ３）成分としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−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、ｔ−ブチル（メタ）アクリレート、ｎ−ペンチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ｎ−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、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、ラウリル（メタ）アクリレート、セチル（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、ベヘニル（メタ）アクリレートのアルキル基の炭素数が１〜３０の鎖状（メタ）アクリレートが挙げられる。特には、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレートが粘着層の高粘着力の点より好ましい。 As the component (a3), methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (Meth) acrylate, n-pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) ) Acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate The number of carbon atoms of the groups has a chain (meth) acrylates having 1 to 30. In particular, ethyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate are preferable from the viewpoint of high adhesive strength of the adhesive layer.
（ａ４）成分としては、（メタ）アクリル酸等のカルボキシル基を有する（メタ）アクリル酸エステル、グリシジル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレートグリシジルエーテル等エポキシ基を有する（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−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（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）アクリレート等の水酸基を有する（メタ）アクリレート、２−ヒドロキシエチルビニルエーテル、４−ヒドロキシブチルビニルエーテル等の水酸基を有するビニルエーテル、２−（メタ）アクリロイルエチルイソシアネート等のイソシアネート基を有する（メタ）アクリレート等が挙げられる。特には、２−ヒドロキシエチル（メタ）アクリレート、グリシジル（メタ）アクリレートが（Ａ）成分の製造において穏和な条件をとることができ好ましい。 As the component (a4), (meth) acrylate having an epoxy group such as (meth) acrylic acid ester having a carboxyl group such as (meth) acrylic acid, glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, etc. , 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate and the like. (Meth) acrylate, vinyl ether having a hydroxyl group such as 2-hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ether, and (meth) acrylate having an isocyanate group such as 2- (meth) acryloylethyl isocyanate. Rate, and the like. In particular, 2-hydroxyethyl (meth) acrylate and glycidyl (meth) acrylate are preferable because mild conditions can be taken in the production of the component (A).
（ａ５）成分としては、シクロヘキシル（メタ）アクリレート、３,３,５−トリメチルシクロヘキシル（メタ）アクリレート、ｔ−ブチルシクロヘキシル（メタ）アクリレート、イソボルニル（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、ジシクロペンタニル（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、１−アダマンチル（メタ）アクリレート、２−メチル−２−アダマンチル（メタ）アクリレート、２−エチル−２−アダマンチル（メタ）アクリレート等の環状構造を有する（メタ）アクリレート；フェノキシエチル（メタ）アクリレート、ベンジル（メタ）アクリレート等の芳香族構造を有する（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート等の複素環式構造を有する（メタ）アクリレート；スチレン、ヒドロキシエチルビニルエーテル、ヒドロキシブチルビニルエーテル、Ｎ−ビニルホルムアミド、Ｎ−ビニルピロリドン、Ｎ−ビニルカプロラクタム等のビニル化合物が挙げられる。特には、シクロヘキシル（メタ）アクリレート、フェノキシエチル（メタ）アクリレートが粘着層の高粘着力の点より好ましい。 As the component (a5), cyclohexyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, di Cyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, etc. (Meth) acrylates having the following cyclic structures: (meth) acrylates having aromatic structures such as phenoxyethyl (meth) acrylate and benzyl (meth) acrylate, and heterocycles such as tetrahydrofurfuryl (meth) acrylate Having the structure (meth) acrylate; styrene, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N- vinyl formamide, N- vinyl pyrrolidone, vinyl compounds such as N- vinyl caprolactam. In particular, cyclohexyl (meth) acrylate and phenoxyethyl (meth) acrylate are preferable from the viewpoint of high adhesive strength of the adhesive layer.
上記（ａ１）成分の重量平均分子量（ゲルパーミエテーションクロマトグラフィーによるポリスチレン換算値）は３００，０００〜１，２００，０００である。重量平均分子量を３００，０００以上とすることで、粘着層の粘着力を向上させることができ、１，２００，０００以下とすることで、粘着剤の粘度を低くすることができハンドリング性が向上する。 The weight average molecular weight (polystyrene conversion value by gel permeation chromatography) of the component (a1) is 300,000 to 1,200,000. By setting the weight average molecular weight to 300,000 or more, the adhesive strength of the adhesive layer can be improved, and by setting the weight average molecular weight to 1,200,000 or less, the viscosity of the adhesive can be lowered and the handling property is improved. To do.
上記（ａ１）成分は、溶液重合、懸濁重合、塊状重合、乳化重合等公知の方法にて製造することができる。中でも、懸濁重合は重量平均分子量の大きいポリマーが得られ、かつ生成ポリマーの単離が容易であるために、（ａ１）成分の製造方法として好ましい。 The component (a1) can be produced by a known method such as solution polymerization, suspension polymerization, bulk polymerization, or emulsion polymerization. Among these, suspension polymerization is preferable as a method for producing the component (a1) because a polymer having a large weight average molecular weight can be obtained and the resulting polymer can be easily isolated.
上記（ａ１）成分と（ａ２）成分との付加反応により、（Ａ）成分が得られる。例えば、
(ａ１) 成分製造時、（ａ４）成分により導入された反応性官能基がカルボキシル基であれば、反応性官能基としてエポキシ基を有しかつエチレン性不飽和結合を有するモノマーを付加反応させることにより、（Ａ）成分を製造することができる。逆に
(ａ１) 成分製造時、（ａ４）成分により導入された反応性官能基がエポキシ基であれば、反応性官能基としてカルボキシル基を有しかつエチレン性不飽和結合を有するモノマーを付加反応させることにより、（Ａ）成分を製造することができる。一方、
(ａ１)製造時、（ａ４）成分により導入された反応性官能基が水酸基であれば、反応性官能基としてイソシアネート基を有しかつエチレン性不飽和結合を有するモノマーを付加反応させることにより、（Ａ）成分を製造することができる。逆に
(ａ１) 成分製造時、（ａ４）成分により導入された反応性官能基がイソシアネート基であれば、反応性官能基として水酸基を有しかつエチレン性不飽和結合を有するモノマーを付加反応させることにより、（Ａ）成分を製造することができる。
(A) component is obtained by addition reaction of the said (a1) component and (a2) component. For example,
(a1) When the reactive functional group introduced by the component (a4) is a carboxyl group at the time of component production, an addition reaction of a monomer having an epoxy group as the reactive functional group and having an ethylenically unsaturated bond is performed. Thus, the component (A) can be produced. vice versa
(a1) When the reactive functional group introduced by the component (a4) is an epoxy group at the time of component production, addition reaction of a monomer having a carboxyl group as the reactive functional group and having an ethylenically unsaturated bond Thus, the component (A) can be produced. on the other hand,
(a1) At the time of production, if the reactive functional group introduced by the component (a4) is a hydroxyl group, an addition reaction of a monomer having an isocyanate group as the reactive functional group and having an ethylenically unsaturated bond, (A) A component can be manufactured. vice versa
(a1) At the time of component production, if the reactive functional group introduced by component (a4) is an isocyanate group, an addition reaction of a monomer having a hydroxyl group as the reactive functional group and having an ethylenically unsaturated bond is performed. , (A) component can be manufactured.
上記（ａ２）成分としては、（メタ）アクリル酸等のカルボキシル基を有する（メタ）アクリル酸エステル、グリシジル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレートグリシジルエーテル等エポキシ基を有する（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−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（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）アクリレート等の水酸基を有する（メタ）アクリル酸エステル、２−ヒドロキシエチルビニルエーテル、４−ヒドロキシブチルビニルエーテル等の水酸基を有するビニルエーテル、２−（メタ）アクリロイルエチルイソシアネート等のイソシアネート基を有する（メタ）アクリレート等が挙げられる。特には、（メタ）アクリル酸、２−（メタ）アクリロイルエチルイソシアネートが（Ａ）成分の製造において穏和な条件をとることができ好ましい。 As said (a2) component, it has epoxy groups, such as (meth) acrylic acid ester which has carboxyl groups, such as (meth) acrylic acid, glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether (meth) Hydroxyl groups such as acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, etc. (Meth) acrylic acid ester, 2-hydroxyethyl vinyl ether, vinyl ether having a hydroxyl group such as 4-hydroxybutyl vinyl ether, and an isocyanate group such as 2- (meth) acryloylethyl isocyanate ( Data) acrylate, and the like. In particular, (meth) acrylic acid and 2- (meth) acryloylethyl isocyanate are preferable because mild conditions can be taken in the production of the component (A).
上記（Ａ）成分は、上記記載のようにして製造されたエチレン性不飽和基含有アクリル系ポリマーである。エチレン性不飽和基を含有しない場合は、紫外線硬化時に他成分のモノマー等と反応せず、粘着層の透明性、粘着力が悪化する。さらには貼り合わせ後、糊残りが多く剥離不可能な粘着層となる。 The component (A) is an ethylenically unsaturated group-containing acrylic polymer produced as described above. When it does not contain an ethylenically unsaturated group, it does not react with other components such as monomers during UV curing, and the transparency and adhesive strength of the adhesive layer deteriorate. Furthermore, after bonding, the adhesive layer has a large amount of adhesive residue and cannot be peeled off.
上記（Ａ）成分の重量平均分子量は３００，０００〜１，２００，０００である。重量平均分子量が３００，０００未満では、粘着層の粘着力が低い。また、粘着層の耐久性が悪化する傾向がある。重量平均分子量が１，２００，０００を超えると、粘着剤の粘度が高くハンドリング性が悪化する。 The weight average molecular weight of the component (A) is 300,000 to 1,200,000. When the weight average molecular weight is less than 300,000, the adhesive strength of the adhesive layer is low. Moreover, there exists a tendency for durability of an adhesion layer to deteriorate. When the weight average molecular weight exceeds 1,200,000, the viscosity of the pressure-sensitive adhesive is high and the handling property is deteriorated.
上記（Ａ）成分の使用量は、粘着剤組成物１００重量％中に対して５〜５０重量％が好ましく、特に１０〜４０重量％が好ましい。（Ａ）成分の割合を５重量％以上にすることで、粘着層の粘着力を向上させることができ、（Ａ）成分の割合を５０重量％以下にすることで、粘着剤のハンドリング性を向上させることができる。 The amount of component (A) used is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, based on 100% by weight of the pressure-sensitive adhesive composition. By making the proportion of the component (A) 5% by weight or more, the adhesive strength of the adhesive layer can be improved, and by making the proportion of the component (A) 50% by weight or less, the handling property of the adhesive can be improved. Can be improved.
上記（Ｂ）成分は、エチレン性不飽和結合を１つ含有し、かつ炭素数が４〜１８の鎖状アルキル基を有するモノマーである。具体例としては、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、ｔ−ブチル（メタ）アクリレート、ｎ−ペンチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ｎ−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、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、ラウリル（メタ）アクリレート、セチル（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）アクリレート等の鎖状アルキル基を有する（メタ）アクリレートが挙げられる。これらの中でも、他成分との相溶性、粘着剤の粘度の点から、２−エチルヘキシル（メタ）アクリレート、イソオクチル（メタ）アクリレート、イソノニル（メタ）アクリレート、ラウリル（メタ）アクリレート、イソステアリル（メタ）アクリレートが好ましい。エチレン性不飽和結合を１つ含有し、炭素数が４未満の鎖状アルキル基を有するモノマーは、皮膚刺激性が高く、無溶剤紫外線硬化型粘着剤の取扱いが困難となる。炭素数が１８を超える鎖状アルキル基を有するモノマーは、高い結晶性のため、他成分との相溶性に劣り、粘着層の透明性が悪化する傾向がある。 The component (B) is a monomer containing one ethylenically unsaturated bond and having a chain alkyl group having 4 to 18 carbon atoms. Specific examples include n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-octyl (meth) acrylate. , Isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, iso (Meth) acrylate having a chain alkyl group such as stearyl (meth) acrylate is exemplified. Among these, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, isostearyl (meth) from the viewpoint of compatibility with other components and the viscosity of the adhesive. Acrylate is preferred. A monomer having one ethylenically unsaturated bond and having a chain alkyl group having less than 4 carbon atoms has high skin irritation and makes it difficult to handle a solventless UV curable adhesive. A monomer having a chain alkyl group having more than 18 carbon atoms has high crystallinity and therefore is inferior in compatibility with other components and tends to deteriorate the transparency of the adhesive layer.
上記（Ｂ）成分の使用量は、粘着剤組成物１００重量％中５〜８０重量％の範囲が好ましく、特に１０〜５０重量％の範囲が好ましい。（Ｂ）成分の割合を５重量％以上にすることで、粘着剤のハンドリング性を向上させることができ、（Ｂ）成分の割合を８０重量％以下にすることで、適度な粘度を得る事ができ、厚膜の粘着剤層を１回の塗工で形成することができる。 The amount of component (B) used is preferably in the range of 5 to 80% by weight, more preferably in the range of 10 to 50% by weight, in 100% by weight of the pressure-sensitive adhesive composition. By making the proportion of the component (B) 5% by weight or more, the handling property of the pressure-sensitive adhesive can be improved, and by making the proportion of the component (B) 80% by weight or less, an appropriate viscosity can be obtained. A thick adhesive layer can be formed by a single coating.
上記（Ｃ）成分は、エチレン性不飽和結合を１つ含有し、かつ炭素数が４〜１８の環状アルキル基を有するモノマーである。具体例としては、シクロヘキシル（メタ）アクリレート、３,３,５‐トリメチルシクロヘキシル（メタ）アクリレート、ｔ-ブチルシクロヘキシル（メタ）アクリレート、イソボルニル（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、ジシクロペンタニル（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、１−アダマンチル（メタ）アクリレート、２−メチル−２−アダマンチル（メタ）アクリレート、２−エチル−２−アダマンチル（メタ）アクリレート等のシクロアルキル基を有する（メタ）アクリレートが挙げられる。これらの中でも、他成分との相溶性、粘着剤の粘度の点から、３,３,５‐トリメチルシクロヘキシル（メタ）アクリレート、ｔ-ブチルシクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレートが好ましい。 The component (C) is a monomer having one ethylenically unsaturated bond and having a cyclic alkyl group having 4 to 18 carbon atoms. Specific examples include cyclohexyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopenta Cyclo such as nyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, etc. (Meth) acrylate having an alkyl group may be mentioned. Among these, 3,3,5-trimethylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, and isobornyl (meth) acrylate are preferable from the viewpoint of compatibility with other components and the viscosity of the pressure-sensitive adhesive.
上記（Ｃ）成分の使用量は、粘着剤組成物１００重量部％中５〜８０重量％の範囲が好ましく、特に１０〜５０重量％の範囲が好ましい。（Ｃ）成分の割合を５重量％以上にすることで、粘着剤の紫外線硬化性を向上させることができ、（Ｃ）成分の割合を８０重量％以下にすることで、適度な粘着性を得る事ができる。 The amount of component (C) used is preferably in the range of 5 to 80% by weight, particularly preferably in the range of 10 to 50% by weight, in 100 parts by weight of the pressure-sensitive adhesive composition. By making the proportion of the component (C) 5% by weight or more, the ultraviolet curable property of the pressure-sensitive adhesive can be improved, and by making the proportion of the component (C) 80% by weight or less, appropriate tackiness can be obtained. I can get it.
上記（Ｄ）成分は、エチレン性不飽和結合を３つ以上有する化合物である。具体例としては、トリメチロールプロパントリ（メタ）アクリレート、イソシアヌル酸エチレンオキサイド変性トリ（メタ）アクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート等の３官能以上の多官能（メタ）アクリレート、トリメチロールプロパントリビニルエーテル、ペンタエリスリトールテトラビニルエーテル等３官能以上の多官能ビニルエーテル、ペンタエリスリトールトリアリルエーテル、トリアリルイソシアヌレート等３官能以上の多官能アリルエーテルが挙げられる。エチレン性不飽和結合が３つ未満の化合物では、紫外線硬化性が悪化し、また硬化物の架橋が不充分となるため粘着層貼り合わせ後の剥離において糊残りが発生しやすい傾向がある。 The component (D) is a compound having three or more ethylenically unsaturated bonds. Specific examples include trifunctional groups such as trimethylolpropane tri (meth) acrylate, isocyanuric acid ethylene oxide-modified tri (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate. Examples of the above polyfunctional (meth) acrylate, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, etc., trifunctional or more polyfunctional vinyl ether, pentaerythritol triallyl ether, triallyl isocyanurate, etc. . When the number of ethylenically unsaturated bonds is less than 3, the ultraviolet curability deteriorates, and the cured product is insufficiently crosslinked.
上記（Ｄ）成分の使用量は、粘着剤組成物１００重量％中０．００５〜５重量％の範囲が好ましく、特に０．１〜３重量％の範囲が好ましい。（Ｄ）成分の割合を０．００５重量％以上にすることで、粘着剤の紫外線硬化性を向上させることができ、さらには貼り合わせ後、糊残りなく剥離可能な粘着層を得ることができる。（Ｄ）成分の割合を５重量％以下にすることで、適度な粘着力の粘着層を得ることができる。 The amount of the component (D) used is preferably in the range of 0.005 to 5% by weight in 100% by weight of the pressure-sensitive adhesive composition, and particularly preferably in the range of 0.1 to 3% by weight. (D) By making the ratio of a component 0.005 weight% or more, the ultraviolet sclerosis | hardenability of an adhesive can be improved, Furthermore, after bonding, the adhesive layer which can be peeled without an adhesive residue can be obtained. . (D) By making the ratio of a component 5 weight% or less, the adhesive layer of moderate adhesive force can be obtained.
上記（Ｅ）成分は、紫外線照射により分解しラジカルを発生する光重合開始剤であれば、各種公知のものを特に制限なく用い得る。具体的には、ベンゾイン化合物、アセトフェノン化合物、アシルフォスフィンオキサイド化合物、チタノセン化合物、チオキサントン化合物、オキシムエステル化合物等の光重合開始剤、アミンやキノン等の光増感剤等が挙げられ、具体的には、２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン、１−ヒドロキシ−シクロヘキシル−フェニル−ケトン、２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン、１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン、オリゴ｛２−ヒドロキシ−２−メチル−１−[４−（１−メチルビニル）フェニル]プロパノン｝、２−ヒドロキシ−１−［４−［４−（２−ヒドロキシ−２−メチル−プロピオニル）−ベンジル］フェニル］−２−メチル−プロパン−１−オン、２−メチル−１−（４−メチルチオフェニル）−２−モルフォリノプロパン−１−オン、２−（ジメチルアミノ）−２−［（４−メチルフェニル）メチル］−１−［４−（４−モルホリニル）フェニル］−１−ブタノン、２，４，６−トリメチルベンゾイル−ジフェニル−フォスフィンオキサイド、ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド、ビス（η５−２，４−シクロペンタジエン−１−イル）−ビス（２，６−ジフルオロ−３−（１Ｈ−ピロール−１−イル）−フェニル）チタニウム、１，２−オクタンジオン１−［４−（フェニルチオ）−２−（Ｏ−ベンゾイルオキシム）］、エタノン１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−１−（０−アセチルオキシム）等が挙げられ、１種を単独で使用しても、２種以上を併用してもよい。この中でも、２，４，６−トリメチルベンゾイル−ジフェニル−フォスフィンオキサイド、オリゴ｛２−ヒドロキシ−２−メチル−１−[４−（１−メチルビニル）フェニル]プロパノン｝が、粘着剤組成物の硬化性が向上し好適である。 As the component (E), various known compounds can be used without particular limitation as long as they are photopolymerization initiators that decompose upon irradiation with ultraviolet rays to generate radicals. Specific examples include photopolymerization initiators such as benzoin compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, thioxanthone compounds, and oxime ester compounds, and photosensitizers such as amines and quinones. Are 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [ 4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] ] Propanone}, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] Enyl] -2-methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methyl Phenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenyl Phosphine oxide, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-ca Bazoru 3-yl] -1- (O-acetyl oxime), and the like, be used singly or in combination of two or more thereof. Among these, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone} is an adhesive composition. The curability is improved, which is preferable.
上記（Ｅ）成分の使用量は、粘着剤組成物１００重量％中に対して０．１〜１０重量％が好ましく、より好ましくは０．２〜５重量％である。（Ｅ）成分の割合を０．１重量％以上にすることで、紫外線照射による重合のばらつきを防止することができ、１０重量％以下にすることで、（Ｅ）成分の分解物による臭気を防止でき、硬化物の着色を防止することができる。 The amount of the component (E) used is preferably 0.1 to 10% by weight, more preferably 0.2 to 5% by weight, based on 100% by weight of the pressure-sensitive adhesive composition. By making the ratio of the component (E) 0.1% by weight or more, variation in polymerization due to ultraviolet irradiation can be prevented, and by making it 10% by weight or less, the odor due to the decomposition product of the component (E) is reduced. It can prevent and coloring of hardened | cured material can be prevented.
本発明の光学用紫外線硬化型粘着剤組成物の製造は、上記（Ａ）〜（Ｅ）成分を混合することによって得られる。混合方法は、特に限定されず、上記（Ａ）〜（Ｅ）成分の添加順序は問わない。 The production of the optical ultraviolet curable pressure-sensitive adhesive composition of the present invention can be obtained by mixing the components (A) to (E). The mixing method is not particularly limited, and the addition order of the components (A) to (E) is not limited.
また、本発明の粘着剤組成物には、必要に応じて、本発明の効果を損なわない範囲において、上記（Ｂ）、（Ｃ）及び（Ｄ）成分以外の他のエチレン性不飽和結合を含有するモノマーを希釈モノマーとして含有させることができる。 In addition, the pressure-sensitive adhesive composition of the present invention may contain, as necessary, other ethylenically unsaturated bonds other than the components (B), (C), and (D) as long as the effects of the present invention are not impaired. The monomer to contain can be contained as a dilution monomer.
上記他のエチレン性不飽和結合を含有するモノマーの具体例としては、フェノキシエチル（メタ）アクリレート、ベンジル（メタ）アクリレート等の芳香族構造を有する（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート等の複素環式構造を有する（メタ）アクリレート；スチレン、ヒドロキシエチルビニルエーテル、ヒドロキシブチルビニルエーテル、Ｎ−ビニルホルムアミド、Ｎ−ビニルピロリドン、Ｎ−ビニルカプロラクタム等のビニル化合物が挙げられる。 Specific examples of the monomer containing the other ethylenically unsaturated bond include (meth) acrylate having an aromatic structure such as phenoxyethyl (meth) acrylate and benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and the like. (Meth) acrylates having a heterocyclic structure of: styrene, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N-vinylformamide, N-vinylpyrrolidone, N-vinylcaprolactam and other vinyl compounds.
本発明の粘着剤組成物には、必要に応じて、本発明の効果を損なわない範囲において、種々の添加剤を含有させることができる。例えば、表面調整剤、界面活性剤、紫外線吸収剤、酸化防止剤、光安定剤、粘着付与剤、可塑剤、無機フィラー、シランカップリング剤、コロイダルシリカ、消泡剤、湿潤剤、防錆剤等の添加剤を含有させることができる。 In the pressure-sensitive adhesive composition of the present invention, various additives can be incorporated as needed within a range not impairing the effects of the present invention. For example, surface conditioner, surfactant, ultraviolet absorber, antioxidant, light stabilizer, tackifier, plasticizer, inorganic filler, silane coupling agent, colloidal silica, antifoaming agent, wetting agent, rust inhibitor Etc. can be contained.
本発明の粘着剤組成物を粘着層にするには、流延製膜（キャスト製膜）と呼ばれる手法をとることが好ましく採用できる。具体的には、シリコーン樹脂などの剥離剤を表面にコートしたポリエチレンテレフタレートフィルム（ＰＥＴフィルム）などの保護フィルム上に薄膜状にキャストした後に、塗膜に紫外線を照射して重合硬化させて粘着層を得る。このような製法によれば、製膜時に光学用粘着剤組成物にかかる応力も少なく、欠陥の形成が少ない。また、膜厚の均一性も高い。 In order to make the pressure-sensitive adhesive composition of the present invention into a pressure-sensitive adhesive layer, it is preferable to adopt a technique called casting film formation (cast film formation). Specifically, after casting into a thin film on a protective film such as a polyethylene terephthalate film (PET film) whose surface is coated with a release agent such as a silicone resin, the coating film is irradiated with ultraviolet rays to be cured by polymerization and then the adhesive layer Get. According to such a manufacturing method, the stress applied to the optical pressure-sensitive adhesive composition during film formation is small, and the formation of defects is small. In addition, the film thickness is highly uniform.
上記紫外線の光源としては、キセノンランプ、高圧水銀灯、メタルハライドランプを有する紫外線照射装置が挙げられる。また、光量、光源、搬送速度等の条件は適宜調整すればよく、光量が通常８０〜１６０Ｗ／ｃｍ程度、搬送速度が通常５〜５０ｍ／分程度である。 Examples of the ultraviolet light source include an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, and a metal halide lamp. Moreover, what is necessary is just to adjust conditions, such as a light quantity, a light source, and a conveyance speed suitably, and a light quantity is about 80-160 W / cm normally, and a conveyance speed is about about 5-50 m / min normally.
また、本発明の粘着層の厚みは特に限定されないが、通常平均１０〜１０００μｍ程度、好ましくは２５〜５００μｍである。厚膜をこの範囲とすることで、タッチパネルの耐衝撃性を向上させることができ、表面の印刷段差を吸収できるので、最前面の保護フィルムとして使用することができる等、粘着層として優れたものとすることができる。本発明の粘着剤組成物を使用すれば、１回の塗工で上記膜圧の粘着層を形成することができる。これにより、粘着層に気泡が入らず、光学用途粘着層として好適に使用することができる。 The thickness of the pressure-sensitive adhesive layer of the present invention is not particularly limited, but is usually about 10 to 1000 μm on average and preferably 25 to 500 μm. By making the thick film within this range, the impact resistance of the touch panel can be improved, and the printing step on the surface can be absorbed, so it can be used as the frontmost protective film, etc. It can be. If the adhesive composition of this invention is used, the adhesion layer of the said film | membrane pressure can be formed by one application | coating. Thereby, a bubble does not enter into an adhesion layer and it can be conveniently used as an optical use adhesion layer.
以下に本発明を実施例により更に具体的に説明する。ただし、本発明はこれら実施例に限定されるものではない。また実施例中、「％」及び「部」は特に断りのない限り「重量％」を意味する。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the examples, “%” and “part” mean “% by weight” unless otherwise specified.
＜（Ａ）成分の合成＞
合成例１
（Ａ−１）成分の合成
撹拌装置、冷却管を備えた反応装置に、水酸基を含有するアクリル系ポリマーの２−エチルヘキシルアクリレート（２−ＥＨＡ）溶液４７９部（根上工業（株）製、商品名「パラクロンＳＹ−１０６２ＫＹ」；アクリル系ポリマー６２ｗｔ％、重量平均分子量５０万，２−ＥＨＡ３８ｗｔ％）、２−メタクリロイルエチルイソシアネート３部、オクチル酸スズ０．２０部を加え、８０℃まで昇温し、４時間保温した後、ＮＣＯ測定にて反応が完結していることを確認、重量平均分子量５０万のエチレン性不飽和結合含有アクリル系ポリマー（以下、（Ａ−１）成分という）の２−ＥＨＡ溶液を得た。なお、重量平均分子量は、市販の分子量測定機（本体製品名「ＨＬＣ−８２２０ＧＰＣ」、東ソー（株）製；カラム製品名「ＴＳＫＧｅｌ Ｇ１０００Ｈ」、「ＴＳＫＧｅｌ Ｇ２０００Ｈ」、東ソー（株）製；展開溶媒 テトラヒドロフラン）を用いて得た値である（以下、同様。）
<Synthesis of component (A)>
Synthesis example 1
(A-1) Component stirrer, reactor equipped with cooling tube, 479 parts of 2-ethylhexyl acrylate (2-EHA) solution of acrylic polymer containing hydroxyl group (trade name, manufactured by Negami Kogyo Co., Ltd.) “Paracron SY-1062KY”; acrylic polymer 62 wt%, weight average molecular weight 500,000, 2-EHA 38 wt%), 2-methacryloyl ethyl isocyanate 3 parts, tin octylate 0.20 parts, and heated to 80 ° C. After incubating for 4 hours, it was confirmed that the reaction was completed by NCO measurement. Ethylenically unsaturated bond-containing acrylic polymer having a weight average molecular weight of 500,000 (hereinafter referred to as component (A-1)) 2-EHA A solution was obtained. The weight average molecular weight was measured using a commercially available molecular weight measuring instrument (main product name “HLC-8220GPC” manufactured by Tosoh Corporation; column product names “TSKGel G1000H”, “TSKGel G2000H” manufactured by Tosoh Corporation; developing solvent tetrahydrofuran. ) (The same applies hereinafter).
合成例２
（Ａ−２）成分の合成
撹拌装置、冷却管を備えた反応装置に、水酸基を含有するアクリル系ポリマーの２−ＥＨＡ溶液２３７部（根上工業（株）製、商品名「パラクロンＳＹ−１０６２ＫＹ」；アクリル系ポリマー６２ｗｔ％、重量平均分子量５０万，２−ＥＨＡ３８ｗｔ％）、イソボルニルアクリレート（ＩＢＸＡ）１４７部、２−メタクリロイルエチルイソシアネート３部、オクチル酸スズ０．１０部を加え、８０℃まで昇温し、６時間保温した後、ＮＣＯ測定にて反応が完結していることを確認、重量平均分子量５０万のエチレン性不飽和結合含有アクリル系ポリマー（以下、（Ａ−２）成分という）の２−ＥＨＡ/ＩＢＸＡ溶液を得た。
Synthesis example 2
(A-2) Component Stirring Device, Reactor equipped with a cooling tube, 237 parts of 2-EHA solution of an acrylic polymer containing a hydroxyl group (manufactured by Negami Kogyo Co., Ltd., trade name “Paraklon SY-1062KY”) Acrylic polymer 62 wt%, weight average molecular weight 500,000, 2-EHA 38 wt%), isobornyl acrylate (IBXA) 147 parts, 2-methacryloylethyl isocyanate 3 parts, tin octylate 0.10 parts, and up to 80 ° C. After raising the temperature and keeping the temperature for 6 hours, it was confirmed that the reaction was completed by NCO measurement. Ethylenically unsaturated bond-containing acrylic polymer having a weight average molecular weight of 500,000 (hereinafter referred to as component (A-2)) A 2-EHA / IBXA solution was obtained.
合成例３
（Ｆ−１）成分の合成
撹拌装置、冷却管を備えた反応装置に、水酸基を含有するアクリル系ポリマーの２−ＥＨＡ溶液１３２部（根上工業（株）製、商品名「パラクロンＳＹ−１０６２ＨＮ１」；アクリル系ポリマー７５ｗｔ％、重量平均分子量２６万、２−ＥＨＡ２５ｗｔ％）、２−メタクリロイルエチルイソシアネート１部、オクチル酸スズ０．０３部を加え、８０℃まで昇温し、２時間保温した後、ＮＣＯ測定にて反応が完結していることを確認、重量平均分子量２６万のエチレン性不飽和結合含有アクリル系ポリマー（以下、（Ｆ−１）成分という）の２−ＥＨＡ溶液を得た。
Synthesis example 3
(F-1) Component Stirring Device, Reactor equipped with a cooling pipe, 132 parts of 2-EHA solution of an acrylic polymer containing a hydroxyl group (manufactured by Negami Kogyo Co., Ltd., trade name “Paracron SY-1062HN1”) Acrylic polymer 75 wt%, weight average molecular weight 260,000, 2-EHA 25 wt%), 2-methacryloylethyl isocyanate 1 part, tin octylate 0.03 part, heated up to 80 ° C. and kept for 2 hours, It was confirmed by NCO measurement that the reaction was complete, and a 2-EHA solution of an ethylenically unsaturated bond-containing acrylic polymer (hereinafter referred to as (F-1) component) having a weight average molecular weight of 260,000 was obtained.
合成例４
（Ｆ−２）成分の合成
撹拌装置、冷却管を備えた反応装置に、水酸基を含有するアクリル系ポリマーの２−ＥＨＡ溶液１９８部（根上工業（株）製、商品名「パラクロンＳＹ−１０６２Ｈ２」；樹脂分５０ｗｔ％、重量平均分子量１１万、２−ＥＨＡ５０ｗｔ％）、２−メタクリロイルエチルイソシアネート１部、オクチル酸スズ０．０３部を加え、８０℃まで昇温し、２時間保温した後、ＮＣＯ測定にて反応が完結していることを確認、重量平均分子量１１万のエチレン性不飽和結合含有アクリル系ポリマー（以下、（Ｆ−２）成分という）の２−ＥＨＡ溶液を得た。
Synthesis example 4
(F-2) Component synthesis apparatus, reactor equipped with a cooling tube, 198 parts of 2-EHA solution of an acrylic polymer containing a hydroxyl group (manufactured by Negami Kogyo Co., Ltd., trade name "PARACRON SY-1062H2") Resin content 50 wt%, weight average molecular weight 110,000, 2-EHA 50 wt%), 2-methacryloyl ethyl isocyanate 1 part, tin octylate 0.03 part, heated to 80 ° C., kept warm for 2 hours, then NCO The measurement confirmed that the reaction was complete, and a 2-EHA solution of an ethylenically unsaturated bond-containing acrylic polymer (hereinafter referred to as (F-2) component) having a weight average molecular weight of 110,000 was obtained.
合成例５
（Ｆ−３）成分の合成
エアバブリング装置、撹拌装置、冷却管を備えた反応装置に、カルボキシル基を含有するアクリル系ポリマーの２−ＥＨＡ溶液２８３部（根上工業（株）製、商品名「パラクロンＳＹ−１０７６」；樹脂分７０ｗｔ％、重量平均分子量２１万、２−ＥＨＡ３０ｗｔ％）、グリシジルメタクリレート（ＧＭＡ）２部、トリフェニルホスフィン（ＰＰｈ３）０．８０部を加え、エアバブリングを行いながら、８０℃まで昇温し、８時間保温した後、重量平均分子量２１万のエチレン性不飽和結合含有アクリル系ポリマー（以下、（Ｆ−３）成分という）の２−ＥＨＡ溶液を得た。
Synthesis example 5
(F-3) Component synthetic air bubbling device, stirring device, 283 parts of 2-EHA solution of acrylic polymer containing carboxyl group (manufactured by Negami Kogyo Co., Ltd., trade name “ Paraclone SY-1076 ”; resin content 70 wt%, weight average molecular weight 210,000, 2-EHA 30 wt%), glycidyl methacrylate (GMA) 2 parts, triphenylphosphine (PPh 3 ) 0.80 parts, and air bubbling The temperature was raised to 80 ° C. and the temperature was kept for 8 hours, and then a 2-EHA solution of an ethylenically unsaturated bond-containing acrylic polymer (hereinafter referred to as (F-3) component) having a weight average molecular weight of 210,000 was obtained.
＜粘着剤組成物の調製＞
実施例１
（Ａ）成分として、（Ａ−１）成分を３０部、（Ｂ）成分として２−ＥＨＡ（以下（Ｂ−１）成分という）を２５部、（Ｃ）成分としてＩＢＸＡ（以下（Ｃ−１）成分という）を４５部、（Ｄ）成分としてトリペンタエリスリトールポリアクリレート（大阪有機化学（株）製、商品名「ビスコート＃８０２」）（以下（Ｄ−１）成分という）を１部、（Ｅ）成分として２，４，６−トリメチルベンゾイル−ジフェニル−フォスフィンオキサイド（ＢＡＳＦジャパン（株）製、商品名「ルシリンＴＰＯ」）（以下（Ｅ−１）成分という）を１部の割合で粘着剤組成物を調製した。また、組成物の色調ガードナーカラー、粘度、溶剤含有率を評価し、結果を表２に示した。
<Preparation of pressure-sensitive adhesive composition>
Example 1
As component (A), 30 parts of component (A-1), 25 parts of 2-EHA (hereinafter referred to as component (B-1)) as component (B), and IBXA (hereinafter referred to as (C-1) as component (C) ) Component) 45 parts, (D) component as tripentaerythritol polyacrylate (manufactured by Osaka Organic Chemical Co., Ltd., trade name “Biscoat # 802”) (hereinafter referred to as (D-1) component), 1 part, E) 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by BASF Japan Ltd., trade name “Lucirin TPO”) (hereinafter referred to as “component (E-1)”) is adhered at a rate of 1 part as component E) An agent composition was prepared. Further, the color tone Gardner color, viscosity, and solvent content of the composition were evaluated, and the results are shown in Table 2.
実施例２
実施例２の（Ａ）成分を（Ａ−２）成分３０部に置換し、他配合は実施例１同様に粘着剤組成物を調製した。組成物の色調ガードナーカラー、粘度、溶剤含有率を評価した結果を表２に示した。
Example 2
The component (A) in Example 2 was replaced with 30 parts of the component (A-2), and other formulations were prepared as in Example 1 to prepare a pressure-sensitive adhesive composition. Table 2 shows the results of evaluating the color tone Gardner color, viscosity, and solvent content of the composition.
実施例３
実施例１の（Ｂ）成分を、（Ｂ−１）成分１８．３部、イソオクチルアクリレート（以下（Ｂ−２）成分という）を６．７部に置換し、他配合は実施例１同様に粘着剤組成物を調製した。組成物の色調ガードナーカラー、粘度、溶剤含有率を評価した結果を表２に示した。
Example 3
The component (B) in Example 1 was replaced with 18.3 parts of the component (B-1) and 6.7 parts of isooctyl acrylate (hereinafter referred to as the component (B-2)), and other formulations were the same as in Example 1. A pressure-sensitive adhesive composition was prepared. Table 2 shows the results of evaluating the color tone Gardner color, viscosity, and solvent content of the composition.
実施例４
実施例１の（Ｂ）成分を、（Ｂ−１）成分１８．３部、イソノニルアクリレート（以下（Ｂ−３）成分という）を６．７部に置換し、他配合は実施例１同様に粘着剤組成物を調製した。組成物の色調ガードナーカラー、粘度、溶剤含有率を評価した結果を表２に示した。
Example 4
The component (B) in Example 1 was replaced with 18.3 parts of the component (B-1) and 6.7 parts of isononyl acrylate (hereinafter referred to as the component (B-3)), and other formulations were the same as in Example 1. A pressure-sensitive adhesive composition was prepared. Table 2 shows the results of evaluating the color tone Gardner color, viscosity, and solvent content of the composition.
実施例５
実施例１の（Ｂ）成分を、（Ｂ−１）成分１８．３部、イソデシルアクリレート（以下（Ｂ−４）成分という）を６．７部に置換し、他配合は実施例１同様に粘着剤組成物を調製した。組成物の色調ガードナーカラー、粘度、溶剤含有率を評価した結果を表２に示した。
Example 5
The component (B) in Example 1 was replaced with 18.3 parts of the component (B-1) and 6.7 parts of isodecyl acrylate (hereinafter referred to as the component (B-4)). A pressure-sensitive adhesive composition was prepared. Table 2 shows the results of evaluating the color tone Gardner color, viscosity, and solvent content of the composition.
実施例６
実施例１の（Ｂ）成分を、（Ｂ−１）成分１８．３部、イソステアリルアクリレート（以下（Ｂ−５）成分という）を６．７部に置換し、他配合は実施例１同様に粘着剤組成物を調製した。組成物の色調ガードナーカラー、粘度、溶剤含有率を評価した結果を表２に示した。
Example 6
The component (B) in Example 1 was replaced with 18.3 parts of the component (B-1) and 6.7 parts of isostearyl acrylate (hereinafter referred to as the component (B-5)), and other formulations were the same as in Example 1. A pressure-sensitive adhesive composition was prepared. Table 2 shows the results of evaluating the color tone Gardner color, viscosity, and solvent content of the composition.
実施例７
実施例１の（Ｂ）成分を、（Ｂ−１）成分１８．３部、ラウリルアクリレート（以下（Ｂ−６）成分という）を６．７部に置換し、他配合は実施例１同様に粘着剤組成物を調製した。組成物の色調ガードナーカラー、粘度、溶剤含有率を評価した結果を表２に示した。
Example 7
The component (B) in Example 1 was replaced with 18.3 parts of the component (B-1) and 6.7 parts of lauryl acrylate (hereinafter referred to as the component (B-6)), and the other formulations were the same as in Example 1. A pressure-sensitive adhesive composition was prepared. Table 2 shows the results of evaluating the color tone Gardner color, viscosity, and solvent content of the composition.
実施例８
実施例１の（Ｃ）成分を、ｔ-ブチルシクロヘキシルアクリレート（以下（Ｃ−２）成分という）４５部に置換し、他配合は実施例１同様に粘着剤組成物を調製した。組成物の色調ガードナーカラー、粘度、溶剤含有率を評価した結果を表２に示した。
Example 8
The component (C) of Example 1 was replaced with 45 parts of t-butylcyclohexyl acrylate (hereinafter referred to as (C-2) component), and the other compounding was prepared in the same manner as in Example 1. Table 2 shows the results of evaluating the color tone Gardner color, viscosity, and solvent content of the composition.
実施例９
実施例２の（Ｄ）成分を、トリアリルイソシアヌレート（日本化成（株）製、商品名「タイクトリアリルイソシアヌレート」）（以下（Ｄ−２）成分という）１部、（Ｅ）成分を、オリゴ｛２−ヒドロキシ−２−メチル−１−[４−（１−メチルビニル）フェニル]プロパノン｝（ＤＫＳＨジャパン（株）製、商品名「ＥＳＡＣＵＲＥ ＯＮＥ」）（以下（Ｅ−２）成分という）１部に置換し、粘着剤組成物を調製した。組成物の色調ガードナーカラー、粘度、溶剤含有率を評価した結果を表２に示した。
Example 9
The component (D) of Example 2 was mixed with 1 part of triallyl isocyanurate (manufactured by Nippon Kasei Chemical Co., Ltd., trade name “Tyctriallyl isocyanurate”) (hereinafter referred to as “component (D-2)”), , Oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone} (manufactured by DKSH Japan, trade name “ESACURE ONE”) (hereinafter referred to as (E-2) component) ) 1 part was substituted and the adhesive composition was prepared. Table 2 shows the results of evaluating the color tone Gardner color, viscosity, and solvent content of the composition.
実施例１０
実施例２の（Ｅ）成分を、（Ｅ−２）成分１部に置換し、他配合は実施例２同様に粘着剤組成物を調製した。組成物の色調ガードナーカラー、粘度、溶剤含有率を評価した結果を表２に示した。
Example 10
The component (E) of Example 2 was replaced with 1 part of the component (E-2), and the other composition was prepared in the same manner as in Example 2 to prepare an adhesive composition. Table 2 shows the results of evaluating the color tone Gardner color, viscosity, and solvent content of the composition.
比較例１
（Ａ−１）の合成原料であるエチレン性不飽和結合を含有しないアクリル系ポリマー（Ｆ−４）の２−ＥＨＡ溶液（根上工業（株）製、商品名「パラクロンＳＹ−１０６２ＫＹ」；アクリル系ポリマー６２ｗｔ％、重量平均分子量５０万、２−ＥＨＡ３８ｗｔ％）を使用し、（Ｆ−４）成分を３０部、（Ｂ）成分として（Ｂ−１）成分を２５部、（Ｃ）成分として（Ｃ−１）成分を４５部、（Ｄ）成分として（Ｄ−１）成分を１部、（Ｅ）成分として（Ｅ−１）成分を１部との割合で粘着剤組成物を調製した。組成物の色調ガードナーカラー、粘度、（溶剤含有率）を評価し、結果を表２に示した。
Comparative Example 1
2-AHA solution of acrylic polymer (F-4) that does not contain an ethylenically unsaturated bond, which is a raw material for synthesis of (A-1) (manufactured by Negami Kogyo Co., Ltd., trade name “Paracron SY-1062KY”; acrylic) Polymer 62 wt%, weight average molecular weight 500,000, 2-EHA 38 wt%), (F-4) component 30 parts, (B) component (B-1) component 25 parts, (C) component (C) A pressure-sensitive adhesive composition was prepared in a ratio of 45 parts for C-1), 1 part for component (D-1) as component (D), and 1 part for component (E-1) as component (E). The color tone Gardner color, viscosity, and (solvent content) of the composition were evaluated, and the results are shown in Table 2.
比較例２
（Ｆ−１）成分を３０部、（Ｂ）成分として、（Ｂ−１）成分を２５部、（Ｃ）成分として（Ｃ−１）成分を４５部、（Ｄ）成分として、（Ｄ−１）成分を１部、（Ｅ）成分として、（Ｅ−１）成分１部の割合で粘着剤組成物を調製した。また、組成物の色調ガードナーカラー、粘度、（溶剤含有率）を評価し、結果を表２に示した。
Comparative Example 2
(F-1) component as 30 parts, (B) component, (B-1) component as 25 parts, (C) component as (C-1) component as 45 parts, (D) component as (D- 1) A pressure-sensitive adhesive composition was prepared at a ratio of 1 part of component (E) and 1 part of component (E-1). Further, the color tone Gardner color, viscosity, and (solvent content) of the composition were evaluated, and the results are shown in Table 2.
比較例３
（Ｆ−１）成分を４０部、（Ｂ）成分として、（Ｂ−１）成分を２０部、（Ｃ）成分として（Ｃ−１）成分を４０部、（Ｄ）成分として、（Ｄ−１）成分を１部、（Ｅ）成分として、（Ｅ−１）成分１部の割合で粘着剤組成物を調製した。また、組成物の色調ガードナーカラー、粘度、（溶剤含有率）を評価し、結果を表２に示した。
Comparative Example 3
(F-1) 40 parts, (B) component, (B-1) component 20 parts, (C) component (C-1) component 40 parts, (D) component (D- 1) A pressure-sensitive adhesive composition was prepared at a ratio of 1 part of component (E) and 1 part of component (E-1). Further, the color tone Gardner color, viscosity, and (solvent content) of the composition were evaluated, and the results are shown in Table 2.
比較例４
（Ｆ‐２）成分を３０部、（Ｂ）成分として（Ｂ−１）を３０部、（Ｃ）成分として（Ｃ−１）成分を４０部、（Ｄ）成分として、（Ｄ−１）を１部、（Ｅ）成分として、（Ｅ−１）１部の割合で粘着剤組成物を調製した。また、組成物の色調ガードナーカラー、粘度、（溶剤含有率）を評価し、結果を表２に示した。
Comparative Example 4
(F-2) Component 30 parts, (B) Component (B-1) 30 parts, (C) Component (C-1) Component 40 parts, (D) Component (D-1) Was 1 part, and (E) component was used, and the adhesive composition was prepared in the ratio of (E-1) 1 part. Further, the color tone Gardner color, viscosity, and (solvent content) of the composition were evaluated, and the results are shown in Table 2.
比較例５
（Ｆ−３）成分を４０部、（Ｂ）成分として、（Ｂ−１）成分を２０部、（Ｃ）成分として、ジシクロペンタニルアクリレート（日立化成（株）製、商品名「ＦＡ−５１３ＡＳ」）（以下（Ｃ-３）成分という）を４０部、（Ｅ）成分として、（Ｅ−１）成分１部の割合で粘着剤組成物を調製した。また、各組成物の色調ガードナーカラー、粘度、（溶剤含有率）を評価し、結果を表２に示した。
Comparative Example 5
(F-3) 40 parts, (B) component, (B-1) component 20 parts, (C) component, dicyclopentanyl acrylate (manufactured by Hitachi Chemical Co., Ltd., trade name "FA- 513AS ") (hereinafter referred to as (C-3) component) as 40 parts and (E) component, an adhesive composition was prepared at a ratio of 1 part of (E-1) component. Further, the color tone Gardner color, viscosity, and (solvent content) of each composition were evaluated, and the results are shown in Table 2.
比較例６
（Ａ−１）成分を５０部、（Ｂ）成分として、（Ｂ−１）成分を５０部、（Ｄ）成分として、（Ｄ−１）を１部、（Ｅ）成分として、（Ｅ−１）成分１部の割合で粘着剤組成物を調製した。また、各組成物の色調ガードナーカラー、粘度、（溶剤含有率）を評価し、結果を表２に示した。
Comparative Example 6
(A-1) 50 parts, (B) component, (B-1) component 50 parts, (D) component, (D-1) 1 part, (E) component, (E- 1) A pressure-sensitive adhesive composition was prepared at a ratio of 1 part of the component. Further, the color tone Gardner color, viscosity, and (solvent content) of each composition were evaluated, and the results are shown in Table 2.
比較例７
（Ａ−２）成分を３０部、（Ｂ）成分として（Ｂ−１）成分を２５部、（Ｃ）成分として、（Ｃ−１）成分を４５部、（Ｅ）成分として、（Ｅ−１）成分１部の割合で粘着剤組成物を調製した。また、各組成物の色調ガードナーカラー、粘度、（溶剤含有率）を評価し、結果を表２に示した。
Comparative Example 7
(A-2) Component 30 parts, (B) Component (B-1) Component 25 parts, (C) Component (C-1) Component 45 parts, (E) Component (E- 1) A pressure-sensitive adhesive composition was prepared at a ratio of 1 part of the component. Further, the color tone Gardner color, viscosity, and (solvent content) of each composition were evaluated, and the results are shown in Table 2.
比較例８
（Ａ−２）成分を３０部、（Ｂ）成分として（Ｂ−１）成分を２５部、（Ｃ）成分として、（Ｃ−１）を成分４５部、（Ｅ）成分として（Ｅ−２）成分を１部との割合で粘着剤組成物を調製した（表１）。また、各組成物の色調ガードナーカラー、粘度、（溶剤含有率）を評価し、結果を表２に示した。
Comparative Example 8
(A-2) Component 30 parts, (B) component (B-1) component 25 parts, (C) component (C-1) component 45 parts, (E) component (E-2) ) A pressure-sensitive adhesive composition was prepared at a ratio of 1 part (Table 1). Further, the color tone Gardner color, viscosity, and (solvent content) of each composition were evaluated, and the results are shown in Table 2.
（色調ガードナーカラー）
ガードナー色数は、ＪＩＳ Ｋ５４００に準拠して測定した。
(Color Gardner color)
The Gardner color number was measured according to JIS K5400.
（粘度）
粘着剤組成物の粘度（ｍＰａ・ｓ）を、Ｅ型粘度計（東機産業株式会社 ＴＶＥ−１０）により２５℃、５分の条件で測定した。
(viscosity)
The viscosity (mPa · s) of the pressure-sensitive adhesive composition was measured with an E-type viscometer (Toki Sangyo Co., Ltd. TVE-10) at 25 ° C. for 5 minutes.
（溶剤含有率）
塗液の溶剤含有率はガスクロマトグラフ装置を用いて測定した。
＜分析装置＞
ＧＣ：Ａｇｉｌｅｎｔ，６８５０
＜ＧＣ測定条件＞
ＧＣカラム：ＨＰ−１
カラム温度：５０℃（１０ｍｉｎ）→１０℃／ｍｉｎ→３００（１０ｍｉｎ）
カラム流量：２．０ｍｌ／ｍｉｎ
Ｃａｒｒｉｅｒ ｇａｓ：ヘリウム
注入方法：Ｓｐｌｉｔ（５０：１）
検出温度：３００℃
(Solvent content)
The solvent content of the coating liquid was measured using a gas chromatograph apparatus.
<Analyzer>
GC: Agilent, 6850
<GC measurement conditions>
GC column: HP-1
Column temperature: 50 ° C. (10 min) → 10 ° C./min→300 (10 min)
Column flow rate: 2.0 ml / min
Carrier gas: Helium injection method: Split (50: 1)
Detection temperature: 300 ° C
（相溶性）
なお、表２中、相溶性は、得られた粘着剤組成物を目視で観察し、以下の基準で判断した。
○：均一完全透明。
×：白濁、完全分離不溶解物がある、もしくは液層分離が確認される。
(Compatibility)
In Table 2, the compatibility was judged based on the following criteria by visually observing the obtained pressure-sensitive adhesive composition.
○: Uniform and completely transparent.
X: There is white turbidity, completely separated insoluble matter, or liquid layer separation is confirmed.
＜粘着層の作製＞
実施例１１〜２０、比較例９〜１６
実施例１〜９、比較例１〜７に係る組成物を、３８μｍ厚の剥離処理ポリエステルフィルム（パナック（株）製、商品名「ＳＰ−ＰＥＴ−０１−３８ＢＵ」）上に、１５０μｍの膜厚になるよう塗布し、空気中、高圧水銀灯（５００ｍＷ／ｃｍ２、６０ｍＪ／ｃｍ２）の下を１度通過させることにより、プレ硬化を行った。この硬化物塗工面と３８μｍ厚の剥離処理ポリエステルフィルムを剥離処理面が接するよう貼り合わせ、空気中、高圧水銀灯（５００ｍＷ／ｃｍ２、３００ｍＪ／ｃｍ２）の下を３度通過させることにより、硬化を行った。
実施例１０と比較例８に係る組成物については、３８μｍ厚の剥離処理ポリエステルフィルム（パナック（株）製、商品名「ＳＰ−ＰＥＴ−０１−３８ＢＵ」）上に、１５０μｍの膜厚になるよう塗布し、空気中、高圧水銀灯（５００ｍＷ／ｃｍ２、１３０ｍＪ／ｃｍ２）の下を１度通過させることにより、プレ硬化を行った。この硬化物塗工面と３８μｍ厚の剥離処理ポリエステルフィルムを剥離処理面が接するよう貼り合わせ、空気中、高圧水銀灯（５００ｍＷ／ｃｍ２、３００ｍＪ／ｃｍ２）の下を３度通過させることにより、硬化を行った。
<Preparation of adhesive layer>
Examples 11-20, Comparative Examples 9-16
The compositions according to Examples 1 to 9 and Comparative Examples 1 to 7 were formed on a release-treated polyester film having a thickness of 38 μm (trade name “SP-PET-01-38BU” manufactured by Panac Co., Ltd.) with a film thickness of 150 μm. And then pre-cured by passing under air in a high-pressure mercury lamp (500 mW / cm 2 , 60 mJ / cm 2 ) once. The cured product coated surface and a 38 μm thick release-treated polyester film were bonded together so that the release-treated surface was in contact with each other, and cured by passing three times under the high-pressure mercury lamp (500 mW / cm 2 , 300 mJ / cm 2 ) in the air. Went.
About the composition which concerns on Example 10 and the comparative example 8, it is set to the film thickness of 150 micrometers on the 38-micrometer-thick peeling process polyester film (The product name "SP-PET-01-38BU" by Panac Co., Ltd.). It was applied and pre-cured by passing once under air in a high-pressure mercury lamp (500 mW / cm 2 , 130 mJ / cm 2 ). The cured product coated surface and a 38 μm thick release-treated polyester film were bonded together so that the release-treated surface was in contact with each other, and cured by passing three times under the high-pressure mercury lamp (500 mW / cm 2 , 300 mJ / cm 2 ) in the air. Went.
［粘着層についての各種試験］
＜粘着力試験＞
作製した実施例１１〜２０、及び比較例９〜１６の粘着層の片面の剥離処理ポリエステルフィルムを剥離し、５０μｍ厚のポリエステルフィルム（東洋紡績（株）製、商品名「コスモシャインＡ−４３００」）をｋｇローラーで貼り合わせ、２時間放置した。残りの剥離処理ポリエステルフィルムを剥離し、ガラスと２ｋｇローラーで貼り合わせた。５０μｍＰＥＴ／粘着層（１５０μｍ）／ガラス試験片を作製した。２５℃５０％ＲＨ下で２４時間放置後、１８０°方向に３００ｍｍ／ｍｉｎの速度で剥離を行うことで、粘着力を測定した（Ｎ／２５ｍｍ）。
[Various tests on adhesive layer]
<Adhesion test>
The prepared adhesive films of Examples 11 to 20 and Comparative Examples 9 to 16 were peeled from the single-sided release polyester film, and a 50 μm thick polyester film (manufactured by Toyobo Co., Ltd., trade name “Cosmo Shine A-4300”). ) With a kg roller and left for 2 hours. The remaining release-treated polyester film was peeled off and bonded to glass with a 2 kg roller. A 50 μm PET / adhesive layer (150 μm) / glass test piece was prepared. After leaving at 25 ° C. and 50% RH for 24 hours, the adhesive strength was measured by peeling in the 180 ° direction at a speed of 300 mm / min (N / 25 mm).
＜ガラス残りの試験＞
ガラス残りは粘着力測定後にガラスに粘着層が残っているかを評価した。評価基準は以下の通りである。
○：ガラスに粘着層が残っていない
△：ガラスに粘着層が一部残っている
×：ガラスに粘着層が残っている
<Remaining glass test>
Whether the adhesive layer remained on the glass after the adhesive strength measurement was evaluated. The evaluation criteria are as follows.
○: Adhesive layer does not remain on glass Δ: Partial adhesive layer remains on glass ×: Adhesive layer remains on glass
＜ヘイズ値の測定＞
作製した実施例５〜８、及び比較例８〜１４の粘着層を粘着力試験と同様に５０μｍＰＥＴ／粘着層（１５０μｍ）／ガラス試験片を作製し、ヘイズ値を、村上色彩技術研究所製カラーへイズメーターを用い、ＪＩＳ Ｋ ５４００に準拠して測定した。結果を表３に示す。なお、各ヘイズ値は基材であるポリエステルフィルムとガラスのヘイズ値を含めた数値である。
<Measurement of haze value>
50 μm PET / adhesive layer (150 μm) / glass test piece was produced from the produced adhesive layers of Examples 5 to 8 and Comparative Examples 8 to 14 in the same manner as in the adhesive strength test, and the haze value was determined as a color manufactured by Murakami Color Research Laboratory. It measured based on JISK5400 using the haze meter. The results are shown in Table 3. In addition, each haze value is a numerical value including the haze value of the polyester film which is a base material, and glass.
＜耐久性試験＞
作製した実施例５〜８、及び比較例８〜１４の粘着層を粘着力試験と同様に５０μｍＰＥＴ／粘着層（１５０μｍ）／ガラス試験片を作製し、耐久性試験を実施した。耐久性試験は６０℃−相対湿度９０％の恒温恒湿槽中に５００時間保管する耐湿熱性試験を行った。耐湿熱性試験後のヘイズ値を、村上色彩技術研究所製カラーへイズメーターを用い、ＪＩＳ Ｋ ５４００に準拠して測定した。結果を表３に示す。なお、各ヘイズ値は基材であるポリエステルフィルムとガラスのヘイズ値を含めた数値である。
耐久性の評価基準は以下の通りである。
○：剥がれ、発泡なし
×：剥がれ、発泡あり
<Durability test>
A 50 μm PET / adhesive layer (150 μm) / glass test piece was produced from the produced adhesive layers of Examples 5 to 8 and Comparative Examples 8 to 14 in the same manner as the adhesive strength test, and a durability test was performed. The durability test was a heat and humidity resistance test stored for 500 hours in a constant temperature and humidity chamber at 60 ° C. and 90% relative humidity. The haze value after the wet heat resistance test was measured according to JIS K 5400 using a color haze meter manufactured by Murakami Color Research Laboratory. The results are shown in Table 3. In addition, each haze value is a numerical value including the haze value of the polyester film which is a base material, and glass.
The evaluation criteria for durability are as follows.
○: Peeling and no foaming ×: Peeling and foaming
Claims (4)
（Ａ）重量平均分子量（ゲルパーミエテーションクロマトグラフィーによるポリスチレン換算値）が３００，０００〜１，２００，０００であるエチレン性不飽和結合含有アクリル系ポリマー
（Ｂ）エチレン性不飽和結合を１つ含有し、かつ炭素数が４〜１８の鎖状アルキル基を有するモノマー
（Ｃ）エチレン性不飽和結合を１つ含有し、かつ炭素数が４〜１８の環状アルキル基を有するモノマー
（Ｄ）エチレン性不飽和結合を３つ以上含有する化合物
（Ｅ）光重合開始剤 UV curing for optics, characterized by having a solvent content of less than 1% by weight, a viscosity at 25 ° C. of 100 to 10,000 mPa · s, a color tone of Gardner color 1 or less, and the following (A) to (E) Type pressure-sensitive adhesive composition.
(A) Ethylenically unsaturated bond-containing acrylic polymer having a weight average molecular weight (polystyrene conversion value by gel permeation chromatography) of 300,000 to 1,200,000 (B) One ethylenically unsaturated bond And a monomer having a chain alkyl group having 4 to 18 carbon atoms (C) a monomer having one ethylenically unsaturated bond and having a cyclic alkyl group having 4 to 18 carbon atoms (D) ethylene Compound (E) Photopolymerization Initiator Containing 3 or More Reactive Unsaturation Bonds
The pressure-sensitive adhesive layer according to claim 3, which has an average thickness of 10 to 1000 µm.
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