JP2017203100A - Curable composition for adhesive sheet, and adhesive sheet using the same - Google Patents
Curable composition for adhesive sheet, and adhesive sheet using the same Download PDFInfo
- Publication number
- JP2017203100A JP2017203100A JP2016095293A JP2016095293A JP2017203100A JP 2017203100 A JP2017203100 A JP 2017203100A JP 2016095293 A JP2016095293 A JP 2016095293A JP 2016095293 A JP2016095293 A JP 2016095293A JP 2017203100 A JP2017203100 A JP 2017203100A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- acrylate
- adhesive sheet
- mass
- acrylic resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 61
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 61
- 239000000203 mixture Substances 0.000 title claims abstract description 56
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 118
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 77
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 77
- -1 acrylate compound Chemical class 0.000 claims abstract description 70
- 239000000178 monomer Substances 0.000 claims abstract description 34
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 28
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 18
- 230000009477 glass transition Effects 0.000 claims abstract description 17
- 125000003368 amide group Chemical group 0.000 claims abstract description 15
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 79
- 239000000470 constituent Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000013329 compounding Methods 0.000 claims description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000003960 organic solvent Substances 0.000 description 12
- 239000011521 glass Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 229920002799 BoPET Polymers 0.000 description 9
- 238000001723 curing Methods 0.000 description 9
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910001873 dinitrogen Inorganic materials 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- 238000004080 punching Methods 0.000 description 8
- 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 7
- 238000000576 coating method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003431 cross linking reagent Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 230000009257 reactivity Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000007870 radical polymerization initiator Substances 0.000 description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 5
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 5
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 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 5
- 125000000524 functional group Chemical group 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 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 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
- JYSDROPYFMOQPO-UHFFFAOYSA-N CC1=C(C(=O)C=2C(=C(C=CC=2)P(C2=CC=CC=C2)=O)C(C2=C(C=C(C=C2C)C)C)=O)C(=CC(=C1)C)C Chemical compound CC1=C(C(=O)C=2C(=C(C=CC=2)P(C2=CC=CC=C2)=O)C(C2=C(C=C(C=C2C)C)C)=O)C(=CC(=C1)C)C JYSDROPYFMOQPO-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
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical compound CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- CMSBLKQHGOOWBO-UHFFFAOYSA-N 1,1,3-trimethyl-5-(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1CC(C)CC(C)(C)C1 CMSBLKQHGOOWBO-UHFFFAOYSA-N 0.000 description 1
- VBQCFYPTKHCPGI-UHFFFAOYSA-N 1,1-bis(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1(OOC(C)(C)CCC)CCCCC1 VBQCFYPTKHCPGI-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- 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
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 1
- SWCYSRKXDQHFQR-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane;5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1.CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 SWCYSRKXDQHFQR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OHLKMGYGBHFODF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=C(CN=C=O)C=C1 OHLKMGYGBHFODF-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- FWWWRCRHNMOYQY-UHFFFAOYSA-N 1,5-diisocyanato-2,4-dimethylbenzene Chemical compound CC1=CC(C)=C(N=C=O)C=C1N=C=O FWWWRCRHNMOYQY-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- VKQJCUYEEABXNK-UHFFFAOYSA-N 1-chloro-4-propoxythioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(OCCC)=CC=C2Cl VKQJCUYEEABXNK-UHFFFAOYSA-N 0.000 description 1
- SDXHBDVTZNMBEW-UHFFFAOYSA-N 1-ethoxy-2-(2-hydroxyethoxy)ethanol Chemical compound CCOC(O)COCCO SDXHBDVTZNMBEW-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、粘着シート用硬化性組成物、それを用いた粘着シート及びその用途に関する。 The present invention relates to a curable composition for pressure-sensitive adhesive sheets, a pressure-sensitive adhesive sheet using the same, and uses thereof.
近年、携帯端末、ゲーム機器、カーナビ等の分野において、液晶ディスプレイ等の画像表示装置や、タッチパネル等の前記画像表示装置と組み合わせて用いられる入力装置が多く見られる。これらの画像表示装置や入力装置には、光学部材を貼り合せる目的で透明粘着シートが用いられる。
そして、携帯端末などでは、低背化、デザインの多様化が進んでおり、それに従って、前面透明板に黒色の額縁印刷を行うのが一般的であったが、意匠性の点から、この額縁印刷を黒色以外の色で形成することが行われ始めている。黒色以外の着色剤は、隠蔽性が低いため、黒色に比べて印刷部を厚くする必要があり、結果として印刷部の厚さが大きくなる傾向がある。そのため、このような厚みの大きい額縁印刷を施された全面透明板の貼り合せに透明粘着シートが使用される場合、額縁印刷に接する部分には大きな応力が掛かる。そして、その応力は、歪みを生じて、結果として光学特性に悪影響を及ぼす、または透明粘着シートの浮き（気泡や空隙）を発生させる可能性がある。
In recent years, in the fields of mobile terminals, game devices, car navigation systems, and the like, many image display devices such as liquid crystal displays and input devices that are used in combination with the image display devices such as touch panels have been seen. In these image display devices and input devices, transparent adhesive sheets are used for the purpose of bonding optical members.
And for mobile devices, etc., height reduction and design diversification are progressing, and it was common to print black frame on the front transparent plate accordingly, but from the viewpoint of design, this frame Forming prints in colors other than black is beginning to take place. Since the colorant other than black has low concealability, it is necessary to make the printed portion thicker than black, and as a result, the thickness of the printed portion tends to increase. For this reason, when a transparent adhesive sheet is used for laminating the entire transparent plate subjected to such a large frame printing, a large stress is applied to a portion in contact with the frame printing. Then, the stress may cause distortion, resulting in an adverse effect on the optical characteristics, or the transparent adhesive sheet may be lifted (bubbles or voids).
このため透明粘着シートなどの貼り合せ部材には、今まで以上に、より良好な段差追従性が求められるようになってきている。この段差追従性を付与するためには、例えば、ガラス転移温度（Ｔｇ）の低いポリマーからなる柔軟な粘着剤を用いて、比較的厚膜の粘着剤層を形成することが考えられる。しかしながら、このような粘着剤層は、打ち抜き加工時に打ち抜き刃に粘着剤が付着し、連続した打ち抜き加工を困難なものにする。また、低背化の要求には応えることができない。このため、透明粘着シートの段差追従性と同時に透明粘着シートの打ち抜き加工性、作業性を確保する必要がある。
このような課題に対して、例えば、特開２０１５−２０９４４７号公報（特許文献１）には、長鎖のアルキルメタクリレート等を含む（メタ）アクリレート共重合体と架橋剤との組成物が、段差追従性に良好であることが開示されている。しかしながら、開示されている実施例では、段差追従性をガラスとポリエチレンテレフタレート（ＰＥＴ）フィルムとの貼り合せで確認したものであり、ガラスとガラスとの間、すなわち固い物どうしの貼り合せで試験したものでないため、貼り合せの構成によっては、十分な段差追従性があるとは言えない。
For this reason, bonding members such as transparent adhesive sheets are required to have better step following ability than ever. In order to impart this step following property, for example, it is conceivable to form a relatively thick adhesive layer using a flexible adhesive made of a polymer having a low glass transition temperature (Tg). However, such a pressure-sensitive adhesive layer causes a pressure-sensitive adhesive to adhere to the punching blade during the punching process, making continuous punching difficult. In addition, it cannot meet the demand for a low profile. For this reason, it is necessary to ensure the punching workability and workability of the transparent adhesive sheet as well as the step following ability of the transparent adhesive sheet.
In response to such a problem, for example, JP-A-2015-209447 (Patent Document 1) discloses a composition comprising a (meth) acrylate copolymer containing a long-chain alkyl methacrylate and the like and a crosslinking agent. It is disclosed that the followability is good. However, in the disclosed examples, step following ability was confirmed by bonding between glass and polyethylene terephthalate (PET) film, and was tested between glass and glass, that is, bonding between hard objects. Since it is not a thing, it cannot be said that there is sufficient level | step difference followability depending on the structure of bonding.
上記事情に鑑みて、本発明は画像表示装置構成部材を、粘着シートを用いて貼り合せする際、貼り合せ面の段差部に追従して隅々まで粘着シートを貼り合せすることができ、しかもシート内に生じる歪み、粘着シートの浮き（気泡や空隙）を緩和することもでき、さらには、打ち抜き加工性等の作業性を損なうことのない新たな粘着シート用硬化性組成物、及び粘着シートを提供することを課題とする。 In view of the above circumstances, the present invention can adhere the adhesive sheet to every corner following the stepped portion of the bonding surface when the image display device constituent member is bonded using the adhesive sheet. A new curable composition for pressure-sensitive adhesive sheets and pressure-sensitive adhesive sheets that can alleviate distortion generated in the sheet and float (bubbles and voids) of the pressure-sensitive adhesive sheet and that do not impair workability such as punching workability It is an issue to provide.
本発明は以下の粘着シート用硬化性組成物、粘着シート、及び透明導電膜積層体に関する。
［１］ （メタ）アクリル樹脂（Ａ）と、多官能（メタ）アクリレート化合物（Ｂ）と、重合開始剤（Ｃ）とを含有する粘着シート用硬化性組成物であって、前記（メタ）アクリル樹脂（Ａ）が、（メタ）アクリル樹脂（Ａ）のモノマー構成単位中、ヒドロキシル基含有（メタ）アクリレート由来のモノマー構成単位を３〜１２質量％及びアミド基含有（メタ）アクリレート由来のモノマー構成単位を５〜１５質量％含み、かつヒドロキシル基含有（メタ）アクリレート由来のモノマー構成単位及びアミド基含有（メタ）アクリレート由来のモノマー構成単位を合計で１０〜２５質量％含み、前記（メタ）アクリル樹脂（Ａ）の重量平均分子量が２０万〜８０万であり、かつ前記（メタ）アクリル樹脂（Ａ）のガラス転移温度（Ｔｇ）が、−８０〜−３０℃であり、前記（メタ）アクリル樹脂（Ａ）及び多官能（メタ）アクリレート化合物（Ｂ）の総量に対し、前記（メタ）アクリル樹脂（Ａ）の配合量が８５〜９９．５質量％であり、前記多官能（メタ）アクリレート化合物（Ｂ）の配合量が０．５〜１５質量％であることを特徴とする粘着シート用硬化性組成物。
［２］ 前記多官能（メタ）アクリレート化合物（Ｂ）が１分子中に２〜２０個の（メタ）アクリロイルオキシ基を含有する請求項１に記載の粘着シート用硬化性組成物。
［３］ 前項１または２に記載の粘着シート用硬化性組成物の硬化物からなる粘着シート。
［４］ 下記式（１）
［５］透明導電膜の導電層面に貼り合わせるための透明導電膜固定用粘着シートである前項４に記載の粘着シート。
［６］前項５に記載の粘着シートを透明導電膜の導電層面に有する透明導電膜積層体。
The present invention relates to the following curable composition for pressure-sensitive adhesive sheets, pressure-sensitive adhesive sheets, and transparent conductive film laminates.
[1] A curable composition for pressure-sensitive adhesive sheets containing a (meth) acrylic resin (A), a polyfunctional (meth) acrylate compound (B), and a polymerization initiator (C), wherein the (meth) Acrylic resin (A) is a monomer derived from hydroxyl group-containing (meth) acrylate in a monomer structural unit of (meth) acrylic resin (A), 3-12 mass%, and monomer derived from amide group-containing (meth) acrylate 5 to 15% by mass of the structural unit, and 10 to 25% by mass in total of the monomer structural unit derived from the hydroxyl group-containing (meth) acrylate and the monomer structural unit derived from the amide group-containing (meth) acrylate, the (meth) The weight average molecular weight of the acrylic resin (A) is 200,000 to 800,000, and the glass transition temperature (Tg) of the (meth) acrylic resin (A) is −8. It is 0-30 degreeC, and the compounding quantity of the said (meth) acrylic resin (A) is 85-99. With respect to the total amount of the said (meth) acrylic resin (A) and a polyfunctional (meth) acrylate compound (B). It is 5 mass%, and the compounding quantity of the said polyfunctional (meth) acrylate compound (B) is 0.5-15 mass%, The curable composition for adhesive sheets characterized by the above-mentioned.
[2] The curable composition for pressure-sensitive adhesive sheets according to claim 1, wherein the polyfunctional (meth) acrylate compound (B) contains 2 to 20 (meth) acryloyloxy groups in one molecule.
[3] A pressure-sensitive adhesive sheet comprising a cured product of the curable composition for pressure-sensitive adhesive sheets according to item 1 or 2.
[4] The following formula (1)
[5] The pressure-sensitive adhesive sheet according to item 4, which is a pressure-sensitive adhesive sheet for fixing a transparent conductive film for bonding to the conductive layer surface of the transparent conductive film.
[6] A transparent conductive film laminate having the pressure-sensitive adhesive sheet according to item 5 on the conductive layer surface of the transparent conductive film.
本発明の粘着シート用硬化性組成物によれば、これを硬化させることにより、透明性、粘着性、段差追従性さらには打ち抜き加工性等の作業性に優れた粘着シートを得ることができる。
また、本発明の粘着シートは段差吸収性に優れているので、額縁印刷の端部周辺におけるシート内に生じる歪み、及び粘着シートの浮き（気泡や空隙）を抑制することができ、視認性に優れたタッチパネルを得ることができる。
According to the curable composition for pressure-sensitive adhesive sheets of the present invention, it is possible to obtain a pressure-sensitive adhesive sheet excellent in workability such as transparency, pressure-sensitive adhesiveness, step following ability and punching workability by curing the composition.
In addition, since the pressure-sensitive adhesive sheet of the present invention is excellent in level difference absorbability, it is possible to suppress distortion generated in the sheet around the edge of the frame printing and floating of the pressure-sensitive adhesive sheet (bubbles and voids), and visibility is improved. An excellent touch panel can be obtained.
以下、本発明の粘着シート用硬化性組成物、それを用いた粘着シート及びその用途について詳細に説明する。 Hereinafter, the curable composition for pressure-sensitive adhesive sheets of the present invention, the pressure-sensitive adhesive sheet using the same, and the use thereof will be described in detail.
［粘着シート用硬化性組成物］
本発明の粘着シート用硬化性組成物（以下、「粘着シート用組成物」という場合がある。）は、（メタ）アクリル樹脂（Ａ）と、多官能（メタ）アクリレート化合物（Ｂ）と、重合開始剤（Ｃ）とを含有する粘着シート用硬化性組成物であって、（メタ）アクリル樹脂（Ａ）が、ヒドロキシル基含有（メタ）アクリレート由来のモノマー構成単位及びアミド基含有（メタ）アクリレート由来のモノマー構成単位を含み、かつ（メタ）アクリル樹脂（Ａ）のモノマー構成単位中合計で１０〜３０質量％含み、（メタ）アクリル樹脂（Ａ）の重量平均分子量が２０万〜８０万であり、かつ（メタ）アクリル樹脂（Ａ）のガラス転移温度（Ｔｇ）が、−８０〜−３０℃であり、（メタ）アクリル樹脂（Ａ）及び多官能（メタ）アクリレート化合物（Ｂ）の総量に対し、（メタ）アクリル樹脂（Ａ）の配合量が８５〜９９．５質量％であり、多官能（メタ）アクリレート化合物（Ｂ）の配合量が０．５〜１５質量％である。なお、以下では「モノマー構成単位」を単に「構成単位」ということがある。
[Curable composition for pressure-sensitive adhesive sheet]
The curable composition for pressure-sensitive adhesive sheets of the present invention (hereinafter sometimes referred to as “composition for pressure-sensitive adhesive sheets”) includes a (meth) acrylic resin (A), a polyfunctional (meth) acrylate compound (B), A curable composition for pressure-sensitive adhesive sheets containing a polymerization initiator (C), wherein the (meth) acrylic resin (A) is a hydroxyl group-containing (meth) acrylate-derived monomer constituent unit and an amide group-containing (meth). Including a monomer constituent unit derived from acrylate and a total of 10 to 30% by mass in the monomer constituent unit of (meth) acrylic resin (A), and the weight average molecular weight of (meth) acrylic resin (A) is 200,000 to 800,000. And the glass transition temperature (Tg) of the (meth) acrylic resin (A) is −80 to −30 ° C., and the (meth) acrylic resin (A) and the polyfunctional (meth) acrylate compound ( ) Of the (meth) acrylic resin (A) is 85 to 99.5 mass%, and the polyfunctional (meth) acrylate compound (B) is 0.5 to 15 mass%. is there. Hereinafter, the “monomer constituent unit” may be simply referred to as “structural unit”.
本発明において、（メタ）アクリル樹脂とは、アクリル樹脂及びメタクリル樹脂の一方または両方を意味し、（メタ）アクリレートを主成分とするモノマーの重合体である。なお、主成分とは（メタ）アクリレートモノマー構成単位の合計が５０モル％超であることを意味する。本明細書において、「（メタ）アクリル」とは、アクリル及びメタクリルの一方または両方を意味し、「（メタ）アクリレート」とは、アクリレート及びメタクリレートの一方または両方を意味する。本明細書において、多官能（メタ）アクリレート化合物とは、（メタ）アクリロイルオキシ基を複数有する化合物を意味する。 In the present invention, the (meth) acrylic resin means one or both of an acrylic resin and a methacrylic resin, and is a polymer of a monomer having (meth) acrylate as a main component. In addition, a main component means that the sum total of a (meth) acrylate monomer structural unit exceeds 50 mol%. In the present specification, “(meth) acryl” means one or both of acryl and methacryl, and “(meth) acrylate” means one or both of acrylate and methacrylate. In the present specification, the polyfunctional (meth) acrylate compound means a compound having a plurality of (meth) acryloyloxy groups.
［（メタ）アクリル樹脂（Ａ）］
（メタ）アクリル樹脂（Ａ）は、粘着シート用硬化性組成物を硬化してなる粘着シートの被着体に対する粘着性に寄与する。
本発明に用いる（メタ）アクリル樹脂（Ａ）は、構成モノマーとしてヒドロキシル基含有（メタ）アクリレート及びアミド基含有（メタ）アクリレートを含有する。（メタ）アクリル樹脂（Ａ）の全構成モノマー中、ヒドロキシル基含有（メタ）アクリレートの含有量は３〜１２質量％、アミド基含有（メタ）アクリレートの含有量は５〜１５質量％、かつヒドロキシル基含有（メタ）アクリレート及びアミド基含有（メタ）アクリレートの合計が１０〜２５質量％である。ヒドロキシル基含有（メタ）アクリレートの含有量は、好ましくは４〜１１質量％、より好ましくは５〜１０質量％である。アミド基含有（メタ）アクリレートの含有量は、好ましくは６〜１４質量％、より好ましくは７〜１３質量％である。ヒドロキシル基含有（メタ）アクリレート及びアミド基含有（メタ）アクリレートの合計は、好ましくは１１〜２４質量％、より好ましくは１２〜２３質量％である。なお、構成モノマーがヒドロキシル基とアミド基の両方を有する場合は、これらの数に応じて、含有量を案分する。すなわち、ヒドロキシル基を２つ、アミド基を１つ有する（メタ）アクリレートモノマーが９質量％のときは、ヒドロキシル基含有（メタ）アクリレートが６質量％、アミド基含有（メタ）アクリレートが３質量％とカウントする。
[(Meth) acrylic resin (A)]
A (meth) acrylic resin (A) contributes to the adhesiveness with respect to the adherend of the adhesive sheet formed by hardening | curing the curable composition for adhesive sheets.
The (meth) acrylic resin (A) used in the present invention contains a hydroxyl group-containing (meth) acrylate and an amide group-containing (meth) acrylate as constituent monomers. In all the constituent monomers of (meth) acrylic resin (A), the content of hydroxyl group-containing (meth) acrylate is 3 to 12% by mass, the content of amide group-containing (meth) acrylate is 5 to 15% by mass, and hydroxyl The sum total of group containing (meth) acrylate and amide group containing (meth) acrylate is 10-25 mass%. The content of the hydroxyl group-containing (meth) acrylate is preferably 4 to 11% by mass, more preferably 5 to 10% by mass. The content of the amide group-containing (meth) acrylate is preferably 6 to 14% by mass, more preferably 7 to 13% by mass. The total of the hydroxyl group-containing (meth) acrylate and the amide group-containing (meth) acrylate is preferably 11 to 24% by mass, more preferably 12 to 23% by mass. In addition, when a constituent monomer has both a hydroxyl group and an amide group, content is apportioned according to these numbers. That is, when the (meth) acrylate monomer having two hydroxyl groups and one amide group is 9% by mass, the hydroxyl group-containing (meth) acrylate is 6% by mass and the amide group-containing (meth) acrylate is 3% by mass. And count.
ヒドロキシル基含有（メタ）アクリレートとしては、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、４−ヒドロキシブチル（メタ）アクリレート、１，３−ブタンジオールモノ（メタ）アクリレート、１，４−ブタンジオールモノ（メタ）アクリレート、１，６−ヘキサンジオールモノ（メタ）アクリレート、３−メチルペンタンジオールモノ（メタ）アクリレート、グリセリンモノ（メタ）アクリレート等が挙げられる。これらの中でも特に入手のし易さ、反応性の観点から、２−ヒドロキシエチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレートが好ましい。 Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,3-butanediol mono (meth) acrylate, 1 , 4-butanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, 3-methylpentanediol mono (meth) acrylate, glycerin mono (meth) acrylate, and the like. Among these, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are particularly preferable from the viewpoint of easy availability and reactivity.
アミド基含有（メタ）アクリレートとしては、（メタ）アクリルアミド、ジメチル（メタ）アクリルアミド、ジエチル（メタ）アクリルアミド、Ｎ−（メタ）アクリロイルモルフォリン等が挙げられる。これらの中でも、入手のし易さ、安全性及び反応性の観点から、特にジメチル（メタ）アクリルアミド、Ｎ−（メタ）アクリロイルモルフォリンが好ましい。
（メタ）アクリル樹脂（Ａ）の製造に使用されるその他の（メタ）アクリレートモノマーとしては、特に限定はない。（メタ）アクリレートモノマーの例としては、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、ｔ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｎ−ヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、イソオクチル（メタ）アクリレート、ラウリル（メタ）アクリレート、イソデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、トリデシル（メタ）アクリレート、イソステアリル（メタ）アクリレート等のアルキル（メタ）アクリレート；シクロヘキシル（メタ）アクリレート、ノルボルニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ノルボルナニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンタニルオキシエチル（メタ）アクリレート、トリシクロデカンジメチロールジ（メタ）アクリレート等の環状アルキル（メタ）アクリレート；メトキシエチル（メタ）アクリレート、エトキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、２−メトキシエトキシエチル（メタ）アクリレート、２−エトキシエトキシエチル（メタ）アクリレート等のアルコキシアルキル（メタ）アクリレート；メトキシジエチレングリコール（メタ）アクリレート、エトキシジエチレングリコール（メタ）アクリレート、メトキシジプロピレングリコール（メタ）アクリレート等のアルコキシ（ポリ）アルキレングリコール（メタ）アクリレート；β−カルボキシエチル（メタ）アクリレート等のカルボキシル基含有（メタ）アクリレート；Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート等のＮ，Ｎ−ジアルキルアミノアルキル（メタ）アクリレート；２−スルホエチル（メタ）アクリレート等のスルホン酸基含有（メタ）アクリレート；オクタフルオロペンチル（メタ）アクリレート等のフッ化アルキル（メタ）アクリレート；α−ブチル−ω−（３−（メタ）アクリロキシプロピル）ポリジメチルシロキサン等のジメチルシロキサン基含有（メタ）アクリレート；グリシジル（メタ）アクリレート等のエポキシ基を有する（メタ）アクリレート等が挙げられる。これらの（メタ）アクリル樹脂（Ａ）の製造に使用される（メタ）アクリレートモノマーは、単独で使用してもよいし、２種類以上を組み合わせて使用してもよい。これらの中でも、特に入手し易さ、反応性の観点から、その他の（メタ）アクリレートモノマーとして、アルキル（メタ）アクリレート、アルコキシアルキル（メタ）アクリレートが好ましく、アルキル（メタ）アクリレートがより好ましく、該アルキル基部分の炭素数が１〜８のアルキル（メタ）アクリレートがさらに好ましい。
Examples of the amide group-containing (meth) acrylate include (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, and N- (meth) acryloylmorpholine. Among these, dimethyl (meth) acrylamide and N- (meth) acryloylmorpholine are particularly preferable from the viewpoints of availability, safety and reactivity.
There is no limitation in particular as another (meth) acrylate monomer used for manufacture of a (meth) acrylic resin (A). Examples of (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and t-butyl (meth). Acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, tridecyl ( Alkyl (meth) acrylates such as meth) acrylate and isostearyl (meth) acrylate; cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate Norbornanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, tricyclodecane dimethylol di Cyclic alkyl (meth) acrylates such as (meth) acrylate; methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-methoxyethoxyethyl (meth) acrylate, 2-ethoxyethoxyethyl ( Alkoxyalkyl (meth) acrylates such as meth) acrylate; methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxydi Alkoxy (poly) alkylene glycol (meth) acrylate such as propylene glycol (meth) acrylate; carboxyl group-containing (meth) acrylate such as β-carboxyethyl (meth) acrylate; N, N-dimethylaminoethyl (meth) acrylate, N N, N-dialkylaminoalkyl (meth) acrylates such as N, diethylaminoethyl (meth) acrylate; sulfonic acid group-containing (meth) acrylates such as 2-sulfoethyl (meth) acrylate; octafluoropentyl (meth) acrylate and the like Alkyl fluoride (meth) acrylate; α-butyl-ω- (3- (meth) acryloxypropyl) polydimethylsiloxane and other dimethylsiloxane group-containing (meth) acrylates; glycidyl (meth) acrylate and other epoxies (Meth) acrylate etc. which have group are mentioned. The (meth) acrylate monomer used for manufacture of these (meth) acrylic resins (A) may be used independently, and may be used in combination of 2 or more types. Among these, alkyl (meth) acrylates and alkoxyalkyl (meth) acrylates are preferred as other (meth) acrylate monomers, and alkyl (meth) acrylates are more preferred, from the viewpoint of easy availability and reactivity. Alkyl (meth) acrylates having 1 to 8 carbon atoms in the alkyl group moiety are more preferred.
また、本発明における（メタ）アクリル樹脂（Ａ）の製造には、重合性を損なわない範囲で、共重合成分としてその他の重合性モノマーを使用することができる。そのような重合性モノマーの例としては、アクリロニトリル、メタクリロニトリル、スチレン、α−メチルスチレン、酢酸ビニル、プロピオン酸ビニル、ステアリン酸ビニル、塩化ビニル、塩化ビニリデン、アルキルビニルエーテル、ビニルトルエン、ビニルピリジン、ビニルピロリドン、イタコン酸ジアルキルエステル、フマル酸ジアルキルエステル、アリルアルコール、アクリルクロライド、メチルビニルケトン、アリルトリメチルアンモニウムクロライド、ジメチルアリルビニルケトン、（メタ）アクリル酸等が挙げられる。 In addition, in the production of the (meth) acrylic resin (A) in the present invention, other polymerizable monomers can be used as a copolymerization component as long as the polymerizability is not impaired. Examples of such polymerizable monomers include acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyl toluene, vinyl pyridine, Vinylpyrrolidone, itaconic acid dialkyl ester, fumaric acid dialkyl ester, allyl alcohol, acrylic chloride, methyl vinyl ketone, allyltrimethylammonium chloride, dimethylallyl vinyl ketone, (meth) acrylic acid and the like.
（メタ）アクリル樹脂（Ａ）の配合量は、前記（メタ）アクリル樹脂（Ａ）及び多官能（メタ）アクリレート化合物（Ｂ）の総量に対し、８５〜９９．５質量％であり、好ましくは９０〜９９質量％である。配合量が８５質量％未満である場合には、（メタ）アクリル樹脂（Ａ）を含む粘着シート用組成物を硬化してなる粘着シートの剥離力が不十分となるため好ましくない。一方、配合量が９９．５質量％を超える場合には、粘着シート用組成物を硬化してなる粘着シートが、凝集破壊する可能性があり好ましくない。 The blending amount of the (meth) acrylic resin (A) is 85 to 99.5% by mass with respect to the total amount of the (meth) acrylic resin (A) and the polyfunctional (meth) acrylate compound (B), preferably 90-99 mass%. When the blending amount is less than 85% by mass, the peeling force of the pressure-sensitive adhesive sheet obtained by curing the composition for pressure-sensitive adhesive sheets containing the (meth) acrylic resin (A) becomes insufficient, which is not preferable. On the other hand, when the blending amount exceeds 99.5% by mass, the pressure-sensitive adhesive sheet obtained by curing the composition for pressure-sensitive adhesive sheets may cause cohesive failure, which is not preferable.
（メタ）アクリル樹脂（Ａ）は、重量平均分子量が２０〜８０万であり、好ましくは３０〜７０万であり、より好ましくは４０〜６０万である。重量平均分子量が２０万以上であれば、粘着シートの凝集力が十分となり凝集破壊することはない。重量平均分子量が８０万以下であれば、段差追従性も問題ない。 The (meth) acrylic resin (A) has a weight average molecular weight of 200 to 800,000, preferably 300 to 700,000, more preferably 400,000 to 600,000. When the weight average molecular weight is 200,000 or more, the cohesive force of the pressure-sensitive adhesive sheet is sufficient and does not cause cohesive failure. If the weight average molecular weight is 800,000 or less, there is no problem in step following ability.
ここで重量平均分子量は、ゲル・パーミエーション・クロマトグラフィー（昭和電工株式会社製、ショウデックス（登録商標）ＧＰＣ−１０１）を用いて、下記条件にて常温で測定し、ポリスチレン換算にて算出されるものである。
カラム：昭和電工株式会社製、ショウデックス（登録商標）ＬＦ−８０４、
カラム温度：４０℃、
試料：（共）重合体の０．２質量％テトラヒドロフラン溶液、
流量：１ｍｌ／分、
溶離液：テトラヒドロフラン、
検出器：ＲＩ検出器（示差屈折率検出器）。
Here, the weight average molecular weight is measured at room temperature under the following conditions using gel permeation chromatography (manufactured by Showa Denko KK, Shodex (registered trademark) GPC-101), and calculated in terms of polystyrene. Is.
Column: Showa Denko KK, Shodex (registered trademark) LF-804,
Column temperature: 40 ° C
Sample: 0.2% by weight tetrahydrofuran solution of (co) polymer,
Flow rate: 1 ml / min
Eluent: tetrahydrofuran,
Detector: RI detector (differential refractive index detector).
（メタ）アクリル樹脂（Ａ）のガラス転移温度（Ｔｇ）は、−８０〜−３０℃であることが好ましく、より好ましくは−７０〜−４０℃である。Ｔｇが−８０より低い場合には、（メタ）アクリル樹脂（Ａ）の凝集力が不十分となり、剥離力が低くなるため好ましくない。また、−３０℃より高い場合には、段差追従性が悪くなる可能性があり好ましくない。（メタ）アクリル樹脂（Ａ）のＴｇは、（メタ）アクリル樹脂（Ａ）の製造に使用される（メタ）アクリレートモノマーの種類及び／または組成比を適宜変更することにより調整できる。 The glass transition temperature (Tg) of the (meth) acrylic resin (A) is preferably −80 to −30 ° C., more preferably −70 to −40 ° C. When Tg is lower than −80, the cohesive force of the (meth) acrylic resin (A) becomes insufficient and the peeling force becomes low, which is not preferable. Moreover, when higher than -30 degreeC, a level | step difference followability may worsen and it is unpreferable. The Tg of the (meth) acrylic resin (A) can be adjusted by appropriately changing the type and / or composition ratio of the (meth) acrylate monomer used for the production of the (meth) acrylic resin (A).
ここで、Ｔｇは、以下の方法を用いて求められたものを指す。
（メタ）アクリル樹脂（Ａ）から１０ｍｇの試料を採取して、示差走査熱量計（ＤＳＣ）を用いて、１０℃／分の昇温速度で−８０℃から１５０℃まで温度を変化させて示差走査熱量測定を行い、ガラス転移による吸熱開始温度をＴｇとする。なお、Ｔｇが２つ観察された場合には、２つのＴｇの単純平均値をとることとする。
Here, Tg refers to that obtained using the following method.
A 10 mg sample was taken from the (meth) acrylic resin (A), and the differential was changed by using a differential scanning calorimeter (DSC) by changing the temperature from −80 ° C. to 150 ° C. at a heating rate of 10 ° C./min. Scanning calorimetry is performed, and the endothermic start temperature due to glass transition is defined as Tg. When two Tg are observed, a simple average value of the two Tgs is taken.
［（メタ）アクリル樹脂（Ａ）の製造方法］
（メタ）アクリル樹脂（Ａ）の製造方法は特に制限されるものではなく、例えば、溶液重合、乳化重合、塊状重合、懸濁重合などの公知の方法により製造できる。また、ラジカル重合、イオン重合のいずれであっても良い。これらの中でも、溶液重合が特に好適である。
また、得られる共重合体は、ランダム共重合体、ブロック共重合体、交互共重合体などいずれでもよい。
[Method for producing (meth) acrylic resin (A)]
The production method of the (meth) acrylic resin (A) is not particularly limited, and can be produced by a known method such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, or the like. Moreover, either radical polymerization or ionic polymerization may be used. Among these, solution polymerization is particularly preferable.
The obtained copolymer may be any of random copolymer, block copolymer, alternating copolymer and the like.
（メタ）アクリル樹脂（Ａ）をラジカル重合により得る際に用いられる重合開始剤は、特に限定されず、公知のものの中から適宜選択して使用できる。例えば、２，２’−アゾビス（イソブチロニトリル）、２，２’−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、２，２’−アゾビス（２−メチルブチロニトリル）、１，１’−アゾビス（シクロヘキサン−１−カルボニトリル）、２，２’−アゾビス（２，４，４−トリメチルペンタン）、ジメチル−２，２’−アゾビス（２−メチルプロピオネート）等のアゾ系重合開始剤；ベンゾイルパーオキサイド、ｔ−ブチルハイドロパーオキサイド、ジ−ｔ−ブチルパーオキサイド、ｔ−ブチルパーオキシベンゾエート、ジクミルパーオキサイド、１，１−ビス（ｔ−ブチルパーオキシ）３，３，５−トリメチルシクロヘキサン、１，１−ビス（ｔ−ブチルパーオキシ）シクロドデカン等の過酸化物系重合開始剤などの油溶性重合開始剤が好ましく例示される。 The polymerization initiator used when the (meth) acrylic resin (A) is obtained by radical polymerization is not particularly limited and can be appropriately selected from known ones. For example, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile) 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2,4,4-trimethylpentane), dimethyl- Azo polymerization initiators such as 2,2′-azobis (2-methylpropionate); benzoyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, t-butyl peroxybenzoate, dicumyl Peroxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) Oil-soluble polymerization initiator such as peroxide polymerization initiators cyclododecane like are preferably exemplified.
これらの重合開始剤は、単独で使用してもよいし、２種以上を組み合わせて使用してもよい。 These polymerization initiators may be used alone or in combination of two or more.
重合開始剤の使用量は、通常の使用量であればよく、例えば、全モノマー１００質量部に対して０．０１〜５質量部とすることができ、０．０２〜４質量部の範囲であることが好ましく、０．０３〜３質量部であることがより好ましい。 The usage-amount of a polymerization initiator should just be a normal usage-amount, for example, can be 0.01-5 mass parts with respect to 100 mass parts of all monomers, and is in the range of 0.02-4 mass parts. It is preferable that it is 0.03 to 3 parts by mass.
（メタ）アクリル樹脂（Ａ）の製造において、モノマーを溶液重合により重合する場合、各種の一般的な溶剤を用いることができる。例えば、溶剤として、酢酸エチル、酢酸ｎ−プロピル、酢酸ｎ−ブチル等のエステル類、トルエン、ベンゼン等の芳香族炭化水素類、ｎ−ヘキサン、ｎ−ヘプタン等の脂肪族炭化水素類、シクロヘキサン、メチルシクロヘキサン等の脂環式炭化水素類、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類などの有機溶剤が挙げられる。これらの溶剤は、単独で使用してもよいし、２種以上を組み合わせて使用してもよい。 In the production of the (meth) acrylic resin (A), when the monomer is polymerized by solution polymerization, various general solvents can be used. For example, as a solvent, esters such as ethyl acetate, n-propyl acetate and n-butyl acetate, aromatic hydrocarbons such as toluene and benzene, aliphatic hydrocarbons such as n-hexane and n-heptane, cyclohexane, Examples thereof include organic solvents such as alicyclic hydrocarbons such as methylcyclohexane, and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. These solvents may be used alone or in combination of two or more.
［多官能（メタ）アクリレート化合物（Ｂ）］
本発明に使用される多官能（メタ）アクリレート化合物（Ｂ）は（メタ）アクリロイルオキシ基を複数個有する化合物である。多官能（メタ）アクリレート化合物（Ｂ）としては、好ましくは多官能（メタ）アクリレートモノマー（Ｂ１）及び多官能アクリルオリゴマー類（Ｂ２）が挙げられる。多官能（メタ）アクリレート化合物（Ｂ）としては、一分子中に２〜２０個の（メタ）アクリロイルオキシ基を含有しているものが好ましく、一分子中に２〜１０個の（メタ）アクリロイルオキシ基を含有しているものがより好ましい。
[Polyfunctional (meth) acrylate compound (B)]
The polyfunctional (meth) acrylate compound (B) used in the present invention is a compound having a plurality of (meth) acryloyloxy groups. The polyfunctional (meth) acrylate compound (B) is preferably a polyfunctional (meth) acrylate monomer (B1) and polyfunctional acrylic oligomers (B2). As the polyfunctional (meth) acrylate compound (B), those containing 2 to 20 (meth) acryloyloxy groups in one molecule are preferable, and 2 to 10 (meth) acryloyl in one molecule. Those containing an oxy group are more preferred.
多官能（メタ）アクリレートモノマー（Ｂ１）の例としては、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、１，９−ノナンジオールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパントリオキシエチル（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、エトキシ化ペンタエリスリトールトリ（メタ）アクリレート、プロポキシ化ペンタエリスリトールトリ（メタ）アクリレート、トリス（２ーヒドロキシエチル）イソシアヌレートトリ（メタ）アクリレート、ε-カプロラクトン変性トリス（２-ヒドロキシエチル）イソシアヌレートトリ（メタ）アクリレート、グリセリンプロポキシトリアクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、プロポキシ化ペンタエリスリトールテトラ（メタ）アクリレート、エトキシ化ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、トリペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等が挙げられる。これらの中でも、入手のし易さ、反応性の観点から、特にトリメチロールプロパントリ（メタ）アクリレート、エトキシ化ペンタエリスリトールトリ（メタ）アクリレート、プロポキシ化ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレートが好ましい。
多官能アクリルオリゴマー類（Ｂ２）の例としては、ポリエステル（メタ）アクリレート、エポキシ（メタ）アクリレート、ウレタン（メタ）アクリレート、ポリエーテル（メタ）アクリレート等で２〜２０個の（メタ）アクリロイルオキシ基を含有する多官能アクリルオリゴマー類が挙げられる。これらの中でも、反応性の観点から、特にポリエステル（メタ）アクリレートで２〜２０個の（メタ）アクリロイルオキシ基を含有する多官能アクリルオリゴマーが好ましい。
Examples of the polyfunctional (meth) acrylate monomer (B1) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tripropylene Glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, trimethylolpropane tri (meth) Acrylate, trimethylolpropane trioxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tri (meth) acrylate, propoxylated pentaerythritol (Meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ε-caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, glycerin propoxytriacrylate, pentaerythritol tetra (meth) Acrylate, propoxylated pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. Can be mentioned. Among these, trimethylolpropane tri (meth) acrylate, ethoxylated pentaerythritol tri (meth) acrylate, propoxylated pentaerythritol tri (meth) acrylate, and dipentaerythritol hexa are particularly preferable from the viewpoint of availability and reactivity. (Meth) acrylate is preferred.
Examples of polyfunctional acrylic oligomers (B2) include 2 to 20 (meth) acryloyloxy groups such as polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, and polyether (meth) acrylate. And polyfunctional acrylic oligomers. Among these, from the viewpoint of reactivity, a polyfunctional acrylic oligomer containing 2 to 20 (meth) acryloyloxy groups is particularly preferable as a polyester (meth) acrylate.
多官能（メタ）アクリレート化合物（Ｂ）は、粘着シート用組成物を硬化してなる粘着シートの凝集力に寄与する。多官能（メタ）アクリレート化合物（Ｂ）は、前記（メタ）アクリル樹脂（Ａ）及び多官能（メタ）アクリレート化合物（Ｂ）の総量に対し、０．５〜２０質量％であり、好ましくは０．６〜３質量％である。配合量が０．５質量％未満である場合には、多官能（メタ）アクリレート化合物（Ｂ）を含む粘着シート用組成物を硬化してなる粘着シートが、剥離時に凝集破壊を起こす可能性があり好ましくない。一方、配合量が２０質量％を超える場合には、粘着シート用組成物を硬化してなる粘着シートの段差追従性が悪くなり好ましくない。 A polyfunctional (meth) acrylate compound (B) contributes to the cohesion force of the adhesive sheet formed by hardening | curing the composition for adhesive sheets. A polyfunctional (meth) acrylate compound (B) is 0.5-20 mass% with respect to the total amount of the said (meth) acrylic resin (A) and a polyfunctional (meth) acrylate compound (B), Preferably it is 0. .6-3 mass%. When the blending amount is less than 0.5% by mass, the pressure-sensitive adhesive sheet obtained by curing the composition for pressure-sensitive adhesive sheets containing the polyfunctional (meth) acrylate compound (B) may cause cohesive failure at the time of peeling. There is not preferable. On the other hand, when the blending amount exceeds 20% by mass, the step following property of the pressure-sensitive adhesive sheet obtained by curing the composition for pressure-sensitive adhesive sheets is deteriorated, which is not preferable.
［重合開始剤（Ｃ）］
本発明の粘着シート用組成物は、重合開始剤（Ｃ）を含む。重合開始剤（Ｃ）は、熱、または光によりラジカルを発生し、多官能（メタ）アクリレート化合物（Ｂ）を反応させることで粘着シートを形成する。
[Polymerization initiator (C)]
The composition for pressure-sensitive adhesive sheets of the present invention contains a polymerization initiator (C). The polymerization initiator (C) generates a radical by heat or light, and forms a pressure-sensitive adhesive sheet by reacting the polyfunctional (meth) acrylate compound (B).
重合開始剤（Ｃ）としては、特に限定されず、熱ラジカル重合開始剤または光ラジカル重合開始剤の公知のものが用いられる。
光ラジカル重合開始剤としては、例えば、ジエトキシアセトフェノン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、ベンジルジメチルケタール、４−（２−ヒドロキシエトキシ）フェニル−（２−ヒドロキシ−２−プロピル）ケトン、１−ヒドロキシシクロヘキシルフェニルケトン、２−メチル−２−モルホリノ（４−チオメチルフェニル）プロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）ブタノン、２−ヒドロキシ−２−メチル−１−［４−（１−メチルビニル）フェニル］プロパノンオリゴマー等のアセトフェノン類；ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル等のベンゾイン類；ベンゾフェノン、ｏ−ベンゾイル安息香酸メチル、４−フェニルベンゾフェノン、４−ベンゾイル−４’−メチル−ジフェニルサルファイド、３，３’，４，４’−テトラ（ｔ−ブチルパーオキシカルボニル）ベンゾフェノン、２，４，６−トリメチルベンゾフェノン、４−ベンゾイル−Ｎ，Ｎ−ジメチル−Ｎ−［２−（１−オキソ−２−プロペニルオキシ）エチル］ベンゼンメタナミニウムブロミド、（４−ベンゾイルベンジル）トリメチルアンモニウムクロリド等のベンゾフェノン類；２−イソプロピルチオキサントン、４−イソプロピルチオキサントン、２，４−ジエチルチオキサントン、２，４−ジクロロチオキサントン、１−クロロ−４−プロポキシチオキサントン、２−（３−ジメチルアミノ−２−ヒドロキシ）−３，４−ジメチル−９Ｈ−チオキサントン−９−オンメソクロリド等のチオキサントン類；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（２，６−ジメトキシベンゾイル）−２，４，４−トリメチル−ペンチ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）−ジフェニルフォスフィンオキサイド等のアシルフォスフィンオキサイド類等が挙げられる。これらの光ラジカル重合開始剤の中でも、透明性の点から、ビス（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及び１−ヒドロキシシクロヘキシルフェニルケトンの少なくとも一方を用いることが好ましい。これらの光ラジカル重合開始剤は、１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
The polymerization initiator (C) is not particularly limited, and a known thermal radical polymerization initiator or photo radical polymerization initiator is used.
Examples of the photo radical polymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy- 2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Acetophenones such as butanone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomers; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. Benzoy Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 2 , 4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium chloride Benzophenones such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3,4-di Thioxanthones such as til-9H-thioxanthone-9-one mesochloride; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphos And acylphosphine oxides such as fin oxide and bis (2,4,6-trimethylbenzoyl) -diphenylphosphine oxide. Among these radical photopolymerization initiators, it is preferable to use at least one of bis (2,4,6-trimethylbenzoyl) -diphenylphosphine oxide and 1-hydroxycyclohexyl phenyl ketone from the viewpoint of transparency. These radical photopolymerization initiators may be used alone or in combination of two or more.
熱ラジカル重合開始剤としては、例えば、有機過酸化物や、過酸化水素などの無機過酸化物などが挙げられる。有機過酸化物としては、例えば、メチルエチルケトンパーオキサイド、メチルイソブチルケトンパーオキサイド、シクロヘキサノンパーオキサイド、アセチルアセトン等のケトンパーオキサイド類；１，１−ジ（ｔ−ヘキシルパーオキシ）シクロヘキサン、１，１−ジ（ｔ−へキシルパーオキシ）−３，３，５−トリメチルシクロヘキサン、１，１−ジ（ｔ−ブチルパーオキシ）シクロヘキサン等のパーオキシケタール類；ｔ−ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、ｐ−メンタンハイドロパーオキサイド等のハイドロパーオキサイド類；ジクミルパーオキサイド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）へキサン、ジ（２−ｔ−ブチルパーオキシイソプロピル）ベンゼン等のジアルキルパーオキサイド類；ジイソブチリルパーオキサイド、ジ（３，５，５−トリメチルヘキサノイル）パーオキサイド、ジラウロイルパーオキサイド等のジアシルパーオキサイド類；クミルパーオキシネオデカノエート、１，１，３，３−テトラメチルブチルパーオキシネオデカノエート、ｔ−ヘキシルパーオキシネオデカノエート等のパーオキシエステル類；ジイソプロピルパーオキシジカーボネート、ジ−ｎ−プロピルパーオキシジカーボネート、ジ（４−ｔ−ブチルシクロヘキシル）パーオキシジカーボネート等のパーオキシジカーボネート類などが挙げられる。これらの熱ラジカル重合開始剤は、１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Examples of the thermal radical polymerization initiator include organic peroxides and inorganic peroxides such as hydrogen peroxide. Examples of the organic peroxide include ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, and acetylacetone; 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di Peroxyketals such as (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-butylperoxy) cyclohexane; t-butyl hydroperoxide, cumene hydroperoxide, Hydroperoxides such as p-menthane hydroperoxide; dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di (2-t-butylperoxyisopropyl) Dialkyl peroxy such as benzene Ids; diacyl peroxides such as diisobutyryl peroxide, di (3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide; cumylperoxyneodecanoate, 1,1,3,3- Peroxyesters such as tetramethylbutylperoxyneodecanoate and t-hexylperoxyneodecanoate; diisopropylperoxydicarbonate, di-n-propylperoxydicarbonate, di (4-t-butylcyclohexyl) ) Peroxydicarbonates such as peroxydicarbonate. These thermal radical polymerization initiators may be used individually by 1 type, and may be used in combination of 2 or more type.
また、本発明の粘着シート用組成物における重合開始剤（Ｃ）の含有量は、反応性の点から、（メタ）アクリル樹脂（Ａ）と多官能（メタ）アクリレート化合物（Ｂ）の総量１００質量部に対して、０．０５〜５質量部であることが好ましく、０．０８〜４質量部であることがより好ましく、０．１〜３質量部であることがさらに好ましい。
重合開始剤（Ｃ）の含有量が０．０５質量部以上であれば、多官能（メタ）アクリレート化合物（Ｂ）が十分に反応できるため粘着シートの凝集力が十分となる。一方、重合開始剤（Ｃ）の含有量が５質量部以下であれば、得られる粘着シートは十分な耐熱黄変性を発現できる。
Moreover, content of the polymerization initiator (C) in the composition for adhesive sheets of this invention is 100 total of (meth) acrylic resin (A) and a polyfunctional (meth) acrylate compound (B) from a reactive point. It is preferable that it is 0.05-5 mass parts with respect to a mass part, It is more preferable that it is 0.08-4 mass parts, It is further more preferable that it is 0.1-3 mass parts.
If content of a polymerization initiator (C) is 0.05 mass part or more, since polyfunctional (meth) acrylate compound (B) can fully react, the cohesion force of an adhesive sheet will become enough. On the other hand, if content of a polymerization initiator (C) is 5 mass parts or less, the obtained adhesive sheet can express sufficient heat-resistant yellowing.
［架橋剤］
本発明の粘着シート用組成物中のアクリル樹脂（Ａ）は、水酸基を有しているが、その他の官能基としてカルボキシル基、エポキシ基等の官能基を有していてもよい。この場合、必要に応じて凝集力を高める目的で前記官能基と反応することのできる官能基を複数個有している架橋剤を本発明の粘着シート用硬化性組成物に添加しても良い。架橋剤は水酸基、カルボキシル基またはエポキシ基に対して反応性を有するものであれば特に限定されず、その他の官能基と反応することを制限するものではない。例えば、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、水素化トリレンジイソシアネート、１，３−キシリレンジイソシアネート、１，４−キシリレンジイソシアネート、ジフェニルメタン−４，４−ジイソシアネート、イソホロンジイソシアネート、１，３−ビス（イソシアナトメチル）シクロヘキサン、テトラメチルキシリレンジイソシアネート、１，５−ナフタレンジイソシアネート、トリメチロールプロパンのトリレンジイソシアネート付加物、トリメチロールプロパンのキシリレンジイソシアネート付加物、トリフェニルメタントリイソシアネート、メチレンビス（４−フェニルメタン）トリイソシアネート等のイソシアネート系化合物；、ビスフェノールＡ・エピクロルヒドリン型のエポキシ樹脂；エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、１，６−ヘキサンジオールジグリシジルエーテル、トリメチロールプロパン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、ポリグリセロ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グリシジルエリスリトール、ジグリセロールポリグリシジルエーテル等のエポキシ系化合物；テトラメチロールメタン−トリ−β−アジリジニルプロピオネート、トリメチロールプロパン−トリ−β−アジリジニルプロピオネート、Ｎ，Ｎ’−ジフェニルメタン−４，４’−ビス（１−アジリジンカルボキシアミド）、Ｎ，Ｎ’−ヘキサメチレン−１，６−ビス（１−アジリジンカルボキシアミド）等のアジリジン系化合物；ヘキサメトキシメチルメラミン、ヘキサエトキシメチルメラミン、ヘキサプロポキシメチルメラミン、ヘキサプトキシメチルメラミン、ヘキサペンチルオキシメチルメラミン、ヘキサヘキシルオキシメチルメラミン等のメラミン系化合物等が挙げられる。これらは、単独で使用してもよいし、２種以上を組み合わせて使用してもよい。中でも、イソシアネート系化合物が、水酸基を有する（メタ）アクリル樹脂（Ａ）との反応性が良好な点で好ましい。
[Crosslinking agent]
Although the acrylic resin (A) in the composition for adhesive sheets of this invention has a hydroxyl group, it may have functional groups, such as a carboxyl group and an epoxy group, as another functional group. In this case, if necessary, a crosslinking agent having a plurality of functional groups capable of reacting with the functional group may be added to the curable composition for pressure-sensitive adhesive sheets of the present invention in order to increase the cohesive force. . A crosslinking agent will not be specifically limited if it has reactivity with respect to a hydroxyl group, a carboxyl group, or an epoxy group, and it does not restrict | limit reacting with another functional group. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hydrogenated tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane-4,4-diisocyanate, isophorone diisocyanate 1,3-bis (isocyanatomethyl) cyclohexane, tetramethylxylylene diisocyanate, 1,5-naphthalene diisocyanate, tolylene diisocyanate adduct of trimethylolpropane, xylylene diisocyanate adduct of trimethylolpropane, triphenylmethanetri Isocyanate compounds such as isocyanate and methylenebis (4-phenylmethane) triisocyanate; bisphenol A / epichlorohydrin type epoxy resin; Tylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, Epoxy compounds such as pentaerythritol polyglycidyl erythritol and diglycerol polyglycidyl ether; tetramethylolmethane-tri-β-aziridinylpropionate, trimethylolpropane-tri-β-aziridinylpropionate, N, N '-Diphenylmethane-4,4'-bis (1-aziridinecarboxamide), N, N'-hexamethylene-1,6-bis (1- Aziridine compounds such as dilysinecarboxyamide); melamine compounds such as hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexaptoxymethylmelamine, hexapentyloxymethylmelamine, hexahexyloxymethylmelamine, etc. Can be mentioned. These may be used alone or in combination of two or more. Especially, an isocyanate type compound is preferable at the point with the favorable reactivity with the (meth) acrylic resin (A) which has a hydroxyl group.
架橋剤を用いる場合の使用量としては、（メタ）アクリル樹脂（Ａ）と多官能（メタ）アクリレート化合物（Ｂ）の合計量１００質量部に対して、０．０１〜２質量部とすることが好ましく、さらには０．０１〜１質量部が好ましい。架橋剤の使用量が２質量部以下であれば、粘着シートの段差追従性に優れるため好ましい。 When using the crosslinking agent, the amount used is 0.01 to 2 parts by mass with respect to 100 parts by mass of the total amount of the (meth) acrylic resin (A) and the polyfunctional (meth) acrylate compound (B). Is more preferable, and 0.01 to 1 part by mass is more preferable. If the usage-amount of a crosslinking agent is 2 mass parts or less, since it is excellent in the level | step difference followability of an adhesive sheet, it is preferable.
［粘着付与樹脂］
本発明の粘着シート用組成物には、得られる粘着シートの接着力を向上させるため、粘着シートの透明性を低下させない範囲で粘着付与樹脂を必要に応じて添加しても良い。粘着付与樹脂の例としては、ロジンやロジンのエステル化物等のロジン系樹脂；ジテルペン重合体やα−ピネン−フェノール共重合体等のテルペン系樹脂；脂肪族系（Ｃ５系）や芳香族系（Ｃ９系）等の石油樹脂；その他、スチレン系樹脂、フェノール系樹脂、キシレン樹脂等が挙げられる。耐光性の点から不飽和二重結合が少ない水添ロジンや不均化ロジンのエステル化物や、脂肪族や芳香族系石油樹脂、高いＴｇを有するアクリル樹脂等を粘着シートに添加することが好ましい。粘着付与樹脂の添加量としては、粘着シート用組成物１００質量部に対して、１〜１０質量部を添加することが好ましい。
[Tackifying resin]
In order to improve the adhesive strength of the resulting pressure-sensitive adhesive sheet, a tackifier resin may be added to the composition for pressure-sensitive adhesive sheets of the present invention as necessary within a range that does not decrease the transparency of the pressure-sensitive adhesive sheet. Examples of tackifier resins include rosin resins such as rosin and rosin esterified products; terpene resins such as diterpene polymers and α-pinene-phenol copolymers; aliphatic (C5) and aromatic ( Petroleum resin such as C9); styrene resin, phenol resin, xylene resin and the like. From the viewpoint of light resistance, it is preferable to add an esterified product of hydrogenated rosin or disproportionated rosin with little unsaturated double bond, aliphatic or aromatic petroleum resin, acrylic resin having high Tg, etc. to the pressure-sensitive adhesive sheet. . As addition amount of tackifying resin, it is preferable to add 1-10 mass parts with respect to 100 mass parts of compositions for adhesive sheets.
［添加剤］
また、本発明の粘着シート用組成物には、透明性を損なわない範囲で、公知の各種添加剤を必要に応じて添加してもよい。
添加剤としては、可塑剤、表面潤滑剤、レベリング剤、軟化剤、酸化防止剤、老化防止剤、紫外線吸収剤、重合禁止剤、ベンゾトリアゾール系等の光安定剤、リン酸エステル系及びその他の難燃剤、界面活性剤のような帯電防止剤等が挙げられる。
[Additive]
Moreover, you may add a well-known various additive to the composition for adhesive sheets of this invention as needed in the range which does not impair transparency.
Additives include plasticizers, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, UV absorbers, polymerization inhibitors, benzotriazole-based light stabilizers, phosphate esters, and other Examples thereof include antistatic agents such as flame retardants and surfactants.
［有機溶媒］
また、本発明の粘着シート用組成物は、塗工時の粘度調整を目的として有機溶媒を用いて希釈してもよい。
有機溶媒としては、例えば、メチルエチルケトン、アセトン、酢酸エチル、テトラヒドロフラン、ジオキサン、シクロヘキサノン、ｎ−へキサン、トルエン、キシレン、ｎ−プロパノール、イソプロパノール、酢酸ｎ−プロピル等が挙げられる。これらの有機溶媒は、単独で使用してもよいし、２種以上を混合して使用してもよい。なお、有機溶媒は塗工後に乾燥除去される。
[Organic solvent]
Moreover, you may dilute the composition for adhesive sheets of this invention using an organic solvent for the purpose of the viscosity adjustment at the time of coating.
Examples of the organic solvent include methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, xylene, n-propanol, isopropanol, and n-propyl acetate. These organic solvents may be used alone or in combination of two or more. The organic solvent is removed by drying after coating.
［粘着シート用組成物の製造方法］
本発明の粘着シート用組成物の製造方法は、特に限定されるものではなく、例えば、上記の（メタ）アクリル樹脂（Ａ）と、多官能（メタ）アクリレート化合物（Ｂ）と、重合開始剤（Ｃ）、必要に応じて添加される添加剤及び有機溶媒とを、公知の方法を用いて混合することにより製造できる。
[Method for producing composition for pressure-sensitive adhesive sheet]
The manufacturing method of the composition for adhesive sheets of this invention is not specifically limited, For example, said (meth) acrylic resin (A), a polyfunctional (meth) acrylate compound (B), and a polymerization initiator (C) It can manufacture by mixing the additive and organic solvent which are added as needed using a well-known method.
［粘着シート］
本発明の粘着シート用組成物は、上記の組成を有しているので、これを光または熱硬化させることにより、透明性、粘着性、段差追従性さらには打ち抜き加工性等の作業性に優れた粘着シートを得ることができる。
使用される用途としては、光学部材を貼り合わせる用途（光学部材貼り合わせ用）や光学製品の製造用途などに用いられる。また、本発明の粘着シートは、基材を有するものであっても、基材を有さず粘着シートのみからなる両面粘着シートであってもよい。光学部材としては、光学的特性を有する部材であれば、特に限定されないが、例えば、画像表示装置、タッチパネルを構成する部材またはこれらの機器に用いられる部材が挙げられる。より具体的には、例えば、偏光板、位相差板、光学補償フィルム、輝度向上フィルム、導光板、反射フィルム、反射防止フィルム、透明導電フィルム、意匠フィルム、装飾フィルム、表面保護フィルム、プリズム、レンズ、カラーフィルター、透明基板や、さらにはこれらが積層されている部材が挙げられる。本発明の粘着シートは、透明性と段差追従性に優れるため、特に透明導電膜固定用に好適に使用することができ、厚みの大きい額縁印刷が施された透明板にも問題なく使用できる。
[Adhesive sheet]
Since the composition for pressure-sensitive adhesive sheets of the present invention has the above composition, it is excellent in workability such as transparency, pressure-sensitive adhesiveness, step following property and punching workability by light or thermosetting the composition. An adhesive sheet can be obtained.
Applications used include applications for bonding optical members (for optical member bonding) and optical product manufacturing applications. Moreover, even if it has a base material, the adhesive sheet of this invention may be a double-sided adhesive sheet which does not have a base material but consists only of an adhesive sheet. Although it will not specifically limit if it is a member which has an optical characteristic as an optical member, For example, the member used for an image display apparatus, a touchscreen, or these apparatuses is mentioned. More specifically, for example, a polarizing plate, a retardation plate, an optical compensation film, a brightness enhancement film, a light guide plate, a reflection film, an antireflection film, a transparent conductive film, a design film, a decorative film, a surface protection film, a prism, a lens , A color filter, a transparent substrate, and a member in which these are laminated. Since the pressure-sensitive adhesive sheet of the present invention is excellent in transparency and step following ability, it can be suitably used particularly for fixing a transparent conductive film, and can be used without any problem on a transparent plate on which a large frame printing is applied.
本発明の粘着シートは、粘着シート用組成物を溶媒に溶解した溶液を、剥離フィルムに塗布し、塗布した溶液を加熱乾燥して光、または熱で架橋させることで得ることができる。粘着シートの膜厚は、５〜２００μｍとすることが好ましく、１０〜１５０μｍとすることがより好ましく、１５〜１００μｍとすることがさらに好ましい。粘着シートの膜厚が５μｍより薄くなると、粘着シートの貼り合わせが困難となる傾向にある。粘着シートの膜厚が２００μｍより厚くなると、溶媒がシートに残り臭気の問題が発生する傾向にある。なお、本発明の粘着シートを形成する際の塗布（塗工）方法としては、公知のコーティング法を用いることが可能であり、慣用のコーター、例えば、グラビヤロールコーター、リバースロールコーター、キスロールコーター、ディップロールコーター、バーコーター、ナイフコーター、スプレーコーター、コンマコーター、ダイレクトコーターなどを用いてコーティングすることができる。 The adhesive sheet of this invention can be obtained by apply | coating the solution which melt | dissolved the composition for adhesive sheets in the solvent to a peeling film, heat-drying the apply | coated solution, and bridge | crosslinking it with light or a heat | fever. The thickness of the pressure-sensitive adhesive sheet is preferably 5 to 200 μm, more preferably 10 to 150 μm, and still more preferably 15 to 100 μm. When the thickness of the pressure-sensitive adhesive sheet is less than 5 μm, it tends to be difficult to bond the pressure-sensitive adhesive sheet. When the thickness of the pressure-sensitive adhesive sheet is greater than 200 μm, the solvent remains on the sheet and the problem of odor tends to occur. In addition, as a coating (coating) method for forming the pressure-sensitive adhesive sheet of the present invention, a known coating method can be used, and a conventional coater, for example, a gravure roll coater, a reverse roll coater, a kiss roll coater. Coating can be performed using a dip roll coater, bar coater, knife coater, spray coater, comma coater, direct coater or the like.
本発明の粘着シート用組成物を光で硬化させる場合、光源としてはブラックライト、低圧水銀灯、高圧水銀灯、超高圧水銀灯、メタルハライドランプ、キセノンランプ等が挙げられる。
照射強度としては、粘着シート用組成物を充分に硬化させることができればよく、例えば、５０〜３０００ｍＷ／ｃｍ2が好ましい。照射強度が弱すぎると硬化に時間がかかりすぎ好ましくない。
When the adhesive sheet composition of the present invention is cured with light, examples of the light source include black light, low-pressure mercury lamp, high-pressure mercury lamp, ultrahigh-pressure mercury lamp, metal halide lamp, and xenon lamp.
As irradiation intensity, the composition for adhesive sheets should just fully be hardened, for example, 50-3000 mW / cm < 2 > is preferable. If the irradiation intensity is too weak, it takes too much time for curing, which is not preferable.
本発明の粘着シート用組成物を熱で硬化させる場合には、重合開始剤（Ｃ）の１時間半減期温度より高い温度まで加熱することが好ましい。 When the composition for pressure-sensitive adhesive sheets of the present invention is cured with heat, it is preferably heated to a temperature higher than the one-hour half-life temperature of the polymerization initiator (C).
本発明の粘着シート用組成物を硬化して得られる粘着シートのゲル分率は４０〜８０％であることが好ましい。
粘着シートは、トルエン中に室温下で２４時間浸漬した際の下記の式（１）で求められるゲル分率が、４０〜８０％であることが好ましく、４５〜７５％であることがより好ましく、５０〜７０％であることがさらに好ましい。粘着シートのゲル分率が４０〜８０％の範囲であれば、粘着シートの剥離力が十分で、粘着シートの打ち抜き加工性も問題がなく、さらに段差追従性も優れ好ましい。なお、ゲル分率の具体的な測定方法は実施例の項に記載する。
The pressure-sensitive adhesive sheet preferably has a gel fraction determined by the following formula (1) when immersed in toluene at room temperature for 24 hours, and is more preferably 45 to 75%. More preferably, it is 50 to 70%. When the gel fraction of the pressure-sensitive adhesive sheet is in the range of 40 to 80%, the peel strength of the pressure-sensitive adhesive sheet is sufficient, there is no problem with the punching processability of the pressure-sensitive adhesive sheet, and the step following property is excellent and preferable. In addition, the specific measuring method of a gel fraction is described in the item of an Example.
また、本発明の粘着シートは、基材を有するものであっても、基材を有さず粘着シートのみからなる両面粘着シートであってもよい。また、粘着シートは単一層からなるものであっても複数層が積層されていてもよい。中でも、透明性の確保や、段差追従性の観点からは、基材を有さず粘着シートのみからなる両面粘着シートであることが好ましい。 Moreover, even if it has a base material, the adhesive sheet of this invention may be a double-sided adhesive sheet which does not have a base material but consists only of an adhesive sheet. Moreover, even if the adhesive sheet consists of a single layer, multiple layers may be laminated | stacked. Among these, from the viewpoint of ensuring transparency and step following ability, a double-sided pressure-sensitive adhesive sheet made of only a pressure-sensitive adhesive sheet without a substrate is preferable.
以下、合成例、実施例及び比較例により本発明を説明するが、本発明は、以下に示す実施例によって何ら限定されるものではない。 EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example demonstrate this invention, this invention is not limited at all by the Example shown below.
以下の例において使用した試薬は以下の通り。
２−ヒドロキシエチルアクリレート（大阪有機化学工業株式会社製 ＨＥＡ）
ジメチルアクリルアミド（ＫＪケミカルズ株式会社製 ＤＭＡＡ）
ｎ−ブチルアクリレート（東亞合成株式会社製 ＢＡ）
２−エチルヘキシルアクリレート（東亞合成株式会社製 ＥＨＡ）
メチルアクリレート（東亞合成株式会社製 ＭＡ）
２，２’−アゾビス（イソブチロニトリル）（和光純薬工業株式会社製 ＡＩＢＮ）
酢酸エチル（昭和電工株式会社製）
トリメチロールプロパントリアクリレート（東亞合成株式会社製 アロニックス（登録商標）Ｍ−３０９）
１，６−ヘキサンジオールジアクリレート（大阪有機化学工業株式会社製 ビスコート＃２３０）
ジペンタエリスリトールヘキサアクリレート（日本化薬株式会社製 ＫＡＹＡＲＡＤ（登録商標） ＤＰＨＡ）
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製 ルシリンＴＰＯ）
１，１３，３−ペルオキシ−２−エチルヘキサノエート（日油株式会社製 パーオクタ（登録商標）Ｏ）
ヘキサメチレンジイソシアネートのイソシアヌレート体（東ソー株式会社製 コロネート（登録商標）ＨＸ）
The reagents used in the following examples are as follows.
2-hydroxyethyl acrylate (HEA manufactured by Osaka Organic Chemical Industry Co., Ltd.)
Dimethylacrylamide (DMAA from KJ Chemicals)
n-Butyl acrylate (BA manufactured by Toagosei Co., Ltd.)
2-Ethylhexyl acrylate (EHA manufactured by Toagosei Co., Ltd.)
Methyl acrylate (MA manufactured by Toagosei Co., Ltd.)
2,2′-azobis (isobutyronitrile) (AIBN manufactured by Wako Pure Chemical Industries, Ltd.)
Ethyl acetate (made by Showa Denko KK)
Trimethylolpropane triacrylate (Aronix (registered trademark) M-309, manufactured by Toagosei Co., Ltd.)
1,6-hexanediol diacrylate (Biscoat # 230, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA manufactured by Nippon Kayaku Co., Ltd.)
2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide (Lucirin TPO manufactured by BASF)
1,13,3-peroxy-2-ethylhexanoate (Perocta (registered trademark) O manufactured by NOF Corporation)
Isocyanurate of hexamethylene diisocyanate (Coronate (registered trademark) HX manufactured by Tosoh Corporation)
合成例１：（メタ）アクリル樹脂（Ａ−１）の合成
冷却管、窒素ガス導入管、温度計及び撹拌装置を備えた反応容器に、有機溶媒である酢酸エチルを５００質量部と、ｎ−ブチルアクリレートを４１８．２質量部（０．８１モル比）、ジメチルアクリルアミドを４９．９質量部（０．１２モル比）、２−ヒドロキシエチルアクリレートを３０．９質量部（０．０７モル比）、重合開始剤としての２，２’−アゾビス（イソブチロニトリル）を１．０質量部（６．０８ｍｍｏｌ）入れ、窒素ガス気流中で８０℃にて８時間重合を行い、ガラス転移温度−４０℃、重量平均分子量５０万のアクリル樹脂（Ａ−１）のポリマー溶液を得た。
Synthesis Example 1: Synthesis of (meth) acrylic resin (A-1) In a reaction vessel equipped with a cooling tube, a nitrogen gas introduction tube, a thermometer, and a stirring device, 500 parts by mass of ethyl acetate as an organic solvent, n- 418.2 parts by mass (0.81 mole ratio) of butyl acrylate, 49.9 parts by weight (0.12 mole ratio) of dimethylacrylamide, and 30.9 parts by weight (0.07 mole ratio) of 2-hydroxyethyl acrylate Then, 1.0 part by mass (6.08 mmol) of 2,2′-azobis (isobutyronitrile) as a polymerization initiator was added, polymerization was performed at 80 ° C. for 8 hours in a nitrogen gas stream, and a glass transition temperature − A polymer solution of an acrylic resin (A-1) having a temperature of 40 ° C. and a weight average molecular weight of 500,000 was obtained.
合成例２：（メタ）アクリル樹脂（Ａ−２）の合成
冷却管、窒素ガス導入管、温度計及び撹拌装置を備えた反応容器に、有機溶媒である酢酸エチルを５００質量部と、２−エチルヘキシルアクリレートを４１８．２質量部（０．７５モル比）、ジメチルアクリルアミドを４９．９質量部（０．１７モル比）、２−ヒドロキシエチルメタクリレートを３０．９質量部（０．０９モル比）、重合開始剤としての２，２’−アゾビス（イソブチロニトリル）を１．０質量部（６．０８ｍｍｏｌ）入れ、窒素ガス気流中で８０℃にて８時間重合を行い、ガラス転移温度−５７℃、重量平均分子量４２万の（メタ）アクリル樹脂（Ａ−２）のポリマー溶液を得た。
Synthesis Example 2: Synthesis of (meth) acrylic resin (A-2)
In a reaction vessel equipped with a cooling pipe, a nitrogen gas introduction pipe, a thermometer, and a stirring device, 500 parts by mass of ethyl acetate as an organic solvent, 418.2 parts by mass of 2-ethylhexyl acrylate (0.75 molar ratio), 49.9 parts by mass (0.17 mole ratio) of dimethylacrylamide, 30.9 parts by weight (0.09 mole ratio) of 2-hydroxyethyl methacrylate, 2,2′-azobis (isobutyro) as a polymerization initiator Nitrile) is added in an amount of 1.0 part by mass (6.08 mmol), polymerized in a nitrogen gas stream at 80 ° C. for 8 hours, and a (meth) acrylic resin (A) having a glass transition temperature of −57 ° C. and a weight average molecular weight of 420,000. -2) polymer solution was obtained.
合成例３：（メタ）アクリル樹脂（Ａ−３）の合成
冷却管、窒素ガス導入管、温度計及び撹拌装置を備えた反応容器に、有機溶媒である酢酸エチルを５００質量部と、ｎ−ブチルアクリレートを４１９．０質量部（０．８１モ比ル）、ジメチルアクリルアミドを４９．９質量部（０．１２モル比）、２−ヒドロキシエチルアクリレートを３０．９質量部（０．０７モル比）、重合開始剤としての２，２’−アゾビス（イソブチロニトリル）を０．５質量部（３．０４ｍｍｏｌ）入れ、窒素ガス気流中で８０℃にて８時間重合を行い、ガラス転移温度−４０℃、重量平均分子量９１万のアクリル樹脂（Ａ−３）のポリマー溶液を得た。
Synthesis Example 3: Synthesis of (meth) acrylic resin (A-3) In a reaction vessel equipped with a cooling pipe, a nitrogen gas introduction pipe, a thermometer and a stirrer, 500 parts by mass of ethyl acetate as an organic solvent, n- 419.0 parts by mass (0.81 mole ratio) of butyl acrylate, 49.9 parts by weight (0.12 mole ratio) of dimethylacrylamide, and 30.9 parts by weight (0.07 mole ratio) of 2-hydroxyethyl acrylate ), 0.5 part by mass (3.04 mmol) of 2,2′-azobis (isobutyronitrile) as a polymerization initiator was added, polymerization was performed at 80 ° C. for 8 hours in a nitrogen gas stream, and a glass transition temperature. A polymer solution of an acrylic resin (A-3) having a weight average molecular weight of 910,000 was obtained at −40 ° C.
合成例４：（メタ）アクリル樹脂（Ａ−４）の合成
重合開始剤として使用した２，２’−アゾビス（イソブチロニトリル）の含有量を４．０質量部（２４．１７ｍｍｏｌ）に変更したこと以外は、（メタ）アクリル樹脂（Ａ−１）と同様にして合成し、ガラス転移温度−４０℃、重量平均分子量１５万の（メタ）アクリル樹脂（Ａ−４）のポリマー溶液を得た。
Synthesis Example 4: Synthesis of (meth) acrylic resin (A-4) The content of 2,2′-azobis (isobutyronitrile) used as a polymerization initiator was changed to 4.0 parts by mass (24.17 mmol). The polymer solution of (meth) acrylic resin (A-4) having a glass transition temperature of −40 ° C. and a weight average molecular weight of 150,000 is obtained in the same manner as in (meth) acrylic resin (A-1). It was.
合成例５：（メタ）アクリル樹脂（Ａ−５）の合成
冷却管、窒素ガス導入管、温度計及び撹拌装置を備えた反応容器に、有機溶媒である酢酸エチルを５００質量部と、ｎ−ブチルアクリレートを２８６．９質量部（０．４９モル比）、メチルアクリレートを１３１．２質量部（０．３４モル比）、ジメチルアクリルアミドを４９．９質量部（０．１１モル比）、２−ヒドロキシエチルアクリレートを３０．９質量部（０．０７モル比）、重合開始剤としての２，２’−アゾビス（イソブチロニトリル）を１．０質量部（６．０８ｍｍｏｌ）入れ、窒素ガス気流中で８０℃にて８時間重合を行い、ガラス転移温度−２５℃、重量平均分子量５１万のアクリル樹脂（Ａ−５）のポリマー溶液を得た。
Synthesis Example 5: Synthesis of (meth) acrylic resin (A-5) In a reaction vessel equipped with a cooling tube, a nitrogen gas introduction tube, a thermometer, and a stirring device, 500 parts by mass of ethyl acetate as an organic solvent, n- 286.9 parts by mass (0.49 molar ratio) of butyl acrylate, 131.2 parts by mass (0.34 molar ratio) of methyl acrylate, 49.9 parts by mass of dimethylacrylamide (0.11 molar ratio), 2- 30.9 parts by mass (0.07 mole ratio) of hydroxyethyl acrylate, 1.0 part by mass (6.08 mmol) of 2,2′-azobis (isobutyronitrile) as a polymerization initiator, and nitrogen gas stream Polymerization was performed at 80 ° C. for 8 hours to obtain a polymer solution of an acrylic resin (A-5) having a glass transition temperature of −25 ° C. and a weight average molecular weight of 510,000.
合成例６：（メタ）アクリル樹脂（Ａ−６）の合成
ｎ−ブチルアクリレートを４４９．１質量部（０．８７モル比）、ジメチルアクリルアミドを４４．９質量部（０．１３モル比）に変更したこと以外は、（メタ）アクリル樹脂（Ａ−１）と同様にして合成し、ガラス転移温度−４２℃、重量平均分子量４８万の（メタ）アクリル樹脂（Ａ−６）のポリマー溶液を得た。
Synthesis Example 6: Synthesis of (meth) acrylic resin (A-6) 449.1 parts by mass (0.87 mole ratio) of n-butyl acrylate and 44.9 parts by weight (0.13 mole ratio) of dimethylacrylamide A polymer solution of (meth) acrylic resin (A-6) having a glass transition temperature of −42 ° C. and a weight average molecular weight of 480,000 was synthesized in the same manner as (meth) acrylic resin (A-1) except for the change. Obtained.
合成例７：（メタ）アクリル樹脂（Ａ−７）の合成
ｎ−ブチルアクリレート４６８．１質量部（０．９３モル比）、２−ヒドロキシエチルアクリレートを３０．９質量部（０．０７モル比）に変更したこと以外は、（メタ）アクリル樹脂（Ａ−１）と同様にして合成し、ガラス転移温度−５０℃、重量平均分子量５５万の（メタ）アクリル樹脂（Ａ−７）のポリマー溶液を得た。
Synthesis Example 7: Synthesis of (meth) acrylic resin (A-7) 468.1 parts by mass (0.93 molar ratio) of n-butyl acrylate, 30.9 parts by mass (0.07 molar ratio) of 2-hydroxyethyl acrylate The polymer of (meth) acrylic resin (A-7) having a glass transition temperature of −50 ° C. and a weight average molecular weight of 550,000, synthesized in the same manner as (meth) acrylic resin (A-1) except that A solution was obtained.
合成例１〜７の（メタ）アクリル樹脂（Ａ−１）〜（Ａ−７）のガラス転移温度及び重量平均分子量は前述の方法で測定した。 The glass transition temperature and the weight average molecular weight of the (meth) acrylic resins (A-1) to (A-7) of Synthesis Examples 1 to 7 were measured by the methods described above.
（メタ）アクリル樹脂（Ａ−１）〜（Ａ−７）について、重合に使用した材料（モノマー）とその含有量（質量％）、ガラス転移温度及び重量平均分子量を表１に示す。
実施例１：
表２に示す組成で、（メタ）アクリル樹脂（Ａ−１）と、多官能（メタ）アクリレート化合物（トリメチロールプロパントリアクリレート；ＴＭＰＴＡ）と、重合開始剤（ルシリンＴＰＯ；Ｌ−ＴＰＯ）とを配合し、さらに、有機溶媒である酢酸エチルで溶媒以外の成分濃度を４０質量％に調節し、室温下でディスパーを用いて混合することで粘着シート用硬化性組成物溶液を得た。
Example 1:
In the composition shown in Table 2, (meth) acrylic resin (A-1), polyfunctional (meth) acrylate compound (trimethylolpropane triacrylate; TMPTA), and polymerization initiator (lucillin TPO; L-TPO) Further, the concentration of components other than the solvent was adjusted to 40% by mass with ethyl acetate, which is an organic solvent, and mixed using a disper at room temperature to obtain a curable composition solution for pressure-sensitive adhesive sheets.
表２に示した（メタ）アクリル樹脂（Ａ−１）の配合比は、合成例で得られた（メタ）アクリル系樹脂（Ａ−１）の酢酸エチル溶液から、溶媒を除いた量を用いている。 The compounding ratio of (meth) acrylic resin (A-1) shown in Table 2 is the amount obtained by removing the solvent from the ethyl acetate solution of (meth) acrylic resin (A-1) obtained in Synthesis Example. ing.
得られた溶液を、厚さ７５μｍの易剥離処理された剥離ＰＥＴフィルムの剥離処理面上に、乾燥後の厚さが１００μｍとなるようにアプリケーターで塗布し、５０℃で１０分間及び８０℃で１０分間、１１０℃で３０分間加熱乾燥させ、さらに厚さ５０μｍの剥離ＰＥＴフィルムの剥離処理面側を粘着剤側にカバーした。 The obtained solution was applied to the release-treated surface of a 75 μm-thick peeled release PET film with an applicator so that the thickness after drying was 100 μm, and at 50 ° C. for 10 minutes and at 80 ° C. The film was dried by heating at 110 ° C. for 10 minutes for 10 minutes, and the release-treated surface side of the 50 μm-thick release PET film was covered on the adhesive side.
重合開始剤として光重合開始剤であるルシリンＴＰＯ（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）を使用したため、次に、紫外線照射装置（アイグラフィックス株式会社製、ＵＶ照射装置３ｋｗ、高圧水銀ランプ）を用い、照射距離２５ｃｍ、ランプ移動速度１．０ｍ／分、照射量約１０００ｍＪ／ｃｍ2の条件で紫外線を照射して粘着シートを光硬化させることで基材無しの両面粘着シートを作製した。 Since lucillin TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide), which is a photopolymerization initiator, was used as a polymerization initiator, an ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd., UV irradiation device 3 kW) was used. , High pressure mercury lamp), UV irradiation under the conditions of irradiation distance of 25 cm, lamp moving speed of 1.0 m / min, irradiation amount of about 1000 mJ / cm 2 , and photo-curing the adhesive sheet to double-sided adhesive without base material A sheet was produced.
両面粘着シートの透明性、剥離力、段差追従性及びゲル分率を以下の方法で評価した。 The transparency, peeling force, step following ability and gel fraction of the double-sided PSA sheet were evaluated by the following methods.
透明性：
得られた両面粘着シートを５０ｍｍ×５０ｍｍの大きさに切り取り、両面粘着シートから厚さ５０μｍの剥離ＰＥＴフィルムを剥がして、両面粘着シートの粘着面をガラス板に貼り合わせ、次いで厚さ７５μｍの剥離ＰＥＴフィルムを剥がして測定用サンプルとした。測定用サンプルについて、ヘイズメーター「ＨＭ−１５０（株式会社村上色彩技術研究所製）」を用いてヘイズ値の測定を行った。ヘイズ値（％）は拡散透過率を全光線透過率で除し、１００を乗じて算出した。ブランクとして、測定用サンプルに使用するガラス板を用いた。なお、ｎ数は３回とし、その平均値を採用した。なお、ヘイズ値は値が小さいほど透明性が高いことを意味する。
transparency:
The obtained double-sided pressure-sensitive adhesive sheet is cut into a size of 50 mm × 50 mm, the peeled PET film having a thickness of 50 μm is peeled off from the double-sided pressure-sensitive adhesive sheet, the pressure-sensitive adhesive surface of the double-sided pressure-sensitive adhesive sheet is bonded to a glass plate, and then peeled off with a thickness of 75 μm. The PET film was peeled off to obtain a measurement sample. About the sample for a measurement, the haze value was measured using haze meter "HM-150 (made by Murakami Color Research Laboratory Co., Ltd.)". The haze value (%) was calculated by dividing the diffuse transmittance by the total light transmittance and multiplying by 100. As a blank, a glass plate used for a measurement sample was used. In addition, n number was made into 3 times and the average value was employ | adopted. In addition, haze value means that transparency is so high that a value is small.
粘着シートの剥離力：
上で得られた両面粘着シートを２５ｍｍ×１５０ｍｍの大きさに切り取り、両面粘着シートの片面の５０μｍ厚の剥離ＰＥＴフィルムを剥がし、片面にコロナ処理が施されている厚さ５０μｍのＰＥＴフィルム（東洋紡社製：東洋紡エステルフィルム Ｅ５１００）に貼り直した後、粘着面（測定面）を試験板に貼付して、２ｋｇのゴムローラー（幅：約５０ｍｍ）を１往復させて、測定用サンプルを作製した。試験板としてガラス板を用いた。得られた測定用サンプルについて、２３℃、湿度５０％の環境下で２４時間放置し、ＪＩＳ Ｋ ６８５４−２に準じて、剥離速度３００ｍｍ／分で１８０°方向の引張試験を行い、両面粘着シートのガラス板に対する粘着力（Ｎ／２５ｍｍ）を測定した。得られた測定値を粘着力とした。
Peel sheet peel strength:
The double-sided pressure-sensitive adhesive sheet obtained above was cut into a size of 25 mm × 150 mm, the 50 μm-thick release PET film on one side of the double-sided pressure-sensitive adhesive sheet was peeled off, and a 50 μm-thick PET film (Toyobo Co., Ltd.) subjected to corona treatment on one side. Company: Toyobo Ester Film (E5100) was applied again, and then the adhesive surface (measurement surface) was attached to the test plate, and a 2 kg rubber roller (width: about 50 mm) was reciprocated once to prepare a measurement sample. . A glass plate was used as a test plate. The obtained measurement sample is left for 24 hours in an environment of 23 ° C. and 50% humidity, and subjected to a tensile test in the 180 ° direction at a peeling rate of 300 mm / min according to JIS K 6854-2. The adhesive force (N / 25 mm) to the glass plate was measured. The obtained measured value was defined as adhesive strength.
段差追従性：
厚さ０．５ｍｍ、長さ５０ｍｍ、幅４０ｍｍのガラス板片面の周囲に、厚さ２０μｍ、幅５ｍｍで窓枠状に印刷された印刷付きガラス板を用意した。上で得られた両面粘着シートを５０ｍｍ×４０ｍｍの大きさに切り取り、５０μｍ厚の剥離ＰＥＴフィルムを剥がし、粘着面をガラス板の印刷面に貼り合わせた。さらに７５μｍ厚の剥離ＰＥＴフィルムを剥がした後、厚さ０．５ｍｍ、長さ５０ｍｍ、幅４０ｍｍのガラス板との貼り合わせを行い、５気圧、４０℃、１０分の条件で加熱加圧処理を行い固定した後、段差部分の粘着層の浮きを目視で観察した。
Step following capability:
A glass plate with printing printed in a window frame shape with a thickness of 20 μm and a width of 5 mm was prepared around one side of a glass plate having a thickness of 0.5 mm, a length of 50 mm, and a width of 40 mm. The double-sided pressure-sensitive adhesive sheet obtained above was cut into a size of 50 mm × 40 mm, the peeled PET film having a thickness of 50 μm was peeled off, and the pressure-sensitive adhesive surface was bonded to the printed surface of the glass plate. Further, after peeling off the 75 μm-thick peeled PET film, it is bonded to a glass plate having a thickness of 0.5 mm, a length of 50 mm, and a width of 40 mm, and subjected to heat and pressure treatment at 5 atm, 40 ° C. for 10 minutes. After performing and fixing, the floating of the pressure-sensitive adhesive layer at the step portion was visually observed.
段差追従性の評価は、下記の基準で行った。
○；段差のある部分にて粘着層の浮きが確認されない状態
△；段差のある部分にて粘着層の僅かな浮き（微小気泡）が確認された状態
×；段差のある部分にて粘着層の明かな浮きが確認された状態
The step following ability was evaluated according to the following criteria.
○: The state where the adhesion layer is not lifted at the stepped portion Δ; The state where the adhesion layer is slightly lifted (microbubbles) at the stepped portion ×: The state of the pressure sensitive adhesive layer at the stepped portion State where clear float was confirmed
ゲル分率測定：
上で得られた両面粘着シートを７０ｍｍ×７０ｍｍの大きさに切り取り、両面のセパレータのＰＥＴフィルムを剥がして、測定用サンプルとした。その後、測定用サンプルを５０ｍｌのトルエンに浸漬し、室温下で２４時間静置した。トルエン浸漬前後の粘着シートの質量を測定し、下記の式（１）によりゲル分率を算出した。ｎ数は２で行い、その平均値を求めた。
The double-sided pressure-sensitive adhesive sheet obtained above was cut into a size of 70 mm × 70 mm, and the PET film of the double-sided separator was peeled off to obtain a measurement sample. Thereafter, the measurement sample was immersed in 50 ml of toluene and allowed to stand at room temperature for 24 hours. The mass of the pressure-sensitive adhesive sheet before and after immersion in toluene was measured, and the gel fraction was calculated by the following formula (1). The n number was 2, and the average value was obtained.
実施例２〜３、５〜６：
表２に示す（メタ）アクリル樹脂（Ａ）、多官能（メタ）アクリレート化合物（Ｂ）及び重合開始剤（Ｃ）を表２に示す配合（質量％）で使用して、実施例１と同様に、粘着シート用硬化性組成物溶液を得た。得られた溶液を用いて実施例１と同様に、両面粘着シートを作製し、評価した。結果を表２に示す。
Examples 2-3 and 5-6:
The same as in Example 1 except that the (meth) acrylic resin (A), polyfunctional (meth) acrylate compound (B) and polymerization initiator (C) shown in Table 2 were used in the formulation (% by mass) shown in Table 2. In addition, a curable composition solution for pressure-sensitive adhesive sheets was obtained. Using the obtained solution, a double-sided PSA sheet was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 2.
実施例４：
表２に示す組成で、実施例１と同様に、粘着シート用硬化性組成物溶液を得た。得られた溶液を用いて実施例１と同様に、両面粘着シートを作製した。実施例４では重合開始剤（Ｃ）として、熱ラジカル重合開始剤であるパーオクタＯ（１，１３，３−ペルオキシ−２−エチルヘキサノエート）を使用したため、光硬化工程がなく、加熱乾燥工程において熱硬化させた。評価結果を表２に示す。
Example 4:
With the composition shown in Table 2, a curable composition solution for pressure-sensitive adhesive sheets was obtained in the same manner as in Example 1. A double-sided PSA sheet was prepared in the same manner as in Example 1 using the obtained solution. In Example 4, since the thermal radical polymerization initiator perocta O (1,13,3-peroxy-2-ethylhexanoate) was used as the polymerization initiator (C), there was no photocuring step, and the heat drying step And heat cured. The evaluation results are shown in Table 2.
比較例１〜９：
表３に示す（メタ）アクリル樹脂（Ａ）、多官能（メタ）アクリレート化合物（Ｂ）及び重合開始剤（Ｃ）を表３に示す配合（質量％）で使用して、実施例１と同様に、比較例の粘着シート用硬化性組成物溶液を得た。得られた溶液を用いて実施例１と同様に、両面粘着シートを作製し、評価した。結果を表３に示す。
Comparative Examples 1-9:
The same as in Example 1 except that the (meth) acrylic resin (A), polyfunctional (meth) acrylate compound (B) and polymerization initiator (C) shown in Table 3 were used in the formulation (mass%) shown in Table 3. In addition, a curable composition solution for a pressure-sensitive adhesive sheet of a comparative example was obtained. Using the obtained solution, a double-sided PSA sheet was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 3.
表２及び表３に示す通り、本発明の（Ａ）〜（Ｃ）成分を含む実施例１〜６の両面粘着シートは優れた透明性、粘着力、段差追従性を両立するものであった。一方、（Ａ）（メタ）アクリル樹脂の含有量が少ない比較例１及び２では、良好な粘着力と段差追従性は得られなかった。また、（Ａ）成分の含有量が多い比較例３では、両面粘着シートのゲル分率が低く、粘着力の測定で凝集破壊を起こし、良好な粘着性が得られなかった。（Ｂ）成分及び（Ｃ）成分の代わりに多官能イソシアネートの架橋剤を用いた比較例４においても良好な段差追従性は得られなかった。重量平均分子量、ガラス転移温度または特定モノマーの含有量が本発明の（メタ）アクリル樹脂成分とは異なるものを用いた比較例５〜９においても、透明性、粘着力及び段差追従性を両立する両面粘着シートは得られなかった。 As shown in Table 2 and Table 3, the double-sided PSA sheets of Examples 1 to 6 containing the components (A) to (C) of the present invention have both excellent transparency, adhesive strength, and step following ability. . On the other hand, in Comparative Examples 1 and 2 with a low content of (A) (meth) acrylic resin, good adhesive force and step following ability were not obtained. Moreover, in the comparative example 3 with much content of (A) component, the gel fraction of a double-sided adhesive sheet was low, the cohesive failure was raise | generated by the measurement of adhesive force, and favorable adhesiveness was not obtained. In Step 4 of Comparative Example using a cross-linking agent of polyfunctional isocyanate instead of the component (B) and the component (C), good step following ability was not obtained. In Comparative Examples 5 to 9 in which the weight average molecular weight, the glass transition temperature, or the content of the specific monomer is different from that of the (meth) acrylic resin component of the present invention, both transparency, adhesive strength, and step following ability are compatible. A double-sided PSA sheet was not obtained.
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