JPWO2016117045A1 - Pressure-sensitive adhesive sheet, method for producing the same, and method for producing an optical member using the same - Google Patents
Pressure-sensitive adhesive sheet, method for producing the same, and method for producing an optical member using the same Download PDFInfo
- Publication number
- JPWO2016117045A1 JPWO2016117045A1 JP2016570391A JP2016570391A JPWO2016117045A1 JP WO2016117045 A1 JPWO2016117045 A1 JP WO2016117045A1 JP 2016570391 A JP2016570391 A JP 2016570391A JP 2016570391 A JP2016570391 A JP 2016570391A JP WO2016117045 A1 JPWO2016117045 A1 JP WO2016117045A1
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- sensitive adhesive
- meth
- adhesive sheet
- acrylate
- 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
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 115
- 230000003287 optical effect Effects 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 53
- 239000000178 monomer Substances 0.000 claims abstract description 53
- 239000010410 layer Substances 0.000 claims abstract description 45
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 39
- -1 acrylate compound Chemical class 0.000 claims abstract description 39
- 239000011342 resin composition Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 28
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 28
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 25
- 239000003999 initiator Substances 0.000 claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 20
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims abstract description 10
- 238000012662 bulk polymerization Methods 0.000 claims abstract description 10
- 230000036961 partial effect Effects 0.000 claims abstract description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 57
- 230000001070 adhesive effect Effects 0.000 claims description 50
- 239000000853 adhesive Substances 0.000 claims description 49
- 239000011521 glass Substances 0.000 claims description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 14
- 230000001678 irradiating effect Effects 0.000 claims description 13
- 239000012790 adhesive layer Substances 0.000 claims description 11
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 11
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 11
- 239000012986 chain transfer agent Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 5
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 claims description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 5
- 239000012964 benzotriazole Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims 1
- 230000003449 preventive effect Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 239000010408 film Substances 0.000 description 24
- 239000004973 liquid crystal related substance Substances 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 12
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 11
- 229910052753 mercury Inorganic materials 0.000 description 11
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 229920002799 BoPET Polymers 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 230000002087 whitening effect Effects 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000003431 cross linking reagent Substances 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
- 239000000463 material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 210000002858 crystal cell Anatomy 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012719 thermal polymerization Methods 0.000 description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 4
- STFXXRRQKFUYEU-UHFFFAOYSA-N 16-methylheptadecyl prop-2-enoate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)C=C STFXXRRQKFUYEU-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000006188 syrup Substances 0.000 description 3
- 235000020357 syrup Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-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
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 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
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000006059 cover glass Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical class C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- TXTIIWDWHSZBRK-UHFFFAOYSA-N 2,4-diisocyanato-1-methylbenzene;2-ethyl-2-(hydroxymethyl)propane-1,3-diol Chemical compound CCC(CO)(CO)CO.CC1=CC=C(N=C=O)C=C1N=C=O TXTIIWDWHSZBRK-UHFFFAOYSA-N 0.000 description 1
- VBZBISQOWJYWCC-UHFFFAOYSA-N 2-(2-carboxypropan-2-yldiazenyl)-2-methylpropanoic acid Chemical compound OC(=O)C(C)(C)N=NC(C)(C)C(O)=O VBZBISQOWJYWCC-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- AKVUWTYSNLGBJY-UHFFFAOYSA-N 2-methyl-1-morpholin-4-ylprop-2-en-1-one Chemical class CC(=C)C(=O)N1CCOCC1 AKVUWTYSNLGBJY-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- SUAJWTBTMNHVBZ-UHFFFAOYSA-N clonitrate Chemical compound [O-][N+](=O)OCC(CCl)O[N+]([O-])=O SUAJWTBTMNHVBZ-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- WQABCVAJNWAXTE-UHFFFAOYSA-N dimercaprol Chemical compound OCC(S)CS WQABCVAJNWAXTE-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- PVBRSNZAOAJRKO-UHFFFAOYSA-N ethyl 2-sulfanylacetate Chemical compound CCOC(=O)CS PVBRSNZAOAJRKO-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- MKIJJIMOAABWGF-UHFFFAOYSA-N methyl 2-sulfanylacetate Chemical compound COC(=O)CS MKIJJIMOAABWGF-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- REJKHFKLPFJGAQ-UHFFFAOYSA-N oxiran-2-ylmethanethiol Chemical compound SCC1CO1 REJKHFKLPFJGAQ-UHFFFAOYSA-N 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Polarising Elements (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Abstract
粘着剤層を有する粘着シートであって、前記粘着剤層が、分子中に不飽和二重結合を１つのみ有する（メタ）アクリル酸エステル（Ａ）５０〜８５質量％及び分子中に不飽和二重結合を１つのみ有する水酸基含有（メタ）アクリル酸エステル（Ｂ）１５〜５０質量％を含むモノマー組成物を塊状重合法により部分重合して得られるシロップ状アクリル樹脂組成物と、多官能性（メタ）アクリレート化合物（Ｃ）と、光重合開始剤とを含む無溶剤型硬化性樹脂組成物を活性エネルギー線の照射により硬化して形成した層であり、前記粘着剤層中に、未反応の（メタ）アクリレート化合物（Ａ）及び（Ｂ）が部分的に残存している粘着シート；及びその製造方法；並びにそれを使用した光学部材の製造方法が開示される。A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive layer has 50 to 85% by mass of (meth) acrylic acid ester (A) having only one unsaturated double bond in the molecule and unsaturated in the molecule. A syrup-like acrylic resin composition obtained by partial polymerization of a monomer composition containing 15 to 50% by mass of a hydroxyl group-containing (meth) acrylic acid ester (B) having only one double bond by a bulk polymerization method, and polyfunctional Is a layer formed by curing a solventless curable resin composition containing a functional (meth) acrylate compound (C) and a photopolymerization initiator by irradiation with active energy rays, A pressure-sensitive adhesive sheet in which the (meth) acrylate compounds (A) and (B) in the reaction partially remain; and a production method thereof; and a production method of an optical member using the same are disclosed.
Description
本発明は、粘着シート及びその製造方法、並びにそれを使用した光学部材の製造方法に関する。より詳しくは、例えば、液晶表示装置の液晶セルと偏光板や位相差板の貼り付け、タッチパネルの意匠板とタッチセンサーの貼り付け、タッチパネルと液晶モジュールの貼り付け等、光学部材の製造における各部品の貼り付けに有用な粘着シートに関する。 The present invention relates to a pressure-sensitive adhesive sheet, a method for producing the same, and a method for producing an optical member using the same. More specifically, for example, each component in the production of an optical member such as a liquid crystal cell of a liquid crystal display device, a polarizing plate or a retardation plate, a touch panel design plate and a touch sensor, a touch panel and a liquid crystal module. The present invention relates to a pressure-sensitive adhesive sheet useful for pasting.
液晶ディスプレイを備えた液晶表示装置は、パソコンやテレビのみならず、スマートフォン、携帯電話、電子手帳、カーナビ等の様々な電子機器の表示装置として使用されている。特に近年、表示画面をタッチして入力するタッチパネル式の液晶表示装置が普及している。また、装飾の為に加飾印刷段差を設けた液晶表示装置が増えて来ている。例えば、スマートフォンの表示部分を構成する部材として枠状の印刷段差が設けられた部材を用いる場合がある。その加飾印刷段差を有する部材を粘着シートで接着固定する場合、粘着シートには段差を十分埋めることができる性能（即ち段差吸収性）が要求される。 A liquid crystal display device including a liquid crystal display is used as a display device for various electronic devices such as a smartphone, a mobile phone, an electronic notebook, and a car navigation system as well as a personal computer and a television. In particular, in recent years, a touch panel type liquid crystal display device in which a display screen is touched for input has become widespread. In addition, an increasing number of liquid crystal display devices are provided with decorative printing steps for decoration. For example, a member provided with a frame-shaped printing step may be used as a member constituting a display part of a smartphone. When the member having the decorative printing step is bonded and fixed with the pressure-sensitive adhesive sheet, the pressure-sensitive adhesive sheet is required to have a performance capable of sufficiently filling the level difference (that is, the step absorbability).
段差吸収性は、粘着シートの粘着剤層を厚くすれば向上する。しかし、段差が大きい場合は粘着剤層を厚くするだけでは不十分である。しかも、粘着剤層を厚くすることは製品の小型化・薄型化の要求に反する。一方、粘着剤層の弾性率を低くすることでも、段差吸収性はある程度向上する。しかし、弾性率が低い粘着剤は高温での凝集力が低いので耐久性が劣り、例えば高温促進又は高湿熱促進試験を行うと段差周辺部に浮きや剥れが生じる傾向にある。また、これに伴い、一般のタッチパネル用粘着剤に必要とされる耐ブリスター性も低下する。 The step absorbability can be improved by thickening the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet. However, when the level difference is large, it is not sufficient to increase the thickness of the pressure-sensitive adhesive layer. Moreover, increasing the thickness of the pressure-sensitive adhesive layer is contrary to the demand for downsizing and thinning of products. On the other hand, even if the elastic modulus of the pressure-sensitive adhesive layer is lowered, the step absorbability is improved to some extent. However, a pressure-sensitive adhesive having a low elastic modulus has a low cohesive force at a high temperature, so that the durability is poor. Along with this, the blister resistance required for general touch panel adhesives also decreases.
特許文献１には、特定の貯蔵弾性率及び特定の引き剥がし粘着力を示すアクリル系粘着剤層を有する粘着シートが開示され、粘着剤層には架橋可能な官能基を有するアクリル系モノマー（成分Ｂ）が使用されている。そして、この粘着シートは薄膜であっても段差吸収性及び耐久性に優れるとされている。しかし、実施例での粘着剤層の厚さは２５μｍと比較的薄く、また８μｍの段差に追従する程度の効果しか奏しない。すなわち、近年のより大きな段差に対する効果は不十分である。 Patent Document 1 discloses a pressure-sensitive adhesive sheet having an acrylic pressure-sensitive adhesive layer exhibiting a specific storage elastic modulus and a specific peeling adhesive force, and the pressure-sensitive adhesive layer has an acrylic monomer (component) having a crosslinkable functional group. B) is used. And even if this adhesive sheet is a thin film, it is supposed that it is excellent in level | step difference absorbability and durability. However, the thickness of the pressure-sensitive adhesive layer in the examples is relatively thin at 25 μm, and only has an effect of following a step of 8 μm. That is, the effect on the larger step in recent years is insufficient.
特許文献２には、溶液重合で製造された官能基含有アクリル系樹脂と架橋剤の架橋物、及びエチレン性不飽和基を一つ含有するエチレン性不飽和化合物を含む粘着剤層を含有する粘着シートが開示されている。そして、この粘着シートは高レベルの段差追従性を示し、粘着物性（粘着力、保持力）、耐湿熱性、耐ブリスター性も優れるとされている。しかし、溶液で塗布、乾燥された粘着シートでは乾燥時に溶剤が発泡し、粘着剤表面が荒れてしまい、これにより耐ブリスター性が悪化し、特に７５μｍ以上の厚さに塗布することが困難である。また薄膜の場合であっても、膜中に残留する溶剤が経時や促進試験中に気泡として現れ、画面表示に支障をもたらす。さらに特許文献２では、溶剤中で重合されたポリマーに極性や溶解度パラメーターが大きく異なる種類のモノマーを添加している。したがって、重合されたポリマーと添加したモノマーの重合体との相容性が悪く、粘着剤自身が白濁する恐れがある。また、水酸基を多く含有するアクリル系粘着剤をイソシアネート系架橋剤で架橋しているので、架橋反応の終点が分からず、熟成工程を経ても経時で特性が変化してしまう。これは接着後の経時的な剥れの原因になる。 Patent Document 2 discloses a pressure-sensitive adhesive containing a pressure-sensitive adhesive layer containing a functional group-containing acrylic resin and a cross-linked product of a cross-linking agent produced by solution polymerization, and an ethylenically unsaturated compound containing one ethylenically unsaturated group. A sheet is disclosed. This pressure-sensitive adhesive sheet exhibits a high level of level-step following property, and is said to be excellent in pressure-sensitive adhesive properties (adhesive strength, holding power), wet heat resistance, and blister resistance. However, in the pressure-sensitive adhesive sheet coated and dried with a solution, the solvent foams during drying and the surface of the pressure-sensitive adhesive is roughened, which deteriorates the blister resistance, and it is particularly difficult to apply to a thickness of 75 μm or more. . Even in the case of a thin film, the solvent remaining in the film appears as bubbles during the time-lapse or accelerated test, causing troubles on the screen display. Furthermore, in Patent Document 2, a monomer of a type having greatly different polarities and solubility parameters is added to a polymer polymerized in a solvent. Therefore, the compatibility between the polymerized polymer and the polymer of the added monomer is poor, and the adhesive itself may become cloudy. In addition, since the acrylic pressure-sensitive adhesive containing a large amount of hydroxyl groups is crosslinked with an isocyanate-based crosslinking agent, the end point of the crosslinking reaction is not known, and the characteristics change over time even after the aging step. This causes peeling over time after bonding.
特許文献３には、（メタ）アクリル酸エステルモノマーと、ベンゾフェノン構造の紫外線架橋性部位を有する（メタ）アクリル酸エステルモノマーと、親水性モノマーとを溶剤中で重合したアクリル系共重合体からなる粘着シートが開示されている。そして、この粘着シートを加熱、加圧することにより段差に追従させ、紫外線照射により紫外線架橋性部位を架橋させ、硬化することにより優れた段差吸収性を示すとされている。ただし、ベンゾフェノン構造はＵＶ−Ａでは励起せず、ＵＶ−Ｂ、ＵＶ−Ｃが必要である。一方、被着体となるガラスやＰＥＴフィルムは、ＵＶ−Ａは透過するが、紫外線吸収処理を施していないものでもＵＶ−Ｂ、ＵＶ−Ｃは吸収してしまう。これでは粘着シートの紫外線による架橋反応は十分進行しない。そこで特許文献３では、ジフェニル（２,４,６−トリメチルベンゾイル）ホスフィンオキシド（ＴＰＯ）を含有して良いと記載している。しかし、ＴＰＯを添加すると粘着シートが黄色味を帯びてしまう。またＴＰＯは可視光でも励起されるので、粘着シートの加工時やパネル製造時に通常の照明で架橋反応が開始されてしまう恐れがあり、保存や作業時の環境調整が煩雑となる。さらに、ベンゾフェノン構造を有するモノマーや光開始剤ＴＰＯは高価であり、粘着シートのコストアップに繋がってしまう。 Patent Document 3 includes an acrylic copolymer obtained by polymerizing a (meth) acrylic acid ester monomer, a (meth) acrylic acid ester monomer having a UV-crosslinkable site having a benzophenone structure, and a hydrophilic monomer in a solvent. An adhesive sheet is disclosed. And it is supposed that this pressure-sensitive adhesive sheet is heated and pressurized to follow a step, and an ultraviolet-crosslinkable site is cross-linked by ultraviolet irradiation and cured to exhibit excellent step absorbability. However, the benzophenone structure is not excited by UV-A, and UV-B and UV-C are required. On the other hand, the glass or PET film as the adherend transmits UV-A, but absorbs UV-B and UV-C even if it is not subjected to ultraviolet ray absorption treatment. In this case, the crosslinking reaction of the pressure-sensitive adhesive sheet by ultraviolet rays does not proceed sufficiently. Therefore, Patent Document 3 describes that diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (TPO) may be contained. However, when TPO is added, the pressure-sensitive adhesive sheet becomes yellowish. Further, TPO is also excited by visible light, so that there is a risk that the crosslinking reaction will be started by normal illumination during processing of the adhesive sheet or panel manufacturing, and the environmental adjustment during storage and work becomes complicated. Further, the monomer having a benzophenone structure and the photoinitiator TPO are expensive, leading to an increase in the cost of the pressure-sensitive adhesive sheet.
特許文献４には、炭素数１０〜２２のアルキル基をエステル末端に有するアルキル（メタ）アクリレートを３０〜９０質量％含むモノマー成分を重合することにより得られた（メタ）アクリル系ポリマーを含有し、かつ炭素−炭素二重結合を有するラジカル重合性官能基を有することを特徴とする放射線硬化型粘着剤が開示されている。そして、この粘着剤は段差吸収性に優れるとされている。しかし、実施例では特許文献２と同様に、溶剤中で粘着剤を合成し、溶液で塗布、乾燥し、水酸基を多く含有するアクリル系粘着剤をイソシアネート系架橋剤で架橋しているので、溶剤発泡や経時安定性の問題が生じる。また、炭素数１０〜２２のアルキル基をエステル末端に有するアルキル（メタ）アクリレートのような特殊なモノマーを多量に使用し、かつポリマーに炭素−炭素不飽和結合を導入したものを使用するので、材料コストが上昇し、実用的でない。 Patent Document 4 contains a (meth) acrylic polymer obtained by polymerizing a monomer component containing 30 to 90% by mass of an alkyl (meth) acrylate having an alkyl group having 10 to 22 carbon atoms at the ester terminal. And a radiation-curable pressure-sensitive adhesive having a radically polymerizable functional group having a carbon-carbon double bond. And this adhesive is supposed to be excellent in step absorbability. However, in Examples, as in Patent Document 2, the pressure-sensitive adhesive is synthesized in a solvent, applied and dried with a solution, and an acrylic pressure-sensitive adhesive containing a large amount of hydroxyl groups is crosslinked with an isocyanate-based crosslinking agent. Problems with foaming and stability over time occur. In addition, since a large amount of a special monomer such as an alkyl (meth) acrylate having an alkyl group having 10 to 22 carbon atoms at the ester end is used, and a polymer having a carbon-carbon unsaturated bond introduced, Material cost increases and is not practical.
一方、シート化した粘着テープでは段差吸収性が不十分と判断し、熱硬化又は紫外線硬化型の液状樹脂を、印刷層の設けられた部材とそれと貼り合せる部材との間に流し込み、加熱又は紫外線照射により樹脂を硬化させ、部材同士を固定する方法もある。この方法は、段差のある部材に有効である。しかし、液状樹脂を一定量塗布する高価な装置が必要であり、さらに液体の流れによっては、部材間の気泡が抜け切れずに段差付近に気泡が溜まったり、硬化工程の熱や紫外線照射が不十分で硬化不足となり気泡発生の原因になる場合がある。また、液状樹脂はハンドリング性が劣る。 On the other hand, it is judged that the stepped absorptivity is insufficient with the adhesive tape formed into a sheet, and a thermosetting or ultraviolet curable liquid resin is poured between the member provided with the printing layer and the member to be bonded to it, and heated or ultraviolet rays. There is also a method of fixing the members by curing the resin by irradiation. This method is effective for members having steps. However, an expensive apparatus for applying a certain amount of liquid resin is required. Further, depending on the flow of the liquid, bubbles between the members are not completely removed, and bubbles are accumulated near the step, and heat and ultraviolet irradiation in the curing process are not required. Insufficient curing may cause bubbles. Moreover, liquid resin is inferior in handling property.
例えば液晶ディスプレイの製造工程において、偏光板を液晶セルの光学部品に貼合せするに際し、貼合せ位置にずれが生じた場合、貼合せからある時間が経過した後に偏光板を剥離し、高価な液晶セルを再利用することが必要となる場合がある。この場合、偏光板に塗布されている粘着剤を介して貼合した後、ある時間経過後であっても液晶セルから比較的容易に剥離することができる、再剥離性能（リワーク性）を有する粘着剤が求められている。このような要求を満足する粘着剤として、様々な粘着剤が提案されている。例えば特許文献５には、光漏れの問題を解決するために、粘着剤に可塑剤等を添加することで、粘着層を適度に軟らかくして応力緩和性を付与する技術が開示されている。しかし、特許文献４の粘着剤では、可塑剤の添加は、偏光板を剥離した際に被着体を汚染するブリスターの原因となる。さらに凝集力を低下させるので経時による浮きや剥れが生じ易くなる。 For example, when a polarizing plate is bonded to an optical part of a liquid crystal cell in a manufacturing process of a liquid crystal display, if the bonding position shifts, the polarizing plate is peeled off after a certain period of time has passed, and an expensive liquid crystal It may be necessary to reuse the cell. In this case, after pasting via the pressure-sensitive adhesive applied to the polarizing plate, it has a re-peeling performance (reworkability) that can be peeled relatively easily from the liquid crystal cell even after a certain period of time. There is a need for an adhesive. Various pressure-sensitive adhesives have been proposed as pressure-sensitive adhesives that satisfy such requirements. For example, Patent Document 5 discloses a technique for imparting stress relaxation properties by appropriately softening an adhesive layer by adding a plasticizer or the like to the adhesive in order to solve the problem of light leakage. However, in the pressure-sensitive adhesive of Patent Document 4, the addition of a plasticizer causes blisters that contaminate the adherend when the polarizing plate is peeled off. Further, since the cohesive force is lowered, the float and peeling with time are likely to occur.
本発明は、以上説明した従来技術の課題を解決すべくなされたものである。すなわち本発明の目的は、段差吸収性に優れ、硬化後は光学部材に要求される透明性、耐ブリスター性、耐湿熱白化性、高接着性、経時安定性等の特性に優れ、また貼り合せ時の位置ずれ等が生じた場合にもリワーク性に優れる粘着シート及びその製造方法、並びにそれを使用した光学部材の製造方法を提供することにある。 The present invention has been made to solve the above-described problems of the prior art. That is, the object of the present invention is excellent in step absorbability, excellent in properties such as transparency, blister resistance, moist heat whitening resistance, high adhesion and stability over time required for optical members after curing and bonding. An object of the present invention is to provide a pressure-sensitive adhesive sheet that is excellent in reworkability even when a positional deviation or the like occurs, a method for manufacturing the same, and a method for manufacturing an optical member using the pressure-sensitive adhesive sheet.
本発明者らは、上記課題を解決すべく鋭意検討した結果、溶剤を一切使用せず、粘着剤層の主な構成成分である（メタ）アクリレート化合物のうちその未反応物を部分的に粘着剤層中に残存させ、光学部材の製造時にその残存する未反応物を反応させることによって完全接着させる方法が非常に有効であることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors did not use any solvent, and partially adhered the unreacted material of the (meth) acrylate compound which is the main component of the pressure-sensitive adhesive layer. The present inventors have found that a method of completely adhering by remaining in the agent layer and reacting the remaining unreacted substance at the time of manufacturing the optical member is very effective, and the present invention has been completed.
本発明は、粘着剤層を有する粘着シートであって、前記粘着剤層が、分子中に不飽和二重結合を１つのみ有する（メタ）アクリル酸エステル（Ａ）５０〜８５質量％及び分子中に不飽和二重結合を１つのみ有する水酸基含有（メタ）アクリル酸エステル（Ｂ）１５〜５０質量％を含むモノマー組成物を塊状重合法により部分重合して得られるシロップ状アクリル樹脂組成物と、多官能性（メタ）アクリレート化合物（Ｃ）と、光重合開始剤とを含む無溶剤型硬化性樹脂組成物を活性エネルギー線の照射により硬化して形成した層であり、前記粘着剤層中に、未反応の（メタ）アクリレート化合物（Ａ）及び（Ｂ）が部分的に残存している粘着シートである。 This invention is an adhesive sheet which has an adhesive layer, Comprising: The said adhesive layer has (meth) acrylic acid ester (A) 50-85 mass% and molecule | numerator which have only one unsaturated double bond in a molecule | numerator. A syrup-like acrylic resin composition obtained by partially polymerizing a monomer composition containing 15 to 50% by mass of a hydroxyl group-containing (meth) acrylic acid ester (B) having only one unsaturated double bond therein by a bulk polymerization method And a pressure-sensitive adhesive layer formed by curing a solventless curable resin composition containing a polyfunctional (meth) acrylate compound (C) and a photopolymerization initiator by irradiation with active energy rays. In the pressure-sensitive adhesive sheet, unreacted (meth) acrylate compounds (A) and (B) partially remain.
さらに本発明は、粘着剤層を有する粘着シートの製造方法であって、分子中に不飽和二重結合を１つのみ有する（メタ）アクリル酸エステル（Ａ）５０〜８５質量％及び分子中に不飽和二重結合を１つのみ有する水酸基含有（メタ）アクリル酸エステル（Ｂ）１５〜５０質量％を含むモノマー組成物を塊状重合法により部分重合して得られるシロップ状アクリル樹脂組成物と、多官能性（メタ）アクリレート化合物（Ｃ）と、光重合開始剤を含む無溶剤型硬化性樹脂組成物を調製する工程（１）、並びに、前記無溶剤型硬化性樹脂組成物を活性エネルギー線の照射により硬化して、未反応の（メタ）アクリレート化合物（Ａ）及び（Ｂ）が部分的に残存している粘着剤層を形成する工程（２）を有する粘着シートの製造方法である。 Furthermore, this invention is a manufacturing method of the adhesive sheet which has an adhesive layer, Comprising: (meth) acrylic acid ester (A) 50-85 mass% which has only one unsaturated double bond in a molecule | numerator, and in a molecule | numerator A syrup-like acrylic resin composition obtained by partial polymerization of a monomer composition containing 15 to 50% by mass of a hydroxyl group-containing (meth) acrylic acid ester (B) having only one unsaturated double bond by a bulk polymerization method; Step (1) of preparing a solvent-free curable resin composition containing a polyfunctional (meth) acrylate compound (C) and a photopolymerization initiator, and the solvent-free curable resin composition as an active energy ray It is the manufacturing method of the adhesive sheet which has the process (2) which forms the adhesive layer in which the unreacted (meth) acrylate compound (A) and (B) remain partially by hardening | curing by irradiation.
さらに本発明は、粘着シートを用いて接着された部品を含む光学部材の製造方法であって、本発明の粘着シートを用いて被接着物を貼り合わせる工程（３）、並びに、前記被接着物を貼り合わせた後の粘着シートの粘着剤層に活性エネルギー線を照射することにより、粘着剤層中に残存する未反応の（メタ）アクリレート化合物（Ａ）及び（Ｂ）を重合させて完全接着する工程（４）を有する光学部材の製造方法である。 Furthermore, this invention is a manufacturing method of the optical member containing the components adhere | attached using the adhesive sheet, Comprising: The process (3) of bonding an adherend using the adhesive sheet of this invention, and the said adherend By irradiating the adhesive layer of the adhesive sheet after bonding the active energy rays, the unreacted (meth) acrylate compounds (A) and (B) remaining in the adhesive layer are polymerized and completely adhered. It is a manufacturing method of the optical member which has the process (4) to do.
本発明の粘着シートは、段差吸収性に優れ、しかも貼り合せ後のリワーク性に優れている。また、本発明の光学部材の製造方法によれば、透明性、耐ブリスター性、耐湿熱白化性、高接着性、経時安定性等の特性に優れた光学部材を提供できる。 The pressure-sensitive adhesive sheet of the present invention is excellent in level difference absorbability and reworkability after bonding. Moreover, according to the method for producing an optical member of the present invention, an optical member excellent in properties such as transparency, blister resistance, moisture and heat whitening resistance, high adhesion, and stability over time can be provided.
＜モノマー組成物＞
本発明に用いるモノマー組成物は、少なくとも（メタ）アクリル酸エステル（Ａ）と水酸基含有（メタ）アクリル酸エステル（Ｂ）を含む。「（メタ）アクリル酸エステル」は、アクリル酸エステルとメタクリル酸エステルの総称である。<Monomer composition>
The monomer composition used in the present invention contains at least a (meth) acrylic acid ester (A) and a hydroxyl group-containing (meth) acrylic acid ester (B). “(Meth) acrylic acid ester” is a general term for acrylic acid ester and methacrylic acid ester.
（メタ）アクリル酸エステル（Ａ）は、分子中に不飽和二重結合を１つのみ有する（メタ）アクリル酸エステルである（ただし、成分（Ｂ）及び（Ｃ）、すなわち水酸基含有（メタ）アクリル酸エステル及び多官能性（メタ）アクリレート化合物は除く）。（メタ）アクリル酸エステル（Ａ）は、望ましくは架橋性官能基（上述した不飽和二重結合以外の架橋性官能基）を含まない化合物である。その具体例としては、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ターシャリーブチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸イソヘキシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸イソデシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸イソドデシル等の脂肪族系（メタ）アクリル酸エステル；イソボルニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート等の脂環構造を有する（メタ）アクリル酸エステル；ベンジル（メタ）アクリレート等の芳香環構造を有する（メタ）アクリル酸エステル；フェノキシエチル（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、フェノキシプロピル（メタ）アクリレート、フェノキシポリ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構造を有する（メタ）アクリル酸エステル；が挙げられる。２種以上の（メタ）アクリル酸エステル（Ａ）を併用しても良い。中でも、脂肪族系（メタ）アクリル酸エステルが好ましく、特に（メタ）アクリル酸２−エチルヘキシル及び／又は（メタ）アクリル酸ブチルを主モノマーとして使用することがより好ましい。 The (meth) acrylic acid ester (A) is a (meth) acrylic acid ester having only one unsaturated double bond in the molecule (however, the components (B) and (C), ie, hydroxyl group-containing (meth) Except acrylic esters and polyfunctional (meth) acrylate compounds). The (meth) acrylic acid ester (A) is desirably a compound that does not contain a crosslinkable functional group (crosslinkable functional group other than the unsaturated double bond described above). Specific examples thereof include 2-ethylhexyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, Tertiary butyl (meth) acrylate, hexyl (meth) acrylate, isohexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate Aliphatic (meth) acrylic esters such as decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, isododecyl (meth) acrylate; isobornyl (meth) acrylate, cyclohexyl (meth) (Meth) acrylic having alicyclic structure such as acrylate Esters; (meth) acrylic acid esters having an aromatic ring structure such as benzyl (meth) acrylate; phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, phenoxypropyl (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate (Meth) acrylic acid ester having an alkoxy structure such as Two or more (meth) acrylic acid esters (A) may be used in combination. Among these, aliphatic (meth) acrylic acid esters are preferable, and 2-ethylhexyl (meth) acrylate and / or butyl (meth) acrylate is particularly preferably used as the main monomer.
水酸基含有（メタ）アクリル酸エステル（Ｂ）は、分子中に不飽和二重結合を１つのみ有し、かつ１つ以上の水酸基を有する（メタ）アクリル酸エステルである。水酸基含有（メタ）アクリル酸エステル（Ｂ）も、望ましくは架橋性官能基（上述した不飽和二重結合及び水酸基以外の架橋性官能基）を含まない化合物である。その具体例としては、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸２−ヒドロキシプロピル、（メタ）アクリル酸２−ヒドロキシブチル、（メタ）アクリル酸４−ヒドロキシブチル、（メタ）アクリル酸６−ヒドロキシヘキシル、（メタ）アクリル酸とポリエチレングリジコール又はポリプロピレングリコールとのモノエステルが挙げられる。２種以上の水酸基含有（メタ）アクリル酸エステル（Ｂ）を併用しても良い。中でも、水酸基を含有する脂肪族系（メタ）アクリル酸エステルが好ましく、特に（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸４−ヒドロキシブチル、（メタ）アクリル酸２−ヒドロキシプロピル、（メタ）アクリル酸２−ヒドロキシブチル、（メタ）アクリル酸６−ヒドロキシヘキシルがより好ましい。 The hydroxyl group-containing (meth) acrylic acid ester (B) is a (meth) acrylic acid ester having only one unsaturated double bond in the molecule and having one or more hydroxyl groups. The hydroxyl group-containing (meth) acrylic acid ester (B) is also preferably a compound that does not contain a crosslinkable functional group (crosslinkable functional group other than the unsaturated double bond and hydroxyl group described above). Specific examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and (meth) acrylic. Examples include acid 6-hydroxyhexyl, monoesters of (meth) acrylic acid and polyethyleneglycol or polypropylene glycol. Two or more hydroxyl group-containing (meth) acrylic acid esters (B) may be used in combination. Among them, an aliphatic (meth) acrylic acid ester containing a hydroxyl group is preferable, and in particular, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ( More preferred are 2-hydroxybutyl (meth) acrylate and 6-hydroxyhexyl (meth) acrylate.
中でも、水酸基含有（メタ）アクリル酸エステル（Ｂ）として、（メタ）アクリル酸２−ヒドロキシエチルと（メタ）アクリル酸４−ヒドロキシブチルの一方又は両方を使用することが、耐湿熱白化性、他の光学部材用特性、液晶パネル等に使用されるガラスに対するリワーク性の点から好ましい。特に、（メタ）アクリル酸２−ヒドロキシエチルと（メタ）アクリル酸４−ヒドロキシブチルの両方を使用することがより好ましい。両者の質量比は、好ましくは１：５〜５：１、より好ましくは１：３〜３：１である。 Among them, it is possible to use one or both of 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate as the hydroxyl group-containing (meth) acrylic acid ester (B). It is preferable from the viewpoint of reworkability for glass used for liquid crystal panels and the like. In particular, it is more preferable to use both 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate. The mass ratio of the two is preferably 1: 5 to 5: 1, more preferably 1: 3 to 3: 1.
モノマー組成物中の（メタ）アクリル酸エステル（Ａ）の量は５０〜８５質量％であり、好ましくは６５〜８０質量％である。また、水酸基含有（メタ）アクリル酸エステル（Ｂ）の量は１５〜５０質量％であり、好ましくは２０〜３５質量％である。 The amount of the (meth) acrylic acid ester (A) in the monomer composition is 50 to 85% by mass, preferably 65 to 80% by mass. Moreover, the quantity of a hydroxyl-containing (meth) acrylic acid ester (B) is 15-50 mass%, Preferably it is 20-35 mass%.
一般に、タッチパネル用部材同志を従来のアクリル系粘着剤によって積層させたものを、高温高湿条件下におくと、フィルム貼り付け面の側端部から水分が浸入して粘着剤層が白濁する場合がある。この場合、透明性が低下し、常温に戻しても透明性は回復しない。一方、水酸基含有（メタ）アクリル酸エステル（Ｂ）を添加すれば、そのような白濁を防止できる。なお、（メタ）アクリル酸やカルボキシル基含有（メタ）アクリル酸アルキルエステルの添加によっても白濁を防止できるが、カルボキシル基等の酸成分は例えばタッチパネルの電極等の金属部分を腐食する恐れがある。一方、水酸基含有（メタ）アクリル酸エステル（Ｂ）は金属部分を腐食する恐れは無い。 In general, when a touch panel member laminated with a conventional acrylic adhesive is placed under high-temperature and high-humidity conditions, moisture enters from the side edge of the film attachment surface and the adhesive layer becomes cloudy There is. In this case, the transparency is lowered and the transparency does not recover even when the temperature is returned to room temperature. On the other hand, if the hydroxyl group-containing (meth) acrylic acid ester (B) is added, such cloudiness can be prevented. Although clouding can be prevented by adding (meth) acrylic acid or a carboxyl group-containing (meth) acrylic acid alkyl ester, an acid component such as a carboxyl group may corrode metal parts such as electrodes of a touch panel. On the other hand, the hydroxyl group-containing (meth) acrylic acid ester (B) has no fear of corroding the metal part.
モノマー組成物は、以上述べた（メタ）アクリル酸エステル（Ａ）と水酸基含有（メタ）アクリル酸エステル（Ｂ）以外に、本発明の効果を損なわない範囲内で、他のエチレン性不飽和基を一つ含有するエチレン性不飽和化合物を含んでいても良い。その具体例としては、アクリロニトリル、メタクリロニトリル、酢酸ビニル、プロピオン酸ビニル、ステアリン酸ビニル、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、メチルビニルケトン、ジメチルアリルビニルケトン、アクリルアミド、メタクリルアミド、Ｎ−アルキル置換アクリルアミド、Ｎ−アルキル置換メタクリルアミド、Ｎ,Ｎ−ジアルキル置換アクリルアミド、Ｎ,Ｎ−ジアルキル置換メタクリルアミド、アクリロイルモルホリン、メタクリロイルモルホリンが挙げられる。これらは２種以上を併用しても良い。 In addition to the (meth) acrylic acid ester (A) and the hydroxyl group-containing (meth) acrylic acid ester (B) described above, the monomer composition may contain other ethylenically unsaturated groups as long as the effects of the present invention are not impaired. An ethylenically unsaturated compound containing one of these may be contained. Specific examples include acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, vinyl stearate, alkyl vinyl ether, vinyl toluene, vinyl pyridine, vinyl pyrrolidone, itaconic acid dialkyl ester, fumaric acid dialkyl ester, allyl alcohol, methyl vinyl. Ketone, dimethylallyl vinyl ketone, acrylamide, methacrylamide, N-alkyl substituted acrylamide, N-alkyl substituted methacrylamide, N, N-dialkyl substituted acrylamide, N, N-dialkyl substituted methacrylamide, acryloylmorpholine, methacryloylmorpholine . Two or more of these may be used in combination.
＜シロップ状アクリル樹脂組成物＞
本発明に用いるシロップ状アクリル樹脂組成物は、モノマー組成物を塊状重合法により部分重合して得られる。<Syrup-like acrylic resin composition>
The syrup-like acrylic resin composition used in the present invention is obtained by partially polymerizing a monomer composition by a bulk polymerization method.
塊状重合法とは、溶媒や水を用いずにモノマーだけを重合する方法である。例えば溶液重合、懸濁重合、乳化重合等の重合法を行うと、最終的に無溶剤型硬化性樹脂組成物を得る為には、重合後に溶剤又は水を揮発除去する必要がある。一方、本発明のように塊状重合法を用いれば、揮発除去のような追加工程は不要である。 The bulk polymerization method is a method in which only a monomer is polymerized without using a solvent or water. For example, when a polymerization method such as solution polymerization, suspension polymerization, emulsion polymerization or the like is performed, in order to finally obtain a solvent-free curable resin composition, it is necessary to volatilize and remove the solvent or water after the polymerization. On the other hand, if the bulk polymerization method is used as in the present invention, an additional step such as volatilization removal is unnecessary.
塊状重合は、例えば、モノマー組成物にラジカル重合開始剤を添加し、窒素下で光重合又は熱重合することにより行う。光重合は、光重合開始剤を添加して紫外線照射により行うことが好ましい。熱重合は、熱重合開始剤を添加して５０〜２００℃の加熱により行うことが好ましい。通常、モノマーをほぼ１００％反応させる為には６〜１０時間程度の時間が必要であるが、塊状重合法による部分重合では、モノマーが部分的に重合していれば良いので２時間程度で良い。 Bulk polymerization is performed, for example, by adding a radical polymerization initiator to the monomer composition and performing photopolymerization or thermal polymerization under nitrogen. The photopolymerization is preferably performed by adding a photopolymerization initiator and irradiating with ultraviolet rays. The thermal polymerization is preferably performed by adding a thermal polymerization initiator and heating at 50 to 200 ° C. Usually, a time of about 6 to 10 hours is required to react almost 100% of the monomer. However, in the partial polymerization by the bulk polymerization method, it is sufficient if the monomer is partially polymerized. .
部分重合とは、モノマー組成物を完全には重合させずに重合反応の途中で反応を停止する方法である。この部分重合によって、生成したポリマーが未反応のモノマーに溶解したシロップ状アクリル樹脂組成物が得られる。例えば、光重合の場合は、光照射を停止して空気に暴露することにより重合反応が容易に停止する。熱重合の場合は、加熱を停止して冷却し空気に暴露することにより重合反応が容易に停止する。なお、重合停止剤を添加することも反応停止には有効である。しかし後の重合を行う際に重合を阻害する可能性があるので、重合停止剤は使用しない方が好ましい。 Partial polymerization is a method of stopping the reaction in the middle of the polymerization reaction without completely polymerizing the monomer composition. By this partial polymerization, a syrup-like acrylic resin composition in which the produced polymer is dissolved in unreacted monomers is obtained. For example, in the case of photopolymerization, the polymerization reaction is easily stopped by stopping light irradiation and exposing to air. In the case of thermal polymerization, the polymerization reaction is easily stopped by stopping heating, cooling and exposing to air. Note that adding a polymerization terminator is also effective for terminating the reaction. However, it is preferable not to use a polymerization terminator because it may inhibit the polymerization when the subsequent polymerization is performed.
モノマー組成物は、ポリマーへの変換率（ポリマー濃度）を調整することにより、粘度調整が容易である。特に粘着シートを製造する際、基材上への塗布に適した粘度にすることが容易となり、生産性や省エネルギーの点でも有用である。 The monomer composition can be easily adjusted in viscosity by adjusting the conversion rate to polymer (polymer concentration). In particular, when producing a pressure-sensitive adhesive sheet, it becomes easy to obtain a viscosity suitable for application on a substrate, which is also useful in terms of productivity and energy saving.
＜無溶剤型硬化性樹脂組成物＞
本発明に用いる無溶剤型硬化性樹脂組成物は、以上説明したシロップ状アクリル樹脂組成物と、多官能性（メタ）アクリレート化合物（Ｃ）と、光重合開始剤を含む組成物である。この無溶剤型硬化性樹脂組成物も、好ましくはシロップ状の組成物である。<Solvent-free curable resin composition>
The solventless curable resin composition used in the present invention is a composition containing the syrup-like acrylic resin composition described above, a polyfunctional (meth) acrylate compound (C), and a photopolymerization initiator. This solventless curable resin composition is also preferably a syrupy composition.
多官能性（メタ）アクリレート化合物（Ｃ）は、分子中に２つ以上の不飽和二重結合を有する（メタ）アクリレート化合物であり、架橋反応によって粘着剤層の凝集力を向上させる為の成分である。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、ペンタエリスリトールテトラ（メタ）アクリレート、１,２−エチレングリコールジ（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、１,４−ブタンジオールジ（メタ）アクリレート、１,１２−ドデカンジオールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコール（メタ）アクリレート等の２官能以上の多価アルキルアクリレート単量体；イソシアネート基やグリシジル基を複数有する化合物にアクリル酸や水酸基含有アクリレートを反応させてオリゴマー化もしくはポリマー化したウレタンアクリレートやエポキシアクリレート；が挙げられる。２種以上の多官能性（メタ）アクリレート化合物（Ｃ）を併用しても良い。中でも、１,６−ヘキサンジオールジ（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、トリメチロールプロパントリ（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、エチレングリコールユニットが４又は９のポリエチレングリコールジ（メタ）アクリレートが好ましい。 The polyfunctional (meth) acrylate compound (C) is a (meth) acrylate compound having two or more unsaturated double bonds in the molecule, and a component for improving the cohesive strength of the pressure-sensitive adhesive layer by a crosslinking reaction. It is. Specific examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,2-ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,4- Bifunctional or higher polyvalent alkyl acrylate monomers such as butanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol (meth) acrylate; isocyanate group And urethane acrylate and epoxy acrylate obtained by reacting acrylic acid or a hydroxyl group-containing acrylate with a compound having a plurality of glycidyl groups to form an oligomer or polymer. Two or more polyfunctional (meth) acrylate compounds (C) may be used in combination. Among them, 1,6-hexanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol unit is 4 or 9 Polyethylene glycol di (meth) acrylate is preferred.
光開始剤の具体例としては、アセトフェノン系開始剤、ベンゾインエーテル系開始剤、ケタール系開始剤、フォスフィンオキシド系開始剤、ベンゾフェノン系開始剤、ベンゾイン系開始剤、ハロゲン化ケトン系開始剤、アシルフォスフォナート系開始剤が挙げられる。中でも、アセトフェノン系開始剤が、光開始剤の色、耐黄変性、励起される紫外線領域の点から好ましい。 Specific examples of photoinitiators include acetophenone initiators, benzoin ether initiators, ketal initiators, phosphine oxide initiators, benzophenone initiators, benzoin initiators, halogenated ketone initiators, acyls Examples thereof include phosphonate initiators. Of these, acetophenone-based initiators are preferable from the viewpoint of the color of the photoinitiator, yellowing resistance, and the ultraviolet region to be excited.
無溶剤型硬化性樹脂組成物は、粘度調整や硬化物の特性改善の為に、追加の共重合性モノマーを添加しても良い。 An additional copolymerizable monomer may be added to the solventless curable resin composition for adjusting the viscosity and improving the properties of the cured product.
無溶剤型硬化性樹脂組成物中の重合体の割合は、好ましくは１０〜５０質量％、より好ましくは２０〜４０質量％である。また、無溶剤型硬化性樹脂組成物の粘度は、２３℃で好ましくは１０,０００〜３０,０００ｍＰａ・ｓ、より好ましくは１５,０００〜２５,０００ｍＰａ・ｓである。無溶剤型硬化性樹脂組成物中の重合体の重量平均分子量は、ポリスチレンを標準としたゲルパーミエーションクロマトグラフィー（ＧＰＣ）による測定で、好ましくは５００,０００〜２０００,０００、より好ましくは７００,０００〜１５００,０００である。この分子量は、例えば反応温度や連鎖移動剤の添加により調整できる。なお、モノマー組成により違いはあるが、無溶剤型硬化性樹脂組成物中の重合体の重量平均分子量が１２００,０００程度のとき、粘度を２０,０００ｍＰａ・ｓ程度に調整すると、重合体の割合は２０質量％程度になる。 The ratio of the polymer in the solventless curable resin composition is preferably 10 to 50% by mass, more preferably 20 to 40% by mass. The viscosity of the solventless curable resin composition is preferably 10,000 to 30,000 mPa · s at 23 ° C., more preferably 15,000 to 25,000 mPa · s. The weight average molecular weight of the polymer in the solventless curable resin composition is preferably 500,000 to 2,000,000, more preferably 700,000, as measured by gel permeation chromatography (GPC) using polystyrene as a standard. 000-1500,000. This molecular weight can be adjusted, for example, by adding a reaction temperature or a chain transfer agent. Although there is a difference depending on the monomer composition, when the weight average molecular weight of the polymer in the solvent-free curable resin composition is about 1200,000, the viscosity is adjusted to about 20,000 mPa · s, and the ratio of the polymer Is about 20% by mass.
無溶剤型硬化性樹脂組成物は、本発明の効果を損なわない範囲内で、以上説明した各成分以外の成分を含んでいても良い。 The solventless curable resin composition may contain components other than the above-described components as long as the effects of the present invention are not impaired.
特に、無溶剤型硬化性樹脂組成物は、さらにシランカップリング剤を含むことが好ましい。本発明においては水酸基含有（メタ）アクリル酸エステル（Ｂ）を比較的多量添加しているが、これにより高温高湿条件下で水分を含む傾向にある。そして、水分を含むと粘着力が一時的に低下するが、高温高湿条件から脱して常態に７２時間程度放置すれば水分は抜け、粘着力は回復する。なお、ホモポリマーのＴｇが高い共重合成単量体（例えばメチル（メタ）アクリレート、イソボロニル（メタ）アクリレート等のＴｇ０℃以上の単量体）を添加すれば粘着力低下は生じ難くなる。しかし、この場合は共重合体のＴｇが高くなり、段差吸収性が低下したり、接着性が上昇してリワーク性が低下したりする。また、Ｔｇが高い共重合成単量体は臭気がきついものが多く、本発明のように単量体を含む組成物の貼り合せ工程において作業性に悪影響をもたらす傾向にある。一方、シランカップリング剤を使用すれば、ホモポリマーのＴｇが高い共重合成単量体を含有させなくても、高温高湿条件下から取り出した直後に水分を含んだことによる粘着力の一時的低下を、リワーク性を維持したまま防ぐことができる。 In particular, the solventless curable resin composition preferably further contains a silane coupling agent. In the present invention, a relatively large amount of the hydroxyl group-containing (meth) acrylic acid ester (B) is added, but this tends to include moisture under high temperature and high humidity conditions. When moisture is included, the adhesive strength temporarily decreases. However, if the moisture is removed from the high temperature and high humidity condition and left in a normal state for about 72 hours, the moisture is removed and the adhesive strength is recovered. In addition, if a copolysynthetic monomer having a high homopolymer Tg (for example, a monomer having a Tg of 0 ° C. or higher such as methyl (meth) acrylate or isoboronyl (meth) acrylate) is added, it is difficult to reduce the adhesive force. However, in this case, the Tg of the copolymer becomes high and the step absorbability is lowered, or the adhesiveness is increased and the reworkability is lowered. Further, many copolysynthetic monomers having a high Tg have a strong odor and tend to have an adverse effect on workability in the step of bonding a composition containing the monomer as in the present invention. On the other hand, if a silane coupling agent is used, even if it does not contain a copolysynthetic monomer having a high Tg of homopolymer, the temporary adhesive force due to the inclusion of moisture immediately after removal from high temperature and high humidity conditions. Can be prevented while maintaining reworkability.
シランカップリング剤は、粘着剤の分野において公知のシランカップリング剤が使用できる。その具体例としては、メルカプト基含有シランカップリング剤、エポキシ基含有シランカップリング剤、アミノ基含有シランカップリング剤、イソシアヌレート基含有シランカップリング剤が挙げられる。シランカップリング剤の含有量は、アクリル樹脂（硬化後樹脂になる成分）１００質量部に対し、好ましくは０.０１〜５質量部、より好ましくは０.２〜１.０質量部である。本発明では、シランカップリング剤と水酸基含有（メタ）アクリル酸エステル（Ｂ）を組み合わせて用いることによって、従来技術とは異なる作用により耐湿熱白化性、リワーク性、高温高湿条件下での接着力の安定化の効果を奏することになる。 As the silane coupling agent, a silane coupling agent known in the field of pressure-sensitive adhesives can be used. Specific examples thereof include a mercapto group-containing silane coupling agent, an epoxy group-containing silane coupling agent, an amino group-containing silane coupling agent, and an isocyanurate group-containing silane coupling agent. The content of the silane coupling agent is preferably 0.01 to 5 parts by mass, more preferably 0.2 to 1.0 parts by mass with respect to 100 parts by mass of the acrylic resin (component that becomes a resin after curing). In the present invention, by using a combination of a silane coupling agent and a hydroxyl group-containing (meth) acrylic acid ester (B), moisture and heat whitening resistance, reworkability, and adhesion under high temperature and high humidity conditions due to actions different from those of conventional techniques This will have the effect of stabilizing the power.
無溶剤型硬化性樹脂組成物は、硬化後の分子量調整の為にさらに連鎖移動剤を含むことが好ましい。連鎖移動剤の具体例としては、ｎ−ドデカンチオール（ラウリルメルカプタン）、グリシジルメルカプタン、メルカプト酢酸、２−メルカプトエタノール、チオグリコール酸、チオグリコール酸メチル、チオグリコール酸エチル、チオグルコール酸２−エチルヘキシル、α−チオグリセロール、２,３−ジメルカプト−１−プロパノールが挙げられる。２種以上の連鎖移動剤を併用しても良い。連鎖移動剤の添加量は、目的とする分子量のレベルにもよるが、無溶剤型硬化性樹脂組成物１００質量％中、好ましくは０.００１〜０.０１質量部である。 The solventless curable resin composition preferably further contains a chain transfer agent for adjusting the molecular weight after curing. Specific examples of the chain transfer agent include n-dodecanethiol (lauryl mercaptan), glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, methyl thioglycolate, ethyl thioglycolate, 2-ethylhexyl thioglycolate, α -Thioglycerol, 2,3-dimercapto-1-propanol. Two or more chain transfer agents may be used in combination. The addition amount of the chain transfer agent is preferably 0.001 to 0.01 part by mass in 100% by mass of the solventless curable resin composition, although it depends on the target molecular weight level.
無溶剤型硬化性樹脂組成物は、さらにベンゾトリアゾール系防錆剤を含むことが好ましい。その具体例としては、特開２０１３−１６６８４６号公報に記載のベンゾトリアゾ−ル及びその誘導体が挙げられる。
なお、無溶剤型硬化性樹脂組成物は、金属腐食の点から、カルボキシル基を有する成分を含まないことが好ましい。The solventless curable resin composition preferably further contains a benzotriazole rust inhibitor. Specific examples thereof include benzotriazole and derivatives thereof described in JP2013-166846A.
In addition, it is preferable that a solventless type curable resin composition does not contain the component which has a carboxyl group from the point of metal corrosion.
＜粘着剤層＞
本発明において粘着剤層は、以上説明した無溶剤型硬化性樹脂組成物を活性エネルギー線の照射により硬化して形成した層である。例えば、無溶剤型硬化性樹脂組成物を剥離フィルム又は基材に塗布し、活性エネルギー線を照射することにより、粘着剤層を有する粘着シートが得られる。<Adhesive layer>
In the present invention, the pressure-sensitive adhesive layer is a layer formed by curing the solventless curable resin composition described above by irradiation with active energy rays. For example, a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer can be obtained by applying a solventless curable resin composition to a release film or a substrate and irradiating active energy rays.
活性エネルギー線の照射は、重合禁止作用のある酸素の影響をできるだけ防いで行うことが好ましい。その照射方法としては、例えば、窒素ガス雰囲気下又は不活性ガス雰囲気下で行う方法、支持体に流延した無溶剤型硬化性樹脂組成物に活性エネルギー線は通過するが酸素を遮断するポリエチレンテレフタレート等のフィルムを積層させて行う方法がある。特に、ランニングコストや表面平滑性の点から、支持体又はポリエチレンテレフタレート等の離型フィルムに流延した無溶剤紫外線硬化型樹脂組成物を、さらにポリエチレンテレフタレート等の離型フィルムで積層してから照射し、硬化させる方法が好ましい。 The irradiation with the active energy ray is preferably performed while preventing the influence of oxygen having a polymerization inhibiting action as much as possible. The irradiation method includes, for example, a method performed in a nitrogen gas atmosphere or an inert gas atmosphere, polyethylene terephthalate that blocks active oxygen rays but blocks oxygen through a solventless curable resin composition cast on a support. There is a method in which films such as the above are laminated. In particular, from the viewpoint of running cost and surface smoothness, the solvent-free UV curable resin composition cast on a support or a release film such as polyethylene terephthalate is further laminated with a release film such as polyethylene terephthalate before irradiation. And curing is preferred.
本発明は、粘着剤層中に未反応の（メタ）アクリレート化合物（Ａ）及び（Ｂ）が部分的に残存していることが重要な特徴の一つである。この特徴は、具体的には粘着剤層中に不飽和二重結合が残存する、いわば半硬化状態の点にある。残存する不飽和二重結合の量は、溶剤抽出したモノマーをガスクロマトグラフィーで定量する方法や、フーリエ変換ＩＲスペクトル（ＦＴ−ＩＲ）にて測定できるＣ＝Ｃ伸縮振動（１６２０〜１６８０ｃｍ−１付近）の吸収強度と、Ｃ＝Ｏ伸縮振動（１７００〜１８００ｃｍ−１付近）の吸収強度との比で残存する不飽和二重結合の量を定量する方法もある。また、半硬化状態の粘着シートを１２０〜１５０℃で２時間程度加熱し、残存している（メタ）アクリル系モノマーを揮発させることにより、半硬化状態を確認する方法もある。この方法の場合、粘着シートに残存するモノマーの量は、粘着シートの粘着剤層の厚さや、吸収させる段差によっても異なるが、５〜２０質量％程度が好ましい。残存するモノマーの量が２０質量％以下であれば、粘着剤層の厚さを維持するのが比較的容易であり、打抜き加工性の低下が抑制され、良好な作業性が維持できる。一方、５質量％以上であれば、良好な段差吸収性が発現する。The present invention is one of the important features that the unreacted (meth) acrylate compounds (A) and (B) partially remain in the pressure-sensitive adhesive layer. Specifically, this feature is in the point of a semi-cured state in which an unsaturated double bond remains in the pressure-sensitive adhesive layer. The amount of the unsaturated double bond remaining is determined by a method of quantifying the solvent-extracted monomer by gas chromatography, or C = C stretching vibration (around 1620 to 1680 cm −1 ) that can be measured by Fourier transform IR spectrum (FT-IR). ) And the absorption intensity of C = O stretching vibration (around 1700 to 1800 cm -1 ), there is also a method for quantifying the amount of the unsaturated double bond remaining. There is also a method for confirming the semi-cured state by heating the semi-cured pressure-sensitive adhesive sheet at 120 to 150 ° C. for about 2 hours and volatilizing the remaining (meth) acrylic monomer. In the case of this method, the amount of the monomer remaining in the pressure-sensitive adhesive sheet varies depending on the thickness of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet and the level difference to be absorbed, but is preferably about 5 to 20% by mass. If the amount of the remaining monomer is 20% by mass or less, it is relatively easy to maintain the thickness of the pressure-sensitive adhesive layer, the deterioration of punching workability is suppressed, and good workability can be maintained. On the other hand, if it is 5% by mass or more, good step absorbability is exhibited.
活性エネルギー線としては、例えば、紫外線、遠紫外線、近紫外線、赤外線等の光線、Ｘ線、γ線等の電磁波、電子線、プロトン線、中性子線を使用できる。特に、硬化速度、照射装置の入手のし易さ、価格等から紫外線照射が好ましい。光源としては、例えば、高圧水銀灯、無電極ランプ、超高圧水銀灯、メタルハライドランプ、ケミカルランプ、蛍光ＵＶランプが挙げられる。特に、無電極ランプや高圧水銀灯のように高強度の紫外線を放射するものよりも、ブラックライトや蛍光型ＵＶランプのような比較的弱い紫外線を放射するものの方が半硬化状態の調整がし易い。 As active energy rays, for example, rays such as ultraviolet rays, far ultraviolet rays, near ultraviolet rays and infrared rays, electromagnetic waves such as X-rays and γ rays, electron beams, proton rays and neutron rays can be used. In particular, ultraviolet irradiation is preferable from the viewpoint of curing speed, availability of an irradiation apparatus, price, and the like. Examples of the light source include a high pressure mercury lamp, an electrodeless lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a chemical lamp, and a fluorescent UV lamp. In particular, it is easier to adjust the semi-cured state of a lamp that emits a relatively weak ultraviolet ray such as a black light or a fluorescent UV lamp than a lamp that emits a high-intensity ultraviolet ray such as an electrodeless lamp or a high-pressure mercury lamp. .
照射時間は、粘着剤層の厚さにもよるが、ブラックライトで３０〜９０秒程度が、優れた段差吸収性を示す。３０秒より短い照射時間では、粘着剤層の凝集力が不足し、剥離フィルムが剥がせなかったり、粘着剤がはみ出したり、所定の形に打抜く、打抜き加工性が極端に悪くなる。６０秒より長い照射時間では、残存する不飽和二重結合が極端に少なくなり、段差吸収性が悪くなる。 Although the irradiation time depends on the thickness of the pressure-sensitive adhesive layer, about 30 to 90 seconds for black light show excellent step absorbability. When the irradiation time is shorter than 30 seconds, the cohesive force of the pressure-sensitive adhesive layer is insufficient, the release film cannot be peeled off, the pressure-sensitive adhesive protrudes, or punching into a predetermined shape is extremely deteriorated. When the irradiation time is longer than 60 seconds, the remaining unsaturated double bonds are extremely reduced, and the step absorbability is deteriorated.
＜粘着シート＞
以上のようにして粘着剤層を形成することにより、本発明の粘着シートが得られる。粘着シートは通常は基材を有し、その基材の片面又は両面に粘着剤層が形成される。基材を有する粘着シートの場合は、特に基材の両面に粘着剤層を有する両面粘着シートが好ましい。<Adhesive sheet>
By forming the pressure-sensitive adhesive layer as described above, the pressure-sensitive adhesive sheet of the present invention is obtained. The pressure-sensitive adhesive sheet usually has a base material, and a pressure-sensitive adhesive layer is formed on one or both surfaces of the base material. In the case of a pressure-sensitive adhesive sheet having a substrate, a double-sided pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer on both surfaces of the substrate is particularly preferable.
基材は特に限定されず、公知の基材を用いれば良い。その具体例としては、ポリエチレンテレフタレート（ＰＥＴ）フィルム、ポリブチレンテレフタレートフィルム、ポリエチレンナフタレート、オレフィン系フィルムなどが挙げられる。基材の厚さは、好ましくは１２〜１８０μｍ、より好ましくは５０〜１２５μｍであり、粘着剤層の厚さは、好ましくは５〜５００μｍ、より好ましくは２５〜３００μｍであり、粘着シートの厚さは、好ましくは３０〜１０００μｍ、より好ましくは１２５〜５５０μｍである。 The substrate is not particularly limited, and a known substrate may be used. Specific examples thereof include polyethylene terephthalate (PET) film, polybutylene terephthalate film, polyethylene naphthalate, and olefin film. The thickness of the base material is preferably 12 to 180 μm, more preferably 50 to 125 μm, and the thickness of the adhesive layer is preferably 5 to 500 μm, more preferably 25 to 300 μm, and the thickness of the adhesive sheet Is preferably 30 to 1000 μm, more preferably 125 to 550 μm.
＜光学部材の製造方法＞
本発明の光学部材の製造方法においては、以上説明した本発明の粘着シートを用いて被接着物を貼り合わせ（好ましくは粘着シートを介して加圧、又は加熱しながら加圧して被接着物を貼り合わせ）、貼り合わせた後の粘着シートの粘着剤層に活性エネルギー線を照射することにより、粘着剤層中に残存する未反応の（メタ）アクリレート化合物（Ａ）及び（Ｂ）を重合させて完全接着する。特に本発明は、被接着物の少なくとも一方が透明な部品である場合に非常に有用である。<Method for producing optical member>
In the method for producing an optical member of the present invention, an adherend is bonded using the pressure-sensitive adhesive sheet of the present invention described above (preferably, pressure is applied through the pressure-sensitive adhesive sheet, or pressure is applied while heating. Bonding), by irradiating the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet after bonding with active energy rays, the unreacted (meth) acrylate compounds (A) and (B) remaining in the pressure-sensitive adhesive layer are polymerized. Adhere completely. In particular, the present invention is very useful when at least one of the adherends is a transparent part.
具体的には、例えば、粘着シートの粘着剤層面と被接着物を貼り合わせた後、オートクレーブで温度２３〜６０℃、圧力０.３〜０.５ＭＰａで３０〜６０分の加熱加圧処理行なう方法が好ましい。被着体と粘着シートとを貼合せた後に活性エネルギー線を照射する際には、基材シートや透明な被着体面から照射する。活性エネルギー線の種類や光源は先に説明したものと同様である。例えば、照射する紫外線照射量は、高圧水銀ランプの場合、３００〜３０００ｍＪ／ｃｍ２程度である。Specifically, for example, after the pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive sheet and an adherend are bonded together, a heat and pressure treatment is performed in an autoclave at a temperature of 23 to 60 ° C and a pressure of 0.3 to 0.5 MPa for 30 to 60 minutes. The method is preferred. When the active energy ray is irradiated after the adherend and the pressure-sensitive adhesive sheet are bonded, the irradiation is performed from the substrate sheet or the transparent adherend surface. The type of active energy ray and the light source are the same as those described above. For example, in the case of a high-pressure mercury lamp, the ultraviolet irradiation amount to be irradiated is about 300 to 3000 mJ / cm 2 .
被着体は特に限定されないが、例えば、ＩＴＯ電極膜やポリチオフェン等の有機系導電幕等の透明電極膜、偏光板、位相差板、楕円偏光板、光学補償フィルム、輝度向上フィルム、電磁波シールドフィルム、近赤外線吸収フィルム、ＡＲ（アンチリフレクション）フィルム等や、各処理を施したガラス等の光学部品が挙げられる。特に、活性エネルギー線が透過できる被着体が好ましい。 The adherend is not particularly limited. For example, transparent electrode films such as ITO electrode films and organic conductive curtains such as polythiophene, polarizing plates, retardation plates, elliptically polarizing plates, optical compensation films, brightness enhancement films, electromagnetic wave shielding films And optical parts such as near-infrared absorbing film, AR (anti-reflection) film and glass subjected to each treatment. In particular, an adherend capable of transmitting active energy rays is preferable.
また、加飾印刷等により３〜１００μｍの段差を有する被着体に対して、本発明の段差追従性に優れた粘着シートを用いることが有用である。ただし、本発明では、主に段差を有する光学部材の貼りあわせに有効であるが、段差の無い光学部材同士（タッチパネルと、画像表示モジュール等）の貼り合せ、特に堅い部材同士の貼り合せにおいても、従来の光学用粘着シートよりも薄い粘着シートで効率よく貼り合せる点で有用である。 Moreover, it is useful to use the adhesive sheet excellent in the level | step difference followability of this invention with respect to the to-be-adhered body which has 3-100 micrometers step by decorative printing etc. However, in the present invention, it is effective mainly for bonding optical members having a level difference, but also for bonding optical members having no level difference (touch panel, image display module, etc.), particularly for bonding rigid members. It is useful in that it can be bonded efficiently with a pressure-sensitive adhesive sheet thinner than a conventional optical pressure-sensitive adhesive sheet.
以下、実施例により本発明をさらに詳細に説明する。以下の記載において「部」及び「％」は「質量部」及び「質量％」を意味する。 Hereinafter, the present invention will be described in more detail with reference to examples. In the following description, “parts” and “%” mean “parts by mass” and “% by mass”.
＜無溶剤型シロップ状アクリル樹脂組成物ａ〜ｃの調製＞
攪拌機、還流冷却器、温度計、ＵＶランプ及び窒素ガス導入口を備えた反応容器に、表１に示す組成（％）のアクリルモノマーを仕込み、さらにモノマー合計１００部に対し、光重合開始剤としてアセトフェノン系開始剤（ＢＡＳＦジャパン社製、商品名ダロキュア１１７３）０.０１部、連鎖移動剤としてｎ−ドデシルメルカプタン０.０１部を添加した。そして窒素雰囲気下、ＵＶ光を照射することにより塊状重合法による部分重合を行い、無溶剤型シロップ状アクリル樹脂組成物ａ〜ｃを得た。組成物中のポリマーの重量平均分子量（Ｍｗ）と濃度（％）を表１に示す。<Preparation of solvent-free syrup-like acrylic resin compositions a to c>
Into a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a UV lamp and a nitrogen gas inlet, an acrylic monomer having the composition (%) shown in Table 1 was charged, and a total of 100 parts of the monomer was used as a photopolymerization initiator. 0.01 parts of an acetophenone-based initiator (trade name DAROCURE 1173 manufactured by BASF Japan Ltd.) and 0.01 parts of n-dodecyl mercaptan were added as a chain transfer agent. And the partial polymerization by a block polymerization method was performed by irradiating UV light in nitrogen atmosphere, and solvent-free syrup-like acrylic resin composition ac was obtained. Table 1 shows the weight average molecular weight (Mw) and concentration (%) of the polymer in the composition.
＜溶剤型アクリル樹脂組成物ｄ〜ｅの調製＞
冷却管、撹拌機及び温度計を備えた反応容器に、表１に示す組成（％）のアクリルモノマーを仕込み、さらにモノマー合計１００部に対して重合開始剤として２,２'−アゾビスイソブチロニトリル０.２部、溶媒として酢酸エチル１００部を加えた。そして雰囲気下、６８℃で４時間重合し、さらに追加の２,２'−アゾビスイソブチロニトリル０.２部を添加して８０℃で２時間重合して、溶剤型アクリル樹脂組成物ｄ〜ｅを得た。組成物中のポリマーの重量平均分子量（Ｍｗ）と濃度（％）を表１に示す。<Preparation of solvent-type acrylic resin compositions de>
An acrylic monomer having the composition (%) shown in Table 1 was charged into a reaction vessel equipped with a condenser, a stirrer and a thermometer, and 2,2′-azobisisobutyrate was used as a polymerization initiator for 100 parts of the total monomer. 0.2 part of ronitrile and 100 parts of ethyl acetate as a solvent were added. Then, polymerization is carried out at 68 ° C. for 4 hours in an atmosphere, and further 0.2 part of 2,2′-azobisisobutyronitrile is added and polymerization is carried out at 80 ° C. for 2 hours to obtain a solvent-type acrylic resin composition d. ~ E was obtained. Table 1 shows the weight average molecular weight (Mw) and concentration (%) of the polymer in the composition.
表１中の略号は以下の通りである。
「２ＥＨＡ」：アクリル酸２−エチルヘキシル
「ＨＥＡ」：アクリル酸２−ヒドロキシエチル
「４ＨＢＡ」：アクリル酸４−ヒドロキシブチル
「ＡＭＥ」：メトキシエチルアクリレートAbbreviations in Table 1 are as follows.
“2EHA”: 2-ethylhexyl acrylate “HEA”: 2-hydroxyethyl acrylate “4HBA”: 4-hydroxybutyl acrylate “AME”: methoxyethyl acrylate
＜実施例１＞
（無溶剤型硬化性樹脂組成物の調製）
シロップ状アクリル樹脂組成物ａ１００部に対して、架橋剤として１,６−ヘキサンジオールジアクリレート（新中村化学工業社製、商品名ＮＫエステルＡ−ＨＤ−Ｎ）０.０５部、追加の光重合開始剤としてアセトフェノン系開始剤（ＢＡＳＦジャパン社製、商品名ダロキュア１１７３）０.５部、ベンゾトリアゾ−ル（共同薬品社製、商品名ＢＴＺ−Ｍ）０.５部を添加して均一に撹拌した。撹拌時に混入した空気泡を脱泡操作により除去して、無溶剤型硬化性樹脂組成物を得た。<Example 1>
(Preparation of solvent-free curable resin composition)
0.05 parts of 1,6-hexanediol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name NK Ester A-HD-N) as a crosslinking agent for 100 parts of syrup acrylic resin composition a, additional photopolymerization As an initiator, 0.5 parts of an acetophenone-based initiator (BASF Japan, trade name Darocur 1173) and 0.5 part of benzotriazole (trade name BTZ-M, trade name BTZ-M) were added and stirred uniformly. . The air bubbles mixed during the stirring were removed by a defoaming operation to obtain a solvent-free curable resin composition.
（粘着シートの作製）
上記無溶剤型硬化性樹脂組成物を、離型剤処理した厚さ５０μｍのポリエチレンテレフタレート（ＰＥＴ）フィルム上に塗工した。その上に厚さ５０μｍの離型剤処理したＰＥＴフィルムで被覆し、ブラックライトにより紫外線を４０秒間照射して、粘着剤層（０.１ｍｍ厚）を有する粘着シートを得た。その粘着剤層中の残存モノマー量を表２に示す。残存モノマー量は、シート化させた無溶剤型硬化性樹脂組成物をアルミトレイに秤量し、ホットプレートなどを用いて１５０℃で２時間加熱し、揮発したモノマーの質量である。(Preparation of adhesive sheet)
The solventless curable resin composition was applied onto a 50 μm thick polyethylene terephthalate (PET) film treated with a release agent. A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer (thickness: 0.1 mm) was obtained by coating with a PET film treated with a release agent having a thickness of 50 μm thereon and irradiating ultraviolet rays with a black light for 40 seconds. Table 2 shows the amount of residual monomer in the pressure-sensitive adhesive layer. The amount of residual monomer is the mass of the monomer volatilized by weighing the solventless curable resin composition formed into a sheet on an aluminum tray and heating it at 150 ° C. for 2 hours using a hot plate or the like.
＜実施例２＞
シロップ状アクリル樹脂組成物ａ１００部に対して、さらに連鎖移動剤としてｎ−ドデカンチオール（ｎＤＳＨ）０.０３部を添加したこと以外は、実施例１と同様にして無溶剤型硬化性樹脂組成物を調製し、粘着シートを作製した。<Example 2>
Solventless curable resin composition in the same manner as in Example 1 except that 0.03 part of n-dodecanethiol (nDSH) was further added as a chain transfer agent to 100 parts of syrup acrylic resin composition a. Was prepared to produce an adhesive sheet.
＜実施例３＞
シロップ状アクリル樹脂組成物ａ１００部に対して、さらに連鎖移動剤としてｎ−ドデカンチオール（ｎＤＳＨ）０.０３部及びエポキシ系シランカップリング剤（信越化学工業社製、商品名ＫＢＭ−４０３）を添加したこと以外は、実施例１と同様にして無溶剤型硬化性樹脂組成物を調製し、粘着シートを作製した。<Example 3>
Addition of 0.03 part of n-dodecanethiol (nDSH) and epoxy silane coupling agent (trade name KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) as chain transfer agent to 100 parts of syrup acrylic resin composition a Except that, a solventless curable resin composition was prepared in the same manner as in Example 1 to prepare an adhesive sheet.
＜実施例４＞
シロップ状アクリル樹脂組成物ａの代わりにシロップ状アクリル樹脂組成物ｂを使用したこと以外は、実施例３と同様にして無溶剤型硬化性樹脂組成物を調製し、粘着シートを作製した。<Example 4>
A solventless curable resin composition was prepared in the same manner as in Example 3 except that the syrup-like acrylic resin composition b was used instead of the syrup-like acrylic resin composition a, and an adhesive sheet was produced.
＜実施例５＞
シロップ状アクリル樹脂組成物ａの代わりにシロップ状アクリル樹脂組成物ｃを使用したこと以外は、実施例３と同様にして無溶剤型硬化性樹脂組成物を調製し、粘着シートを作製した。<Example 5>
A solventless curable resin composition was prepared in the same manner as in Example 3 except that the syrup-like acrylic resin composition c was used instead of the syrup-like acrylic resin composition a, and an adhesive sheet was produced.
＜比較例１＞
紫外線の照射時間を４０秒から１２０秒間に変更したこと以外は、実施例２と同様にして粘着シートを作製した。<Comparative Example 1>
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 2 except that the ultraviolet irradiation time was changed from 40 seconds to 120 seconds.
＜比較例２（特許文献２の実施例に相当）＞
（粘着剤組成物の調製）
溶剤型アクリル樹脂組成物ｄ１００部（固形分５０質量％）に対して、架橋剤として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の５５％酢酸エチル溶液（日本ポリウレタン社製、コロネートＬ−５５Ｅ）０.２部（固形分５０質量％）イソステアリルアクリレート（大阪有機化学工業製、商品名ＩＳＴＡ）２０部、ヘキサンジオールジアクリレート（新中村化学工業社製、商品名ＮＫエステルＡ−ＨＤ−Ｎ）２部、光重合開始剤（ＢＡＳＦジャパン社製、商品名ダロキュア１１７３）２部を配合し、粘着剤組成物溶液を得た。<Comparative Example 2 (corresponding to Example of Patent Document 2)>
(Preparation of adhesive composition)
To 100 parts of solvent-type acrylic resin composition d (solid content: 50% by mass), a 55% ethyl acetate solution of trimethylolpropane tolylene diisocyanate adduct as a cross-linking agent (Coronate L-55E, manufactured by Nippon Polyurethane Co., Ltd.) was added. 2 parts (solid content 50% by mass) 20 parts isostearyl acrylate (trade name ISTA, manufactured by Osaka Organic Chemical Industry), 2 parts hexanediol diacrylate (trade name NK ester A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.) , 2 parts of a photopolymerization initiator (trade name DAROCURE 1173, manufactured by BASF Japan Ltd.) was blended to obtain an adhesive composition solution.
（粘着シートの作製）
上記粘着剤組成物溶液を、離型剤処理したＰＥＴフィルムに、乾燥後の厚みが０.１０ｍｍとなるように塗布し、１００℃で５分間乾燥し、粘着剤層を形成した。この粘着剤層を離型剤処理したＰＥＴフィルムで挟み、４０℃で３日間エージングさせて粘着シートを得た。(Preparation of adhesive sheet)
The pressure-sensitive adhesive composition solution was applied to a release film-treated PET film so that the thickness after drying was 0.10 mm, and dried at 100 ° C. for 5 minutes to form a pressure-sensitive adhesive layer. This pressure-sensitive adhesive layer was sandwiched between release film-treated PET films and aged at 40 ° C. for 3 days to obtain a pressure-sensitive adhesive sheet.
＜比較例３（特許文献１の実施例に相当）＞
（粘着剤組成物の調製）
溶剤型アクリル樹脂ｅ１００部に、架橋剤として多官能イソシアネート化合物（日本ポリウレタン工業社製、商品名コロネートＨＬ）１.４部を配合し、粘着剤組成物溶液を得た。<Comparative Example 3 (corresponding to Example of Patent Document 1)>
(Preparation of adhesive composition)
1.4 parts of a polyfunctional isocyanate compound (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name Coronate HL) was blended with 100 parts of a solvent-type acrylic resin to obtain a pressure-sensitive adhesive composition solution.
（粘着シートの作製）
上記粘着剤組成物溶液を用いたこと以外は、比較例２と同様にして粘着シートを作製した。(Preparation of adhesive sheet)
A pressure-sensitive adhesive sheet was prepared in the same manner as in Comparative Example 2 except that the pressure-sensitive adhesive composition solution was used.
表２中の略号は以下の通りである。
「Ｄ.１１７３」：アセトフェノン系光重合開始剤（ＢＡＳＦジャパン社製、商品名ダロキュア１１７３）
「Ａ−ＨＤ−Ｎ」：１,６−ヘキサンジオールジアクリレート（新中村化学工業社製、商品名ＮＫエステルＡ−ＨＤ−Ｎ）
「ｎＤＳＨ」：ｎ−ドデカンチオール
「ＫＢＭ−４０３」：３−グリシドキシプロピルトリエトキシシラン（信越化学工業社製）
「ＢＴＺ−Ｍ」：ベンゾトリアゾ−ル（共同薬品社製、商品名ＢＴＺ−Ｍ）
「ＩＳＴＡ」：イソステアリルアクリレート（大阪有機化学工業製、商品名ＩＳＴＡ）
「Ｌ−５５Ｅ」：ＴＤＩ変性イソシアネート（固形分５５％、日本ポリウレタン社製、商品名コロネートＬ−５５Ｅ）
「ＨＬ」：ＨＤＩ変性イソシアネート（日本ポリウレタン社製、商品名コロネートＨＬ）Abbreviations in Table 2 are as follows.
"D.1173": Acetophenone photopolymerization initiator (BASF Japan, trade name Darocur 1173)
“A-HD-N”: 1,6-hexanediol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name NK ester A-HD-N)
“NDSH”: n-dodecanethiol “KBM-403”: 3-glycidoxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
“BTZ-M”: Benzotriazole (manufactured by Kyodo Yakuhin Co., Ltd., trade name BTZ-M)
"ISTA": Isostearyl acrylate (trade name ISTA, manufactured by Osaka Organic Chemical Industry)
"L-55E": TDI-modified isocyanate (solid content 55%, manufactured by Nippon Polyurethane Co., Ltd., trade name Coronate L-55E)
“HL”: HDI-modified isocyanate (manufactured by Nippon Polyurethane Co., Ltd., trade name Coronate HL)
＜評価試験方法＞
実施例及び比較例の粘着シートに対して以下の試験を行った。その結果を表３に示す。<Evaluation test method>
The following test was done with respect to the adhesive sheet of an Example and a comparative example. The results are shown in Table 3.
（透明性）
粘着シートをカバーガラス（０.１５ｍｍ厚）に貼り付け、高圧水銀灯で８００ｍＪ／ｍｍ２の紫外線を照射し、硬化させた。その後、剥離フィルムを剥し、ＨａｚｅメーターにてＨａｚｅ、色差計にて色味を測定し、Ｈａｚｅ＝０.６以下、△Ｅ＊ａｂ＝３.２以下を合格（〇）とし、それ以上を不合格（×）とした。(transparency)
The pressure-sensitive adhesive sheet was attached to a cover glass (0.15 mm thickness), and cured by irradiating with 800 mJ / mm 2 of ultraviolet light with a high-pressure mercury lamp. Thereafter, the release film is peeled off, the haze is measured with a haze meter, and the color tone is measured with a color difference meter. Haze = 0.6 or less, ΔE * ab = 3.2 or less is passed (◯), and more than that is not acceptable. It was set as a pass (x).
（耐湿熱白化性）
ＩＴＯ蒸着ＰＥＴフィルムとカバーガラス（０.１５ｍｍ厚）とを粘着シートで積層し、高圧水銀灯で８００ｍＪ／ｍｍ２の紫外線を照射し、硬化させた。その後、８５℃、８５％ＲＨの雰囲気下に２５０時間放置し、室温に１時間放置し、白化を目視で確認した。また、湿熱放置前後のＨａｚｅを測定し、値の変化が２０％未満を合格（○）とし、それ以上を不合格（×）とした。(Moisture and heat whitening resistance)
An ITO-deposited PET film and a cover glass (0.15 mm thickness) were laminated with an adhesive sheet, and cured by irradiating with 800 mJ / mm 2 ultraviolet rays with a high-pressure mercury lamp. After that, it was left in an atmosphere of 85 ° C. and 85% RH for 250 hours, left at room temperature for 1 hour, and whitening was confirmed visually. Further, the haze before and after being left in the wet heat was measured, and a change in value of less than 20% was determined to be acceptable (◯), and more than that was determined to be unacceptable (x).
（耐ＩＴＯ導電劣化性）
電極部分としてＡｇペーストを塗布したＩＴＯ蒸着ＰＥＴフィルム（東洋紡社製、商品名３００ＲＫ）に、基材無し粘着シートを貼り合せ、反対側の面にＰＥＴフィルムを貼り合せたサンプルを、高圧水銀灯で８００ｍＪ／ｍｍ２の紫外線を照射し、硬化させた。その後６５℃、９０％ＲＨ雰囲気下に５００時間放置し、粘着シートを貼り合せていないＩＴＯフィルムをブランクとして、マルチメーターにて促進前後の抵抗値を測定し、ブランクとの抵抗値変化率が２０％以内を合格（○）とし、それ以上を不合格（×）とした。(ITO conductive resistance)
An ITO-deposited PET film (product name: 300RK, manufactured by Toyobo Co., Ltd.) coated with an Ag paste as an electrode part is bonded to a non-substrate adhesive sheet, and a PET film is bonded to the opposite side with a high-pressure mercury lamp at 800 mJ The resin was cured by irradiating UV light of / mm 2 . Thereafter, the film was left in an atmosphere of 65 ° C. and 90% RH for 500 hours, and the resistance value before and after the acceleration was measured with a multimeter using an ITO film without an adhesive sheet as a blank. % Was acceptable (◯), and more than that was unacceptable (x).
（耐発泡性）
粘着シートをガラス板貼り付け、その反対側にＰＥＴ＃１２５を貼り付け、積層サンプルを作製した。この積層サンプルに高圧水銀灯で８００ｍＪ／ｍｍ２の紫外線を照射し、硬化させた。その後８５℃、８５％ＲＨの雰囲気下に２５０時間放置し、積層した部分の発泡、浮きがないことを目視で確認した。浮き及び気泡が無いものを合格（○）とし、浮き又は気泡有るものを不合格（×）とした。(Foam resistance)
A pressure-sensitive adhesive sheet was attached to a glass plate, and PET # 125 was attached to the opposite side to produce a laminated sample. This laminated sample was cured by irradiating with 800 mJ / mm 2 of ultraviolet light with a high-pressure mercury lamp. Thereafter, it was allowed to stand in an atmosphere of 85 ° C. and 85% RH for 250 hours, and it was visually confirmed that the laminated portion did not foam or float. The thing without a float and a bubble was set as the pass ((circle)), and the thing with a float or a bubble was set as the rejection (x).
（段差吸収性）
ガラス板の上に、段差として所定の厚さで、幅１０ｍｍのＬ字型に切り抜いたフィルムを置き、粘着シート（４０ｍｍ×５０ｍｍ）で段差を挟むようにガラス板に貼付け、その反対側にＰＥＴ＃１２５を貼り付け、積層サンプルを作製した。この積層サンプルをオートクレーブにて６０℃、０.５ＭＰａ×３０分間加熱加圧し、高圧水銀灯で８００ｍＪ／ｍｍ２の紫外線を照射し硬化させた。硬化させた積層体を８５℃、８５％ＲＨの雰囲気下に２５０時間放置し、段差の周りに浮きや気泡のないことを目視で確認した。浮き及び気泡が無いものを合格（○）とし、浮き又は気泡有るものを不合格（×）とした。(Step absorbency)
On the glass plate, a 10 mm wide L-shaped film with a predetermined thickness is placed as a step, and is attached to the glass plate so that the step is sandwiched between adhesive sheets (40 mm x 50 mm). # 125 was pasted to prepare a laminated sample. This laminated sample was heated and pressurized at 60 ° C. and 0.5 MPa × 30 minutes in an autoclave, and cured by irradiating with an ultraviolet ray of 800 mJ / mm 2 with a high-pressure mercury lamp. The cured laminate was left in an atmosphere of 85 ° C. and 85% RH for 250 hours, and it was visually confirmed that there were no floating or bubbles around the step. The thing without a float and a bubble was set as the pass ((circle)), and the thing with a float or a bubble was set as the rejection (x).
（対ガラス９０°粘着力）
粘着シート（２５ｍｍ幅）をガラス板に貼り付け、その反対側にＰＥＴ＃１２５を貼り付け、積層サンプルを作製した。この積層サンプルに高圧水銀灯で８００ｍＪ／ｍｍ２の紫外線を照射し硬化させた。その２時間後に、引っ張り試験機にて、ＰＥＴフィルムと粘着シートをガラス板に対して９０°方向に、３００ｍｍ／ｍｉｎの速度で剥がし、そのときの粘着力を測定した。(Adhesive strength to glass 90 °)
A pressure-sensitive adhesive sheet (25 mm wide) was attached to a glass plate, and PET # 125 was attached to the opposite side to produce a laminated sample. This laminated sample was cured by irradiating with 800 mJ / mm 2 ultraviolet rays with a high-pressure mercury lamp. Two hours later, the PET film and the pressure-sensitive adhesive sheet were peeled off at a rate of 300 mm / min in a 90 ° direction with respect to the glass plate with a tensile tester, and the adhesive force at that time was measured.
また湿熱促進試験は、硬化させた積層サンプルを、８５℃、８５％ＲＨ雰囲気下に２５０ｈｒ放置し、室温に取り出した２ｈｒ後に、９０°粘着力を測定した。 In the moist heat acceleration test, the cured laminated sample was left in an atmosphere of 85 ° C. and 85% RH for 250 hours, and after 2 hours of taking out to room temperature, 90 ° adhesive strength was measured.
（リワーク性）
粘着シート２５ｍｍ幅をガラス板貼り付け、その反対側にＰＥＴ＃１２５を貼り付け、積層サンプルを作製した。作製した積層サンプルに高圧水銀灯で８００ｍＪ／ｍｍ２の紫外線を照射し、硬化させた。その後９０℃雰囲気下に７２時間放置し、取り出し２時間後に、ＰＥＴフィルムと粘着シートをガラス板に対して９０°方向に３００ｍｍ／ｍｉｎの速度で剥がし、ガラス板への糊残りの有無を確認した。(Reworkability)
A 25 mm width adhesive sheet was attached to a glass plate, and PET # 125 was attached to the opposite side to produce a laminated sample. The produced laminated sample was irradiated with UV light of 800 mJ / mm 2 with a high-pressure mercury lamp and cured. Thereafter, it was left in an atmosphere of 90 ° C. for 72 hours, and after 2 hours of removal, the PET film and the pressure-sensitive adhesive sheet were peeled off at a rate of 300 mm / min in the direction of 90 ° with respect to the glass plate, and the presence of adhesive residue on the glass plate was confirmed. .
＜評価＞
表３に示すように、実施例１〜５の粘着シートは、段差吸収性、リワーク性に優れ、なお且つ、光学部材用粘着剤として要求される特性を兼ね備えており、高温高湿環境下でも安定した接着力を得られた。<Evaluation>
As shown in Table 3, the pressure-sensitive adhesive sheets of Examples 1 to 5 are excellent in step absorbability and reworkability, and also have the characteristics required as a pressure-sensitive adhesive for optical members, even in a high-temperature and high-humidity environment. Stable adhesion was obtained.
比較例１ではアクリル樹脂組成物ａを使用したので、透明性、耐白化性、耐発泡性、リワーク性が良好であった。しかし、粘着剤層中に未反応のモノマーが実質的に残存していない状態（残存モノマー量：０.２％）の粘着シートなので、段差吸収性が劣り、３０μｍの段差も吸収できていなかった。これに対し、同じアクリル樹脂組成物ａを使用している実施例１では、粘着剤層中に未反応のモノマーが残存している状態（残存モノマー量：１４.３％）の粘着シートなので、５０μｍの段差を吸収できていた。実施例２ではさらに連鎖移動剤を加えているので、７５μｍの段差も吸収でき、他の特性やリワーク性も良好であった。実施例３ではさらにシランカップリング剤も添加しているので、段差吸収性やリワーク性を維持したまま、湿熱促進後の対ガラス粘着力も低下することなく安定していた。 In the comparative example 1, since the acrylic resin composition a was used, transparency, whitening resistance, foam resistance and reworkability were good. However, since the pressure-sensitive adhesive sheet has no unreacted monomer remaining in the pressure-sensitive adhesive layer (residual monomer amount: 0.2%), the level difference absorbability is inferior and the level difference of 30 μm cannot be absorbed. . On the other hand, in Example 1 using the same acrylic resin composition a, it is a pressure-sensitive adhesive sheet in a state where unreacted monomers remain in the pressure-sensitive adhesive layer (residual monomer amount: 14.3%). A step of 50 μm was absorbed. In Example 2, since a chain transfer agent was further added, a step of 75 μm could be absorbed, and other characteristics and reworkability were good. In Example 3, since a silane coupling agent was further added, the adhesiveness to glass after promotion of wet heat was stable without decreasing while maintaining the step absorbability and reworkability.
水酸基含有（メタ）アクリル酸エステル（Ｂ）の比率を変えた実施例４、５でも粘着剤厚さが１００μｍでありながら７５μｍの段差も吸収できていた。また、２−ヒドロキシエチルアクリレートと４−ヒドロキシブチルアクリレートを、各々３：１、１：３割合で含有することにより、リワーク性も良好となっている。また、シランカップリング剤を添加したことにより、段差吸収性やリワーク性を維持したまま、湿熱促進後の対ガラス粘着力も低下することなく安定していた。 Even in Examples 4 and 5 in which the ratio of the hydroxyl group-containing (meth) acrylic acid ester (B) was changed, a step of 75 μm could be absorbed while the thickness of the adhesive was 100 μm. Moreover, reworkability is also good by containing 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate in a ratio of 3: 1 and 1: 3, respectively. Moreover, by adding the silane coupling agent, the adhesiveness to glass after the promotion of wet heat was stable without decreasing while maintaining the step absorbability and reworkability.
比較例２では溶剤型のアクリル樹脂組成物ｄとイソステアリルアクリレートを使用したので、紫外線照射後の粘着剤自身が白濁し、透明性や耐湿熱白化性が劣っていた。また、イソシアネート化合物で架橋しているため経時安定性が悪く、高温高湿下で発泡や浮きが生じ、段差吸収性も劣っていた。 In Comparative Example 2, since the solvent-type acrylic resin composition d and isostearyl acrylate were used, the pressure-sensitive adhesive itself after being irradiated with ultraviolet rays became cloudy, and transparency and wet heat whitening resistance were inferior. Moreover, since it was bridge | crosslinked with the isocyanate compound, stability with time was bad, foaming and floating occurred under high temperature and high humidity, and the step absorbability was inferior.
比較例３では溶剤型のアクリル樹脂組成物ｅを使用したので、高温高湿下に置いたとき残存する溶剤が揮発し、発泡を生じた。また、溶液重合時にモノマーをほぼ完全にポリマー化しているので、段差吸収性も劣っていた。ただし、粘着剤に官能基含有モノマーをほとんど使用しなかったので粘着力が弱いがリワーク性は良好であった。 In Comparative Example 3, since the solvent-type acrylic resin composition e was used, the remaining solvent volatilized and foamed when placed under high temperature and high humidity. Further, since the monomer was almost completely polymerized during the solution polymerization, the step absorbability was inferior. However, since almost no functional group-containing monomer was used for the adhesive, the adhesive strength was weak, but the reworkability was good.
本発明の粘着シートは、段差吸収性、リワーク性に優れている。さらに、硬化後は光学部材に要求される透明性、耐ブリスター性、耐湿熱白化性、高接着性、経時安定性等の特性にも優れている。したがって、例えばスマートフォン、携帯電話、電子手帳、カーナビ、パソコン、テレビ等、種々の製品における各種光学部材の部品を接着固定する用途において有用である。特に、加飾印刷段差等の段差を有する部品を接着固定する用途においてはより有用である。特に有用な用途の具体例としては、液晶表示装置の液晶セルと偏光板や位相差板の貼り付け、タッチパネルの意匠板とタッチセンサーの貼り付け、タッチパネルと液晶モジュールの貼り付け等、光学部材の製造における各部品の貼り付けが挙げられる。 The pressure-sensitive adhesive sheet of the present invention is excellent in step absorbability and reworkability. Furthermore, after curing, the optical member is also excellent in properties such as transparency, blister resistance, moist heat whitening resistance, high adhesion, and stability over time. Therefore, it is useful in applications where various optical member parts in various products such as smartphones, mobile phones, electronic notebooks, car navigation systems, personal computers, and televisions are bonded and fixed. In particular, it is more useful in applications in which parts having a step such as decorative printing steps are bonded and fixed. Specific examples of particularly useful applications include the attachment of liquid crystal cells and polarizing plates and retardation plates of liquid crystal display devices, the attachment of touch panel design plates and touch sensors, the attachment of touch panels and liquid crystal modules, etc. The pasting of each part in manufacture is mentioned.
Claims (10)
前記粘着剤層が、分子中に不飽和二重結合を１つのみ有する（メタ）アクリル酸エステル（Ａ）５０〜８５質量％及び分子中に不飽和二重結合を１つのみ有する水酸基含有（メタ）アクリル酸エステル（Ｂ）１５〜５０質量％を含むモノマー組成物を塊状重合法により部分重合して得られるシロップ状アクリル樹脂組成物と、多官能性（メタ）アクリレート化合物（Ｃ）と、光重合開始剤とを含む無溶剤型硬化性樹脂組成物を活性エネルギー線の照射により硬化して形成した層であり、
前記粘着剤層中に、未反応の（メタ）アクリレート化合物（Ａ）及び（Ｂ）が部分的に残存している粘着シート。An adhesive sheet having an adhesive layer,
The pressure-sensitive adhesive layer contains 50 to 85% by mass of (meth) acrylic acid ester (A) having only one unsaturated double bond in the molecule and a hydroxyl group containing only one unsaturated double bond in the molecule ( A syrup-like acrylic resin composition obtained by partially polymerizing a monomer composition containing 15-50% by mass of (meth) acrylic acid ester (B) by a bulk polymerization method, a polyfunctional (meth) acrylate compound (C), It is a layer formed by curing a solventless curable resin composition containing a photopolymerization initiator by irradiation with active energy rays,
A pressure-sensitive adhesive sheet in which unreacted (meth) acrylate compounds (A) and (B) partially remain in the pressure-sensitive adhesive layer.
分子中に不飽和二重結合を１つのみ有する（メタ）アクリル酸エステル（Ａ）５０〜８５質量％及び分子中に不飽和二重結合を１つのみ有する水酸基含有（メタ）アクリル酸エステル（Ｂ）１５〜５０質量％を含むモノマー組成物を塊状重合法により部分重合して得られるシロップ状アクリル樹脂組成物と、多官能性（メタ）アクリレート化合物（Ｃ）と、光重合開始剤を含む無溶剤型硬化性樹脂組成物を調製する工程（１）、並びに、
前記無溶剤型硬化性樹脂組成物を活性エネルギー線の照射により硬化して、未反応の（メタ）アクリレート化合物（Ａ）及び（Ｂ）が部分的に残存している粘着剤層を形成する工程（２）
を有する粘着シートの製造方法。A method for producing a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer,
(Meth) acrylic acid ester (A) having only one unsaturated double bond in the molecule (A) 50 to 85% by mass and hydroxyl group-containing (meth) acrylic acid ester having only one unsaturated double bond in the molecule ( B) A syrup-like acrylic resin composition obtained by partial polymerization of a monomer composition containing 15 to 50% by mass by a bulk polymerization method, a polyfunctional (meth) acrylate compound (C), and a photopolymerization initiator. A step (1) of preparing a solvent-free curable resin composition, and
A step of curing the solventless curable resin composition by irradiation with active energy rays to form a pressure-sensitive adhesive layer in which the unreacted (meth) acrylate compounds (A) and (B) partially remain. (2)
The manufacturing method of the adhesive sheet which has this.
請求項１記載の粘着シートを用いて被接着物を貼り合わせる工程（３）、並びに、
前記被接着物を貼り合わせた後の粘着シートの粘着剤層に活性エネルギー線を照射することにより、粘着剤層中に残存する未反応の（メタ）アクリレート化合物（Ａ）及び（Ｂ）を重合させて完全接着する工程（４）
を有する光学部材の製造方法。A method for producing an optical member including a component bonded using an adhesive sheet,
A step (3) of bonding an adherend using the pressure-sensitive adhesive sheet according to claim 1, and
By irradiating active energy rays to the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet after bonding the adherend, the unreacted (meth) acrylate compounds (A) and (B) remaining in the pressure-sensitive adhesive layer are polymerized. Step (4)
The manufacturing method of the optical member which has this.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2015/051468 WO2016117045A1 (en) | 2015-01-21 | 2015-01-21 | Pressure-sensitive adhesive sheet, process for producing same, and process for producing optical member using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPWO2016117045A1 true JPWO2016117045A1 (en) | 2017-08-17 |
| JP6479856B2 JP6479856B2 (en) | 2019-03-06 |
Family
ID=56416611
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2016570391A Active JP6479856B2 (en) | 2015-01-21 | 2015-01-21 | Pressure-sensitive adhesive sheet, method for producing the same, and method for producing an optical member using the same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6479856B2 (en) |
| KR (1) | KR101927012B1 (en) |
| CN (1) | CN107207914B (en) |
| WO (1) | WO2016117045A1 (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017159788A1 (en) * | 2016-03-17 | 2017-09-21 | 王子ホールディングス株式会社 | Adhesive composition and adhesive sheet |
| JP6813988B2 (en) * | 2016-08-12 | 2021-01-13 | ニッタ株式会社 | Temperature-sensitive adhesive tape and temperature-sensitive adhesive sheet |
| WO2018034230A1 (en) * | 2016-08-17 | 2018-02-22 | 日本合成化学工業株式会社 | Acrylic adhesive composition, adhesive obtained using same, polarizing plate adhesive, and image display device |
| KR102159496B1 (en) | 2017-09-15 | 2020-09-24 | 주식회사 엘지화학 | Pressure sensitive adhesive composition, polarizing plate, and optical element |
| WO2019054778A1 (en) * | 2017-09-15 | 2019-03-21 | 주식회사 엘지화학 | Adhesive composition, polarizing plate, and optical member |
| KR101903906B1 (en) * | 2017-09-22 | 2018-10-02 | 주식회사 엘지화학 | Photocurable resin composition for protective layer, polarizing plate and image display apparatus comprising the same |
| WO2019065268A1 (en) * | 2017-09-27 | 2019-04-04 | Dic株式会社 | Method for producing layered product including curable joining material |
| JP2021509427A (en) * | 2017-12-28 | 2021-03-25 | 日東電工株式会社 | Glass unit manufacturing method and adhesive sheet |
| JP7305939B2 (en) | 2018-09-12 | 2023-07-11 | 王子ホールディングス株式会社 | Adhesive sheet, laminate, and method for producing laminate |
| JP7367469B2 (en) * | 2018-11-06 | 2023-10-24 | 三菱ケミカル株式会社 | Solvent-free adhesive compositions, solvent-free adhesives and adhesive sheets |
| WO2021141160A1 (en) | 2020-01-09 | 2021-07-15 | 엘지전자 주식회사 | Flexible display device |
| JP7465101B2 (en) | 2020-02-10 | 2024-04-10 | 三星エスディアイ株式会社 | Pressure-sensitive adhesive composition for photocurable optical film, pressure-sensitive adhesive layer for photocurable optical film, optical member, and image display device |
| JP7465102B2 (en) * | 2020-02-10 | 2024-04-10 | 三星エスディアイ株式会社 | Pressure-sensitive adhesive composition for photocurable optical film, pressure-sensitive adhesive layer for photocurable optical film, optical member and image display device |
| CN113249037B (en) * | 2020-02-10 | 2024-03-01 | 三星Sdi株式会社 | Photocurable adhesive composition for optical film, photocurable adhesive layer for optical film, optical element, and display device |
| WO2023074553A1 (en) * | 2021-10-27 | 2023-05-04 | 日東電工株式会社 | Photocurable adhesive sheet |
| WO2023074556A1 (en) * | 2021-10-27 | 2023-05-04 | 日東電工株式会社 | Optical pressure-sensitive adhesive sheet |
| WO2023074554A1 (en) * | 2021-10-27 | 2023-05-04 | 日東電工株式会社 | Photocurable adhesive sheet |
| WO2023074555A1 (en) * | 2021-10-27 | 2023-05-04 | 日東電工株式会社 | Photocurable adhesive sheet |
| WO2023100866A1 (en) * | 2021-12-03 | 2023-06-08 | リンテック株式会社 | Adhesive sheet and method for manufacturing adhesive sheet |
| CN115124954A (en) * | 2022-06-08 | 2022-09-30 | 恒美光电股份有限公司 | Ultraviolet curing pressure-sensitive adhesive and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013061938A (en) * | 2011-08-23 | 2013-04-04 | Canon Marketing Japan Inc | Identification system, control method and program |
| JP2013166846A (en) * | 2012-02-15 | 2013-08-29 | Teraoka Seisakusho:Kk | Self-adhesive sheet, sheet for adhesion, photocurable adhesive composition, and optical member |
| JP2013256552A (en) * | 2012-06-11 | 2013-12-26 | Soken Chem & Eng Co Ltd | Photopolymerizable adhesive, adhesive sheet, and laminate for touch panel |
| JP2014094976A (en) * | 2012-11-07 | 2014-05-22 | Hitachi Chemical Co Ltd | Method for manufacturing pressure-sensitive adhesive sheet for image display device |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110007687A (en) * | 2009-07-17 | 2011-01-25 | 공주대학교 산학협력단 | Acrylic adhesive compositions of non-solvent uv hardening type and fabrication method thereof |
| KR101928727B1 (en) * | 2011-10-24 | 2018-12-13 | 오지 홀딩스 가부시키가이샤 | Pressure-sensitive adhesive sheet, method for using same, and laminate |
| US20140226085A1 (en) * | 2013-02-14 | 2014-08-14 | Nitto Denko Corporation | Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer, pressure-sensitive adhesive sheet, optical component and touch panel |
-
2015
- 2015-01-21 CN CN201580073793.2A patent/CN107207914B/en active Active
- 2015-01-21 JP JP2016570391A patent/JP6479856B2/en active Active
- 2015-01-21 WO PCT/JP2015/051468 patent/WO2016117045A1/en active Application Filing
- 2015-01-21 KR KR1020177016453A patent/KR101927012B1/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013061938A (en) * | 2011-08-23 | 2013-04-04 | Canon Marketing Japan Inc | Identification system, control method and program |
| JP2013166846A (en) * | 2012-02-15 | 2013-08-29 | Teraoka Seisakusho:Kk | Self-adhesive sheet, sheet for adhesion, photocurable adhesive composition, and optical member |
| JP2013256552A (en) * | 2012-06-11 | 2013-12-26 | Soken Chem & Eng Co Ltd | Photopolymerizable adhesive, adhesive sheet, and laminate for touch panel |
| JP2014094976A (en) * | 2012-11-07 | 2014-05-22 | Hitachi Chemical Co Ltd | Method for manufacturing pressure-sensitive adhesive sheet for image display device |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2016117045A1 (en) | 2016-07-28 |
| JP6479856B2 (en) | 2019-03-06 |
| CN107207914B (en) | 2020-10-16 |
| KR101927012B1 (en) | 2018-12-07 |
| KR20170085095A (en) | 2017-07-21 |
| CN107207914A (en) | 2017-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6479856B2 (en) | Pressure-sensitive adhesive sheet, method for producing the same, and method for producing an optical member using the same | |
| TWI702272B (en) | Adhesive sheet, manufacturing method of laminated body with adhesive layer, laminated body with adhesive layer, image display device and touch panel | |
| JP5801514B1 (en) | Photocurable pressure-sensitive adhesive composition, pressure-sensitive adhesive sheet, and laminate | |
| CN105143378B (en) | Adhesive sheet, laminate, and method for producing same | |
| JP5406456B2 (en) | Ionizing radiation curable adhesive composition for re-peeling and use thereof | |
| US9809731B2 (en) | Adhesive resin composition | |
| TWI695873B (en) | Adhesive composition and adhesive sheet | |
| TWI516563B (en) | Adhesive composition | |
| JP2010132755A (en) | Ionizing radiation-curable re-releasable adhesive composition | |
| JP2013166846A (en) | Self-adhesive sheet, sheet for adhesion, photocurable adhesive composition, and optical member | |
| JP7282687B2 (en) | OPTICAL TRANSPARENT ADHESIVE SHEET, COMPOSITION FOR MANUFACTURING THE SAME AND FLAT DISPLAY DEVICE USING THE SAME | |
| CN107922808B (en) | Adhesive composition, adhesive sheet, and touch panel and display device provided with adhesive sheet | |
| JP7253903B2 (en) | Adhesive sheet, method for producing same, and method for producing image display device | |
| JPWO2017204248A1 (en) | Laminated adhesive sheet | |
| JP2010043184A (en) | Method for producing removable pressure-sensitive adhesive film | |
| JP7278967B2 (en) | Optical transparent adhesive sheet | |
| JP6986666B2 (en) | Adhesive sheet for image display device | |
| JP2020128492A (en) | Adhesive sheet and laminate | |
| TWI824013B (en) | Adhesive composition for surface protection sheet and surface protective sheet | |
| JP7285794B2 (en) | PSA SHEET, MANUFACTURING METHOD THEREOF, AND IMAGE DISPLAY DEVICE | |
| KR20180136712A (en) | Adhesive Composition and Adhesive Sheet Using the Same | |
| KR20150045107A (en) | Solvent-type adhesive composition by photopolymerisation | |
| JP7112227B2 (en) | Acrylic pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet | |
| KR20200109320A (en) | Double-sided adhesive sheet with double-sided adhesive sheet and release sheet attached |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A524 | Written submission of copy of amendment under article 19 pct |
Free format text: JAPANESE INTERMEDIATE CODE: A527 Effective date: 20170426 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20170426 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20180612 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20180807 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20181010 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20190205 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20190206 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6479856 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |