JP6091990B2 - Composition for transparent adhesive sheet - Google Patents
Composition for transparent adhesive sheet Download PDFInfo
- Publication number
- JP6091990B2 JP6091990B2 JP2013100717A JP2013100717A JP6091990B2 JP 6091990 B2 JP6091990 B2 JP 6091990B2 JP 2013100717 A JP2013100717 A JP 2013100717A JP 2013100717 A JP2013100717 A JP 2013100717A JP 6091990 B2 JP6091990 B2 JP 6091990B2
- Authority
- JP
- Japan
- Prior art keywords
- meth
- adhesive sheet
- transparent adhesive
- transparent
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
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- 239000000853 adhesive Substances 0.000 title claims description 111
- 230000001070 adhesive effect Effects 0.000 title claims description 111
- 239000000203 mixture Substances 0.000 title claims description 56
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 57
- 239000004925 Acrylic resin Substances 0.000 claims description 36
- 229920000178 Acrylic resin Polymers 0.000 claims description 36
- 239000000178 monomer Substances 0.000 claims description 28
- 229920005862 polyol Polymers 0.000 claims description 23
- 150000003077 polyols Chemical class 0.000 claims description 23
- 229920001228 polyisocyanate Polymers 0.000 claims description 20
- 239000005056 polyisocyanate Substances 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 11
- 230000009477 glass transition Effects 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 44
- -1 alkoxyalkyl acrylate Chemical compound 0.000 description 20
- 239000010410 layer Substances 0.000 description 20
- 238000005259 measurement Methods 0.000 description 13
- 229920002799 BoPET Polymers 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 9
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- 229920006243 acrylic copolymer Polymers 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 5
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 5
- 239000012790 adhesive layer Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 206010040844 Skin exfoliation Diseases 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000005536 corrosion prevention Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- 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 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-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
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- SDXHBDVTZNMBEW-UHFFFAOYSA-N 1-ethoxy-2-(2-hydroxyethoxy)ethanol Chemical compound CCOC(O)COCCO SDXHBDVTZNMBEW-UHFFFAOYSA-N 0.000 description 1
- 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
- AGPIWTRJDSRFDH-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile;2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N.CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C AGPIWTRJDSRFDH-UHFFFAOYSA-N 0.000 description 1
- YHYCMHWTYHPIQS-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-methoxyethanol Chemical compound COC(O)COCCO YHYCMHWTYHPIQS-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
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-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
- BYPFICORERPGJY-UHFFFAOYSA-N 3,4-diisocyanatobicyclo[2.2.1]hept-2-ene Chemical compound C1CC2(N=C=O)C(N=C=O)=CC1C2 BYPFICORERPGJY-UHFFFAOYSA-N 0.000 description 1
- SKKHNUKNMQLBTJ-UHFFFAOYSA-N 3-bicyclo[2.2.1]heptanyl 2-methylprop-2-enoate Chemical compound C1CC2C(OC(=O)C(=C)C)CC1C2 SKKHNUKNMQLBTJ-UHFFFAOYSA-N 0.000 description 1
- YHFGMFYKZBWPRW-UHFFFAOYSA-N 3-methylpentane-1,1-diol Chemical compound CCC(C)CC(O)O YHFGMFYKZBWPRW-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-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
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 108091034057 RNA (poly(A)) Proteins 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 238000012648 alternating copolymerization Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000007869 azo polymerization initiator Substances 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- WPKWPKDNOPEODE-UHFFFAOYSA-N bis(2,4,4-trimethylpentan-2-yl)diazene Chemical compound CC(C)(C)CC(C)(C)N=NC(C)(C)CC(C)(C)C WPKWPKDNOPEODE-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- JCCAVOLDXDEODY-UHFFFAOYSA-N dimethyldiazene Chemical compound CN=NC JCCAVOLDXDEODY-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 229930004069 diterpene Natural products 0.000 description 1
- 150000004141 diterpene derivatives Chemical class 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
- 230000005611 electricity Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 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
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-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
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000005593 norbornanyl group Chemical group 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- TZYULTYGSBAILI-UHFFFAOYSA-M trimethyl(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC=C TZYULTYGSBAILI-UHFFFAOYSA-M 0.000 description 1
- ZQYKGADTDCTWSZ-UHFFFAOYSA-N trimethyl-[(prop-2-enoylamino)methyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CNC(=O)C=C ZQYKGADTDCTWSZ-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 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
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2551/00—Optical elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Description
本発明は、透明粘着シート用組成物、透明粘着シート用組成物からなる透明粘着シート、透明粘着シートが透明導電膜の貼り合せに使用されることを特徴とする透明導電膜固定用透明粘着シート及び、透明導電膜固定用透明粘着シートが透明導電膜の導電層面に接着されていることを特徴とする積層体に関する。 The present invention relates to a transparent adhesive sheet for fixing a transparent conductive film, wherein the composition for transparent adhesive sheet, the transparent adhesive sheet comprising the composition for transparent adhesive sheet, and the transparent adhesive sheet are used for laminating a transparent conductive film And the transparent adhesive sheet for transparent conductive film fixation is related with the laminated body characterized by adhere | attaching on the conductive layer surface of a transparent conductive film.
近年、携帯電話、ゲーム機器などにタッチパネルが搭載され始めている。タッチパネルは、銀、ＩＴＯ（酸化インジウムスズ）などの透明導電膜を表層に有する透明基材やガラスとこれらを保護する透明保護シート、さらには液晶ディスプレイなどの表示装置といった光学部材を、光学用の透明粘着シートを用いて貼り合せた積層体である。 In recent years, touch panels have begun to be mounted on mobile phones, game machines and the like. The touch panel is a transparent substrate or glass having a transparent conductive film such as silver or ITO (indium tin oxide) as a surface layer, a transparent protective sheet for protecting them, and an optical member such as a display device such as a liquid crystal display. It is the laminated body bonded together using the transparent adhesive sheet.
タッチパネルには、主に入力時の圧力で検知する抵抗膜方式のタッチパネルと、入力時の人体からの静電気で入力箇所を検知する静電容量方式のタッチパネルがある。静電容量方式のタッチパネルにおいては、透明導電膜の導電層面が、粘着シートの粘着剤層表面と接するように固定される。そのため、粘着剤に含まれる酸成分によって、透明導電膜において金属成分の酸化反応が起こり、導電機能が低下するという問題がある。このため、酸成分をほとんど含まず、高い金属腐食防止性と良好な接着性を有する透明導電膜固定用の粘着シートが求められている。 There are two types of touch panels: a resistance film type touch panel that detects mainly by pressure at the time of input and a capacitance type touch panel that detects an input location by static electricity from the human body at the time of input. In the capacitive touch panel, the conductive layer surface of the transparent conductive film is fixed so as to be in contact with the pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive sheet. Therefore, the acid component contained in the pressure-sensitive adhesive causes the oxidation reaction of the metal component in the transparent conductive film, resulting in a problem that the conductive function is lowered. For this reason, there is a demand for a pressure-sensitive adhesive sheet for fixing a transparent conductive film that contains almost no acid component and has high metal corrosion prevention and good adhesion.
金属腐食防止性を有する粘着シートとしては、金属腐食防止剤を含有する粘着シート（例えば、特許文献１）が提案されている。また、粘着剤層の酸成分に対して、特定量の窒素原子含有成分を含有させることで、透明導電膜に対する腐食性を低下させた粘着シート（例えば、特許文献２）が提案されている。 As a pressure-sensitive adhesive sheet having metal corrosion prevention properties, a pressure-sensitive adhesive sheet containing a metal corrosion inhibitor (for example, Patent Document 1) has been proposed. Moreover, the adhesive sheet (for example, patent document 2) which reduced the corrosivity with respect to a transparent conductive film by containing a specific amount of nitrogen atom containing components with respect to the acid component of an adhesive layer is proposed.
しかしながら、金属腐食防止剤を含有する粘着シートは、耐久性試験を行った場合に金属腐食防止剤により変色し、光学特性を低下させる等の問題があった。また、特定量の窒素原子含有成分を含有させた粘着シートは、粘着剤層に含まれる酸成分が原因で、ＩＴＯの電気抵抗値の上昇を十分に抑えられない問題があった。 However, the pressure-sensitive adhesive sheet containing a metal corrosion inhibitor has a problem that, when a durability test is performed, the metal sheet is discolored by the metal corrosion inhibitor and optical properties are deteriorated. In addition, the pressure-sensitive adhesive sheet containing a specific amount of a nitrogen atom-containing component has a problem that an increase in the electrical resistance value of ITO cannot be sufficiently suppressed due to the acid component contained in the pressure-sensitive adhesive layer.
一方、タッチパネル等の中には、金属配線や印刷段差等の段差を有する部材を含むものがある。例えば携帯電話などにおいては、枠状の印刷部分が施された部材を有するタッチパネルなどが用いられている。このような用途においては、粘着シートには、部材を貼付固定する性能と同時に段差を埋める性能、即ち、優れた段差追従性が要求される。透明粘着シートが段差を吸収できない場合、段差の周辺で被着体からの透明粘着シートの浮き（気泡や空隙）が発生し、この浮き（気泡や空隙）による光の反射損失が生じて、液晶ディスプレイの視認性が低下するおそれがある。 On the other hand, some touch panels and the like include members having steps such as metal wiring and printing steps. For example, in a mobile phone or the like, a touch panel having a member provided with a frame-like printed portion is used. In such an application, the pressure-sensitive adhesive sheet is required to have the ability to fill a step at the same time as the performance of sticking and fixing a member, that is, excellent step following ability. If the transparent adhesive sheet cannot absorb the step, the transparent adhesive sheet floats (bubbles or voids) from the adherend around the step, and light reflection loss occurs due to the float (bubbles or voids), resulting in liquid crystal The visibility of the display may be reduced.
優れた段差追従性を得るためには、透明粘着シートは柔らかく、且つ、接着力が高いものが有利であるが、先に記載した理由から、酸成分を含まなくても、高い接着性を有することが要求される。この要求に応えるのもとして、アルコキシアルキルアクリレートを主たるモノマーとする酸成分を含まない特定分子量のアクリル系ポリマーと架橋剤とからなる粘着剤組成物が、良好な接着性と金属腐食防止性を両立しうる透明粘着シートを与えること（例えば、特許文献３）が開示されている。 In order to obtain excellent step followability, it is advantageous that the transparent pressure-sensitive adhesive sheet is soft and has high adhesive strength, but for the reasons described above, it has high adhesiveness even if it does not contain an acid component. Is required. The pressure-sensitive adhesive composition consisting of a specific molecular weight acrylic polymer that does not contain an acid component with an alkoxyalkyl acrylate as the main monomer and a crosslinking agent provides both good adhesion and metal corrosion resistance. Giving a transparent adhesive sheet that can be used (for example, Patent Document 3) is disclosed.
しかしながら、アルコキシアルキルアクリレートを主たるモノマーとする酸成分を含まない特定分子量のアクリル系ポリマーと架橋剤とからなる粘着剤組成物は、酸成分を含まないためにイソシアネート架橋剤による硬化が遅くなり、透明粘着シートの養生に時間がかかるといった問題があった。この問題解決のために、複数のヒドロキシル基を含有するアミン系化合物を添加することも開示されているが、アミン系化合物は経時的に透明粘着シートを黄変させるおそれがある。 However, the pressure-sensitive adhesive composition comprising an acrylic polymer having a specific molecular weight not containing an acid component mainly composed of alkoxyalkyl acrylate and a crosslinking agent does not contain an acid component, so that curing with an isocyanate crosslinking agent is delayed and transparent. There was a problem that it took time to cure the adhesive sheet. In order to solve this problem, addition of an amine compound containing a plurality of hydroxyl groups is also disclosed, but the amine compound may cause yellowing of the transparent adhesive sheet over time.
要するに、金属腐食防止性、段差追従性、透明性、硬化性などの全ての特性を高いレベルで両立した優れた透明粘着シート用組成物は得られていないのが現状である。 In short, at present, an excellent composition for a transparent pressure-sensitive adhesive sheet in which all the properties such as metal corrosion prevention property, step following property, transparency and curability are compatible at a high level has not been obtained.
本発明が解決しようとする課題は、硬化性に優れ、得られる透明粘着シートが、透明導電膜の導電層面に対して直接貼り合わせても導電層を腐食させず、金属配線や印刷枠への段差追従性及び透明性にも優れる、透明粘着シート用組成物を提供することである。 The problem to be solved by the present invention is excellent in curability, and the obtained transparent adhesive sheet does not corrode the conductive layer even if it is directly bonded to the conductive layer surface of the transparent conductive film. It is providing the composition for transparent adhesive sheets which is excellent also in level | step difference followability and transparency.
本発明者らは、タッチパネル用透明粘着シートが抱える前記の問題点を背景にして、鋭意検討を重ねた結果、特定重量平均分子量の（メタ）アクリル系樹脂、特定数平均分子量のポリオキシアルキレンポリオール、ポリイソシアネート、及びスズ系触媒を特定の重量割合で含む透明粘着シート用組成物が、硬化性に優れ、得られる透明粘着シートの透明性、粘着性、透明導電膜の金属腐食防止性、及び、段差追従性が良好であることを見出し、この知見に基づいて本発明を完成した。 As a result of intensive studies against the above-mentioned problems of the transparent adhesive sheet for touch panel, the present inventors have obtained a (meth) acrylic resin having a specific weight average molecular weight and a polyoxyalkylene polyol having a specific number average molecular weight. , A composition for transparent adhesive sheet containing a polyisocyanate and a tin-based catalyst in a specific weight ratio is excellent in curability, transparency of the obtained transparent adhesive sheet, adhesiveness, metal corrosion prevention property of a transparent conductive film, and The present inventors have found that the step following ability is good and completed the present invention based on this finding.
本発明は、以下の（１）〜（９）で示される。 The present invention is shown by the following (1) to (9).
（１）固形分比で、（Ａ）（メタ）アクリル系樹脂６５〜８５質量％と、（Ｂ）ポリオキシアルキレンポリオール１０〜３０質量％と、（Ｃ）ポリイソシアネート１．０〜５．０質量％と、（Ｄ）スズ系触媒０．００５〜０．１質量％とを含み、酸価が０〜５ｍｇＫＯＨ／ｇであって、（Ａ）（メタ）アクリル系樹脂の重量平均分子量が１０万〜６０万であり、且つ、（Ｂ）ポリオキシアルキレンポリオールの数平均分子量が５００〜１５００である透明粘着シート用組成物。 (1) (A) (meth) acrylic resin 65-85 mass%, (B) polyoxyalkylene polyol 10-30 mass%, and (C) polyisocyanate 1.0-5.0 by solid content ratio. And (D) a tin-based catalyst 0.005 to 0.1% by mass, an acid value of 0 to 5 mg KOH / g, and the weight average molecular weight of (A) (meth) acrylic resin is 10 The composition for transparent adhesive sheets which is 10,000 to 600,000, and (B) the polyoxyalkylene polyol has a number average molecular weight of 500 to 1500.
（２）（Ａ）（メタ）アクリル系樹脂が、水酸基含有（メタ）アクリル系モノマー由来の構成単位０．５〜１０ｍｏｌ％を含む前記（１）に記載の透明粘着シート用組成物。 (2) The composition for transparent adhesive sheets as described in said (1) in which (A) (meth) acrylic-type resin contains 0.5-10 mol% of structural units derived from a hydroxyl-containing (meth) acrylic-type monomer.
（３）前記水酸基含有（メタ）アクリル系モノマーが、２−ヒドロキシエチル（メタ）アクリレートであることを特徴とする前記（２）に記載の透明粘着シート用組成物。 (3) The composition for a transparent pressure-sensitive adhesive sheet as described in (2) above, wherein the hydroxyl group-containing (meth) acrylic monomer is 2-hydroxyethyl (meth) acrylate.
（４）前記（Ａ）（メタ）アクリル系樹脂が、メチル（メタ）アクリレート由来の構成単位５〜５０ｍｏｌ％を含む前記（１）〜（３）のいずれかに記載の透明粘着シート用組成物。 (4) The composition for transparent adhesive sheets according to any one of (1) to (3), wherein the (A) (meth) acrylic resin contains 5 to 50 mol% of a structural unit derived from methyl (meth) acrylate. .
（５）前記（Ａ）（メタ）アクリル系樹脂のガラス転移点が−８０〜０℃である前記（１）〜（４）のいずれかに記載の透明粘着シート用組成物。 (5) The composition for transparent adhesive sheets according to any one of (1) to (4), wherein the glass transition point of the (A) (meth) acrylic resin is -80 to 0 ° C.
（６）前記（１）〜（５）のいずれかに記載の透明粘着シート用組成物を硬化させて得られる透明粘着シート。 (6) The transparent adhesive sheet obtained by hardening the composition for transparent adhesive sheets in any one of said (1)-(5).
（７）ゲル分率が４０〜８０％である前記（６）に記載の透明粘着シート。 (7) The transparent adhesive sheet according to (6), wherein the gel fraction is 40 to 80%.
（８）前記（６）又は（７）に記載の透明粘着シートが透明導電膜の貼り合せに使用されることを特徴とする透明導電膜固定用透明粘着シート。 (8) A transparent adhesive sheet for fixing a transparent conductive film, wherein the transparent adhesive sheet according to (6) or (7) is used for bonding a transparent conductive film.
（９）前記（８）に記載の透明導電膜固定用透明粘着シートが、透明導電膜の導電層面に接着されていることを特徴とする積層体。 (9) A laminate, wherein the transparent conductive sheet fixing transparent adhesive sheet according to (8) is adhered to the conductive layer surface of the transparent conductive film.
本発明の透明粘着シート用組成物は、組成物中に特定の構造単位、すなわちポリオキシアルキレン骨格を有することで、得られる透明粘着シートの段差追従性、及び、基材への粘着力が良好となる。さらに、（Ｄ）スズ系触媒を含むことで（Ｃ）ポリイソシアネートの硬化性が良好となり、透明粘着シートの養生時間も短縮することが可能である。また、本発明の透明粘着シート用組成物は実質的に酸を含まないため、酸成分による透明導電膜の導電層面の腐食を抑制できる。 The composition for a transparent adhesive sheet of the present invention has a specific structural unit, that is, a polyoxyalkylene skeleton in the composition, so that the step following property of the obtained transparent adhesive sheet and the adhesive force to the substrate are good. It becomes. Furthermore, (C) the curability of (C) polyisocyanate is improved by including the tin-based catalyst, and the curing time of the transparent adhesive sheet can be shortened. Moreover, since the composition for transparent adhesive sheets of this invention does not contain an acid substantially, it can suppress the corrosion of the conductive layer surface of the transparent conductive film by an acid component.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
尚、本明細書中で（メタ）アクリロイル基とはＣＨ２＝ＣＨ−ＣＯ−またはＣＨ２＝Ｃ（ＣＨ３）−ＣＯ−を意味する。 In the present specification, the (meth) acryloyl group means CH 2 ═CH—CO— or CH 2 ═C (CH 3 ) —CO—.
（透明粘着シート用組成物）
本発明の透明粘着シート用組成物は、固形分比で、（Ａ）（メタ）アクリル系樹脂６５〜８５質量％と、（Ｂ）ポリオキシアルキレンポリオール１０〜３０質量％と、（Ｃ）ポリイソシアネート１．０〜５．０質量％と、（Ｄ）スズ系触媒０．００５〜０．１質量％とを含み、酸価が０〜５ｍｇＫＯＨ／ｇであって、（Ａ）（メタ）アクリル系樹脂の重量平均分子量が１０万〜６０万であり、且つ（Ｂ）ポリオキシアルキレンポリオールの数平均分子量が５００〜１５００である透明粘着シート用組成物である。
(Composition for transparent adhesive sheet)
The composition for transparent adhesive sheets of the present invention is (A) (meth) acrylic resin 65 to 85% by mass, (B) polyoxyalkylene polyol 10 to 30% by mass, and (C) poly (A) (meth) acrylic containing 1.0 to 5.0% by mass of an isocyanate and (D) 0.005 to 0.1% by mass of a tin-based catalyst, having an acid value of 0 to 5 mgKOH / g It is a composition for transparent adhesive sheets in which the weight average molecular weight of the system resin is 100,000 to 600,000 and the number average molecular weight of the (B) polyoxyalkylene polyol is 500 to 1500.
（（Ａ）（メタ）アクリル系樹脂）
本発明において（Ａ）（メタ）アクリル系樹脂とは、（メタ）アクリル系樹脂を構成するモノマー由来の全構成単位に対して、（メタ）アクリロイル基を有するモノマーに由来する構成単位５０ｍｏｌ％以上を有する樹脂であり、構成単位７０ｍｏｌ％以上が好ましく、９０ｍｏｌ％以上がより好ましい。また、本発明における（Ａ）（メタ）アクリル系樹脂の重合に使用される（メタ）アクリル系モノマー（（メタ）アクリロイル基を有するモノマー）としては、特に限定はないが、カルボキシル基（化学式：−ＣＯＯＨ）を含有しないものが好ましい。カルボキシル基を含有する（メタ）アクリル系モノマーを使用する場合には、（Ａ）（メタ）アクリル系樹脂中に、カルボキシル基を含有する（メタ）アクリル系モノマーに由来する構成単位が０．５ｍｏｌ％以下であることが好ましく、０．１ｍｏｌ％以下であることがより好ましい。（メタ）アクリル系モノマーの例としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｎ−ヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、イソオクチル（メタ）アクリレート、ラウリル（メタ）アクリレート、イソデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、トリデシル（メタ）アクリレート、イソステアリル（メタ）アクリレート等のアルキル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ノルボルニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ノルボルナニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンタニルオキシエチル（メタ）アクリレート、トリシクロデカンジメチロールジ（メタ）アクリレート等の環状アルキル（メタ）アクリレート、メトキシエチル（メタ）アクリレート、エトキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、２−メトキシエトキシエチル（メタ）アクリレート、２−エトキシエトキシエチル（メタ）アクリレート等のアルコキシアルキル（メタ）アクリレート、メトキシジエチレングリコール（メタ）アクリレート、エトキシジエチレングリコール（メタ）アクリレート、メトキシジプロピレングリコール（メタ）アクリレート等のアルコキシ（ポリ）アルキレングリコール（メタ）アクリレート、オクタフルオロペンチル（メタ）アクリレート等のフッ素化アルキル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート等のジアルキルアミノアルキル（メタ）アクリレート、（メタ）アクリルアミド、ダイアセトン（メタ）アクリルアミド等のアミド基含有（メタ）アクリレート、グリシジル（メタ）アクリレート等のエポキシ基含有（メタ）アクリレート、シリコーン変性（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、ジエチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート等の多官能性（メタ）アクリレート等が挙げられる。これらは、単独で使用してもよいし、２種類以上を組み合わせて使用してもよい。
((A) (meth) acrylic resin)
In the present invention, the (A) (meth) acrylic resin is a structural unit derived from a monomer having a (meth) acryloyl group with respect to all structural units derived from the monomer constituting the (meth) acrylic resin. The structural unit is preferably 70 mol% or more, more preferably 90 mol% or more. In addition, the (meth) acrylic monomer (monomer having a (meth) acryloyl group) used in the polymerization of the (A) (meth) acrylic resin in the present invention is not particularly limited, but a carboxyl group (chemical formula: Those not containing -COOH) are preferred. When a (meth) acrylic monomer containing a carboxyl group is used, 0.5 mol of the structural unit derived from the (meth) acrylic monomer containing a carboxyl group is contained in the (A) (meth) acrylic resin. % Or less, and more preferably 0.1 mol% or less. Examples of (meth) acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) ) Acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, tridecyl Alkyl (meth) acrylates such as (meth) acrylate and isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate , Norbornanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, tricyclodecandi Cyclic alkyl (meth) acrylates such as methylol di (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-methoxyethoxyethyl (meth) acrylate, 2-ethoxyethoxy Alkoxyalkyl (meth) acrylates such as ethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxy Alkoxy (poly) alkylene glycol (meth) acrylate such as dipropylene glycol (meth) acrylate, fluorinated alkyl (meth) acrylate such as octafluoropentyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N Dialkylaminoalkyl (meth) acrylates such as N, diethylaminoethyl (meth) acrylate, amide group-containing (meth) acrylates such as (meth) acrylamide, diacetone (meth) acrylamide, and epoxy groups such as glycidyl (meth) acrylate (Meth) acrylate, silicone-modified (meth) acrylate, polyethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate Examples thereof include polyfunctional (meth) acrylates such as relate, triethylene glycol di (meth) acrylate, and tripropylene glycol di (meth) acrylate. These may be used alone or in combination of two or more.
（Ａ）（メタ）アクリル系樹脂と（Ｂ）ポリオキシアルキレンポリオールとの相溶性、すなわち透明粘着シート用組成物を硬化してなる粘着剤層の透明性を考慮すると、（Ａ）（メタ）アクリル系樹脂を構成するモノマー由来の全構成単位に対して、メチルアクリレート及び／又はメチルメタアクリレート由来の構成単位の含有量が５〜５０ｍｏｌ％であることが好ましく、１０〜４５ｍｏｌ％であることがより好ましく、１５〜４０ｍｏｌ％であることがさらに好ましい。メチルアクリレート及び／又はメチルメタアクリレート由来の構成単位の含有量が５ｍｏｌ％より少なくなると、ポリオキシアルキレンポリオールとの相溶性が悪くなる傾向にあり、５０ｍｏｌ％より多くなると、透明粘着シートの粘着力が小さくなる傾向にある。なお、メチルアクリレート及び／又はメチルメタアクリレート由来の構成単位の含有量とは、メチルアクリレート及びメチルメタアクリレート由来の構成単位の合計量をいう。 Considering the compatibility of (A) (meth) acrylic resin and (B) polyoxyalkylene polyol, that is, the transparency of the pressure-sensitive adhesive layer obtained by curing the composition for transparent pressure-sensitive adhesive sheet, (A) (meth) The content of the structural unit derived from methyl acrylate and / or methyl methacrylate is preferably 5 to 50 mol%, and preferably 10 to 45 mol% with respect to all the structural units derived from the monomers constituting the acrylic resin. More preferably, it is 15-40 mol%, and it is still more preferable. When the content of the structural unit derived from methyl acrylate and / or methyl methacrylate is less than 5 mol%, the compatibility with the polyoxyalkylene polyol tends to be poor, and when it exceeds 50 mol%, the adhesive strength of the transparent adhesive sheet is increased. It tends to be smaller. In addition, content of the structural unit derived from methyl acrylate and / or methyl methacrylate means the total amount of the structural unit derived from methyl acrylate and methyl methacrylate.
また、本発明における（Ａ）（メタ）アクリル系樹脂は、ポリイソシアネートを介してポリオキシアルキレンポリオールと反応させ一体化させるという観点から、共重合成分として水酸基含有（メタ）アクリル系モノマーを含むことが好ましい。水酸基含有（メタ）アクリル系モノマーの例としては、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、１，３−ブタンジオール（メタ）アクリレート、１，４−ブタンジオール（メタ）アクリレート、１，６−ヘキサンジオール（メタ）アクリレート、３−メチルペンタンジオール（メタ）アクリレート等の水酸基含有（メタ）アクリレート等が挙げられる。中でも、他のモノマーとの共重合性、反応性の点で、２−ヒドロキシエチル（メタ）アクリレートが好ましい。水酸基含有（メタ）アクリル系モノマー由来の構成単位は、（Ａ）（メタ）アクリル系樹脂を構成するモノマー由来の全構成単位に対して、０．５〜１０ｍｏｌ％含まれることが好ましく、０．６〜８ｍｏｌ％含まれることがより好ましく、０．７〜５ｍｏｌ％含まれることがさらに好ましい。水酸基含有（メタ）アクリル系モノマー由来の構成単位の含有量が０．５ｍｏｌ％より少なくなると、ポリオキシアルキレンポリオールと反応が少なくなり得られる透明粘着シートの凝集力が小さくなる傾向にあり、１０ｍｏｌ％より多くなると架橋密度が高くなりすぎるため得られる透明粘着シートが硬くなる傾向にある。 In addition, the (A) (meth) acrylic resin in the present invention contains a hydroxyl group-containing (meth) acrylic monomer as a copolymer component from the viewpoint of reacting and integrating with a polyoxyalkylene polyol via a polyisocyanate. Is preferred. Examples of hydroxyl group-containing (meth) acrylic monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,3-butanediol (meth) acrylate , 1,4-butanediol (meth) acrylate, 1,6-hexanediol (meth) acrylate, hydroxyl group-containing (meth) acrylate such as 3-methylpentanediol (meth) acrylate, and the like. Among these, 2-hydroxyethyl (meth) acrylate is preferable from the viewpoint of copolymerization with other monomers and reactivity. The structural unit derived from a hydroxyl group-containing (meth) acrylic monomer is preferably contained in an amount of 0.5 to 10 mol% based on all structural units derived from the monomer constituting the (A) (meth) acrylic resin. It is more preferable that 6-8 mol% is contained, and it is still more preferable that 0.7-5 mol% is contained. When the content of the structural unit derived from the hydroxyl group-containing (meth) acrylic monomer is less than 0.5 mol%, the reaction with the polyoxyalkylene polyol tends to decrease and the cohesive force of the transparent adhesive sheet that can be obtained tends to be small. If the amount is larger, the crosslink density becomes too high and the resulting transparent pressure-sensitive adhesive sheet tends to be hard.
また、本発明における（Ａ）（メタ）アクリル系樹脂には、重合性を損なわない範囲で、共重合成分としてその他の重合性モノマーを使用することができる。そのような重合性モノマーの例としては、アクリロニトリル、メタクリロニトリル、スチレン、α−メチルスチレン、酢酸ビニル、プロピオン酸ビニル、ステアリン酸ビニル、塩化ビニル、塩化ビニリデン、アルキルビニルエーテル、ビニルトルエン、ビニルピリジン、ビニルピロリドン、イタコン酸ジアルキルエステル、フマル酸ジアルキルエステル、アリルアルコール、アクリルクロライド、メチルビニルケトン、Ｎ−アクリルアミドメチルトリメチルアンモニウムクロライド、アリルトリメチルアンモニウムクロライド、ジメチルアリルビニルケトン等が挙げられる。 In the (A) (meth) acrylic resin in the present invention, other polymerizable monomers can be used as a copolymerization component as long as the polymerizability is not impaired. Examples of such polymerizable monomers include acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyl toluene, vinyl pyridine, Examples include vinyl pyrrolidone, itaconic acid dialkyl ester, fumaric acid dialkyl ester, allyl alcohol, acrylic chloride, methyl vinyl ketone, N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, and dimethylallyl vinyl ketone.
本発明における（Ａ）（メタ）アクリル系樹脂は、重量平均分子量が１０万〜６０万であることが必要であり、１５万〜５０万であることが好ましく、２０万〜４０万であることがより好ましい。（Ａ）（メタ）アクリル系樹脂の重量平均分子量が１０万より小さくなると、得られる透明粘着シートの凝集力が小さくなるため好ましくない。一方、重量平均分子量が６０万より大きくなると、（Ａ）（メタ）アクリル系樹脂と（Ｂ）ポリオキシアルキレンポリオールとの相溶性が悪くなり、得られる透明粘着シートの透明性が悪くなる。 The (A) (meth) acrylic resin in the present invention needs to have a weight average molecular weight of 100,000 to 600,000, preferably 150,000 to 500,000, and 200,000 to 400,000. Is more preferable. When the weight average molecular weight of (A) (meth) acrylic resin is smaller than 100,000, the cohesive force of the resulting transparent adhesive sheet is decreased, which is not preferable. On the other hand, when the weight average molecular weight is larger than 600,000, the compatibility between the (A) (meth) acrylic resin and the (B) polyoxyalkylene polyol is deteriorated, and the transparency of the obtained transparent adhesive sheet is deteriorated.
ここで重量平均分子量は、ゲル・パーミエーション・クロマトグラフィー（昭和電工株式会社製、ショウデックス（登録商標） ＧＰＣ−１０１）を用いて、下記条件にて常温で測定し、ポリスチレン換算にて算出されるものである。
カラム：昭和電工株式会社製、ショウデックス（登録商標） ＬＦ−８０４
カラム温度：４０℃
試料：（メタ）アクリル系樹脂の０．２質量％テトラヒドロフラン溶液
流量：１ｍｌ／分
溶離液：テトラヒドロフラン
検出器：ＲＩ検出器
Here, the weight average molecular weight is measured at room temperature under the following conditions using gel permeation chromatography (manufactured by Showa Denko KK, Showex (registered trademark) GPC-101), and is calculated in terms of polystyrene. Is.
Column: Showa Denko KK, Shodex (registered trademark) LF-804
Column temperature: 40 ° C
Sample: 0.2 wt% tetrahydrofuran solution of (meth) acrylic resin Flow rate: 1 ml / min Eluent: Tetrahydrofuran Detector: RI detector
また、本発明における（Ａ）（メタ）アクリル系樹脂のガラス転移点（Ｔｇ）は、−８０〜０℃であることが好ましく、−７０〜−５℃であることがより好ましく、−６０〜−１０℃であることがさらに好ましい。Ｔｇが０℃より高くなると、透明粘着シートが固くなるため段差追従性が悪くなる傾向にある。一方、Ｔｇが−８０℃より低くなると、凝集力が小さくなり、透明粘着シートの強度が不十分となる傾向にある。なお、（Ａ）（メタ）アクリル系樹脂のＴｇは、重合に用いるモノマー成分の種類や組成比を変えることにより適宜調整することができる。 The glass transition point (Tg) of the (A) (meth) acrylic resin in the present invention is preferably -80 to 0 ° C, more preferably -70 to -5 ° C, and more preferably -60 to More preferably, it is −10 ° C. When Tg is higher than 0 ° C., the transparent pressure-sensitive adhesive sheet becomes hard and the step following ability tends to deteriorate. On the other hand, when Tg is lower than −80 ° C., the cohesive force is reduced, and the strength of the transparent adhesive sheet tends to be insufficient. In addition, Tg of (A) (meth) acrylic-type resin can be suitably adjusted by changing the kind and composition ratio of the monomer component used for superposition | polymerization.
ここで、Ｔｇは、以下の方法から求められたものを指す。（Ａ）（メタ）アクリル系樹脂から１０ｍｇの試料を採取して、示差走査熱量計（ＤＳＣ）を用いて、１０℃／分の昇温速度で−８０℃から２００℃まで温度を変化させて示差走査熱量測定を行い、ガラス転移による吸熱開始温度をＴｇとする。なお、Ｔｇが２つ以上観察された場合には、それらのＴｇの絶対温度での単純平均値をとることとする。 Here, Tg refers to that obtained from the following method. (A) A 10 mg sample was taken from the (meth) acrylic resin, and the temperature was changed from −80 ° C. to 200 ° C. at a rate of temperature increase of 10 ° C./min using a differential scanning calorimeter (DSC). Differential scanning calorimetry is performed, and the endothermic start temperature due to glass transition is defined as Tg. When two or more Tg are observed, a simple average value of the Tg at the absolute temperature is taken.
本発明における（Ａ）（メタ）アクリル系樹脂の重合方法は特に制限されるものではなく、溶液重合、乳化重合、塊状重合、懸濁重合、交互共重合などの公知の方法を用いることができる。中でも、溶液重合が透明性、耐水性などの点で特に好適である。また、得られる共重合体は、ランダム共重合体、ブロック共重合体など何れでもよい。 The polymerization method of the (A) (meth) acrylic resin in the present invention is not particularly limited, and known methods such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, and alternating copolymerization can be used. . Among these, solution polymerization is particularly preferable in terms of transparency and water resistance. In addition, the obtained copolymer may be any of a random copolymer, a block copolymer, and the like.
（Ａ）（メタ）アクリル系樹脂の重合に際して用いられる重合開始剤は、特に限定されず、公知のものの中から適宜選択して使用することができる。例えば、２，２’−アゾビス（イソブチロニトリル）、２，２’−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、２，２’−アゾビス（２−メチルブチロニトリル）、１，１’−アゾビス（シクロヘキサン−１−カルボニトリル）、２，２’−アゾビス（２，４，４−トリメチルペンタン）、ジメチル−２，２’−アゾビス（２−メチルプロピオネート）等のアゾ系重合開始剤や、ベンゾイルパーオキサイド、ｔ−ブチルハイドロパーオキサイド、ジ−ｔ−ブチルパーオキサイド、ｔ−ブチルパーオキシベンゾエート、ジクミルパーオキサイド、１，１−ビス（ｔ−ブチルパーオキシ）３，３，５−トリメチルシクロヘキサン、１，１−ビス（ｔ−ブチルパーオキシ）シクロドデカン等の過酸化物系重合開始剤などの油溶性重合開始剤が好ましく例示される。これらの重合開始剤は、単独で使用してもよいし、２種以上を組み合わせて使用してもよい。重合開始剤の使用量は、通常の使用量であればよく、例えば、モノマー１００質量部に対して０．０１〜５質量部程度の範囲から選択することができ、０．０１５〜４質量部の範囲であることが好ましく、０．０２〜３質量部であることがより好ましい。 (A) The polymerization initiator used in the polymerization of the (meth) acrylic resin is not particularly limited, and can be appropriately selected from known ones. For example, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile) 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2,4,4-trimethylpentane), dimethyl- Azo polymerization initiators such as 2,2′-azobis (2-methylpropionate), benzoyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, t-butyl peroxybenzoate, dialkyl Milperoxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) ) An oil-soluble polymerization initiator such as peroxide polymerization initiators such as cyclododecane is preferably exemplified. These polymerization initiators may be used alone or in combination of two or more. The usage-amount of a polymerization initiator should just be a normal usage-amount, for example, can be selected from the range of about 0.01-5 mass parts with respect to 100 mass parts of monomers, 0.015-4 mass parts It is preferable that it is the range of this, and it is more preferable that it is 0.02-3 mass parts.
なお、溶液重合では、各種の一般的な溶剤を用いることができる。このような溶剤としては、酢酸エチル、酢酸ｎ−プロピル、酢酸ｎ−ブチル等のエステル類、トルエン、ベンゼン等の芳香族炭化水素類、ｎ−ヘキサン、ｎ−ヘプタン等の脂肪族炭化水素類、シクロヘキサン、メチルシクロヘキサン等の脂環式炭化水素類、メチルエチルケトン、メチルイソブチルケトン等のケトン類などの有機溶剤が挙げられる。これらの溶剤は、単独で使用してもよいし、２種以上を組み合わせて使用してもよい。 In solution polymerization, various common solvents can be used. Examples of such solvents include esters such as ethyl acetate, n-propyl acetate, and n-butyl acetate, aromatic hydrocarbons such as toluene and benzene, aliphatic hydrocarbons such as n-hexane and n-heptane, Examples thereof include organic solvents such as cycloaliphatic hydrocarbons such as cyclohexane and methylcyclohexane, and ketones such as methyl ethyl ketone and methyl isobutyl ketone. These solvents may be used alone or in combination of two or more.
また、本発明の透明粘着シート用組成物中の（Ａ）（メタ）アクリル系樹脂の配合量としては、透明粘着シート用組成物の全固形分に対して６５〜８５質量％であることが必要であり、７０〜８５質量％であることが好ましく、７５〜８５質量％であることがより好ましい。（Ａ）（メタ）アクリル系樹脂の配合量が６５質量％未満であると、凝集力が小さくなり透明粘着シートの強度が不十分となる。一方、（Ａ）（メタ）アクリル系樹脂の配合量が８５質量％を超えると、十分な段差追従性を得ることができない。 Moreover, as a compounding quantity of (A) (meth) acrylic-type resin in the composition for transparent adhesive sheets of this invention, it is 65-85 mass% with respect to the total solid of the composition for transparent adhesive sheets. It is necessary and it is preferable that it is 70-85 mass%, and it is more preferable that it is 75-85 mass%. When the blending amount of the (A) (meth) acrylic resin is less than 65% by mass, the cohesive force becomes small and the strength of the transparent adhesive sheet becomes insufficient. On the other hand, if the blending amount of the (A) (meth) acrylic resin exceeds 85% by mass, sufficient step following ability cannot be obtained.
（（Ｂ）ポリオキシアルキレンポリオール）
本発明で用いられる（Ｂ）ポリオキシアルキレンポリオールとしては、エーテル結合を有するポリマーポリオールであれば特に限定されず、公知のポリマーポリオールが適宜使用できる。（Ｂ）ポリオキシアルキレンポリオールの例としては、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレンエーテルグリコール及びこれらの誘導体又は共重合体等が挙げられる。中でも、アクリル樹脂との相溶性を調整しやすいという理由で、ポリプロピレングリコールが好ましい。これらは、単独で使用してもよいし、２種以上を混合して使用してもよい。
((B) polyoxyalkylene polyol)
The (B) polyoxyalkylene polyol used in the present invention is not particularly limited as long as it is a polymer polyol having an ether bond, and a known polymer polyol can be appropriately used. Examples of (B) polyoxyalkylene polyols include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and derivatives or copolymers thereof. Among these, polypropylene glycol is preferable because it is easy to adjust the compatibility with the acrylic resin. These may be used alone or in combination of two or more.
本発明で用いられる（Ｂ）ポリオキシアルキレンポリオールは、数平均分子量が５００〜１５００であることが必要であり、７００〜１３００であることが好ましく、８００〜１２００であることがより好ましい。数平均分子量が５００より小さくなると、透明粘着シートの段差追従性が悪くなり好ましくない。一方、数平均分子量が１５００を超えると、得られる透明粘着シートの透明性が悪くなる。なお、数平均分子量はＧＰＣ（ゲル・パーミエーション・クロマトグラフィー）により（Ａ）（メタ）アクリル系樹脂の重量平均分子量と同じ方法で測定することができる。 The polyoxyalkylene polyol (B) used in the present invention needs to have a number average molecular weight of 500 to 1500, preferably 700 to 1300, and more preferably 800 to 1200. When the number average molecular weight is smaller than 500, the step following property of the transparent adhesive sheet is deteriorated, which is not preferable. On the other hand, when the number average molecular weight exceeds 1500, the transparency of the obtained transparent adhesive sheet is deteriorated. The number average molecular weight can be measured by GPC (gel permeation chromatography) in the same manner as the weight average molecular weight of the (A) (meth) acrylic resin.
また、本発明の透明粘着シート用組成物中の（Ｂ）ポリオキシアルキレンポリオールの配合量としては、透明粘着シート用組成物の全固形分に対して１０〜３０質量％であることが必要であり、１３〜２５質量％であることが好ましく、１５〜２０質量％であることがより好ましい。（Ｂ）ポリオキシアルキレンポリオールの配合量が１０質量％より少なくなると、透明粘着シートの十分な段差追従性を得ることができない。一方、（Ｂ）ポリオキシアルキレンポリオールの配合量が３０質量％を超えると、凝集力が小さくなり透明粘着シートの強度が不十分となる。 Moreover, as a compounding quantity of (B) polyoxyalkylene polyol in the composition for transparent adhesive sheets of this invention, it is required that it is 10-30 mass% with respect to the total solid of the composition for transparent adhesive sheets. Yes, it is preferably 13 to 25% by mass, more preferably 15 to 20% by mass. (B) When the compounding quantity of polyoxyalkylene polyol becomes less than 10 mass%, sufficient level | step difference followable | trackability of a transparent adhesive sheet cannot be obtained. On the other hand, if the blending amount of (B) polyoxyalkylene polyol exceeds 30% by mass, the cohesive force becomes small and the strength of the transparent adhesive sheet becomes insufficient.
（（Ｃ）ポリイソシアネート）
本発明における（Ｃ）ポリイソシアネートとしては、芳香族系ポリイソシアネート、脂肪族系ポリイソシアネート、脂環式系ポリイソシアネート等が挙げられる。（Ｃ）ポリイソシアネートの例としては、１，４−テトラメチレンジイソシアネート、１，６−ヘキサメチレンジイソシアネート（ＨＤＩ）、２−メチル−１，５−ペンタンジイソシアネート、３−メチル−１，５−ペンタンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、イソホロンジイソシアネート、シクロヘキシルジイソシアネート、トリレンジイソシアネート（ＴＤＩ）、水素添加トリレンジイソシアネート、ジフェニルメタンジイソシアネート、水素添加ジフェニルメタンジイソシアネート、ポリフェニルメタンポリイソシアネート、キシレンジイソシアネート、水素添加キシレンジイソシアネート、テトラメチルキシリレンジイソシアネート、ノルボルネンジイソシアネート、ナフタレンジイソシアネート、トリメチロールプロパン／トリレンジイソシアネート３量体付加物、トリメチロールプロパン／ヘキサメチレンジイソシアネート３量体付加物、ヘキサメチレンジイソシアネートのイソシアヌレート体などのイソシアネート付加物、ポリエーテルポリイソシアネート、ポリエステルポリイソシアネート等が挙げられる。これらは、単独で使用してもよいし、２種以上を組み合わせて使用してもよい。
((C) Polyisocyanate)
Examples of (C) polyisocyanate in the present invention include aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate. Examples of (C) polyisocyanate include 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate. , Trimethylhexamethylene diisocyanate, isophorone diisocyanate, cyclohexyl diisocyanate, tolylene diisocyanate (TDI), hydrogenated tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, tetramethylxylylene Diisocyanate, norbornene diisocyanate, naphthalene diisocyanate, Examples include methylol propane / tolylene diisocyanate trimer adduct, trimethylol propane / hexamethylene diisocyanate trimer adduct, isocyanate adducts such as hexamethylene diisocyanate isocyanurate, polyether polyisocyanate, polyester polyisocyanate and the like. . These may be used alone or in combination of two or more.
また、本発明の透明粘着シート用組成物中の（Ｃ）ポリイソシアネートの配合量としては、透明粘着シート用組成物の全固形分に対して１．０〜５．０質量％であることが必要であり、１．５〜４．５質量％であることが好ましく、２．０〜４．０質量％であることがより好ましい。（Ｃ）ポリイソシアネートの配合量が１．０質量％より少なくなると、十分な凝集力が得られず透明粘着シートの強度が不十分となる。一方、（Ｃ）ポリイソシアネートの配合量が５．０質量％を超えると、得られる透明粘着シートの柔軟性が不十分となり十分な段差追従性を得ることができない。 Moreover, as a compounding quantity of (C) polyisocyanate in the composition for transparent adhesive sheets of this invention, it is 1.0-5.0 mass% with respect to the total solid of the composition for transparent adhesive sheets. It is necessary and it is preferable that it is 1.5-4.5 mass%, and it is more preferable that it is 2.0-4.0 mass%. (C) When the compounding quantity of polyisocyanate becomes less than 1.0 mass%, sufficient cohesion force will not be obtained but the intensity | strength of a transparent adhesive sheet will become inadequate. On the other hand, when the blending amount of (C) polyisocyanate exceeds 5.0% by mass, the flexibility of the obtained transparent pressure-sensitive adhesive sheet becomes insufficient, and sufficient step following ability cannot be obtained.
（（Ｄ）スズ系触媒）
本発明において用いられる（Ｄ）スズ系触媒としては、ジブチル錫ジラウレート、ジブチル錫ジエチルヘキソエート、ジオクチル錫ジラウレート等があげられる。中でも、（C）ポリイソシアネートの硬化性が良好で、安全性の点から、ジオクチル錫ジラウレートが好ましい。
((D) Tin-based catalyst)
Examples of the (D) tin-based catalyst used in the present invention include dibutyltin dilaurate, dibutyltin diethylhexoate, dioctyltin dilaurate and the like. Of these, (C) polyisocyanate has good curability and is preferably dioctyltin dilaurate from the viewpoint of safety.
また、本発明の透明粘着シート用組成物中の（Ｄ）スズ系触媒の配合量としては、透明粘着シート用組成物の全固形分に対して０．００５〜０．１質量％であることが必要であり、０．０１〜０．０９質量％であることが好ましく、０．０２〜０．０８０質量％であることがより好ましい。（Ｄ）スズ系触媒の配合量が０．００５質量％より少なくなると、透明粘着シート用組成物の硬化性が十分でなく、凝集力が小さくなり、０．１質量％より多くなると、透明粘着シート作製時のポットライフが短くなる。 Moreover, as a compounding quantity of the (D) tin-type catalyst in the composition for transparent adhesive sheets of this invention, it is 0.005-0.1 mass% with respect to the total solid of the composition for transparent adhesive sheets. Is necessary, and it is preferable that it is 0.01-0.09 mass%, and it is more preferable that it is 0.02-0.080 mass%. (D) When the blending amount of the tin-based catalyst is less than 0.005% by mass, the curability of the transparent adhesive sheet composition is not sufficient, the cohesive force is reduced, and when it exceeds 0.1% by mass, the transparent adhesive Pot life during sheet production is shortened.
（透明粘着シート用組成物）
本発明の透明粘着シート用組成物は、酸価が０〜５ｍｇＫＯＨ／ｇであることが必要であり、０〜１ｍｇＫＯＨ／ｇであることが好ましく、０〜０．３ｍｇＫＯＨ／ｇであることがより好ましく、０〜０．１ｍｇＫＯＨ／ｇであることが特に好ましい。透明粘着シート用組成物の酸価が５ｍｇＫＯＨ／ｇより高くなると、透明導電膜の導電層面の腐食の抑制が困難となる。なお、透明粘着シート用組成物の酸価はＪＩＳ Ｋ００７０に準拠して測定した値である。例えば、以下のように測定する。
(Composition for transparent adhesive sheet)
The composition for transparent adhesive sheet of the present invention requires an acid value of 0 to 5 mgKOH / g, preferably 0 to 1 mgKOH / g, more preferably 0 to 0.3 mgKOH / g. It is preferably 0 to 0.1 mgKOH / g. When the acid value of the transparent adhesive sheet composition is higher than 5 mgKOH / g, it becomes difficult to suppress corrosion of the conductive layer surface of the transparent conductive film. In addition, the acid value of the composition for transparent adhesive sheets is the value measured based on JISK0070. For example, measurement is performed as follows.
精密天秤で１００ｍｌ三角フラスコに試料約２ｇ程度を精秤し、これにエタノール／ジエチルエーテル＝１／１（質量比）の混合溶媒１０ｍｌを加えて溶解する。更に、この容器に指示薬としてフェノールフタレインエタノール溶液を１〜３滴添加し、試料が均一になるまで充分に攪拌する。これを、０．１Ｎ水酸化カリウム−エタノール溶液で滴定し、指示薬のうすい紅色が３０秒間続いたときを、中和の終点とする。その結果から下記の式（１）を用いて得た値を、透明粘着シート用組成物の酸価とする。
ｆ：０．１Ｎ水酸化カリウム−エタノール溶液のファクター
Ｓ：試料の採取量（ｇ）
About 2 g of a sample is precisely weighed into a 100 ml Erlenmeyer flask with a precision balance, and 10 ml of a mixed solvent of ethanol / diethyl ether = 1/1 (mass ratio) is added and dissolved therein. Further, 1 to 3 drops of phenolphthalein ethanol solution is added to this container as an indicator, and the mixture is sufficiently stirred until the sample becomes uniform. This is titrated with a 0.1N potassium hydroxide-ethanol solution, and the end point of neutralization is taken when the indicator is light red for 30 seconds. The value obtained from the result using the following formula (1) is defined as the acid value of the transparent adhesive sheet composition.
f: Factor of 0.1N potassium hydroxide-ethanol solution S: Amount of sample collected (g)
本発明の透明粘着シート用組成物には、必要に応じて、得られる透明粘着シートの接着力を向上させるため、透明粘着シートの透明性を低下させない範囲で粘着付与樹脂を添加しても良い。粘着付与樹脂の例としては、ロジンやロジンのエステル化物等のロジン系樹脂；ジテルペン重合体やα−ピネン−フェノール共重合体等のテルペン系樹脂；脂肪族系（Ｃ５系）や芳香族系（Ｃ９系）等の石油樹脂；その他、スチレン系樹脂、フェノール系樹脂、キシレン樹脂等が挙げられる。耐光性の点から不飽和二重結合が少ない水添ロジンや不均化ロジンのエステル化物や、脂肪族や芳香族系石油樹脂、高いＴｇを有するアクリル樹脂等を透明粘着シートに添加することが好ましい。粘着付与樹脂の添加量としては、透明粘着シート用組成物１００質量部に対して、１〜１０質量部を添加することが好ましい。 In the composition for transparent pressure-sensitive adhesive sheet of the present invention, if necessary, a tackifier resin may be added within a range not reducing the transparency of the transparent pressure-sensitive adhesive sheet in order to improve the adhesive strength of the obtained transparent pressure-sensitive adhesive sheet. . Examples of tackifier resins include rosin resins such as rosin and rosin esterified products; terpene resins such as diterpene polymers and α-pinene-phenol copolymers; aliphatic (C5) and aromatic ( Petroleum resin such as C9); styrene resin, phenol resin, xylene resin and the like. It is possible to add a hydrogenated rosin or a disproportionated rosin ester, an aliphatic or aromatic petroleum resin, an acrylic resin having a high Tg, or the like to the transparent pressure-sensitive adhesive sheet from the viewpoint of light resistance. preferable. As addition amount of tackifying resin, it is preferable to add 1-10 mass parts with respect to 100 mass parts of compositions for transparent adhesive sheets.
また、本発明の透明粘着シート用組成物には、必要に応じて、透明性を損なわない範囲で、公知の各種添加剤を含んでいてもよい。添加剤としては、可塑剤、表面潤滑剤、レベリング剤、軟化剤、酸化防止剤、老化防止剤、紫外線吸収剤、重合禁止剤、ベンゾトリアゾール系等の光安定剤、リン酸エステル系およびその他の難燃剤、界面活性剤のような帯電防止剤などが挙げられる。 Moreover, the composition for transparent adhesive sheets of this invention may contain the well-known various additives in the range which does not impair transparency as needed. Additives include plasticizers, surface lubricants, leveling agents, softeners, antioxidants, antioxidants, ultraviolet absorbers, polymerization inhibitors, light stabilizers such as benzotriazoles, phosphate esters and other Examples thereof include flame retardants and antistatic agents such as surfactants.
また、本発明の透明粘着シート用組成物は、塗工時の粘度調整を目的として有機溶媒を用いて希釈してもよい。用いられる有機溶媒としては、たとえば、メチルエチルケトン、アセトン、酢酸エチル、テトラヒドロフラン、ジオキサン、シクロヘキサノン、ｎ−へキサン、トルエン、キシレン、ｎ−プロパノール、イソプロパノール、酢酸ｎ−プロピルなどが挙げられる。これらの有機溶媒は単独で使用してもよく、また２種以上を混合してもよい。 Moreover, you may dilute the composition for transparent adhesive sheets of this invention using an organic solvent for the purpose of the viscosity adjustment at the time of coating. Examples of the organic solvent used include methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, xylene, n-propanol, isopropanol, and n-propyl acetate. These organic solvents may be used alone or in combination of two or more.
（透明粘着シート）
本発明の透明粘着シートは、上記透明粘着シート用組成物を硬化して得られる。より具体的には、光学部材を貼り合わせる用途（光学部材貼り合わせ用）や光学製品の製造用途などに用いられる。また、本発明の透明粘着シートは、基材を有するものであっても、基材を有さず粘着剤層のみからなる両面粘着シートであってもよい。光学部材としては、光学的特性を有する部材であれば、特に限定されないが、例えば、画像表示装置、タッチパネルを構成する部材又はこれらの機器に用いられる部材が挙げられる。より具体的には、例えば、偏光板、位相差板、光学補償フィルム、輝度向上フィルム、導光板、反射フィルム、反射防止フィルム、透明導電フィルム、意匠フィルム、装飾フィルム、表面保護フィルム、プリズム、レンズ、カラーフィルター、透明基板や、さらにはこれらが積層されている部材が挙げられる。
(Transparent adhesive sheet)
The transparent adhesive sheet of the present invention is obtained by curing the composition for transparent adhesive sheet. More specifically, it is used for applications for bonding optical members (for optical member bonding), optical product manufacturing applications, and the like. Moreover, even if the transparent adhesive sheet of this invention has a base material, it may be a double-sided adhesive sheet which does not have a base material but consists only of an adhesive layer. Although it will not specifically limit if it is a member which has an optical characteristic as an optical member, For example, the member used for an image display apparatus, a touchscreen, or these apparatuses is mentioned. More specifically, for example, a polarizing plate, a retardation plate, an optical compensation film, a brightness enhancement film, a light guide plate, a reflection film, an antireflection film, a transparent conductive film, a design film, a decorative film, a surface protection film, a prism, a lens , A color filter, a transparent substrate, and a member in which these are laminated.
本発明の透明粘着シートは、透明粘着シート用組成物を溶媒に溶解した溶液を、剥離フィルムに塗布し、塗布した溶液を加熱乾燥して架橋させることで得ることができる。透明粘着シートの膜厚は、５〜２００μｍとすることが好ましく、１０〜１５０μｍとすることがより好ましく、１５〜１００μｍとすることがさらに好ましい。透明粘着シートの膜厚が５μｍより薄くなると、透明粘着シートの貼り合わせが困難となる傾向にある。透明粘着シートの膜厚が２００μｍより厚くなると、溶媒がシートに残り臭気の問題が発生する傾向にある。なお、本発明の透明粘着シートを形成する際の塗布（塗工）方法としては、公知のコーティング法を用いることが可能であり、慣用のコーター、例えば、グラビヤロールコーター、リバースロールコーター、キスロールコーター、ディップロールコーター、バーコーター、ナイフコーター、スプレーコーター、コンマコーター、ダイレクトコーターなどを用いてコーティングすることができる。 The transparent adhesive sheet of this invention can be obtained by apply | coating the solution which melt | dissolved the composition for transparent adhesive sheets in the solvent to a peeling film, heat-drying, and making it bridge | crosslink. The film thickness of the transparent adhesive sheet is preferably 5 to 200 μm, more preferably 10 to 150 μm, and still more preferably 15 to 100 μm. When the film thickness of the transparent pressure-sensitive adhesive sheet is thinner than 5 μm, it tends to be difficult to bond the transparent pressure-sensitive adhesive sheet. When the film thickness of a transparent adhesive sheet becomes thicker than 200 micrometers, it exists in the tendency for a solvent to remain in a sheet | seat and to generate | occur | produce the problem of an odor. In addition, as a coating (coating) method when forming the transparent adhesive sheet of the present invention, a known coating method can be used, and a conventional coater, for example, a gravure roll coater, a reverse roll coater, a kiss roll. Coating can be performed using a coater, dip roll coater, bar coater, knife coater, spray coater, comma coater, direct coater, and the like.
本発明の透明粘着シートのゲル分率は、４０〜８０％であることが好ましく、４５〜７５％であることがより好ましく、５０〜７０％であることがさらに好ましい。ゲル分率が４０％より小さい場合でも使用は可能であるが、透明粘着シートの凝集力が小さくなる傾向にある。また、ゲル分率が８０％より大きくなると、透明粘着シートの段差追従性が悪くなる傾向がある。 The gel fraction of the transparent adhesive sheet of the present invention is preferably 40 to 80%, more preferably 45 to 75%, and still more preferably 50 to 70%. Although it can be used even when the gel fraction is less than 40%, the cohesive force of the transparent adhesive sheet tends to be small. Moreover, when the gel fraction is larger than 80%, the step following property of the transparent adhesive sheet tends to be deteriorated.
なお、透明粘着シートのゲル分率は、トルエン浸漬前と、トルエン中に室温下で２４時間浸漬し、８０℃で５時間乾燥した後の試料の質量をもとに、下記の式（２）で求められる。
（透明導電膜固定用透明粘着シート）
本発明の透明導電膜固定用透明粘着シートは、上記の透明粘着シート用組成物を硬化させてなる透明導電膜固定用透明粘着シートであって、透明導電膜の導電層面と好適に接着でき、かつ導電層の腐食が生じ難いものである。したがって、透明導電膜固定用シートを透明導電膜の導電層面と接着させた積層体はタッチパネルとして好適に用いることができる。また、本発明の透明導電膜固定用透明粘着シートは、基材を有するものであっても、基材を有さず粘着剤層のみからなる両面粘着シートであってもよい。また、粘着剤層は単一層からなるものであっても複数層が積層されていてもよい。なかでも、透明性の確保や、段差追従性の観点からは、基材を有さず、粘着剤層のみからなる両面粘着シートであることが好ましい。
(Transparent adhesive sheet for fixing transparent conductive film)
The transparent pressure-sensitive adhesive sheet for fixing a transparent conductive film of the present invention is a transparent pressure-sensitive adhesive sheet for fixing a transparent conductive film obtained by curing the composition for transparent pressure-sensitive adhesive sheet, and can be suitably bonded to the conductive layer surface of the transparent conductive film, In addition, the conductive layer is hardly corroded. Therefore, a laminate in which the transparent conductive film fixing sheet is bonded to the conductive layer surface of the transparent conductive film can be suitably used as a touch panel. Further, the transparent adhesive sheet for fixing a transparent conductive film of the present invention may have a base material, or may be a double-sided pressure-sensitive adhesive sheet having only a pressure-sensitive adhesive layer without having a base material. Moreover, even if the adhesive layer consists of a single layer, multiple layers may be laminated | stacked. Especially, it is preferable that it is a double-sided adhesive sheet which does not have a base material but consists only of an adhesive layer from a viewpoint of ensuring transparency and level | step difference followable | trackability.
本発明の透明導電膜固定用透明粘着シートが使用される透明導電膜としては、少なくとも片面の表層に導電層を有するものであればよく、透明基材の表層に導電物質が蒸着やコーティングにより設けられた透明導電膜を挙げられる。透明導電膜の導電層において蒸着やコーティングされる導電物質は、特に限定されないが、具体的には、銀、酸化インジウムスズ、酸化インジウム、酸化スズ、酸化亜鉛、酸化カドミウム、酸化ガリウム、酸化チタンなどが挙げられる。なかでも、透明性、導電性に優れる銀、酸化インジウムスズが好適に用いられる。透明導電膜において、導電物質が蒸着またはコーティングされる基材としては、特に限定されるものではないが、ガラス、樹脂フィルムなどが挙げられる。 As the transparent conductive film in which the transparent adhesive sheet for fixing the transparent conductive film of the present invention is used, it is sufficient that it has a conductive layer on at least one surface layer, and the conductive material is provided on the surface layer of the transparent substrate by vapor deposition or coating. The obtained transparent conductive film is mentioned. The conductive material to be deposited or coated on the conductive layer of the transparent conductive film is not particularly limited, and specifically, silver, indium tin oxide, indium oxide, tin oxide, zinc oxide, cadmium oxide, gallium oxide, titanium oxide, etc. Is mentioned. Of these, silver and indium tin oxide, which are excellent in transparency and conductivity, are preferably used. In the transparent conductive film, the substrate on which the conductive material is deposited or coated is not particularly limited, and examples thereof include glass and resin films.
なお、本発明の透明導電膜固定用透明粘着シートは、前記の透明粘着シートと同様の方法によって得ることが出来る。 In addition, the transparent adhesive sheet for transparent conductive film fixation of this invention can be obtained by the method similar to the said transparent adhesive sheet.
以下に実施例、及び比較例により本発明をより具体的に説明するが、本発明は、これらの例によってなんら限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.
＜（メタ）アクリル系樹脂（Ａ−１）〜（Ａ−３）の合成＞
各々の（メタ）アクリル系モノマーの添加割合（ｍｏｌ％）は、（メタ）アクリル系樹脂の製造に使用する（メタ）アクリル系モノマーの合計量（ｍｏｌ）から算出した。冷却管、窒素導入管、温度計および撹拌装置を備えた反応容器に、酢酸ｎ−プロピル５００質量部、２−エチルヘキシルアクリレート３２０質量部（５３ｍｏｌ％）、メチルメタアクリレート１２５質量部（３８ｍｏｌ％）、イソボルニルアクリレート５０質量部（８ｍｏｌ％）、２−ヒドロキシエチルメタクリレート５質量部（１ｍｏｌ％）、２，２’−アゾビス（イソブチロニトリル）０．１質量部を入れ、窒素気流中で９５℃にて８時間重合処理した後、３０℃まで冷却して、（メタ）アクリル共重合体（Ａ−１）を得た。得られた（メタ）アクリル共重合体（Ａ−１）は、ガラス転移温度が−３０℃であり、重量平均分子量が２０万であった。なお、（メタ）アクリル共重合体のガラス転移温度、重量平均分子量の測定は、上で述べた方法により行った。また、表１に記載の（メタ）アクリロイル基含有モノマーの組成比を変更する以外は、（メタ）アクリル共重合体（Ａ−１）と同様にして、（メタ）アクリル共重合体（Ａ−２）〜（Ａ−３）を得た。また、（メタ）アクリル共重合体（Ａ−１）と同様、（メタ）アクリル共重合体（Ａ−２）〜（Ａ−３）についても、ガラス転移温度、重量平均分子量の測定を行った。結果を表１に示す。
<Synthesis of (meth) acrylic resins (A-1) to (A-3)>
The addition ratio (mol%) of each (meth) acrylic monomer was calculated from the total amount (mol) of (meth) acrylic monomer used for the production of the (meth) acrylic resin. In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer, n-propyl acetate 500 parts by mass, 2-ethylhexyl acrylate 320 parts by mass (53 mol%), methyl methacrylate 125 parts by mass (38 mol%), 50 parts by mass (8 mol%) of isobornyl acrylate, 5 parts by mass of 2-hydroxyethyl methacrylate (1 mol%), 0.1 part by mass of 2,2′-azobis (isobutyronitrile) were added, and 95 in a nitrogen stream. After carrying out the polymerization process at 8 ° C. for 8 hours, it was cooled to 30 ° C. to obtain a (meth) acrylic copolymer (A-1). The obtained (meth) acrylic copolymer (A-1) had a glass transition temperature of −30 ° C. and a weight average molecular weight of 200,000. In addition, the measurement of the glass transition temperature of a (meth) acryl copolymer and a weight average molecular weight was performed by the method described above. Moreover, except changing the composition ratio of the (meth) acryloyl group containing monomer of Table 1, it is the same as the (meth) acryl copolymer (A-1), and the (meth) acryl copolymer (A- 2) to (A-3) were obtained. Moreover, similarly to the (meth) acrylic copolymer (A-1), the glass transition temperature and the weight average molecular weight were also measured for the (meth) acrylic copolymers (A-2) to (A-3). . The results are shown in Table 1.
＜（メタ）アクリル系樹脂（Ａ−４）の合成＞
各々の（メタ）アクリル系モノマーの添加割合（ｍｏｌ％）は、（メタ）アクリル系樹脂の製造に使用する（メタ）アクリル系モノマーの合計量（ｍｏｌ）から算出した。冷却管、窒素導入管、温度計および撹拌装置を備えた反応容器に、酢酸ｎ−プロピル５００質量部、２−エチルヘキシルアクリレート３２０質量部（５３ｍｏｌ％）、メチルメタアクリレート１１８質量部（３６ｍｏｌ％）、イソボルニルアクリレート５０質量部（７ｍｏｌ％）、２−ヒドロキシエチルメタクリレート５質量部（１ｍｏｌ％）、アクリル酸６質量部（３ｍｏｌ％）、２，２’−アゾビス（イソブチロニトリル）０．１質量部を入れ、窒素気流中で９５℃にて８時間重合処理した後、３０℃まで冷却して、（メタ）アクリル共重合体（Ａ−４）を得た。得られた（メタ）アクリル共重合体（Ａ−４）は、ガラス転移温度が−３０℃であり、重量平均分子量が２３万であった。なお、（メタ）アクリル共重合体のガラス転移温度、重量平均分子量の測定は、上で述べた方法により行った。また、（メタ）アクリル共重合体（Ａ−１）〜（Ａ−３）と同様、（メタ）アクリル共重合体（Ａ−４）についても、ガラス転移温度、重量平均分子量の測定を行った。結果を表１に示す。
<Synthesis of (meth) acrylic resin (A-4)>
The addition ratio (mol%) of each (meth) acrylic monomer was calculated from the total amount (mol) of (meth) acrylic monomer used for the production of the (meth) acrylic resin. In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer, n-propyl acetate 500 parts by mass, 2-ethylhexyl acrylate 320 parts by mass (53 mol%), methyl methacrylate 118 parts by mass (36 mol%), Isobornyl acrylate 50 parts by mass (7 mol%), 2-hydroxyethyl methacrylate 5 parts by mass (1 mol%), acrylic acid 6 parts by mass (3 mol%), 2,2′-azobis (isobutyronitrile) 0.1 After putting a mass part, it superposed | polymerized at 95 degreeC in nitrogen stream for 8 hours, Then, it cooled to 30 degreeC and obtained the (meth) acryl copolymer (A-4). The obtained (meth) acrylic copolymer (A-4) had a glass transition temperature of −30 ° C. and a weight average molecular weight of 230,000. In addition, the measurement of the glass transition temperature of a (meth) acryl copolymer and a weight average molecular weight was performed by the method described above. Moreover, the glass transition temperature and the weight average molecular weight were measured also about the (meth) acrylic copolymer (A-4) similarly to the (meth) acrylic copolymer (A-1)-(A-3). . The results are shown in Table 1.
（実施例１〜３及び比較例１〜５）
表２に示す組成で、（メタ）アクリル系樹脂、ポリオキシアルキレンポリオール、ポリイソシアネート及びスズ系触媒を配合し、さらに酢酸ｎ−プロピルで固形分濃度を５０質量％に調節して、得られた溶液を室温下でディスパーを用いて混合することで透明粘着シート用組成物溶液を得た。なお、表２中の、（メタ）アクリル系樹脂、ポリオキシアルキレンポリオール、ポリイソシアネート及びスズ系触媒に関する数値は、透明粘着シート用組成物の全固形分に対する質量％を表す。この透明粘着シート用組成物溶液を、厚さ５０μｍのポリエチレンテレフタレート（ＰＥＴ）フィルムの片面に剥離処理が施されているセパレータの剥離処理面上に、乾燥後の厚さが１００μｍとなるように流延塗布（塗布層厚さ２００μｍ）し、５０℃で１０分間および８０℃で１０分間、１１０℃で２０分間、加熱乾燥させ、さらに厚さ３８μｍのＰＥＴフィルムの片面に剥離処理が施されているセパレータの剥離処理面側を粘着剤側にカバーする。そして、４０℃で７２時間エージングを行い、両面粘着シート（基材レスタイプ）を作製した。
(Examples 1-3 and Comparative Examples 1-5)
The composition shown in Table 2 was obtained by blending (meth) acrylic resin, polyoxyalkylene polyol, polyisocyanate and tin-based catalyst, and further adjusting the solid content concentration to 50% by mass with n-propyl acetate. The solution was mixed using a disper at room temperature to obtain a transparent adhesive sheet composition solution. In addition, the numerical value regarding (meth) acrylic-type resin, polyoxyalkylene polyol, polyisocyanate, and a tin-type catalyst of Table 2 represents the mass% with respect to the total solid of the composition for transparent adhesive sheets. The composition solution for transparent adhesive sheet is flowed on the release-treated surface of a separator on which one side of a 50 μm-thick polyethylene terephthalate (PET) film has been subjected to a release treatment so that the thickness after drying becomes 100 μm. The coated film is applied by coating (applied layer thickness 200 μm), dried by heating at 50 ° C. for 10 minutes, 80 ° C. for 10 minutes, and 110 ° C. for 20 minutes, and one side of a 38 μm thick PET film is subjected to a peeling treatment. Cover the release side of the separator to the adhesive side. And aging was performed at 40 degreeC for 72 hours, and the double-sided adhesive sheet (base material-less type) was produced.
（酸価）
前記の方法で各透明粘着シート用組成物の酸価を測定した。結果を表２に示す。
(Acid value)
The acid value of each composition for transparent adhesive sheets was measured by the above method. The results are shown in Table 2.
（酸化インジウムスズ膜の電気抵抗値測定）
上で得られた両面粘着シートを５０ｍｍ×５０ｍｍの大きさに切り取り、片側の３８μｍ厚のＰＥＴフィルムを剥がし、両面粘着シートの一方の辺と１００ｍｍ×１００ｍｍの酸化インジウムスズ蒸着ＰＥＴフィルムの一方の辺が平行となり、かつ、両面粘着シートの位置が縦方向及び横方向において酸化インジウムスズ蒸着ＰＥＴフィルムの略中央になるようにして、両面粘着シートを酸化インジウムスズ膜面に貼り合わせた。両面粘着シートを貼り合わせた酸化インジウムスズ蒸着ＰＥＴフィルムについて、酸化インジウムスズ膜面上であって、該フィルムの１つの角と、その対角線上にある角の両端間における初期の電気抵抗値（Ｒ１）を、電気抵抗値測定機（三菱化学株式会社製「ロレスターＧＰ」）を使用して測定した。また、両面粘着シートを貼り合わせた酸化インジウムスズ蒸着ＰＥＴフィルムを６０℃、９０％ＲＨ条件下に５００時間放置し、２３℃、５０％ＲＨ条件下に１時間放置した後、初期の電気抵抗値を測定した箇所と同じ箇所で電気抵抗値（Ｒ２）を測定した。酸化インジウムスズ膜の電気抵抗値上昇率は、下記の式（３）で算出した。
○；電気抵抗値上昇率５％未満
△；電気抵抗値上昇率５〜１０％未満
×；電気抵抗値上昇率１０％以上
(Measurement of electrical resistance of indium tin oxide film)
The double-sided pressure-sensitive adhesive sheet obtained above was cut to a size of 50 mm × 50 mm, the PET film with a thickness of 38 μm was peeled off on one side, and one side of the double-sided pressure-sensitive adhesive sheet and one side of the 100 mm × 100 mm indium tin oxide vapor-deposited PET film And the double-sided PSA sheet was bonded to the indium tin oxide film surface so that the double-sided PSA sheet was positioned approximately at the center of the indium tin oxide-deposited PET film in the vertical and horizontal directions. About the indium tin oxide vapor-deposited PET film on which the double-sided pressure-sensitive adhesive sheet is bonded, the initial electrical resistance value (R) on the indium tin oxide film surface between one corner of the film and the opposite corner of the film. 1 ) was measured using an electrical resistance measuring machine (“Lorestar GP” manufactured by Mitsubishi Chemical Corporation). In addition, the indium tin oxide-deposited PET film on which the double-sided pressure-sensitive adhesive sheet was bonded was allowed to stand for 500 hours at 60 ° C. and 90% RH, and left for 1 hour at 23 ° C. and 50% RH. The electrical resistance value (R 2 ) was measured at the same location as the location where the measurement was made. The increase rate of the electric resistance value of the indium tin oxide film was calculated by the following formula (3).
○: Electrical resistance value increase rate of less than 5% Δ; Electrical resistance value increase rate of less than 5 to 10% ×: Electrical resistance value increase rate of 10% or more
（全光線透過率測定）
上で得られた両面粘着シートを３０ｍｍ×３０ｍｍの大きさに切り取り、両面粘着シートの両面に存在する剥離ＰＥＴフィルムのうち片面の３８μｍ厚の剥離ＰＥＴフィルムを剥がし、ガラス板に貼り合わせたものを測定用サンプルとした。測定用サンプルについて、株式会社村上色彩技術研究所製「ＨＲ−１００型」を使用し、全光線透過率（％）を測定した。結果を表２に示す。
(Total light transmittance measurement)
The double-sided pressure-sensitive adhesive sheet obtained above was cut into a size of 30 mm × 30 mm, and the 38 μm-thick peeled PET film on one side of the peeled PET film present on both sides of the double-sided pressure-sensitive adhesive sheet was peeled off and bonded to a glass plate. A sample for measurement was used. About the sample for a measurement, the total light transmittance (%) was measured using "HR-100 type" by Murakami Color Research Laboratory. The results are shown in Table 2.
（両面粘着シートの粘着力測定）
上で得られた両面粘着シートを２５ｍｍ×１００ｍｍの大きさに切り取り、両面粘着シートの片面の３８μｍ厚の剥離ＰＥＴフィルムを剥がし、片面にコロナ処理が施されている厚さ５０μｍのＰＥＴフィルム貼り直した後、粘着面（測定面）を試験板に貼付して、２ｋｇのゴムローラー（幅：約５０ｍｍ）を１往復させて、測定用サンプルを作製した。試験板としてガラス板を用いた。得られた測定用サンプルについて、２３℃、湿度５０％の環境下で２４時間放置し、ＪＩＳ Ｚ０２３７に準じて、剥離速度３００ｍｍ／分で１８０°方向の引張試験を行い、両面粘着シートのガラス板に対する粘着力（Ｎ／２５ｍｍ）を測定した。得られた測定値を粘着力とした。結果を表２に示す。
(Measurement of adhesive strength of double-sided PSA sheet)
The double-sided pressure-sensitive adhesive sheet obtained above is cut into a size of 25 mm × 100 mm, the 38 μm-thick release PET film on one side of the double-sided pressure-sensitive adhesive sheet is peeled off, and a 50 μm-thick PET film with corona treatment applied to one side is reattached After that, the adhesive surface (measurement surface) was affixed to the test plate, and a 2 kg rubber roller (width: about 50 mm) was reciprocated once to produce a measurement sample. A glass plate was used as a test plate. The obtained sample for measurement is allowed to stand for 24 hours in an environment of 23 ° C. and 50% humidity, and subjected to a tensile test in the 180 ° direction at a peeling rate of 300 mm / min in accordance with JIS Z0237. The adhesive force (N / 25 mm) to was measured. The obtained measured value was defined as adhesive strength. The results are shown in Table 2.
（段差追従性評価）
上で得られた両面粘着シートの片面の３８μｍ厚の剥離ＰＥＴフィルムを剥がし、この両面粘着シートを、厚さ０．５ｍｍ、長さ５０ｍｍ、幅４０ｍｍのガラス板に、厚さ１５μｍ、幅５ｍｍで窓枠状に印刷された印刷付きガラス板に貼り合わせ、さらにもう一方の面の剥離ＰＥＴフィルムを剥がした後、厚さ０．５ｍｍ、長さ５０ｍｍ、幅４０ｍｍのガラス板との貼り合わせを行い、５気圧、７０℃、１０分の条件で加熱加圧処理を行い固定した後、段差部分の粘着層の浮きを目視で観察した。
(Step following ability evaluation)
The double-sided pressure-sensitive adhesive sheet obtained above was peeled off from one side of the 38 μm-thick release PET film, and this double-sided pressure-sensitive adhesive sheet was applied to a glass plate having a thickness of 0.5 mm, a length of 50 mm, and a width of 40 mm at a thickness of 15 μm and a width of 5 mm. After bonding to a glass plate with printing printed in the shape of a window frame, and then peeling off the peeled PET film on the other side, it is bonded to a glass plate having a thickness of 0.5 mm, a length of 50 mm, and a width of 40 mm. After fixing by heating and pressing under conditions of 5 atm and 70 ° C. for 10 minutes, the floating of the adhesive layer at the step portion was visually observed.
段差追従性の評価は、下記の基準で行なった。結果を表２に示す。
○；段差のある部分にて粘着層の浮きが確認されない状態
△；段差のある部分にて粘着層の僅かな浮きが確認された状態
×；段差のある部分にて粘着層の明かな浮きが確認された状態
The step following ability was evaluated according to the following criteria. The results are shown in Table 2.
○: The state in which the pressure-sensitive adhesive layer is not lifted at the stepped portion Δ: The state in which the pressure-sensitive adhesive layer is slightly lifted at the stepped portion ×: The pressure-sensitive adhesive layer is clearly lifted at the stepped portion Confirmed state
（ゲル分率測定）
得られた透明粘着シートを用いて、上で述べた方法により、ゲル分率を測定した。結果を表２に示す。
(Gel fraction measurement)
The gel fraction was measured by the method described above using the obtained transparent adhesive sheet. The results are shown in Table 2.
Claims (9)
（Ａ）（メタ）アクリル系樹脂６５〜８５質量％と、
（Ｂ）ポリオキシアルキレンポリオール１０〜３０質量％と、
（Ｃ）ポリイソシアネート１．０〜５．０質量％と、
（Ｄ）スズ系触媒０．００５〜０．１質量％と
を含み、酸価が０〜５ｍｇＫＯＨ／ｇであって、
（Ａ）（メタ）アクリル系樹脂の重量平均分子量が１０万〜６０万であり、且つ、（Ｂ）ポリオキシアルキレンポリオールの数平均分子量が５００〜１５００である透明粘着シート用組成物。 Solid content ratio
(A) (meth) acrylic resin 65-85 mass%,
(B) 10 to 30% by mass of a polyoxyalkylene polyol,
(C) 1.0 to 5.0% by mass of polyisocyanate;
(D) containing 0.005 to 0.1% by mass of a tin-based catalyst, having an acid value of 0 to 5 mgKOH / g,
(A) The composition for transparent adhesive sheets whose weight average molecular weight of (meth) acrylic-type resin is 100,000-600,000 and whose number average molecular weight of (B) polyoxyalkylene polyol is 500-1500.
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| JP2013100717A JP6091990B2 (en) | 2013-05-10 | 2013-05-10 | Composition for transparent adhesive sheet |
| KR1020140054013A KR102234826B1 (en) | 2013-05-10 | 2014-05-07 | Composition for transparent adhesive sheet |
| CN201410192772.XA CN104140775B (en) | 2013-05-10 | 2014-05-08 | Transparent pressure-sensitive adhesive sheet composition |
| TW103116391A TWI609937B (en) | 2013-05-10 | 2014-05-08 | Transparent adhesive sheet composition |
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| CN109313963B (en) * | 2016-06-10 | 2022-10-25 | 日东电工株式会社 | Transparent conductive film and touch panel |
| JP6759374B2 (en) * | 2018-02-05 | 2020-09-23 | 日東電工株式会社 | Adhesive sheet and adhesive sheet peeling method |
| CN117794740A (en) | 2021-08-05 | 2024-03-29 | 信越化学工业株式会社 | Article with water and oil repellent surface layer |
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| JP2005314476A (en) * | 2004-04-27 | 2005-11-10 | Nitto Denko Corp | Adhesive composition, adhesive sheet and surface-protective film |
| JP4562070B2 (en) * | 2004-05-14 | 2010-10-13 | 日東電工株式会社 | Adhesive composition, adhesive sheet, and surface protective film |
| JP5299804B2 (en) | 2004-08-03 | 2013-09-25 | 綜研化学株式会社 | Adhesive sheet for attaching metal |
| JP4531628B2 (en) * | 2004-09-16 | 2010-08-25 | 日東電工株式会社 | Adhesive composition, adhesive sheet, and surface protective film |
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| JP5210078B2 (en) * | 2008-07-31 | 2013-06-12 | ビッグテクノス株式会社 | Electrically peelable pressure-sensitive adhesive composition, electrically peelable adhesive product, and method for peeling |
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| JP4800363B2 (en) | 2008-09-26 | 2011-10-26 | 日東電工株式会社 | Adhesive sheet for bonding optical members |
| JP5277937B2 (en) | 2008-12-17 | 2013-08-28 | Ｄｉｃ株式会社 | Double-sided adhesive sheet for fixing transparent conductive film, transparent conductive film laminate, touch panel device |
| JP5580069B2 (en) * | 2009-02-26 | 2014-08-27 | 日東電工株式会社 | Adhesive composition for surface protective film and use thereof |
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| JP5725760B2 (en) * | 2010-08-19 | 2015-05-27 | 大同化成工業株式会社 | Acrylic polymer compounds used in pressure-sensitive adhesive compositions for touch panels |
| JP6097473B2 (en) * | 2010-12-13 | 2017-03-15 | 日東電工株式会社 | Optical film pressure-sensitive adhesive composition, optical film pressure-sensitive adhesive layer, pressure-sensitive adhesive optical film, and image display device |
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