JP5230879B2 - Adhesive products - Google Patents
Adhesive products Download PDFInfo
- Publication number
- JP5230879B2 JP5230879B2 JP2000300838A JP2000300838A JP5230879B2 JP 5230879 B2 JP5230879 B2 JP 5230879B2 JP 2000300838 A JP2000300838 A JP 2000300838A JP 2000300838 A JP2000300838 A JP 2000300838A JP 5230879 B2 JP5230879 B2 JP 5230879B2
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- polymer
- mass
- sensitive adhesive
- adhesive
- 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.)
- Expired - Lifetime
Links
- 230000001070 adhesive effect Effects 0.000 title description 110
- 239000000853 adhesive Substances 0.000 title description 99
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 104
- 229920000642 polymer Polymers 0.000 claims description 88
- 239000000178 monomer Substances 0.000 claims description 69
- 238000004132 cross linking Methods 0.000 claims description 41
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 33
- 239000003431 cross linking reagent Substances 0.000 claims description 31
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 27
- 230000008961 swelling Effects 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- 229920006037 cross link polymer Polymers 0.000 claims description 21
- 239000010410 layer Substances 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 11
- 239000002998 adhesive polymer Substances 0.000 claims description 10
- 239000012790 adhesive layer Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 8
- 239000005056 polyisocyanate Substances 0.000 claims description 7
- 229920001228 polyisocyanate Polymers 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 33
- 239000000203 mixture Substances 0.000 description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 26
- 239000000243 solution Substances 0.000 description 24
- 238000006116 polymerization reaction Methods 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 18
- -1 polyethylene terephthalate Polymers 0.000 description 18
- 229920006158 high molecular weight polymer Polymers 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 238000005259 measurement Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 14
- 239000000123 paper Substances 0.000 description 13
- 239000000758 substrate Substances 0.000 description 11
- 230000007423 decrease Effects 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- 239000003505 polymerization initiator Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 238000000691 measurement method Methods 0.000 description 5
- 230000000379 polymerizing effect Effects 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000002313 adhesive film Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 238000000045 pyrolysis gas chromatography Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 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 2
- 239000008096 xylene Substances 0.000 description 2
- 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
- NLBJAOHLJABDAU-UHFFFAOYSA-N (3-methylbenzoyl) 3-methylbenzenecarboperoxoate Chemical compound CC1=CC=CC(C(=O)OOC(=O)C=2C=C(C)C=CC=2)=C1 NLBJAOHLJABDAU-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- IEQWWMKDFZUMMU-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethyl)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)CCOC(=O)C=C IEQWWMKDFZUMMU-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
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- UXTGJIIBLZIQPK-UHFFFAOYSA-N 3-(2-prop-2-enoyloxyethyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(CCOC(=O)C=C)=C1C(O)=O UXTGJIIBLZIQPK-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-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
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-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
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000004849 alkoxymethyl 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
- 230000003712 anti-aging effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000007869 azo polymerization initiator Substances 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- HASGOCLZFTZSTN-UHFFFAOYSA-N cyclohexane;hexane Chemical compound CCCCCC.C1CCCCC1 HASGOCLZFTZSTN-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
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 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
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group 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
- 239000002655 kraft paper Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000005968 oxazolinyl group Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005507 spraying Methods 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
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000004448 titration Methods 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
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
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- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、凝集力と粘着力との両性能がバランスよく良好であり、しかも、糊残りを起こさずに被着体から剥離することのできる粘着製品およびそのような粘着製品に用いられる粘着剤に関するものである。 The present invention has a good balance between cohesive strength and adhesive strength, and can be peeled off from an adherend without causing adhesive residue, and an adhesive used in such an adhesive product It is about.
（メタ）アクリル酸アルキルエステルを主たる構成成分とするアクリル系粘着剤は、タック、粘着力、凝集力等の基本物性に加え、耐熱性、耐候性、耐水性、耐油性等に優れていることから、粘着ラベル、シート、テープ等の粘着製品に幅広く使用されている。 In addition to basic physical properties such as tack, adhesive strength, and cohesive strength, acrylic pressure-sensitive adhesives containing (meth) acrylic acid alkyl ester as the main constituent are excellent in heat resistance, weather resistance, water resistance, oil resistance, etc. Therefore, it is widely used for adhesive products such as adhesive labels, sheets and tapes.
一般的に、これらの粘着製品は、被着体に貼付した後は剥離されることがほとんどない永久接着型と、被着体に貼付した後に再び剥離することが想定される再剥離型に分類することができ、近年は、環境対応やリサイクルの必然性から、再剥離型粘着製品の使用量が増大している。 Generally, these adhesive products are classified into a permanent adhesive type that hardly peels after being applied to an adherend and a re-peelable type that is expected to be peeled again after being applied to an adherend. In recent years, the amount of re-peelable pressure-sensitive adhesive products used has increased due to environmental concerns and the necessity of recycling.
再剥離型粘着製品に用いられる粘着剤は、被着体に貼付されてから長時間経過した後であっても、糊残り等の被着体汚染を起こさずに、きれいに剥離できることが要求される。このため、例えば、永久接着型の粘着剤の架橋密度を上げる、あるいは、粘着剤用ポリマーのガラス転移温度を高める、といった手段で、凝集力の向上を図れば、糊残りがなくなって再剥離性が向上すると考えられる。しかし、これらの手段では、再剥離性は向上するが、粘着力が低下してしまうという問題があった。 Adhesives used for re-peelable adhesive products are required to be able to be peeled cleanly without causing adherend contamination such as glue residue even after a long time has passed since being applied to the adherend. . For this reason, for example, if the cohesive strength is improved by increasing the crosslink density of the permanent adhesive pressure sensitive adhesive or by increasing the glass transition temperature of the pressure sensitive adhesive polymer, the adhesive residue is eliminated and the removability is eliminated. Is thought to improve. However, with these means, the removability is improved, but there is a problem that the adhesive strength is reduced.
そこで、本発明者等は、再剥離性に優れた粘着剤を提供するため、糊残り現象の原因を追究した。その結果、被着体に残存するのは、下記に示すように、架橋度の低い低分子量のポリマーであることが見出された。 Accordingly, the present inventors have investigated the cause of the adhesive residue phenomenon in order to provide an adhesive having excellent removability. As a result, it was found that what remains in the adherend is a low molecular weight polymer having a low degree of crosslinking as shown below.
一般的に、２液タイプのアクリル系粘着剤用のポリマーは、ブチルアクリレートや２−エチルヘキシルアクリレートといったアルキル基の炭素数が４〜８の（メタ）アクリル酸アルキルエステル等の粘着性付与用モノマーと、アルコール性ＯＨ基（以下断りがない限りＯＨ基はアルコール性ＯＨ基を指す）を含有するモノマーと、凝集力向上成分となるＣＯＯＨ基含有モノマーとを共重合することによって製造されている。また、架橋剤には、イソシアネート基を有するポリイソシアネート化合物が用いられることが多い。そして、イソシアネート基との反応性を有するＯＨ基含有モノマーは、架橋密度が大きくならないようにその量が制限され、通常はＣＯＯＨ基含有モノマーよりも少なくなるように調整されている。 In general, a polymer for a two-component type acrylic pressure-sensitive adhesive is a tackifier such as (meth) acrylic acid alkyl ester having an alkyl group having 4 to 8 carbon atoms such as butyl acrylate and 2-ethylhexyl acrylate, and the like. It is produced by copolymerizing a monomer containing an alcoholic OH group (hereinafter, OH group indicates an alcoholic OH group unless otherwise specified) and a COOH group-containing monomer serving as a cohesive force improving component. Moreover, the polyisocyanate compound which has an isocyanate group is often used for a crosslinking agent. The amount of the OH group-containing monomer having reactivity with an isocyanate group is limited so that the crosslinking density does not increase, and is usually adjusted to be less than the COOH group-containing monomer.
上記モノマーを重合する際に、各モノマーを均一に混合して反応容器に添加すると、ＯＨ基含有モノマーの量がＣＯＯＨ基含有モノマーより少ないため、高分子量のポリマーにはＯＨ基があるが、低分子量のポリマーにはＯＨ基が少ないかまたは存在しないことになりがちである。しかし、イソシアネート基に対する反応性はＯＨ基の方がＣＯＯＨ基よりも高いので、ＯＨ基が存在する高分子量のポリマーが優先的に架橋して、低分子量ポリマーがＣＯＯＨ基を有していても架橋しない可能性が高い。このため、架橋されなかった低分子量ポリマーが、再剥離性評価等の際に「糊残り」として被着体に付着してしまうと考えられる。 When the monomers are polymerized, if the monomers are uniformly mixed and added to the reaction vessel, the amount of the OH group-containing monomer is less than that of the COOH group-containing monomer. Molecular weight polymers tend to have few or no OH groups. However, since the reactivity with respect to isocyanate groups is higher for OH groups than for COOH groups, high molecular weight polymers in which OH groups exist are preferentially crosslinked, and even if low molecular weight polymers have COOH groups, they are crosslinked. There is a high possibility of not. For this reason, it is considered that the low molecular weight polymer that has not been cross-linked adheres to the adherend as “adhesive residue” during re-peeling evaluation or the like.
このような低分子量ポリマーを含む粘着剤に対し、架橋剤の添加量を増やしていくと、低分子量ポリマー中のＣＯＯＨ基が関与する架橋反応が起こるため次第に糊残りが少なくなっていくが、高分子量ポリマーの架橋密度が高くなり過ぎて、粘着力（ピール値）が著しく低下してしまうという問題が、依然として残っている。 Increasing the amount of crosslinking agent added to such a pressure-sensitive adhesive containing a low molecular weight polymer causes a cross-linking reaction involving COOH groups in the low molecular weight polymer, and the adhesive residue gradually decreases. The problem remains that the crosslink density of the molecular weight polymer becomes too high and the adhesive strength (peel value) is significantly reduced.
そこで本発明では、カルボキシル基を架橋反応点とすることとし、どの程度架橋させれば粘着力が良好で再剥離性にも優れた粘着剤を得ることができるかを明確にして、再剥離性等の特性に優れた粘着製品を提供することを課題として掲げた。 Therefore, in the present invention, the carboxyl group is used as a cross-linking reaction point, and it is clarified how much pressure-sensitive adhesive can be obtained with good adhesive strength and re-peelability by re-releasability. It was raised as an issue to provide adhesive products with excellent properties such as.
本発明の粘着製品は、（メタ）アクリル酸アルキルエステルとカルボキシル基含有モノマーを必須的に含むモノマー成分から導かれる粘着剤用ポリマーが、架橋した状態で含まれている粘着層が形成された粘着製品であって、前記粘着層中の架橋ポリマーは、ゲル分率Ｘ（質量％）と膨潤度Ｙ（体積倍）が、下記式（１）を満足するところに要旨を有する。
Ｙ≦−（６．５／３）Ｘ＋（５３５／３） …（１）
ただし、Ｙ＞０，Ｘ＞０である。The pressure-sensitive adhesive product of the present invention is a pressure-sensitive adhesive layer in which a pressure-sensitive adhesive polymer derived from a monomer component containing a (meth) acrylic acid alkyl ester and a carboxyl group-containing monomer is contained in a crosslinked state. The crosslinked polymer in the pressure-sensitive adhesive layer is a product where the gel fraction X (mass%) and the degree of swelling Y (volume times) satisfy the following formula (1).
Y ≦ − (6.5 / 3) X + (535/3) (1)
However, Y> 0 and X> 0.
前記式（１）において、Ｙ＜８０であることがより好ましい。再剥離性に優れると共に、耐薬品性等の特性に優れるからである。 In the formula (1), it is more preferable that Y <80. It is because it is excellent in re-peelability and excellent characteristics such as chemical resistance.
架橋前の粘着剤用ポリマーの水酸基濃度は、ポリマー１ｇあたり０．０１ｍｍｏｌ（ミリモル）以下であることが好ましい。本発明では、カルボキシル基が架橋点となる架橋システムの構築を目指すものであるため、水酸基が少ない方が好ましいのである。 The hydroxyl group concentration of the pressure-sensitive adhesive polymer before crosslinking is preferably 0.01 mmol (mmol) or less per 1 g of the polymer. In this invention, since it aims at construction of the bridge | crosslinking system in which a carboxyl group becomes a crosslinking point, the one where there are few hydroxyl groups is preferable.
本発明には、（メタ）アクリル酸アルキルエステルとカルボキシル基含有モノマーを必須的に含むモノマー成分から導かれる粘着剤用ポリマーを含有する粘着剤であって、前記粘着剤用ポリマーに対し、１分子中にイソシアネート基を２個有する架橋剤を特定条件で反応させて架橋ポリマーとなした場合に、この架橋ポリマーにおけるゲル分率Ｇ（質量％）が５５〜７５％、膨潤度Ｓ（体積倍）が１５〜４０である粘着剤も含まれる。 The present invention is a pressure-sensitive adhesive containing a pressure-sensitive adhesive polymer derived from a monomer component essentially containing a (meth) acrylic acid alkyl ester and a carboxyl group-containing monomer, and one molecule for the pressure-sensitive adhesive polymer When a cross-linking agent having two isocyanate groups is reacted under specific conditions to form a cross-linked polymer, the gel fraction G (% by mass) in this cross-linked polymer is 55 to 75%, and the degree of swelling S (volume times) Also included is a pressure sensitive adhesive of 15 to 40.
また、本発明の粘着剤と、カルボキシル基と反応し得る官能基を２個以上持つ架橋剤とを含む粘着剤組成物を、５０μｍのポリエチレンテレフタレートフィルム上に乾燥後の厚さが２５μｍとなるように塗布し、加熱して架橋反応を終了させて粘着フィルムとなしたとき、ステンレス鋼板に対する２３℃、相対湿度６５％での１８０°剥離粘着力が２．０Ｎ／ｃｍ以上であることが好ましい。 Further, the pressure-sensitive adhesive composition containing the pressure-sensitive adhesive of the present invention and a cross-linking agent having two or more functional groups capable of reacting with a carboxyl group is dried on a 50 μm polyethylene terephthalate film so that the thickness becomes 25 μm. When the film is coated and heated to finish the crosslinking reaction to form an adhesive film, the 180 ° peel adhesive strength at 23 ° C. and 65% relative humidity to the stainless steel plate is preferably 2.0 N / cm or more.
前記したように、低分子量ポリマーにはＯＨ基が存在しないことが多く、このため、ＯＨ基を架橋点とする架橋システムでは、低分子量ポリマーが未架橋のまま残存し、糊残りの原因になる。そこで、本発明者等は、粘着剤用ポリマーのＣＯＯＨ基を架橋点として利用することを考えた。すなわち、ＣＯＯＨ基を架橋点とするとＯＨ基を架橋点とする場合に比べ架橋反応が進み過ぎることがないため、ＣＯＯＨ基含有モノマーはＯＨ基含有モノマーよりも多量に使用することができ、この結果、高分子量ポリマーにも低分子量ポリマーにも比較的均一に導入されて、低分子量ポリマーも架橋させることができると考えられる。 As described above, OH groups often do not exist in low molecular weight polymers. For this reason, in a cross-linking system using OH groups as cross-linking points, low molecular weight polymers remain uncrosslinked and cause glue residue. . Therefore, the present inventors considered using the COOH group of the adhesive polymer as a crosslinking point. That is, if the COOH group is used as a crosslinking point, the crosslinking reaction does not proceed excessively as compared with the case where the OH group is used as a crosslinking point, so that the COOH group-containing monomer can be used in a larger amount than the OH group-containing monomer. It is considered that the low molecular weight polymer can be cross-linked by being introduced relatively uniformly into the high molecular weight polymer and the low molecular weight polymer.
そこで、粘着剤用ポリマーに導入すべきＣＯＯＨ基の量と架橋剤量を種々検討した結果、下記条件で測定される架橋ポリマーのゲル分率Ｘ（質量％）と膨潤度Ｙ（体積倍）とが次の関係式を満足するものが、粘着力が良好で再剥離性にも優れたものであることを見出し、本発明に想到した。
Ｙ≦−（６．５／３）Ｘ＋（５３５／３） …（１）
ただし、Ｙ＞０，Ｘ＞０である。Therefore, as a result of various investigations on the amount of COOH groups to be introduced into the adhesive polymer and the amount of the crosslinking agent, the gel fraction X (mass%) and the swelling degree Y (volume times) of the crosslinked polymer measured under the following conditions: However, it has been found that those satisfying the following relational expression have good adhesive strength and excellent removability, and have arrived at the present invention.
Y ≦ − (6.5 / 3) X + (535/3) (1)
However, Y> 0 and X> 0.
・ゲル分率Ｘ（質量％）：架橋ポリマー約０．２ｇを精密に秤量した後、秤量した架橋ポリマーを、５０ｍｌのテトラヒドロフランに２４時間浸漬する。この液を＃２００メッシュ金網で濾過し、金網上に残存したゲルを集めて、１５０℃で１時間乾燥させ、乾燥後の質量を精密に秤量し、下記式に基づいてゲル分率Ｘ（質量％）を求める：
ゲル分率Ｘ（質量％）＝１００×［ゲルを乾燥した後の質量／溶解前の架橋ポリマーの質量］Gel fraction X (mass%): After about 0.2 g of the crosslinked polymer was accurately weighed, the weighed crosslinked polymer was immersed in 50 ml of tetrahydrofuran for 24 hours. This liquid is filtered through a # 200 mesh wire mesh, the gel remaining on the wire mesh is collected, dried at 150 ° C. for 1 hour, the dried mass is accurately weighed, and the gel fraction X (mass %):
Gel fraction X (mass%) = 100 × [mass after drying gel / mass of crosslinked polymer before dissolution]
・膨潤度Ｙ（体積倍）：１０ｍｍ×２５ｍｍ×１００μｍの架橋ポリマー試験片を５０ｍｌのテトラヒドロフランに２４時間浸漬する。テトラヒドロフラン中から、試料片を離型紙上に取り出して、長辺および短辺の長さを測定する。浸漬前の試料片の長辺および短辺の長さに対する倍率をそれぞれ算出して平均し、この平均倍率を３棄して膨潤度（体積倍）とする。なお、膨潤度は試料片の長辺、短辺の長さを基準にして、浸漬前後の長さの変化倍率で算出するため、試料片の厚みは特に限定されないが、膨潤度合いに影響を及ぼすことも考えられるため、１００μｍとしている。 Swelling degree Y (volume ratio): A 10 mm × 25 mm × 100 μm cross-linked polymer test piece is immersed in 50 ml of tetrahydrofuran for 24 hours. A sample piece is taken out from tetrahydrofuran on a release paper, and the lengths of the long side and the short side are measured. The magnification with respect to the length of the long side and the short side of the sample piece before immersion is calculated and averaged, and this average magnification is discarded to obtain the degree of swelling (volume times). In addition, since the degree of swelling is calculated by the change rate of the length before and after immersion based on the length of the long side and the short side of the sample piece, the thickness of the sample piece is not particularly limited, but affects the degree of swelling. This is considered to be 100 μm.
図１に、種々の共重合組成で、種々の架橋条件の架橋ポリマーについて上記方法でゲル分率Ｘと膨潤度Ｙを測定した結果を示した。粘着特性が良好なもの（●）とそうでないもの（▲）は、Ｙ＝−（６．５／３）Ｘ＋（５３５／３）で示される直線で分けられることが分かる。なお粘着特性（測定方法・評価方法等は実施例で詳述）については、初期粘着力が２Ｎ／ｃｍ以上であり、かつ、加熱７日後の破壊状態が凝集破壊（ＣＦ）でないもの（ＳＦ、ＴＦ、Ｃ）を良好なものとして示した。 FIG. 1 shows the results of measuring the gel fraction X and the swelling degree Y by the above-mentioned method for crosslinked polymers having various copolymerization compositions and various crosslinking conditions. It can be seen that those having good adhesive properties (●) and those having no good (▲) are separated by a straight line represented by Y = − (6.5 / 3) X + (535/3). Regarding the adhesive properties (measurement method / evaluation method and the like are described in detail in Examples), the initial adhesive strength is 2 N / cm or more, and the fracture state after heating 7 days is not cohesive failure (CF) (SF, TF, C) was shown as good.
ゲル分率Ｘ（質量％）と膨潤度Ｙ（体積倍）が上記式を満足する架橋ポリマー、すなわち、Ｙ＝−（６．５／３）Ｘ＋（５３５／３）で示される直線と、Ｙ＝０およびＸ＝０の３本の直線で囲まれた領域（斜線部）に存在する架橋ポリマーを含む粘着層が形成されている粘着製品が、本発明に包含される粘着製品である。なお、粘着製品の粘着層には、粘着付与剤やその他の添加剤が含まれていることがあるが、ゲル分率Ｘの測定では溶剤と共に除去されるので、測定値には影響を及ぼさない。また、本発明では、ホモポリマーはもとより、コポリマー、ターポリマー等の２元以上の共重合体を含めて「ポリマー」と表現している。 A crosslinked polymer having a gel fraction X (mass%) and a degree of swelling Y (volume times) satisfying the above formula, that is, a straight line represented by Y = − (6.5 / 3) X + (535/3), and Y A pressure-sensitive adhesive product in which a pressure-sensitive adhesive layer containing a crosslinked polymer existing in a region (shaded portion) surrounded by three straight lines of = 0 and X = 0 is formed is a pressure-sensitive adhesive product included in the present invention. The pressure-sensitive adhesive layer of the pressure-sensitive adhesive product may contain a tackifier and other additives, but it is removed together with the solvent in the measurement of the gel fraction X, so it does not affect the measured value. . In the present invention, the term “polymer” includes not only homopolymers but also two or more copolymers such as copolymers and terpolymers.
架橋ポリマーのゲル分率Ｘ（質量％）と膨潤度Ｙ（体積倍）が上記式を満足しないもの、すなわち図１の斜線部以外のところにプロットされる粘着剤用ポリマーは、架橋後の再剥離性に劣るか、粘着力が低いため好ましくない。 The cross-linked polymer gel fraction X (mass%) and the degree of swelling Y (volume times) that do not satisfy the above formula, that is, the pressure-sensitive adhesive polymer plotted other than the shaded area in FIG. Since it is inferior in peelability or has low adhesive strength, it is not preferable.
Ｙは８０以下が好ましく、Ｘは４０以上が好ましい。膨潤度Ｙが８０を超えるものあるいはゲル分率Ｘが４０未満のものは糊残りが多くなって再剥離性が低下する傾向にあるからである。また、Ｙは１０以上が、Ｘは７５以下が好ましい。Ｙが１０未満のものやＸが７５を超えるものは、架橋し過ぎとなり、粘着剤としたときの粘着力が低下する傾向にあるからである。Ｙ≧−（６．５／３）Ｘ＋１４０であることも、粘着特性の点から好ましい。すなわち、１０≦Ｙ≦８０、４０≦Ｘ≦７５、Ｙ≦−（６．５／３）Ｘ＋（５３５／３）、Ｙ≧−（６．５／３）Ｘ＋１４０、という各条件で規定される好ましい領域を図２に示した。この範囲にプロットされる架橋ポリマーは、凝集力と粘着力のバランスに一層優れている。Ｘの下限は４５がより好ましく、５５が最も好ましい。Ｙの上限は７０がより好ましく、６０が最も好ましい。 Y is preferably 80 or less, and X is preferably 40 or more. This is because when the swelling degree Y exceeds 80 or the gel fraction X is less than 40, the adhesive residue tends to increase and the removability tends to decrease. Y is preferably 10 or more and X is preferably 75 or less. This is because when Y is less than 10 or X exceeds 75, crosslinking is excessive and the adhesive strength when used as an adhesive tends to decrease. Y ≧ − (6.5 / 3) X + 140 is also preferable from the viewpoint of adhesive properties. That is, it is defined by the following conditions: 10 ≦ Y ≦ 80, 40 ≦ X ≦ 75, Y ≦ − (6.5 / 3) X + (535/3), Y ≧ − (6.5 / 3) X + 140. A preferred region is shown in FIG. Crosslinked polymers plotted in this range are more excellent in the balance between cohesive strength and adhesive strength. As for the minimum of X, 45 is more preferable and 55 is the most preferable. The upper limit of Y is more preferably 70, and 60 is most preferable.
上記図１、図２においては、架橋剤の量や反応条件は問われず、架橋後のポリマーのゲル分率Ｘと膨潤度Ｙが、各図で示される領域に含まれれば、本発明の範囲に含まれる。 In FIG. 1 and FIG. 2, the amount of the crosslinking agent and the reaction conditions are not limited, and the gel fraction X and the swelling degree Y of the polymer after crosslinking are included in the regions shown in the respective drawings. include.
本発明では、特定のイソシアネート系架橋剤を用い、一定条件で一定量架橋させたときの粘着剤用ポリマーについても、ゲル分率Ｇと膨潤度Ｓの好ましい範囲を見出している。すなわち、本発明の粘着剤用ポリマーは、下記条件で架橋させたときに、ゲル分率Ｇ：５５〜７５％でかつ膨潤度Ｓ：１５〜４０を示すものである。なお、ゲル分率Ｇ、膨潤度Ｓは、それぞれゲル分率Ｘ、膨潤度Ｙと同じ測定方法で求められる。 In the present invention, the preferred range of the gel fraction G and the degree of swelling S is also found for the pressure-sensitive adhesive polymer when a specific isocyanate-based crosslinking agent is used and a certain amount of crosslinking is performed under a certain condition. That is, the polymer for pressure-sensitive adhesives of the present invention exhibits a gel fraction G of 55 to 75% and a swelling degree S of 15 to 40 when crosslinked under the following conditions. The gel fraction G and the degree of swelling S are determined by the same measurement method as the gel fraction X and the degree of swelling Y, respectively.
・架橋条件：粘着剤用ポリマー１ｇに対し、コロネートＬ−５５Ｅ（日本ポリウレタン工業製；「コロネート」は登録商標）を０．０７５ｇ（ウエット）となるように溶剤の存在下で混合して架橋前ポリマー混合物を作り、この混合物を離型紙上に乾燥後の厚みが１００μｍになるように塗工して、２３℃、相対湿度６５％の雰囲気下で１週間養生することにより、架橋ポリマーを得る。 ・ Crosslinking conditions: Coronaate L-55E (manufactured by Nippon Polyurethane Industry; “Coronate” is a registered trademark) is mixed in the presence of a solvent so as to be 0.075 g (wet) with respect to 1 g of the polymer for pressure-sensitive adhesive. A polymer mixture is prepared, and this mixture is coated on a release paper so that the thickness after drying is 100 μm, and is cured under an atmosphere of 23 ° C. and a relative humidity of 65% for 1 week to obtain a crosslinked polymer.
上記架橋条件は、種々の粘着剤用ポリマーについて同条件で架橋度合いを調べてゲル分率Ｇと膨潤度Ｓの好ましい範囲を導くことによって、適切な条件で架橋したときに良好な粘着特性を発現することのできる粘着剤用ポリマーを見出すために設定されており、架橋剤の量は、粘着剤組成物として最適な架橋剤量ではない。すなわちゲル分率Ｇと膨潤度Ｓは、優れた粘着特性を示す粘着剤用ポリマーを選定するときの目安である。なお、粘着剤用ポリマーに対する最適架橋剤量は後で詳しく説明する。上記架橋条件で架橋したポリマーのゲル分率Ｇが５５未満のものあるいは膨潤度Ｓが４０を超えるものは、糊残りが多くなって再剥離性が低下する傾向にあり、また、Ｇが７５を超えるものやＳが１５未満のものは、粘着剤としたときの粘着力が低下する傾向にあるからである。 The above cross-linking conditions show good adhesive properties when cross-linking under appropriate conditions by examining the degree of cross-linking under the same conditions for various pressure-sensitive adhesive polymers and deriving preferable ranges of gel fraction G and swelling degree S. It is set to find an adhesive polymer that can be used, and the amount of the crosslinking agent is not the optimum amount of the crosslinking agent for the adhesive composition. That is, the gel fraction G and the degree of swelling S are guidelines when selecting a pressure-sensitive adhesive polymer that exhibits excellent adhesive properties. The optimum amount of the crosslinking agent for the adhesive polymer will be described in detail later. When the gel fraction G of the polymer cross-linked under the above-mentioned cross-linking conditions is less than 55 or the degree of swelling S exceeds 40, the adhesive residue tends to increase and the re-peelability tends to decrease. This is because when the amount exceeds S or when S is less than 15, the adhesive strength of the pressure-sensitive adhesive tends to decrease.
粘着剤用ポリマーを形成するために用いられるモノマー成分としてほ、粘着力を発現させるための（メタ）アクリル酸アルキルエステルと、架橋点となるＣＯＯＨ基含有モノマーとが必須成分として挙げられる。 As monomer components used for forming a polymer for pressure-sensitive adhesives, (meth) acrylic acid alkyl esters for developing adhesive force and COOH group-containing monomers serving as crosslinking points can be mentioned as essential components.
（メタ）アクリル酸アルキルエステルとしては、アルキル基の炭素数が１〜１２のものが好ましく、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸ｎ−オクチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸ステアリル等が挙げられる。これらは１種または２種以上を用いることができる。粘着特性を考慮すれば、モノマー成分１００質量％中の（メタ）アクリル酸アルキルエステル類の含有量を、７０〜９９．９質量％とすることが好ましい。９９．９質量％を超えると、ＣＯＯＨ基含有モノマー量が少なくなって、充分架橋させることができない恐れがある。 As the (meth) acrylic acid alkyl ester, those having 1 to 12 carbon atoms in the alkyl group are preferable. For example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) Isobutyl acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, etc. Is mentioned. These can use 1 type (s) or 2 or more types. Considering the adhesive properties, the content of (meth) acrylic acid alkyl esters in 100% by mass of the monomer component is preferably 70 to 99.9% by mass. If it exceeds 99.9% by mass, the amount of the COOH group-containing monomer is decreased, and there is a possibility that it cannot be sufficiently crosslinked.
ＣＯＯＨ基含有モノマーの具体例としては、（メタ）アクリル酸、イタコン酸、クロトン酸、無水マレイン酸、マレイン酸、２−アクリロイルオキシエチルコハク酸、２−アクリロイルオキシエチルフタル酸、２−アクリロイルオキシエチルヘキサヒドロフタル酸等が挙げられる。これらは１種または２種以上を用いることができる。中でも、（メタ）アクリル酸が好ましい。ＣＯＯＨ基含有モノマーは、０．１〜１５質量％用いることが好ましい。０．１質量％より少ないと、架橋が不充分となって再剥離性を向上させることが難しい。しかし、１５質量％を超えて用いると、耐水性が低下していくため好ましくない。粘着剤用ポリマー１ｇ当たりのＣＯＯＨ基濃度で示すと、０．１〜２ｍｍｏｌが好ましい範囲である。 Specific examples of the COOH group-containing monomer include (meth) acrylic acid, itaconic acid, crotonic acid, maleic anhydride, maleic acid, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, and 2-acryloyloxyethyl. And hexahydrophthalic acid. These can use 1 type (s) or 2 or more types. Of these, (meth) acrylic acid is preferred. It is preferable to use 0.1 to 15% by mass of the COOH group-containing monomer. When it is less than 0.1% by mass, crosslinking is insufficient and it is difficult to improve the removability. However, if it exceeds 15% by mass, the water resistance is lowered, which is not preferable. In terms of the COOH group concentration per gram of the pressure-sensitive adhesive polymer, 0.1 to 2 mmol is a preferable range.
粘着剤用ポリマーを形成するためのモノマー成分には、さらに、アクリロニトリルが含まれていることが好ましい。粘着剤の凝集力が向上し、保持力、再剥離性等の特性が良好となる。この効果を発現させるためには、モノマー成分中、アクリロニトリルを１質量％以上用いることが好ましい。より好ましい下限は２質量％である。ただしあまり多く用いると粘着力が低下するので上限は１０質量％に抑えることが好ましい。より好ましい上限は８質量％である。 It is preferable that the monomer component for forming the polymer for pressure-sensitive adhesives further contains acrylonitrile. The cohesive force of the pressure-sensitive adhesive is improved, and properties such as holding power and removability are improved. In order to express this effect, it is preferable to use 1% by mass or more of acrylonitrile in the monomer component. A more preferred lower limit is 2% by mass. However, if the amount is too much, the adhesive strength decreases, so the upper limit is preferably suppressed to 10% by mass. A more preferred upper limit is 8% by mass.
上記モノマー成分には、その他のモノマーが含まれていてもよい。その他のモノマーの具体例としては、スチレン、α−メチルスチレン等の芳香族系モノマー；酢酸ビニル、プロピオン酸ビニル等のビニルエステル；Ｎ−ビニルピロリドン、アクリロイルモルホリン等のＮ基含有モノマー；メタクリロニトリル；（メタ）アクリルアミド、Ｎ−メチロールアクリルアミド等のアミド系モノマー等が挙げられるが、特に限定されるものではない。これらのその他のモノマーは、モノマー成分中０〜２０質量％とすることが好ましい。２０質量％を超えると、粘着剤用ポリマーのＴｇが上がって硬くなるので、粘着力・耐反発性等の特性が低下するため好ましくない。 The monomer component may contain other monomers. Specific examples of other monomers include aromatic monomers such as styrene and α-methylstyrene; vinyl esters such as vinyl acetate and vinyl propionate; N group-containing monomers such as N-vinylpyrrolidone and acryloylmorpholine; methacrylonitrile Amide monomers such as (meth) acrylamide and N-methylol acrylamide, and the like can be mentioned, but are not particularly limited. These other monomers are preferably 0 to 20% by mass in the monomer component. If it exceeds 20% by mass, the Tg of the polymer for pressure-sensitive adhesives will increase and become hard, which is not preferable because properties such as adhesive strength and repulsion resistance will decrease.
さらに、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸３−ヒドロキシプロピル、（メタ）アクリル酸２−ヒドロキシプロピル、（メタ）アクリル酸４−ヒドロキシブチル、（メタ）アクリル酸２−ヒドロキシエチルのポリカプロラクトン変性物である「プラクセルＦ」シリーズ（ダイセル化学工業社製）等のＯＨ基含有モノマーを少量であれば用いてもよい。 Furthermore, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy (meth) acrylate An OH group-containing monomer such as “Placcel F” series (manufactured by Daicel Chemical Industries), which is a modified polycaprolactone of ethyl, may be used in a small amount.
ただし、本発明ではＣＯＯＨ基を用いて架橋を行うものであるため、原則としてＯＨ基は不要である。さらに、例えば、イソシアネート基含有架橋剤を使用する場合には、ＯＨ基がＣＯＯＨ基よりも先にイソシアネート基と反応してしまうので、低分子量ポリマーを架橋させるという本発明の目的を達成するためには、ＯＨ基は少ないほうが好ましい。従って、ポリマー１ｇ中のＯＨ基の濃度が、平均で、０．０１ｍｍｏｌ（ミリモル）以下となるように、ＯＨ基含有モノマー量を調整することが好ましい。特に、粘着力発生に寄与する高分子量ポリマー側にＯＨ基があると、高分子量ポリマーの架橋反応に架橋剤が消費されて、低分子量ポリマーを架橋させようとする本発明の目的を達成するために好ましくないので、高分子量ポリマーのＯＨ基の量は０．０１ｍｍｏｌ／ｇ以下にすることが推奨される。なお、本発明における「高分子量ポリマー」とは、ポリスチレン標準試料換算の分子量をゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いて測定したとき、重量平均分子量が１７．６×１０4以上のものをいう。However, in the present invention, since crosslinking is performed using COOH groups, OH groups are not necessary in principle. Furthermore, for example, when an isocyanate group-containing crosslinking agent is used, the OH group reacts with the isocyanate group before the COOH group, so that the object of the present invention for crosslinking a low molecular weight polymer is achieved. The number of OH groups is preferably small. Therefore, it is preferable to adjust the amount of the OH group-containing monomer so that the average concentration of OH groups in 1 g of the polymer is 0.01 mmol (mmol) or less. In particular, when an OH group is present on the high molecular weight polymer side that contributes to the generation of adhesive force, the crosslinking agent is consumed in the crosslinking reaction of the high molecular weight polymer, thereby achieving the object of the present invention to crosslink the low molecular weight polymer. Therefore, it is recommended that the amount of OH groups in the high molecular weight polymer be 0.01 mmol / g or less. The “high molecular weight polymer” in the present invention means a polymer having a weight average molecular weight of 17.6 × 10 4 or more when the molecular weight in terms of polystyrene standard sample is measured using gel permeation chromatography (GPC). .
ＯＨ基濃度は、粘着剤用ポリマー溶液からエバポレーター等で溶媒を除去し、後に残ったポリマー、あるいはＧＰＣを用いて分取した高分子量ポリマーについて、熱分解ガスクロマトグラフ質量分析計（熱分解ＧＣ／ＭＳと省略する）を用いて熱分解する方法等を利用して求めることができる。滴定等の公知の方法を用いてもよい。 The OH group concentration was determined using a pyrolysis gas chromatograph mass spectrometer (pyrolysis GC / MS) for the polymer remaining after removal of the adhesive polymer solution with an evaporator or the like, or for the high molecular weight polymer fractionated using GPC. And the like, and the like, and the like. A known method such as titration may be used.
本発明で用いたＧＰＣによる分取条件および熱分解ＧＣ／ＭＳの測定条件は以下の通りである。 The preparative conditions by GPC used in the present invention and the measurement conditions for pyrolysis GC / MS are as follows.
［ＧＰＣによる分取条件］
ＧＰＣ測定装置：Liquid Chromatography Model 510（Waters社製）
検出器：M410示差屈折計
カラム：Ultra Styragel Linear（１９ｍｍ×３０ｃｍ）
Ultra Styragel 100A（１９ｍｍ×３０ｃｍ）
Ultra Styragel 500A（１９ｍｍ×３０ｃｍ）
溶媒：ＴＨＦ
試料濃度は１％、注入量は２０００マイクロリットル／回とした。[Preparation conditions by GPC]
GPC measuring device: Liquid Chromatography Model 510 (manufactured by Waters)
Detector: M410 differential refractometer Column: Ultra Styragel Linear (19 mm x 30 cm)
Ultra Styragel 100A (19mm x 30cm)
Ultra Styragel 500A (19mm x 30cm)
Solvent: THF
The sample concentration was 1%, and the injection amount was 2000 microliters / time.
［熱分解ＧＣ／ＭＳの測定条件］
ＧＣ／ＭＳ測定装置：ＱＰ−５０００（島津製作所製）
キャピラリーカラム：ＤＢ−１（長さ３０ｍ×内径０．２５８ｍｍ：J&W SCIENTIFIC社製）（非極性タイプ）
ＤＢ−ＷＡＸ（長さ３０ｍ×内径０．２５８ｍｍ：J&W SCIENTIFIC社製）（極性タイプ）
熱分解装置：キューリーポイントパイロライザー ＪＰＳ−３３０（日本分析工業社製）
熱分解温度・時間：５９０℃×５秒間。[Measurement conditions for pyrolysis GC / MS]
GC / MS measuring device: QP-5000 (manufactured by Shimadzu Corporation)
Capillary column: DB-1 (length 30m x inner diameter 0.258mm: manufactured by J & W SCIENTIFIC) (nonpolar type)
DB-WAX (length 30m x inner diameter 0.258mm: J & W SCIENTIFIC) (polar type)
Pyrolysis device: Curie point pyrolyzer JPS-330 (manufactured by Nippon Analytical Industrial Co., Ltd.)
Thermal decomposition temperature / time: 590 ° C. × 5 seconds.
粘着剤用ポリマーを合成する際には、（メタ）アクリル酸グリシジル、脂環エポキシ基含有モノマーである「サイクロマー」シリーズ（ダイセル化学工業社製）、（メタ）アクリル酸メチルグリシジル等のエポキシ基含有モノマー；（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸ジエチルアミノエチル、ジメチルアミノプロピル（メタ）アクリルアミド等のアミノ基含有モノマー；等を少量であれば使用してもよい。なお、反応性を有する２種類以上の官能基を同一の粘着剤用ポリマー中に導入すると、ゲル化の原因となるので好ましくない。互いに反応性のない２種以上の官能基であれば、併存可能である。 When synthesizing polymers for pressure-sensitive adhesives, epoxy groups such as glycidyl (meth) acrylate, “cyclomer” series (manufactured by Daicel Chemical Industries) that are alicyclic epoxy group-containing monomers, and methyl glycidyl (meth) acrylate Containing monomers; amino group-containing monomers such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide; In addition, it is not preferable to introduce two or more types of functional groups having reactivity into the same polymer for pressure-sensitive adhesives because it causes gelation. Two or more functional groups that are not reactive with each other can coexist.
本発明で用いられる粘着剤用ポリマーは、常温で粘着性を有していることが好ましく、タックおよび粘着力のバランスの観点から、重合後のポリマーのガラス転移温度（Ｔｇ）が−６５℃〜−３０℃になるように、上記例示したモノマーを選択することが好ましい。ＴｇはＤＳＣ（示差走査熱量測定装置）、ＤＴＡ（示差熱分析装置）、ＴＭＡ（熱機械測定装置）によって求めることができる。また、ホモポリマーのＴｇ（Ｋ）と、モノマーの重量分率等から求められる計算値を目安にしてもよい。 The polymer for pressure-sensitive adhesives used in the present invention preferably has pressure-sensitive adhesive properties at room temperature, and the glass transition temperature (Tg) of the polymer after polymerization is from −65 ° C. to the balance of tack and adhesive strength. It is preferable to select the monomers exemplified above so that the temperature becomes −30 ° C. Tg can be determined by DSC (Differential Scanning Calorimetry), DTA (Differential Thermal Analysis), and TMA (Thermomechanical Measurement). Moreover, you may use the calculated value calculated | required from Tg (K) of a homopolymer, the weight fraction of a monomer, etc. as a standard.
モノマー成分を重合するに際しては、従来公知の重合方法を採用することができ、その重合方法は特に限定されない。例えば、溶液重合法やバルク重合法等を用いることができ、工業的には溶液重合法が好ましい。溶液重合法は、重合時の重合熱の除去が容易であり、操業性が良いからである。 In polymerizing the monomer component, a conventionally known polymerization method can be employed, and the polymerization method is not particularly limited. For example, a solution polymerization method or a bulk polymerization method can be used, and the solution polymerization method is preferred industrially. This is because the solution polymerization method is easy to remove the polymerization heat during polymerization and has good operability.
溶液重合法やバルク重合法では、残存モノマーを減らすために、ブースターと呼ばれる後添加重合開始剤を添加することが好ましい。このブースター添加時に添加されるモノマー以外のモノマー成分を一括仕込みで重合する方法と、モノマーを滴下しながら重合する方法、一部を一括で仕込んでおき、残りのモノマーを滴下しながら重合する方法等、いずれも採用できる。一括仕込みで重合する場合、重合開始剤は最初の仕込みのときおよびブースターとして添加するとき以外、重合系に加えないようにすることが好ましい。粘着力発現に有効な高分子量のポリマーを生成するためである。モノマー滴下の際は、反応容器中のモノマーと重合開始剤の比率をなるべく一定にするために、モノマーと重合開始剤の混合物を滴下することが好ましい。 In the solution polymerization method and the bulk polymerization method, it is preferable to add a post-addition polymerization initiator called a booster in order to reduce the residual monomer. A method of polymerizing monomer components other than the monomer added at the time of booster addition, a method of polymerizing while dropping monomers, a method of polymerizing while charging a part of the monomers and dropping the remaining monomers, etc. Any of them can be adopted. When polymerizing by batch charging, it is preferable not to add the polymerization initiator to the polymerization system except for the initial charging and when adding as a booster. This is to produce a high molecular weight polymer that is effective in developing adhesive strength. In dropping the monomer, it is preferable to drop a mixture of the monomer and the polymerization initiator in order to make the ratio of the monomer and the polymerization initiator in the reaction vessel as constant as possible.
重合開始剤としては、メチルエチルケトンパーオキサイド、ベンゾイルパーオキサイド、ジクミルパーオキサイド、ｔ−ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、ｔ−ブチルパーオキシオクトエート、ｔ−ブチルパーオキシベンゾエート、ラウロイルパーオキサイド、商品名「ナイパーＢＭＴ−Ｋ４０」（日本油脂社製；ｍ−トルオイルパーオキサイドとベンゾイルパーオキサイドの混合物）等の有機過酸化物や、アゾビスイソブチロニトリル、商品名「ＡＢＮ−Ｅ」［日本ヒドラジン工業：２，２’−アゾビス（２−メチルブチロニトリル）］等のアゾ系化合物等の公知のものを利用することができる。重合開始剤は、ブースター添加前においては反応容器内のモノマーの質量に対して、０．０１〜１質量％となるように使用することが好ましい。あまり多いと、所望とする高分子量のポリマーが得られない。なお、粘着特性の点から、粘着剤用ポリマー全体としての重量平均分子量Ｍｗは４０万以上が好ましく、６０万以上がより好ましく、７０万以上がさらに好ましい。 As the polymerization initiator, methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxy octoate, t-butyl peroxy benzoate, lauroyl peroxide, Organic peroxides such as trade name “Niper BMT-K40” (manufactured by NOF Corporation; mixture of m-toluoyl peroxide and benzoyl peroxide), azobisisobutyronitrile, trade name “ABN-E” [ Nippon Hydrazine Kogyo: Known compounds such as azo compounds such as 2,2′-azobis (2-methylbutyronitrile)] can be used. The polymerization initiator is preferably used so as to be 0.01 to 1% by mass relative to the mass of the monomer in the reaction vessel before the booster is added. If the amount is too large, a desired high molecular weight polymer cannot be obtained. In addition, from the point of adhesive property, the weight average molecular weight Mw as the whole adhesive polymer is preferably 400,000 or more, more preferably 600,000 or more, and further preferably 700,000 or more.
ブースターとなる後添加用の重合開始剤は、反応容器内の残存モノマーの質量（重合率の測定等から導くことができる）に対して、重合開始剤の質量が１〜１０質量％となるように使用することが好ましい。ブースターが少な過ぎると、残存モノマーのポリマーへの転化率が小さくて、最終ポリマー中にモノマーが残留してしまう。ブースターが多すぎると、低分子量ポリマーというよりもオリゴマーレベルの生成物が多数出来てしまい、ＣＯＯＨ基を利用した架橋システムでもって架橋させても、糊残りを起こさなくなるだけの分子量のポリマーにすることができず、再剥離性に劣ることとなる。 The post-addition polymerization initiator serving as a booster is such that the mass of the polymerization initiator is 1 to 10% by mass with respect to the mass of the residual monomer in the reaction vessel (which can be derived from measurement of the polymerization rate, etc.). It is preferable to use for. If the booster is too small, the conversion rate of the remaining monomer to the polymer is small, and the monomer remains in the final polymer. If there are too many boosters, there will be many oligomer-level products rather than low molecular weight polymers, and the polymer should have a molecular weight that will not cause adhesive residue even if it is crosslinked with a crosslinking system using COOH groups. Cannot be removed and the removability is poor.
溶液重合で用いられる溶媒としては、具体的には、例えば、トルエン、キシレン等の芳香族炭化水素類；酢酸エチル、酢酸ブチル等の脂肪族エステル類；シクロヘキサン等の脂環族炭化水素類；ヘキサン、ペンタン等の脂肪族炭化水素類等が挙げられるが、上記重合反応を阻害しなければ、特に限定されない。これらの溶媒は、１種類のみを用いてもよく、２種類以上を便宜混合して用いてもよい。なお、溶媒の使用量は、適宜決定すればよい。 Specific examples of the solvent used in the solution polymerization include aromatic hydrocarbons such as toluene and xylene; aliphatic esters such as ethyl acetate and butyl acetate; alicyclic hydrocarbons such as cyclohexane; hexane And aliphatic hydrocarbons such as pentane and the like, but are not particularly limited as long as the polymerization reaction is not inhibited. These solvents may be used alone or in combination of two or more. In addition, what is necessary is just to determine the usage-amount of a solvent suitably.
反応温度や反応時間等の反応条件は、例えば、モノマー成分の組成や、重合方法、あるいは、得られる（メタ）アクリル系粘着剤用ポリマーの要求特性、粘着剤の用途等に応じて便宜設定すればよく、特に限定されない。また、反応圧力も特に限定されるものではなく、常圧（大気圧）、減圧、加圧のいずれであってもよい。なお、重合反応は、窒素ガス等の不活性ガスの雰囲気下で行うことが望ましい。 The reaction conditions such as reaction temperature and reaction time are conveniently set according to, for example, the composition of the monomer component, the polymerization method, the required properties of the resulting (meth) acrylic pressure-sensitive adhesive polymer, the use of the pressure-sensitive adhesive, and the like. There is no particular limitation. Further, the reaction pressure is not particularly limited, and may be any of normal pressure (atmospheric pressure), reduced pressure, and increased pressure. The polymerization reaction is desirably performed in an atmosphere of an inert gas such as nitrogen gas.
粘着剤用ポリマーは、粘着製品として用いられるときには架橋していることが必要である。架橋剤は、ＣＯＯＨ基との反応性を有する官能基を１分子中に２個以上有するものが使用可能である。このような官能基としては、イソシアネート基、エポキシ基、アミノ基、メチロール基、アルコキシメチル基、イミノ基、金属キレート基、オキサゾリニル基等が挙げられるが、これらの中でも、使いやすさやカルボキシル基との反応性等の点で、イソシアネート基が好ましい。 The pressure-sensitive adhesive polymer needs to be cross-linked when used as a pressure-sensitive adhesive product. As the cross-linking agent, one having two or more functional groups having reactivity with a COOH group can be used. Examples of such a functional group include an isocyanate group, an epoxy group, an amino group, a methylol group, an alkoxymethyl group, an imino group, a metal chelate group, and an oxazolinyl group. An isocyanate group is preferable in terms of reactivity.
イソシアネート基を２個以上有するポリイソシアネート化合物としては、トリレンジイソシアネート（ＴＤＩ）、４，４’−ジフェニルメタンジイソシアネート（ＭＤＩ）、ヘキサメチレンジイソシアネート、キシリレンジイソシアネート、メタキシリレンジイソシアネート、１，５−ナフタレンジイソシアネート、水素化ジフェニルメタンジイソシアネート、水素化トリレンジイソシアネート、水素化キシリレンジイソシアネート、イソホロンジイソシアネート等のジイソシアネート化合物；「スミジュールＮ」（住友バイエルウレタン社製）等のビュレットポリイソシアネート化合物：「デスモジュールＩＬ」、「デスモジュールＨＬ」（いずれもバイエルＡ．Ｇ．社製）、「コロネートＥＨ」（日本ポリウレタン工業社製）等として知られるイソシアヌレート環を有するポリイソシアネート化合物；「スミジュールＬ」（住友バイエルウレタン社製）等のアダクトポリイソシアネート化合物；「コロネートＬ（ＴＤＩのトリメチロールプロパンアダクト物）」および「コロネートＬ−５５Ｅ」（いずれも日本ポリウレタン工業社製）等のアダクトポリイソシアネート化合物等を挙げることができる。これらは、単独で使用し得るほか、２種以上を併用することもできる。また、これらの化合物のイソシアネート基を活性水素を有するマスク剤と反応させて不活性化したいわゆるブロックイソシアネートも使用可能である。 Polyisocyanate compounds having two or more isocyanate groups include tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, 1,5-naphthalene diisocyanate. Diisocyanate compounds such as hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate; Burette polyisocyanate compounds such as “Sumijour N” (manufactured by Sumitomo Bayer Urethane Co., Ltd.): “Desmodur IL” Known as “Death Module HL” (all manufactured by Bayer AG), “Coronate EH” (manufactured by Nippon Polyurethane Industry), etc. Polyisocyanate compounds having an isocyanurate ring; adduct polyisocyanate compounds such as “Sumidur L” (manufactured by Sumitomo Bayer Urethane Co., Ltd.); Examples thereof include adduct polyisocyanate compounds such as those manufactured by Nippon Polyurethane Industry Co., Ltd. These can be used alone or in combination of two or more. In addition, so-called blocked isocyanates in which the isocyanate groups of these compounds are inactivated by reacting with a masking agent having active hydrogen can also be used.
粘着剤用ポリマーと架橋剤を含む粘着剤組成物を各種用途に応じた形態にして、粘着剤用ポリマーと架橋剤とを架橋反応させることにより、本発明の粘着製品を得ることができる。なお本発明では、「粘着剤」は、粘着剤用ポリマーと、溶剤（水を含む）および必要により用いられる粘着付与剤等の添加剤との混合物を言い、溶剤以外の固形分中、本発明の粘着剤用ポリマーが３０質量％以上含まれるものを本発明の「粘着剤」とする。粘着剤用ポリマーは４０質量％以上含まれることが好ましく、１００質量％であっても良い。「粘着剤組成物」は、この粘着剤と架橋剤との混合物を、「粘着層」は、粘着剤組成物を塗工して乾燥した後に形成されている層（架橋反応が終了したもの）を、「粘着製品」は、この粘着層を有する製品または粘着層そのものを、それぞれ指すものとする。また、本発明の粘着製品とは、本発明に含まれる架橋ポリマーが３０質量％以上含まれるものである。架橋ポリマーは４０質量％以上含まれることが好ましく、１００質量％であっても良い。 The pressure-sensitive adhesive product of the present invention can be obtained by making a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive polymer and a cross-linking agent into a form suitable for various uses and causing a cross-linking reaction between the pressure-sensitive adhesive polymer and the cross-linking agent. In the present invention, the “pressure-sensitive adhesive” refers to a mixture of a pressure-sensitive adhesive polymer and a solvent (including water) and additives such as a tackifier used as necessary. The “adhesive” of the present invention is a polymer containing 30% by mass or more of the above polymer for an adhesive. The polymer for pressure-sensitive adhesive is preferably contained in an amount of 40% by mass or more, and may be 100% by mass. The “adhesive composition” is a mixture of the adhesive and the crosslinking agent, and the “adhesive layer” is a layer formed after the adhesive composition is applied and dried (the crosslinking reaction is completed). The “adhesive product” refers to the product having the adhesive layer or the adhesive layer itself. The pressure-sensitive adhesive product of the present invention includes 30% by mass or more of the crosslinked polymer included in the present invention. The cross-linked polymer is preferably contained in an amount of 40% by mass or more, and may be 100% by mass.
粘着剤用ポリマーに対する架橋剤の量は、特に限定されないが、ＣＯＯＨ基量Ｐ（ｍｏｌ）に対する架橋剤の官能基量Ｑ（ｍｏｌ）、すなわちＱ／Ｐを２／１００〜３００／１とすることが好ましい。粘着製品の再剥離性と粘着力を優れたものにすることができる。ＣＯＯＨ基に対して架橋剤の官能基量が少なすぎると、架橋が不充分となることがある。架橋剤が多くても、粘着剤用ポリマーにＣＯＯＨ基が余っていない限り架橋度が過剰になることはあり得ないので、上限は３００モル倍が好ましい。Ｑ／Ｐのより好ましい下限は１／１００である。Ｑ／Ｐのより好ましい上限は１００／１、さらに好ましい上限は１／１である。 The amount of the crosslinking agent relative to the polymer for the pressure-sensitive adhesive is not particularly limited, but the functional group amount Q (mol) of the crosslinking agent with respect to the COOH group amount P (mol), that is, Q / P is set to 2/100 to 300/1. Is preferred. The removability and adhesive strength of the adhesive product can be made excellent. If the amount of the functional group of the crosslinking agent is too small with respect to the COOH group, crosslinking may be insufficient. Even if there are many cross-linking agents, the degree of cross-linking cannot be excessive unless the COOH group remains in the pressure-sensitive adhesive polymer, so the upper limit is preferably 300 moles. A more preferable lower limit of Q / P is 1/100. A more preferable upper limit of Q / P is 100/1, and a more preferable upper limit is 1/1.
本発明に係る粘着剤用ポリマーは、ポリマー自身が高分子量であり優れた粘着力を示すが、粘着剤（粘着剤組成物に対しても同様）に、用途に応じて、必要により、粘着付与剤が配合されていてもよい。粘着付与剤としては、（重合）ロジン系、（重合）ロジンエステル系、テルペン系、テルペンフェノール系、クマロン系、クマロンインデン系、スチレン樹脂系、キシレン樹脂系、フェノール樹脂系、石油樹脂系等が挙げられる。これらは１種または２種以上組み合わせて使用できる。 The polymer for pressure-sensitive adhesives according to the present invention has a high molecular weight and exhibits excellent adhesive strength. However, depending on the application, if necessary, the pressure-sensitive adhesive is applied to the pressure-sensitive adhesive (also for the pressure-sensitive adhesive composition). An agent may be blended. Tackifiers include (polymerized) rosin, (polymerized) rosin ester, terpene, terpene phenol, coumarone, coumarone indene, styrene resin, xylene resin, phenol resin, petroleum resin, etc. Is mentioned. These can be used alone or in combination of two or more.
粘着付与剤の量は、特に限定されないが、粘着剤用ポリマー１００質量部に対して、通常、５〜１００質量部とするのが好ましい。粘着付与剤の添加量が５質量部より少ないと、粘着付与剤による粘着力向上効果が発揮されないことがある。一方、上記粘着付与剤の添加量が１００質量部より多いと、逆にタックが減少して粘着力が低下するおそれがある。１０質量部〜５０質量部の範囲内がさらに好ましい。 Although the quantity of a tackifier is not specifically limited, Usually, it is preferable to set it as 5-100 mass parts with respect to 100 mass parts of polymers for adhesives. When the addition amount of the tackifier is less than 5 parts by mass, the effect of improving the tackiness by the tackifier may not be exhibited. On the other hand, when the addition amount of the tackifier is more than 100 parts by mass, there is a possibility that tack is reduced and the adhesive strength is reduced. More preferably within the range of 10 to 50 parts by mass.
粘着剤（組成物）には、さらに、必要に応じて、粘着剤に通常配合される充填剤、顔料、希釈剤、老化防止剤、紫外線吸収剤、紫外線安定剤等の従来公知の添加剤を添加してもよい。これらの添加剤は、１種類または２種以上、使用可能である。これらの添加剤の添加量は、所望する物性が得られるように適宜設定すればよい。 The pressure-sensitive adhesive (composition) may further contain conventionally known additives such as fillers, pigments, diluents, anti-aging agents, ultraviolet absorbers, and ultraviolet stabilizers that are usually blended in the pressure-sensitive adhesive, if necessary. It may be added. These additives can be used alone or in combination of two or more. What is necessary is just to set the addition amount of these additives suitably so that the desired physical property may be acquired.
本発明の粘着剤用ポリマーと前記架橋剤、必要により、上記各種添加剤、溶剤等を混合して調製された粘着剤組成物は、例えば、粘着シート、粘着ラベル、粘着テープ、両面テープ等の各種粘着製品の製造に好適に用いることができる。このような粘着製品は、基材レスで、または基材に粘着剤組成物の層を形成した後、架橋反応を行うことにより製造される。 The pressure-sensitive adhesive composition of the present invention and the cross-linking agent, and if necessary, the pressure-sensitive adhesive composition prepared by mixing the above-mentioned various additives, solvents, etc. are, for example, pressure-sensitive adhesive sheets, pressure-sensitive adhesive labels, pressure-sensitive adhesive tapes, double-sided tapes and the like. It can use suitably for manufacture of various adhesive products. Such a pressure-sensitive adhesive product is produced by performing a cross-linking reaction without a base material or after forming a layer of a pressure-sensitive adhesive composition on the base material.
基材としては、上質紙、クラフト紙、クレープ紙、グラシン紙等の従来公知の紙類；ポリエチレン、ポリプロピレン、ポリエステル、ポリスチレン、ポリエチレンテレフテレート、ポリ塩化ビニル、セロファン等のプラスチック；織布、不織布等の繊維製品等を利用できる。基材の形状は、例えば、フィルム状、シート状、テープ状、板状、発泡体等が挙げられるが、特に限定されるものではない。 As the base material, conventionally known papers such as fine paper, kraft paper, crepe paper, glassine paper; plastics such as polyethylene, polypropylene, polyester, polystyrene, polyethylene terephthalate, polyvinyl chloride, cellophane; woven fabric, non-woven fabric Can be used. Examples of the shape of the substrate include, but are not particularly limited to, a film shape, a sheet shape, a tape shape, a plate shape, and a foam.
基材の片面に粘着剤組成物を公知の方法で塗布することによって、粘着層が形成された粘着シート、粘着テープ、粘着ラベル等の片面タイプの粘着製品を得ることができる。また、紙、合成紙、プラスチックフィルム等のシート状物に離型剤が塗布されている離型紙等に粘着剤組成物を塗布することにより、基材レス（単層構造）の粘着製品が得られ、基材レスの両面テープとして使用することができる。また、上記基材の両面に同種または異種の粘着剤組成物を塗布して、両面テープとしてもよい。 By applying the pressure-sensitive adhesive composition to one side of the substrate by a known method, a single-sided type pressure-sensitive adhesive product such as a pressure-sensitive adhesive sheet, a pressure-sensitive adhesive tape, or a pressure-sensitive adhesive label on which a pressure-sensitive adhesive layer is formed can be obtained. In addition, by applying an adhesive composition to release paper, etc., where a release agent is applied to a sheet of paper, synthetic paper, plastic film, etc., a substrateless (single-layer structure) adhesive product is obtained. And can be used as a baseless double-sided tape. Moreover, it is good also as a double-sided tape by apply | coating the same kind or different kind of adhesive composition to both surfaces of the said base material.
粘着剤組成物を基材に塗布する方法は、特に限定されるものではなく、ロールコーティング法、スプレーコーティング法、ディッピング法等の公知の方法を採用することができる。この場合、粘着剤組成物を基材に直接塗布する方法、離型紙等に粘着剤組成物を塗布した後、この塗布物を基材上に転写する方法等いずれも採用可能である。 The method for applying the pressure-sensitive adhesive composition to the substrate is not particularly limited, and a known method such as a roll coating method, a spray coating method, or a dipping method can be employed. In this case, any of a method for directly applying the pressure-sensitive adhesive composition to the substrate, a method for applying the pressure-sensitive adhesive composition to a release paper, and then transferring the coated material onto the substrate can be employed.
粘着剤組成物を塗布した後、乾燥させることにより、粘着層が形成される。乾燥温度は、特に限定されるものではないが、加熱乾燥時に架橋反応が進行するので、架橋剤の種類に応じて架橋反応が速やかに進行する温度で乾燥することが好ましい。なお、用途によっては、粘着剤組成物を被着体に直接、塗布してもよい。 An adhesive layer is formed by applying and then drying the adhesive composition. The drying temperature is not particularly limited. However, since the crosslinking reaction proceeds at the time of heat drying, it is preferable to dry at a temperature at which the crosslinking reaction proceeds rapidly according to the type of the crosslinking agent. In addition, depending on a use, you may apply | coat an adhesive composition directly to a to-be-adhered body.
基材上に形成された粘着層の表面には、例えば、離型紙を貼着してもよい。粘着層表面を好適に保護・保存することができる。剥離紙は、粘着製品を使用する際に、粘着層表面から引き剥がされる。なお、シート状やテープ状等の基材の片面に粘着層が形成されている場合は、この基材の背面に公知の離型剤を塗布して離型剤層を形成しておけば、粘着層を内側にして、粘着シート（テープ）をロール状に巻くことにより、粘着層は、基材背面の離型剤層と当接することとなるので、粘着層表面が保護・保存される。 For example, a release paper may be attached to the surface of the adhesive layer formed on the substrate. The adhesive layer surface can be suitably protected and preserved. The release paper is peeled off from the surface of the adhesive layer when the adhesive product is used. In addition, when an adhesive layer is formed on one side of a substrate such as a sheet or tape, if a release agent layer is formed by applying a known release agent to the back surface of this substrate, By winding the pressure-sensitive adhesive sheet (tape) in a roll shape with the pressure-sensitive adhesive layer on the inside, the pressure-sensitive adhesive layer comes into contact with the release agent layer on the back surface of the substrate, so that the surface of the pressure-sensitive adhesive layer is protected and preserved.
以上のようにして製造された本発明の粘着製品は、再剥離性に優れ、しかも、良好な粘着力を示す。粘着力の目安としては、５０μｍのポリエチレンテレフタレートフィルム上に乾燥後の厚さが２５μｍとなるように粘着剤組成物を塗布し、加熱して架橋反応を終了させて粘着フィルムとなしたとき、下記条件で測定されるステンレス鋼板に対する２３℃、相対湿度６５％での１８０°剥離粘着力が２．０Ｎ／ｃｍ以上であることが好ましく、３．０Ｎ／ｃｍ以上がより好ましい。 The pressure-sensitive adhesive product of the present invention produced as described above is excellent in removability and exhibits good adhesive strength. As a measure of adhesive strength, when a pressure-sensitive adhesive composition was applied on a 50 μm polyethylene terephthalate film so that the thickness after drying was 25 μm, and the crosslinking reaction was terminated by heating, a pressure-sensitive adhesive film was obtained. The 180 ° peel adhesion at 23 ° C. and 65% relative humidity with respect to the stainless steel plate measured under the conditions is preferably 2.0 N / cm or more, and more preferably 3.0 N / cm or more.
〔１８０°剥離粘着力測定条件〕
ステンレス鋼板（ＳＵＳ３０４）板を被着体とし、２３℃、相対湿度６５％の雰囲気下でステンレス鋼板に幅１．０ｃｍの試験テープを２ｋｇのゴムローラで貼り付け、ゴムローラが試験テープ上を合計で３往復するように圧着する。圧着後、２０分放置した後、剥離速度を３００ｍｍ／ｍｉｎとし、２３℃、相対湿度６５％の雰囲気下で、ＪＩＳ Ｋ ６８５４に準じて１８０°剥離粘着力を測定する。[Measurement conditions for 180 ° peel adhesion]
A stainless steel plate (SUS304) plate is used as an adherend, and a test tape having a width of 1.0 cm is attached to the stainless steel plate in an atmosphere of 23 ° C. and a relative humidity of 65% with a 2 kg rubber roller. Crimp to reciprocate. After the pressure bonding, the film is allowed to stand for 20 minutes, and then the peeling speed is set to 300 mm / min, and the 180 ° peeling adhesive strength is measured according to JIS K 6854 in an atmosphere of 23 ° C. and
以下実施例によって本発明を詳細に説明するが、本発明の範囲はこれら実施例のみに限定されるものではない。なお以下特にことわりのない場合、「％」は「質量％」を、「部」は「質量部」をそれぞれ示すものとする。 EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the scope of the present invention is not limited only to these examples. Unless otherwise specified, “%” indicates “mass%” and “part” indicates “part by mass”.
合成例１（粘着剤用ポリマー溶液Ａ１の合成）
温度計、攪拌機、不活性ガス導入管、還流冷却器および滴下ロートを備えた４つ口フラスコに、アクリル酸ブチル２９１部、アクリル酸２−エチルヘキシル２９１部およびアクリル酸１８部からなるモノマー成分６００部のうちの２００部（モノマー初期仕込み分）と、酢酸エチル３００部を加えてから昇温し、８０℃になったところで過酸化物系開始剤（ナイパーＢＭＴ−Ｋ４０：日本油脂（株）社製）を０．６部を添加して重合を開始した。重合開始から１５分後に、残りのモノマー成分３００部（モノマー滴下分）と、ナイパーＢＭＴ−Ｋ４０を０．８部、および酢酸エチル１６部を１時間半かけて滴下し、３時間反応させた後、１回目希釈溶剤としてトルエンを２８３部加えた。次いでブースター（後添加開始剤）としてアゾ系重合開始剤（商品名ＡＢＮ−Ｅ：日本ヒドラジン工業（株）社製）を１．８部とトルエン５０部を添加し、さらに４時間反応を続けた。重合終了時に２回目希釈溶剤としてトルエン２４８部を加えた。Synthesis example 1 (synthesis | combination of polymer solution A1 for adhesives)
A monomer component consisting of 291 parts of butyl acrylate, 291 parts of 2-ethylhexyl acrylate, and 18 parts of acrylic acid in a four-necked flask equipped with a thermometer, stirrer, inert gas introduction tube, reflux condenser and dropping funnel Of these, 200 parts (initial monomer charge) and 300 parts of ethyl acetate were added, the temperature was raised, and when the temperature reached 80 ° C., a peroxide initiator (Nyper BMT-K40: manufactured by Nippon Oil & Fats Co., Ltd.) ) Was added in an amount of 0.6 part to initiate polymerization. After 15 minutes from the start of polymerization, 300 parts of the remaining monomer component (monomer added part), 0.8 part of Nipper BMT-K40, and 16 parts of ethyl acetate were added dropwise over 1 hour and a half and reacted for 3 hours. 283 parts of toluene was added as a first dilution solvent. Next, 1.8 parts of azo polymerization initiator (trade name ABN-E: manufactured by Nippon Hydrazine Kogyo Co., Ltd.) and 50 parts of toluene were added as a booster (post-addition initiator), and the reaction was further continued for 4 hours. . At the end of the polymerization, 248 parts of toluene was added as a second dilution solvent.
その結果、固形分４０．０％、粘度５９４０ｍＰａ・ｓ（２５℃、Ｂ型粘度計、以下同様）、重量平均分子量６７．７×１０4（ＧＰＣ測定：標準ポリスチレン換算、以下同様）の粘着剤用ポリマー溶液Ａ１を得た。得られた粘着剤用ポリマー溶液Ａ１について、前記した方法でＧＰＣを用いて、重量平均分子量が１７．６×１０4以上の高分子量ポリマーを分取して、高分子量ポリマーについて熱分解ＧＣ／ＭＳ測定装置でＯＨ基濃度を分析したところ、高分子量ポリマー１ｇ当たり０ｍｍｏｌ／ｇであった。As a result, an adhesive having a solid content of 40.0%, a viscosity of 5940 mPa · s (25 ° C., B-type viscometer, the same applies hereinafter), and a weight average molecular weight of 67.7 × 10 4 (GPC measurement: standard polystyrene conversion, the same applies hereinafter). Polymer solution A1 was obtained. About the obtained polymer solution A1 for adhesives, the high molecular weight polymer whose weight average molecular weight is 17.6 * 10 < 4 > or more is fractionated using GPC by the above-mentioned method, Thermal decomposition GC / MS is carried out about high molecular weight polymer. When the OH group concentration was analyzed with a measuring device, it was 0 mmol / g per gram of the high molecular weight polymer.
合成例２（粘着剤用ポリマー溶液Ａ２の合成）
粘着剤用ポリマー溶液Ａ１における１回目希釈溶剤の添加時間を、モノマー滴下５時間後に変更した以外は合成例１と同様の操作を行って、粘着剤用ポリマー溶液Ａ２を得た。物性評価結果を表１に示す。Synthesis example 2 (synthesis | combination of polymer solution A2 for adhesives)
A polymer solution A2 for pressure-sensitive adhesives was obtained by performing the same operation as in Synthesis Example 1 except that the addition time of the first dilution solvent in the polymer solution A1 for pressure-sensitive adhesives was changed 5 hours after the monomer dropping. The physical property evaluation results are shown in Table 1.
合成例３（粘着剤用ポリマー溶液Ａ３の合成）
モノマー組成を表１に示したように変更した以外は合成例１と同様の操作を行って、粘着剤用ポリマー溶液Ａ３を得た。物性評価結果を表１に示す。Synthesis Example 3 (Synthesis of pressure-sensitive adhesive polymer solution A3)
Except having changed the monomer composition as shown in Table 1, the same operation as the synthesis example 1 was performed, and the polymer solution A3 for adhesives was obtained. The physical property evaluation results are shown in Table 1.
合成例４（粘着剤用ポリマー溶液Ａ４の合成）
温度計、攪拌機、不活性ガス導入管、還流冷却器および滴下ロートを備えた４つ口フラスコに、アクリル酸ブチル２７６部、アクリル酸２−エチルヘキシル２７６部およびアクリル酸４８部からなるモノマー成分６００部のうちの２００部と、酢酸エチル２３０部を加えてから昇温し、８０℃になったところでナイパーＢＭＴ−Ｋ４０を０．４部を添加して重合を開始した。重合開始から１５分後に残りのモノマー成分４００部と、ナイパーＢＭＴ−Ｋ４０を０．４部、および酢酸エチル１５７部を１時間半かけて滴下し、３時間反応させた後、１回目の希釈溶剤として酢酸エチルを６３６部加えた。次いでＡＢＮ−Ｅを１．８部と酢酸エチル５２部を添加し、さらに４時間反応を続けた。重合終了時に２回目の希釈溶剤としてトルエン２４８部を加えた。その結果、固形分３３．８％、粘度３０３０ｍＰａ・ｓ、重量平均分子量６８．１×１０4の粘着剤用ポリマー溶液Ａ４を得た。Synthesis example 4 (synthesis | combination of polymer solution A4 for adhesives)
A monomer component consisting of 276 parts of butyl acrylate, 276 parts of 2-ethylhexyl acrylate and 48 parts of acrylic acid in a four-necked flask equipped with a thermometer, stirrer, inert gas introduction tube, reflux condenser and dropping funnel 200 parts of them and 230 parts of ethyl acetate were added and the temperature was raised. When the temperature reached 80 ° C., 0.4 parts of Nyper BMT-K40 was added to initiate polymerization. 15 minutes after the start of polymerization, 400 parts of the remaining monomer component, 0.4 part of Niper BMT-K40, and 157 parts of ethyl acetate were added dropwise over 1 hour and a half, and reacted for 3 hours. As ethyl acetate. Next, 1.8 parts of ABN-E and 52 parts of ethyl acetate were added, and the reaction was further continued for 4 hours. At the end of the polymerization, 248 parts of toluene was added as a second dilution solvent. As a result, an adhesive polymer solution A4 having a solid content of 33.8%, a viscosity of 3030 mPa · s, and a weight average molecular weight of 68.1 × 10 4 was obtained.
合成例５〜７（粘着剤用ポリマー溶液Ａ５〜Ａ７の合成）
モノマー組成を表１〜２に示すとおりに変更した以外は合成例４と同様の操作を行って、粘着剤用ポリマー溶液Ａ５〜Ａ７を得た。物性評価結果を表１〜２に示す。Synthesis Examples 5 to 7 (Synthesis of pressure-sensitive adhesive polymer solutions A5 to A7)
Except having changed the monomer composition as shown to Tables 1-2, operation similar to the synthesis example 4 was performed, and polymer solution A5-A7 for adhesives was obtained. The physical property evaluation results are shown in Tables 1-2.
合成例８（粘着剤用ポリマー溶液Ａ８の合成）
温度計、攪拌機、不活性ガス導入管、還流冷却器および滴下ロートを備えた４つ口フラスコに、アクリル酸ブチル２８８部、アクリル酸２−エチルヘキシル２８８部およびアクリル酸１８部からなるモノマー成分５９４部のうちの２４０部と、酢酸エチル３００部を加えてから昇温し、８０℃になったところでナイパーＢＭＴ−Ｋ４０を０．６部を添加して重合を開始した。重合開始から１５分後に残りのモノマー成分２５４部と、ナイパーＢＭＴ−Ｋ４０を０．８部、および酢酸エチル１６部を１時間半かけて滴下し、３時間反応させたところで、１回目の希釈溶剤としてトルエンを２７３部加えた。ついでＡＢＮ−Ｅを１．８部とトルエン５０部と、アクリル酸２−ヒドロキシエチル６部を添加し、さらに４時間反応を続けた。重合終了時に２回目の希釈溶剤としてトルエン２５８部を加えた。得られた粘着剤用ポリマー溶液Ａ８の物性測定結果を表２に示す。Synthesis Example 8 (Synthesis of polymer solution A8 for pressure-sensitive adhesive)
In a four-necked flask equipped with a thermometer, stirrer, inert gas introduction tube, reflux condenser and dropping funnel, 594 parts of a monomer component consisting of 288 parts of butyl acrylate, 288 parts of 2-ethylhexyl acrylate and 18 parts of acrylic acid Of these, 240 parts and 300 parts of ethyl acetate were added and the temperature was raised. When the temperature reached 80 ° C., 0.6 parts of Nyper BMT-K40 was added to initiate polymerization. 15 minutes after the start of polymerization, 254 parts of the remaining monomer component, 0.8 part of Nipper BMT-K40, and 16 parts of ethyl acetate were added dropwise over 1 hour and a half, and reacted for 3 hours. 273 parts of toluene was added. Subsequently, 1.8 parts of ABN-E, 50 parts of toluene and 6 parts of 2-hydroxyethyl acrylate were added, and the reaction was continued for another 4 hours. At the end of the polymerization, 258 parts of toluene was added as a second dilution solvent. The physical property measurement results of the resulting polymer solution A8 for pressure-sensitive adhesive are shown in Table 2.
合成例９（粘着剤用ポリマー溶液Ａ９〜Ａ１１およびＢ１〜Ｂ２の合成）
モノマー組成を表２〜３に示すとおりに変更した以外は合成例Ａ８と同様の操作を行って、粘着剤用ポリマー溶液Ａ９〜Ａ１１およびＢ１〜Ｂ２を得た。物性測定結果を表２〜３に示す。なお、粘着剤用ポリマー溶液Ｂ１およびＢ２は比較例用である。Synthesis Example 9 (Synthesis of polymer solutions A9 to A11 and B1 to B2 for pressure-sensitive adhesives)
Except having changed the monomer composition as shown to Tables 2-3, operation similar to the synthesis example A8 was performed, and polymer solution A9-A11 for adhesives and B1-B2 were obtained. The physical property measurement results are shown in Tables 2-3. In addition, the polymer solutions B1 and B2 for adhesives are for comparative examples.
合成例１０（粘着剤用ポリマー溶液Ｂ３の合成）
温度計、攪拌機、不活性ガス導入管、還流冷却器および滴下ロートを備えた４つ口フラスコに、アクリル酸ブチル２８４．４部、アクリル酸２−エチルヘキシル２８４．４部、アクリル酸１８部、およびメタクリル酸２−ヒドロキシエチル２．６４部からなるモノマー成分５８９．３６部と、酢酸エチル７２０部を加えて昇温し、８０℃になったところで過酸化物系開始剤（ナイパーＢＭＴ−Ｋ４０）を１．７６部を添加して重合を開始した。重合開始から２０分毎にメタクリル酸２−ヒドロキシエチル１０．５６部と酢酸エチル１００部からなるモノマー成分溶液を９分の１ずつ加えた。反応開始から３時間後にＡＢＮ−Ｅを１．８部とトルエン４０部とを添加し、さらに４時間反応を続け、最後に希釈溶剤としてトルエン２０部を加えた。その結果、固形分４０．３％、粘度１３２０ｍＰａ・ｓ、重量平均分子量３３．１×１０4の粘着剤用ポリマー溶液Ｂ３が得られた。Synthesis Example 10 (Synthesis of pressure-sensitive adhesive polymer solution B3)
In a four-necked flask equipped with a thermometer, stirrer, inert gas inlet tube, reflux condenser and dropping funnel, 284.4 parts butyl acrylate, 284.4 parts 2-ethylhexyl acrylate, 18 parts acrylic acid, and 58.36 parts of a monomer component consisting of 2.64 parts of 2-hydroxyethyl methacrylate and 720 parts of ethyl acetate were added and the temperature was raised. When the temperature reached 80 ° C., a peroxide-based initiator (Nyper BMT-K40) was added. 1.76 parts were added to initiate the polymerization. Every 20 minutes from the start of polymerization, a monomer component solution consisting of 10.56 parts of 2-hydroxyethyl methacrylate and 100 parts of ethyl acetate was added by 1/9. Three hours after the start of the reaction, 1.8 parts of ABN-E and 40 parts of toluene were added, and the reaction was further continued for 4 hours. Finally, 20 parts of toluene was added as a diluent solvent. As a result, an adhesive polymer solution B3 having a solid content of 40.3%, a viscosity of 1320 mPa · s, and a weight average molecular weight of 33.1 × 10 4 was obtained.
実施例１（実験Ｎｏ．１〜３１）および比較例１（実験Ｎｏ．３２〜４２）
粘着剤用ポリマー溶液Ａ１〜Ａ１４およびＢ１〜Ｂ３のそれぞれの溶液を適当量採り、その中に含まれるポリマー１質量部に対して、架橋剤としてコロネートＬ−５５Ｅ（固形分５５％）を表５〜表９に示した量（ウエット）混合して、粘着剤組成物を作製した。下記の方法で試験片を作成し、粘着特性を評価した。また、前記した方法でゲル分率Ｘと膨潤度Ｙを測定し、図１にプロットした。図１においては、初期粘着力が２Ｎ／ｃｍ以上であり、かつ、加熱７日後の破壊状態が凝集破壊（ＣＦ）でないもの（ＳＦ、ＴＦ、Ｃ）を●、初期粘着力が２Ｎ／ｃｍ未満で、または加熱７日後の破壊状態が凝集破壊（ＣＦ）のものを▲として示した。●が実施例、▲が比較例である。Example 1 (Experiment Nos. 1-31) and Comparative Example 1 (Experiment Nos. 32-42)
Appropriate amounts of each of the polymer solutions A1 to A14 and B1 to B3 for the pressure-sensitive adhesive were taken, and Coronate L-55E (
［試験片の作成方法］
基材としてポリエチレンテレフタレートフィルム（東レ株式会社製、厚さ５０μｍ）を用い、粘着剤組成物を乾燥後の厚さが２５μｍとなるように塗布した後、１００℃で３分間乾燥させることにより、粘着フィルムを作成した。粘着剤表面に離型紙（サンエー化研株式会社製、商品名Ｋ−８０ＨＳ）を貼着して保護した後、温度２３℃、相対湿度６５％の雰囲気下で７日間養生した。養生後の粘着フィルムを所定の大きさに切断して、試験片を作製した。なお、離型紙は各種測定試験を実施する際に引き剥がした。[How to create a test piece]
A polyethylene terephthalate film (manufactured by Toray Industries, Inc.,
［保持力の測定方法］
温度２３℃、相対湿度６５％の雰囲気下で、ステンレス鋼板（ＳＵＳ３０４：以下「ＳＵＳ板」と記す）に、貼付面積が２５ｍｍ×２５ｍｍとなるように粘着フィルム試験片を貼着する。２５分間放置後、この試験片が貼着されたＳＵＳ板を８０℃の恒温機に入れて、鉛直に吊り下げる。２０分間経過した後、９．８Ｎの力を試験片に掛けて、ＳＵＳ板から試験片が落下するまでの時間、または２４時間後のズレ距離を測定した。ＮＣとあるのは、全くズレなかったものである。[Method of measuring holding force]
In an atmosphere having a temperature of 23 ° C. and a relative humidity of 65%, an adhesive film test piece is attached to a stainless steel plate (SUS304: hereinafter referred to as “SUS plate”) so that the application area is 25 mm × 25 mm. After leaving for 25 minutes, the SUS plate on which the test piece is adhered is placed in a thermostat at 80 ° C. and suspended vertically. After 20 minutes, a force of 9.8 N was applied to the test piece, and the time until the test piece dropped from the SUS plate or the deviation distance after 24 hours was measured. There is no deviation from NC.
［初期粘着力の測定方法］
温度２３℃、相対湿度６５％の雰囲気下で、被着体であるＳＵＳ板に幅１．０ｃｍの粘着フィルム試験片を貼着した。貼着は、試験片の上を２ｋｇの質量のゴムローラーで３往復させることによって行った。貼着してから２０分経過後に、試験片の一端を１８０度方向に速度３００ｍｍ／分でＳＵＳ板から剥離させた時の強度（１８０°剥離粘着力：Ｎ／ｃｍ）を測定した。また、剥離状態を下記基準で目視評価した。
ＳＦ：粘着剤と被着体との界面剥離
ＴＦ：粘着剤と基材との界面剥離（粘着剤が被着体側へ移行）
Ｃ：粘着剤の跡が「曇り」となって残っている。
ＣＦ：多量に粘着剤が残っており、凝集破壊を起こしている。[Measurement method of initial adhesive strength]
In an atmosphere at a temperature of 23 ° C. and a relative humidity of 65%, an adhesive film test piece having a width of 1.0 cm was attached to a SUS plate as an adherend. The sticking was performed by reciprocating the
SF: Interfacial peeling between adhesive and adherend TF: Interfacial peeling between adhesive and substrate (adhesive moves to adherend)
C: The adhesive mark remains “cloudy”.
CF: A large amount of adhesive remains, causing cohesive failure.
［常態粘着力の測定方法］
初期粘着力測定と同様にして、ＳＵＳ板に試験片を貼着した。貼着してから２４時間経過後に、試験片の一端を１８０度方向に速度３００ｍｍ／分でＳＵＳ板から剥離させた時の強度（１８０°剥離粘着力：Ｎ／ｃｍ）を測定した。[Measurement method of normal adhesive strength]
The test piece was stuck on the SUS board like the initial adhesive force measurement. After 24 hours from the pasting, the strength (180 ° peel adhesive strength: N / cm) when one end of the test piece was peeled from the SUS plate at a speed of 300 mm / min in the 180 ° direction was measured.
［加熱促進後の粘着力の測定方法］
初期粘着力測定と同様にして、ＳＵＳ板に試験片を貼着した。貼着してから７０℃で２４時間（１日）放置したものと、７０℃で７日間放置したものについて、初期粘着力測定と同様にして１８０°剥離粘着力（Ｎ／ｃｍ）を測定した。なお、粘着力は、それぞれ加熱状態からサンプルを取り出し、２３℃、相対湿度６５％の雰囲気下で１時間放置してから測定した。また、剥離状態を上記のように評価した。[Measurement method of adhesive strength after heating]
The test piece was stuck on the SUS board like the initial adhesive force measurement. 180 ° peel adhesive strength (N / cm) was measured in the same manner as the initial adhesive strength measurement for those left for 24 hours (1 day) at 70 ° C. and those left for 7 days at 70 ° C. . The adhesive strength was measured after taking a sample from a heated state and leaving it for 1 hour in an atmosphere of 23 ° C. and a relative humidity of 65%. Further, the peeled state was evaluated as described above.
表５〜８から、実施例のもの（実験Ｎｏ．１〜３１）は、粘着力と再剥離性が両立していることがわかる。一方、表９によれば、比較用粘着剤用ポリマーＢ１を用いた実験Ｎｏ．３２〜３４では架橋剤が少ないのに粘着力が低い。また、架橋剤量の増加に伴って粘着力が極めて低い値へと低下していくが、加熱７日後の剥離状態は凝集破壊であって、再剥離性の向上は認められない。これは、高分子量ポリマーにＯＨ基があって高分子量ポリマーの架橋が優先されるので、低分子量物が架橋できず、糊残りの原因となっているためである。Ｎｏ．３５〜３６も同様の傾向を示している。Ｎｏ．３９〜４２では、架橋剤の増加に伴い粘着力が低下する上に、再剥離性は依然として向上しない。高分子量ポリマーと低分子量ポリマーの両方にＯＨ基があるポリマーを用いていて、高分子量ポリマーの架橋が優先され、低分子量物が架橋されなかったことによるものと考えられる。 From Tables 5-8, it turns out that the thing (Experiment No. 1-31) of an Example is compatible with adhesive force and removability. On the other hand, according to Table 9, the experiment No. using the comparative adhesive polymer B1. In 32-34, although there are few crosslinking agents, adhesive force is low. In addition, the adhesive strength decreases to a very low value as the amount of the crosslinking agent increases, but the peeled state after 7 days of heating is cohesive failure, and no improvement in removability is observed. This is because the high molecular weight polymer has an OH group and the cross-linking of the high molecular weight polymer is prioritized, so that the low molecular weight material cannot be cross-linked, causing the adhesive residue. No. 35-36 also shows the same tendency. No. In 39-42, adhesive force falls with the increase in a crosslinking agent, and re-peelability still does not improve. This is probably because a polymer having an OH group is used for both the high molecular weight polymer and the low molecular weight polymer, and the high molecular weight polymer is preferentially crosslinked and the low molecular weight material is not crosslinked.
実施例２（実験Ｎｏ．４３〜４９）および比較例２（実験Ｎｏ．５０〜５２）
粘着剤用ポリマー溶液Ａ１〜Ａ３、Ａ８〜Ａ１１およびＢ１〜Ｂ３のそれぞれの溶液を適当量採り、その中に含まれるポリマー１質量部に対して、架橋剤としてコロネートＬ−５５Ｅ（固形分５５％）を０．０７５質量部（ウエット）混合して、粘着剤組成物を作製した。前記した方法でゲル分率Ｘと膨潤度Ｙと粘着特性を評価し、それぞれの測定結果を表１０〜１１に示した。Example 2 (Experiment No. 43 to 49) and Comparative Example 2 (Experiment No. 50 to 52)
Appropriate amounts of each of the polymer solutions A1 to A3, A8 to A11, and B1 to B3 for the pressure-sensitive adhesive were taken. Coronate L-55E (
実施例３（実験Ｎｏ．５３〜６０）
粘着剤用ポリマー溶液Ａ１、Ａ３、Ａ６およびＡ１２のそれぞれを適当量採り、その中に含まれるポリマー１質量部に対して、コロネートＬ−５５Ｅ（固形分５５％）を表に示した量混合して、粘着剤組成物を作製した。なお架橋剤量として、ＮＣＯ基のｍｏｌ数をポリマー中のＣＯＯＨ基のｍｏｌ数で割った値も併記した。前記した方法で粘着特性を評価し、測定結果を表１２に示した。Example 3 (Experiment No. 53-60)
Appropriate amounts of each of the polymer solutions A1, A3, A6 and A12 for the pressure-sensitive adhesive were taken, and 1 part by weight of the polymer contained therein was mixed with the amount shown in the table for coronate L-55E (
架橋剤量が、ＮＣＯ／ＣＯＯＨ（モル比）で０．１〜１．０であれば、凝集力、粘着力、再剥離性のバランスが良好であることが分かる。 If the amount of the crosslinking agent is 0.1 to 1.0 in NCO / COOH (molar ratio), it can be seen that the balance of cohesive force, adhesive force and removability is good.
本発明は、カルボキシル基を利用した架橋システムの採用によって、ゲル分率Ｘと膨潤度Ｙが一定の関係にある架橋ポリマーが粘着力と再剥離性といった相反する特性を両立させ得ることを見出した。また、カルボキシル基を利用した架橋システムでは低分子量ポリマーも架橋するため、糊残りを低減させることができた。さらに、架橋剤を多めに入れても粘着力が極端に低下しないことも見出された。従って、粘着力と凝集力の両性能が良好で、再剥離性が要求される用途に適した、しかも、品質にばらつきの少ない粘着製品を提供することができた。 The present invention has found that by adopting a cross-linking system using a carboxyl group, a cross-linked polymer having a fixed relationship between the gel fraction X and the swelling degree Y can achieve both conflicting properties such as adhesive strength and removability. . Moreover, since the low molecular weight polymer is also cross-linked by the cross-linking system using the carboxyl group, the adhesive residue can be reduced. Furthermore, it was also found that the adhesive strength does not extremely decrease even when a large amount of a crosslinking agent is added. Therefore, it was possible to provide a pressure-sensitive adhesive product having both good adhesive strength and cohesive strength, suitable for applications requiring re-peelability, and having little variation in quality.
Claims (3)
前記粘着剤用ポリマー中のＣＯＯＨ基量Ｐ（ｍｏｌ）に対する前記架橋剤の官能基量Ｑ（ｍｏｌ）の値（Ｑ／Ｐ）が０．０１以上０．７５２以下であり、
前記粘着剤用ポリマーの重量平均分子量Ｍｗは４０万以上であり、
前記粘着層中の架橋ポリマーは、下記測定方法で測定されるゲル分率Ｘ（質量％）と膨潤度Ｙ（体積倍）が、下記式（１）〜（４）を満足することを特徴とする粘着製品。
Ｙ≦−（６．５／３）Ｘ＋（５３５／３） …（１）
Ｙ≧−（６．５／３）Ｘ＋１４０ …（２）
１０≦Ｙ≦８０ …（３）
４０≦Ｘ≦７５ …（４）
ただし、Ｙ＞０，Ｘ＞０である。
・ゲル分率Ｘ（質量％）：架橋ポリマーをテトラヒドロフランに２４時間浸漬した後、残留したゲルの量から、下記式に基づいてゲル分率（質量％）を求める：
ゲル分率Ｘ（質量％）＝１００×［ゲルを乾燥した後の質量／溶解前の架橋ポリマーの質量］
・膨潤度Ｙ（体積倍）：１０ｍｍ×２５ｍｍ×１００μｍの架橋ポリマー試料片をテトラヒドロフランに２４時間浸漬し、浸漬後の膨潤度（体積倍）を求める。
(Meth) acrylic acid alkyl ester 88-97 mass% and a polymer for pressure-sensitive adhesives derived from a monomer component essentially containing a carboxyl group-containing monomer 3-12 mass% cross-links a polyisocyanate compound having two or more isocyanate groups. A pressure-sensitive adhesive product in which a pressure-sensitive adhesive layer containing a plasticizer is formed while being included in a crosslinked state as an agent,
The value (Q / P) of the functional group amount Q (mol) of the crosslinking agent relative to the COOH group amount P (mol) in the adhesive polymer is 0.01 or more and 0.752 or less,
The weight average molecular weight Mw of the pressure-sensitive adhesive polymer is 400,000 or more,
The crosslinked polymer in the adhesive layer is characterized in that a gel fraction X (mass%) and a swelling degree Y (volume times) measured by the following measuring method satisfy the following formulas (1) to (4). To sticky products.
Y ≦ − (6.5 / 3) X + (535/3) (1)
Y ≧ − (6.5 / 3) X + 140 (2)
10 ≦ Y ≦ 80 (3)
40 ≦ X ≦ 75 (4)
However, Y> 0 and X> 0.
Gel fraction X (mass%): After immersing the crosslinked polymer in tetrahydrofuran for 24 hours, the gel fraction (mass%) is determined from the amount of remaining gel based on the following formula:
Gel fraction X (mass%) = 100 × [mass after drying gel / mass of crosslinked polymer before dissolution]
Swelling degree Y (volume times): A cross-linked polymer sample piece of 10 mm × 25 mm × 100 μm is immersed in tetrahydrofuran for 24 hours, and the degree of swelling (volume times) after immersion is determined.
The pressure-sensitive adhesive product according to claim 1, wherein the hydroxyl group concentration of the pressure-sensitive adhesive polymer before crosslinking is 0.01 mmol or less per 1 g of the polymer.
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| KR100932888B1 (en) * | 2006-07-21 | 2009-12-21 | 주식회사 엘지화학 | Optically compensated acrylic pressure sensitive adhesive composition, polarizing plate and liquid crystal display device comprising the same |
| DE102009011482A1 (en) * | 2009-03-06 | 2010-09-09 | Tesa Se | Pressure-sensitive adhesives for bonding printing plates |
| JP2012184327A (en) * | 2011-03-05 | 2012-09-27 | Mitsubishi Plastics Inc | Base material-less double-sided pressure-sensitive adhesive sheet |
| JP2012207166A (en) * | 2011-03-30 | 2012-10-25 | Mitsubishi Plastics Inc | Substrate-less double-sided pressure-sensitive adhesive sheet |
| WO2017199463A1 (en) * | 2016-05-16 | 2017-11-23 | 株式会社寺岡製作所 | Pressure-sensitive adhesive composition and pressure-sensitive adhesive tape |
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