JP2007131838A - Method for producing acrylic polymer, the resultant acrylic polymer, acrylic adhesive composition, and adhesive tape - Google Patents
Method for producing acrylic polymer, the resultant acrylic polymer, acrylic adhesive composition, and adhesive tape Download PDFInfo
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- JP2007131838A JP2007131838A JP2006275739A JP2006275739A JP2007131838A JP 2007131838 A JP2007131838 A JP 2007131838A JP 2006275739 A JP2006275739 A JP 2006275739A JP 2006275739 A JP2006275739 A JP 2006275739A JP 2007131838 A JP2007131838 A JP 2007131838A
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- acrylic polymer
- acrylic
- polymerization initiator
- monomer
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- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 104
- 239000000203 mixture Substances 0.000 title claims abstract description 49
- 239000002390 adhesive tape Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 239000003522 acrylic cement Substances 0.000 title claims abstract description 7
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 58
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 46
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 24
- 239000012790 adhesive layer Substances 0.000 claims abstract description 11
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims description 95
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 72
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 56
- 238000006243 chemical reaction Methods 0.000 claims description 55
- 229930195733 hydrocarbon Natural products 0.000 claims description 37
- 239000004215 Carbon black (E152) Substances 0.000 claims description 33
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 239000011347 resin Substances 0.000 claims description 22
- 229920005989 resin Polymers 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 12
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 19
- 230000003467 diminishing effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 41
- 238000006116 polymerization reaction Methods 0.000 description 38
- 239000012855 volatile organic compound Substances 0.000 description 38
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 25
- 238000001035 drying Methods 0.000 description 20
- 239000010410 layer Substances 0.000 description 18
- 230000001070 adhesive effect Effects 0.000 description 17
- 239000003431 cross linking reagent Substances 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- -1 ketone peroxide Chemical class 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 239000000853 adhesive Substances 0.000 description 14
- 238000009835 boiling Methods 0.000 description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 11
- 239000003999 initiator Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 239000012535 impurity Substances 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 9
- 229920002554 vinyl polymer Polymers 0.000 description 9
- 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 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- 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 8
- 238000010992 reflux Methods 0.000 description 8
- 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 8
- 239000004743 Polypropylene Substances 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 6
- RTEZVHMDMFEURJ-UHFFFAOYSA-N 2-methylpentan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCCC(C)(C)OOC(=O)C(C)(C)C RTEZVHMDMFEURJ-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 6
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- NFWPZNNZUCPLAX-UHFFFAOYSA-N 4-methoxy-3-methylaniline Chemical compound COC1=CC=C(N)C=C1C NFWPZNNZUCPLAX-UHFFFAOYSA-N 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000002516 radical scavenger Substances 0.000 description 3
- 150000003333 secondary alcohols Chemical class 0.000 description 3
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 2
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 239000012933 diacyl peroxide Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 125000000075 primary alcohol group Chemical group 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- FYRCDEARNUVZRG-UHFFFAOYSA-N 1,1,5-trimethyl-3,3-bis(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1(OOC(C)(C)CCC)CC(C)CC(C)(C)C1 FYRCDEARNUVZRG-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
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- MUOYRBYBTJDAOT-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)CC(C)(C)OOC(=O)C(C)(C)C MUOYRBYBTJDAOT-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-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
- XKBHBVFIWWDGQX-UHFFFAOYSA-N 2-bromo-3,3,4,4,5,5,5-heptafluoropent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Br)=C XKBHBVFIWWDGQX-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- GVBOWJZGTZIZDH-UHFFFAOYSA-N C(C)(C)(CCC)OOC1C(C(CCC1)(C)C)(C)OOC(C)(C)CCC Chemical compound C(C)(C)(CCC)OOC1C(C(CCC1)(C)C)(C)OOC(C)(C)CCC GVBOWJZGTZIZDH-UHFFFAOYSA-N 0.000 description 1
- 239000013032 Hydrocarbon resin Substances 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 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
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002788 crimping 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
- 238000003795 desorption Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 230000014759 maintenance of location Effects 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
- 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
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- MMCOUVMKNAHQOY-UHFFFAOYSA-L oxido carbonate Chemical compound [O-]OC([O-])=O MMCOUVMKNAHQOY-UHFFFAOYSA-L 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000013014 purified material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 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
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Adhesive Tapes (AREA)
- Polymerization Catalysts (AREA)
Abstract
Description
本発明は、有機過酸化物を重合開始剤として用いたアクリル系重合体の製造において、粘着テープとしたときにＶＯＣの原因となる重合開始剤の分解生成物を殆ど生成せず、得られたアクリル系重合体を用いてなる粘着剤層を有する粘着テープから発生するＶＯＣ量及び臭気を低減することができるアクリル系重合体の製造方法、アクリル系重合体、アクリル系粘着組成物及び粘着テープに関する。 In the production of an acrylic polymer using an organic peroxide as a polymerization initiator, the present invention was obtained with almost no decomposition product of a polymerization initiator causing VOC when used as an adhesive tape. The present invention relates to an acrylic polymer production method, an acrylic polymer, an acrylic adhesive composition, and an adhesive tape that can reduce the amount of VOC and odor generated from an adhesive tape having an adhesive layer made of an acrylic polymer. .
部材を接着固定するための粘着テープは、自動車等の車両や住宅内、更には電子機器の内部等においても広く用いられている。しかし、近年、これらの粘着テープから発生する揮発性有機化合物（ＶＯＣ：Ｖｏｌａｔｉｌｅ Ｏｒｇａｎｉｃ Ｃｏｍｐｏｕｎｄｓ）が問題となっている。 Adhesive tapes for bonding and fixing members are widely used in vehicles such as automobiles and houses, as well as inside electronic devices. However, in recent years, volatile organic compounds (VOC: Volatile Organic Compounds) generated from these adhesive tapes have become a problem.
このようなＶＯＣの問題に対して、例えば、日本では、住宅分野において、シックハウス対策としてこれまでの個別の室内揮発性有機化合物の低減だけではなく、揮発性有機化合物の総量を低減する指針が厚生労働省より出されている。また、例えば、ドイツ自動車工業会（ＶＤＡ）では、自動車内部に用いられる部材の臭いの評価法をＶＤＡ２７０で定めており、揮発性成分の評価法としてＤＶＡ２７７、ＶＤＡ２７８を定めている。更に、ドイツ工業会では、部材より発生する揮発成分による曇りの挙動を判定するために、ドイツ工業規格第７５２０１号を定めている。 In response to such VOC problems, for example, in Japan, in the residential field, guidelines for reducing the total amount of volatile organic compounds as well as reducing individual indoor volatile organic compounds as a countermeasure against sick house are welfare. Issued by the Ministry of Labor. In addition, for example, the German Automobile Manufacturers Association (VDA) defines a method for evaluating the odor of a member used in an automobile by VDA270, and DVA277 and VDA278 are defined as a method for evaluating volatile components. Furthermore, the German Industrial Association has established German Industrial Standard No. 75201 in order to determine the behavior of fogging due to volatile components generated from members.
従来、粘着テープの粘着剤層に用いられるアクリル系重合体は、トルエンを用いたトルエン重合により行われていたが、このようにして製造されるアクリル系重合体にはトルエンが残留しており、この残留トルエンを完全除去することができず、ＶＯＣ発生の原因となっていた。そのため、粘着テープの粘着剤層となるアクリル系重合体の重合を脱トルエンで行うことが盛んに行われている（例えば、特許文献１、２参照）。 Conventionally, the acrylic polymer used in the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape has been performed by toluene polymerization using toluene, but toluene remains in the acrylic polymer produced in this way, This residual toluene could not be completely removed, causing VOC generation. Therefore, polymerization of an acrylic polymer that becomes an adhesive layer of an adhesive tape is actively performed by toluene removal (see, for example, Patent Documents 1 and 2).
しかしながら、脱トルエンで得られたアクリル系重合体を用いた場合、トルエン由来のＶＯＣは低減できるが、アクリル系重合体の重合段階において生成される別の化合物に起因したＶＯＣが問題となっていた。更に、粘着テープの粘着剤層とした場合、アクリル系重合体とともに添加する粘着付与樹脂等やその他の物質が揮発成分として粘着剤層中に残留し、これがＶＯＣ発生の原因となっていた。
本発明は、上記現状に鑑み、有機過酸化物を重合開始剤として用いたアクリル系重合体の製造において、粘着テープとしたときにＶＯＣの原因となる重合開始剤の分解生成物を殆ど生成せず、得られたアクリル系重合体を用いてなる粘着剤層を有する粘着テープから発生するＶＯＣ量及び臭気を低減することができるアクリル系重合体の製造方法、アクリル系重合体、アクリル系粘着組成物及び粘着テープを提供することを目的とする。 In view of the above situation, the present invention produces almost no decomposition product of a polymerization initiator that causes VOC when used as an adhesive tape in the production of an acrylic polymer using an organic peroxide as a polymerization initiator. First, a method for producing an acrylic polymer, an acrylic polymer, and an acrylic pressure-sensitive adhesive composition capable of reducing the amount of VOC and odor generated from the pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer using the obtained acrylic polymer It aims at providing a thing and an adhesive tape.
本発明は、下記一般式（１）で表される有機過酸化物を有する重合開始剤を用いるアクリル系重合体の製造方法である。
以下に本発明を詳述する。
The present invention is a method for producing an acrylic polymer using a polymerization initiator having an organic peroxide represented by the following general formula (1).
The present invention is described in detail below.
本発明者らは、アクリル系重合体を粘着剤層として用いてなる粘着テープから発生するＶＯＣの原因として、アクリル系重合体を製造する際に使用する重合開始剤である有機過酸化物の分解生成物に注目し、鋭意検討の結果、特定の構造の有機過酸化物を有する重合開始剤を用いて重合したアクリル系重合体は、粘着テープの粘着剤層として使用した場合に、ＶＯＣの原因となる有機過酸化物の分解性生物の生成を抑制でき、更に、このようにして製造したアクリル系重合体と特定の粘着付与剤とを併用してなるアクリル系粘着組成物は、粘着テープの粘着剤層に用いた場合、発生するＶＯＣの量を低減することができることを見出し、本発明を完成するに至った。 As a cause of VOC generated from a pressure-sensitive adhesive tape using an acrylic polymer as a pressure-sensitive adhesive layer, the present inventors have decomposed an organic peroxide that is a polymerization initiator used when producing an acrylic polymer. As a result of diligent investigation, the acrylic polymer polymerized using a polymerization initiator having an organic peroxide having a specific structure is the cause of VOC when used as an adhesive layer of an adhesive tape. In addition, the acrylic adhesive composition comprising the acrylic polymer produced in this manner and a specific tackifier in combination can be suppressed in the adhesive tape. When used for the pressure-sensitive adhesive layer, it was found that the amount of VOC generated can be reduced, and the present invention has been completed.
本発明のアクリル系重合体の製造方法は、上記一般式（１）で表される有機過酸化物（以下、本発明に係る有機過酸化物ともいう）を有する重合開始剤を用いてアクリル系モノマーの重合を行う。
上記本発明に係る有機過酸化物は、パーオキシエステル化合物であり、上記一般式（１）中、Ｒは、炭素数の下限が２、上限が７の炭化水素である。このような本発明に係る有機過酸化物は、１次分解によりＲ部分を含むラジカルを生成し、該ラジカルは、更に分解して上記Ｒ部分からなる炭化水素ラジカルとアセトンとを生成する。上記炭化水素ラジカルは、モノマー重合時に取り込まれるか、溶剤から水素を引き抜き炭化水素となる。モノマー重合時に取り込まれた場合は、本発明により製造されるアクリル系重合体の反応溶液中に不純物として残留することがなく、また、炭化水素になった場合は、その生成物は沸点が低くなり、乾燥によって容易に除去される。更に、上記アセトンも、乾燥によって容易に除去される。従って、本発明に係る有機過酸化物を有する重合開始剤（以下、本発明に係る重合開始剤ともいう）を用いる本発明のアクリル系重合体の製造方法によると、製造するアクリル系重合体中に、本発明に係る有機過酸化物の分解生成物に起因するＶＯＣの発生を抑制することができる。
上記Ｒにおける炭素数が２未満であると、本発明に係る有機過酸化物の１次分解により生成されるラジカルが溶剤から水素を引き抜いてｔ−ブタノール、又は、ｔ−ペンタノールとなり、該ｔ−ブタノール、又は、ｔ−ペンタノールに起因するＶＯＣの問題が生じる。７を超えると、本発明に係る有機過酸化物の１次分解により生成されたラジカルが更に分解して生成するＲ部分からなる炭化水素ラジカルの炭素数が７を超えるものとなり、このような炭化水素ラジカルは、溶剤から水素を引き抜き炭化水素になった場合、高沸点不純物となって製造するアクリル系重合体中に残存し、粘着テープの粘着剤層に用いた際にＶＯＣ発生の原因となる。
The method for producing an acrylic polymer of the present invention is an acrylic system using a polymerization initiator having an organic peroxide represented by the general formula (1) (hereinafter also referred to as an organic peroxide according to the present invention). Polymerize the monomer.
The organic peroxide according to the present invention is a peroxyester compound, and in the general formula (1), R is a hydrocarbon having a lower limit of 2 carbon atoms and an upper limit of 7. Such an organic peroxide according to the present invention generates a radical including an R moiety by primary decomposition, and the radical further decomposes to generate a hydrocarbon radical composed of the R moiety and acetone. The hydrocarbon radical is taken in at the time of monomer polymerization or becomes hydrogenated hydrocarbon by extracting hydrogen from the solvent. When taken in during monomer polymerization, it does not remain as an impurity in the reaction solution of the acrylic polymer produced according to the present invention, and when it becomes hydrocarbon, the product has a low boiling point. Easily removed by drying. Furthermore, the acetone is also easily removed by drying. Therefore, according to the method for producing the acrylic polymer of the present invention using the polymerization initiator having the organic peroxide according to the present invention (hereinafter also referred to as the polymerization initiator according to the present invention), the acrylic polymer to be produced Furthermore, the generation of VOC caused by the decomposition product of the organic peroxide according to the present invention can be suppressed.
When the carbon number in R is less than 2, radicals generated by the primary decomposition of the organic peroxide according to the present invention extract hydrogen from the solvent to become t-butanol or t-pentanol, and the t -VOC problems due to butanol or t-pentanol arise. If it exceeds 7, the radical generated by the primary decomposition of the organic peroxide according to the present invention further decomposes and the hydrocarbon radical consisting of the R moiety exceeds 7 carbon atoms. When hydrogen radicals are extracted from a solvent to become hydrocarbons, hydrogen radicals remain in the acrylic polymer produced as high-boiling impurities and cause VOC generation when used in an adhesive layer of an adhesive tape. .
上記一般式（１）中、Ｒ’は、炭素数の下限が１、上限が７の炭化水素、又は、酸素原子を有する炭素数の下限が１、上限が７の炭化水素である。このような本発明に係る有機過酸化物は、１次分解によりＲ’部分を含むラジカルを生成し、該ラジカルは、更に分解して上記Ｒ’部分からなる炭化水素ラジカルと二酸化炭素とを生成する。炭素数が７を超えると、本発明に係る有機過酸化物の１次分解により生成されたラジカルが更に分解して生成するＲ’部分からなる炭化水素ラジカルの炭素数が７を超えるものとなり、このような炭化水素ラジカルは、溶剤から水素を引き抜き炭化水素になった場合、高沸点不純物となって製造するアクリル系重合体中に残存し、粘着テープの粘着剤層に用いた際にＶＯＣ発生の原因となる。 In the general formula (1), R ′ is a hydrocarbon having a lower limit of 1 carbon number and an upper limit of 7 or a hydrocarbon having a lower limit of 1 carbon atom having an oxygen atom and an upper limit of 7. Such an organic peroxide according to the present invention generates a radical including an R ′ portion by primary decomposition, and the radical further decomposes to generate a hydrocarbon radical including the R ′ portion and carbon dioxide. To do. When the carbon number exceeds 7, the radical generated by the primary decomposition of the organic peroxide according to the present invention is further decomposed and the hydrocarbon radical consisting of the R ′ portion is generated to exceed 7, Such hydrocarbon radicals, when hydrogen is extracted from the solvent and become hydrocarbons, remain in the acrylic polymer produced as high-boiling impurities and generate VOCs when used in the adhesive layer of adhesive tapes. Cause.
このような本発明に係る有機過酸化物としては、例えば、ｔ−ヘキシルパーオキシ−２−エチルヘキサノエート、ｔ−ブチルパーオキシ−２−エチルヘキサノエート、ｔ−ブチルパーオキシ−３，５，５−トリメチルヘキサノエート、ｔ−ブチルパーオキシラウレート、ｔ−ヘキシルパーオキシピバレート等が挙げられる。 Examples of the organic peroxide according to the present invention include t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy-3, Examples include 5,5-trimethylhexanoate, t-butyl peroxylaurate, t-hexyl peroxypivalate, and the like.
本発明のアクリル系重合体の製造方法において、本発明に係る重合開始剤は、１０時間半減温度が９０℃以下である化合物を８０重量％以上含有することが好ましい。また、１０時間半減温度が８０℃以下である化合物を８０重量％以上含有することがより好ましい。
このような本発明に係る重合開始剤を用いることで、後述するモノマーの重合を行った際に、本発明に係る重合開始剤やその残渣が揮発成分として反応溶液中に残存することを好適に防止することができる。８０重量％未満であると、製造したアクリル系重合体の反応溶液中に本発明に係る有機過酸化物やその残渣が残存することがある。
上記１０時間半減温度が９０℃以下である化合物としては、例えば、上述した本発明に係る有機過酸化物等が挙げられる。
In the method for producing an acrylic polymer of the present invention, the polymerization initiator according to the present invention preferably contains 80% by weight or more of a compound having a 10-hour half-temperature of 90 ° C. or less. Moreover, it is more preferable to contain 80% by weight or more of a compound having a 10 hour half-life temperature of 80 ° C. or less.
By using such a polymerization initiator according to the present invention, it is preferable that the polymerization initiator according to the present invention and its residue remain in the reaction solution as a volatile component when the monomer described below is polymerized. Can be prevented. If it is less than 80% by weight, the organic peroxide or the residue thereof according to the present invention may remain in the reaction solution of the produced acrylic polymer.
Examples of the compound having a 10-hour half-life temperature of 90 ° C. or less include the organic peroxides according to the present invention described above.
本発明のアクリル系重合体の製造方法で使用する本発明に係る重合開始剤は、上記本発明に係る有機過酸化物のみからなることが好ましいが、本発明に係る有機過酸化物以外の化合物を重合開始剤として含有していてもよい。本発明に係る有機過酸化物以外の化合物としては特に限定されず、例えば、パーオキシカーボネート、ケトンパーオキサイド、パーオキシケタール、ハイドロパーオキサイド、ジアルキルパーオキサイド、ジアシルパーオキサイド（ラウロイルパーオキサイド、ベンゾイルパーオキサイド、３，５，５−トリメチルヘキサノイルパーオキサイド）等が挙げられる。
これらの化合物を重合開始剤として含有する場合、本発明に係る有機過酸化物１００重量部に対して、好ましい下限は０．００１重量部、好ましい上限５０重量部である。０．００１重量部未満であると、上記化合物を添加する効果を殆ど得ることができず、５０重量部を超えると、本発明により製造したアクリル系重合体を用いた粘着剤層を有する粘着テープに、上記化合物に起因したＶＯＣが発生することがある。
The polymerization initiator according to the present invention used in the method for producing an acrylic polymer according to the present invention preferably comprises only the organic peroxide according to the present invention, but the compound other than the organic peroxide according to the present invention. May be contained as a polymerization initiator. The compound other than the organic peroxide according to the present invention is not particularly limited. For example, peroxycarbonate, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide (lauroyl peroxide, benzoyl peroxide). Oxide, 3,5,5-trimethylhexanoyl peroxide) and the like.
When these compounds are contained as a polymerization initiator, the preferred lower limit is 0.001 part by weight and the preferred upper limit is 50 parts by weight with respect to 100 parts by weight of the organic peroxide according to the present invention. When the amount is less than 0.001 part by weight, the effect of adding the above compound can hardly be obtained. When the amount exceeds 50 parts by weight, the pressure-sensitive adhesive tape has a pressure-sensitive adhesive layer using the acrylic polymer produced according to the present invention. In addition, VOCs resulting from the above compounds may occur.
本発明に係る重合開始剤を用いて重合を行うアクリル系モノマーとしては特に限定されないが、（メタ）アクリル酸エステルモノマーが好適に用いられる。
上記（メタ）アクリル酸エステルモノマーとしては、例えば、アルキル基の炭素数が１〜１２の１級又は２級アルコールと、アクリル酸又はメタクリル酸とのエステルが好適に用いられる。なお、本明細書において、（メタ）アクリル酸とは、アクリル酸又はメタクリル酸を意味する。
Although it does not specifically limit as an acryl-type monomer which superposes | polymerizes using the polymerization initiator which concerns on this invention, A (meth) acrylic acid ester monomer is used suitably.
As the (meth) acrylic acid ester monomer, for example, an ester of a primary or secondary alcohol having 1 to 12 carbon atoms in an alkyl group and acrylic acid or methacrylic acid is preferably used. In the present specification, (meth) acrylic acid means acrylic acid or methacrylic acid.
上記アルキル基の炭素数が１〜１２の１級又は２級アルコールと、アクリル酸又はメタクリル酸とのエステルとしては、例えば、ｎ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、エチル（メタ）アクリレート、メチル（メタ）アクリレート等が挙げられる。 Examples of the ester of a primary or secondary alcohol having 1 to 12 carbon atoms of the alkyl group and acrylic acid or methacrylic acid include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyl ( Examples include meth) acrylate and methyl (meth) acrylate.
本発明のアクリル系重合体の製造方法では、上記アクリル系モノマーと、該アクリル系モノマーと共重合可能な他のビニルモノマーとを共重合させてもよい。
上記ビニルモノマーは、本発明により製造されるアクリル系重合体を改質して凝集力を高めるために用いられるものであり、例えば、分子内に含有する官能基と外部架橋剤との架橋反応によりポリマー同士の網目形成に寄与するもの等が用いられる。
In the method for producing an acrylic polymer of the present invention, the above acrylic monomer and another vinyl monomer copolymerizable with the acrylic monomer may be copolymerized.
The vinyl monomer is used to modify the acrylic polymer produced according to the present invention to increase the cohesive force. For example, the vinyl monomer is subjected to a crosslinking reaction between a functional group contained in the molecule and an external crosslinking agent. What contributes to the network formation between polymers is used.
分子内に含有する官能基と外部架橋剤との架橋反応によりポリマー同士の網目形成に寄与するビニルモノマーとしては、例えば、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、イタコン酸、無水マレイン酸等のカルボキシル基含有モノマー；２−ヒドロキシエチル（メタ）アクリレート、ｎ−メチロールアクリルアミド等の水酸基含有モノマー；グリシジルアクリレート、アリルグリシジルエーテル等のエポキシ基含有モノマー等が挙げられる。 Examples of vinyl monomers that contribute to the formation of a network between polymers by a cross-linking reaction between a functional group contained in the molecule and an external cross-linking agent include acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, maleic anhydride, etc. Carboxyl group-containing monomers; hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate and n-methylolacrylamide; and epoxy group-containing monomers such as glycidyl acrylate and allyl glycidyl ether.
本発明のアクリル系重合体の製造方法において、上記（メタ）アクリル酸エステルモノマーとこれと共重合可能な他のビニルモノマーとを共重合体させる場合、上記（メタ）アクリル酸エステルモノマーの含有量は、モノマー組成中の好ましい下限は７０重量％である。７０重量％未満であると、得られるアクリル系重合体を粘着テープにした際に、粘着性能が低下することがある。 In the method for producing an acrylic polymer of the present invention, when the (meth) acrylate monomer and another vinyl monomer copolymerizable therewith are copolymerized, the content of the (meth) acrylate monomer The preferred lower limit in the monomer composition is 70% by weight. If it is less than 70% by weight, the adhesive performance may be lowered when the resulting acrylic polymer is used as an adhesive tape.
また、上記他のビニルモノマーが分子内に含有する官能基と外部架橋剤との架橋反応によりポリマー同士の網目形成に寄与するものである場合、このようなビニルモノマーの含有量の好ましい下限は０．０１重量％、好ましい上限は１０重量％である。０．０１重量％未満であると、製造するアクリル系重合体の凝集力を充分に高めることができないことがあり、１０重量％を超えると、得られるアクリル系重合体を粘着テープにした際に、粘着性能が低下することがある。より好ましい下限は０．０５重量％、より好ましい上限は５重量％である。 When the other vinyl monomer contributes to network formation between polymers by a crosslinking reaction between a functional group contained in the molecule and an external crosslinking agent, the preferred lower limit of the content of such a vinyl monomer is 0. 0.01% by weight, and a preferred upper limit is 10% by weight. When the amount is less than 0.01% by weight, the cohesive force of the acrylic polymer to be produced may not be sufficiently increased. When the amount exceeds 10% by weight, the resulting acrylic polymer is used as an adhesive tape. Adhesive performance may be reduced. A more preferred lower limit is 0.05% by weight, and a more preferred upper limit is 5% by weight.
上記（メタ）アクリル系モノマー等のモノマーの重合方法としては特に限定されず、例えば、溶液重合（沸点重合、沸点未満重合）、乳化重合、懸濁重合、塊状重合、リビング重合等の公知の重合方法を用いることができる。なかでも、界面活性剤や分散剤等を使用しない溶液重合が好ましい。 The method for polymerizing the monomer such as the (meth) acrylic monomer is not particularly limited. For example, known polymerization such as solution polymerization (boiling point polymerization, polymerization below boiling point), emulsion polymerization, suspension polymerization, bulk polymerization, living polymerization, etc. The method can be used. Among these, solution polymerization that does not use a surfactant or a dispersant is preferable.
上記（メタ）アクリル系モノマー等のモノマーの重合時に添加する本発明に係る重合開始剤の量としては特に限定されないが、好ましい下限は０．０１重量％、好ましい上限は２０重量％である。０．０１重量％未満であると、上記モノマーの重合を充分に行うことができないことがあり、２０重量％を超えると、本発明に係る重合開始剤やその残渣が不純物として製造するアクリル系重合体の反応世液中に残存することがある。より好ましい下限は０．１重量％であり、より好ましい上限は５重量％である。 The amount of the polymerization initiator according to the present invention added at the time of polymerization of the monomer such as the (meth) acrylic monomer is not particularly limited, but a preferable lower limit is 0.01% by weight and a preferable upper limit is 20% by weight. When the amount is less than 0.01% by weight, the above-mentioned monomer may not be sufficiently polymerized. When the amount exceeds 20% by weight, the acrylic heavy polymer produced as an impurity by the polymerization initiator and its residue according to the present invention is used. May remain in the combined reaction solution. A more preferred lower limit is 0.1% by weight, and a more preferred upper limit is 5% by weight.
上記（メタ）アクリル系モノマー等のモノマーを重合する際には、重合条件として本発明に係る重合開始剤の１０時間半減温度より高い反応温度に保ち、できる限り長時間反応を行うことが好ましい。この場合、反応時間の好ましい下限は５時間である。５時間以上とすることで、反応溶液中に本発明に係る重合開始剤やその残渣が揮発成分として残存することを防止することができる。
特に、反応終了時の反応温度ｔが重合開始剤の１０時間半減温度Ｔに対して、Ｔ＋３５≧ｔ≧Ｔとなるようにすることが好ましく、Ｔ＋２５≧ｔ≧Ｔ＋５となるようにすることがより好ましい。このようにすることで反応時にゲル等の異物が発生することを防止することができ、かつ、効率的に残存モノマーや開始剤残渣を低減させることが可能となる。
When the monomer such as the (meth) acrylic monomer is polymerized, it is preferable to carry out the reaction for as long as possible while keeping the reaction temperature higher than the 10-hour half-temperature of the polymerization initiator according to the present invention as the polymerization conditions. In this case, the preferred lower limit of the reaction time is 5 hours. By setting it as 5 hours or more, it can prevent that the polymerization initiator which concerns on this invention, or its residue remains in a reaction solution as a volatile component.
In particular, the reaction temperature t at the end of the reaction is preferably T + 35 ≧ t ≧ T with respect to the 10-hour half-life temperature T of the polymerization initiator, and more preferably T + 25 ≧ t ≧ T + 5. preferable. By doing in this way, it can prevent that foreign materials, such as a gel, generate | occur | produce at the time of reaction, and it becomes possible to reduce a residual monomer and initiator residue efficiently.
上記（メタ）アクリル系モノマー等のモノマーを重合する際には、未反応モノマーを効率的に消費させるため、本発明に係る重合開始剤の未分解物濃度が、モノマー反応率が８０％以下の状態で、投入モノマー１００重量部に対して１０−３〜１０重量部に保持されることが好ましい。１０−３重量部未満であると、本発明に係る重合開始剤の未分解物濃度が低すぎ、未反応モノマーが消費されず反応溶液中に残ることがあり、１０重量部を超えると、本発明に係る重合開始剤の濃度が高すぎ、反応が暴走する危険性が高まる。 When polymerizing monomers such as the (meth) acrylic monomer, the unreacted monomer concentration of the polymerization initiator according to the present invention is such that the monomer reaction rate is 80% or less in order to efficiently consume unreacted monomers. In the state, it is preferable that 10 <-3 > -10 weight part is hold | maintained with respect to 100 weight part of input monomers. If it is less than 10-3 parts by weight, the undegraded product concentration of the polymerization initiator according to the present invention is too low, and unreacted monomers may not be consumed and may remain in the reaction solution. The concentration of the polymerization initiator according to the invention is too high, increasing the risk of runaway reaction.
本発明に係る重合開始剤の未分解物濃度を上記範囲に保持する方法としては、例えば、本発明に係る重合開始剤を反応初期から連続投入する方法や、複数回に分割して投入する方法等が挙げられる。これらの方法を用いることにより、効率的に未反応モノマーを消費することができ、重合後のアクリル系重合体の反応溶液中に残存する未反応モノマー（残留モノマー）、未反応重合開始剤（残留重合開始剤）及び他の不純物が少ないアクリル系重合体を得ることができる。 Examples of the method for maintaining the undegraded product concentration of the polymerization initiator according to the present invention in the above range include, for example, a method of continuously adding the polymerization initiator according to the present invention from the initial reaction, and a method of adding it divided into a plurality of times. Etc. By using these methods, the unreacted monomer can be consumed efficiently, and the unreacted monomer (residual monomer) remaining in the reaction solution of the acrylic polymer after polymerization, the unreacted polymerization initiator (residual) A polymerization initiator) and an acrylic polymer with few other impurities can be obtained.
このような本発明により製造したアクリル系重合体の反応溶液中には、未反応モノマー、未反応重合開始剤又は他の不純物は、殆ど残留しないが、更に未反応モノマー、未反応重合開始剤又は他の不純物を減少させるために、重合時又は重合終了後、必要に応じて残留モノマー、残留重合開始剤、他の不純物を除去する操作を施すことが好ましい。 In the reaction solution of the acrylic polymer produced according to the present invention, almost no unreacted monomer, unreacted polymerization initiator or other impurities remain, but the unreacted monomer, unreacted polymerization initiator or In order to reduce other impurities, it is preferable to perform an operation for removing the residual monomer, the residual polymerization initiator, and other impurities as necessary during or after the polymerization.
上記重合段階で残留モノマーを低減する具体的な手段としては、例えば、重合終期に、還流溶媒中の残存モノマーを分離・除去する方法；アクリル系モノマーやビニルモノマーと反応し揮発除去され易い低沸点のスキャベンジャーモノマーを重合中に添加する方法等が挙げられる。 Specific means for reducing the residual monomer in the polymerization stage include, for example, a method of separating and removing the residual monomer in the refluxing solvent at the end of the polymerization; a low boiling point that easily reacts with the acrylic monomer and the vinyl monomer to be removed by volatilization And a method of adding the scavenger monomer in the polymerization.
また、重合系から残留モノマーを除去する方法としては、例えば、重合溶媒の還流液を新鮮な溶媒で置換する方法；重合開始時及び重合中に酢酸ビニル、ビニルブチルエーテル、アクリル酸メチル、スチレン等の比較的低沸点のスキャベンジャーモノマーを添加し、スキャベンジャーとともに除去する方法；重合終了時に、アクリル系重合体に対する貧溶媒、例えば、メタノール、エタノール、ｎ−ヘキサン、ｎ−へプタン等の低沸点溶媒を用いてアクリル系重合体を洗浄する方法等が挙げられる。 Further, as a method for removing the residual monomer from the polymerization system, for example, a method of replacing the reflux solution of the polymerization solvent with a fresh solvent; vinyl acetate, vinyl butyl ether, methyl acrylate, styrene, etc. at the start and during the polymerization A method of adding a scavenger monomer having a relatively low boiling point and removing it together with the scavenger; a poor solvent for the acrylic polymer at the end of the polymerization, for example, a low boiling solvent such as methanol, ethanol, n-hexane, n-heptane, etc. And a method of washing an acrylic polymer using
本発明のアクリル系重合体の製造方法では、上記方法を単独又は２つ以上併用することで、反応終了時における残存モノマー濃度及び残留重合開始剤濃度を、いずれも５００ｐｐｍ以下にすることが好ましい。反応終了時における残存モノマー濃度及び残存重合開始剤濃度が５００ｐｐｍを超えると、本発明により製造されるアクリル系重合体を用いてなる粘着テープからＶＯＣが発生してしまうことがある。 In the method for producing an acrylic polymer of the present invention, it is preferable that the residual monomer concentration and the residual polymerization initiator concentration at the end of the reaction are both 500 ppm or less by using one or more of the above methods in combination. When the residual monomer concentration and the residual polymerization initiator concentration at the end of the reaction exceed 500 ppm, VOC may be generated from the adhesive tape using the acrylic polymer produced according to the present invention.
本発明のアクリル系重合体の製造方法では、上記モノマーの重合時に上記一般式（１）に示す構造の有機過酸化物を有する重合開始剤を用いる。上記有機過酸化物は、１次分解によりＲ部分を含むラジカルを生成し、該ラジカルは、更に分解して上記Ｒ部分からなる炭化水素ラジカルとアセトンとが生成する。この生成した炭化水素ラジカルは、モノマー重合時に取り込まれるか、溶剤から水素を引き抜き炭化水素となる。モノマー重合時に取り込まれた場合は、本発明により製造されるアクリル系重合体の反応溶液中に不純物として残留することがなく、また、炭化水素になった場合は、その生成物は沸点が低くなり、乾燥によって容易に除去される。更に、上記アセトンも、乾燥によって容易に除去される。また、上記有機過酸化物は、１次分解によりＲ’部分を含むラジカルを生成し、該ラジカルは、更に分解して上記Ｒ’部分からなる炭化水素ラジカルと二酸化炭素とを生成するが、生成した炭化水素ラジカルは、低沸点であるため乾燥によって容易に除去される。
従って、本発明のアクリル系重合体の製造方法により製造するアクリル系重合体は、その反応溶液中に上記一般式（１）で表される有機過酸化物の分解生成物が殆ど残存しておらず、製造したアクリル系重合体を用いてなる粘着テープは、上記有機過酸化物の分解生成物に起因したＶＯＣの発生を抑制することができる。
In the method for producing an acrylic polymer of the present invention, a polymerization initiator having an organic peroxide having a structure represented by the general formula (1) is used during the polymerization of the monomer. The organic peroxide generates a radical including an R portion by primary decomposition, and the radical is further decomposed to generate a hydrocarbon radical composed of the R portion and acetone. The generated hydrocarbon radicals are taken in at the time of monomer polymerization, or hydrogen is extracted from the solvent to become hydrocarbons. When taken in during monomer polymerization, it does not remain as an impurity in the reaction solution of the acrylic polymer produced according to the present invention, and when it becomes hydrocarbon, the product has a low boiling point. Easily removed by drying. Furthermore, the acetone is also easily removed by drying. The organic peroxide generates a radical containing an R ′ portion by primary decomposition, and the radical is further decomposed to generate a hydrocarbon radical consisting of the R ′ portion and carbon dioxide. The hydrocarbon radicals having a low boiling point are easily removed by drying.
Therefore, in the acrylic polymer produced by the method for producing an acrylic polymer of the present invention, almost no decomposition product of the organic peroxide represented by the general formula (1) remains in the reaction solution. First, the pressure-sensitive adhesive tape using the produced acrylic polymer can suppress the occurrence of VOC caused by the decomposition product of the organic peroxide.
下記一般式（１）で表される有機過酸化物を有する重合開始剤を用いて製造されてなるアクリル系重合体であって、反応終了時における残留モノマー濃度及び残留重合開始剤濃度が、いずれも５００ｐｐｍ以下であるアクリル系重合体もまた、本発明の１つである。 An acrylic polymer produced using a polymerization initiator having an organic peroxide represented by the following general formula (1), wherein the residual monomer concentration and the residual polymerization initiator concentration at the end of the reaction are: An acrylic polymer having a concentration of 500 ppm or less is also one aspect of the present invention.
本発明のアクリル系重合体において、上記一般式（１）で表される有機過酸化物は、上述した本発明のアクリル系重合体の製造方法における有機過酸化物と同様のものが挙げられる。 In the acrylic polymer of the present invention, examples of the organic peroxide represented by the general formula (1) include the same organic peroxides in the above-described method for producing an acrylic polymer of the present invention.
本発明のアクリル系重合体は、アルキル部分の炭素数が１〜１２であるアルキル（メタ）アクリレートを有するモノマー成分と、上記一般式（１）で表される有機過酸化物を有する重合開始剤とを用いて製造されてなることが好ましい。このような本発明のアクリル系重合体は、粘着テープの粘着剤層を構成する材料として好適に用いることができる。 The acrylic polymer of the present invention is a polymerization initiator having a monomer component having an alkyl (meth) acrylate having an alkyl moiety of 1 to 12 carbon atoms and an organic peroxide represented by the general formula (1). It is preferable that it is manufactured using. Such an acrylic polymer of the present invention can be suitably used as a material constituting the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape.
上記アルキル部分の炭素数が１〜１２であるアルキル（メタ）アクリレートとしては特に限定されず、上述した本発明のアクリル系重合体の製造方法において説明したアルキル基の炭素数が１〜１２の１級又は２級アルコールと、アクリル酸又はメタクリル酸とのエステルが挙げられる。 The alkyl (meth) acrylate having 1 to 12 carbon atoms in the alkyl moiety is not particularly limited, and the alkyl group described in the above-described method for producing an acrylic polymer of the present invention has 1 to 12 carbon atoms. Examples thereof include esters of a secondary or secondary alcohol and acrylic acid or methacrylic acid.
このような本発明のアクリル系重合体は、上述した本発明のアクリル系重合体の製造方法により好適に製造することができる。 Such an acrylic polymer of the present invention can be suitably produced by the above-described method for producing an acrylic polymer of the present invention.
上記アルキル部分の炭素数が１〜１２であるアルキル（メタ）アクリレートを有するモノマー成分と、上記一般式（１）で表される有機過酸化物を有する重合開始剤とを用いて製造されてなる本発明のアクリル系重合体と、粘着付与樹脂とを含有するアクリル系粘着組成物であって、前記粘着付与樹脂は、重量平均分子量が６００以下の成分の含有量が１３重量％以下であり、かつ、０．１〜５０重量％含有されているアクリル系粘着組成物もまた、本発明の１つである。 It is produced using a monomer component having an alkyl (meth) acrylate having 1 to 12 carbon atoms in the alkyl portion and a polymerization initiator having an organic peroxide represented by the general formula (1). An acrylic pressure-sensitive adhesive composition containing the acrylic polymer of the present invention and a tackifier resin, wherein the tackifier resin has a content of a component having a weight average molecular weight of 600 or less and 13% by weight or less, An acrylic pressure-sensitive adhesive composition containing 0.1 to 50% by weight is also one aspect of the present invention.
本発明のアクリル系粘着組成物は、アクリル系重合体と、粘着付与樹脂とを含有する。
上記アクリル系重合体は、上述した本発明のアクリル系重合体であって、アルキル部分の炭素数が１〜１２であるアルキル（メタ）アクリレートと、上記一般式（１）で表される有機過酸化物を有する重合開始剤とを用いて製造されてなるものである。
The acrylic pressure-sensitive adhesive composition of the present invention contains an acrylic polymer and a tackifier resin.
The acrylic polymer is an acrylic polymer of the present invention described above, and an alkyl (meth) acrylate having an alkyl moiety having 1 to 12 carbon atoms and an organic polymer represented by the general formula (1). It is produced using a polymerization initiator having an oxide.
上記粘着付与剤は、本発明のアクリル系粘着組成物の粘着力や耐剥離性等の粘着物性を改善する役割を果たし、このような粘着付与剤としては、重量平均分子量６００以下の成分の含有量が１３重量％以下である。このような粘着付与剤を用いれば、本発明のアクリル系粘着組成物の粘着物性を損なうことなく粘着付与剤より発生する揮発成分を低く抑え、粘着物性を改善し、かつ、本発明のアクリル系粘着組成物を用いてなる粘着テープから発生するＶＯＣを抑制することができる。なお、上記粘着付与剤の重量平均分子量及びその含有量は、ＧＰＣにより測定し、ポリスチレン換算値及び面積比により算出できる。 The tackifier plays a role of improving adhesive properties such as adhesive strength and peel resistance of the acrylic pressure-sensitive adhesive composition of the present invention, and such a tackifier includes a component having a weight average molecular weight of 600 or less. The amount is 13% by weight or less. If such a tackifier is used, the volatile component generated from the tackifier is kept low without impairing the adhesive physical properties of the acrylic adhesive composition of the present invention, the adhesive physical properties are improved, and the acrylic of the present invention VOC generated from the pressure-sensitive adhesive tape using the pressure-sensitive adhesive composition can be suppressed. In addition, the weight average molecular weight of the said tackifier and its content can be measured by GPC, and can be calculated by a polystyrene conversion value and an area ratio.
上記粘着付与剤としては、例えば、ロジン樹脂、ロジン変性フェノール樹脂、不均化ロジンエステル樹脂類、重合ロジンエステル樹脂、水添ロジン樹脂、水添ロジンエステル樹脂類、テルペンフェノール樹脂類、クマロンインデン樹脂、アルキルフェノール樹脂、石油樹脂類等が挙げられる。なかでも、不均化ロジンエステル樹脂類、重合ロジンエステル樹脂、石油樹脂類に位置する脂環族飽和炭化水素樹脂等は、低分子量成分を除去可能であることから好適である。特に、ポリプロピレン樹脂等の難被着体に対しても粘着力が強く耐剥離性に優れる点で、重合ロジンエステル樹脂がより好ましい。 Examples of the tackifier include rosin resins, rosin-modified phenol resins, disproportionated rosin ester resins, polymerized rosin ester resins, hydrogenated rosin resins, hydrogenated rosin ester resins, terpene phenol resins, coumarone indene. Resins, alkylphenol resins, petroleum resins and the like can be mentioned. Of these, disproportionated rosin ester resins, polymerized rosin ester resins, alicyclic saturated hydrocarbon resins located in petroleum resins, and the like are preferable because they can remove low molecular weight components. In particular, a polymerized rosin ester resin is more preferable because it has a strong adhesive force even on difficult adherends such as polypropylene resin and is excellent in peel resistance.
上記粘着付与剤から分子量６００以下の成分を除去する方法としては、例えば、粘着付与剤を軟化点以上に加熱溶融する方法、水蒸気を吹き込む方法等が挙げられる。
上記粘着付与剤を加熱溶融する方法においては、空気中の酸素との酸化反応を防ぐために、窒素、ヘリウム等の不活性ガス中で加熱することが好ましい。また、加熱時間は、加熱による粘着付与剤の分解を避けるために１〜５時間程度が好ましい。
上記水蒸気を吹き込む方法においては、粘着付与剤を加熱溶融後に１〜５０ｋＰａ程度に減圧してから水蒸気を吹き込むと、揮発性成分の低減、臭気の低減が達成される。水蒸気を吹き込む時間としては、１〜５時間程度が好ましい。１時間未満であると、大きな揮発性ガスの低減と、それに伴う臭気の低減効果が少なく、５時間を超えて処理しても処理効果はあまり変わらない。
Examples of the method for removing a component having a molecular weight of 600 or less from the tackifier include a method of heating and melting the tackifier above the softening point, and a method of blowing water vapor.
In the method of heating and melting the tackifier, it is preferable to heat in an inert gas such as nitrogen or helium in order to prevent an oxidation reaction with oxygen in the air. The heating time is preferably about 1 to 5 hours in order to avoid decomposition of the tackifier by heating.
In the method of blowing water vapor, when the tackifier is decompressed to about 1 to 50 kPa after heating and melting and then water vapor is blown, reduction of volatile components and reduction of odor are achieved. The time for blowing water vapor is preferably about 1 to 5 hours. If it is less than 1 hour, the effect of reducing large volatile gases and the accompanying odor is small, and the treatment effect does not change much even if the treatment is performed for more than 5 hours.
本発明のアクリル系粘着組成物において、上記粘着付与剤の含有量の下限は０．１重量％、上限は５０重量％である。０．１重量％未満であると、本発明のアクリル系粘着組成物の粘着物性の改善が不充分となり、５０重量％を超えると、本発明のアクリル系粘着組成物を用いてなる粘着テープに上記粘着付与剤に起因したＶＯＣが発生してしまう。好ましい下限は５重量％、好ましい上限は３０重量％である。 In the acrylic pressure-sensitive adhesive composition of the present invention, the lower limit of the content of the tackifier is 0.1% by weight, and the upper limit is 50% by weight. If it is less than 0.1% by weight, the improvement of the adhesive properties of the acrylic pressure-sensitive adhesive composition of the present invention is insufficient, and if it exceeds 50% by weight, the pressure-sensitive adhesive tape using the acrylic pressure-sensitive adhesive composition of the present invention is used. VOC resulting from the said tackifier will generate | occur | produce. A preferred lower limit is 5% by weight and a preferred upper limit is 30% by weight.
このような粘着付与剤を含有する本発明のアクリル系粘着組成物は、粘着テープの粘着剤層に用いたときに、発生するＶＯＣの量を少なくすることができ、具体的には、上記粘着テープを９０℃、３０分間加熱したときに放出される、下記式（１）で表される揮発成分濃度（Ａ）を３００ｐｐｍ以下に、１２０℃、３０分間加熱したときに放出される、下記式（２）で表される揮発成分濃度（Ｂ）を４００ｐｐｍ以下にそれぞれ抑えることができ、更に、乾燥で除去が困難な高沸点成分である保持時間３０分以上の揮発成分量を５０ｐｐｍ以下にすることができる。 The acrylic pressure-sensitive adhesive composition of the present invention containing such a tackifier can reduce the amount of VOC generated when used in a pressure-sensitive adhesive layer of a pressure-sensitive adhesive tape. Volatile component concentration (A) expressed by the following formula (1) released when the tape is heated at 90 ° C. for 30 minutes is released to 300 ppm or less and heated at 120 ° C. for 30 minutes. The volatile component concentration (B) represented by (2) can be suppressed to 400 ppm or less, and the amount of volatile components having a retention time of 30 minutes or more, which is a high-boiling component that is difficult to remove by drying, is 50 ppm or less. be able to.
本発明のアクリル系粘着組成物は、架橋剤を含有していてもよい。架橋剤を含有することにより、アクリル系重合体又は粘着付与剤中に導入された官能基と反応し、アクリル系重合体同士又はアクリル系重合体と粘着付与剤との架橋構造が形成され、凝集力が高められる。
上記架橋剤としては特に限定されず、例えば、イソシアネート系架橋剤、アジリジン系架橋剤、エポキシ系架橋剤、金属キレート型架橋剤等が挙げられる。
The acrylic pressure-sensitive adhesive composition of the present invention may contain a crosslinking agent. By containing the cross-linking agent, it reacts with the functional group introduced into the acrylic polymer or tackifier, and a cross-linked structure between the acrylic polymers or between the acrylic polymer and the tackifier is formed. Power is increased.
It does not specifically limit as said crosslinking agent, For example, an isocyanate type crosslinking agent, an aziridine type crosslinking agent, an epoxy-type crosslinking agent, a metal chelate type crosslinking agent etc. are mentioned.
本発明のアクリル系粘着組成物が上記架橋剤を含有する場合、その含有量としては特に限定されないが、好ましい下限は０．１重量％、好ましい上限は１０重量％である。０．１重量％未満であると、上述したアクリル系重合体同士等を架橋する効果を殆ど得ることができず、１０重量％を超えると、本発明のアクリル系粘着組成物を用いてなる粘着テープから上記架橋剤に起因したＶＯＣが発生することがある。より好ましい下限は０．５重量％、より好ましい上限は３重量％である。 When the acrylic pressure-sensitive adhesive composition of the present invention contains the crosslinking agent, the content thereof is not particularly limited, but the preferred lower limit is 0.1% by weight and the preferred upper limit is 10% by weight. When the amount is less than 0.1% by weight, the above-mentioned effect of crosslinking the acrylic polymers can hardly be obtained. When the amount exceeds 10% by weight, the pressure-sensitive adhesive composition using the acrylic pressure-sensitive adhesive composition of the present invention is used. VOCs resulting from the crosslinking agent may occur from the tape. A more preferred lower limit is 0.5% by weight, and a more preferred upper limit is 3% by weight.
また、本発明のアクリル系粘着組成物は、必要に応じて、可塑剤、乳化剤、軟化剤、充填剤、顔料、染料等の添加剤を含有していてもよい。これらの添加剤も上記粘着付与剤と同様に適宜揮発成分を可能な限り除去していることが好ましい。 The acrylic pressure-sensitive adhesive composition of the present invention may contain additives such as a plasticizer, an emulsifier, a softener, a filler, a pigment, and a dye as necessary. It is preferable that these additives also remove volatile components as much as possible as in the case of the tackifier.
本発明のアクリル系粘着組成物は、上述した本発明のアクリル系重合体の製造方法により製造されるアクリル系重合体と、上述した粘着性付与剤とを有するものである。従って、本発明のアクリル系粘着組成物は、粘着テープの粘着剤層に用いた場合、上記アクリル系重合体の製造過程において使用した有機過酸化物に起因したＶＯＣの発生、及び、上記粘着性付与剤に起因したＶＯＣの発生を、いずれも好適に抑制することができる。 The acrylic pressure-sensitive adhesive composition of the present invention has an acrylic polymer produced by the above-described method for producing an acrylic polymer of the present invention and the above-described tackifier. Therefore, when the acrylic pressure-sensitive adhesive composition of the present invention is used in the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape, the occurrence of VOCs caused by the organic peroxide used in the process of producing the acrylic polymer, and the pressure-sensitive adhesive property Any occurrence of VOC caused by the imparting agent can be suitably suppressed.
本発明のアクリル系粘着組成物は、粘着テープの粘着剤層として好適である。本発明のアクリル系粘着組成物からなる粘着剤層を有する粘着テープは、車両、住宅内及び電子機器内部等のＶＯＣの発生が問題となるものに利用される部材の接着固定に好ましく用いることができる。このような本発明のアクリル系粘着組成物を含有する粘着剤層を有する粘着テープもまた、本発明の１つである。 The acrylic pressure-sensitive adhesive composition of the present invention is suitable as a pressure-sensitive adhesive layer for pressure-sensitive adhesive tapes. The pressure-sensitive adhesive tape having the pressure-sensitive adhesive layer made of the acrylic pressure-sensitive adhesive composition of the present invention is preferably used for bonding and fixing a member used in a vehicle, a house, an electronic device, or the like where the occurrence of VOC is a problem. it can. Such a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer containing the acrylic pressure-sensitive adhesive composition of the present invention is also one aspect of the present invention.
本発明の粘着テープは、上述した本発明のアクリル系粘着組成物からなる粘着剤層のみから構成されていてもよいし、基材の片面又は両面に上記粘着剤層が積層されているものであってもよい。 The pressure-sensitive adhesive tape of the present invention may be composed of only the pressure-sensitive adhesive layer made of the acrylic pressure-sensitive adhesive composition of the present invention described above, or the above-mentioned pressure-sensitive adhesive layer is laminated on one side or both sides of the substrate. There may be.
上記基材としては特に限定されず、例えば、紙、不織布や、ポリエステル、ポリオレフィン、ポリウレタン、ポリクロロプレン、塩化ビニル樹脂、アクリル樹脂等からなるシート状成形体が挙げられる。また、上記基材としては、発泡処理を行ったものを用いてもよい。これらの基材も、発生するＶＯＣの量を低減させるために、予め精製された材料により構成され、又は、揮発成分の除去がされていることが好ましい。 It does not specifically limit as said base material, For example, the sheet-like molded object which consists of paper, a nonwoven fabric, polyester, polyolefin, a polyurethane, a polychloroprene, a vinyl chloride resin, an acrylic resin etc. is mentioned. Moreover, you may use the thing which performed the foaming process as said base material. In order to reduce the amount of VOC generated, these base materials are also preferably composed of a previously purified material or have volatile components removed.
本発明の粘着テープの製造方法としては特に限定されず、従来公知の方法を用いることができる。例えば、基材上に直接粘着剤層を形成する方法；離型処理された工程紙上に一旦粘着剤層を形成し、該工程紙上の粘着剤層を基材に転写する方法等が挙げられる。 It does not specifically limit as a manufacturing method of the adhesive tape of this invention, A conventionally well-known method can be used. For example, a method of directly forming an adhesive layer on a substrate; a method of once forming an adhesive layer on a release-processed process paper, and transferring the adhesive layer on the process paper to the substrate, and the like.
上記粘着剤層を形成する方法としては、例えば、本発明のアクリル系粘着組成物を基材又は工程紙上に所定の厚さで塗布した後に、溶剤を乾燥させる方法が挙げられる。上記溶剤を乾燥させる際には、基材や工程紙が発泡しない範囲内においてできるだけ乾燥温度を高める方法、乾燥炉内における滞留時間を長くする方法、乾燥炉内を負圧に設定する方法、乾燥風量を大きくする方法等を行うことにより、本発明の粘着テープに残留する揮発成分量を更に低減することができる。これらの方法は、単独で用いられてもよく、２種以上を組み合わせて用いられてもよい。
また、本発明の粘着テープを養生保管する際においても、養生温度の調節、養生雰囲気の減圧等により、粘着剤層に含まれる揮発成分を減少させ、発生するＶＯＣの量を低減することができる。
Examples of the method for forming the pressure-sensitive adhesive layer include a method of drying the solvent after applying the acrylic pressure-sensitive adhesive composition of the present invention on a substrate or process paper to a predetermined thickness. When drying the solvent, a method of increasing the drying temperature as much as possible within a range where the base material and the process paper do not foam, a method of increasing the residence time in the drying furnace, a method of setting the drying furnace at a negative pressure, drying By performing a method of increasing the air volume, the amount of volatile components remaining on the pressure-sensitive adhesive tape of the present invention can be further reduced. These methods may be used independently and may be used in combination of 2 or more type.
Also, when the adhesive tape of the present invention is cured and stored, by adjusting the curing temperature, reducing the curing atmosphere, etc., the volatile components contained in the adhesive layer can be reduced and the amount of VOC generated can be reduced. .
本発明のアクリル系重合体の製造方法は、上記一般式（１）で表される構造の有機過酸化物を有する重合開始剤を用いる。該有機過酸化物は、１次分解によりＲ部分を含むラジカルを生成し、該ラジカルは、更に分解して上記Ｒ部分からなる炭化水素ラジカルとアセトンとが生成される。この生成した炭化水素ラジカルは、モノマー重合時に取り込まれるか、溶剤から水素を引き抜き炭化水素となる。モノマー重合時に取り込まれた場合は、本発明により製造されるアクリル系重合体の反応溶液中に不純物として残留することがなく、また、炭化水素になった場合は、その生成物は沸点が低くなり、乾燥によって容易に除去される。更に、上記アセトンも、乾燥によって容易に除去される。また、上記有機過酸化物は、１次分解によりＲ’部分を含むラジカルを生成し、該ラジカルは、更に分解して上記Ｒ’部分からなる炭化水素ラジカルと二酸化炭素とを生成するが、生成した炭化水素ラジカルは、低沸点であるため乾燥によって容易に除去される。
従って、上記有機過酸化物を有する重合開始剤を用いる本発明のアクリル系重合体の製造方法によると、製造するアクリル系重合体中に、上記有機過酸化物の分解生成物に起因するＶＯＣの発生を抑制することができる。
すなわち、本発明によると、有機過酸化物を重合開始剤として用いたアクリル系重合体の製造において、粘着テープとしたときにＶＯＣの原因となる重合開始剤の分解生成物を殆ど生成せず、得られたアクリル系重合体を用いてなる粘着剤層を有する粘着テープから発生するＶＯＣ量及び臭気を低減することができるアクリル系重合体の製造方法、アクリル系重合体、アクリル系粘着組成物及び粘着テープを提供できる。
The method for producing an acrylic polymer of the present invention uses a polymerization initiator having an organic peroxide having a structure represented by the general formula (1). The organic peroxide generates a radical including an R portion by primary decomposition, and the radical is further decomposed to generate a hydrocarbon radical composed of the R portion and acetone. The generated hydrocarbon radicals are taken in at the time of monomer polymerization, or hydrogen is extracted from the solvent to become hydrocarbons. When taken in during monomer polymerization, it does not remain as an impurity in the reaction solution of the acrylic polymer produced according to the present invention, and when it becomes hydrocarbon, the product has a low boiling point. Easily removed by drying. Furthermore, the acetone is also easily removed by drying. The organic peroxide generates a radical containing an R ′ portion by primary decomposition, and the radical is further decomposed to generate a hydrocarbon radical consisting of the R ′ portion and carbon dioxide. The hydrocarbon radicals having a low boiling point are easily removed by drying.
Therefore, according to the method for producing an acrylic polymer of the present invention using the polymerization initiator having the organic peroxide, the VOC resulting from the decomposition product of the organic peroxide is contained in the produced acrylic polymer. Occurrence can be suppressed.
That is, according to the present invention, in the production of an acrylic polymer using an organic peroxide as a polymerization initiator, almost no decomposition product of the polymerization initiator that causes VOC when used as an adhesive tape, Production method of acrylic polymer capable of reducing VOC amount and odor generated from pressure-sensitive adhesive tape having pressure-sensitive adhesive layer using the obtained acrylic polymer, acrylic polymer, acrylic pressure-sensitive adhesive composition, and Adhesive tape can be provided.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
（実施例１）
温度計、攪拌機、冷却管を備えた反応器にて、ｎ−ブチルアクリレート７９ｇ、２−エチルヘキシルアクリレート１８ｇ、アクリル酸３ｇ、２−ヒドロキシエチルメタクリレート０．１ｇ、及び、ドデカンチオール０．０５ｇからなるモノマー混合物を、酢酸エチル８２ｇに半分溶解し、還流点において、重合開始剤としてパーオキシエステル（ｔ−ヘキシルパーオキシピバレート、１０時間半減温度：５０℃）０．６８ｇを重合開始時〜７時間に適宜加え、残り半分のモノマー混合物を反応開始後１．０〜２．５時間の間に滴下してアクリルモノマーを重合させた。残留モノマーを低減した後、更なる残留モノマー低減、及び、残留開始剤低減のため、１０時間反応させた（重合終期）。なお、反応終了時の反応温度は７５℃であった。得られた溶液を冷却し、アクリル系重合体溶液を得た。
Example 1
Monomer composed of 79 g of n-butyl acrylate, 18 g of 2-ethylhexyl acrylate, 3 g of acrylic acid, 0.1 g of 2-hydroxyethyl methacrylate, and 0.05 g of dodecanethiol in a reactor equipped with a thermometer, a stirrer and a condenser. Half of the mixture was dissolved in 82 g of ethyl acetate, and at the reflux point, 0.68 g of a peroxyester (t-hexylperoxypivalate, 10-hour half-temperature: 50 ° C.) was used as a polymerization initiator at the beginning of polymerization to 7 hours. The acrylic monomer was polymerized by adding dropwise the remaining half of the monomer mixture within 1.0 to 2.5 hours after the start of the reaction. After reducing the residual monomer, the reaction was carried out for 10 hours (end of polymerization) in order to further reduce the residual monomer and the residual initiator. The reaction temperature at the end of the reaction was 75 ° C. The obtained solution was cooled to obtain an acrylic polymer solution.
（実施例２）
パーオキシエステル（ｔ−ヘキシルパーオキシピバレート、１０時間半減温度：５０℃）に代えて、パーオキシエステル（１，１，３，３−テトラメチルブチルパーオキシピバレート、１０時間半減温度：４５℃）を用いた以外は、実施例１と同様にしてアクリル系重合体を得た。なお、反応終了時の反応温度は７５℃であった。
(Example 2)
Instead of peroxyester (t-hexylperoxypivalate, 10-hour half-temperature: 50 ° C.), peroxyester (1,1,3,3-tetramethylbutyl peroxypivalate, 10-hour half-temperature: 45 Acrylic polymer was obtained in the same manner as in Example 1 except that [° C.] was used. The reaction temperature at the end of the reaction was 75 ° C.
（実施例３）
パーオキシエステル（ｔ−ヘキシルパーオキシピバレート、１０時間半減温度：５０℃）に代えて、パーオキシエステル（１，１，３，３−テトラメチルヘキシルパーオキシピバレート、１０時間半減温度：４０℃）を用いた以外は、実施例１と同様にしてアクリル系重合体を得た。なお、反応終了時の反応温度は７５℃であった。
(Example 3)
Instead of peroxyester (t-hexylperoxypivalate, 10-hour half-temperature: 50 ° C.), peroxyester (1,1,3,3-tetramethylhexylperoxypivalate, 10-hour half-temperature: 40 Acrylic polymer was obtained in the same manner as in Example 1 except that [° C.] was used. The reaction temperature at the end of the reaction was 75 ° C.
（実施例４）
温度計、攪拌機、冷却管を備えた反応器にて、ｎ−ブチルアクリレート７９ｇ、２−エチルヘキシルアクリレート１８ｇ、アクリル酸３ｇ、２−ヒドロキシエチルメタクリレート０．１ｇ、ドデカンチオール０．０５ｇからなるモノマー混合物を、酢酸エチル８２ｇに半分溶解し、還流点において、重合開始剤としてパーオキシエステル（ｔ−ヘキシルパーオキシ−２−エチルヘキサノエート、１０時間半減温度：７０℃）０．０３ｇを重合開始時に加え、更にパーオキシエステル（ｔ−ヘキシルパーオキシピバレート、１０時間半減温度：５０℃）１．４７ｇを１〜７時間に適宜加え、残り半分のモノマー混合物を反応開始後１．０〜２．５時間の間に滴下して、アクリルモノマーを重合させた。残留モノマーを低減した後、更なる残留モノマー低減、及び、残留開始剤低減のため、１０時間反応させた（重合終期）。なお、反応終了時の反応温度は７５℃であった。得られた溶液を冷却し、アクリル系重合体溶液を得た。
Example 4
In a reactor equipped with a thermometer, a stirrer, and a condenser, a monomer mixture consisting of 79 g of n-butyl acrylate, 18 g of 2-ethylhexyl acrylate, 3 g of acrylic acid, 0.1 g of 2-hydroxyethyl methacrylate, and 0.05 g of dodecanethiol. In the reflux point, 0.03 g of peroxyester (t-hexylperoxy-2-ethylhexanoate, 10 hour half-temperature: 70 ° C.) was added at the start of polymerization. Further, 1.47 g of a peroxy ester (t-hexyl peroxypivalate, 10 hour half-temperature: 50 ° C.) is appropriately added to 1 to 7 hours, and the remaining half of the monomer mixture is added to 1.0 to 2.5 after the start of the reaction. The acrylic monomer was polymerized by dropping during the time. After reducing the residual monomer, the reaction was carried out for 10 hours (end of polymerization) in order to further reduce the residual monomer and the residual initiator. The reaction temperature at the end of the reaction was 75 ° C. The obtained solution was cooled to obtain an acrylic polymer solution.
（実施例５）
温度計、攪拌機、冷却管を備えた反応器にて、ｎ−ブチルアクリレート７９ｇ、２−エチルヘキシルアクリレート１８ｇ、アクリル酸３ｇ、２−ヒドロキシエチルメタクリレート０．１ｇ、ドデカンチオール０．０５ｇ、及び、酢酸ビニルモノマー５ｇからなるモノマー混合物を、酢酸エチル８２ｇに半分溶解し、還流点において、重合開始剤としてパーオキシエステル（ｔ−ヘキシルパーオキシ−２−エチルヘキサノエート、１０時間半減温度：７０℃）０．０３ｇを重合開始時に加え、更にパーオキシエステル（ｔ−ヘキシルパーオキシピバレート、１０時間半減温度：５０℃）０．９７ｇを、１〜７時間に適宜加え、残り半分のモノマー混合物を反応開始後１．０〜２．５時間の間に滴下して、アクリルモノマーを重合させた。残留モノマーを低減した後、更なる残留モノマー低減、及び、残留開始剤低減のため、１０時間反応させた（重合終期）。なお、反応終了時の反応温度は７５℃であった。得られた溶液を冷却し、アクリル系重合体溶液を得た。
(Example 5)
In a reactor equipped with a thermometer, stirrer, and condenser, n-butyl acrylate 79 g, 2-ethylhexyl acrylate 18 g, acrylic acid 3 g, 2-hydroxyethyl methacrylate 0.1 g, dodecanethiol 0.05 g, and vinyl acetate A monomer mixture composed of 5 g of monomer was dissolved in half in 82 g of ethyl acetate, and at the reflux point, a peroxyester (t-hexylperoxy-2-ethylhexanoate, 10 hour half-temperature: 70 ° C.) 0 as a polymerization initiator 0.03 g is added at the start of polymerization, and 0.97 g of peroxyester (t-hexylperoxypivalate, 10 hour half-temperature: 50 ° C.) is added as appropriate in 1 to 7 hours, and the remaining half of the monomer mixture is initiated. Thereafter, the acrylic monomer was polymerized by dropwise addition within 1.0 to 2.5 hours. After reducing the residual monomer, the reaction was carried out for 10 hours (end of polymerization) in order to further reduce the residual monomer and the residual initiator. The reaction temperature at the end of the reaction was 75 ° C. The obtained solution was cooled to obtain an acrylic polymer solution.
（実施例６）
温度計、攪拌機、冷却管を備えた反応器にて、ｎ−ブチルアクリレート７９ｇ、２−エチルヘキシルアクリレート１８ｇ、アクリル酸３ｇ、２−ヒドロキシエチルメタクリレート０．１ｇ、ドデカンチオール０．０５ｇ、及び、酢酸ビニルモノマー５ｇからなるモノマー混合物を、酢酸エチル８２ｇに溶解し、還流点において、重合開始剤としてパーオキシケタール（ジ（ｔ−ヘキシルパーオキシ）トリメチルシクロヘキサン、１０時間半減温度：９０℃）０．０１ｇを重合開始時に加え、パーオキシエステル（ｔ−ヘキシルパーオキシ−２−エチルヘキサノエート、１０時間半減温度：７０℃）０．０１ｇを０．５時間に加え、更に、パーオキシエステル（ｔ−ヘキシルパーオキシピバレート、１０時間半減温度：５０℃）０．７８ｇを１〜４．５時間に適宜加え、アクリルモノマーを重合させた。残留モノマーを低減した後、更なる残留モノマー低減、及び、残留開始剤低減のため、６．５時間反応させた（重合終期）。なお、反応終了時の反応温度は７５℃であった。得られた溶液を冷却し、アクリル系重合体溶液を得た。
(Example 6)
In a reactor equipped with a thermometer, stirrer, and condenser, n-butyl acrylate 79 g, 2-ethylhexyl acrylate 18 g, acrylic acid 3 g, 2-hydroxyethyl methacrylate 0.1 g, dodecanethiol 0.05 g, and vinyl acetate A monomer mixture composed of 5 g of monomer is dissolved in 82 g of ethyl acetate, and at the reflux point, 0.01 g of peroxyketal (di (t-hexylperoxy) trimethylcyclohexane, 10-hour half-temperature: 90 ° C.) is used as a polymerization initiator. Peroxyester (t-hexylperoxy-2-ethylhexanoate, 10 hour half-temperature: 70 ° C.) 0.01 g was added to 0.5 hour at the start of polymerization, and further peroxyester (t-hexyl) was added. 1) 0.78g peroxypivalate, 10 hour half-life temperature: 50 ° C) Appropriately added to 4.5 hours to polymerize the acrylic monomers. After the residual monomer was reduced, the reaction was carried out for 6.5 hours (polymerization end) for further residual monomer reduction and residual initiator reduction. The reaction temperature at the end of the reaction was 75 ° C. The obtained solution was cooled to obtain an acrylic polymer solution.
（比較例１）
温度計、攪拌機、冷却管を備えた反応器にて、ｎ−ブチルアクリレート７９ｇ、２−エチルヘキシルアクリレート１８ｇ、アクリル酸３ｇ、２−ヒドロキシエチルメタクリレート０．１ｇ、及び、ドデカンチオール０．０５ｇ、及び、酢酸ビニルモノマー５ｇからなるモノマー混合物を、酢酸エチル８２ｇに溶解し、還流点において、重合開始剤としてパーオキシケタール（１，１−ジ（ｔ−ヘキシルパーオキシ）−３，５，５−トリメチルシクロヘキサン、１０時間半減温度：９０℃）０．０４ｇを重合開始時〜１時間に適宜加え、更にジアシルパーオキサイド（ジ（３，５，５−トリメチルヘキサノイル）パーオキサイド、１０時間半減温度：６０℃）１．１６ｇを１．５〜７時間に適宜加え、アクリルモノマーを重合させた。残留モノマーを低減した後、更なる残留モノマー低減、及び、残留開始剤低減のため１０時間反応させた（重合終期）。なお、反応終了時の反応温度は７５℃であった。得られた溶液を冷却し、アクリル系重合体溶液を得た。
(Comparative Example 1)
In a reactor equipped with a thermometer, stirrer, and condenser, n-butyl acrylate 79 g, 2-ethylhexyl acrylate 18 g, acrylic acid 3 g, 2-hydroxyethyl methacrylate 0.1 g, and dodecanethiol 0.05 g A monomer mixture composed of 5 g of vinyl acetate monomer was dissolved in 82 g of ethyl acetate, and at the reflux point, peroxyketal (1,1-di (t-hexylperoxy) -3,5,5-trimethylcyclohexane was used as a polymerization initiator. 10 hours half-temperature: 90 ° C.) 0.04 g is appropriately added at the start of polymerization to 1 hour, and further diacyl peroxide (di (3,5,5-trimethylhexanoyl) peroxide, 10 hours half-temperature: 60 ° C. ) 1.16 g was added appropriately over 1.5-7 hours to polymerize the acrylic monomer. After reducing the residual monomer, the reaction was carried out for 10 hours for further residual monomer reduction and residual initiator reduction (end of polymerization). The reaction temperature at the end of the reaction was 75 ° C. The obtained solution was cooled to obtain an acrylic polymer solution.
（比較例２）
温度計、攪拌機、冷却管を備えた反応器にて、ｎ−ブチルアクリレート７９ｇ、２−エチルヘキシルアクリレート１８ｇ、アクリル酸３ｇ、２−ヒドロキシエチルメタクリレート０．１ｇ、及び、ドデカンチオール０．０５ｇからなるモノマー混合物をトルエン８２ｇに溶解し、還流点において、重合開始剤としてベンゾイルパーオキサイド（１０時間半減温度：７４℃）０．５３ｇを重合開始時〜１時間に適宜加え、更に重合開始から１時間後に酢酸ビニルモノマー７ｇを投入しアクリルモノマーを重合させた。残留モノマーを低減した後、更なる残留モノマー低減、及び、残留開始剤低減のため３．２５時間反応させた（重合終期）。なお、反応終了時の反応温度は７５℃であった。得られた溶液を冷却し、アクリル系重合体溶液を得た。
(Comparative Example 2)
Monomer composed of 79 g of n-butyl acrylate, 18 g of 2-ethylhexyl acrylate, 3 g of acrylic acid, 0.1 g of 2-hydroxyethyl methacrylate, and 0.05 g of dodecanethiol in a reactor equipped with a thermometer, a stirrer and a condenser. The mixture was dissolved in 82 g of toluene, and at the reflux point, 0.53 g of benzoyl peroxide (10-hour half-temperature: 74 ° C.) as a polymerization initiator was appropriately added from the start of polymerization to 1 hour, and acetic acid was further added 1 hour after the start of polymerization. 7 g of vinyl monomer was added to polymerize the acrylic monomer. After reducing the residual monomer, the reaction was continued for 3.25 hours to further reduce the residual monomer and the residual initiator (end of polymerization). The reaction temperature at the end of the reaction was 75 ° C. The obtained solution was cooled to obtain an acrylic polymer solution.
（粘着テープの作製）
実施例１〜６及び比較例１、２で作製したアクリル系重合体１００ｇに、官能性イソシアネート系架橋剤（日本ポリウレタン社製、コロネートＬ（有効成分５５％））１．２〜２．０ｇを加え均一になるよう再度攪拌してアクリル系粘着組成物を得た。得られたアクリル系粘着組成物を厚み５０μｍのポリエチレンテレフタレートフィルムからなるセパレータの片面に、乾燥後の厚みが６０μｍになるように塗布し、１００℃で３分間溶剤を完全に乾燥除去し、不織布を挟み、粘着テープを作製した。
なお、官能性イソシアネート系架橋剤の添加量は、実施例１、２及び比較例１、２では１．２ｇ；実施例３、５、６では１．４ｇ；実施例４では２．０ｇとした。
(Production of adhesive tape)
To 100 g of the acrylic polymer prepared in Examples 1 to 6 and Comparative Examples 1 and 2, 1.2 to 2.0 g of a functional isocyanate crosslinking agent (manufactured by Nippon Polyurethane Co., Ltd., Coronate L (active ingredient 55%)) In addition, the mixture was stirred again to be uniform to obtain an acrylic pressure-sensitive adhesive composition. The obtained acrylic pressure-sensitive adhesive composition was applied to one side of a separator made of a polyethylene terephthalate film having a thickness of 50 μm so that the thickness after drying was 60 μm, and the solvent was completely removed by drying at 100 ° C. for 3 minutes. The adhesive tape was produced by pinching.
The addition amount of the functional isocyanate-based crosslinking agent was 1.2 g in Examples 1 and 2 and Comparative Examples 1 and 2; 1.4 g in Examples 3, 5, and 6; 2.0 g in Example 4. .
（実施例７〜９、比較例３、４）
表２に示す組み合わせのベースアクリル系重合体及び粘着付与樹脂を用いて粘着テープを作製した。即ち、表２に示すベースアクリル系重合体１００ｇに対して、表２に示す粘着付与樹脂２０ｇ（固形分比）を添加して混合することにより、アクリル系粘着剤を作製した。これに官能性イソシアネート系架橋剤（日本ポリウレタン社製、コロネートＬ（有効成分５５％））１．２〜２．０ｇを加え均一になるよう再度攪拌してアクリル系粘着組成物を得た。得られたアクリル系粘着組成物を厚み５０μｍのポリエチレンテレフタレートフィルムからなるセパレータの片面に、乾燥後の厚みが６０μｍになるように塗布し、１００℃で３分間溶剤を完全に乾燥除去し、不織布を挟み、粘着テープを作製した。
なお、官能性イソシアネート系架橋剤の添加量は、実施例７及び比較例３、４では２．０ｇ；実施例８では１．４ｇ；実施例９では１．２ｇとした。
(Examples 7 to 9, Comparative Examples 3 and 4)
A pressure-sensitive adhesive tape was prepared using a combination of the base acrylic polymer and the tackifier resin shown in Table 2. That is, an acrylic pressure-sensitive adhesive was produced by adding and mixing 20 g (solid content ratio) of the tackifier resin shown in Table 2 to 100 g of the base acrylic polymer shown in Table 2. To this, 1.2 to 2.0 g of a functional isocyanate-based cross-linking agent (manufactured by Nippon Polyurethane Co., Ltd., Coronate L (active ingredient 55%)) was added and stirred again uniformly to obtain an acrylic pressure-sensitive adhesive composition. The obtained acrylic pressure-sensitive adhesive composition was applied to one side of a separator made of a polyethylene terephthalate film having a thickness of 50 μm so that the thickness after drying was 60 μm, and the solvent was completely removed by drying at 100 ° C. for 3 minutes. The adhesive tape was produced by pinching.
The addition amount of the functional isocyanate-based crosslinking agent was 2.0 g in Example 7 and Comparative Examples 3 and 4, 1.4 g in Example 8, and 1.2 g in Example 9.
（比較例５）
粘着テープの作製において、乾燥条件を１２０℃、３０分間とした以外は比較例４と同様にして粘着テープを作成した。
(Comparative Example 5)
In the production of the pressure-sensitive adhesive tape, a pressure-sensitive adhesive tape was produced in the same manner as in Comparative Example 4 except that the drying conditions were 120 ° C. and 30 minutes.
実施例１〜６及び比較例１、２で作製したアクリル系重合体を用いて調製したアクリル系粘着組成物について、以下の方法により残留モノマー量、残留開始剤量を評価し、更に作製した粘着テープについて揮発成分濃度（ＴＶＯＣ）、臭気及び粘着性能を評価した。結果を表１に示した。
また、実施例７〜９及び比較例３〜５で作成した粘着テープについても、以下の方法により揮発成分濃度、臭気及び粘着性能を評価した。結果を表２に示した。
About the acrylic adhesive composition prepared using the acrylic polymers prepared in Examples 1 to 6 and Comparative Examples 1 and 2, the residual monomer amount and the residual initiator amount were evaluated by the following method, and the adhesive prepared further The tape was evaluated for volatile component concentration (TVOC), odor, and adhesive performance. The results are shown in Table 1.
Moreover, about the adhesive tape created in Examples 7-9 and Comparative Examples 3-5, the volatile component density | concentration, the odor, and the adhesive performance were evaluated with the following method. The results are shown in Table 2.
（残留モノマー量評価）
メスフラスコに秤量したアクリル系重合体溶液を酢酸エチルセルソルブが０．０３％入ったアセトン溶液で溶解し、ＧＣ装置（ＧＣ−１７Ａ、島津製作所社製）を用いて測定し、ピーク比からアクリル系粘着組成物中の残留モノマー濃度を測定した。
(Residual monomer amount evaluation)
The acrylic polymer solution weighed in the volumetric flask was dissolved in an acetone solution containing 0.03% ethyl acetate cellosolve, and measured using a GC apparatus (GC-17A, manufactured by Shimadzu Corporation). The residual monomer concentration in the system adhesive composition was measured.
（残留開始剤量評価）
重合時における反応温度を測定し、有機過酸化物の分解性データ（温度における半減期時間データ）により、開始剤投入経過時間、反応温度から、アクリル系重合体溶液中の残留開始剤濃度を算出した。
(Residual initiator amount evaluation)
Measure the reaction temperature at the time of polymerization, and calculate the residual initiator concentration in the acrylic polymer solution from the elapsed time of initiator charging and reaction temperature from the decomposability data of organic peroxide (temperature half-life time data) did.
（揮発成分濃度の測定）
熱脱着装置（パーキンエルマー社製「ＡＴＤ−４００」）を用い、秤量した粘着テープを９０℃で３０分間加熱したとき、及び、１２０℃で３０分間加熱したときに放出された揮発成分量を、ＧＣ−ＭＳ装置（日本電子社製、「ＡｕｔｏｍａｓｓＩＩ−１５」）を用いることにより揮発成分量を測定し、下記式（１）及び（２）により揮発成分濃度を算出した。
なお、ＧＣ−ＭＳ測定には、無極性のキャピラリーカラム（アジレントテクノロジー社製「ＨＰ−１」：０．３２ｍｍ×６０ｍ×０．２５μｍ）を使用し、１２０℃で３０分間加熱を行い、加熱により揮発してきた成分をカラムに通し、カラムの温度を５０℃で２分維持した後、毎分２５℃で１６０℃まで昇温して、毎分１０℃の昇温速度で３００℃まで昇温し、２０分保持し、その揮発成分を測定し、下記式（２）により、揮発成分濃度を算出した。
ＭＳ測定範囲は３０〜４００ａｍｕ、Ｈｅ流量は１．５ｍＬ／ｍｉｎ、イオン化電圧は７０ｅＶ、イオン源は２３０℃、インターフェイスは２５０℃、トランスファーラインは２２５℃とした。
なお、９０℃３０分間加熱した場合については、保持時間３０分以降（具体的には３０分〜４０分）の揮発成分濃度についても同様にして測定した。
(Measurement of volatile component concentration)
Using a thermal desorption device (“ATD-400” manufactured by PerkinElmer), the amount of volatile components released when the weighed adhesive tape was heated at 90 ° C. for 30 minutes and when heated at 120 ° C. for 30 minutes, The amount of volatile components was measured by using a GC-MS apparatus (manufactured by JEOL Ltd., “Automass II-15”), and the concentration of volatile components was calculated by the following formulas (1) and (2).
For GC-MS measurement, a non-polar capillary column (“HP-1” manufactured by Agilent Technologies: 0.32 mm × 60 m × 0.25 μm) was used, heated at 120 ° C. for 30 minutes, and volatilized by heating. The components were passed through the column, the column temperature was maintained at 50 ° C. for 2 minutes, then the temperature was increased to 160 ° C. at 25 ° C. per minute, the temperature was increased to 300 ° C. at a temperature increase rate of 10 ° C. per minute, Holding for 20 minutes, the volatile component was measured, and the concentration of the volatile component was calculated by the following formula (2).
The MS measurement range was 30 to 400 amu, the He flow rate was 1.5 mL / min, the ionization voltage was 70 eV, the ion source was 230 ° C., the interface was 250 ° C., and the transfer line was 225 ° C.
In addition, about the case where it heats at 90 degreeC for 30 minutes, the volatile component density | concentration after holding time 30 minutes (specifically 30 minutes-40 minutes) was measured similarly.
（臭気の測定）
ＶＤＡ２７０に準じ、以下の方法で臭気の評価を行った。１Ｌのガラス瓶中に５０ｃｍ２の粘着テープを封入し、４０℃の雰囲気下で２４時間経過後、取り出してすぐの臭気を下記の６点法で評価した。評価に際しては、３人以上のパネラーがそれぞれ粘着テープを評価し、その平均値を求めた。
１：知覚できない
２：知覚できるが、不快ではない
３：はっきりと知覚できるが、それほど不快ではない
４：不快
５：とても不快
６：我慢できない
(Odor measurement)
The odor was evaluated according to the following method in accordance with VDA270. A 50 cm 2 adhesive tape was sealed in a 1 L glass bottle, and the odor immediately after removal after 24 hours in an atmosphere of 40 ° C. was evaluated by the following 6-point method. At the time of evaluation, three or more panelists evaluated the adhesive tape, and determined the average value.
1: Not perceptible 2: Perceptible but not unpleasant 3: Perceptible but not so uncomfortable 4: Uncomfortable 5: Very uncomfortable 6: Unbearable
（粘着性能の測定）
（１）対ポリプロピレン板粘着力
ＪＩＳ Ｚ ０２３７に準拠した方法により、ポリプロピレン板に対する粘着力を測定した。具体的には、２３℃、６５％ＲＨ雰囲気下において、厚さ２３μｍのポリエステルフィルムをバッキング材として貼り付けた幅２５ｍｍの粘着テープをポリプロピレン板に貼り合わせ、重さ２ｋｇのローラーで１往復させて圧着した後、２３℃、６５％ＲＨで２４時間放置した。その後、２３℃の雰囲気下で引っ張り試験機を用いて、３００ｍｍ／分の引っ張り速度で引っ張ることにより、１８０度剥離力を測定した。
(Measurement of adhesive performance)
(1) Adhesive strength to polypropylene plate The adhesive strength to a polypropylene plate was measured by a method based on JIS Z 0237. Specifically, in an atmosphere of 23 ° C. and 65% RH, a 25 mm wide adhesive tape with a 23 μm thick polyester film attached as a backing material is attached to a polypropylene plate and reciprocated once with a 2 kg roller. After crimping, it was left at 23 ° C. and 65% RH for 24 hours. Thereafter, the 180-degree peeling force was measured by pulling at a pulling speed of 300 mm / min using a tensile tester in an atmosphere of 23 ° C.
（２）対ポリプロピレン板定加重剥離
「（１）対ポリプロピレン板粘着力」と同様にして、貼り付け部分の長さが１００ｍｍとなるように粘着テープをポリプロピレン板に貼り合わせた後、５０℃のオーブン中にて粘着テープの一端に１００ｇの錘を剥離角度が９０度となるようにぶら下げた。そして、５０℃で５時間放置した後の剥離長さを測定した。
(2) Fixed load separation against polypropylene plate In the same manner as “(1) Adhesive strength against polypropylene plate”, the adhesive tape was attached to the polypropylene plate so that the length of the applied portion was 100 mm, A 100 g weight was suspended at one end of the adhesive tape in the oven so that the peel angle was 90 degrees. And the peeling length after leaving to stand at 50 degreeC for 5 hours was measured.
本発明によれば、有機過酸化物を重合開始剤として用いたアクリル系重合体の製造において、粘着テープとしたときにＶＯＣの原因となる重合開始剤の分解生成物を殆ど生成せず、得られたアクリル系重合体を用いてなる粘着剤層を有する粘着テープから発生するＶＯＣ量及び臭気を低減することができるアクリル系重合体の製造方法、アクリル系重合体、アクリル系粘着組成物及び粘着テープを提供できる。 According to the present invention, in the production of an acrylic polymer using an organic peroxide as a polymerization initiator, a decomposition product of a polymerization initiator that causes VOC when formed as an adhesive tape is hardly generated. A method for producing an acrylic polymer, an acrylic polymer, an acrylic pressure-sensitive adhesive composition, and a pressure-sensitive adhesive capable of reducing the amount of VOC and odor generated from a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer using the obtained acrylic polymer Can provide tape.
Claims (5)
前記粘着付与樹脂は、重量平均分子量が６００以下の成分の含有量が１３重量％以下であり、かつ、０．１〜５０重量％含有されている
ことを特徴とするアクリル系粘着組成物。 An acrylic pressure-sensitive adhesive composition comprising the acrylic polymer according to claim 3 and a tackifier resin,
The acrylic pressure-sensitive adhesive composition, wherein the tackifying resin contains a component having a weight average molecular weight of 600 or less in a content of 13% by weight or less and 0.1 to 50% by weight.
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