JP4665446B2 - Aqueous pressure-sensitive adhesive composition and method for producing the same - Google Patents
Aqueous pressure-sensitive adhesive composition and method for producing the same Download PDFInfo
- Publication number
- JP4665446B2 JP4665446B2 JP2004196384A JP2004196384A JP4665446B2 JP 4665446 B2 JP4665446 B2 JP 4665446B2 JP 2004196384 A JP2004196384 A JP 2004196384A JP 2004196384 A JP2004196384 A JP 2004196384A JP 4665446 B2 JP4665446 B2 JP 4665446B2
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- Prior art keywords
- monomer
- copolymer
- glass transition
- transition temperature
- aqueous
- 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
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims description 55
- 239000000203 mixture Substances 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 30
- 229920001577 copolymer Polymers 0.000 claims description 82
- 239000000178 monomer Substances 0.000 claims description 80
- 239000006185 dispersion Substances 0.000 claims description 63
- 230000009477 glass transition Effects 0.000 claims description 40
- 238000006116 polymerization reaction Methods 0.000 claims description 26
- 239000003995 emulsifying agent Substances 0.000 claims description 25
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 239000003505 polymerization initiator Substances 0.000 claims description 14
- 239000012736 aqueous medium Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 description 45
- 230000001070 adhesive effect Effects 0.000 description 45
- -1 polyethylene terephthalate Polymers 0.000 description 41
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 34
- 239000000758 substrate Substances 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000000463 material Substances 0.000 description 21
- 239000000839 emulsion Substances 0.000 description 17
- 239000002985 plastic film Substances 0.000 description 17
- 229920006255 plastic film Polymers 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229920000642 polymer 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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 239000012790 adhesive layer Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- HFGHRUCCKVYFKL-UHFFFAOYSA-N 4-ethoxy-2-piperazin-1-yl-7-pyridin-4-yl-5h-pyrimido[5,4-b]indole Chemical compound C1=C2NC=3C(OCC)=NC(N4CCNCC4)=NC=3C2=CC=C1C1=CC=NC=C1 HFGHRUCCKVYFKL-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- BIIBYWQGRFWQKM-JVVROLKMSA-N (2S)-N-[4-(cyclopropylamino)-3,4-dioxo-1-[(3S)-2-oxopyrrolidin-3-yl]butan-2-yl]-2-[[(E)-3-(2,4-dichlorophenyl)prop-2-enoyl]amino]-4,4-dimethylpentanamide Chemical compound CC(C)(C)C[C@@H](C(NC(C[C@H](CCN1)C1=O)C(C(NC1CC1)=O)=O)=O)NC(/C=C/C(C=CC(Cl)=C1)=C1Cl)=O BIIBYWQGRFWQKM-JVVROLKMSA-N 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 2
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-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
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910019142 PO4 Inorganic materials 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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- YAQXJPBLJAFSFJ-UHFFFAOYSA-N acetyl acetate;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=O)OC(C)=O YAQXJPBLJAFSFJ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000012769 display material Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- AYOOGWWGECJQPI-NSHDSACASA-N n-[(1s)-1-(5-fluoropyrimidin-2-yl)ethyl]-3-(3-propan-2-yloxy-1h-pyrazol-5-yl)imidazo[4,5-b]pyridin-5-amine Chemical compound N1C(OC(C)C)=CC(N2C3=NC(N[C@@H](C)C=4N=CC(F)=CN=4)=CC=C3N=C2)=N1 AYOOGWWGECJQPI-NSHDSACASA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 2
- 239000010452 phosphate 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
- 230000001681 protective effect Effects 0.000 description 2
- 238000007717 redox polymerization reaction Methods 0.000 description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 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
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- 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
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-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
- FZLSDZZNPXXBBB-KDURUIRLSA-N 5-chloro-N-[3-cyclopropyl-5-[[(3R,5S)-3,5-dimethylpiperazin-1-yl]methyl]phenyl]-4-(6-methyl-1H-indol-3-yl)pyrimidin-2-amine Chemical compound C[C@H]1CN(Cc2cc(Nc3ncc(Cl)c(n3)-c3c[nH]c4cc(C)ccc34)cc(c2)C2CC2)C[C@@H](C)N1 FZLSDZZNPXXBBB-KDURUIRLSA-N 0.000 description 1
- CMXNFXBFNYHFAL-UHFFFAOYSA-N 5-methylhex-1-en-3-one Chemical compound CC(C)CC(=O)C=C CMXNFXBFNYHFAL-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-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
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol 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
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
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- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
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- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
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- 150000001412 amines Chemical class 0.000 description 1
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- 230000002421 anti-septic effect Effects 0.000 description 1
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- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-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
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- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- PBZROIMXDZTJDF-UHFFFAOYSA-N hepta-1,6-dien-4-one Chemical compound C=CCC(=O)CC=C PBZROIMXDZTJDF-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 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
- 230000007257 malfunction Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 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
- VOVZXURTCKPRDQ-CQSZACIVSA-N n-[4-[chloro(difluoro)methoxy]phenyl]-6-[(3r)-3-hydroxypyrrolidin-1-yl]-5-(1h-pyrazol-5-yl)pyridine-3-carboxamide Chemical compound C1[C@H](O)CCN1C1=NC=C(C(=O)NC=2C=CC(OC(F)(F)Cl)=CC=2)C=C1C1=CC=NN1 VOVZXURTCKPRDQ-CQSZACIVSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000003097 polyterpenes Chemical class 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は水性粘着剤組成物に関するものである。詳しくは、特にポリオレフィン被着体に対する良好な接着力及び優れた曲面貼り付け性を有し、かつ基材と粘着剤層間の密着性に優れており被着体に貼り付けられた粘着剤塗工物を剥がした際に被着体面上への糊残りが生じない水性粘着剤組成物に関する。
さらに詳しくは、特定の組成を有する樹脂組成物水性分散体を複数組み合わせる事により得られる、上記の特徴を有する水性粘着剤組成物に関する。
さらに、本発明は、上記水性粘着剤組成物の製造方法に関する。
The present invention relates to an aqueous pressure-sensitive adhesive composition. Specifically, the pressure-sensitive adhesive coating applied to the adherend has particularly good adhesion to the polyolefin adherend and excellent curved surface adhesion, and excellent adhesion between the substrate and the pressure-sensitive adhesive layer. The present invention relates to an aqueous pressure-sensitive adhesive composition that does not cause adhesive residue on an adherend surface when an object is peeled off.
More specifically, the present invention relates to an aqueous pressure-sensitive adhesive composition having the above characteristics, which is obtained by combining a plurality of aqueous resin composition dispersions having a specific composition.
Furthermore, this invention relates to the manufacturing method of the said aqueous adhesive composition.
近年安全衛生および環境問題に対する配慮から脱溶剤化が進行し、粘着剤においても溶剤型から水性型への移行が望まれている。
しかしながら水性粘着剤においては塗工後の乾燥工程においてエマルジョン粒子が融着して乾燥被膜を形成するため、溶剤型粘着剤に比べて塗膜の緻密さに欠け、特にポリオレフィン被着体に対する接着力に劣り、さらには曲面貼り付け性に劣るという欠点を有していた。
In recent years, solvent removal has progressed in consideration of health and safety and environmental problems, and it is desired to shift from a solvent type to a water-based type for adhesives.
However, in water-based adhesives, emulsion particles are fused in the drying process after coating to form a dry film, so that the coating film is not as dense as solvent-based adhesives. In addition to the curved surface sticking property.
曲面貼り付け性とは、曲面状の被着体上に粘着剤塗工物を貼り付ける場合の適性の事を示す用語である。平面上に貼り付けた場合と異なり、曲面上に貼り付けた場合には、塗工物基材が曲面状態から平坦状態に復元しようとする応力が発生するため、塗工物は被着体から自ずと剥がれるように作用する。
そのため塗工物に塗工されている粘着剤の接着力が十分でないと、貼り付け後ある時間経過すると被着体から自然に剥離してしまう。
また、粘着剤の接着力が十分高いにもかかわらず、粘着剤の凝集力が低すぎてしまうと、通常「凝集破壊」と言われる現象を引き起こして、基材が平坦状に戻ろうとする応力にうち勝てずに粘着剤自身がその層の途中で破断されてしまい、塗工物が被着体から剥がれてしまう。この場合には被着体側及び基材側の両方に粘着剤が残存する状態で剥離する事となる。
故に、曲面貼り付け性を良好にならしめるためには、粘着剤の接着力と凝集力という２つの物性項目が、どちらか一方に大幅に偏る事なくその両方が満足されていなければならない。
The curved surface sticking property is a term indicating aptitude in the case of sticking a pressure-sensitive adhesive coated product on a curved adherend. Unlike when pasted on a flat surface, when pasted on a curved surface, a stress is generated that causes the coated substrate to recover from a curved surface to a flat state. It works to peel off naturally.
Therefore, if the adhesive force of the pressure-sensitive adhesive applied to the coated material is not sufficient, it will peel off naturally from the adherend after a certain period of time has elapsed after application.
In addition, if the adhesive cohesive force is too low even though the adhesive adhesive strength is sufficiently high, a stress that causes the substrate to return to a flat state is usually caused by a phenomenon called “cohesive failure”. However, the adhesive itself is broken in the middle of the layer without winning, and the coated material is peeled off from the adherend. In this case, it will peel in the state in which an adhesive remains on both the adherend side and the substrate side.
Therefore, in order to improve the curved surface sticking property, the two physical property items of the adhesive force and the cohesive force of the pressure-sensitive adhesive must be satisfied without being significantly biased to either one.
また、水性粘着剤を用いた粘着剤塗工物のうち、ポリエチレンテレフタレート（以下ＰＥＴという）製や延伸ポリプロピレン（以下ＯＰＰという）製等のプラスチックフィルムを基材とする場合、前記基材と粘着剤層間との密着性が不十分となりやすい。その結果、被着体に貼り付けた後、被着体から粘着剤層及び基材を剥がす際に、基材と粘着剤層との界面で剥離が生じてしまい、基材のみが引き剥がされて粘着剤層はほとんど全部被着体上に残ってしまう、いわゆる「転着」現象が生じる。転着現象が生じると、貼り付け前の清浄な被着体表面を復元させるために、被着体表面に残存してしまった粘着剤層を除去する手間が生じてしまう事となり、極めて作業効率を低下せしめる結果となる。このような現象は、被着体がガラスや金属等の無機材料である場合に特に起こりやすい。 In the case of using a plastic film made of polyethylene terephthalate (hereinafter referred to as PET) or stretched polypropylene (hereinafter referred to as OPP), among the pressure-sensitive adhesive coated products using an aqueous pressure-sensitive adhesive, the substrate and the pressure-sensitive adhesive are used. Adhesion between layers tends to be insufficient. As a result, when the adhesive layer and the substrate are peeled from the adherend after being attached to the adherend, peeling occurs at the interface between the substrate and the adhesive layer, and only the substrate is peeled off. Thus, almost all the pressure-sensitive adhesive layer remains on the adherend, so-called “transfer” phenomenon occurs. When the transfer phenomenon occurs, it takes time and effort to remove the adhesive layer remaining on the adherend surface in order to restore the clean adherend surface before pasting. As a result, Such a phenomenon is particularly likely to occur when the adherend is an inorganic material such as glass or metal.
なお、水性粘着剤を用いた粘着剤塗工物基材であっても、紙を基材とする場合には、この不具合は生じにくい。これは紙の構造が一般に多孔質であるため、粘着剤が塗布された際に粘着剤の一部が紙の内部に浸透しやすく、紙と粘着剤層の間の密着性が高まるためであると考えられる。
これに対し、プラスチックフィルムを基材とする場合には、このような効果を期待する事ができないので、プラスチックフィルム基材と粘着剤層間の密着性は不十分となりやすく、上記のような、被着体面上の糊残りが生じやすくなる。
In addition, even if it is the adhesive coated base material using an aqueous adhesive, when using paper as a base material, this malfunction is hard to arise. This is because the paper structure is generally porous, so that when the adhesive is applied, part of the adhesive easily penetrates into the paper, and the adhesion between the paper and the adhesive layer is increased. it is conceivable that.
On the other hand, when a plastic film is used as a base material, such an effect cannot be expected, so that the adhesion between the plastic film base material and the pressure-sensitive adhesive layer tends to be insufficient. Adhesive residue on the surface of the bonded body tends to occur.
プラスチックフィルムを基材として用いた粘着剤塗工物は、紙を基材に用いたものに比べて耐久性に優れ、また透明であるという特徴を有する。そこで、プラスチックフィルムの表面に図柄や文字を印刷し、あるいは全面が透明なままの状態にて、耐久性や透明性の要求される表示材や保護材用途に好んで用いられている。例えば、説明書きや注意書き、識別記号などを表示するための表示ラベル、装飾用材料としてのシール、あるいは成型物や印刷物の表面に貼り合わせてそれらの表面を保護するための保護フィルム、さらには大きな形状を有する標識や看板などの表示材料用途等に広範に用いられている。
しかし、上記のように水性粘着剤は、プラスチックフィルム基材に対する密着性が十分に得られにくい事も一つの大きな原因となって、これらの用途における粘着剤の溶剤型から水性型への置き換えは速やかに進行していないのが現状である。
A pressure-sensitive adhesive coated product using a plastic film as a base material has characteristics that it is excellent in durability and transparent as compared with those using paper as a base material. In view of this, it is used favorably for display materials and protective materials that require durability and transparency, with designs and characters printed on the surface of the plastic film, or with the entire surface being transparent. For example, display labels for displaying explanatory notes, cautionary notes, identification symbols, etc., seals as decorative materials, or protective films that are attached to the surface of molded or printed materials to protect those surfaces, and It is widely used for display materials such as signs and signboards having large shapes.
However, as described above, the water-based pressure-sensitive adhesive is one of the main reasons that it is difficult to obtain sufficient adhesion to the plastic film substrate. The current situation is not progressing promptly.
これらの欠点を改善するため、従来から水性粘着剤を構成する主原料であるエチレン性不飽和単量体中のソフト成分の比率を増やし、重合物のガラス転移温度を低下させる事により粘着剤の接着性を高めて、ポリオレフィン被着体に対する接着力及びプラスチックフィルム基材への密着性を向上させることが試みられている。あるいは重合時に使用する重合開始剤量を増量したり、連鎖移動剤を多量添加したりして、得られる重合物の分子量を低下させる事により接着性を高めて、同様にポリオレフィン被着体に対する接着力及びプラスチックフィルム基材への密着性を向上させる試みがなされている。
しかし、これらの手法を用いた場合、プラスチックフィルム基材への密着性に関しては向上が認められるのであるが、粘着剤層の凝集力が低下してしまうため、凝集破壊が生じやすくなり、上で述べた理由により曲面貼り付け性は改善を見ないばかりか、塗工物を剥離する際に被着体面上に粘着剤が残存してしまうという問題も解消する事ができない。
In order to improve these disadvantages, the ratio of the pressure-sensitive adhesive can be reduced by increasing the ratio of the soft component in the ethylenically unsaturated monomer, which is the main raw material constituting the aqueous pressure-sensitive adhesive, and lowering the glass transition temperature of the polymer. Attempts have been made to improve adhesion and improve adhesion to polyolefin adherends and adhesion to plastic film substrates. Alternatively, increase the amount of polymerization initiator used during polymerization or add a large amount of chain transfer agent to increase the adhesion by decreasing the molecular weight of the resulting polymer, and similarly adhere to polyolefin adherends Attempts have been made to improve force and adhesion to plastic film substrates.
However, when these methods are used, an improvement is observed with respect to the adhesion to the plastic film substrate. However, the cohesive force of the pressure-sensitive adhesive layer is reduced, so that cohesive failure is likely to occur. For the reasons described above, not only the curved surface sticking property is improved, but also the problem that the adhesive remains on the adherend surface when the coated product is peeled off cannot be solved.
本発明の課題は、ポリオレフィン被着体に対する高い接着力及び優れた曲面貼り付け性、さらにはプラスチックフィルム基材に対する良好な密着性を有する水性粘着剤組成物、およびその製造方法を提供する事である。 An object of the present invention is to provide an aqueous pressure-sensitive adhesive composition having high adhesion to polyolefin adherend and excellent curved surface sticking property, and also good adhesion to a plastic film substrate, and a method for producing the same. is there.
第１の発明は、カルボキシル基含有単量体（ａ）０．５〜５重量％及び該単量体（ａ）と共重合可能な他の単量体（ｂ）を、乳化剤、重合開始剤を用い、水性媒体中で重合してなるガラス転移温度が９０℃以上１０５℃以下の高ガラス転移温度共重合体の水性分散体（Ａ）と、
アルキル基の炭素数が４〜１４であるアルキルアクリレート（ｃ）５５〜９５重量％及びカルボキシル基含有単量体（ａ）０．５〜５重量％を含有する単量体を、乳化剤及び重合開始剤を用い、水性媒体中で重合してなるガラス転移温度が−７５℃以上−４５℃以下の低ガラス転移温度共重合体の水性分散体（Ｂ）とを、
（Ａ）／（Ｂ）＝１／９９〜１５／８５（固形分重量比率）の割合にて含有し、さらに粘着付与剤と、架橋剤とを含有する事を特徴とする水性粘着剤組成物に関し、
第２の発明は、共重合可能な他の単量体（ｂ）として、メチルメタクリレートを必須成分として含有する事を特徴とする上記第１の発明に記載の水性粘着剤組成物に関する。
In the first invention, 0.5 to 5% by weight of the carboxyl group-containing monomer (a) and another monomer (b) copolymerizable with the monomer (a) are used as an emulsifier and a polymerization initiator. An aqueous dispersion (A) of a high glass transition temperature copolymer having a glass transition temperature of 90 ° C. or higher and 105 ° C. or lower obtained by polymerization in an aqueous medium,
A monomer containing 55 to 95% by weight of alkyl acrylate (c) whose alkyl group has 4 to 14 carbon atoms and 0.5 to 5% by weight of carboxyl group-containing monomer (a), emulsifier and polymerization initiation An aqueous dispersion (B) of a low glass transition temperature copolymer having a glass transition temperature of −75 ° C. or higher and −45 ° C. or lower formed by polymerization in an aqueous medium using an agent,
(A) / (B) = 1/99 to 15/85 (solid content weight ratio) The aqueous pressure-sensitive adhesive composition characterized by containing a tackifier and a crosslinking agent . Regarding
The second invention relates to the aqueous pressure-sensitive adhesive composition according to the first invention, wherein methyl methacrylate is contained as an essential component as another copolymerizable monomer (b).
第３の発明は、カルボキシル基含有単量体（ａ）０．５〜５重量％及び該単量体（ａ）と共重合可能な他の単量体（ｂ）を、乳化剤、重合開始剤を用い、水性媒体中で重合してなるガラス転移温度が９０℃以上１０５℃以下の高ガラス転移温度共重合体の水性分散体（Ａ）と、
アルキル基の炭素数が４〜１４であるアルキルアクリレート（ｃ）５５〜９５重量％及びカルボキシル基含有単量体（ａ）０．５〜５重量％を含有する単量体を、乳化剤及び重合開始剤を用い、水性媒体中で重合してなるガラス転移温度が−７５℃以上−４５℃以下の低ガラス転移温度共重合体の水性分散体（Ｂ）とを、
（Ａ）／（Ｂ）＝１／９９〜１５／８５（固形分重量比率）の割合で混合し、さらに粘着付与剤と、架橋剤とを混合する事を特徴とする水性粘着剤組成物の製造方法に関し、
第４の発明は、共重合可能な単量体（ｂ）として、メチルメタクリレートを必須成分として含有する事を特徴とする上記第３の発明に記載の水性粘着剤組成物の製造方法に関する。
The third invention comprises 0.5 to 5% by weight of a carboxyl group-containing monomer (a) and another monomer (b) copolymerizable with the monomer (a), an emulsifier and a polymerization initiator. An aqueous dispersion (A) of a high glass transition temperature copolymer having a glass transition temperature of 90 ° C. or higher and 105 ° C. or lower obtained by polymerization in an aqueous medium,
A monomer carbon number of A alkyl groups contain alkyl acrylates (c) 55 to 95 wt% and the carboxyl group-containing monomer (a) 0.5 to 5% by weight is 4 to 14, an emulsifier and a polymerization An aqueous dispersion (B) of a low glass transition temperature copolymer having a glass transition temperature of −75 ° C. or higher and −45 ° C. or lower formed by polymerization in an aqueous medium using an initiator,
(A) / (B) = 1/99 to 15/85 (solid content weight ratio) is mixed, and a tackifier and a crosslinking agent are further mixed. Regarding the manufacturing method,
4th invention is related with the manufacturing method of the aqueous adhesive composition as described in the said 3rd invention characterized by containing methyl methacrylate as an essential component as a copolymerizable monomer (b).
本発明の水性粘着剤組成物は、従来良好な接着性を得る事が困難であったポリオレフィン被着体に対する優れた接着性能、特に曲面貼り付け性を有しているのに加え、プラスチックフィルム基材に対する密着性が良好であり、被着体に貼り付けられた粘着剤塗工物を剥がす際に被着体面上への糊残りが生じない。そのため本発明の水性粘着剤組成物が塗工された塗工物は、曲面形状を有する被着体に対しても好んで用いる事ができるのに加え、ラベル用途等としての使用を目的として、粘着剤層との密着性の得られにくいプラスチックフィルム基材を用いた場合でも、粘着剤塗工物を被着体に貼り付けた後、目的とする期間が経過して当該塗工物を剥がして被着体表面を復元する必要が生じた場合でも、被着体面上に粘着剤を残存させる事なく塗工物を除去できるため、被着体表面を汚染なく復元できる。 The water-based pressure-sensitive adhesive composition of the present invention has excellent adhesion performance to polyolefin adherends, in which it has been difficult to obtain good adhesion in the past, in particular, a curved film sticking property, Adhesiveness to the material is good, and no adhesive residue is left on the adherend surface when the pressure-sensitive adhesive coated material attached to the adherend is peeled off. Therefore, the coated product coated with the aqueous pressure-sensitive adhesive composition of the present invention can be preferably used for an adherend having a curved shape, and for the purpose of use as a label application, etc. Even when using a plastic film substrate that is difficult to obtain adhesion to the pressure-sensitive adhesive layer, after applying the pressure-sensitive adhesive coated material to the adherend, the coated material is peeled off after the target period has elapsed. Even when it is necessary to restore the adherend surface, the coated material can be removed without leaving the adhesive on the adherend surface, so that the adherend surface can be restored without contamination.
＜高ガラス転移温度共重合体の水性分散体（Ａ）＞
本発明に用いられるラジカル重合可能なエチレン性不飽和単量体において、カルボキシル基含有単量体（ａ）としては、（メタ）アクリル酸、［アクリル酸とメタクリル酸を併せて（メタ）アクリル酸と表記する。以下同様。］、マレイン酸、フマル酸、イタコン酸などが例示できる。
単量体（ａ）は、高ガラス転移温度共重合体（以下、高Ｔｇ共重合体という）を構成するラジカル重合可能なエチレン性不飽和単量体の合計１００重量％中０．５〜５重量％含有され、単独で、または２種類以上を併用して用いる事ができる。使用量が０．５重量％より少ないと重合が不安定になりやすく、また共重合体自身の安定性も不足し、分散体粒子が沈降する等の不都合を生じやすくなる。使用量が５重量％を超えると耐水性の低下等の弊害を引き起こすため好ましくない。
<Aqueous dispersion of high glass transition temperature copolymer (A)>
In the ethylenically unsaturated monomer capable of radical polymerization used in the present invention, as the carboxyl group-containing monomer (a), (meth) acrylic acid, [(acrylic acid and methacrylic acid together (meth) acrylic acid) Is written. The same applies hereinafter. ], Maleic acid, fumaric acid, itaconic acid and the like.
Monomer (a) is 0.5 to 5 in a total of 100% by weight of radically polymerizable ethylenically unsaturated monomers constituting a high glass transition temperature copolymer (hereinafter referred to as high Tg copolymer). It is contained by weight and can be used alone or in combination of two or more. When the amount used is less than 0.5% by weight, the polymerization tends to be unstable, and the stability of the copolymer itself is insufficient, and inconveniences such as sedimentation of the dispersion particles tend to occur. If the amount used exceeds 5% by weight, it is not preferable because it causes adverse effects such as a decrease in water resistance.
単量体（ａ）と共重合可能な他の単量体（ｂ）としては、アルキル基の炭素数が１〜１４であるアルキル（メタ）アクリレート（ｂ−１）が好ましく用いられる。
アルキル基の炭素数が１〜１４であるアルキル（メタ）アクリレート（ｂ−１）としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、ラウリル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレートなどの直鎖または分岐脂肪族アルコールのアクリル酸エステル及び対応するメタクリル酸エステルなどが例示でき、これらは単独で、あるいは２種類以上併用して用いる事ができる。
上記（ｂ−１）以外の単量体としては、水酸基を含有するヒドロキシアルキル（メタ）アクリレート（ｂ−２）、例えばヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート等、
またはカルボニル基を有する単量体（ｂ−３）、例えばアクロレイン、ジアセトン（メタ）アクリルアミド、好ましくは４〜７個の炭素原子を有するビニルアルキルケトン（例えばビニルメチルケトン、ビニルエチルケトン、ビニルイソブチルケトンなど）、ジアセトン（メタ）アクリレート、アセトニル（メタ）アクリレート、アセトアセトキシエチル（メタ）アクリレート、ジアセトン（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート−アセチルアセテート、ブタンジオール−１，４−（メタ）アクリレート−アセチルアセテート等、
さらには不飽和結合を２個以上有する単量体（ｂ−４）、例えばフタル酸（オルソフタル酸、イソフタル酸、テレフタル酸）のジアリルエステル、メチレンビス（メタ）アクリルアミド、１、６−ヘキサンジオールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等、
及びこれら以外の単量体（ｂ−５）として、ポリエチレングリコール（メタ）アクリレート、グリシジル（メタ）アクリレート、モノ−（２−ヒドロキシルエチル−α−クロロ（メタ）アクリレート）アシッドホスフェート、ビニルブロックトイソシアネート、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−メチルアミノエチル（メタ）アクリレート、Ｎ−トリブチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート、（メタ）アクリルアミド、ビニルピロリドン、ビニルピリジン、酢酸ビニル、プロピオン酸ビニル、スチレン、（メタ）アクリロニトリル、ブタジエン、クロロプレンなどが例示でき、それぞれ単独で、あるいは２種類以上併用して用いる事ができる。
As the other monomer (b) copolymerizable with the monomer (a), an alkyl (meth) acrylate (b-1) having an alkyl group having 1 to 14 carbon atoms is preferably used.
Examples of the alkyl (meth) acrylate (b-1) having 1 to 14 carbon atoms in the alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl ( Examples thereof include acrylic acid esters of linear or branched aliphatic alcohols such as meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, and 2-ethylhexyl (meth) acrylate, and corresponding methacrylic acid esters. Or it can be used in combination of two or more.
As monomers other than the above (b-1), hydroxyalkyl (meth) acrylate (b-2) containing a hydroxyl group, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) Acrylate, etc.
Or a monomer (b-3) having a carbonyl group, such as acrolein, diacetone (meth) acrylamide, preferably a vinyl alkyl ketone having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl isobutyl ketone) Etc.), diacetone (meth) acrylate, acetonyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, diacetone (meth) acrylate, 2-hydroxypropyl (meth) acrylate-acetyl acetate, butanediol-1,4- (meth) ) Acrylate-acetyl acetate, etc.
Furthermore, the monomer (b-4) having two or more unsaturated bonds, for example, diallyl ester of phthalic acid (orthophthalic acid, isophthalic acid, terephthalic acid), methylenebis (meth) acrylamide, 1,6-hexanediol di ( (Meth) acrylate, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate,
And other monomers (b-5) such as polyethylene glycol (meth) acrylate, glycidyl (meth) acrylate, mono- (2-hydroxylethyl-α-chloro (meth) acrylate) acid phosphate, vinyl blocked isocyanate N-methylol (meth) acrylamide, N-methylaminoethyl (meth) acrylate, N-tributylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) Examples include acrylate, (meth) acrylamide, vinyl pyrrolidone, vinyl pyridine, vinyl acetate, vinyl propionate, styrene, (meth) acrylonitrile, butadiene, and chloroprene, each alone or in combination of two or more. It can be used in.
本発明において用いられる高Ｔｇ共重合体の水性分散体（Ａ）は、共重合体のガラス転移温度（以下、Ｔｇという）が９０℃以上１０５℃以下となるように上記単量体（ａ）及び（ｂ）を適宜選択することが重要である。
単量体（ａ）及び（ｂ）から形成される共重合体のＴｇが９０℃未満では、得られる粘着剤組成物の曲面貼り付け性及び粘着剤層とプラスチックフィルム基材との間の密着性向上効果が十分に得られず、１０５℃を超えると接着力が低下傾向となるため好ましくない。
このようなＴｇの共重合体を得るためには、以下の理由により、単量体（ｂ）として、メチルメタクリレートを必須成分として含有する事が好ましい。
メチルメタクリレートは、その単独重合体のガラス転移温度が１０５℃である。そこでメチルメタクリレートを高Ｔｇ共重合体の主たる構成成分とし、単量体（ａ）以外の適当量の、低いガラス転移温度を与える単量体を併用する事により、上記高Ｔｇ共重合体を容易に得る事ができる。また、メチルメタクリレートは、重合反応において高い重合率が得られやすい単量体である。従って、粘着剤としての物性を低下せしめたり、不快な臭気の原因となる残留単量体の量を低減する事ができる。さらに、メチルメタクリレートは、安価な汎用の単量体である。
In the aqueous dispersion (A) of the high Tg copolymer used in the present invention, the monomer (a) is prepared so that the glass transition temperature (hereinafter referred to as Tg) of the copolymer is 90 ° C. or higher and 105 ° C. or lower. It is important to select (b) and (b) as appropriate.
When the Tg of the copolymer formed from the monomers (a) and (b) is less than 90 ° C., the curved adhesiveness of the resulting pressure-sensitive adhesive composition and the adhesion between the pressure-sensitive adhesive layer and the plastic film substrate The effect of improving the properties cannot be obtained sufficiently, and if it exceeds 105 ° C., the adhesive force tends to decrease, which is not preferable.
In order to obtain such a Tg copolymer, it is preferable to contain methyl methacrylate as an essential component as the monomer (b) for the following reasons.
Methyl methacrylate has a homopolymer having a glass transition temperature of 105 ° C. Therefore, by using methyl methacrylate as a main component of the high Tg copolymer and using an appropriate amount of a monomer other than the monomer (a) that gives a low glass transition temperature, the above high Tg copolymer can be easily prepared. You can get to Further, methyl methacrylate is a monomer that can easily obtain a high polymerization rate in the polymerization reaction. Accordingly, it is possible to reduce the amount of residual monomer that causes the physical properties of the pressure-sensitive adhesive to deteriorate and causes an unpleasant odor. Furthermore, methyl methacrylate is an inexpensive general-purpose monomer.
なお、ここで言う高Ｔｇ共重合体のＴｇ、及び後述する低Ｔｇ共重合体のＴｇとは、共重合に供する各単量体からそれぞれ形成される単独重合体のガラス転移温度の数値を基に、ＦＯＸの式により理論的に求められ値であり、各単量体の単独重合体のガラス転移温度については各種便覧、文献等に記載されている周知の値を用いる事ができる。 The Tg of the high Tg copolymer and the Tg of the low Tg copolymer described later are based on the numerical values of the glass transition temperatures of the homopolymers formed from the respective monomers used for the copolymerization. In addition, it is a value theoretically determined by the FOX equation, and known values described in various manuals and literatures can be used for the glass transition temperature of the homopolymer of each monomer.
本発明の高Ｔｇ共重合体の水性分散体（Ａ）を得る際に用いる乳化剤としては、反応性乳化剤、非反応性乳化剤などが、単独であるいは２種類以上併用して用いることができるが、耐水性などを考慮すれば、反応性乳化剤を用いる方が好ましいのであるが、これに限定されるものではない。 As the emulsifier used when obtaining the aqueous dispersion (A) of the high Tg copolymer of the present invention, a reactive emulsifier, a non-reactive emulsifier and the like can be used alone or in combination of two or more. In consideration of water resistance and the like, it is preferable to use a reactive emulsifier, but it is not limited thereto.
反応性乳化剤としては以下の化合物を例示することができる。
アニオン系乳化剤としてはノニルフェニル骨格の旭電化工業株式会社製「アデカリアソープＳＥ−１０Ｎ」、第一工業製薬株式会社製「アクアロンＨＳ−１０、ＨＳ−２０」等、長鎖アルキル骨格の第一工業製薬株式会社製「アクアロンＫＨ−０５、ＫＨ−１０」、旭電化工業株式会社製「アデカリアソープＳＲ−１０Ｎ」等、燐酸エステル骨格の日本化薬株式会社製「ＫＡＹＡＲＡＤ」等が例示できる。
ノニオン系乳化剤としては、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルフェニルエーテル類、ソルビタン高級脂肪酸エステル類、グリセリン高級脂肪酸エステル類等の分子末端あるいは中間部に不飽和二重結合を有し、単量体と共重合するものであり、旭電化工業株式会社製「アデカリアソープＮＥ−１０」、第一工業製薬株式会社製「アクアロンＲＮ−１０、ＲＮ−２０、ＲＮ−５０」、日本乳化剤株式会社製「アントックスＮＡ−１６」等が例示できる。
Examples of the reactive emulsifier include the following compounds.
Examples of anionic emulsifiers include nonylphenyl skeleton "Adekaria Soap SE-10N" manufactured by Asahi Denka Kogyo Co., Ltd. and "Aqualon HS-10, HS-20" manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Examples include “AQUALON KH-05, KH-10” manufactured by Kogyo Seiyaku Co., Ltd., “ADEKA rear soap SR-10N” manufactured by Asahi Denka Kogyo Co., Ltd., and “KAYARAD” manufactured by Nippon Kayaku Co., Ltd. having a phosphate ester skeleton.
Nonionic emulsifiers include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, sorbitan higher fatty acid esters, glycerin higher fatty acid esters and the like having an unsaturated double bond at the molecular terminal or in the middle. Asahi Denka Kogyo Co., Ltd. “Adekaria Soap NE-10”, Daiichi Kogyo Seiyaku Co., Ltd. “Aqualon RN-10, RN-20, RN-50”, Japan Emulsifier Stock Examples include “Antox NA-16” manufactured by the company.
また非反応性乳化剤としては、以下の化合物を例示する事ができる。
アニオン系乳化剤としてはステアリン酸ナトリウム等の高級脂肪酸塩類、ドデシルベンゼンスルホン酸ナトリウム等のアルキルアリールスルホン酸塩類、ラウリル硫酸ナトリウム等のアルキル硫酸エステル塩類、ポリオキシエチレンラウリルエーテル硫酸ナトリウム等のポリオキシエチレンアルキルエーテル硫酸エステル塩類、ポリオキシエチレンノニルフェニルエーテル硫酸ナトリウム等のポリオキシエチレンアルキルアリールエーテル硫酸エステル塩類等が例示できる。
ノニオン系乳化剤としては、ポリオキシエチレンラウリルエーテル等のポリオキシエチレンアルキルエーテル類、ポリオキシエチレンノニルフェニルエーテル等のポリオキシエチレンアルキルフェニルエーテル類、ソルビタンモノステアレート等のソルビタン高級脂肪酸エステル類、オレイン酸モノグリセライド等のグリセリン高級脂肪酸エステル類等が例示できる。
Moreover, the following compounds can be illustrated as a non-reactive emulsifier.
Anionic emulsifiers include higher fatty acid salts such as sodium stearate, alkylaryl sulfonates such as sodium dodecylbenzene sulfonate, alkyl sulfate salts such as sodium lauryl sulfate, and polyoxyethylene alkyl such as sodium polyoxyethylene lauryl ether sulfate. Examples thereof include ether sulfate esters and polyoxyethylene alkylaryl ether sulfate salts such as sodium polyoxyethylene nonylphenyl ether sulfate.
Nonionic emulsifiers include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene alkyl phenyl ethers such as polyoxyethylene nonylphenyl ether, sorbitan higher fatty acid esters such as sorbitan monostearate, oleic acid Examples include glycerin higher fatty acid esters such as monoglyceride.
高Ｔｇ共重合体の水性分散体（Ａ）を得る際に用いる重合開始剤としては、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩またはアゾビス系カチオン塩または水酸基付加物質などの水溶性の熱分解型重合触媒、またはレドックス系重合触媒を用いることができる。レドックス系重合触媒としては、ｔ−ブチルハイドロパーオキサイド、ベンゾイルパーオキサイド、クメンハイドロパーオキサイドなどの有機過酸化物とロンガリット、メタ重亜硫酸ナトリウムなどの還元剤との組み合わせ、または過硫酸カリウム、過硫酸アンモニウムとロンガリット、チオ硫酸ナトリウムなどの組み合わせ、過酸化水素水とアスコルビン酸の組み合わせなどが挙げられる。 As a polymerization initiator used in obtaining the aqueous dispersion (A) of a high Tg copolymer, water-soluble pyrolysis such as persulfates such as potassium persulfate and ammonium persulfate, azobis cation salts, or hydroxylated substances. A type polymerization catalyst or a redox polymerization catalyst can be used. The redox polymerization catalyst includes a combination of an organic peroxide such as t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide and a reducing agent such as Rongalite, sodium metabisulfite, or potassium persulfate or ammonium persulfate. And combinations of Rongalite and sodium thiosulfate, and combinations of hydrogen peroxide and ascorbic acid.
高Ｔｇ共重合体の水性分散体（Ａ）は、エチレン性不飽和単量体を重合する際に、分子量や分子量分布を制御するための連鎖移動剤として、メルカプタン系、チオグリコール系、βメルカプトプロピオン酸などのチオール系化合物などを用いることができる。添加量は、（Ａ）を構成するエチレン性不飽和単量体の総量１００重量部に対して０．０１〜１０．０重量部であることが好ましい。 The aqueous dispersion (A) of the high Tg copolymer is a mercaptan, thioglycol, or β mercapto as a chain transfer agent for controlling the molecular weight or molecular weight distribution when polymerizing an ethylenically unsaturated monomer. Thiol compounds such as propionic acid can be used. The addition amount is preferably 0.01 to 10.0 parts by weight with respect to 100 parts by weight of the total amount of the ethylenically unsaturated monomers constituting (A).
次に、エチレン性不飽和単量体を、乳化剤及び重合開始剤を用い、水性媒体中で重合し、高Ｔｇ共重合体の水性分散体（Ａ）を得る方法について説明する。
まず本発明で使用するエチレン性不飽和単量体を混合し、均一な混合溶液とする。この混合溶液はそのままで重合に供しても良いし、水および乳化剤の一部又は全量を加えて攪拌し、乳化液とした後に重合に供しても良い。
これらの混合溶液又は乳化液を調製後、重合開始剤の存在下で重合をおこなうのであるが、その方法としては混合溶液又は乳化液を全量反応容器に仕込んで重合を開始しても良く、一部を反応容器に仕込んで重合を開始した後にさらに数回に分けて分割添加しても良く、一部を反応容器に仕込んで重合を開始した後に残りを連続滴下しても良く、あるいはあらかじめ水および必要に応じて乳化剤の一部又は全量を反応容器に仕込んでおき、全量を連続滴下しても良い。混合溶液を用いて重合する場合にはあらかじめ反応容器に乳化剤の全量および水の一部又は全量を仕込んでおく事が好ましい。
重合開始剤の添加方法としては、あらかじめ全量を反応容器に仕込んでおいても良く、昇温後に全量を添加しても良く、一部を反応容器に仕込んでおき重合を開始した後にさらに数回に分けて分割添加しても良く、一部を反応容器に仕込んでおき重合を開始した後に残りを連続滴下しても良く、あるいは全量を連続滴下しても良い。重合開始剤を分割添加又は連続滴下する場合には、単独で反応容器内に分割添加又は連続滴下しても良く、混合溶液又は乳化液と混合された状態にて分割添加または連続滴下されても良い。なおこれらの手法により重合開始剤を添加した後、反応率を高める目的で１回又は２回以上重合開始剤を追加添加しても良い。
かくして本発明の高Ｔｇ共重合体の水性分散体（Ａ）を得る事ができる。
Next, a method for obtaining an aqueous dispersion (A) of a high Tg copolymer by polymerizing an ethylenically unsaturated monomer in an aqueous medium using an emulsifier and a polymerization initiator will be described.
First, the ethylenically unsaturated monomer used in the present invention is mixed to obtain a uniform mixed solution. This mixed solution may be used for polymerization as it is, or a part or all of water and an emulsifier may be added and stirred to obtain an emulsion, which may be used for polymerization.
After preparing these mixed solutions or emulsions, polymerization is carried out in the presence of a polymerization initiator. As a method, the entire amount of the mixed solution or emulsion may be charged into a reaction vessel and polymerization may be started. After the polymerization is started by adding a part to the reaction vessel, it may be added in several divided portions, or after a part of the reaction vessel is started and the polymerization is started, the remainder may be continuously added dropwise, or water may be added in advance. If necessary, a part or the whole amount of the emulsifier may be charged into the reaction vessel, and the whole amount may be continuously dropped. When the polymerization is performed using the mixed solution, it is preferable to prepare the total amount of the emulsifier and a part or the total amount of water in the reaction vessel in advance.
As a method for adding the polymerization initiator, the whole amount may be charged in the reaction vessel in advance, or the whole amount may be added after the temperature rise, and several times after the polymerization is started after partly charged in the reaction vessel. It may be divided and added in portions, or after a part of the reaction vessel is charged and polymerization is started, the remainder may be continuously dropped, or the entire amount may be dropped continuously. When the polymerization initiator is dividedly added or continuously dropped, it may be added separately or continuously dropped into the reaction vessel alone, or may be dividedly added or continuously dropped in a mixed state with the mixed solution or emulsion. good. In addition, after adding a polymerization initiator by these methods, you may add a polymerization initiator once more in order to raise a reaction rate, or 2 times or more.
Thus, an aqueous dispersion (A) of the high Tg copolymer of the present invention can be obtained.
＜低Ｔｇ共重合体の水性分散体（Ｂ）＞
カルボキシル基含有単量体（ａ）としては、高Ｔｇ共重合体の水性分散体（Ａ）の項にて例示したものを用いる事ができ、これらは低Ｔｇ共重合体を構成するエチレン性不飽和単量体の合計１００重量％中０．５〜５重量％含有され、単独で、または２種類以上を併用して用いる事ができる。使用量が０．５重量％より少ないと重合が不安定になりやすく、また重合物自身の安定性も不足し、分散体粒子が沈降する等の不都合を生じやすくなる。使用量が５重量％を超えると耐水性の低下等の弊害を引き起こすため好ましくない。
<Aqueous dispersion of low Tg copolymer (B)>
As the carboxyl group-containing monomer (a), those exemplified in the section of the aqueous dispersion (A) of the high Tg copolymer can be used, and these are ethylenic polymers constituting the low Tg copolymer. It is contained in 0.5 to 5% by weight in a total of 100% by weight of saturated monomers, and can be used alone or in combination of two or more. When the amount used is less than 0.5% by weight, the polymerization tends to become unstable, and the stability of the polymer itself is insufficient, so that inconveniences such as sedimentation of the dispersion particles tend to occur. If the amount used exceeds 5% by weight, it is not preferable because it causes adverse effects such as a decrease in water resistance.
アルキル基の炭素数が４〜１４であるアルキルアクリレート（ｃ）としては、高Ｔｇ共重合体の水性分散体（Ａ）の項にて例示した単量体（ｂ−１）の内、アルキル基の炭素数が４〜１４であるアルキルアクリレートを用いる事ができ、中でもアルキル基の炭素数が４〜１２であるアルキルアクリレートが本発明で特定する低Ｔｇ共重合体のＴｇを満足するために好ましく用いられる。これらは低Ｔｇ共重合体を構成するエチレン性不飽和単量体の合計１００重量％中５５〜９５重量％含有され、単独で、あるいは２種類以上併用して用いる事ができる。使用量が５５重量％より少ないと接着力が不十分となりやすく、使用量が９５重量％を超えると重合物の凝集力の低下を引き起こし、粘着剤の凝集破壊が生じやすくなるため好ましくない。 The alkyl acrylate (c) having 4 to 14 carbon atoms in the alkyl group includes an alkyl group among the monomers (b-1) exemplified in the section of the aqueous dispersion (A) of the high Tg copolymer. Alkyl acrylates having 4 to 14 carbon atoms can be used. Among them, alkyl acrylates having 4 to 12 carbon atoms in the alkyl group are preferable in order to satisfy the Tg of the low Tg copolymer specified in the present invention. Used. These are contained in an amount of 55 to 95% by weight in a total of 100% by weight of the ethylenically unsaturated monomers constituting the low Tg copolymer, and can be used alone or in combination of two or more. If the amount used is less than 55% by weight, the adhesive strength tends to be insufficient, and if the amount used exceeds 95% by weight, the cohesive strength of the polymer is reduced and cohesive failure of the pressure-sensitive adhesive tends to occur.
低Ｔｇ共重合体の水性分散体（Ｂ）を得る際には、（ａ）及び（ｃ）以外の単量体を必要に応じて用いる事ができる。それらの例としては、高Ｔｇ共重合体の水性分散体（Ａ）の項にて例示した単量体（ｂ−１）の内、アルキル基の炭素数が１〜３であるアルキルアクリレート、及びアルキル基の炭素数が１〜１４であるアルキルメタクリレートが例示でき、これらは単独で、あるいは２種類以上併用して用いる事ができる。
さらには高Ｔｇ共重合体の水性分散体（Ａ）の項にて例示した、水酸基を含有するヒドロキシアルキル（メタ）アクリレート（ｂ−２）、カルボニル基を有する単量体（ｂ−３）、不飽和結合を２個以上有する単量体（ｂ−４）、これら以外の単量体（ｂ−５）などを用いる事ができ、それぞれ単独で、あるいは２種類以上併用して用いる事ができる。
When obtaining the aqueous dispersion (B) of a low Tg copolymer, monomers other than (a) and (c) can be used as needed. Examples thereof include, among the monomers (b-1) exemplified in the section of the aqueous dispersion (A) of the high Tg copolymer, alkyl acrylates having 1 to 3 carbon atoms in the alkyl group, and An alkyl methacrylate having 1 to 14 carbon atoms in the alkyl group can be exemplified, and these can be used alone or in combination of two or more.
Furthermore, the hydroxyalkyl (meth) acrylate (b-2) containing a hydroxyl group, the monomer (b-3) having a carbonyl group exemplified in the section of the aqueous dispersion (A) of the high Tg copolymer, A monomer (b-4) having two or more unsaturated bonds, a monomer (b-5) other than these can be used, and each can be used alone or in combination of two or more. .
本発明において用いられる低Ｔｇ共重合体の水性分散体（Ｂ）は、共重合体のガラス転移温度（以下、Ｔｇという）が−７５℃以上−４５℃以下となるように上記単量体（ａ）、（ｃ）及び必要に応じて他の単量体を適宜用いることが重要である。
単量体（ａ）、（ｃ）、及び必要に応じて用いる他の単量体から形成され得る共重合体のＴｇが−７５℃未満では、得られる粘着剤組成物の凝集力が低くなるため凝集破壊を引き起こしやすくなり、−４５℃を超えると接着力が低下傾向となるため好ましくない。
In the aqueous dispersion (B) of the low Tg copolymer used in the present invention, the monomer (in which the glass transition temperature (hereinafter referred to as Tg) of the copolymer is −75 ° C. or higher and −45 ° C. or lower is used. It is important to use a), (c) and other monomers as necessary.
When the Tg of the copolymer that can be formed from the monomers (a) and (c) and other monomers used as necessary is less than −75 ° C., the cohesive force of the resulting pressure-sensitive adhesive composition becomes low. Therefore, cohesive failure is likely to occur, and if it exceeds −45 ° C., the adhesive force tends to decrease, such being undesirable.
本発明の低Ｔｇ共重合体の水性分散体（Ｂ）を得る際に用いる乳化剤としては、高Ｔｇ共重合体の水性分散体（Ａ）の項にて例示したものを用いる事ができる。
本発明の低Ｔｇ共重合体の水性分散体（Ｂ）を得る際に用いる重合開始剤としては、高Ｔｇ共重合体の水性分散体（Ａ）の項にて例示したものを用いる事ができる。
低Ｔｇ共重合体の水性分散体（Ｂ）は、エチレン性不飽和単量体を重合する際に、高Ｔｇ共重合体の水性分散体（Ａ）の項にて例示した連鎖移動剤を用いる事ができる。
エチレン性不飽和単量体を乳化剤、重合開始剤、及び水を必須成分とする水性媒体中で重合し、低Ｔｇ共重合体の水性分散体（Ｂ）を得る方法については、高Ｔｇ共重合体の水性分散体（Ａ）の項にて説明した方法による事ができる。
かくして低Ｔｇ共重合体の水性分散体（Ｂ）を得る事ができる。
As the emulsifier used in obtaining the aqueous dispersion (B) of the low Tg copolymer of the present invention, those exemplified in the section of the aqueous dispersion (A) of the high Tg copolymer can be used.
As the polymerization initiator used when obtaining the aqueous dispersion (B) of the low Tg copolymer of the present invention, those exemplified in the section of the aqueous dispersion (A) of the high Tg copolymer can be used. .
The aqueous dispersion (B) of the low Tg copolymer uses the chain transfer agent exemplified in the section of the aqueous dispersion (A) of the high Tg copolymer when polymerizing the ethylenically unsaturated monomer. I can do things.
For a method of polymerizing an ethylenically unsaturated monomer in an aqueous medium containing an emulsifier, a polymerization initiator, and water as essential components to obtain an aqueous dispersion (B) of a low Tg copolymer, The method described in the section of the combined aqueous dispersion (A) can be used.
Thus, an aqueous dispersion (B) of a low Tg copolymer can be obtained.
得られた高Ｔｇ共重合体の水性分散体（Ａ）及び低Ｔｇ共重合体の水性分散体（Ｂ）を、（Ａ）／（Ｂ）＝１／９９〜１５／８５（固形分重量比率）の割合となるように混合・配合する事により本発明の水性粘着剤組成物を得ることができ、３／９７〜１０／９０の混合・割合で配合する事が好ましい。
水性分散体（Ａ）の固形分重量比率が１重量％より少ないと、粘着剤中の高Ｔｇ共重合体の含有率が少なくなり接着力及び曲面貼り付け性、さらには粘着剤層とプラスチックフィルム基材との間の密着性向上効果が十分に得られなくなる。一方、水性分散体（Ａ）の固形分重量比率が１５重量％を超えると、粘着剤中の高Ｔｇ共重合体の割合が多くなりすぎ、接着力および曲面貼り付け性が低下傾向となるため、好ましくない。
The obtained aqueous dispersion (A) of the high Tg copolymer and aqueous dispersion (B) of the low Tg copolymer were converted into (A) / (B) = 1/99 to 15/85 (solid content weight ratio). ), The aqueous pressure-sensitive adhesive composition of the present invention can be obtained by mixing and blending so that the ratio is 3/97 to 10/90.
When the solid content weight ratio of the aqueous dispersion (A) is less than 1% by weight, the content of the high Tg copolymer in the pressure-sensitive adhesive is reduced, and the adhesive force and curved surface sticking property, and further the pressure-sensitive adhesive layer and the plastic film The effect of improving the adhesion with the substrate cannot be obtained sufficiently. On the other hand, when the solid content weight ratio of the aqueous dispersion (A) exceeds 15% by weight, the ratio of the high Tg copolymer in the pressure-sensitive adhesive is excessively increased, and the adhesive force and the curved surface sticking property tend to decrease. Is not preferable.
本発明の水性粘着剤組成物は、上記高Ｔｇ共重合体の水性分散体（Ａ）及び低Ｔｇ共重合体の水性分散体（Ｂ）を主たる成分とするものであり、この他に必要に応じて、本発明で特定する高Ｔｇ共重合体、低Ｔｇ共重合体以外のエチレン性不飽和単量体の重合体を添加しても良い。また粘着力調整のために、適当な粘着付与剤、例えば、ロジン樹脂、フェノール樹脂、ポリテルペン、アセチレン樹脂、石油系炭化水素樹脂、エチレン酢酸ビニル共重合体、合成ゴム、天然ゴム等を適当量添加することができる。さらに、粘度調整剤、消泡剤、レベリング剤、可塑剤、充填剤、中和剤、着色剤、シランカップリング剤、防腐剤なども添加しても良い。
またさらに、本発明の水性粘着剤組成物中の各共重合体の分散粒子を粒子間架橋させるため、任意の架橋剤を配合しても良く、例えばエチレン性不飽和単量体成分として水酸基を有する単量体を用いた場合には、イソシアネート化合物、チタンやジルコニウムなどのアルコキシド化合物等を用いる事ができ、カルボニル基を有する単量体を用いた場合には、アミン類、ヒドラジド化合物等を用いる事ができる。
The aqueous pressure-sensitive adhesive composition of the present invention is mainly composed of the aqueous dispersion (A) of the high Tg copolymer and the aqueous dispersion (B) of the low Tg copolymer. Accordingly, a polymer of an ethylenically unsaturated monomer other than the high Tg copolymer and the low Tg copolymer specified in the present invention may be added. In addition, an appropriate amount of tackifier such as rosin resin, phenol resin, polyterpene, acetylene resin, petroleum hydrocarbon resin, ethylene vinyl acetate copolymer, synthetic rubber, natural rubber, etc. is added to adjust the adhesive strength. can do. Furthermore, a viscosity modifier, an antifoaming agent, a leveling agent, a plasticizer, a filler, a neutralizing agent, a colorant, a silane coupling agent, an antiseptic, and the like may be added.
Furthermore, in order to cross-link the dispersed particles of each copolymer in the aqueous pressure-sensitive adhesive composition of the present invention, an arbitrary cross-linking agent may be blended, for example, a hydroxyl group as an ethylenically unsaturated monomer component. In the case of using a monomer having an isocyanate compound, an alkoxide compound such as titanium or zirconium can be used, and in the case of using a monomer having a carbonyl group, an amine, a hydrazide compound or the like is used. I can do things.
本発明の粘着剤組成物を、コンマコーター、リバースコーター、スロットダイコーター、リップコーター、グラビアチャンバーコーター、カーテンコーター等の各種コーティング装置により、紙またはプラスチックフィルム基材、もしくは剥離性シート上に塗布し、乾燥することによって、粘着シート、粘着ラベル等の各種粘着塗工物を得ることができる。紙等に粘着剤組成物を塗布した後、８０℃〜１２０℃で乾燥することが好ましい。乾燥温度が８０℃以下では乾燥しにくく、乾燥に長時間を要する。他方、１２０℃よりも高温で乾燥すると、基材または剥離性シートの熱劣化を生じ、好ましくない。
紙またはプラスチックフィルム基材上に粘着剤組成物を塗布した場合は、乾燥後に剥離性シートと貼り合わせることにより、また剥離性シート上に粘着剤組成物を塗布した場合は、乾燥後に紙またはプラスチックフィルム基材と貼りあわせることにより、どちらの手法によっても各種粘着塗工物を得ることができる。
剥離性シートは、セパレーターとも称されるものであり、紙やプラスチックフィルムの少なくとも一方の面が剥離処理されてなるものである。剥離処理剤としては従来公知のものを用いることができる。
The pressure-sensitive adhesive composition of the present invention is applied onto a paper or plastic film substrate or a release sheet by various coating apparatuses such as a comma coater, a reverse coater, a slot die coater, a lip coater, a gravure chamber coater, and a curtain coater. By drying, various adhesive coated products such as an adhesive sheet and an adhesive label can be obtained. It is preferable to dry at 80 ° C. to 120 ° C. after applying the pressure-sensitive adhesive composition to paper or the like. When the drying temperature is 80 ° C. or lower, it is difficult to dry, and it takes a long time to dry. On the other hand, drying at a temperature higher than 120 ° C. is not preferable because it causes thermal deterioration of the substrate or the peelable sheet.
When the pressure-sensitive adhesive composition is applied on a paper or plastic film substrate, it is bonded to the peelable sheet after drying. When the pressure-sensitive adhesive composition is applied to the peelable sheet, the paper or plastic is dried after drying. By adhering to the film substrate, various adhesive coated products can be obtained by either method.
The peelable sheet is also called a separator, and is formed by peeling at least one surface of paper or a plastic film. A conventionally known release treatment agent can be used.
以下に実施例によって本発明を説明するが、これに限定されるものではない。実施例中にある部とは重量部を、％とは重量％をそれぞれ示す。 The present invention will be described below with reference to examples, but is not limited thereto. In the examples, “part” means “part by weight” and “%” means “% by weight”.
（製造例−１）
２−エチルヘキシルアクリレート３部、メチルメタクリレート９５部、アクリル酸２部、これら全エチレン性不飽和単量体１００部に対して反応性アンモニア中和型アニオン性乳化剤として第一工業製薬（株）製「アクアロンＫＨ−１０」２部を脱イオン水３０．５部に溶解したものを加えて攪拌して乳化物を得、これを滴下ロートに入れた。
撹拌機、冷却管、温度計および上記滴下ロートを取り付けた４つ口フラスコに、脱イオン水を５７部、「アクアロンＫＨ−１０」を０．１部仕込み、フラスコ内部を窒素ガスで置換し、撹拌しながら内温を８０℃まで昇温し、３％過硫酸カリウム水溶液を固形分として０．１部添加した。５分後、上記滴下ロートから上記乳化物の滴下を開始し、これと並行して３％過硫酸カリウム水溶液を固形分として０．３部を別の滴下口から３時間かけて滴下した。
内温を８０℃に保ったまま、上記乳化物および３％過硫酸カリウム水溶液滴下終了３０分後に、３％過硫酸カリウム水溶液を固形分として０．０６部を２回に分けて３０分おきに添加した。
さらに撹拌しながら８０℃にて２時間熟成した後冷却し、固形分５０％の高Ｔｇ共重合体の水性分散体（Ａ−１）を得た。
各単量体の単独重合体のガラス転移温度として表１に示した数値を用い、ＦＯＸの式により算出した（Ａ−１）中の共重合体のガラス転移温度は９４℃であった。
(Production Example-1)
2-ethylhexyl acrylate 3 parts, methyl methacrylate 95 parts, acrylic acid 2 parts, 100 parts of all ethylenically unsaturated monomers as a reactive ammonia neutralizing anionic emulsifier manufactured by Daiichi Kogyo Seiyaku Co., Ltd. A solution prepared by dissolving 2 parts of Aqualon KH-10 in 30.5 parts of deionized water was added and stirred to obtain an emulsion, which was placed in a dropping funnel.
A four-necked flask equipped with a stirrer, a condenser, a thermometer and the above dropping funnel was charged with 57 parts of deionized water and 0.1 part of “AQUALON KH-10”, and the inside of the flask was replaced with nitrogen gas. While stirring, the internal temperature was raised to 80 ° C., and 0.1 part of a 3% potassium persulfate aqueous solution was added as a solid content. After 5 minutes, the dropping of the emulsion was started from the dropping funnel, and in parallel, 0.3 part of 3% potassium persulfate aqueous solution was added dropwise from another dropping port over 3 hours.
While maintaining the internal temperature at 80 ° C., 30 minutes after the completion of dropwise addition of the above emulsion and 3% aqueous potassium persulfate solution, 0.06 parts were divided into two portions each containing 30% aqueous 3% potassium persulfate solution every 30 minutes. Added.
Further, the mixture was aged at 80 ° C. for 2 hours with stirring, and then cooled to obtain an aqueous dispersion (A-1) of a high Tg copolymer having a solid content of 50%.
Using the numerical values shown in Table 1 as the glass transition temperature of the homopolymer of each monomer, the glass transition temperature of the copolymer in (A-1) calculated by the formula of FOX was 94 ° C.
（製造例−２）
ブチルアクリレート３部、メチルメタクリレート９４部、メタクリル酸３部、これら全エチレン性不飽和単量体１００部に対して「アクアロンＫＨ−１０」２部を脱イオン水３０．５部に溶解したものを加えて攪拌して乳化物を得、これを滴下ロートに入れた。
以下、製造例−１と同様にして高Ｔｇ共重合体の水性分散体（Ａ−２）を得た。（Ａ−２）中の共重合体のガラス転移温度は９８℃であった。
(Production Example-2)
3 parts of butyl acrylate, 94 parts of methyl methacrylate, 3 parts of methacrylic acid, 100 parts of all ethylenically unsaturated monomers, 2 parts of "Aqualon KH-10" dissolved in 30.5 parts of deionized water In addition, the mixture was stirred to obtain an emulsion, which was placed in a dropping funnel.
Thereafter, an aqueous dispersion (A-2) of a high Tg copolymer was obtained in the same manner as in Production Example-1. The glass transition temperature of the copolymer in (A-2) was 98 ° C.
（製造例−３）
エチルメタクリレート６部、メチルメタクリレート９２部、アクリル酸２部、これら全エチレン性不飽和単量体１００部に対して「アクアロンＫＨ−１０」２部を脱イオン水３０．５部に溶解したものを加えて攪拌して乳化物を得、これを滴下ロートに入れた。
以下、製造例−１と同様にして高Ｔｇ共重合体の水性分散体（Ａ−３）を得た。（Ａ−３）中の共重合体のガラス転移温度は１０２℃であった。
(Production Example-3)
6 parts of ethyl methacrylate, 92 parts of methyl methacrylate, 2 parts of acrylic acid, 100 parts of all ethylenically unsaturated monomers, 2 parts of “AQUALON KH-10” dissolved in 30.5 parts of deionized water In addition, the mixture was stirred to obtain an emulsion, which was placed in a dropping funnel.
Thereafter, an aqueous dispersion (A-3) of a high Tg copolymer was obtained in the same manner as in Production Example-1. The glass transition temperature of the copolymer in (A-3) was 102 ° C.
（製造例−４）
２−エチルヘキシルアクリレート６部、メチルメタクリレート９２部、アクリル酸２部、これら全エチレン性不飽和単量体１００部に対して「アクアロンＫＨ−１０」２部を脱イオン水３０．５部に溶解したものを加えて攪拌して乳化物を得、これを滴下ロートに入れた。
以下、製造例−１と同様にして粘着剤用樹脂組成物水性分散体（Ａ−４）を得た。（Ａ−４）の重合物のガラス転移温度は８３℃であった。
(Production Example-4)
6 parts of 2-ethylhexyl acrylate, 92 parts of methyl methacrylate, 2 parts of acrylic acid, 2 parts of "Aqualon KH-10" were dissolved in 30.5 parts of deionized water with respect to 100 parts of these all ethylenically unsaturated monomers. The mixture was added and stirred to obtain an emulsion, which was placed in a dropping funnel.
Hereafter, the resin composition aqueous dispersion (A-4) for adhesives was obtained like manufacture example-1. The glass transition temperature of the polymer (A-4) was 83 ° C.
（製造例−５）
イソボルニルメタクリレート１０部、メチルメタクリレート８７部、メタクリル酸３部、これら全エチレン性不飽和単量体１００部に対して「アクアロンＫＨ−１０」２部を脱イオン水３０．５部に溶解したものを加えて攪拌して乳化物を得、これを滴下ロートに入れた。
以下、製造例−１と同様にして高Ｔｇ共重合体の水性分散体（Ａ−５）を得た。（Ａ−５）中の共重合体のガラス転移温度は１１１℃であった。
(Production Example-5)
10 parts of isobornyl methacrylate, 87 parts of methyl methacrylate, 3 parts of methacrylic acid, 100 parts of all ethylenically unsaturated monomers, 2 parts of "Aqualon KH-10" were dissolved in 30.5 parts of deionized water. The mixture was added and stirred to obtain an emulsion, which was placed in a dropping funnel.
Thereafter, an aqueous dispersion (A-5) of a high Tg copolymer was obtained in the same manner as in Production Example-1. The glass transition temperature of the copolymer in (A-5) was 111 ° C.
（製造例−６）
２−エチルヘキシルアクリレート２０部、ブチルアクリレート６９．８部、メチルメタクリレート８部、アクリル酸２部、ジアセトンアクリルアミド０．２部、これら全エチレン性不飽和単量体１００部に対して「アクアロンＫＨ−１０」２部を脱イオン水３０．５部に溶解したものを加えて攪拌して乳化物を得、これを滴下ロートに入れた。
以下、製造例−１と同様にして低Ｔｇ共重合体の水性分散体（Ｂ−１）を得た。（Ｂ−１）中の共重合体のガラス転移温度は−５２℃であった。
(Production Example-6)
20 parts of 2-ethylhexyl acrylate, 69.8 parts of butyl acrylate, 8 parts of methyl methacrylate, 2 parts of acrylic acid, 0.2 part of diacetone acrylamide, 100 parts of these all ethylenically unsaturated monomers are referred to as “Aqualon KH— A solution prepared by dissolving 2 parts of 10 "in 30.5 parts of deionized water was added and stirred to obtain an emulsion, which was placed in a dropping funnel.
Hereafter, the aqueous dispersion (B-1) of the low Tg copolymer was obtained like manufacture example-1. The glass transition temperature of the copolymer in (B-1) was -52 ° C.
（製造例−７）
２−エチルヘキシルアクリレート７０部、ブチルアクリレート１８．８部、メチルメタクリレート１０部、アクリル酸１部、ジアセトンアクリルアミド０．２部、これら全エチレン性不飽和単量体１００部に対して「アクアロンＫＨ−１０」２部を脱イオン水３０．５部に溶解したものを加えて攪拌して乳化物を得、これを滴下ロートに入れた。
以下、製造例−１と同様にして低Ｔｇ共重合体の水性分散体（Ｂ−２）を得た。（Ｂ−２）中の共重合体のガラス転移温度は−６８℃であった。
(Production Example-7)
70 parts of 2-ethylhexyl acrylate, 18.8 parts of butyl acrylate, 10 parts of methyl methacrylate, 1 part of acrylic acid, 0.2 part of diacetone acrylamide and 100 parts of all ethylenically unsaturated monomers are referred to as “Aqualon KH— A solution prepared by dissolving 2 parts of 10 "in 30.5 parts of deionized water was added and stirred to obtain an emulsion, which was placed in a dropping funnel.
Thereafter, an aqueous dispersion (B-2) of a low Tg copolymer was obtained in the same manner as in Production Example-1. The glass transition temperature of the copolymer in (B-2) was −68 ° C.
（製造例−８）
２−エチルヘキシルアクリレート９７．８部、アクリル酸２部、ジアセトンアクリルアミド０．２部、これら全エチレン性不飽和単量体１００部に対して「アクアロンＫＨ−１０」２部を脱イオン水３０．５部に溶解したものを加えて攪拌して乳化物を得、これを滴下ロートに入れた。
以下、製造例−１と同様にして低Ｔｇ共重合体の水性分散体（Ｂ−３）を得た。（Ｂ−３）中の共重合体のガラス転移温度は−８３℃であった。
(Production Example-8)
9 parts of 2-ethylhexyl acrylate, 2 parts of acrylic acid, 0.2 parts of diacetone acrylamide, 2 parts of “AQUALON KH-10” with 100 parts of all ethylenically unsaturated monomers 30. What was melt | dissolved in 5 parts was added and stirred, the emulsion was obtained, and this was put into the dropping funnel.
Thereafter, an aqueous dispersion (B-3) of a low Tg copolymer was obtained in the same manner as in Production Example-1. The glass transition temperature of the copolymer in (B-3) was -83 ° C.
（製造例−９）
ブチルアクリレート８２．８部、メチルメタクリレート１５部、アクリル酸２部、ジアセトンアクリルアミド０．２部、これら全エチレン性不飽和単量体１００部に対して「アクアロンＫＨ−１０」２部を脱イオン水３０．５部に溶解したものを加えて攪拌して乳化物を得、これを滴下ロートに入れた。
以下、製造例−１と同様にして低Ｔｇ共重合体の水性分散体（Ｂ−４）を得た。（Ｂ−４）中の共重合体のガラス転移温度は−３７℃であった。
(Production Example-9)
82.8 parts of butyl acrylate, 15 parts of methyl methacrylate, 2 parts of acrylic acid, 0.2 part of diacetone acrylamide, and 2 parts of "Aqualon KH-10" are deionized against 100 parts of these all ethylenically unsaturated monomers What was dissolved in 30.5 parts of water was added and stirred to obtain an emulsion, which was placed in a dropping funnel.
Thereafter, an aqueous dispersion (B-4) of a low Tg copolymer was obtained in the same manner as in Production Example-1. The glass transition temperature of the copolymer in (B-4) was -37 ° C.
（製造例−１０）
２−エチルヘキシルアクリレート１８．８１部、ブチルアクリレート６４．９１部、メチルメタクリレート１４．０９部、アクリル酸２部、ジアセトンアクリルアミド０．１９部、これら全エチレン性不飽和単量体１００部に対して「アクアロンＫＨ−１０」２部を脱イオン水３０．５部に溶解したものを加えて攪拌して乳化物を得、これを滴下ロートに入れた。
以下、製造例−１と同様にして共重合体の水性分散体（Ｃ−１）を得た。（Ｃ−１）中の共重合体のガラス転移温度は−４５℃であった。
(Production Example-10)
18.81 parts of 2-ethylhexyl acrylate, 64.91 parts of butyl acrylate, 14.09 parts of methyl methacrylate, 2 parts of acrylic acid, 0.19 part of diacetone acrylamide, and 100 parts of these all ethylenically unsaturated monomers A solution obtained by dissolving 2 parts of “AQUALON KH-10” in 30.5 parts of deionized water was added and stirred to obtain an emulsion, which was placed in a dropping funnel.
Thereafter, an aqueous copolymer dispersion (C-1) was obtained in the same manner as in Production Example-1. The glass transition temperature of the copolymer in (C-1) was -45 ° C.
表２に各製造例で得られた粘着剤用樹脂組成物水性分散体の組成を示す。 Table 2 shows the composition of the aqueous resin composition dispersion for pressure-sensitive adhesives obtained in each production example.
（実施例−１）
高Ｔｇ共重合体の水性分散体（Ａ）として製造例−１で得られた（Ａ−１）を固形分として７部、及び低Ｔｇ共重合体の水性分散体（Ｂ）として製造例−６で得られた（Ｂ−１）を固形分として９３部を混合した後アンモニア水にてｐＨ＝７．５に調整し、消泡剤、レベリング剤、防腐剤を加え、さらにロジン系粘着付与樹脂として荒川化学（株）製「スーパーエステルＥ−７２０」（固形分５０％）を固形分として１５部、および架橋剤として６％アジピン酸ジヒドラジド水溶液を固形分として０．２部加え、さらに粘度調整剤で粘度を３０００ｍＰａ・ｓ（ＢＬ型粘度計、＃４ローター使用、６０ｒｐｍにて測定）に調整し、水性粘着剤組成物を得た。
これをコンマコーターで剥離紙上に乾燥塗膜量が２０ｇ／ｍ2になるように塗工し、１００℃の乾燥オーブンで４０秒間乾燥させ、厚さ５０μｍのＰＥＴフィルムとラミネートして巻き取り、粘着剤塗工物を得、後述する試験方法で、粘着塗工物としての性能を評価し、その結果を表３に示した。
(Example-1)
As an aqueous dispersion (A) of a high Tg copolymer, 7 parts (A-1) obtained in Production Example-1 as a solid content and as an aqueous dispersion (B) of a low Tg copolymer, Production Example- After mixing 93 parts with (B-1) obtained in 6 as a solid content, the pH was adjusted to 7.5 with aqueous ammonia, an antifoaming agent, a leveling agent and a preservative were added, and rosin-based tackifier was further added. Arakawa Chemical Co., Ltd. "Superester E-720" (solid content 50%) as a solid, 15 parts as a solid, and 6% adipic acid dihydrazide aqueous solution as a crosslinking agent as a solid, 0.2 parts as a resin, and viscosity The viscosity was adjusted to 3000 mPa · s (with a BL type viscometer, using a # 4 rotor, measured at 60 rpm) with an adjusting agent to obtain an aqueous pressure-sensitive adhesive composition.
This was coated on a release paper with a comma coater so that the dry coating amount was 20 g / m 2 , dried in a drying oven at 100 ° C. for 40 seconds, laminated with a PET film having a thickness of 50 μm, wound up, and adhered. An agent coated product was obtained, and the performance as an adhesive coated product was evaluated by the test method described below. The results are shown in Table 3.
（実施例−２〜７、比較例−１〜７）
高Ｔｇ共重合体の水性分散体（Ａ）及び低Ｔｇ共重合体の水性分散体（Ｂ）の種類、混合比率を表３に示すように変更した以外は実施例−１と同様にして水性粘着剤組成物を得、粘着塗工物としての性能を評価した。なお製造例−１０で得られた粘着剤用樹脂組成物水性分散体（Ｃ−１）については、単独で固形分として１００部を用いた以外は実施例−１と同様にして水性粘着剤組成物を得、粘着塗工物としての性能を評価した。
(Examples 2-7, Comparative Examples-1-7)
Except that the type and mixing ratio of the aqueous dispersion (A) of the high Tg copolymer and the aqueous dispersion (B) of the low Tg copolymer were changed as shown in Table 3, it was aqueous in the same manner as in Example-1. The pressure-sensitive adhesive composition was obtained, and the performance as a pressure-sensitive adhesive coated product was evaluated. In addition, about the resin composition aqueous dispersion for adhesives (C-1) obtained by manufacture example-10, it was the same as Example 1 except having used 100 parts as solid content independently. The product was obtained, and the performance as an adhesive coated product was evaluated.
［試験方法］
１）接着力
粘着剤塗工物を幅２５ｍｍの短冊状にカットし剥離紙を剥がし、表面を研磨した３ｃｍ×１１ｃｍのステンレス鋼板、及びガラス板、またポリエチレン板に貼り付け、２ｋｇロールで１往復した後、２３℃雰囲気下にて２４時間放置した。所定時間経過後、２３℃雰囲気下で、３００ｍｍ／分の速さで塗工物を１８０゜方向に剥離した際の接着強度を測定した。
[Test method]
1) Adhesive strength The adhesive coated product was cut into a 25 mm wide strip, the release paper was peeled off, and the surface was polished and pasted onto a 3 cm x 11 cm stainless steel plate, glass plate, or polyethylene plate, and 1 round trip with a 2 kg roll. And then left in a 23 ° C. atmosphere for 24 hours. After a predetermined time, the adhesive strength was measured when the coated material was peeled in the 180 ° direction at a speed of 300 mm / min in an atmosphere of 23 ° C.
２）曲面貼り付け性
粘着剤塗工物を幅２０ｍｍ、長さ１５ｍｍの大きさにカットし剥離紙を剥がして、長さが３０ｃｍ、直径が１０ｍｍのポリエチレン製の棒の周囲に貼り付けた。貼り付ける方向としては、塗工物試料の幅方向（長手方向）がポリエチレン棒の長さ方向と平行となるようにした。貼り付け後、指にて強く圧着し、２３℃雰囲気下にて７日間放置した。所定期間経過後、試料が剥離しているかどうかを目視にて観察した。
○：剥離なし。
△：試料の端部が剥離している。
×：全面剥離し、基材が平坦になっている。
2) Curved surface sticking property The pressure-sensitive adhesive coated material was cut into a size of 20 mm in width and 15 mm in length, the release paper was peeled off, and pasted around a polyethylene rod having a length of 30 cm and a diameter of 10 mm. As the direction of application, the width direction (longitudinal direction) of the coated sample was made parallel to the length direction of the polyethylene rod. After pasting, it was strongly pressure-bonded with a finger and allowed to stand in a 23 ° C. atmosphere for 7 days. After a predetermined period of time, it was visually observed whether the sample was peeled off.
○: No peeling.
(Triangle | delta): The edge part of a sample has peeled.
X: The entire surface was peeled off and the substrate was flat.
３）基材密着性
粘着剤塗工物の剥離紙を剥がして、粘着剤層にカッターにてクロスカットを施し、指にてクロスカット部を３回強くこすり、こすった箇所の粘着剤が基材から剥離したかどうかを目視にて観察した。
○：剥離なし。
△：一部剥離あり。
×：全面的に剥離。
3) Adhesiveness of base material Peel off the release paper of the coated adhesive, cross-cut the adhesive layer with a cutter, and rub the cross-cut part 3 times with your fingers. It was visually observed whether it peeled from the material.
○: No peeling.
Δ: Partial peeling occurred.
X: It peels entirely.
比較例−１に示されるように、高Ｔｇ共重合体の水性分散体（Ａ）のガラス転移温度が本発明で特定する値よりも低い場合、曲面貼り付け性及び基材密着性が劣っている。比較例−２に示されるように、高Ｔｇ共重合体の水性分散体（Ａ）のガラス転移温度が本発明で特定する値よりも高い場合、接着力が低いのに加えて曲面貼り付け性が劣っている。比較例−３に示されるように、低Ｔｇ共重合体の水性分散体（Ｂ）のガラス転移温度が本発明で特定する値よりも低い場合、凝集力が低下したため曲面貼り付け性が著しく劣っている。比較例−４に示されるように、低Ｔｇ共重合体の水性分散体（Ｂ）のガラス転移温度が本発明で特定する値よりも高い場合、接着力が低いのに加えて曲面貼り付け性が劣っている。比較例−５に示されるように、高Ｔｇ共重合体の水性分散体（Ａ）の使用量が本発明で特定する量よりも少ない場合、曲面貼り付け性及び基材密着性が劣っている。さらに比較例−６に示されるように、高Ｔｇ共重合体の水性分散体（Ａ）の使用量が本発明で特定する量よりも多い場合、接着力が低いのに加えて曲面貼り付け性が劣っている。
またさらに、比較例−７においては、実施例−１における（Ａ−１）／（Ｂ−１）の固形分比率が７／９３である混合物の、全体としての各単量体量を平均化して単一の粘着剤用樹脂組成物水性分散体として重合した例を示したのであるが、実施例−１とは相反して、曲面貼り付け性及び基材密着性が劣っている。
As shown in Comparative Example-1, when the glass transition temperature of the aqueous dispersion (A) of the high Tg copolymer is lower than the value specified in the present invention, the curved surface sticking property and the substrate adhesion are inferior. Yes. As shown in Comparative Example-2, when the glass transition temperature of the aqueous dispersion (A) of the high Tg copolymer is higher than the value specified in the present invention, the adhesive strength is low and the curved surface sticking property is also shown. Is inferior. As shown in Comparative Example-3, when the glass transition temperature of the aqueous dispersion (B) of the low Tg copolymer is lower than the value specified in the present invention, the curved surface sticking property is remarkably inferior because the cohesive force is lowered. ing. As shown in Comparative Example-4, when the glass transition temperature of the aqueous dispersion (B) of the low Tg copolymer is higher than the value specified in the present invention, the adhesive force is low and the curved surface sticking property is also shown. Is inferior. As shown in Comparative Example-5, when the amount of the high-Tg copolymer aqueous dispersion (A) used is less than the amount specified in the present invention, the curved surface sticking property and the substrate adhesion are inferior. . Further, as shown in Comparative Example-6, when the amount of the high-Tg copolymer aqueous dispersion (A) used is larger than the amount specified in the present invention, the adhesive strength is low and the curved surface sticking property is also shown. Is inferior.
Furthermore, in Comparative Example-7, the amount of each monomer as a whole of the mixture having a solid content ratio of (A-1) / (B-1) in Example-1 of 7/93 was averaged. However, contrary to Example-1, the curved surface sticking property and the substrate adhesion were inferior.
これに対し、本発明における実施例においては、高い接着力および優れた曲面貼り付け性が得られているのに加えて、粘着剤層とプラスチックフィルム基材との間の密着性が良好である。そのため、本発明により得られる水性粘着剤を使用した粘着剤塗工物は、従来水性粘着剤の使用が困難であったポリエチレン等のポリオレフィン被着体に対しても好んで用いる事ができ、さらに曲面貼り付け性が良好であるため、曲面形状を有する被着体に対しても好んで用いる事ができる。また、被着体上に粘着剤が残存する事なく塗工物を剥離する事ができるため、貼り付ける前の被着体の外観を粘着剤により汚染する事なく復元する事ができる。 On the other hand, in the Example in this invention, in addition to the high adhesive force and the outstanding curved surface sticking property being obtained, the adhesiveness between an adhesive layer and a plastic film base material is favorable. . Therefore, the pressure-sensitive adhesive coated product using the water-based pressure-sensitive adhesive obtained according to the present invention can be preferably used for polyolefin adherends such as polyethylene, which have conventionally been difficult to use water-based pressure-sensitive adhesives. Since the curved surface sticking property is good, it can be preferably used for an adherend having a curved surface shape. Moreover, since the coated product can be peeled without the adhesive remaining on the adherend, the appearance of the adherend before being attached can be restored without being contaminated by the adhesive.
その機構は明らかではないが、特に比較例−７の結果に見られるように、全体としての平均組成は同一組成であっても、単一の樹脂組成物とした場合には本発明の効果が得られていない事から、本発明の粘着剤組成物から得られる粘着剤塗膜中においては、組成の異なる分散体粒子が完全に複合化する事なく独立して存在しており、それに起因する組成の異なる粒子間の相互作用によって上記のような効果を奏しているものと推察される。
Although the mechanism is not clear, especially as seen in the results of Comparative Example-7, even if the average composition as a whole is the same composition, the effect of the present invention is obtained when a single resin composition is used. In the pressure-sensitive adhesive coating film obtained from the pressure-sensitive adhesive composition of the present invention, the dispersion particles having different compositions are present independently without being completely complexed due to the fact that they are not obtained. It is inferred that the above-described effects are exhibited by the interaction between particles having different compositions.
Claims (4)
アルキル基の炭素数が４〜１４であるアルキルアクリレート（ｃ）５５〜９５重量％及びカルボキシル基含有単量体（ａ）０．５〜５重量％を含有する単量体を、乳化剤及び重合開始剤を用い、水性媒体中で重合してなるガラス転移温度が−７５℃以上−４５℃以下の低ガラス転移温度共重合体の水性分散体（Ｂ）とを、
（Ａ）／（Ｂ）＝１／９９〜１５／８５（固形分重量比率）の割合にて含有し、さらに粘着付与剤と、架橋剤とを含有する事を特徴とする水性粘着剤組成物。 In an aqueous medium, 0.5 to 5% by weight of the carboxyl group-containing monomer (a) and another monomer (b) copolymerizable with the monomer (a) are used in an aqueous medium using an emulsifier and a polymerization initiator. An aqueous dispersion (A) of a high glass transition temperature copolymer having a glass transition temperature of 90 ° C. or higher and 105 ° C. or lower obtained by polymerization in
A monomer containing 55 to 95% by weight of alkyl acrylate (c) whose alkyl group has 4 to 14 carbon atoms and 0.5 to 5% by weight of carboxyl group-containing monomer (a), emulsifier and polymerization initiation An aqueous dispersion (B) of a low glass transition temperature copolymer having a glass transition temperature of −75 ° C. or higher and −45 ° C. or lower formed by polymerization in an aqueous medium using an agent,
(A) / (B) = 1/99 to 15/85 (solid content weight ratio) The aqueous pressure-sensitive adhesive composition characterized by containing a tackifier and a crosslinking agent . .
アルキル基の炭素数が４〜１４であるアルキルアクリレート（ｃ）５５〜９５重量％及びカルボキシル基含有単量体（ａ）０．５〜５重量％を含有する単量体を、乳化剤及び重合開始剤を用い、水性媒体中で重合してなるガラス転移温度が−７５℃以上−４５℃以下の低ガラス転移温度共重合体の水性分散体（Ｂ）とを、
（Ａ）／（Ｂ）＝１／９９〜１５／８５（固形分重量比率）の割合で混合し、さらに粘着付与剤と、架橋剤とを混合する事を特徴とする水性粘着剤組成物の製造方法。 In an aqueous medium, 0.5 to 5% by weight of the carboxyl group-containing monomer (a) and another monomer (b) copolymerizable with the monomer (a) are used in an aqueous medium using an emulsifier and a polymerization initiator. An aqueous dispersion (A) of a high glass transition temperature copolymer having a glass transition temperature of 90 ° C. or higher and 105 ° C. or lower obtained by polymerization in
A monomer carbon number of A alkyl groups contain alkyl acrylates (c) 55 to 95 wt% and the carboxyl group-containing monomer (a) 0.5 to 5% by weight is 4 to 14, an emulsifier and a polymerization An aqueous dispersion (B) of a low glass transition temperature copolymer having a glass transition temperature of −75 ° C. or higher and −45 ° C. or lower formed by polymerization in an aqueous medium using an initiator,
(A) / (B) = 1/99 to 15/85 (solid content weight ratio) is mixed, and a tackifier and a crosslinking agent are further mixed. Production method.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108624240A (en) * | 2018-05-10 | 2018-10-09 | 华南农业大学 | Room temperature ketone hydrazine self-crosslinking acrylic resin aqueous dispersion and its preparation method and application |
| CN108794682A (en) * | 2018-05-31 | 2018-11-13 | 华南农业大学 | A kind of room temperature ketone hydrazine self-crosslinking acrylic resin lotion and its preparation method and application |
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| JP5421545B2 (en) * | 2008-04-24 | 2014-02-19 | 日本カーバイド工業株式会社 | Aqueous pressure-sensitive adhesive composition for low temperature rough surface |
| JP5552364B2 (en) * | 2010-05-18 | 2014-07-16 | 日東電工株式会社 | Water-dispersed pressure-sensitive adhesive composition for optical film, pressure-sensitive adhesive layer for optical film, pressure-sensitive optical film, and image display device |
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| JP2001200227A (en) * | 2000-01-18 | 2001-07-24 | Mitsubishi Chemicals Corp | Heat-sensitive, pressure-sensitive adhesive composition; and heat-sensitive, pressure-sensitive adhesive sheet or label |
| JP2001323235A (en) * | 2000-05-15 | 2001-11-22 | Mitsubishi Chemicals Corp | Adhesive composition and adhesive label or tape |
| JP2003313528A (en) * | 2002-04-19 | 2003-11-06 | Basf Dispersions Co Ltd | Aqueous pressure-sensitive adhesive composition |
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| JPH08269431A (en) * | 1995-03-31 | 1996-10-15 | Mitsubishi Chem Basf Co Ltd | Pressure-sensitive adhesive composition |
| JP3465833B2 (en) * | 1995-06-07 | 2003-11-10 | 株式会社日本触媒 | Solvent type pressure sensitive adhesive composition |
| JPH1036788A (en) * | 1996-07-19 | 1998-02-10 | Toagosei Co Ltd | Heat sensitive tacky sheet |
| JPH1135608A (en) * | 1997-07-23 | 1999-02-09 | Mitsubishi Chem Basf Co Ltd | Production of aqueous pressure-sensitive type acrylic tacky agent |
| JPH11172218A (en) * | 1997-12-08 | 1999-06-29 | Toyo Ink Mfg Co Ltd | Tacky adhesive composition and use thereof |
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| JP2001200227A (en) * | 2000-01-18 | 2001-07-24 | Mitsubishi Chemicals Corp | Heat-sensitive, pressure-sensitive adhesive composition; and heat-sensitive, pressure-sensitive adhesive sheet or label |
| JP2001323235A (en) * | 2000-05-15 | 2001-11-22 | Mitsubishi Chemicals Corp | Adhesive composition and adhesive label or tape |
| JP2003313528A (en) * | 2002-04-19 | 2003-11-06 | Basf Dispersions Co Ltd | Aqueous pressure-sensitive adhesive composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108624240A (en) * | 2018-05-10 | 2018-10-09 | 华南农业大学 | Room temperature ketone hydrazine self-crosslinking acrylic resin aqueous dispersion and its preparation method and application |
| CN108794682A (en) * | 2018-05-31 | 2018-11-13 | 华南农业大学 | A kind of room temperature ketone hydrazine self-crosslinking acrylic resin lotion and its preparation method and application |
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