JP5053566B2 - Emulsion adhesive - Google Patents
Emulsion adhesive Download PDFInfo
- Publication number
- JP5053566B2 JP5053566B2 JP2006124839A JP2006124839A JP5053566B2 JP 5053566 B2 JP5053566 B2 JP 5053566B2 JP 2006124839 A JP2006124839 A JP 2006124839A JP 2006124839 A JP2006124839 A JP 2006124839A JP 5053566 B2 JP5053566 B2 JP 5053566B2
- Authority
- JP
- Japan
- Prior art keywords
- emulsion
- acid
- adhesive
- polylactic acid
- rosin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
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- 230000001070 adhesive effect Effects 0.000 title claims description 82
- 239000000839 emulsion Substances 0.000 title claims description 81
- 239000000853 adhesive Substances 0.000 title claims description 77
- -1 hydrazine compound Chemical class 0.000 claims description 79
- 229920005989 resin Polymers 0.000 claims description 73
- 239000011347 resin Substances 0.000 claims description 73
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 69
- 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 claims description 68
- 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 claims description 68
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 61
- 239000004626 polylactic acid Substances 0.000 claims description 61
- 239000003431 cross linking reagent Substances 0.000 claims description 42
- 239000007787 solid Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 claims description 11
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 8
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 150000001718 carbodiimides Chemical class 0.000 claims description 3
- 230000009257 reactivity Effects 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 31
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 19
- 238000003860 storage Methods 0.000 description 15
- 239000003995 emulsifying agent Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 11
- 238000004945 emulsification Methods 0.000 description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229920001228 polyisocyanate Polymers 0.000 description 9
- 239000005056 polyisocyanate Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- 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 5
- 239000012298 atmosphere Substances 0.000 description 5
- 229920005601 base polymer Polymers 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000002657 fibrous material Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000004310 lactic acid Substances 0.000 description 4
- 235000014655 lactic acid Nutrition 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- MWZFQMUXPSUDJQ-KVVVOXFISA-M sodium;[(z)-octadec-9-enyl] sulfate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCCOS([O-])(=O)=O MWZFQMUXPSUDJQ-KVVVOXFISA-M 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- MHVJRKBZMUDEEV-UHFFFAOYSA-N (-)-ent-pimara-8(14),15-dien-19-oic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)C=C1CC2 MHVJRKBZMUDEEV-UHFFFAOYSA-N 0.000 description 2
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 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
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 229920000881 Modified starch Polymers 0.000 description 2
- 239000004368 Modified starch Substances 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000012874 anionic emulsifier Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 239000000835 fiber 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
- MXYATHGRPJZBNA-KRFUXDQASA-N isopimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@@](C=C)(C)CC2=CC1 MXYATHGRPJZBNA-KRFUXDQASA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 235000019426 modified starch Nutrition 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920002961 polybutylene succinate Polymers 0.000 description 2
- 239000004631 polybutylene succinate Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- MHVJRKBZMUDEEV-APQLOABGSA-N (+)-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@](C=C)(C)C=C2CC1 MHVJRKBZMUDEEV-APQLOABGSA-N 0.000 description 1
- ZNGSVRYVWHOWLX-KHFUBBAMSA-N (1r,2s)-2-(methylamino)-1-phenylpropan-1-ol;hydrate Chemical compound O.CN[C@@H](C)[C@H](O)C1=CC=CC=C1.CN[C@@H](C)[C@H](O)C1=CC=CC=C1 ZNGSVRYVWHOWLX-KHFUBBAMSA-N 0.000 description 1
- 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 1
- SNVRDQORMVVQBI-OWOJBTEDSA-N (e)-but-2-enedihydrazide Chemical compound NNC(=O)\C=C\C(=O)NN SNVRDQORMVVQBI-OWOJBTEDSA-N 0.000 description 1
- UKQHQVOBYJZEGO-OLGQORCHSA-N (z)-2-methylbut-2-enedioic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C(/C)=C\C(O)=O UKQHQVOBYJZEGO-OLGQORCHSA-N 0.000 description 1
- SNVRDQORMVVQBI-UPHRSURJSA-N (z)-but-2-enedihydrazide Chemical compound NNC(=O)\C=C/C(=O)NN SNVRDQORMVVQBI-UPHRSURJSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- KATAXDCYPGGJNJ-UHFFFAOYSA-N 1,3-bis(oxiran-2-ylmethoxy)propan-2-ol Chemical compound C1OC1COCC(O)COCC1CO1 KATAXDCYPGGJNJ-UHFFFAOYSA-N 0.000 description 1
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 1
- HRWPIKQDMKGDCC-UHFFFAOYSA-N 2,5-bis(aziridin-1-yl)-2,5-dimethylhexanedioic acid Chemical compound C1CN1C(C(O)=O)(C)CCC(C)(C(O)=O)N1CC1 HRWPIKQDMKGDCC-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
- BQBSIHIZDSHADD-UHFFFAOYSA-N 2-ethenyl-4,5-dihydro-1,3-oxazole Chemical compound C=CC1=NCCO1 BQBSIHIZDSHADD-UHFFFAOYSA-N 0.000 description 1
- PBYIFPWEHGSUEY-UHFFFAOYSA-N 2-ethenyl-4-methyl-4,5-dihydro-1,3-oxazole Chemical compound CC1COC(C=C)=N1 PBYIFPWEHGSUEY-UHFFFAOYSA-N 0.000 description 1
- NYEZZYQZRQDLEH-UHFFFAOYSA-N 2-ethyl-4,5-dihydro-1,3-oxazole Chemical compound CCC1=NCCO1 NYEZZYQZRQDLEH-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- GUXJXWKCUUWCLX-UHFFFAOYSA-N 2-methyl-2-oxazoline Chemical compound CC1=NCCO1 GUXJXWKCUUWCLX-UHFFFAOYSA-N 0.000 description 1
- NEWFQHAOPHWBPR-UHFFFAOYSA-N 2-methylidenebutanedihydrazide Chemical compound NNC(=O)CC(=C)C(=O)NN NEWFQHAOPHWBPR-UHFFFAOYSA-N 0.000 description 1
- AUZRCMMVHXRSGT-UHFFFAOYSA-N 2-methylpropane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CC(C)CS(O)(=O)=O AUZRCMMVHXRSGT-UHFFFAOYSA-N 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- LPIQIQPLUVLISR-UHFFFAOYSA-N 2-prop-1-en-2-yl-4,5-dihydro-1,3-oxazole Chemical compound CC(=C)C1=NCCO1 LPIQIQPLUVLISR-UHFFFAOYSA-N 0.000 description 1
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Images
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Description
本発明はポリ乳酸系のエマルション粘着剤に関して、保持力に優れ、糊残りがないうえ、良好な保存安定性を示すものを提供する。 The present invention provides a polylactic acid-based emulsion pressure-sensitive adhesive having excellent holding power, no adhesive residue, and good storage stability.
一般に、溶剤型、ホットメルト型、或は感圧型の粘・接着剤には、接着性向上の見地から、アクリル系、天然ゴム系、ＳＢＲ系、ＳＩＳ系、ＥＶＡ系、ウレタン系又はＣＲ系などの各種ベースポリマーに粘着付与剤樹脂を添加している。
この粘着付与剤樹脂には、ロジン系、テルペン系、或は石油系などの各種樹脂があり、これらの一種以上を上記ベースポリマーに添加することにより、系の粘度を低下させ、可塑化効果の付与による被着体への濡れを良くし、接着剤と被着体との界面の結合力を高めて、粘着物性を付与改質している。
ちなみに、粘着剤は剥離の際に基材と被着面の間で界面破壊を起こすため、被着面には粘着剤が残らず（糊残りがなく）、圧力を負荷した場合の接着（感圧接着）と被着面からの剥離を反復できる機能を有するものをいう。
これに対して、接着剤は液体が何らかの化学変化で固体になって被着面に接着するものをいい、接着後に剥離すると基材と被着面の間でなき分かれを起こし（接着剤が基材と被着面の両方に分離付着して、いわば凝集破壊的な現象を示し）、従って、接着を主眼とし、接着後の剥離を前提しない。
In general, for solvent-type, hot-melt type, or pressure-sensitive type adhesives / adhesives, acrylic, natural rubber-based, SBR-based, SIS-based, EVA-based, urethane-based, CR-based, etc. from the viewpoint of improving adhesiveness A tackifier resin is added to various base polymers.
This tackifier resin includes various resins such as rosin, terpene, and petroleum. By adding one or more of these to the base polymer, the viscosity of the system is lowered, and the plasticizing effect is increased. It improves wettability to the adherend by the application, enhances the bonding force at the interface between the adhesive and the adherend, and imparts and modifies the adhesive physical properties.
By the way, the adhesive causes interfacial breakage between the substrate and the adherend surface at the time of peeling, so no adhesive remains on the adherend surface (no adhesive residue) and adhesion (sensitivity) when pressure is applied. It has a function capable of repeating pressure bonding and peeling from the adherend surface.
On the other hand, adhesive refers to a liquid that becomes a solid due to some chemical change and adheres to the adherend surface. When it is peeled off after adhesion, a separation occurs between the substrate and the adherend surface (the adhesive is based on the adhesive). The material adheres separately to both the material and the adherend surface, so to speak, it exhibits a phenomenon of cohesive failure).
一般に、上記粘着剤には粘着付与剤樹脂としてロジン系樹脂が使用されており、このロジン系樹脂にあっては、ロジン類や変性ロジン類と、多価アルコールを加熱脱水縮合させて得られるロジンエステルが多用され、ロジン類の変性方法と多価アルコールの種類を組み合わせることにより、常温で液状のものから高軟化点の固形状樹脂まで多様な樹脂を得ることが可能であり、必要な各種粘着物性への対応が容易である。
また、例えば、アクリル系粘着剤では、アクリル系ポリマーに粘着付与剤樹脂としてロジン系樹脂を使用するが、粘着剤の物性を向上させる見地から、ポリイソシアネート系化合物を微量添加することにより、アクリル系ポリマーを架橋し、硬化させて内部凝集力を高めることが行われている。
In general, a rosin resin is used as a tackifier resin in the above-mentioned pressure-sensitive adhesive. In this rosin-based resin, a rosin obtained by heat-dehydrating condensation of a rosin or a modified rosin and a polyhydric alcohol. Ester is often used, and by combining the modification method of rosins and the type of polyhydric alcohol, it is possible to obtain a variety of resins from liquids at room temperature to solid resins with a high softening point. Easy to deal with physical properties.
In addition, for example, in an acrylic pressure-sensitive adhesive, a rosin resin is used as a tackifier resin for an acrylic polymer. From the viewpoint of improving the physical properties of the pressure-sensitive adhesive, a small amount of a polyisocyanate compound is added to the acrylic polymer. It has been practiced to crosslink and cure the polymer to increase internal cohesion.
近年、粘・接着剤の分野では、環境保全及び製造時の安全衛生の観点から、水系エマルションの利用価値が高まっている。
粘着付与剤樹脂エマルションは、各種アクリル酸重合物又は各種ラテックス等に代表されるベースポリマーに対して、粘着特性を向上するために添加されるが、当該エマルションを用いた粘・接着剤は、用途が益々多岐にわたり、性能もより高度なものが求められ、特に、保持力（凝集力）の向上が強く要求されている。
In recent years, in the field of adhesives and adhesives, the utility value of water-based emulsions is increasing from the viewpoints of environmental protection and safety and health during production.
The tackifier resin emulsion is added to the base polymer typified by various acrylic acid polymers or various latexes, etc. to improve the adhesive properties. However, there is a growing demand for more advanced performance, and in particular, there is a strong demand for improved holding power (cohesive strength).
一方、近年では、ポリ乳酸に代表される生分解性樹脂は環境負荷の軽減やごみの減量などに寄与する点で注目されており、特に、ポリ乳酸は実用に十分な耐熱性を備え、比較的安価でもあるため、今後の有効活用が期待されている。
このポリ乳酸樹脂はエマルション形態でも利用されるが、上記粘着付与剤樹脂を添加したポリ乳酸エマルションは保持力に欠け、又は凝集物が発生するなどの問題がある。
On the other hand, in recent years, biodegradable resins typified by polylactic acid have attracted attention because they contribute to reducing the environmental burden and reducing the amount of waste. In particular, polylactic acid has sufficient heat resistance for practical use. It is expected to be used effectively in the future.
This polylactic acid resin is also used in the form of an emulsion, but the polylactic acid emulsion to which the tackifier resin is added has problems such as lack of holding power or generation of aggregates.
そこで、ポリ乳酸エマルションを用いた粘・接着剤の従来技術を挙げると、次の通りである。
(1)特許文献１
柔軟性や粘接着性の向上を目的として（段落６〜７参照）、ポリ乳酸系樹脂に対してロジン系化合物及び／又はテルペン系化合物を特定割合で含有するポリ乳酸系樹脂エマルション、当該エマルションを含む接着剤、粘着剤が開示され（請求項１〜４）、このエマルションにはさらに用途目的に応じて架橋剤、可塑剤などを添加できることが記載されている（段落１７）。
Therefore, the following is a list of conventional technologies for adhesives and adhesives using polylactic acid emulsions.
(1) Patent Document 1
For the purpose of improving flexibility and adhesiveness (see paragraphs 6 to 7), a polylactic acid resin emulsion containing a rosin compound and / or a terpene compound in a specific ratio with respect to the polylactic acid resin, the emulsion (Embodiment 1 to 4), it is described that a crosslinking agent, a plasticizer and the like can be further added to the emulsion according to the purpose of use (paragraph 17).
(2)特許文献２
安全性や貯蔵安定性などの改善を目的として（段落６、２２）、ロジン系樹脂を含有するポリ乳酸水性エマルションが開示されている（請求項１〜８）。また、ポリ乳酸の水性エマルションを含有するコーティング剤は各種基材への密着性、透明性などに優れることが記載されている（請求項９、段落２２）。
(2) Patent Document 2
For the purpose of improving safety and storage stability (paragraphs 6 and 22), polylactic acid aqueous emulsions containing a rosin resin are disclosed (claims 1 to 8). Moreover, it is described that the coating agent containing the aqueous emulsion of polylactic acid is excellent in the adhesiveness, transparency, etc. to various base materials (Claim 9, Paragraph 22).
(3)特許文献３
接着強度の改善を目的として（段落８、８９）、ポリ乳酸などの生分解性ポリエステルの水分散液にポリイソシアネート類化合物を配合してなる生分解性水分散系接着剤組成物が開示され（請求項１）、この接着剤組成物には、必要に応じて粘着付与剤樹脂、可塑剤などを含有できることが記載されている（段落５０）。また、被着体が非多孔質材料では、ヒートシールで接着することが述べられている（段落５１）。
同文献３の実施例４には、ロジン系タッキファイヤーを加えたポリ乳酸水分散液に、ポリイソシアネートを添加して水性接着剤組成物を調製し、これをＰＥＴフィルムに塗布して得られた試料をヒートシール試験することが記載されている（段落７２）。
(3) Patent Document 3
For the purpose of improving adhesive strength (paragraphs 8 and 89), a biodegradable water-dispersed adhesive composition comprising a polyisocyanate compound blended in an aqueous dispersion of biodegradable polyester such as polylactic acid is disclosed ( Claim 1) describes that this adhesive composition can contain a tackifier resin, a plasticizer, and the like as necessary (paragraph 50). Further, it is described that the adherend is bonded by heat sealing when the non-porous material is used (paragraph 51).
Example 4 of the same document 3 was obtained by adding a polyisocyanate to a polylactic acid aqueous dispersion to which a rosin tackifier was added to prepare an aqueous adhesive composition, which was applied to a PET film. It is described that the sample is heat sealed (paragraph 72).
(4)特許文献４
分散液の保存安定性や皮膜の接着性を向上する目的で（段落８、５４）、エポキシ化合物、アミン化合物、イソシアネート化合物、オキサゾリン化合物、カルボジイミド化合物、シランカップリング剤の少なくとも一種を配合したポリ乳酸水性分散液が開示されている（請求項１）。
また、この水性分散液にガムロジン、ロジンエステルなどの天然樹脂系の粘着付与剤樹脂を添加できることが記載されている（段落３２、３４、３６）。
尚、同文献４の実施例１などでは、ポリ乳酸分散液にエポキシ化合物（グリセロールポリグリシジルエーテル）を添加した水性分散液をポリ乳酸フィルムに塗布して、ヒートシール試験を行っている（段落４０〜４５）。
(4) Patent Document 4
Polylactic acid containing at least one of an epoxy compound, an amine compound, an isocyanate compound, an oxazoline compound, a carbodiimide compound, and a silane coupling agent for the purpose of improving the storage stability of the dispersion and the adhesion of the film (paragraphs 8 and 54). An aqueous dispersion is disclosed (claim 1).
Further, it is described that a natural resin-based tackifier resin such as gum rosin and rosin ester can be added to this aqueous dispersion (paragraphs 32, 34, and 36).
In Example 1 of the same document 4, an aqueous dispersion obtained by adding an epoxy compound (glycerol polyglycidyl ether) to a polylactic acid dispersion is applied to a polylactic acid film, and a heat seal test is performed (paragraph 40). ~ 45).
上記特許文献１〜４においては、粘着特性、特に保持力が不充分であるとともに、これらの粘・接着剤を塗工したシート材を被着面に接着した場合には、被着面に接着剤成分が残存して糊残りが多く（つまり、前述のなき分かれを起こし）、粘着剤用途では製品としての実用性に乏しいという問題がある。
また、上記特許文献３〜４は塗工材のヒートシール試験を行っていることからも分かるように、これらは感熱型のエマルション接着剤を用途とするため、常温で感圧接着性を有し、且つ、糊残りがない（つまり、前述の界面破壊を起こす）ことが要求される粘着剤用途にそのまま利用することは、さらに容易でない。
本発明はポリ乳酸系のエマルション粘着剤において、保持力を向上し、糊残りを改善することを技術的課題とする。
In the above Patent Documents 1 to 4, the adhesive properties, particularly the holding power are insufficient, and when the sheet material coated with these adhesives / adhesives is adhered to the adherend surface, it adheres to the adherend surface. There is a problem that the adhesive component remains and a large amount of adhesive remains (that is, the above-mentioned separation occurs), and the practical use as a product is poor in the adhesive application.
Moreover, since the said patent documents 3-4 are also performing the heat seal test of a coating material, since these use heat sensitive emulsion adhesives, they have pressure sensitive adhesiveness at normal temperature. In addition, it is not easy to use it as it is for adhesives that are required to have no adhesive residue (that is, to cause the above-mentioned interface fracture).
This invention makes it a technical subject to improve holding power and to improve adhesive residue in a polylactic acid-based emulsion adhesive.
本発明者らは、ポリ乳酸系のエマルション粘着剤の粘着特性を鋭意研究した結果、ポリ乳酸に粘着付与剤樹脂として所定酸価のロジン系樹脂を特定比率で混合してポリ乳酸エマルションを製造し、さらにオキサゾリン系化合物、カルボジイミド系化合物、アジリジン系化合物などの特定の架橋剤を添加して内部凝集力を増すと、保持力に優れ、糊残りのないエマルション粘着剤が得られること、また、架橋剤として汎用されるエポキシ系化合物やポリイソシアネートとは異なり、オキサゾリン系化合物などの特定の架橋剤を使用するために保存安定性にも優れることを見い出して、本発明を完成した。 The present inventors have made intensive studies adhesive properties of the polylactic acid-based emulsion adhesive, to prepare a polylactic acid emulsion by mixing at a specific ratio a predetermined acid value of the rosin resin as a tackifier resin in polylactic acid Furthermore, adding a specific cross-linking agent such as an oxazoline compound, a carbodiimide compound, or an aziridine compound to increase the internal cohesive force can provide an emulsion pressure-sensitive adhesive with excellent holding power and no adhesive residue. In contrast to epoxy compounds and polyisocyanates that are widely used as agents, the present invention has been completed by finding that it is excellent in storage stability because of the use of a specific crosslinking agent such as an oxazoline compound.
即ち、本発明１は、ポリ乳酸と粘着付与剤樹脂としてロジン系樹脂を混和したポリ乳酸エマルションに、オキサゾリン系、カルボジイミド系、アジリジン系、ヒドラジン系化合物よりなる群から選ばれたカルボキシル基との反応性を有する架橋剤を添加するとともに、
上記ロジン系樹脂が酸価１〜３００のロジン誘導体であり、
固形分換算で、ポリ乳酸１００重量部に対してロジン系樹脂５〜５０重量部を配合することを特徴とするエマルション粘着剤である。
That is, the present invention 1 is a reaction with a carboxyl group selected from the group consisting of an oxazoline-based, carbodiimide-based, aziridine-based, and hydrazine-based compound in a polylactic acid emulsion in which polylactic acid and a rosin-based resin are mixed as a tackifier resin. While adding a cross-linking agent having properties ,
The rosin resin is a rosin derivative having an acid value of 1 to 300,
An emulsion pressure-sensitive adhesive comprising 5 to 50 parts by weight of a rosin resin based on 100 parts by weight of polylactic acid in terms of solid content .
本発明２は、上記本発明１において、固形分換算で、ポリ乳酸エマルション１００重量部に対して架橋剤５〜２０重量部を配合することを特徴とするエマルション粘着剤である。 The present invention 2 is the emulsion pressure-sensitive adhesive according to the present invention 1, wherein 5 to 20 parts by weight of a crosslinking agent is blended with respect to 100 parts by weight of the polylactic acid emulsion in terms of solid content.
粘着付与剤樹脂として所定酸価のロジン系樹脂を特定比率で混合したポリ乳酸エマルションに、さらにオキサゾリン系化合物、カルボジイミド系化合物などの特定の架橋剤を添加するため、保持力（凝集力）に優れるとともに、糊残りを良好に改善することができ、界面破壊を属性とする粘着剤として好適である。
また、本発明のエマルション粘着剤は、後述の試験例に示す通り、ポリシソシアネートやエポキシ系化合物とは異なる特定の架橋剤を使用するため、保存安定性に優れ、操作性が容易である。
さらに、ポリ乳酸は生分解性を有し、ロジン系樹脂も天然物由来の素材（バイオマス）であることから、本発明のエマルション粘着剤は環境への負荷もなく、幅広い分野での利用が期待できる。
Since a specific cross-linking agent such as an oxazoline compound or a carbodiimide compound is added to a polylactic acid emulsion in which a rosin resin having a predetermined acid value is mixed as a tackifier resin at a specific ratio, it has excellent holding power (cohesion). At the same time, the adhesive residue can be improved satisfactorily, and it is suitable as an adhesive having interface fracture as an attribute.
Moreover, since the emulsion adhesive of this invention uses the specific crosslinking agent different from polyisocyanate and an epoxy-type compound as shown in the below-mentioned test example, it is excellent in storage stability and operability is easy.
Furthermore, since polylactic acid is biodegradable and rosin resin is a material derived from natural products (biomass), the emulsion adhesive of the present invention has no impact on the environment and is expected to be used in a wide range of fields. it can.
本発明は、ポリ乳酸と粘着付与剤樹脂として所定酸価のロジン系樹脂を特定比率で混和したポリ乳酸エマルションに、オキサゾリン系化合物、カルボジイミド系化合物などの特定の架橋剤を添加したエマルション粘着剤である。 The present invention is an emulsion pressure-sensitive adhesive in which a specific cross-linking agent such as an oxazoline compound or a carbodiimide compound is added to a polylactic acid emulsion in which polylactic acid and a rosin resin having a predetermined acid value are mixed as a tackifier resin in a specific ratio. is there.
本発明のポリ乳酸は乳酸を重合して得られるポリエステル樹脂であれば特に制限されず使用できる。重合に用いられる乳酸はＤ−体、Ｌ−体を問わず、Ｄ−体とＬ−体の混合物であっても良い。なお、Ｄ−体とＬ−体の混合物を使用する場合には、Ｄ−体とＬ−体の使用割合は使用目的に応じて任意に決定できる。
また、上記ポリ乳酸は、ポリ乳酸のホモポリマーに限らず、コポリマー、ブレンドポリマーなどであっても良い。
上記コポリマーを形成する成分としては、例えばグリコール酸、３−ヒドロキシ酪酸、５−ヒドロキシ吉草酸、６−ヒドロキシカプロン酸などに代表されるヒドロキシカルボン酸、コハク酸、アジピン酸、セバシン酸、グルタル酸、デカンジカルボン酸、テレフタル酸、イソフタル酸などに代表されるジカルボン酸、エチレングリコール、プロパンジオール、オクタンジオール、ドデカンジオール、グリセリン、ソルビタン、ポリエチレングリコールなどに代表される多価アルコール、グリコリド、ε−カプロラクトン、δ−ブチロラクトンに代表されるラクトン類が挙げられる。
ポリ乳酸とブレンドするポリマーとしては、セルロース、硝酸セルロース、メチルセルロース、再生セルロース、グリコーゲン、キチン、キトサン、修飾化工澱粉系樹脂などが挙げられる。
ポリ乳酸の利用については、上述の範囲で使用することにより、樹脂の柔軟性を向上させるとともに、透明性を損なわず、経時的な物性低下の少ない、樹脂組成物を提供することができる。また、必要に応じて本発明で提示されるポリ乳酸を２種以上同時に使用しても良い。
尚、本発明のエマルション粘着剤はポリ乳酸をベースポリマーとするが、ポリブチレンサクシネート、ポリエチレンサクシネート、ポリブチレンアジペート、ポリエチレンサクシネー ト、ポリカプロラクトン、ポリグリコール酸などの他種の生分解性ポリエステル樹脂をベースポリマーとし、或は、これら他種のポリエステル樹脂とポリ乳酸の混合物をベースポリマーに使用しても、本発明に準じたエマルション粘着剤を製造できる。
The polylactic acid of the present invention can be used without particular limitation as long as it is a polyester resin obtained by polymerizing lactic acid. The lactic acid used for the polymerization may be a mixture of D-form and L-form regardless of D-form or L-form. In addition, when using the mixture of D-form and L-form, the usage-amount of D-form and L-form can be arbitrarily determined according to the intended purpose.
The polylactic acid is not limited to a homopolymer of polylactic acid but may be a copolymer, a blend polymer, or the like.
Examples of the components that form the copolymer include hydroxycarboxylic acids such as glycolic acid, 3-hydroxybutyric acid, 5-hydroxyvaleric acid, and 6-hydroxycaproic acid, succinic acid, adipic acid, sebacic acid, glutaric acid, Dicarboxylic acid typified by decanedicarboxylic acid, terephthalic acid, isophthalic acid, etc., polyhydric alcohol typified by ethylene glycol, propanediol, octanediol, dodecanediol, glycerin, sorbitan, polyethylene glycol, glycolide, ε-caprolactone, Examples include lactones typified by δ-butyrolactone.
Examples of the polymer blended with polylactic acid include cellulose, cellulose nitrate, methyl cellulose, regenerated cellulose, glycogen, chitin, chitosan, and modified starch-based resin.
About utilization of polylactic acid, while using in the above-mentioned range, while improving the softness | flexibility of resin, without impairing transparency, there can be provided the resin composition with few physical properties fall over time. Moreover, you may use 2 or more types of polylactic acid shown by this invention simultaneously as needed.
The emulsion adhesive of the present invention is based on polylactic acid, but other biodegradable types such as polybutylene succinate, polyethylene succinate, polybutylene adipate, polyethylene succinate, polycaprolactone and polyglycolic acid. Even when a polyester resin is used as a base polymer, or a mixture of these other types of polyester resins and polylactic acid is used as a base polymer, an emulsion adhesive according to the present invention can be produced.
一方、粘着付与剤樹脂としてのロジン系樹脂は、ロジン類及び各種ロジン誘導体を単用又は併用できる。
上記ロジン類は、アビエチン酸、パラストリン酸、ネオアビエチン酸、ピマール酸、イソピマール酸、或いはデヒドロアビエチン酸などの樹脂酸を主成分とするトール油ロジン、ガムロジン、ウッドロジンなどの未変性ロジンを初め、不均化ロジン、重合ロジン、水素化ロジン、或いはその他の化学的に修飾されたロジンなどをいう。
On the other hand, the rosin resin as the tackifier resin can be used singly or in combination with rosins and various rosin derivatives.
The rosins include unmodified rosins such as tall oil rosin, gum rosin, wood rosin and the like mainly composed of resin acids such as abietic acid, parastrinic acid, neoabietic acid, pimaric acid, isopimaric acid, or dehydroabietic acid. It means leveled rosin, polymerized rosin, hydrogenated rosin, or other chemically modified rosin.
上記ロジン誘導体としては、ロジンエステル類、ホルマリン変性ロジン類、不飽和カルボン酸変性ロジン類、フェノール変性ロジン類などが挙げられる。
上記ロジンエステル類は、ロジン類とアルコール類を公知のエステル化法により反応させたものをいう。エステル化反応は、不活性ガスの雰囲気下でロジン系樹脂とアルコールを２００〜３００℃に加熱し、生成した水を系外に除去することにより実施される。
ロジン類に対するアルコールの混合過剰率は任意であるが、一般的には０.１〜２.０程度が好ましい。エステル化に際して、反応促進用にリン酸、ｐ−トルエンスルホン酸、水酸化リチウム、水酸化カルシウム、酸化マグネシウム、酸化亜鉛、酢酸カルシウムなどの公知の触媒を用いることができる。
上記アルコール類としては、ｎ−オクチルアルコール、２−エチルヘキシルアルコール、デシルアルコール、ラウリルアルコール、ステアリルアルコール等の１価アルコール、エチレングリコール、ジエチレングリコール、ポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、ポリプロピレングリコール、ネオペンチルグリコール、トリメチレ ングリコール、テトラメチレングリコール、１,３−ブタンジオール、１,６−ヘキサンジオール等の２価アルコール、グリセリン、トリメチロールプロパン、トリメチロールプロパン、トリメチロールエタン、トリエチロールエタン等の３価アルコール、ペンタエリスリトール、ジグリセリン等の４価アルコール、或いは、ジペンタエリスリトール、ソルビトール等の６価アルコールなどを単用又は併用できる。製造工程の簡略性及び経済性の見地から、特にグリセリン、ペンタエリスリトールが好ましい。
Examples of the rosin derivative include rosin esters, formalin-modified rosins, unsaturated carboxylic acid-modified rosins, and phenol-modified rosins.
The rosin esters are those obtained by reacting rosins and alcohols by a known esterification method. The esterification reaction is carried out by heating the rosin resin and alcohol to 200 to 300 ° C. in an inert gas atmosphere and removing the generated water out of the system.
The mixing excess of alcohol with respect to rosins is arbitrary, but generally about 0.1 to 2.0 is preferable. In the esterification, a known catalyst such as phosphoric acid, p-toluenesulfonic acid, lithium hydroxide, calcium hydroxide, magnesium oxide, zinc oxide, calcium acetate can be used for reaction promotion.
Examples of the alcohols include monohydric alcohols such as n-octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, lauryl alcohol, stearyl alcohol, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl. Divalent alcohols such as glycol, trimethylene glycol, tetramethylene glycol, 1,3-butanediol, and 1,6-hexanediol, trivalents such as glycerin, trimethylolpropane, trimethylolpropane, trimethylolethane, and triethylolethane Tetravalent alcohols such as alcohol, pentaerythritol and diglycerin, or hexavalent alcohols such as dipentaerythritol and sorbitol. Call and can be used alone or in combination. Glycerin and pentaerythritol are particularly preferred from the standpoint of simplicity of the production process and economy.
上記ホルマリン変性ロジン類は、ロジン類にホルマリン類を付加させたものである。このホルマリン類は、ホルムアルデヒド、パラホルムアルデヒド、トリオキシメチレンなどが挙げられ、製造工程の簡略性及び経済性の見地から、特にパラホルムアルデヒドが好ましい。
上記ホルマリン類の付加反応は、不活性ガス雰囲気下でロジン系樹脂とホルマリン類を１３０〜２００℃に加熱するなどの公知の方法で実施される。ロジン系樹脂に対するホルムアルデヒドの重合比率は０.１〜１０％程度が好ましい。
この反応は比較的速やかに進行するが、場合によっては、リン酸、ｐ−トルエンスルホン酸などの公知の酸触媒を使用できる。
The formalin-modified rosins are obtained by adding formalins to rosins. Examples of the formalins include formaldehyde, paraformaldehyde, and trioxymethylene, and paraformaldehyde is particularly preferable from the viewpoint of simplicity of the manufacturing process and economy.
The formalin addition reaction is carried out by a known method such as heating the rosin resin and formalin to 130 to 200 ° C. in an inert gas atmosphere. The polymerization ratio of formaldehyde to rosin resin is preferably about 0.1 to 10%.
Although this reaction proceeds relatively quickly, in some cases, a known acid catalyst such as phosphoric acid or p-toluenesulfonic acid can be used.
上記不飽和カルボン酸変性ロジン類は、ロジン類にα,β−不飽和カルボン酸類を反応させたものである。このα,β−不飽和カルボン酸類は、α,β−不飽和カルボン酸又はその酸無水物などであり、具体的には、(無水)マレイン酸、フマル酸、イタコン酸、(無水)シトラコン酸、アクリル酸、メタクリル酸などが挙げられる。
ロジン系樹脂とα,β−不飽和カルボン酸類の反応は、不活性ガス雰囲気下で両者を１５０〜２８０℃に加熱するなどの公知の方式で実施される。ロジン系樹脂に対するα,β−不飽和カルボン酸類の重量比率は０.１〜２０％程度が好ましい。
さらに、ロジン類を不飽和カルボン酸で変性するとともに、上記エステル化反応を行って、不飽和カルボン酸変性ロジンエステルとしても良い。
The unsaturated carboxylic acid-modified rosins are those obtained by reacting rosins with α, β-unsaturated carboxylic acids. These α, β-unsaturated carboxylic acids are α, β-unsaturated carboxylic acids or acid anhydrides thereof. Specifically, (anhydrous) maleic acid, fumaric acid, itaconic acid, (anhydrous) citraconic acid Acrylic acid, methacrylic acid and the like.
The reaction between the rosin resin and the α, β-unsaturated carboxylic acids is carried out by a known method such as heating both to 150 to 280 ° C. in an inert gas atmosphere. The weight ratio of α, β-unsaturated carboxylic acids to rosin resin is preferably about 0.1 to 20%.
Furthermore, the rosins may be modified with an unsaturated carboxylic acid, and the esterification reaction may be performed to obtain an unsaturated carboxylic acid-modified rosin ester.
上記フェノール変性ロジン類は、ロジン類にフェノールを反応させたものである。硫酸、ｐ−トルエンスルホン酸、メタンスルホン酸等の強酸触媒共存下で、ロジン類とフェノールを１００〜２００℃で反応させることにより得られる。
場合によっては、強酸触媒を水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム等のアルカリ物質で中和しても良い。ロジン系樹脂に対するフェノールの重量比率は０.１〜５０％程度が好ましい。
The phenol-modified rosins are obtained by reacting rosins with phenol. It can be obtained by reacting rosins and phenol at 100 to 200 ° C. in the presence of a strong acid catalyst such as sulfuric acid, p-toluenesulfonic acid and methanesulfonic acid.
In some cases, the strong acid catalyst may be neutralized with an alkaline substance such as lithium hydroxide, sodium hydroxide, potassium hydroxide, or calcium hydroxide. The weight ratio of phenol to rosin resin is preferably about 0.1 to 50%.
本発明で使用するロジン系樹脂は酸価１〜３００のロジン誘導体であることが必要であり、酸価５〜１００のロジン系樹脂が好ましい。酸価が少な過ぎると前記架橋剤との架橋が不足し、多くなり過ぎると架橋が局在化して、かえって凝集力が低下してしまう。
また、上記ロジン誘導体ではロジンエステル類、不飽和カルボン酸変性ロジン、不飽和カルボン酸変性ロジンエステルが好ましい。
The rosin resin used in the present invention is required to be a rosin derivative having an acid value of 1 to 300 , and a rosin resin having an acid value of 5 to 100 is preferable . If the acid value is too small, the crosslinking with the crosslinking agent is insufficient, and if it is too large, the crosslinking is localized, and the cohesive force is lowered.
Of the rosin derivatives, rosin esters, unsaturated carboxylic acid-modified rosins, and unsaturated carboxylic acid-modified rosin esters are preferred.
本発明のポリ乳酸エマルションは前記ポリ乳酸をロジン系樹脂（粘着付与剤樹脂）と共に乳化剤を用いて水中に分散させて製造する。
この場合、ポリ乳酸とロジン系樹脂との混合物を水中に分散することが好ましいが、ポリ乳酸の水性エマルションと粘着付与剤樹脂の水性エマルションを別々に製造して混合しても差し支えない。
本発明では、ポリ乳酸とロジン系樹脂の混合割合は、固形分換算でポリ乳酸１００重量部に対してロジン系樹脂５〜５０重量部であることが必要であり、１５〜３５重量部が好ましい。ロジン系樹脂の割合が少な過ぎると凝集力不足になる。逆に、ロジン系樹脂が多くなり過ぎると乳化が困難になり、ポリ乳酸とロジン系樹脂が相分離を起こす恐れがある。
The polylactic acid emulsion of the present invention is produced by dispersing the polylactic acid in water together with a rosin resin (tackifier resin) using an emulsifier.
In this case, it is preferable to disperse a mixture of polylactic acid and rosin resin in water, but an aqueous emulsion of polylactic acid and an aqueous emulsion of tackifier resin may be separately produced and mixed.
In the present invention, the mixing ratio of polylactic acid and rosin resin is required to be 5 to 50 parts by weight of rosin resin with respect to 100 parts by weight of polylactic acid in terms of solid content , and preferably 15 to 35 parts by weight. . If the ratio of the rosin resin is too small, the cohesive force becomes insufficient. Conversely, if the amount of rosin resin is too large, emulsification becomes difficult, and there is a risk that polylactic acid and rosin resin undergo phase separation.
ポリ乳酸エマルションを製造する際に用いる乳化剤は特に制限はなく、アニオン系、ノニオン系、カチオン系の各種の乳化剤が使用できる。また、その使用量も特に制限されないが、固形の樹脂１００重量部に対して固形分換算で１〜６０重量部、好ましくは５〜５０重量部である。
上記アニオン系乳化剤には、有機スルホン酸、硫酸エステルのアルカリ金属塩、アンモニウム塩などが挙げられ、具体的には下記の(1)〜(6)などである。
(1)ドデシルベンゼンスルホン酸ナトリウムなどのアルキルアリールスルホン酸塩類。
(2)ラウリル硫酸ナトリウム、オレイル硫酸ナトリウムなどのアルキル（又はアルケニル）硫酸エステル塩類。
(3)ポリオキシエチレンラウリルエーテル硫酸ナトリウム、ポリオキシエチレンオレイルエーテル硫酸ナトリウムなどのポリオキシエチレンアルキル（又はアルケニル）エーテル硫酸エステル塩類。
(4)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、ポリオキシエチレンスチリルフェニルエーテル硫酸ナトリウムなど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。
(5)モノオクチルスルホコハク酸ナトリウム、ジオクチルスルホコハク酸ナトリウム、ポリオキシエチレンラウリルスルホコハク酸２ナトリウムなどのアルキルスルホコハク酸エステル塩並びにその誘導体類。
(6)アルキルジフェニルエーテルジスルホン酸ナトリウムなどのアルキルジアリール
エーテルジスルホン酸塩並びにその誘導体類。
The emulsifier used in producing the polylactic acid emulsion is not particularly limited, and various anionic, nonionic and cationic emulsifiers can be used. Moreover, the usage-amount is although it does not restrict | limit in particular, It is 1-60 weight part in conversion of solid content with respect to 100 weight part of solid resin, Preferably it is 5-50 weight part.
Examples of the anionic emulsifier include organic sulfonic acids, alkali metal salts of sulfuric esters, ammonium salts, and the like, and specifically include the following (1) to (6).
(1) Alkyl aryl sulfonates such as sodium dodecylbenzene sulfonate.
(2) Alkyl (or alkenyl) sulfate esters such as sodium lauryl sulfate and sodium oleyl sulfate.
(3) Polyoxyethylene alkyl (or alkenyl) ether sulfates such as sodium polyoxyethylene lauryl ether sulfate and sodium polyoxyethylene oleyl ether sulfate.
(4) Polyoxyethylene alkylaryl ether sulfates such as sodium polyoxyethylene nonylphenyl ether sulfate and sodium polyoxyethylene styryl phenyl ether sulfate.
(5) Alkylsulfosuccinic acid ester salts such as sodium monooctylsulfosuccinate, sodium dioctylsulfosuccinate, disodium polyoxyethylene laurylsulfosuccinate, and derivatives thereof.
(6) Alkyl diaryl ether disulfonates such as sodium alkyl diphenyl ether disulfonate and derivatives thereof.
また、上記ノニオン系乳化剤としては下記の(1)〜(7)などが挙げられる。
(1)ポリオキシエチレンラウリルエーテル、ポリオキシエチレンオレイルエーテルなどのポリオキシエチレンアルキル（又はアルケニル）エーテル類。
(2)ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンスチリルフェニルエーテルなどのポリオキシエチレンアルキルフェニルエーテル類。
(3)ソルビタンモノラウレート、ソルビタントリオレエートなどのソルビタン高級脂肪酸エステル類。
(4)ポリオキシエチレンソルビタンモノラウレートなどのポリオキシエチレンソルビタン高級脂肪酸エステル類。
(5)ポリオキシエチレンモノラウレート、ポリオキシエチレンモノオレエートなどのポリオキシエチレン高級脂肪酸エステル類。
(6)オレイン酸モノグリセライド、ステアリン酸モノグリセライドなどのグリセリン高級脂肪酸エステル類。
(7)ポリオキシエチレン・ポリオキシプロピレン・ブロックコポリマー。
Examples of the nonionic emulsifier include the following (1) to (7).
(1) Polyoxyethylene alkyl (or alkenyl) ethers such as polyoxyethylene lauryl ether and polyoxyethylene oleyl ether.
(2) Polyoxyethylene alkyl phenyl ethers such as polyoxyethylene nonyl phenyl ether and polyoxyethylene styryl phenyl ether.
(3) Higher sorbitan fatty acid esters such as sorbitan monolaurate and sorbitan trioleate.
(4) Polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate.
(5) Polyoxyethylene higher fatty acid esters such as polyoxyethylene monolaurate and polyoxyethylene monooleate.
(6) Glycerin higher fatty acid esters such as oleic acid monoglyceride and stearic acid monoglyceride.
(7) Polyoxyethylene / polyoxypropylene block copolymer.
ポリ乳酸エマルションを製造する際の乳化剤には、その他、必要に応じて合成高分子系の乳化剤を使用することもできる。
上記合成高分子系乳化剤としては、スチレン、α−メチルスチレン、ビニルトルエン、（メタ）アクリル酸、マレイン酸、（メタ）アクリル酸エステル類、アクリルアマイド、酢酸ビニル、スチレンスルホン酸、イソプレンスルホン酸、ビニルスルホン酸、アリルスルホン酸、２−（メタ）アクリルアミド−２−メチルプロパンスルホン酸などの重合性モノマーを2種以上重合させて得られる重合体を水酸化ナトリウム、水酸化カリウム、アンモニアなどのアルカリ類で塩形成させて水に分散又は可溶化させた水分散性重合体が挙げられる。また、上記モノマーの他にも、重合可能なモノマー類を限定することなく使用でき、重合方法も特に制約されることはない。
As the emulsifier for producing the polylactic acid emulsion, a synthetic polymer emulsifier may be used as necessary.
Examples of the synthetic polymer-based emulsifier include styrene, α-methylstyrene, vinyl toluene, (meth) acrylic acid, maleic acid, (meth) acrylic acid esters, acrylic amide, vinyl acetate, styrene sulfonic acid, isoprene sulfonic acid, Polymers obtained by polymerizing two or more polymerizable monomers such as vinyl sulfonic acid, allyl sulfonic acid, and 2- (meth) acrylamide-2-methylpropane sulfonic acid are converted to alkalis such as sodium hydroxide, potassium hydroxide, and ammonia. And water-dispersible polymers which are salt-formed and dispersed or solubilized in water. In addition to the above monomers, polymerizable monomers can be used without limitation, and the polymerization method is not particularly limited.
本発明のポリ乳酸エマルションは、溶剤型乳化法、無溶剤型乳化法、転相乳化法、或はその他の公知の乳化法によって製造される。
上記溶剤型乳化法は、粘着付与剤樹脂をメチレンクロライド等の塩素系炭化水素溶剤、トルエン、キシレン等の芳香族系溶剤、メチルケトン、メチルイソブチルケトンなどのケトン系溶剤、或は溶解可能な溶剤類などの有機溶剤に溶解させ、乳化剤と水を混合溶解した乳化水を予備混合して、粗粒子の水性エマルションを調製した後、各種ミキサー、コロイドミル、高圧乳化機、高圧吐出型乳化機、高剪断型乳化分散機などを用いて微細乳化した後、常圧或は減圧下で加熱しながら上記有機溶剤を除去する方法である。
上記無溶剤乳化法は、常圧或は加圧下で溶融した粘着付与剤樹脂と乳化剤水溶液を予備混合し、粗粒子の水性エマルションを調製した後、各種乳化分散機を用いて同様に微細乳化させる方法である。
また、上記転相乳化法は、常圧或は加圧下で粘着付与剤樹脂を加熱溶融した後、撹拌しながら乳化剤水溶液を徐々に加えて先ず油中水型エマルションを形成させ、次いで水中油型エマルションに相反転させる方法であり、溶剤法或は無溶剤法いずれの方法でも可能である。
尚、ポリ乳酸エマルションを製造するには、上述の通り、水を分散媒及び反応の場として、乳化剤などの存在下で乳化を行うが、さらに、エマルション粒子の安定化のために、保護コロイドとしてポリビニルアルコール及びその誘導体や、カルボキシメチルセルロース、ヒドロキシエチルセルロースなどのセルロース誘導体などの水溶性高分子を添加することもできる。また、乳化に際して使用する乳化剤の種類は前述した通りである。
The polylactic acid emulsion of the present invention is produced by a solvent type emulsion method, a solventless type emulsion method, a phase inversion emulsion method, or other known emulsion methods.
The solvent-type emulsification method may be carried out by using a tackifier resin as a chlorine-based hydrocarbon solvent such as methylene chloride, an aromatic solvent such as toluene or xylene, a ketone-based solvent such as methyl ketone or methyl isobutyl ketone, or a soluble solvent. After preparing an aqueous emulsion of coarse particles by pre-mixing emulsified water in which an emulsifier and water are mixed and dissolved in an organic solvent such as, various mixers, colloid mills, high pressure emulsifiers, high pressure discharge emulsifiers, high In this method, after finely emulsifying using a shearing type emulsifying disperser or the like, the organic solvent is removed while heating under normal pressure or reduced pressure.
In the above solventless emulsification method, a tackifier resin melted at normal pressure or under pressure and an aqueous emulsifier solution are premixed to prepare an aqueous emulsion of coarse particles, and then finely emulsified in the same manner using various emulsifying dispersers. Is the method.
In the above phase inversion emulsification method, after the tackifier resin is heated and melted at normal pressure or under pressure, an aqueous emulsifier solution is gradually added while stirring to form a water-in-oil emulsion, followed by an oil-in-water type. This is a method for reversing the phase of the emulsion, and any of the solvent method and the solventless method can be used.
In order to produce a polylactic acid emulsion, as described above, water is used as a dispersion medium and a reaction field, and emulsification is performed in the presence of an emulsifier and the like. Water-soluble polymers such as polyvinyl alcohol and derivatives thereof and cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose can also be added. The type of emulsifier used for emulsification is as described above.
本発明の架橋剤はカルボキシル基に対して反応性を有する架橋剤であり（主に、ロジン系樹脂のカルボキシル基と架橋反応する）、オキサゾリン系化合物、カルボジイミド系化合物、アジリジン系化合物、ヒドラジン系化合物よりなる群から選ばれた少なくとも一種であり、なかでも環境保全や労働衛生の見地から、オキサゾリン系化合物、カルボジイミド系化合物が好ましい。
上記オキサゾリン系化合物としては、オキサゾリン基を少なくとも２個以上有するものであれば良く、具体的には、２−メチル−２−オキサゾリン、２−エチル−２−オキサゾリン、２−イソプロピル−２−オキサゾリン、２−n−プロピル−２−オキサゾリン、２−ビニル−２−オキサゾリン、２−ビニル−４−メチル−２−オキサゾリン、２−イソプロペニル−２−オキサゾリン、２−イソプロペニル−４−メチル−２−オキサゾリンなどであり、市販品にはエポクロス（日本触媒(株)製）などがある。
上記カルボジイミド系化合物としては、カルボジイミド基を少なくとも２個以上有するものであれば良く、市販品にはカルボジライト（日清紡績(株)製）などがある。
上記アジリジン系化合物としては、アジリジン基を少なくとも２個以上有するものであれば良く、具体的には、１−(メチレン−ジ−ｐ−フェニレン)ビス−３,３−アジリジニル尿素、１,１′−(ヘキサメチレン)ビス−３,３−アジリジニル尿素、エチレンビス−(２−アジリジニルプロピオネート)、２,４,６−トリアジリジニル−１,３,５−トリアジンなどであり、市販品にはケミタイト（日本触媒(株)製）などがある。
上記ヒドラジン系化合物としては、ヒドラジン基を少なくとも２個以上有するものであれば良く、具体的には、シュウ酸ジヒドラジド、マロン酸ジヒドラジド、コハク酸ジヒドラジド、グルタル酸ジヒドラジド、アジピン酸ジヒドラジド、セバシン酸ジヒドラジド、マレイン酸ジヒドラジド、フマル酸ジヒドラジド、イタコン酸ジヒドラジドなどが挙げられる。
The crosslinking agent of the present invention is a crosslinking agent having reactivity with a carboxyl group (mainly, a crosslinking reaction with a carboxyl group of a rosin resin), an oxazoline compound, a carbodiimide compound, an aziridine compound, a hydrazine compound. Of these, at least one selected from the group consisting of oxazoline compounds and carbodiimide compounds are preferred from the viewpoints of environmental protection and occupational health.
The oxazoline-based compound may be any compound having at least two oxazoline groups. Specifically, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-isopropyl-2-oxazoline, 2-n-propyl-2-oxazoline, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2- Examples include oxazoline, and commercially available products include Epocross (manufactured by Nippon Shokubai Co., Ltd.).
The carbodiimide compound may be any compound having at least two carbodiimide groups, and commercially available products include carbodilite (manufactured by Nisshinbo Industries, Inc.).
The aziridine compound may be any compound having at least two aziridine groups. Specifically, 1- (methylene-di-p-phenylene) bis-3,3-aziridinylurea, 1,1 ′ -(Hexamethylene) bis-3,3-aziridinylurea, ethylenebis- (2-aziridinylpropionate), 2,4,6-triaziridinyl-1,3,5-triazine, etc. Is chemitite (manufactured by Nippon Shokubai Co., Ltd.).
The hydrazine-based compound may be any compound having at least two hydrazine groups. Specifically, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, Examples thereof include maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide and the like.
上記オキサゾリン系化合物、カルボジイミド系化合物、アジリジン系化合物、ヒドラジン系化合物よりなる群から選ばれた特定の架橋剤は、上述のように、各化合物を単用又は併用でき、また、異なる化合物同士を組み合わせて複用しても良い。
本発明２に示すように、上記架橋剤の配合割合は、固形分換算でポリ乳酸エマルション１００重量部に対して５〜２０重量部を配合するのが好ましく、１０〜１５重量部がより好ましい。５重量部より少ないとロジン系樹脂との架橋反応不足で高分子量化が阻害され、凝集力が不足するとともに、２０重量部を越えると過剰硬化により(凝集力が高くなり過ぎて)密着性が悪くなるうえ、コスト高でもある。
また、本発明のエマルション粘着剤には、その他、必要に応じて可塑剤、充填剤、増粘剤、耐水化剤、酸化防止剤、紫外線吸収剤、顔料、防腐剤などの各種添加剤を含有できる。
The specific cross-linking agent selected from the group consisting of the oxazoline compound, carbodiimide compound, aziridine compound, and hydrazine compound can be used alone or in combination as described above, and different compounds can be combined. May be used together.
As shown in the present invention 2 , the blending ratio of the crosslinking agent is preferably 5 to 20 parts by weight, more preferably 10 to 15 parts by weight based on 100 parts by weight of the polylactic acid emulsion in terms of solid content. When the amount is less than 5 parts by weight, the high molecular weight is hindered due to insufficient crosslinking reaction with the rosin resin, and the cohesive force is insufficient. When the amount exceeds 20 parts by weight, the adhesiveness is increased by excessive curing (cohesive force becomes too high). It gets worse and the cost is high.
In addition, the emulsion pressure-sensitive adhesive of the present invention contains various additives such as a plasticizer, a filler, a thickener, a water-resistant agent, an antioxidant, an ultraviolet absorber, a pigment, and an antiseptic as necessary. it can.
本発明のエマルション粘着剤は任意の被着体に使用することができる。
この被着体の種類は特に限定されず、例えば、ＳＵＳ板、シート、フィルム、紙、各種繊維質素材からなる織布もしくは不織布などが挙げられる。
上記シート、フィルム素材としては、ポリエチレン、ポリプロピレン、ポリエステル、ナイロン、ポリスチレン、ポリエチレンテレフタレート、塩化ビニル、ポリ乳酸、乳酸とその他のヒドロキシカルボン酸から誘導された乳酸系ポリマー、ポリブチレンサクシネート系ポリエステル、ポリカプロラクトン系樹脂、修飾澱粉系樹脂などが挙げられる。
上記繊維質素材としては、例えば、麻、絹、綿、羊毛等の天然繊維； レーヨン、キュプラ等の再生繊維； アクリル、ポリウレタン、ポリエステル、ポリエチレン、ポリエチレンテレフタレート、ポリ塩化ビニルナイロン、ポリプロピレン等の合成繊維が挙げられる。
上記織布としては、例えば、前記繊維質素材から作られた織物、編物などが挙げられる。
また、上記不織布としては、前記繊維質素材を化学的方法、機械的方法、又はそれらの組合せにより絡み合わせてウエッブとしたものが挙げられる。
The emulsion adhesive of this invention can be used for arbitrary adherends.
The kind of the adherend is not particularly limited, and examples thereof include a SUS board, a sheet, a film, paper, and a woven fabric or a nonwoven fabric made of various fibrous materials.
The above sheet and film materials include polyethylene, polypropylene, polyester, nylon, polystyrene, polyethylene terephthalate, vinyl chloride, polylactic acid, lactic acid polymers derived from lactic acid and other hydroxycarboxylic acids, polybutylene succinate polyesters, poly Examples include caprolactone-based resins and modified starch-based resins.
Examples of the fibrous material include natural fibers such as hemp, silk, cotton, and wool; recycled fibers such as rayon and cupra; synthetic fibers such as acrylic, polyurethane, polyester, polyethylene, polyethylene terephthalate, polyvinyl chloride nylon, and polypropylene. Is mentioned.
Examples of the woven fabric include woven fabrics and knitted fabrics made from the fibrous material.
In addition, examples of the nonwoven fabric include webs obtained by intertwining the fibrous material with a chemical method, a mechanical method, or a combination thereof.
以下、本発明のエマルション粘着剤の製造実施例、得られたエマルション粘着剤の保存安定性試験例、同エマルション粘着剤を用いた粘着テープの製造例、得られた粘着テープの性能評価試験例を順次説明する。上記実施例、製造例、試験例中の「部」及び「％」は、特記しない限りすべて重量基準である。
尚、本発明は下記の実施例、製造例、試験例などに拘束されるものではなく、本発明の技術的思想の範囲内で任意の変形をなし得ることは勿論である。
Hereinafter, production examples of the emulsion pressure-sensitive adhesive of the present invention, storage stability test example of the obtained emulsion pressure-sensitive adhesive, pressure-sensitive adhesive tape production example using the emulsion pressure-sensitive adhesive, performance evaluation test example of the pressure-sensitive adhesive tape obtained A description will be made sequentially. Unless otherwise specified, “parts” and “%” in the examples, production examples, and test examples are based on weight.
It should be noted that the present invention is not limited to the following examples, production examples, and test examples, and it is needless to say that arbitrary modifications can be made within the scope of the technical idea of the present invention.
《エマルション粘着剤の製造実施例》
下記の実施例１〜３のうち、実施例１は架橋剤にオキサゾリン系化合物を使用した例、実施例２は架橋剤にアジリジン系化合物を使用した例、実施例３は架橋剤にカルボジイミド系化合物を使用した例である。
下記の比較例１〜５のうち、比較例１はロジン系樹脂と架橋剤のブランク例、比較例２は架橋剤のブランク例、比較例３はロジン系樹脂のブランク例、比較例４は冒述の特許文献３に準拠して架橋剤にポリイソシアネートを使用した例、比較例４は冒述の特許文献４に準拠して架橋剤にエポキシ系化合物を使用した例である。
<< Embodiment Example of Emulsion Adhesive >>
Of Examples 1 to 3 below, Example 1 is an example using an oxazoline compound as a crosslinking agent, Example 2 is an example using an aziridine compound as a crosslinking agent, and Example 3 is a carbodiimide compound as a crosslinking agent. It is an example using.
Of Comparative Examples 1 to 5 below, Comparative Example 1 is a rosin resin and a crosslinking agent blank example, Comparative Example 2 is a crosslinking agent blank example, Comparative Example 3 is a rosin resin blank example, and Comparative Example 4 is An example in which a polyisocyanate is used as a cross-linking agent in accordance with Patent Document 3 described above, and Comparative Example 4 is an example in which an epoxy-based compound is used as a cross-linking agent in accordance with Patent Document 4 described above.
(1)実施例１
温度計、窒素導入管、撹拌機及び冷却管を備えた反応容器に、ポリ乳酸（バイロエコール BE-910、東洋紡社製）１５０部とロジン系樹脂（ハリエスターDS-70L（ロジンエステル）、ハリマ化成社製：酸価７、軟化点７５℃）５０部をトルエン３００部に溶解させ、あらかじめ２０７部の水に溶解させたポリビニルアルコール（ポバール405、クラレ社製）５１.６部及びアニオン系乳化剤（ハイテノール NF-13、第一工業製薬社製）１６.７部を加えて、４５℃において３０分間、撹拌混合して予備乳化を行った。
次いで、上記予備乳化物を高圧乳化機（マントンガウリン社製）によって３００Kg/cm2の圧力で乳化して、乳化物を得た。
この乳化物を１３０mmHgの条件下で加熱減圧蒸留してトルエンを除去した後、固形分を調整して固形分５０％、ｐＨ２.４、粒子径０.３８μｍのポリ乳酸エマルションを得た後、２５％アンモニア水にてｐＨ７.０に調整した。
次いで、このポリ乳酸エマルションに増粘剤（プライマルASE-60、ロームアンドハースジャパン社製）を１.２部添加し、カルボン酸に反応する水系のオキサゾリン系架橋剤（エポクロスK-2010E、日本触媒社製）を固形分換算で１０部加え、固形分を４５％に調整したエマルション粘着剤を得た。
尚、上記ｐＨ値は２５℃での測定値であり、下記の実施例及び比較例においても同様である。
(1) Example 1
In a reaction vessel equipped with a thermometer, nitrogen introduction tube, stirrer and cooling tube, 150 parts of polylactic acid (Vylo Ecole BE-910, manufactured by Toyobo Co., Ltd.), rosin resin (Harristar DS-70L (rosin ester), Harima Made by Kasei Co., Ltd .: 51.6 parts of polyvinyl alcohol (Poval 405, made by Kuraray Co., Ltd.) dissolved in 300 parts of toluene in advance of 50 parts of acid number 7, softening point 75 ° C.) and an anionic emulsifier (Hytenol NF-13, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 16.7 parts was added and pre-emulsified by stirring and mixing at 45 ° C. for 30 minutes.
Next, the preliminary emulsion was emulsified with a high pressure emulsifier (mantongaurin) at a pressure of 300 kg / cm 2 to obtain an emulsion.
The emulsion was heated and distilled under a condition of 130 mmHg to remove toluene, and then the solid content was adjusted to obtain a polylactic acid emulsion having a solid content of 50%, pH 2.4, and particle size of 0.38 μm. The pH was adjusted to 7.0 with% ammonia water.
Next, 1.2 parts of a thickener (Primal ASE-60, manufactured by Rohm and Haas Japan) was added to this polylactic acid emulsion, and an aqueous oxazoline-based cross-linking agent (Epocross K-2010E, Nippon Shokubai Co., Ltd.) that reacts with carboxylic acid. 10 parts in terms of solid content was added to obtain an emulsion pressure-sensitive adhesive having a solid content adjusted to 45%.
In addition, the said pH value is a measured value in 25 degreeC, and is the same also in the following Example and comparative example.
(2)実施例２
上記実施例１を基本として、実施例１のオキサゾリン系架橋剤をアジリジン系架橋剤（ケミタイトDZ-22E、日本触媒社製）に代えた以外は、実施例１と同様に処理してエマルション粘着剤を得た。
(2) Example 2
Based on Example 1 above, the emulsion pressure-sensitive adhesive was treated in the same manner as in Example 1 except that the oxazoline-based crosslinking agent of Example 1 was replaced with an aziridine-based crosslinking agent (Chemite DZ-22E, manufactured by Nippon Shokubai Co., Ltd.). Got.
(3)実施例３
上記実施例１を基本として、実施例１のオキサゾリン系架橋剤をカルボジイミド系架橋剤（カルボジライトE-02、日清紡社製）に代えた以外は、実施例１と同様に処理してエマルション粘着剤を得た。
(3) Example 3
Based on the above Example 1, except that the oxazoline-based crosslinking agent of Example 1 was replaced with a carbodiimide-based crosslinking agent (Carbodilite E-02, manufactured by Nisshinbo Co., Ltd.), the emulsion adhesive was treated in the same manner as in Example 1. Obtained.
(4)比較例１
上記実施例１を基本として、実施例１のオキサゾリン系架橋剤及びロジン系樹脂を加えなかった以外は、実施例１と同様に処理してエマルション粘着剤を得た。
(4) Comparative Example 1
Based on Example 1 above, an emulsion pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that the oxazoline-based crosslinking agent and rosin-based resin of Example 1 were not added.
(5)比較例２
上記実施例１を基本として、実施例１のオキサゾリン系架橋剤を加えなかった以外は、実施例１と同様に処理して、エマルション粘着剤を得た。
(5) Comparative example 2
Based on the above Example 1, an emulsion pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that the oxazoline-based crosslinking agent of Example 1 was not added.
(6)比較例３
上記実施例１を基本として、実施例１のロジン系樹脂を加えなかった以外は、実施例１と同様に処理して、エマルション粘着剤を得た。
(6) Comparative Example 3
Based on the above Example 1, an emulsion adhesive was obtained in the same manner as in Example 1 except that the rosin resin of Example 1 was not added.
(7)比較例４
上記実施例１を基本として、実施例１のオキサゾリン系架橋剤をポリイソシアネート系架橋剤（バーノックDNW−5000、大日本インキ化学工業社製）に代えた以外は、実施例１と同様に処理してエマルション粘着剤を得た。
(7) Comparative example 4
Based on the above Example 1, the same treatment as in Example 1 was conducted except that the oxazoline-based crosslinking agent of Example 1 was replaced with a polyisocyanate-based crosslinking agent (Bernock DNW-5000, manufactured by Dainippon Ink & Chemicals, Inc.). Thus, an emulsion adhesive was obtained.
(8)比較例５
上記実施例１を基本として、実施例１のオキサゾリン系架橋剤をエポキシ系架橋剤（デナコールEX313、ナガセケムテックス社製）に代えた以外は、実施例１と同様に処理してエマルション粘着剤を得た。
(8) Comparative Example 5
Based on the above Example 1, except that the oxazoline-based crosslinking agent of Example 1 was replaced with an epoxy-based crosslinking agent (Denacol EX313, manufactured by Nagase ChemteX Corp.), the emulsion adhesive was treated in the same manner as in Example 1. Obtained.
そこで、上記実施例１〜３及び比較例１〜５で得られた各エマルション粘着剤の保存安定性を調べるとともに、当該エマルション粘着剤を基材に塗工して粘着シートを製造し、各種粘着特性を調べた。
《エマルション粘着剤の保存安定性試験例》
実施例１〜３及び比較例１〜５の各エマルション粘着剤１００ｇをマヨネーズ瓶に入れて密封し、セイフティーオーブン（SPHH-100、TABAI社製）により４０℃、１週間の条件で、静置保存した。
次いで、１週間経過後のエマルション状態を目視観察して、次の基準で保存安定性の優劣を評価した。
○：エマルションに変化なく、相分離は認められなかった。
×：エマルションが水相とエマルション相に分離した。
Then, while examining the storage stability of each emulsion adhesive obtained in Examples 1 to 3 and Comparative Examples 1 to 5, the emulsion adhesive was coated on a substrate to produce an adhesive sheet, and various adhesives The characteristics were investigated.
<< Example of storage stability test of emulsion adhesive >>
100 g of each emulsion pressure-sensitive adhesive of Examples 1 to 3 and Comparative Examples 1 to 5 was put in a mayonnaise bottle and sealed, and left still in a safety oven (SPHH-100, manufactured by TABAI) at 40 ° C. for 1 week. saved.
Subsequently, the emulsion state after one week passed was visually observed, and the superiority or inferiority of storage stability was evaluated according to the following criteria.
○: No change in emulsion and no phase separation was observed.
X: The emulsion was separated into an aqueous phase and an emulsion phase.
《粘着シートの製造例》
上記実施例１〜３及び比較例１〜５の各エマルション粘着剤を乾燥後の塗膜厚が２５μｍとなるように、丸型アプリケータ２５μｍ（ベーカ式アプリケーター、太佑機材株式会社）を用いて自動塗工機（PI-1210、テスター産業社製）にてＰＥＴフィルム（トーレルミラーTタイプ、東レ社製）上に塗工し、セイフティーオーブン（SPHH-100、TABAI社製）により１２０℃、３分間の条件で乾燥させて、各粘着シートを作成した。
<< Manufacturing example of adhesive sheet >>
Automatic using a
《粘着シートによる粘着特性試験例》
そこで、上記粘着シートを２３℃の雰囲気下で１日静置した後、下記の保持力及び糊残り度合の性能評価試験に供した。
(ａ)保持力
JIS-Z0237に準拠して、被着体としてステンレス板（SUS304を280番研磨紙で研磨して表面加工したもの）を用いて、これに２５×２５mmの上記粘着シートを貼り付けた。その後、４０℃雰囲気下で、重力方向に２００ｇの荷重を１時間かけた後のずれ幅(mm)、或は錘の落下時間(分)を測定した。
《Example of adhesive property test using adhesive sheet》
Then, after leaving the said adhesive sheet still for one day in 23 degreeC atmosphere, it used for the performance evaluation test of the following retention strength and adhesive residue degree.
(a) Holding power
In accordance with JIS-Z0237, a stainless steel plate (SUS304 polished with surface No. 280 and surface-treated) was used as an adherend, and the 25 × 25 mm adhesive sheet was attached thereto. Thereafter, in a 40 ° C. atmosphere, the displacement width (mm) after dropping a load of 200 g in the direction of gravity for 1 hour or the falling time (minute) of the weight was measured.
(ｂ)糊残りの有無
粘着シートをステンレス板（SUS304を280版研磨紙で研磨して表面加工したもの）に貼着し、２０分後に１８０°方向へ３００mm/分の速度にて引き剥がし、ステンレス表面の糊残りを目視観察して、次の基準でその優劣を評価した。
○：糊残りは認められなかった。
×：糊残りが認められた。
(b) Presence or absence of adhesive residue The adhesive sheet was attached to a stainless steel plate (SUS304 polished with 280 polishing paper and surface-treated), and after 20 minutes, peeled off at a speed of 300 mm / min in the 180 ° direction. The adhesive residue on the stainless steel surface was visually observed, and the superiority or inferiority was evaluated according to the following criteria.
○: No adhesive residue was observed.
X: Adhesive residue was recognized.
図１はその試験結果を示す。
(1)保持力（４０℃）について
実施例１〜３では錐の落下はなく、極めて優れた評価であった。これに対して、比較例１〜３では共に錐が５０〜５５分の範囲内で落下した。また、架橋剤にポリイソシアネートを使用した比較例４は実施例１〜３と同水準であったが、エポキシ系化合物を使用した比較例５では実施例１〜３に比べてズレ幅が大きかった。
これにより、実施例での優れた保持力が確認され、ポリ乳酸とロジン系樹脂を混和したポリ乳酸エマルションにオキサゾリン系化合物、カルボジイミド系化合物などの特定の架橋剤を添加することの重要性が明らかになった。
FIG. 1 shows the test results.
(1) Holding power (40 ° C.) In Examples 1 to 3, there was no fall of the cone, and the evaluation was extremely excellent. On the other hand, in Comparative Examples 1 to 3, the cones fell within a range of 50 to 55 minutes. Moreover, although the comparative example 4 which uses polyisocyanate for the crosslinking agent was the same level as Examples 1-3, the gap width was large in Comparative Example 5 which used the epoxy-type compound compared with Examples 1-3. .
As a result, the excellent holding power in the examples was confirmed, and the importance of adding a specific cross-linking agent such as an oxazoline compound or a carbodiimide compound to a polylactic acid emulsion in which polylactic acid and a rosin resin were mixed was clarified. Became.
(2)糊残りについて
実施例１〜３及び架橋剤を含みロジン系樹脂を含まない比較例３では、被着体のステンレス板に糊残りが見られなかったのに対して、比較例１〜２並びに比較例４〜５では糊残りが確認された。
従って、ポリ乳酸エマルション粘着剤に優れた保持力を付与し、且つ、被着体の糊残りをなくすためには、乳化時にポリ乳酸とロジン系樹脂を混和し、その乳化組成物に水系架橋剤を添加することの重要性が確認できた。
(2) About adhesive residue In Examples 1 to 3 and Comparative Example 3 containing a crosslinking agent and no rosin resin, no adhesive residue was found on the stainless steel plate of the adherend, whereas Comparative Examples 1 to 2 and Comparative Examples 4 to 5 showed adhesive residue.
Therefore, in order to give excellent holding power to the polylactic acid emulsion pressure-sensitive adhesive and eliminate the adhesive residue of the adherend, polylactic acid and rosin resin are mixed at the time of emulsification, and an aqueous crosslinking agent is added to the emulsion composition. This confirmed the importance of adding.
(3)エマルション粘着剤の保存安定性
比較例４〜５では１週間経過時点でエマルションの相分離が進み、実用性は顕著に損なわれていた。
これに対して、実施例１〜３のエマルション粘着剤では相分離は認められず、優れた保存安定性が確認できた。
(3) Storage stability of emulsion adhesives In Comparative Examples 4 to 5, the phase separation of the emulsion progressed after 1 week, and the practicality was significantly impaired.
On the other hand, phase separation was not recognized in the emulsion adhesives of Examples 1 to 3, and excellent storage stability could be confirmed.
(4)総合評価
実施例１〜３を比較例１〜２に対比すると、実施例１〜３は保持力に優れ、且つ糊残りもないのに対して、比較例１〜２では保持力及び糊残りの評価ともに顕著に劣った。尚、比較例３では糊残りの評価は実施例と同水準であったが、保持力が顕著に劣った。これにより、被着体に対する優れた保持力と糊残りの無い粘着物性を良好に兼備させるには、ポリ乳酸とロジン系樹脂を混和したポリ乳酸エマルションに架橋剤を添加することの重要性が裏付けられた。
また、実施例１〜３を比較例４〜５に対比すると、実施例１〜３では保持力及び糊残りに加えて、保存安定性の評価も良好であった。これに対して、比較例４では保持力の評価は実施例と同水準であったが、糊残り及び保存安定性の評価は顕著に劣った。比較例５でも比較例４とほぼ同様の評価であった（但し、保持力は比較例４より劣った）。
即ち、架橋剤にポリイソシアネートやエポキシ系化合物を使用すると、保存安定性に劣り、糊残りの評価も同様に劣ることから、ポリ乳酸エマルションに添加する架橋剤をオキサゾリン系化合物、カルボジイミド系化合物、アジリジン系化合物などに特定化することの重要性が明確になった。
尚、前述したように、環境保全や労働衛生の観点から、本発明の架橋剤では、オキサゾリン系化合物、カルボジイミド系化合物が好ましい。
(4) Comprehensive evaluation When comparing Examples 1 to 3 with Comparative Examples 1 and 2, Examples 1 to 3 have excellent holding power and no adhesive residue, whereas Comparative Examples 1 and 2 have holding power and The evaluation of adhesive residue was significantly inferior. In Comparative Example 3, the evaluation of the adhesive residue was the same as that in the example, but the holding power was significantly inferior. As a result, the importance of adding a cross-linking agent to a polylactic acid emulsion mixed with polylactic acid and rosin resin is supported in order to combine excellent holding power on the adherend and adhesive properties without adhesive residue. It was.
Moreover, when Examples 1-3 were contrasted with Comparative Examples 4-5, in Examples 1-3, in addition to holding power and adhesive residue, the storage stability was also evaluated well. On the other hand, in Comparative Example 4, the evaluation of the holding power was the same level as in the Examples, but the evaluation of the adhesive residue and the storage stability was significantly inferior. In Comparative Example 5, the evaluation was almost the same as in Comparative Example 4 (however, the holding power was inferior to that of Comparative Example 4).
That is, when a polyisocyanate or an epoxy compound is used as a crosslinking agent, the storage stability is inferior, and the evaluation of the adhesive residue is also inferior, so the crosslinking agent added to the polylactic acid emulsion is an oxazoline compound, carbodiimide compound, aziridine The importance of specializing in chemical compounds became clear.
As described above, from the viewpoints of environmental protection and occupational health, the crosslinking agent of the present invention is preferably an oxazoline compound or a carbodiimide compound.
Claims (2)
上記ロジン系樹脂が酸価１〜３００のロジン誘導体であり、
固形分換算で、ポリ乳酸１００重量部に対してロジン系樹脂５〜５０重量部を配合することを特徴とするエマルション粘着剤。 Polylactic acid emulsion were mixed rosin-based resin as a polylactic acid and a tackifier resin, adding an oxazoline-based, carbodiimide-based, aziridine-based, cross-linking agent having reactivity with the carboxyl group selected from the group consisting of hydrazine compound And
The rosin resin is a rosin derivative having an acid value of 1 to 300,
An emulsion adhesive comprising 5 to 50 parts by weight of a rosin resin based on 100 parts by weight of polylactic acid in terms of solid content .
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